Transition metal Dichalcogenide MoS2in the monolayer and few-layer form have generated intense interest in the fundamental and applied research community due to its surprisingly strong light-matter interactions, strong excitonic effect, and unique elec-tronic and chemical activity at the edges. In this thesis work, I have conducted a series of synergistic experimental and computational investigations focused on understanding the fundamental optical properties of few-layer MoS2(experiment with supporting computational calculations) and its potential application into the electrochemical reduction of CO2(computational)In the first part of the thesis, I show that sulfur vacancies affect the optical properties of few-layer thin films deposited using magnetron sputtering. In particular, I show that sulfur vacancies can obscure the well-defined A/B excitons in MoS2. Next, while contributing with the process of developing high-quality MoS2films, I designed an approach to accurately determine the optical constants by combining transmission spectroscopy with spectroscopic ellipsometry. The method, which we call Transmission-assisted spectroscopic ellipsometry (TASE), is demonstrated on high-quality MoS2films deposited on transparent and absorbing substrates. Next, Transmission spectroscopy combined with the Kramers-Kronig consistent optical model was employed to determine the complex dielectric function of few-layer MoS2in the broadband energy range of 0.7-6.5 eV. Optical transitions leading to peaks in the dielectric functions are assigned to the band structure. In particular, a new peak is observed and assigned at 4.5 eV in few-layer MoS2. Finally, I have examined the effectiveness of doped MoS2on the catalytic activity for CO reduction using density functional theory method. The structural calculation shows that doping Mo edge site of MoS2with transition metals that have higher work function than Mo atom results a lowering in the CO adsorption energy which suppresses the dissociation reaction and enhances the hydrogenation reaction. The Bader charge analysis shows that the dopant atom does not contribute to CO adsorption directly but it reduces the charge density at the edge atom that is indicated from the Density of states.

We present the dielectric function of a bcc-In2O3 thin film in the wide spectral range from nearinfrared to vacuum-ultraviolet and for temperatures 10 K–300K, determined by spectroscopic ellipsometry. From the temperature dependence of electronic transition energies, we derive electron-phonon coupling properties and found hints that the direct parabolic band-band transitions involve In-d states. Further we discuss possible excitonic contributions to the dielectric function.

<p> </p><p><p> </p></p><p><p><p> </p></p></p><p>MAX-phase materials are a new type of material class. These materials are potentiallyt echnologically important as they show unique physical properties due to the combination of metals and ceramics. In this project, spectroscopic ellipsometry in the spectral range of 0.06 eV –6.0 eV was used to probe the linear optical response of MAX-phases in terms of the complexd dielectric function <em>ε(ω) = ε1(ω) + iε2(ω<em>). </em></em>Measured data were fit to theoretical models using the Lorentz and generalized oscillator models. Data from seven different samples of MAX-phase materials were obtained using two ellipsometers. Each sample dielectric function was determined, including their infrared spectrum.</p>

MAX-phase materials are a new type of material class. These materials are potentiallyt echnologically important as they show unique physical properties due to the combination of metals and ceramics. In this project, spectroscopic ellipsometry in the spectral range of 0.06 eV –6.0 eV was used to probe the linear optical response of MAX-phases in terms of the complexd dielectric function ε(ω) = ε1(ω) + iε2(ω). Measured data were fit to theoretical models using the Lorentz and generalized oscillator models. Data from seven different samples of MAX-phase materials were obtained using two ellipsometers. Each sample dielectric function was determined, including their infrared spectrum.

GaAs(1-x)Bi(x) (x = 0 to 17%) optical properties were investigated by spectroscopic ellipsometry (in energy ranges of 0.37–9.0 eV). Optical features in the dielectric function, known as the critical points, were distinguished and modeled using standard analytic line shapes. The energy dependence of the critical points energies was thoroughly investigated as a function of Bi content and thin film strain. Critical points analysis in the Brillion zone showed that the top of the valence band is most strongly dependent on Bi content compared to other parts of the band structure. In addition, an interesting new critical point was observed that is attributed to alternative allowed optical transitions made possible by changes to the top of the valence band caused by resonant interactions with Bi orbitals. Several of the critical points were extrapolated to 100% Bi and showed reasonable agreement with the calculated band structure of GaBi. GaAs(1-x)Bi(x) (x= 03, 0.7 and 1.1%) based p+/n and n+/p heterostructure photovoltaic performance was characterized through IV and CV measurement. By introduction of Bi into GaAs, a non-zero EQE below the GaAs band edge energy was observed while the highest efficiency was obtained by ~ 0.7% Bi incorporation. EQE spectrum was modeled to find the minority carrier diffusion lengths of ~ Ln = 1600 and Lp = 140 nm for p-doped and n-doped GaAs92Bi08 in the doping profile of 10^15 - 10^16 cm^-3. Analysis of the CV measurement confirmed the background n-doping effect of Bi atom and the essential role of the cap layer to reduce multi-level recombination mechanisms at the cell edge to improve ideality factor. Low temperature grown GaAs was optimized to be used as photoconductive antenna in THz time-domain spectroscopy setup. The As content was investigated to optimize photo-carrier generation using 1550 nm laser excitation while maintaining high mobility and resistivity required for optical switching. A barrier layer of AlAs was added below the LT-GaAs to limit carrier diffusion into the GaAs substrate. Moreover, LT-GaAs layer thickness and post-growth annealing condition was optimized. The optimized structure (2-µm LT-GaAs on 60-nm AlAs, under As2:Ga BEP of ~7, annealed at 550°C for 1 minute) outperformed a commercial InGaAs antenna by a factor of 15 with 4.5 THz bandwidth and 75 dB signal-to-noise ratio at 1550 nm wavelength. / Graduate

Ce travail de thèse consiste en une étude approfondie du comportement de l'oxyde de silicium implanté Kr ou Xe pour son application comme matériau à faible constante diélectrique. Deux volets sont examinés: une étude structurale par l'utilisation de plusieurs techniques (RBS, PL, MET et PAS) et une étude de la variation de la constante diélectrique par utilisation de la spectroscopie IR avec le développement d'un modèle de la fonction diélectrique et des mesures C(V). Pour la caractérisation structurale, les principaux résultats confirment pour le cas du Kr, une distribution homogène de ce dernier jusqu'à 400°C. Pour le cas du Xe, le profil de distribution en profondeur de Xe est quasi-gaussien. Le Xe reste stable dans le SiO2 jusqu'à 900°C et désorbe à 1100°C et les bulles se transforment en cavités. Les bulles sont formées au niveau du pic des lacunes (p(lacunes)R). Alors qu’en l’absence des bulles, le Xe se localise à la profondeur de fin de parcours du Xe (RpXe) calculée par SRIM. On note aussi la présence de défauts chargés négativement et des défauts paramagnétiques E'. Ces défauts négatifs disparaissent après un recuit à 750°C. La forme des bulles, pour les deux cas Xe et Kr, est influencée par la position de l'interface SiO2/Si; sans doute à cause de la différence des modules d'Young des deux matrices. L'IR et les mesures C(V) ont permis de montrer que l'implantation des deux gaz fait diminuer la valeur de la constante diélectrique jusqu'à 2.8 pour le cas Kr et entre 1.8 et 2.4 pour le cas Xe. La cohérence des résultats obtenus par les deux techniques montrent bien que ces deux gaz rares peuvent être utilisés pour la réalisation de SiO2 de faible constante diélectrique avec un impact plus important quand le Xe est utilisé. Cette étude a permis aussi de montrer la contribution de la polarisabilité et de la porosité sur la réduction de la valeur de la constante diélectrique du SiO2 implanté. / This thesis aims to get a deep insight of Kr and Xe-implanted amorphous SiO2 for its possible application as low-k material. This work is divided in two parts: Two sides are examined: a structural study by using several techniques (RBS, PL, MET et PAS) and investigation of the evolution of the dielectric constant by using IR spectroscopy with a dielectric function model developing and C-V measurements. From structural characterization, our main results confirm, in the case of Kr implantation, an homogeneous distribution for temperature up to 400°C. For Xe, the distribution profile is quasi-gaussian. Xe remains stable in SiO2 then desorbs completely at 1100°C. We demonstrated that Xe-bubbles are located at the projected range of vacancies (RPV) as simulated by SRIM. However, we also showed that if Xe dose is not higher enough to induce bubbles, Xe is located at RP. Such a behavior helps understanding the formation of Xe-bubbles in SiO2. We reported the presence of negative defects charge and the paramagnetic defects E'. These defects disappear after 750°C annealing. The shape of bubbles induced by both Kr and Xe is SiO2/Si interface dependent. They are spherically shaped when interface is closed and quite irregular when this one is far. Differences in Young Modulus of Si and SiO2 can probably explain such a behavior. IR and C-V measurements show that Xe and Kr implantation result in decreasing the dielectric constant value down to 2.8 in the Kr case and in the range 1.8-2.4 in the Xe case. The good agreement between k values provided by IR and C-V measurements clearly valids the fact that Kr or Xe-implantation in SiO2 is a powerful approach to building low-k dielectrics. With Xe leading to a higher decrease. This study has also pointed out the contribution of both the polarisability and the porosity in the reduction of the dielectric constant of the implanted SiO2.

The objective of this dissertation is to understand the structural and optoelectronic properties of group III-nitride materials grown by High-Pressure Metal Organic Chemical Vapor Deposition (HP-MOCVD) and Migration Enhanced Plasma Assisted MOCVD by FTIR reflectance spectroscopy, Raman spectroscopy, X-ray diffraction, and Atomic Force Microscopy. The influence of the substrates/templates (Sapphire, AlN, Ga-polar GaN, N-polar GaN, n-GaN, and p-GaN) on the free carrier concentration, carrier mobility, short-range crystalline ordering, and surface morphology of the InN layers grown on HP-MOCVD were investigated using those techniques. The lowest carrier concentration of 7.1×1018 cm-3 with mobility of 660 cm2V-1s-1 was found in the InN film on AlN template, by FTIR reflectance spectra analysis. Furthermore, in addition to the bulk layer, an intermediate InN layers with different optoelectronic properties were identified in these samples. The best local crystalline order was observed in the InN/AlN/Sapphire by the Raman E2 high analysis. The smoothest InN surface was observed on the InN film on p-GaN template. The influence of reactor pressures (2.5–18.5 bar) on the long-range crystalline order, in plane structural quality, local crystalline order, free carrier concentration, and carrier mobility of the InN epilayers deposited on GaN/sapphire by HP-MOCVD has also been studied using those methods. Within the studied process parameter space, the best material properties were achieved at a reactor pressure of 12.5 bar and a group-V/III ratio of 2500 with a free carrier concentration of 1.5x1018 cm-3, a mobility in the bulk InN layer of 270 cm2 V-1s-1 and the Raman (E2 high) FWHM of 10.3 cm-1. The crystalline properties, probed by XRD 2θ–ω scans have shown an improvement with the increasing reactor pressure. The effect of an AlN buffer layer on the free carrier concentration, carrier mobility, local crystalline order, and surface morphology of InN layers grown by Migration-Enhanced Plasma Assisted MOCVD were also investigated. Here, the AlN nucleation layer was varied to assess the physical properties of the InN layers. This study was focused on optimization of the AlN nucleation layer (e.g. temporal precursor exposure, nitrogen plasma exposure, and plasma power) and its effect on the InN layer properties.

In the course of this thesis gold nanoparticle/polyelectrolyte multilayer structures were prepared, characterized, and investigated according to their static and ultrafast optical properties. Using the dip-coating or spin-coating layer-by-layer deposition method, gold-nanoparticle layers were embedded in a polyelectrolyte environment with high structural perfection. Typical structures exhibit four repetition units, each consisting of one gold-particle layer and ten double layers of polyelectrolyte (cationic+anionic polyelectrolyte). The structures were characterized by X-ray reflectivity measurements, which reveal Bragg peaks up to the seventh order, evidencing the high stratication of the particle layers. In the same measurements pronounced Kiessig fringes were observed, which indicate a low global roughness of the samples. Atomic force microscopy (AFM) images veried this low roughness, which results from the high smoothing capabilities of polyelectrolyte layers. This smoothing effect facilitates the fabrication of stratified nanoparticle/polyelectrolyte multilayer structures, which were nicely illustrated in a transmission electron microscopy image. The samples' optical properties were investigated by static spectroscopic measurements in the visible and UV range. The measurements revealed a frequency shift of the reflectance and of the plasmon absorption band, depending on the thickness of the polyelectrolyte layers that cover a nanoparticle layer. When the covering layer becomes thicker than the particle interaction range, the absorption spectrum becomes independent of the polymer thickness. However, the reflectance spectrum continues shifting to lower frequencies (even for large thicknesses). The range of plasmon interaction was determined to be in the order of the particle diameter for 10 nm, 20 nm, and 150 nm particles. The transient broadband complex dielectric function of a multilayer structure was determined experimentally by ultrafast pump-probe spectroscopy. This was achieved by simultaneous measurements of the changes in the reflectance and transmittance of the excited sample over a broad spectral range. The changes in the real and imaginary parts of the dielectric function were directly deduced from the measured data by using a recursive formalism based on the Fresnel equations. This method can be applied to a broad range of nanoparticle systems where experimental data on the transient dielectric response are rare. This complete experimental approach serves as a test ground for modeling the dielectric function of a nanoparticle compound structure upon laser excitation. / Im Rahmen dieser Arbeit wurden Gold-Nanopartikel/Polyelektrolyt Multischichtstrukturen hergestellt, strukturell charakterisiert und bezüglich ihrer optischen Eigenschaften sowohl statisch als auch zeitaufgelöst analysiert. Die Strukturen wurden mithilfe der Dip-coating oder der Spin-coating Methode hergestellt. Beide Methoden ermöglichen das Einbetten einzelner Partikellagen in eine Polyelektrolytumgebung. Typische Strukturen in dieser Arbeit bestehen aus vier Wiederholeinheiten, wobei jede aus einer Nanopartikelschicht und zehn Polyelektrolyt-Doppellagen (kationisches und anionisches Polyelektrolyt) zusammengesetzt ist. Die Stratizierung der Gold-Nanopartikellagen wurde mittels Röntgenreflektometrie-Messungen im Kleinwinkelbereich nachgewiesen, welche Bragg Reflexionen bis zur siebten Ordnung aufzeigen. Das ausgeprägte Kiessig Interferenzmuster dieser Messungen weist zudem auf eine geringe globale Rauheit hin, die durch Oberflächenanalysen mit einem Rasterkraftmikroskop bestätigt werden konnte. Diese geringe Rauheit resultiert aus den glättenden Eigenschaften der Polyelektrolyte, die die Herstellung von Multilagensystemen mit mehreren Partikellagen erst ermöglichen. Die Aufnahme eines Transmissionselektronenmikroskops veranschaulicht eindrucksvoll die Anordnung der Partikel in einzelne Schichten. Durch photospektroskopische Messungen wurden die optischen Eigenschaften der Strukturen im UV- und sichtbaren Bereich untersucht. Beispielsweise wird eine Verschiebung und Verstärkung der Plasmonenresonanz beobachtet, wenn eine Goldnanopartikellage mit transparenten Polyelektrolyten beschichtet wird. Erst wenn die bedeckende Schicht dicker als die Reichweite der Plasmonen wird, bleibt die Absorption konstant. Die spektrale Reflektivität jedoch ändert sich auch mit jeder weiteren adsorbierten Polyelektrolytschicht. Die Reichweite der Plasmonenresonanz konnte auf diese Art für Partikel der Größe 10 nm, 20 nm und 150 nm bestimmt werden. Die Ergebnisse wurden im Kontext einer Effektiven Mediums Theorie diskutiert. Die komplexe dielektrische Funktion einer Multilagenstruktur wurde zeitabhängig nach Laserpulsanregung für einen breiten spektralen Bereich bestimmt. Dazu wurden zuerst die Änderungen der Reflektivität und Transmittivität simultan mittels der Pump-Probe (Anrege-Abtast) Spektroskopie gemessen. Anschließend wurden aus diesen Daten, mithilfe eines Formalismus, der auf den Fresnelschen Formeln basiert, die Änderungen im Real- und Imaginärteil der dielektrischen Funktion ermittelt. Diese Methode eignet sich zur Bestimmung der transienten dielektrischen Funktion einer Vielzahl von Nanopartikelsystemen. Der rein experimentelle Ansatz ermöglicht es, effektive Medien Theorien und Simulationen der dielektrischen Funktion nach Laserpulsanregung zu überprüfen.

This thesis is on the topic of investigation of the characteristics of DC Glow Discharge plasmas. Emphasis is given on characterizing the plasma electron density. The methods of generating and detecting THz pulses are described. THz transmission spectroscopy and plasma emission spectroscopy is examined. Transmission spectrum is taken for Air, gaseous Nitrogen and Argon plasmas. Moreover, emission spectrum of Air, N2 and Ar plasma analysis were done respectively. It was found that the transmission of terahertz pulses through nitrogen plasma was considerably affected compared to that of the argon plasma. Initially Drude model theory of electron conduction is employed to analyze the plasma density.

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