The objective of this Ph.D. project is to investigate Arctic middle atmosphere chemistry using solar infrared absorption spectroscopy. These measurements were made at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, which is operated by the Canadian Network for the Detection of Atmospheric Change (CANDAC). This research is part of the CANDAC/PEARL Arctic Middle Atmosphere Chemistry theme and aims to improve our understanding of the processes controlling the stratospheric ozone budget using measurements of the concentrations of stratospheric constituents. The instrument, a Bruker IFS 125HR Fourier transform infrared (FTIR) spectrometer, has been specifically designed for high-resolution measurements over a broad spectral range and has been used to measure reactive species, source gases, reservoirs, and dynamical tracers at PEARL since August 2006. The first part of this research focuses on the optimization of ozone retrievals, for which 22 microwindows were studied and compared. The spectral region from 1000 to 1005 cm-1 was found to be the most sensitive in both the stratosphere and troposphere, giving the highest number of independent pieces of information and the smallest total error for retrievals at Eureka. iii Similar studies were performed in coordination with the Network for the Detection of Atmospheric Composition Change for nine other species, with the goal of improving and harmonizing the retrieval parameters among all Infrared Working Group sites. Previous satellite validation exercises have identified the highly variable polar conditions of the spring period to be a challenge. In this work, comparisons between the 125HR and ACE-FTS (Atmospheric Chemistry Experiment-Fourier transform spectrometer) from 2007 to 2010 have been used to develop strict criteria that allow the ground and satellite-based instruments to be confidently compared. After applying these criteria, the differences between the two instruments were generally small and in good agreement with previous ground-based FTIR/ACE-FTS comparisons. No clear bias was seen from year-to-year, and, in all cases, the difference between the measurements was within one standard deviation. The mean biases between the ACE-FTS and 125HR partial columns for 2007-2010 were -5.61 to 1.11%, -0.23 to 4.86%, -15.33 to -2.86%, -4.77 to 1.09%, and -0.34 to 5.23% for O3, HCl, ClONO2, HNO3, and HF, respectively. The 125HR measurements and three atmospheric models (CMAM-DAS, GEM-BACH, and SLIMCAT) were used to derive an NOy partial column data product for Eureka. This data product includes the five primary species NO, NO2, HNO3, N2O5, and ClONO2 and was used to study the seasonal and interannual variability of NOy from 2007 to 2010. The NOy 15-40 km partial column was found to be approximately constant through the sunlit part of the year, with greater variability during the spring. The mean partial column averaged for the spring period was (2.5±0.2)x1016 molec cm-2, while for the summer, it was (2.3±0.1)x1016 molec cm-2. The springtime evolution of NOy and its constituent nitrogen species, was also examined for all four years. The variability of the 5-NOy partial column was seen to be dominated by that of HNO3. iv The evolution of the individual nitrogen species was found to be consistent with the current understanding of the chemical and dynamical processes that occur in the polar stratosphere. Unusually low ozone columns were measured at Eureka from mid-February to late March 2011 and compared to the previous 14 years of measurements by the 125HR and its predecessor, Environment Canada’s Bomem DA8. The normalized O3/HF, HCl/HF, and HNO3/HF ratios, for which the effects of dynamics have been reduced, also showed record minima over this period. The SLIMCAT chemical transport model was used to quantify chemical ozone loss using the passive subtraction method. Chemical ozone depletion inside the vortex above Eureka was estimated to be 35%, which is the largest observed there in the past 15 years.

The near- through mid-infrared offers a unique and, as this thesis aims to show, essential view of extragalactic stellar populations both nearby, at intermediate redshifts and at very high redshift. In chapter 2, I demonstrate that rest-frame near-IR photometry obtained by the Spitzer Space Telescope provides more robust stellar mass estimates for a spectroscopic sample of ~100 galaxies in the redshift desert (0.5<z<2), and is crucial for modeling galaxies with young star-forming populations. From this analysis, a surprising result emerges in the data. Although the rest-frame light short of 2 micron improves stellar mass estimates, the models and observations disagree beyond 2 micron and emission from non-stellar sources becomes significant. At wavelengths from 1-30 micron, stellar and non-stellar emission contribute equally to a galaxy's global spectral energy distribution. This is unlike visible wavelengths where stellar emission dominates or the far-IR where dust emission provides the bulk of a galaxy's luminosity. Using the sample of high-z galaxies, in chapter 3, I quantify the statistical significance of the excess emission at 2-5 micron and find the emission to correlate with the OII luminosity, suggesting a link between the excess emission and star formation. The origin of the excess emission is not clear, although I explore a number of non-stellar candidates in this chapter. Nearby resolved observations provide a clearer picture of the excess by spatially resolving 68 nearby galaxies. By analyzing the pixel-by-pixel near-IR colours within each galaxy at ~1-5 micron, increasingly red near-IR colors are mapped to spatial regions in chapter 4. For regions with red NIR colors and high star formation rates, I find the broad near- through mid-IR spectrum is constant, varying only in amplitude as a function of the intensity of star formation, suggesting the infrared emission of a young, dusty stellar populations can be added to stellar population synthesis models as an additional component tied to the star formation rate. In closing the thesis, the focus is moved to the detection of stellar populations in the earliest star-forming galaxies. By z>6, all visible wavelength emission is redshifted into near-IR wavelengths. In chapter 5, I show how a tunable near-IR filter I have helped develop holds promise for finding bright Lyman alpha emitting galaxies at redshifts of 8<z<11.

Mid-infrared lasers in the 3-5 µm range are important for wide variety of applications including trace gas sensing, infrared counter measures, free space optical communications, etc. GaSb-based type-I quantum well (QW) diode lasers are an attractive choice due to their relatively simple design and growth tolerances, as compared with quantum cascade lasers and interband cascade lasers. Excellent diode lasers have been demonstrated for wavelengths up to ~3.0 µm, employing GaInAsSb/AlGaAsSb QW active regions. But, device performance tends to degrade at longer wavelengths, due to Auger recombination and decreasing QW valence band offsets. In this work we look into the feasibility of using highly strained GaInAsSb/GaSb QWs as active regions for diode lasers operating at wavelengths beyond 3.0 µm. Heavy strain in the QW can improve valence band offset and also increase the splitting between the heavy and light hole bands which can help minimize Auger recombination. Through optimized molecular beam epitaxy (MBE) growth conditions we were able to incorporate up to 2.45 % compressive strain in these QWs enabling laser operation up to 3.4 µm at room temperature. An alternate path to extend the emission wavelength is to incorporate dilute quantities of nitrogen into the QW. Incorporating dilute quantities of substitutional nitrogen into traditional III-V’s strongly reduces the bandgap of the alloy. The advantage for the case of GaSb based dilute-nitrides is that the bandgap reduction is almost exclusively due to the lowering of the conduction band leaving the valence band offsets unaffected; thus providing a path to mitigating hole leakage while extending the emission wavelength. Although GaSb-based dilute-nitrides are a potentially elegant solution for extending the operating wavelength of GaSb-based type-I QW diode lasers, the luminescence efficiency of this material system has been relatively poor. This is most likely due to the presence of a high concentration of point defects, like nitrogen substitutional clusters. Through careful optimization of MBE growth conditions and post growth annealing, we demonstrate improved luminescence efficiency. With further optimization this material system can potentially extend the emission wavelength of GaSb-based type-I QW diode lasers even further into the mid-infrared spectrum. / text

The mid-infrared (MIR) system presented in the thesis is based on a sub-100-fs erbium-doped fiber laser operating at 1.55 µm. The output of the laser is split in two, each arm seeding an erbium-doped fiber amplifier. The output of the first amplifier is sent to a grating-based stretcher to be stretched to 50 ps before seeding the optical parametric chirped-pulse amplifier (OPCPA). The output of the second amplifier is coupled to a highly nonlinear fiber to generate the 1 µm needed to seed the a neodymium-doped yttrium lithium fluoride (Nd:YLF) system. This work represents the first time this synchronization scheme is used, and the timing jitter between the two arms at the OPCPA is reduced to 333 fs. The pump laser for the OPCPA is a regenerative amplifier producing 1.6 W followed by a double-pass amplifier, for a final output power of 2.5 W at 1 kHz. Etalons were inserted into the cavity of the regenerative amplifier to stretch the pulses to 50 ps The OPCPA consists of two potassium titanyl arsenate crystals in a noncollinear configuration. With three passes, the gain is 3.8 · 10 6 . Using a grating compressor, the pulse duration is reduced to 140 fs, with a power of 300 mW. Because of the reduction of the timing jitter, the amplitude stability is 1 %, which is a great improvement compare to existing systems. To generate ultrafast light in the MIR, an optical parametric amplifier is used, pumped ii by the output of the OPCPA and seeded with its 3-µm idler. Two crystals were tested, both in a single-pass configuration. For the first crystal, a 4-mm thick silver thiogallate, an efficiency of 7.4 % was reached, with 8.76 mW in the signal and 7.2 mW in the idler. For the second crystal, a 2-mm thick lithium gallium selenide, the efficiency was higher, reaching 10.8 %. The power for the signal was 11.5 mW, and for the idler, 11.11 mW. Using this new scheme, energies on par with current systems are achieved with much higher efficiencies.

The mid-infrared (MIR) system presented in the thesis is based on a sub-100-fs erbium-doped fiber laser operating at 1.55 µm. The output of the laser is split in two, each arm seeding an erbium-doped fiber amplifier. The output of the first amplifier is sent to a grating-based stretcher to be stretched to 50 ps before seeding the optical parametric chirped-pulse amplifier (OPCPA). The output of the second amplifier is coupled to a highly nonlinear fiber to generate the 1 µm needed to seed the a neodymium-doped yttrium lithium fluoride (Nd:YLF) system. This work represents the first time this synchronization scheme is used, and the timing jitter between the two arms at the OPCPA is reduced to 333 fs. The pump laser for the OPCPA is a regenerative amplifier producing 1.6 W followed by a double-pass amplifier, for a final output power of 2.5 W at 1 kHz. Etalons were inserted into the cavity of the regenerative amplifier to stretch the pulses to 50 ps The OPCPA consists of two potassium titanyl arsenate crystals in a noncollinear configuration. With three passes, the gain is 3.8 · 10 6 . Using a grating compressor, the pulse duration is reduced to 140 fs, with a power of 300 mW. Because of the reduction of the timing jitter, the amplitude stability is 1 %, which is a great improvement compare to existing systems. To generate ultrafast light in the MIR, an optical parametric amplifier is used, pumped ii by the output of the OPCPA and seeded with its 3-µm idler. Two crystals were tested, both in a single-pass configuration. For the first crystal, a 4-mm thick silver thiogallate, an efficiency of 7.4 % was reached, with 8.76 mW in the signal and 7.2 mW in the idler. For the second crystal, a 2-mm thick lithium gallium selenide, the efficiency was higher, reaching 10.8 %. The power for the signal was 11.5 mW, and for the idler, 11.11 mW. Using this new scheme, energies on par with current systems are achieved with much higher efficiencies.

Sensing systems for mid-infrared wavelengths (2 to 5 μm) have important applications in biomedical, atmospheric and process gas monitoring systems. For lack of a suitable substrate, the full potential of GaSb-based materials, which are particularly suitable for operating in these wavelengths, are not completely realized. Hence, metamorphic growth technology, that allows the growth of semiconductor epilayers of arbitrary composition on any substrate, has been explored for antimony materials in this research. This makes the growth of device layers, containing arbitrary composition of GaSb-based materials, possible on commercially available 6"-GaAs substrates, and thereby reducing fabrication cost. Metamorphic growth of In(0.15)Ga(0.85)Sb was achieved using gas-source molecular beam epitaxy by growing compositionally graded ln(x)Ga(1-x)Sb buffer layers on a GaSb substrate. The effects of growth temperature on the quality of the metamorphic buffer layers along with the etching issues (both wet and dry) of GaSb-based materials were studied. Homo-junction n-i-p and p-i-n diodes were fabricated on In(0.15)Ga(0.85)Sb metamorphic layers. The dark current and its temperature dependence were measured and the extraction of area and perimeter components of dark current was done. The modeling of the components of dark current suggests that the diode currents were dominated by surface leakage. Surface passivation by silicon nitride and polyimide were investigated and our findings suggest that the former resulted in a better passivated surface. Responsivity measurements show that In(0.18)Ga(0.82)Sb diodes, metamorphically grown on GaSb substrates, have a cut-off wavelength of 2270 nm. Finally, hole (β) and previously unreported electron (α) ionization coefficients, at room temperature and 90° C, were extracted from these structures. The results show that α>β for ln(0.10)Ga(0.90)Sb for both temperatures. These photodetectors can be implemented m practical receiver systems for mid-infrared applications, such as atmospheric CO2 and methane detection at 2.0 μm. The possibility of growing antimony-based device layers on larger substrates, paves the way for future optoelectronic receiver systems operating at longer wavelengths, where both the photodetector and the amplifier can be integrated in the same module. / Thesis / Doctor of Philosophy (PhD)

Large-scale optoelectronic integration is limited by the lack of efficient light sources and broadband photodetectors, which could be integrated with the silicon complementary metal-oxide-semiconductor (CMOS) technology. Persistent efforts continue to achieve efficient light emission as well as broadband photodetection from silicon in extending the silicon technology into fully integrated optoelectronic circuits. Recent breakthroughs, including the demonstration of high-speed optical modulators, photodetectors, and waveguides in silicon, have brought the concept of transition from electrical to optical interconnects closer to realization. The on-chip light sources based on silicon are still a key challenge due to the indirect bandgap of silicon that impedes coherent light sources. To overcome this issue, we have studied, fabricated, and characterized nanostructures including single semiconductor epilayers, multiple quantum wells, and graphene-semiconductor heterostructures to develop coherent light sources and photodetectors in silicon. To develop coherent light sources, we reported the demonstration of room-temperature lasing at the technologically crucial 1.5 m wavelength range from Er-doped GaN epilayers and Er-doped GaN multiple-quantum wells grown on silicon and sapphire. The realization of room-temperature lasing at the minimum loss window of optical fiber and in the eye-safe wavelength region of 1.5 m is highly sought-after for use in many applications in various fields including defense, industrial processing, communication, medicine, spectroscopy and imaging. The results laid the foundation for achieving hybrid GaN-Si lasers providing a new pathway towards full photonic integration for silicon optoelectronics. Silicon photodiodes contribute a large portion in the photodetector market. However, silicon photodetectors are sensitive in the UV to near infrared region. Photodetection in the mid-infrared is based on thermal radiation detectors, narrow bandgap materials (InGaAs, HgCdTe) semiconductors, photo-ionization of shallow impurities in semiconductors (Si:As, Ge:Ga), and quantum well structures. Such technology requires complicated fabrication processes or cryogenic operation, resulting in manufacturing costs and severe integration issues. To develop broadband photodetectors, we focus on graphene photodetectors on silicon. Graphene generates photocarriers by absorbing photons in a broadband spectrum from the deep-ultraviolet to the terahertz region. Graphene can be realized as the next generation broadband photodetection material, especially in the infrared to terahertz region. Here, we have demonstrated high-performance hybrid photodetectors operating from the deep-ultraviolet to the mid-infrared region with high sensitivity and ultrafast response by coupling graphene with a p-type semiconductor photosensitizer, nitrogen-doped Ta2O5 thin film. / Doctor of Philosophy / According to Moor's law, the number of transistors per die area doubles every 18 months with no increase in power consumption, which means that digital devices including smart phones and computers will become significantly faster and more energy-efficient than those of the previous generation. Photons (light) travel with the highest speed permitted by the known law of physics. The idea of optical interconnects, using photons instead of electrons, enables faster data transfer. Two important elements of the integrated circuits (ICs) based on photons are the coherent light source (laser) and the photodetector. We investigated the optical properties of erbium doped gallium nitride epilayers and multiple quantum wells grown on silicon and sapphire and demonstrated lasing from these materials at 1.5 µm. We also fabricated and characterized graphene photodetectors that can detect the light from the deep ultraviolet to the mid-infrared region. The results provided a new pathway towards full photonic integration for silicon optoelectronics. Besides, they are the heart of many important applications ranging from gas sensing, aerospace sensors and systems, thermal imaging, biomedical imaging, infrared spectroscopy, and lidar-to-optical telecommunications.

Master of Science / Department of Physics / Brian Washburn / This research sought to characterize the length dependent loss of hollow core photonic crystal fibers (HC-PCF) in the mid-infrared. These fibers are used in gas-filled fiber lasers that operate in the mid-infrared range. A black body source which provided a broad mid-infrared spectrum was coupled into a HC-PCF and a fiber cut-back method was implemented to make the length dependent loss measurement. A monochromator was used to observe narrow bands of the broad spectrum provided by the black body source and the loss as a function of wavelength was constructed. The loss for four unique HC-PCF fibers was characterized across the wavelength range [lambda] =1754 nm to [lambda] =3220 nm. The best fibers demonstrated a loss of less than 2 dB/m across this range, with some fibers even exhibiting loss below 1 dB/m.

Applications of laser absorption spectroscopy for trace gas detection are many and diverse, ranging from the environmental and atmospheric to the medical and industrial. The aim of creating a spectrometer which combines high sensitivities and selectivities (in order to measure small amounts of absorbers or species that are only weakly absorbing, in a complex background matrix) with a wide spectral coverage (to allow broadband absorbers or multi-component samples to be studied) can be realised by implementing three separate concepts: the exploitation of the strong, fundamental transitions of the mid-infrared; the use of sensitive spectroscopic techniques; and the selection of a widely tunable laser source. In this thesis, these ideas are investigated individually and in combination in order to achieve such a goal. Laser spectroscopic techniques based on optical cavities are used to build a high resolution spectrometer covering a large spectral range capable of selectively detecting low levels of gaseous compounds of interest, especially those of medical or environmental significance. Work in both the near- and mid-infrared is presented, including much of the initial, developmental work which was conducted in the former region. The thesis begins with an overview of both narrowband and broadband near-infrared radiation sources, with a particular emphasis on commonly available diode lasers (DLs). A novel laser source, the digital supermode distributed Bragg reector (DS-DBR) laser, is introduced as a useful laser source for spectroscopy, combining the usual benefits of telecom DLs with a wide tunability (1563 – 1613 nm). The laser can be operated in an internal or external ramping mode, allowing the output wavelength to be scanned or stepped across a desired region. The observation of mode-hopping during the application of the scanning methodology is examined and rationalised. The ability of the DS-DBR laser to perform high resolution spectroscopy over its entire spectral coverage is demonstrated by recording spectra of carbon dioxide (CO₂) over this range, covering transitions from two of the four Fermi resonance components of the 3ν₁ + ν₃ combination band. The results of conducting wavelength modulation spectroscopy on CO₂ are also reported. A system developed for performing cavity ring-down spectroscopy (CRDS), capable of the real-time retrieval of ring-down times (RDTs), is presented and discussed. The outcomes of initial tests performed with a conventional DL at 1557 nm, to study a calibrated mixture of CO₂ in air at various pressures, are given. In addition, the results of combining this system with the DS-DBR laser are discussed. The bandwidth of the DS-DBR laser was found to be larger than that of a standard DFB DL, resulting in the presence of noisy cavity modes. Despite this, the acquisition of reproducible RDTs is demonstrated, with single wavelength studies of an evacuated cavity at 1605.5 nm yielding a RDT of 24.54 ± 0.04 µs and Allan variance calculations signalling an attainable minimum detectable absorption coefficient, α_min, of 2.8 x 10^-10 cm^-1 over 20 s. The ability to perform CRDS across the whole DSDBR laser wavelength range without the need for cavity re-alignment is illustrated, and studies conducted on CO₂ in air, calibrated mixtures and breath are reported. Investigations are also described into the accurate determination of the ¹³C/¹²C ratio in exhaled CO₂ undertaken using CRDS and cavity enhanced absorption spectroscopy (CEAS) on CO₂ isotopologues, an approach which can be utilised as a diagnostic aid in determining Helicobacter pylori infection. The focus of the thesis then moves to the mid-infrared, to describe quasi phase matching difference frequency generation (QPM-DFG) and its use to generate laser light at 3 µm by optically mixing near-infrared DLs. The theory behind this non-linear optical interaction is outlined, and the construction of a free-space QPM-DFG system using periodically poled lithium niobate is detailed and characterised. This DL-based QPM-DFG arrangement has been coupled with the CRDS system developed to create a mid-infrared CRD spectrometer. The results of single wavelength studies indicate RDTs of ~ 6 µs and an achievable αmin of 2.9 x 10^-9 cm^-1 over 44 s for an evacuated cavity. Spectroscopic investigations carried out on methane (CH₄), acetone and deuterium are documented; for the latter species, Dicke narrowing of the electric quadrupole ν(1←0) Q(2) transition at 2987.29 cm^-1 is observed and the integrated absorption cross-section for the same transition measured as 2.29 ± 0.03 x 10^-27 cm²cm^-1molec^-1. The results of modifications made to the system, namely the use of a more powerful Nd:YAG laser as the pump radiation source, as well as a faster detector combined with a variable amplifier, are presented; these include the observation of an improved optimal α_min of 6.4 x 10^-10 cm^-1 over 151 s for an empty cavity. Finally, work utilising the DS-DBR laser as one of the near-infrared sources for the QPM-DFG set-up is presented. This configuration generates radiation covering a wide mid-infrared range (3130 – 3330 nm) and has been used to perform direct absorption and wavelength modulation spectroscopy on ro-vibrational transitions within the fundamental ν₃ (F₂) band of CH₄. The spectrum of methanethiol (CH₃SH) over this region has also been investigated, with preliminary studies identifying a feature at 3040 cm^-1 as a potential indicator for monitoring this biomarker in breath. The results of coupling this mid-infrared radiation with an optical cavity to perform CEAS combined with phase sensitive detection are subsequently reported. Studies were conducted on calibrated CH₄ mixtures and ambient air to examine two transitions of the fundamental ν₃ (F₂) band of CH₄ in order to characterise the system: effective path lengths of ~ 700 m and α_min of 6.2 x 10^-8 cm^-1 over 8 s were found. The ^RQ₄ CH₃SH absorption feature at 3040 cm^-1 was also further studied with this system using prepared samples of CH₃SH in N₂ at different concentrations, yielding a CH₃SH detection limit of 2.4 ppm at 19 Torr. The potential of such a cavity-based, DS-DBR sourced, QPM-DFG mid-infrared spectrometer for trace gas sensing having thus been demonstrated, possible improvements that could be implemented to increase the sensitivity of the system are then discussed.

The characterization of exozodiacal light emission is both important for the understanding of planetary systems evolution and for the preparation of future space missions aiming to characterize low mass planets in the habitable zone of nearby main sequence stars. The Large Binocular Telescope Interferometer (LBTI) exozodi survey aims at providing a ten-fold improvement over current state of the art, measuring dust emission levels down to a typical accuracy of similar to 12 zodis per star, for a representative ensemble of similar to 30+ high priority targets. Such measurements promise to yield a final accuracy of about 2 zodis on the median exozodi level of the targets sample. Reaching a 1. measurement uncertainty of 12 zodis per star corresponds to measuring interferometric cancellation ("null") levels, i.e visibilities at the few 100 ppm uncertainty level. We discuss here the challenges posed by making such high accuracy mid-infrared visibility measurements from the ground and present the methodology we developed for achieving current best levels of 500 ppm or so. We also discuss current limitations and plans for enhanced exozodi observations over the next few years at LBTI.