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<p>The ability to detect infrared radiation is vital for a host of applications that include optical communication, medical diagnosis, thermal imaging, atmospheric monitoring, and space science. The need to actively cool infrared photon detectors increases their operation cost and weight, and the focus of much recent research has been to limit the dark current and create room-temperature infrared photodetectors appropriate for mid-to-long-wave infrared detection. Quantum dot infrared photodetectors (QDIPs) provide electron quantum confinement in three dimensions and have been shown to demonstrate high temperature operation (T>150 K) due to lower dark currents. However, these inorganic devices have not achieved sensitivity comparable to state-of-the-art photon detectors, due in large part to the inability to control the uniformity (size and shape) of QDs during strained-layer epitaxy.</p><p>The purpose of this dissertation research was to investigate the feasibility of room-temperature infrared photodetection that could overcome the shortfalls of QDIPs by using chemically synthesized inorganic colloidal quantum dots (CQDs). CQDs are coated with organic molecules known as surface ligands that prevent the agglomeration of dots while in solution. When CQDs are suspended in a semiconducting organic polymer, these materials are known as organic/inorganic hybrid nanocomposites. The novel approach investigated in this work was to use intraband transitions in the conduction band of the polymer-embedded CQD for room-temperature photodetection in the mid-wave, and possibly long-wave, infrared ranges. Hybrid nanocomposite materials promise room-temperature operation due to: (i) large bandgaps of the inorganic CQDs and the semiconducting polymer that reduce thermionic emission; and (ii) low dark current due to the three-dimensional electron confinement in the CQD and low carrier mobility in the semiconducting polymer. The primary material system investigated in this research was CdSe CQDs embedded in the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-(1-cyanovinylene)phenylene] (MEH-CN-PPV). </p><p>Photoluminescence (PL) spectroscopy of MEH-CN-PPV thin films was conducted to determine the dependence of polymer morphology on deposition method in order to identify a reliable device fabrication technique. Three different deposition methods were investigated: drop-casting and spin-casting, which are solution-based; and matrix-assisted pulsed laser evaporation (MAPLE), which is a vacuum-based method that gently evaporates polymers (or hybrid nanocomposites) and limits substrate exposure to solvents. It was found that MAPLE deposition provides repeatable control of the thin film morphology and thickness, which is important for nanocomposite device optimization. </p><p>Ultra-fast PL spectroscopy of MEH-CN-PPV/CdSe thin films was investigated to determine the charge generation and relaxation dynamics in the hybrid nanocomposite thin films. The mathematical fitting of time-integrated and time-resolved PL provided a rigorous and unique model of the charge dynamics, which enabled calculation of the radiative and non-radiative decay lifetimes in the polymer and CQD. These results imply that long-lived electrons exist in the conduction band of the CQD, which demonstrate that it should be possible to generate a mid- to long-wave infrared photocurrent based on intraband transitions. In fact, room-temperature, intraband, mid-infrared absorption was measured in thin films of MEH-CN-PPV/CdSe hybrid nanocomposites by Fourier transform infrared (FTIR) absorbance spectroscopy. In addition, the hybrid nanocomposite confined energy levels and corresponding oscillator strengths were calculated in order to model the absorption spectrum. The calculated absorption peaks agree well with the measured peaks, demonstrating that the developed computer model provides a useful design tool for determining the impact of important materials system properties, such as CQD size, organic surface ligand material choice, and conduction band offset due to differences in CQD and polymer electron affinities.</p><p>Finally, a room-temperature, two terminal, hybrid nanocomposite mid-infrared photoconductor based on intraband transitions was demonstrated by FTIR spectral response measurements, measuring a spectral responsivity peak of 4.32 µA/W at 5.5µm (5 volts), and calibrated blackbody spectral photocurrent measurements, measuring a spectral responsivity peak of 4.79 µA/W at 5.7 µm (22 volts). This device characterization demonstrated that while the novel approach of intraband infrared photodetection in hybrid nanocomposites is feasible, significant challenges exist related to device fabrication and operation. Future work is proposed that could address some of these important issues.</p> / Dissertation

Growth Mechanism and Infrared Detection of High-temperature Superconducting and Colossal Magnetoresistance Films Department of Electrical Engineering, National Sun Yat-Sen University Meng-Tsong Hong* Ying-Chung Chen**, Hsiung Chou** -------------------------------------------------- Abstract---- The growth mechanism of YBa2Cu3O7-d (YBCO) films grown by RF sputtering has been investigated. When growing films by RF sputtering, the shape of the plasma and the degree of resputtering effect were varied by setting different relative positions of the heater to the gun. As the substrate was near the plasma, the negative oxygen ions resputtered part of the mobile atoms from the surface of film back into the plasma, which caused the composition distortion, delayed the merge of grains and left uncovered holes. Setting a longer relative distance, the resputtering effect was suppressed and the precipitates appeared on the surface of films resulting in a rough surface. At an optimum relative position between heater and gun, the function of resputtering produced a polishing effect on the surface of films. This polishing effect suppressed the growth of precipitates without slowing down the growth of grains, a smooth and precipitate-free YBCO film might obtain. We also found that the film with smooth and precipitate-free morphology exhibited suppressed superconductivity. The most direct way to enhance the photoresponse of a bolometer is by modifying the microbridge from a single straight bridge to a meander or change the thermal coupling configuration between bolometer and heat sink. In the study of high-temperature superconducting (HTSC) bolometers, it is found that the geometry and thermal coupling configuration play very important roles on the behavior of heat conduction, which alter the thermal conversion efficiency, DT/WD. Actually, DT/WD is a matter of the absorption of the AC thermal irradiation and the dissipation of both the irradiation and the DC joule heat generated by the bias current. The competition between the capability of heat dissipation and the thermal generation determined the magnitude of DT/WD. The La0.67Ca0.33MnO3-y (LCMO) thin films with epitaxial structure and smooth surface morphology have been deposited. A LCMO thin-film microbridge was fabricated into a microbridge by conventional photolithography and dry etching for optical detection. The measured photoresponse, DV, of this LCMO thin-film microbridge reveals that it is bolometric in nature. The photoresponse is linearly proportional to the bias current Ib and the power density of irradiation WD, which strongly suggests the applicability of an LCMO thin-film microbridge to a linear optical detector. The ratio of the photoresponse to the irradiated power density, DV/WD, is independent of the incident-light wavelength l from 0.633 to 3.5 mm. The dependence of the photoresponse on modulated frequency f, follows the DV &#x00B5; f -0.21 relation. Under Ib = 100 mA and f = 5 Hz at an operating temperature Top = 223 K, the responsivity S and noise voltage Vn are 685 V/W and 20 nV¡ÑHz -0.5, respectively, for this LCMO thin-film microbridge. From the measured S and Vn, the noise equivalent power (NEP) and detectivity D* were be calculated to be 2.92&#x00B4;10-11 W¡ÑHz -0.5 and 2.76&#x00B4;109 cm¡ÑHz 0.5¡ÑW -1, respectively, for this LCMO thin-film microbridge. The experimental results from this LCMO thin-film microbridge show the practical applicability of this new detector system compared to other established detectors. *Student **Advisor

A sol-gel stationary phase was developed for in-situ infrared (IR) detection of analytes on thin-layer chromatography (TLC) plates. These sol-gel-based TLC plates have improved optical properties compared with conventional TLC plates in IR spectroscopic analysis. Samples can be analyzed in transmission geometry, requiring no special attachments. The sol-gel-based TLC plates demonstrate significantly better light throughput and a wider spectral range than conventional TLC plates analyzed in diffuse reflectance geometries.The sol-gel precursor, methyltrimethoxyorthosilicate (MTES), was templated with cetyltrimethylammonium bromide (CTAB) and urea in order to form a porous sol-gel. Aerosol deposition was used to apply the sol-gel solution onto either glass slides or silicon wafers within an enclosed chamber. Many variables were studied to determine their effect on the quality of the sol-gel stationary phases, including the ratio of MTES:methanol:water:CTAB:urea:HCl:, gelation times and temperatures, and deposition rate. Sol-gel films prepared using MTES/methanol/water/CTAB at ratios of 1 : 20 : 7 : 0.2 containing 5 wt% urea (relative to MTES) and pH 1.5 were crack-free, mechanically stable, and uniform in appearance. The films were tens of microns thick with a highly interconnected porous structure.For chromatographic separations, the films exhibited good solvent migration velocity and could be repeatedly washed and reused for TLC separations without showing degradation in the separation. Several different classes of compounds, including polyaromatic hydrocarbons and dyes, were successfully separated. Theoretical plate values measured on the MTES-based sol-gel films were comparable to those obtained on commercially available TLC plates.

Malgré les remarquables performances démontrées par les photo-détecteurs quantiques pour l'infrarouge, les progrès dans cette filière stagnent. La principale limitation est due au bruit lié à leur courant d'obscurité, qui impose, aux plus grandes longueurs d'onde, un fonctionnement à des températures cryogéniques. Ce travail de thèse a pour principal objectif de dépasser cette limite intrinsèque en combinant des structures photo-détectrices innovantes et des nano-résonateurs optiques. La réduction par plus d'un ordre de grandeur de l'épaisseur de la zone absorbante, modifie considérablement les propriétés optiques et électroniques de la structure, imposant de revisiter entièrement ses modes de fonctionnement. Dans ce contexte, ce travail de thèse vise à valider expérimentalement l'apport de la nano-photonique à l'amélioration des performances des photodiodes InGaAs.La première partie est dédiée à l'étude de photodiodes InGaAs à double hétérojonction dans le but de réduire à la fois le courant d'obscurité et l'épaisseur de la structure pour la rendre compatible à celle des nano-résonateurs optiques. La seconde partie est dévolue à la conception, la fabrication et la caractérisation de photo-détecteurs InGaAs nano-structurés de type résonateurs de mode guidé. Dans la troisième partie, les remarquables propriétés de ces photo-détecteurs sont étudiées dans un contexte de mini-matrices, premier pas vers la réalisation de caméras.Les concepts développés durant cette thèse et les résultats expérimentaux obtenus, ouvrent la voie vers une nouvelle génération de photo-détecteurs pour l'imagerie infrarouge. / Despite the outstanding performances reached by today's infrared quantum photo-detectors, progresses have been stagnating for years. The main limitation is due to the noise generated by the dark current, which requires, cooling down the devices at a cryogenic temperature for the largest wavelengths. The main objective of this thesis is to propose new concepts for overcoming these fundamental limits. By combining innovative photo-detector structures and optical nano-resonators, new structures are proposed. By reducing by more than order of magnitude the thickness of the absorbing layer, optical and electrical properties of the structure are deeply modified. As a result operating modes have to be entirely revisited. In this context, the purpose of this thesis is to characterize the behaviors, to find new compromise and to experimentally validate the nano-photonics potential to improve the performances of InGaAs photodiodes.The first part is dedicated to the study of double heterojunction InGaAs photodiodes in order to reduce both the dark current and the thickness of the structure to make it compatible with that of optical nano-resonators. The second part is devoted to the design, the fabrication and the characterization of guided mode resonant nanostructured InGaAs photo-detectors. In the third part, the remarkable properties of these photo-detectors are studied in the context of mini-arrays, the first step towards cameras realization.The concepts developed during this thesis and experimental results, pave the way to a new generation of infrared photodetector.

Detecting long wave infrared (LWIR) light at room temperature has posed a persistent challenge due to the low energy of photons. The pursuit of an affordable, high-performance LWIR camera capable of room temperature detection has spanned several decades. In the realm of contemporary LWIR detectors, they can be broadly classified into two categories: cooled and uncooled detectors. Cooled detectors, such as MCT detectors, excel in terms of high detectivity and fast response times. However, their reliance on cryogenic cooling significantly escalates their cost and restricts their practical applications. In contrast, uncooled detectors, exemplified by microbolometers, are capable of functioning at room temperature and come at a relatively lower cost. Nonetheless, they exhibit somewhat lower detectivity and slower response times. Within the scope of this work, I will showcase two innovative approaches aimed at advancing the next generation of LWIR detectors. These approaches are designed to offer high detectivity, swift response times, and room temperature operation. The first approach involves harnessing Dirac plasmon and the Seebeck effect in graphene to create a photo-thermoelectric detector. In addition, I will introduce the application of scanning near-field microscopy for revealing the plasmons generated in graphene, employing both imaging and spectroscopy techniques. The second approach entails the use of an oscillating circuit integrated with phase change materials and the modulation of frequency induced by infrared illumination to achieve LWIR detection. Finally, I will present the progress made in integrating graphene-based detectors in this work onto readout circuits to enable the development of dense pixel focal plane array.

Les travaux de cette thèse ont porté sur les micro-bolomètres (détecteurs infrarouges non refroidis) qui fonctionnent selon le principe suivant : le rayonnement infrarouge incident provoque l’échauffement d’une membrane suspendue dont la résistivité électrique dépend de la température. Deux voies ont été explorées pour les améliorer, grâce aux nanotechnologies. D’une part, les propriétés optiques et électroniques (transport et bruit) des films de nanotube de carbone ont été étudiées afin d’évaluer le potentiel de ce nouveau matériau comme thermistor. Pour ce faire des procédés technologiques en salle blanche, des caractérisations et des modèles théoriques ont été mis au point. Après avoir obtenu les figures de mérite adaptées, cette étude a conclu au manque de potentiel de ce matériau pour une application aux micro-bolomètres. D’autre part, nous avons étudié des résonateurs sub-longueur d’onde basés sur des cavités métal-isolant-métal permettant d’obtenir des absorbants totaux, et omnidirectionnels. Un modèle analytique permettant de les décrire et de les concevoir rapidement a été mis au point. La combinaison de ces résonateurs à l’échelle sub-longueur d’onde a permis de mettre en évidence un phénomène de tri de photon et la possibilité de concevoir des absorbants large bande. Nous avons ainsi proposé (et breveté) l’utilisation de ces antennes comme absorbants pour les micro-bolomètres. En effet leur capacité à focaliser le champ dans des volumes sub-longueur d’onde permet d’introduire une rupture conceptuelle pour la conception de bolomètres à hautes performances. / This work was focused on bolometers (uncooled infrared sensors), which are based on the following principle: the incoming infrared radiation is absorbed by a self-standing membrane whose resistivity depends on temperature. In order to improve their design and performances, we explored two solutions based on nanotechnologies. On the one hand, optical and electronic (transport and noise) properties of carbon nanotube films have been investigated in order to evaluate the potential of this new material as a thermistor. Clean room processes, characterization benches and theoretical models have been developed. The obtained figures of merit allow to concluding on the lack of potential for applications in uncooled infrared sensors. On the second hand, subwavelength resonators based on metal-insulator-metal cavities, have been investigated and exhibit perfect, tunable and omni-directional absorption. An analytical model allowing a fast study and design of these resonators has been developed. Photon sorting and wideband absorption have been demonstrated thanks to the combination of these resonators at the sub-wavelength scale. We have thus proposed (and patented) the use of such “antennas” as micro-bolometer’s absorber. Indeed their capacity to focalize the incoming radiation at a subwavelength scale paves the way to the conception of high performance micro-bolometers.

Face à l’émergence de l’imagerie multi et hyperspectrale, il existe une demande croissante de connaissance fine de la réponse spectrale des détecteurs infrarouge. Dans ce travail de thèse, nous proposons une démarche de modélisation optique des réponses spectrales des plans focaux infrarouge HgCdTe. L’objectif est de mieux maîtriser les origines physiques des oscillations observées sur les réponses spectrales des pixels d’une matrice de détection, ainsi que des disparités de longueurs d’onde de coupure. Ces phénomènes étaient peu étudiés dans la littérature; pourtant, ils sont responsables en partie du bruit spatial fixe qui limite les performances des détecteurs. Nous proposons une description qui conserve l’interprétation physique des phénomènes observés (absorption, interférences,…), tout en permettant d’extraire les paramètres technologiques (responsables de ces non-uniformités) de la façon la plus indépendante possible. Le principe repose sur la décomposition du comportement global du détecteur, qui peut sembler complexe, en une multitude de briques élémentaires, simples à modéliser. L’étude a été appliquée au cas particulier d’un micro-spectromètre infrarouge intégré au plan de détection. Une analyse de sensibilité sur le modèle proposé a alors permis d’évaluer la précision nécessaire sur les paramètres technologique afin d’obtenir une bonne qualité de restitution de spectres. Cette démarche est généralisable à d’autres architectures de détecteurs et d’autres technologies de fabrication, à condition de maîtriser les propriétés optiques des matériaux mis en jeu. / Due to the emergence of multi and hyperspectral imaging, there is an increasing demand for the control of the spectral response of infrared detectors. In this thesis, we propose an optical modelling approach of the spectral response of HgCdTe focal plane arrays. The aim is to better identify the physical origins of the oscillations observed on the spectral responses of the pixels belonging to the same detector array, as well as the cutoff wavelength disparities. These phenomena were not studied in the literature; though, they are partly responsible for the fixed pattern noise that limits the performance of the detectors. We propose a description that takes account of the physical interpretation of the observed phenomena (absorption, interference…), while allowing the extraction of the technological parameters (that are responsible for such non-uniformities) in the most independent way possible. The principle is based on the decomposition of the global behaviour of the detector, which may seem complex, as a multitude of elementary phenomena, which are easy to model. The study was applied to the particular case of a micro-spectrometer integrated to an infrared detection array. A sensitivity analysis of the proposed model was then performed to deduce the necessary precision on the technological parameters to obtain good quality spectra restitution. This approach can be generalized to other architectures detectors and other manufacturing technologies, provided that the optical properties of the materials involved are well known.

<p>Infrared absorption spectra can provide analytically useful information on a large variety of compounds, ranging from small ions to large biological molecules. In fact, all analytes that possess a dipole moment that changes during vibration are infrared-active. The infrared (IR) spectrum can be subdivided into far-, mid- and near- regions. The focus of attention in this thesis is the mid-IR region, in which the fundamental vibrations of most organic compounds are located, thus providing scope for positive structural identification. However, while such near-ubiquitous signals can be very useful for monitoring simple molecules in simple systems, they can be increasingly disadvantageous as the number of analytes and/or the complexity of the sample matrix increases. Thus, hyphenation to a separation system prior to detection is desirable. Paper I appended to this thesis presents (for the first time) the on-line hyphenation between Fourier transform infrared spectroscopy, FTIR, and capillary zone electrophoresis, CZE. CZE is a highly efficient separation technique that separates ionic analytes with respect to their charge-to-size ratio. It is most commonly performed in aqueous buffers in fused silica capillaries. Since these capillaries absorb virtually all infrared light an IR-transparent flow cell had to be developed. In further studies (Paper II) the applicability of CZE is expanded to include neutral analytes by the addition of micelles to the buffer, and micellar electrokinetic chromatography, MEKC, was successfully hyphenated to FTIR for the first time. Paper III describes an application of the on-line CZE-FTIR technique in which non-UV-absorbing analytes in a complex matrix were separated, identified and quantified in one run.</p><p>Measuring aqueous solutions in the mid-IR region is not straightforward since water absorbs intensely in this region, sometimes completely, leaving no transmitted, detectable light. For this reason, quantum cascade lasers are interesting. These lasers represent a new type of mid-IR semiconducting lasers with high output power due to their ingenious design. The laser action lies within one conduction band (intersubband) and can be tailored to emit light in the entire mid-IR region using the same semiconducting material. To investigate their potential to increase the optical path length in aqueous solutions, these lasers were used with an aqueous flow system (Paper IV), and the experience gained in these experiments enabled hyphenation of such lasers to a CZE system (Paper V).</p>