The terahertz (THz) spectral range is devoid of commercially feasible radiation sources, detectors, and components. In particular, THz sources are bulky, complex to operate, and cost-prohibitive - more suited for a research laboratory than a commercial setting. Developing compact and mass-producible sources in the 1 to 6 THz spectral range will open up new avenues for this technology to make a mainstream societal impact. The focus of this thesis is the development of compact, room-temperature terahertz sources based on quantum cascade lasers (QCL) and quantum well technology. QCLs are semiconductor lasers that operate with high power at mid-infrared (mid-IR) and THz frequencies. THz QCLs are the only mW-level average power sources with spectral coverage from 0.8 to 5 THz. However they only work at cryogenic temperatures because they cannot maintain population inversion across the lasing transition at elevated temperatures. Cryogenic cooling makes these sources cumbersome to operate and expensive to manufacture. Room-temperature operation significantly enhances their commercial appeal and a portion of this dissertation investigated the improvement in THz QCL temperature performance using GaAs-Al₀.₁₅Ga₀.₈₅As double-phonon resonant active region designs. These devices worked up to 173 K and were a substantial improvement compared to prior implementations of double-phonon resonant designs. Room-temperature THz sources that do not require population inversion across the lasing transition can be engineered by combining the field of nonlinear optics with intersubband transitions in quantum well structures. One method of creating inversionless THz lasing is based upon the principle of Raman gain in semiconductors and this thesis explores the design of an intersubband Raman laser (IRL) with GaAs-Al₀.₃₃Ga₀.₆₇As heterostructures. The primary focus of this dissertation is developing room-temperature, broadly-tunable, monolithic THz sources based on difference-frequency generation (DFG) in mid-IR QCLs. The source active region is quantum-engineered to provide lasing at mid-IR frequencies, ω₁ and ω₂, and simultaneously have giant second-order optical nonlinearity for THz generation at frequency ω [subscript THz]=ω₁–ω₂. This dissertation developed a Cherenkov emission scheme that produced devices with a narrow emission linewidth, 0.12 mW peak power and tuning from 1.55 to 5.7 THz - the largest tuning bandwidth compared to semiconductor technology of similar size and cost. / text

La détection de gaz est un domaine d’intérêt pour de nombreuses applications telles que la surveillance de la pollution atmosphérique, la détection d’explosifs, l’analyse des émissions respiratoire de patients, etc... La spectrométrie par lasers accordables permet la réalisation d’instruments compacts et bénéficiant de performances élevées (sélectivité, résolvance et résolution temporelle). Par ailleurs, l’utilisation de lasers à cascade quantique (QCL) permet d’accéder au moyen infrarouge (Mid-IR), où les raies d’absorption des molécules d’intérêt sont plus intenses, ce qui améliore la sensibilité des dispositifs. Les travaux de cette thèse ont porté sur le développement de dispositifs basés sur des QCL pour la détection de gaz. La première partie des travaux porte sur l’exploitation de nouvelles sources Mid-IR telles que les barrettes de QCL multiplexées et les barrettes de QCL cohérents. La seconde partie concerne le développement d’un dispositif intracavité sur lequel une technique de détection par mesure de la tension du laser a été validée. Cette technique possède l’avantage de ne pas nécessiter de détecteur optique et de fonctionner quelle que soit la longueur d’onde du laser. / The field of gas detection is interesting for many applications such as monitoring of air pollution, explosives detection, breath analysis, etc. Tunable laser spectrometry allows to create compact instruments with high performances (selectivity, spectral and temporal resolution). Mid-Infrared (Mid-IR) region can be accessed with the use of Quantum Cascade Laser (QCL). In this region, absorption lines of the molecules of interest are more intense, which improves the devices sensitivity. The work presented in this thesis is focused on the development of QCL-based gas detection devices. First part presents the use of new Mid-IR sources such as multiplexed QCL array and coherent QCL array. Second part is focused on the development of an intracavity setup and a detection technique based on the QCL voltage measurement. This technique does not need the use of an optical detector and can be performed whatever the laser wavelength.

Les nitrures d’éléments III (III-N) sont des matériaux prometteurs pour la réalisation de dispositifs intersousbandes (ISB) : leur discontinuité de potentiel élevée en bande de conduction (1.75 eV) leur permet de couvrir une grande gamme de longueur d’onde du proche infrarouge jusqu’au Térahertz (THz), et enfin l’énergie élevée de phonon optique (90meV) laisse entrevoir la possibilité de réaliser des sources émettant dans le THz tout en fonctionnant à température ambiante. Mes travaux portent sur les détecteurs à cascade quantique (QCD) et sur les lasers à cascade quantique (QCL) à base de III-N fonctionnant dans le THz.Dans un premier temps, j’expose les concepts, la réalisation et la caractérisation de plusieurs détecteurs à cascade quantique (QCDs) à base de nitrures (AlGaN/GaN) fonctionnant dans le proche IR entre 1 et 2 µm.. Ensuite, je propose la conception de dispositifs devant fonctionner dans le THz. Je commence par décrire les difficultés inhérentes à l’obtention de transitions ISB dans la gamme THz dans les puits de nitrures polaires et je propose une approche pour les contourner. Je détaille après la conception de QCDs devant fonctionner à 5 et 6 THz. Puis, je propose une structure de QCL devant émettre à 2.5 THz.En parallèle, j’ai aussi travaillé sur les oxydes d’éléments VI (II-VI). Ces matériaux possèdent les mêmes avantages que les nitrures d’éléments III. J’ai caractérisé une série d’échantillons épitaxiés contenant des puits de ZnO/ZnMgO. Les mesures attestent de la présence d’une transition ISB et m’ont permis de donner une estimation de la discontinuité en bande de conduction, valeur jusque-là très mal connue. / Nitrides are promising materials for producing intersubband devices (ISB): their high potential discontinuity in conduction band (1.75 eV) allows them to cover a wide wavelength range from near infrared to terahertz (THz), and finally the high energy optical phonon (90 meV) suggests the possibility of producing sources emitting THz while operating at room temperature. My research focuses on quantum cascade detector (QCD) and quantum cascade lasers (QCL) based on III-N operating in the THz.First, I outline the concepts, realization and characterization of several quantum cascade detectors (QCDs) based on nitrides (AlGaN / GaN) operating in near infrared between 1 and 2 microns. Then, I propose design of devices working in the THz range: I describe difficulties inherent in getting ISB transitions in THz fields in polar nitride quantum well. I detail the design of QCDs operating at 5 and 6 THz. Then I worked on QCL operating at 2.5 THz.In parallel, I also worked on VI elements oxides (II-VI). These materials have the same benefits as III nitrides. I characterized a series of samples containing quantum wells ZnO / ZnMgO. Measurements show the presence of ISB transitions and allow me to provide an estimation of the conduction band offset, which value was not well known prior to this work.

This thesis is concerned with coherent effects in high resolution mid-infrared gas phase spectroscopy using quantum cascade lasers (QCLs). An introductory chapter explains the importance of QCLs as radiation sources in the mid-infrared region of the spectrum and goes on to detail their development and structure. A discussion of coherent effects in spectroscopy follows, leading into the second chapter which discusses the theories relevant to the experimental sections of the thesis. In chapter 2 the theory underpinning direct and velocity selective, Doppler-free spectroscopy is discussed and a density matrix formalism is followed to derive the equations of motion that govern coherent excitation effects in two-level systems. In the final part of the chapter this treatment is extended to three-level systems. The equations derived in this chapter form the basis of quantitative interpretations of the phenomena observed in experimental data and presented in the remainder of the thesis. In chapter 3 the characterisation of a high power, narrow linewidth QCL is carried out. This laser is then used to perform direct and sub-Doppler resolution spectroscopy on NO, demonstrating non-linear absorption at high laser intensities and providing a measurement of the laser linewidth in the limit of slow frequency tuning. As the slow tuning rate increases, evidence of coherent transient effects is presented and density matrix theory used to model this behaviour. The data presented include the first observations of asymmetric Lamb dips and the onset of rapid passage oscillations from a Lamb dip. Pump-probe experiments on NO, utilising two cw QCLs are presented in chapter 4. The high level of velocity selection afforded by QCL excitation leads to coherent transient signals at far lower probe scan rates than previously reported. The effect of altering both the scan rate and the gas pressure and the importance of hyperfine structure are presented. A radio frequency noise source applied to one of the lasers is shown to broaden the laser linewidth, leading to rapid dephasing. A two-colour polarisation spectroscopy experiment is also presented which allows the measurement of both the absorption and the Doppler-free dispersion signals and the three-level density matrix formalism presented at the end of chapter 2 used to model the non-linear response of the system. The final chapter details the use of an acousto-optic modulator to create a pulse of mid-IR light using a cw QCL and the application of this to time resolved pump-probe spectroscopy. This capability suggests the prospect of achieving coherent population transfer by stimulated Raman adiabatic passage (STIRAP) using two such pulses. Simulations based on a simple three-level model and including Zeeman coherences are presented, which take the measured properties of the lasers used in this thesis as inputs to predict the potential population transfer achievable in NO as well as providing useful information about the angular momentum polarisation of the excited molecules. An experimental realisation of STIRAP would require the lasers to be stabilised, and so the final part of the chapter details experimental attempts to achieve stabilisation of an external cavity QCL, and suggests future avenues for improved implementation.

Quantum cascade laser (QCL) diodes have potential applications in many areas including emissions analysis and explosives detection, but like many solid-state devices they suer from degraded performance at higher temperatures. To alleviate this drawback, the thermal properties of the QCL diodes must be better understood. Using molecular dynamics (MD) and photothermal radiometry (PTR), the thermal conductivity of a representative QCL diode is computed and measured respectively. The MD results demonstrate that size eects are present in the simulated systems, but if these are accounted for by normalization to experimental results the thermal conductivity of the QCL can be reasonably obtained. The cross-plane conductivity is found to be in the range of 1.8 to 4.3 W=m K, while the in-plane results are in the range of 3.7 to 4.0 W=m K. These values compare well with experimental results from the literature for both QCL materials and for AlInAs and GaInAs, which the QCL is composed of. The cross-plane conductivity results are lower than those of either AlInAs or GaInAs, which demonstrates the phonon scattering at the interfaces. The in-plane results are between AlInAs and GaInAs, which is to be expected. The PTR results are less concrete, as there seem to be heat transfer eects active in the samples which are not included in the models used to t the frequency scans. These effects are not 2D heat transfer artifacts nor are they the result of volumetric absorption. It is possible that they are the results of plasmon induction, but this is only supposition. As the data stand, the PTR and MD results are within an order of magnitude of each other and follow reasonable trends, which suggests that both results are not too far o from reality. While the experimental results are not entirely conclusive, the simulations and experiments corroborate each other suciently to warrant further investigation using these techniques. Additionally, the simulations present sucient internal consistency so as to be useful for thermal property investigation independent of the PTR results.

No description available.

Terahertz (THz) technology stands to solve a number of problems in everyday life, from next generation wireless communication to spectroscopic identification and imaging. However it is technically challenging to make a high power, compact source for terahertz radiation. The Quantum Cascade Laser (QCL), which produces gain at THz frequencies by exploiting inter-sub-band transitions in quantum wells, offers one solution to this problem. However controlling and detecting the emission from such sources remains a major challenge. This thesis investigates the theory and measurement of emission frequencies from aperiodic lattice THz QCLs. Crucially, realising both frequency control and detection provides a complete system for coherent THz characterisation of devices at precise, user defined frequencies. The author starts by studying the emission frequencies and threshold of discretely tuned aperiodic lattice lasers. This is achieved using a numerical transfer matrix method (TMM), which allows the calculation of the aperiodic lattice threshold spectrum for the first time. Calculations reveal that the low threshold modes of aperiodic lattice lasers form at peaks in the electromagnetic density of modes. This shows that lasing in aperiodic lattices arises from slow light propagation induced by multiple photonic band gaps, leading to both band edge and defect laser modes. Frequency selective lasing is maintained even under the influence of external facet feedback, albeit at the cost of precise knowledge of the mode frequency. Importantly this framework allows the understanding of essentially any aperiodic lattice laser system. Most significantly, the TMM is exploited in order to understand how graphene can be used to control a THz laser. Graphene interacts strongly with THz waves, and can be easily integrated with semiconductor structures such as lasers and waveguides. Here, numerical calculations reveal that graphene can be introduced into the waveguide of a THz QCL, generating electrically tunable THz surface plasmons. Such surface plasmons couple into an aperiodic lattice to change the scattering strength of each individual grating element. The TMM reveals that this change in scattering strength controls the modal selectivity of an aperiodic lattice THz QCL. This hypothesis successfully explains both earlier experiments and those performed by the author. Crucially, this model was central to a publication in the journal Science. Finally, this thesis demonstrates a novel coherent detection system for the characterisation of THz QCL emission. The technique exploits non-linear up-conversion of THz waves to a telecoms frequency side-band, a process shown to be sensitive to THz waveguide dispersion. By mixing the up-converted THz wave with a near infra-red local oscillator laser, coherent detection of QCL emission using all fibre coupled components is demonstrated for the first time. This measurement allows for the characterisation of laser emission with high frequency and temporal resolution. Specifically sub-microsecond pulses of THz emission and transients can be detected. When taken as a whole, the work of this thesis constitutes a major step towards realising cost effective THz characterisation and spectroscopy using QCLs.

Les polaritons inter-sous-bandes, observés pour la première fois il y a une quinzaine d’années, sont des quasi-particules dont de nombreuses propriétés restent encore à découvrir. La recherche dans ce domaine se focalise actuellement sur la réalisation de condensats de Bose-Einstein. Une telle découverte pourrait révolutionner l’optoélectronique du moyen infra-rouge jusqu’au THz ouvrant la voie à l’instauration de nouveaux concepts de sources lumineuses,de détecteurs ou de systèmes logiques en couplage fort. Dans cette quête, le choix de la cavité résonnante est critique. Dans ce manuscrit nous proposons d’utiliser des cavités métal-isolant-métal (M-I-M) avec un réseau dispersif sur le métal supérieur. Ce type de cavité,conservant un confinement élevé entre les deux plans métalliques, offre de nombreuses possibilités d’ajustement de la résonance de cavité : via la géométrie de la cavité ( épaisseur de la cavité, période et recouvrement du réseau) ainsi que par le couplage de la lumière avec la cavité (vecteur d’onde incident). Les cavités M-I-M dispersives ouvrent donc un nouveau champ d’exploration des polaritons inter-sous-bande. Dans un premier temps nous avons introduit ces cavités dans le domaine du THz afin d’étudier les phénomènes de relaxation polariton-polariton. Un système expérimental dédié à cette exploration a été conçu pour mesurer la réflectivité des polaritons THz avec une fine résolution en angle. Dans une second temps, des capteurs moyen infrarouge en couplage fort avec une cavité M-I-M dispersive ont été conçus, fabriqués et mesurés dans le but d’explorer la génération de photo-courant à partir de polaritons et d’utiliser le couplage fort pour dissocier l’ énergie de détection de l’énergie d’activation. Cette seconde étude s’inscrit dans l’objectif de pompage électrique des polaritons ISB. Parallèlement à l’étude des polaritons, nous avons également participé au développement de techniques(interféromètre Gires-Tournois et revêtement anti-réflection) pour compresser les impulsions optiques de lasers à cascade quantique THz. / After fifteen years of intersubband polaritons development some of the peculiar properties of these quasi-particles are still unexplored. A deeper comprehension of the polaritons is needed to access their fundamental properties and assess their applicative potential as efficient emitters or detectors in the mid-infrared and THz.In this manuscript we used Metal-Insulator-Metal (MI-M) cavities with a top metal periodic grating as a platform to deepen the understanding of ISB polaritons.The advantages of M-I-M are twofold : first they confine the TM00 mode, second the dispersion of the cavity -over a large set of in-plane wave-vectors- offers various experimental configurations to observe the polaritons in both reflection and photo-current. We reexamined the properties of ISB polaritons in the mid-infrared and in the THz using these resonators. In the first part, we explore the implementation of dispersive M-I-M cavities with THz intersubband transitions. In the THz domain, the scattering mechanisms of the THz ISB polaritons need to be understood. The dispersive cavity is a major asset to study these mechanisms because it provides more degrees of freedom to the system. For this purpose, we fabricated a new experimental set-up to measure the polariton dispersion at liquid Helium temperature. After the characterization of the polaritons in reflectivity, a pump-probe experiment was performed on the polaritonic devices. The second part of this manuscript presents the implementation of M-I-M dispersive cavities with abound-to-quasi-bound quantum well infrared photo detector designed to detect in strong coupling. Beyond electrical probing of the polaritons, the strong coupling can disentangle the frequency of detection from the thermal activation energy and reduce the dark current at a given frequency. In parallel to the exploration of THz polaritons, we developed two techniques (Gires-Tournois Interferometer and Anti-reflection coating) in order to shorten the pulses of THz quantum cascade lasers with metal-metal waveguides.

L'histologie tridimensionnelle (3D) est un nouvel outil avancé de cancérologie. L'ensemble du profil chimique et des caractéristiques physiologiques d'un tissu est essentiel pour comprendre la logique du développement d'une pathologie. Cependant, il n'existe aucune technique analytique, in vivo ou histologique, capable de découvrir de telles caractéristiques anormales et de fournir une distribution3D à une résolution microscopique. Nous présentons ici une méthode unique de microscopie infrarouge (IR) à haut débit combinant une correction d'image automatisée et une analyse ultérieure des données spectrales pour la reconstruction d'image 3D-IR. Nous avons effectué l'analyse spectrale d'un organe complet pour un petit modèle animal, un cerveau de souris avec une tumeur de gliome implantée. L'image 3D-IR est reconstruite à partir de 370 coupes de tissus consécutives et corrigée à l'aide du tomogramme à rayons X de l'organe pour une analyse quantitative précise du contenu chimique. Une matrice 3D de spectres IR 89 x 106 est générée, ce qui nous permet de séparer la masse tumorale des tissus cérébraux sains en fonction de divers paramètres anatomiques,chimiques et métaboliques. Nous démontrons pour la première fois que des paramètres métaboliques quantitatifs (glucose, glycogène et lactate) peuvent être extraits et reconstruits en 3D à partir des spectres IR pour la caractérisation du métabolisme cérébral / tumoral (évaluation de l'effet de Warburg dans les tumeurs). Notre méthode peut être davantage exploitée en recherchant l'ensemble du profil spectral, en distinguant différents points de repère anatomiques dans le cerveau.Nous le démontrons par la reconstruction du corps calleux et de la région des noyaux gris centraux du cerveau. / Three-dimensional (3D) histology is a new advanced tool for cancerology. The whole chemical profile and physiological characteristics of a tissue is essential to understand the rationale of pathology development. However, there is no analytical technique, in vivo or histological, that is able to discover such abnormal features and provide a 3D distribution at microscopic resolution.Here, we introduce a unique high- throughput infrared (IR) microscopy method that combines automated image correction and subsequent spectral data analysis for 3D-IR image reconstruction. I performed spectral analysis of a complete organ for a small animal model, a mouse brain with animplanted glioma tumor. The 3D-IR image is reconstructed from 370 consecutive tissue sectionsand corrected using the X-ray tomogram of the organ for an accurate quantitative analysis of thechemical content. A 3D matrix of 89 x 106 IR spectra is generated, allowing us to separate the tumor mass from healthy brain tissues based on various anatomical, chemical, and metabolic parameters. I demonstrate for the first time that quantitative metabolic parameters (glucose, glycogen and lactate) can be extracted and reconstructed in 3D from the IR spectra for the characterization of the brain vs. tumor metabolism (assessing the Warburg effect in tumors). Our method can be further exploited by searching for the whole spectral profile, discriminating different anatomical landmarks in the brain. I demonstrate this by the reconstruction of the corpus callosum and basal ganglia region of the brain.

Live cell imaging with FTIR spectroscopy offers a high throughput, non-damage and lab-free method to study the cells in vivo which has significant advantages in the field of cancer diagnosis and drug screening. However, due to the strong absorbance of water, using infrared spectroscopy in such field remains to be an underdeveloped topic. This project demonstrates a novel method to perform IR imaging of cells in solution. A novel water correction method, which avoids the using of water combination band, is proposed. A buffer reference and a cell reference spectra were introduced to fitting the contribution based on protein bands. This method was implemented on three types of IR spectrometers, namely conventional FTIR spectrometer, synchrotron-based FTIR spectrometer and quantum cascade laser (QCL) microscope. To date, most of the live cell imaging carried out with IR sources utilise synchrotron radiation. Recently, a new bench top system, QCL microscope, has been developed. It incorporates four tunable QCL laser sources covering the wavenumber range 900-1800 cm-1 which are many orders of magnitude brighter than conventional sources. The proposed water correction method is, therefore, capable of processing the data recorded by all three types of IR spectrometers. Three prostate cancer cell lines were employed to evaluate the water correction method and the performance of three spectrometers on imaging of cell in solution. The obtained spectra was analysed with multivariate analysis, PCA and PC-LDA which shows good separation between cell lines. The data was also examined with Random Forest algorithm to establish a classifier and the diagnostic capability of the water corrected spectra was proven.