Dissertations / Theses on the topic 'Phosphide telluride'

The two-photon absorption (TPA) coefficient is measured in indium phosphide (InP) using femtosecond pulses to be 45cm/GW at 1.32μm. Nanosecond pulses are subsequently used to find the free-carrier refractive index cross-section, σ_r, and the free-carrier absorption coefficient, σ_fca. The quantity βσ_r is measured to be -113x10⁻²ºcm⁴/GW at 1.064μm and -84x10⁻²ºcm⁴/GW at 1.534μm. At 1.064μm, with β assumed to be 22cm/GW, the value suggested by theory, σ_r is -5.1x10⁻²ºcm³. Similarly, at 1.534μm, assuming β to be 20cm/GW gives a σ_r value of -4.1x10⁻²ºcm³. Due to refraction affecting the measurements of σ_fca, only an upper limit of 1x10⁻¹⁵cm² can be put on its value. The free-carrier experiments are repeated on two samples of cadmium mercury telluride (CMT) having bandgaps of 0.89eV and 0.82eV. For the first sample, β_σr is measured to be -148x10⁻²ºcm⁴/GW. Assuming β to be 89cm/GW gives a σ_r value of -1.7x10⁻²ºcm³ whilst σ_fca is found to be at most 3x10⁻¹⁵cm². Significant linear absorption occurs in the second sample which generates a large free-carrier population. It is shown that this significantly enhances the nonlinearities. Finally, the results of the work are tested by modelling a nonlinear transmission experiment, and the results found in this work give a closer fit to experimental results than the result of theory. Four-wave mixing (FWM) in a photonic crystal fibre is exploited to create a high output power optical parametric amplifier (OPA). To optimise the OPA conversion efficiency, the fibre length has to be increased to 150m, well beyond the walk-off distance between the pump and signal/idler. In this regime, the Raman process can take over from the FWM process and lead to supercontinuum generation. The OPA exhibits up to 40% conversion efficiency, with the idler (0.9μm) and the signal (1.3μm) having a combined output power of over 1.5W.

Die ternären Systeme Ti/P/Te, Ce/P/Te und Si/P/Te wurden in der vorliegenden Dissertation hinsichtlich der Existenz neuer Verbindungen untersucht. Diese Verbindungen wurden insbesondere in Bezug auf ihre thermochemischen Eigenschaften charakterisiert. Durch Kombination von experimentellen Untersuchungen und thermodynamischen Modellierungen der ablaufenden Festkörper-Gasphasen-Gleichgewichte konnten die Synthesen der neuen Verbindungen optimiert werden. Abschließend erfolgte zudem die physikalische und kristallographische Charakterisierung der gefundenen Phosphidtelluride.

Die ternären Systeme Ti/P/Te, Ce/P/Te und Si/P/Te wurden in der vorliegenden Dissertation hinsichtlich der Existenz neuer Verbindungen untersucht. Diese Verbindungen wurden insbesondere in Bezug auf ihre thermochemischen Eigenschaften charakterisiert. Durch Kombination von experimentellen Untersuchungen und thermodynamischen Modellierungen der ablaufenden Festkörper-Gasphasen-Gleichgewichte konnten die Synthesen der neuen Verbindungen optimiert werden. Abschließend erfolgte zudem die physikalische und kristallographische Charakterisierung der gefundenen Phosphidtelluride.

Concentration quenching effect in ytterbium (Yb) and neodymium (Nd) doped phosphate glasses, thulium (Tm) doped germanate glass, and praseodymium (Pr) doped tellurite glass were studied. The fluorescence and lifetime of these rare-earth doped glasses with different concentrations were measured. Ion pair and clustering are included in the model to explain the quenching effect occurring in highly doped glasses. This study will help us in designing and fabricating high unit gain optical fibers.

Philosophiae Doctor - PhD
Electroanalytical and optical properties of nanoscale materials are very important for biosensing applications as well as for understanding the unique one-dimensional carrier transport mechanism. One-dimensional semiconductor nanomaterials such as semiconductor quantum dots are extremely attractive for designing high-density protein arrays. Because of their high surfaceto-volume ratio, electro-catalytic activity as well as good biocompatibility and novel electron transport properties make them highly attractive materials for ultra-sensitive detection of biological macromolecules via bio-electronic or bio-optic devices. A genosensor or gene based biosensor is an analytical device that employs immobilized deoxyribonucleic acid (DNA) probes as the recognition element and measures specific binding processes such as the formation of deoxyribonucleic acid-deoxyribonucleic acid (DNA-DNA), deoxyribonucleic acid- ribonucleic acid (DNA-RNA) hybrids, or the interactions between proteins or ligand molecules with DNA at the sensor surface.In this thesis, I present four binary and two ternary-electrochemically and optically modulated selenide and telluride quantum dots, all synthesised at room temperature in aqueous media. Cationic gallium (Ga3+) synthesized in form of hydrated gallium perchlorate salt[Ga(ClO4)3.6H2O] from the reaction of hot perchloric acid and gallium metal was used to tailor the optical and electrochemical properties of the selenide and telluride quantum dots. The synthesized cationic gallium also allowed successful synthesis of novel water soluble and biocompatible capped gallium selenide nanocrystals and gallium telluride quantum dots. Cyclic voltammetric studies inferred that presence of gallium in a ZnSe-3MPA quantum dot lattice improved its conductivity and significantly increased the electron transfer rate in ZnTe-3MPA.Utraviolet-visible (UV-vis) studies showed that incorporation of gallium into a ZnSe-3MPA lattice resulted in a blue shift in the absorption edge of ZnSe-3MPA from 350 nm to 325 nm accompanied by decrease in particle size. An amphiphilic bifunctional molecule, 3-Mercaptopropionic acid (3-MPA) was used as a capping agent for all quantum dots. It was found that 3-MPA fully solubilised the quantum dots, made them stable, biocompatible, non agglomerated and improved their electron transfer kinetics when immobilized on gold electrodes.Retention of the capping agent on the quantum dot surface was confirmed by Fourier transform infrared spectroscopy (FTIR) which gave scissor type bending vibrations of C-H groups in the region 1365 cm-1 to 1475 cm-1, stretching vibrations of C=O at 1640 cm-1, symmetric and asymmetric vibrations of the C-H in the region 2850 cm-1 to 3000 cm-1 as well as stretching vibrations of –O-H group at 3435 cm-1. The particle size and level of non-agglomeration of the quantum dots was studied by high resolution transmission electron microscopy (HRTEM). The optical properties of the quantum dots were studied using UV-vis and fluorescence spectroscopic techniques.Quantum dot/nanocrystal modified gold electrodes were prepared by immersing thoroughly cleaned electrodes in the quantum dot/nanocrystal solution, in dark conditions for specific periods of time. The electrochemical properties of the modified electrodes were characterized by cyclic voltammetry (CV), square wave voltammetry (SWV), electrochemical impedance and spectroscopy (EIS). Six sensing platforms were then prepared using quantum dot/nanocrystal, one of which was used for detection of dopamine while the rest were used for detection of a DNA sequence related to 5-enolpyruvylshikimate-3-phosphate synthase, a common vector gene in glyphosate resistant transgenic plants.The first sensing platform, consisting of ZnSe-3MPA modified gold electrode (Au|ZnSe-3MPA) gave rise to a novel method of detecting dopamine in presence of excess uric acid and ascorbic acid. Using a potential window of 0 to 400 mV, the ZnSe-3MPA masked the potential for oxidation of uric and ascorbic acids, allowing detection of dopamine with a detection limit of 2.43 x 10-10 M (for SWV) and 5.65 x 10-10 M (for steady state amperometry), all in presence of excess uric acid (>6500 higher) and ascorbic acid (>16,000 times higher). The detection limit obtained in this sensor was much lower than the concentration of dopamine in human blood(1.31 x 10-9 M), a property that makes this sensor a potential device for detection of levels of dopamine in human blood.The other sensing platforms were prepared by bioconjugation of amine-terminated 20 base oligonucleotide probe DNA (NH2-5′-CCC ACC GGT CCT TCA TGT TC-3′) onto quantum dot modified electrodes with the aid of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). The prepared DNA electrodes were electrostatically hybridized with different sequences which included 5′-GAA CAT GAA GGA CCG GTG GG-3′ (complementary target), 5′-CATAGTTGCAGCTGCCACTG-3′ (non complementary target) and 5′-GATCATGAAGCACCGGAGGG-3′ (3-base mismatched target).The hybridization events were monitored using differential pulse voltammetry (DPV) and SWV by monitoring the guanine oxidation signal or using EIS by monitoring changes in the charge transfer resistance. The quantum dot genosensors were characterized by low detection limits (in the nanomolar range), long linear range (40 - 150 nM) and were able to discriminate among complementary, non-complementary and 3-base mismatched target sequences.

Interest in Raman amplification has undergone a revival due to the rapidly increasing bandwidth requirements for communications transmission, both for long haul and local area networks, and recent developments in the telecom fiber industry and diode laser technology. In contrast to rare earth doped fiber amplifiers, for which the range of wavelengths is fixed and limited, Raman gain bandwidths are larger and the operating wavelength is fixed only by the pump wavelength and the bandwidth of the Raman active medium. In this context, glasses are the material of choice for this application due to their relatively broad spectral response, and ability of making them into optical fiber. This dissertation summarizes findings on different oxide-based glasses that have been synthesized and characterized for their potential application as Raman gain media. Two main glass families were investigated: phosphate-based glass matrices for broadband Raman gain application and TeO2-based glasses for high Raman gain amplification. A phosphate network was preferred for the broadband application since the phosphate Raman active modes can provide amplification above 1000 cm-1, whilst TeO2-based glasses were selected for the high gain application due to their enhanced nonlinearities and polarizabilities among the other oxide-based network formers. The results summarized in this dissertation show that phosphate-based glasses can provide Raman amplification bandwidths of up to 40 THz, an improvement of almost 5 times the bandwidth of SiO2. On the other hand, tellurite-based glasses appear to be promising candidates for high gain discrete Raman applications, providing peak Raman gain coefficients of up to 50 times higher than SiO2, at 1064 nm. Although, visible spontaneous Raman scattering cross-section measurement is the most frequently used tool for estimating the strength and spectral distribution of Raman gain in materials, especially glasses, there are some issues that one needs to be aware when conducting these measurements near the absorption band edge of the material. This led to the detection of an inherent frequency-dispersion in the Raman susceptibility and a resonant enhancement phenomenon when measurements were conducted near the absorption edge of the material.
Ph.D.
Optics and Photonics
Optics

Des thiols, sélénols et tellurols fonctionnalisés et cinétiquement non-stabilisés ont été préparés dans des conditions particulières de réaction sous vide. De façon plus précise, le 3-mercapto-2-propènenitrile, des allényl- et alcynylsélénols, des alcényl- ou cyclopropyl-tellurols ont ainsi pu être isolés et caractérisés par spectroscopie. Les synthèses ont ensuite été adaptées à diverses études spectroscopiques. Les spectres Infrarouge de l’éthènetellurol et l’éthènylphosphine-borane ont été enregistrés. Les spectres de photoélectron des sélénols et tellurols insaturés ont permis de rationaliser les interactions existant entre la paire libre d’électrons de l’hétéroatome et l’insaturation en fonction de leur éloignement relatif. La complexation des systèmes réactifs a été abordée par la complexation des phosphines primaires par le borane. Une étude générale a été menée sur ces phosphine-boranes en phase gazeuse par diffraction électronique. L’influence de la complexation sur les paramètres géométriques (longueurs de liaisons, angles) par rapport aux systèmes libres correspondants a ainsi été précisée
Primary heterocompounds (Thiols, Selenols, Tellurols and Phosphine-boranes) have been prepared in particular conditions on a preparative scale and with a high purity. Allenyl- and alkynylselenols, cyclopropyl- and alkenyltellurols as well as primary ,-unsaturated phosphines-boranes have thus been isolated and characterized by spectroscopy. The microwave, infrared or photoelectron spectra of several of these kinetically unstable compounds have been recorded. Thus, by photoelectron spectroscopy and quantum calculations, the type and extent of the interaction between the SeH or TeH group and the unsaturated moiety has been clarified for compounds with gradual increasing distance between the heteroatom and the unsaturated group. On the other hand, a general study was undertaken on the primary phosphine-boranes in gas phase by electronic diffraction. The modification of the interatomic lengths and angles by complexation with borane has been precised

The need for more bandwidth in communications has stimulated the search for new fiberizable materials with properties superior to fused silica which is the current state-of-the-art. One of the key properties is Raman gain by which a pump beam amplifies a signal beam of longer wavelength. An apparatus capable of directly measuring the spectral dependence and absolute magnitude of the material Raman gain coefficient using nonlinear optics techniques has been built. Using radiation from a 1064 nm Nd:YAG laser as the pump and from a tunable Optical Parametric Generator and Amplifier as the signal, the Raman gain spectrum was measured for different families of glass samples with millimeter thickness. A number of glass families were investigated. Tellurites with added oxides of tungsten, niobium, and thallium produced the largest Raman gain coefficients of any oxide family reported to date, typically 30-50 times higher than that of fused silica. On the other hand, phosphate families were found with spectrally broad Raman gain response, 5 times broader than fused silica and flat to [plus or minus] dB over the full spectral range in some compositions. Although the chalcogenides were found to photodamage easily, coefficients 50 - 80 times that of fused silica were measured. Finally, a numerical study was undertaken to predict the theoretical performance and noise properties of tellurite fibers for communications. Included in the computer modeling were linear loss; the interaction among multiple pumps and signals; forward and/or backward propagating pump beams; forward, backward and double Rayleigh scattering; noise properties of amplifiers; excess noise, etc. This led to a comparison of the optical signal-to-noise characteristics for Raman gain in a tellurite versus a silica fiber.
Ph.D.
Optics and Photonics
Optics

L'etude porte sur la variation de la conductivite electrique des systemes borotellurates et borophosphates suivants : lio::(2)-b::(2)o::(3)-te::(2)o::(4) et li::(2)o-b::(2)o::(3)-p::(2)o::(6)-lix (x=f, cl, br). L'effet de formateur mixte pour le premier systeme et l'effet de sel dopant dans le second systeme ont ete interpretes a l'aide de la theorie de l'electrolyte faible et d'un modele de solutions regulieres

Determination, par diffraction rx de la variation de volume de composes du cerium et de l'uranium a haute pression, dans une presse a enclumes diamant. Cas de ceal::(2), cein::(3), ces et de ceo. Resultats interpretes par une augmentation continue de la valence du cerium et de la temperature de kondo. Etude des composes up, uas, usb, et ute. Existence d'une hybridation f-d ou p-f

La premiere partie de cette these est consacree a l'etude des structures magnetiques des monopnictures et des monochalcogenures de neptunium. Dans la seconde partie, nous avons etudie les excitations magnetiques des solutions solides de u(ru#1#-#xrh#x)#2si#2. Par la determination des structures magnetiques de npp et de npbi, nous avons termine la serie des monopnictures de neptunium. Tous ces composes ont une structure magnetique avec un vecteur de propagation et des composantes de fourier selon les axes quatre. En utilisant cette propriete, nous avons etabli un modele de type annni qui nous a permis de suivre l'evolution des integrales d'echange avec le pnictogene. Les monochalcogenures de neptunium ont tous une structure antiferromagnetique de type ii. Cependant, nps presente une transition du premier ordre, tandis que la transition magnetique de npse et npte est du second ordre. En utilisant des proprietes de symetrie du cristal, les resultats de spectroscopie mossbauer ainsi que les resultats de diffraction neutronique, nous avons determine des solutions possibles pour les structures magnetiques de nps et npse. Ces solutions sont multi-k et assez compliquees. Pour npte, l'etude du facteur de forme et l'evolution thermique du moment magnetique ont montre que ce compose avait un comportement magnetique tres particulier. Nous avons utilise trois methodes pour etudier les solutions solides de u(ru#1#-#x-rh#x)#2si#2s: chaleur specifique, diffraction elastique et inelastique de neutrons. Par un modele simple, nous avons pu relier la dependance en temperature du gap des excitations antiferromagnetiques a l'anomalie de la chaleur specifique a t#n. Les excitations magnetiques ont ete decrites comme etant dues a un champ cristallin a deux niveaux couples par une interaction anisotrope de type rkky. Nous avons vu aussi que l'evolution du moment magnetique avec la concentration de rhodium est tres particuliere: la temperature de transition decroit, alors que la valeur du moment a basse temperature augmente

Mesures de la conductivite electrique, de la magnetoconductivite et de l'effet hall sur echantillons monocristallins de npas::(2) et pusb::(1-x)te::(x); analyse des variations en fonction de la temperature et du champ magnetique, modes de diffusion dominants. Etude de l'effet d'un champ magnetique intense sur la conductivite de uas et up et attribution des variations observees soit a un changement de structure antiferromagnetique soit a l'anisotropie du tenseur de conductivite par rapport au vecteur de modulation de la structure magnetique

Ce manuscrit présente l'étude de l'effet photorefractif dans le proche infrarouge et, plus particulièrement, l'étude des matériaux sensibles dans cette gamme de longueurs d'onde. la première partie du travail a consiste a étudier les matériaux existants, provenant de la microélectronique, le GaAs et l'InP. Les études réalisées, tant expérimentales que théoriques, ont permis de comprendre leurs propriétés et de mettre en évidence leurs limitations, notamment pour les applications dans la gamme de longueurs d'onde autour de 1,3 m. au vu de ces résultats, nous avons propose une technique d'optimisation des performances de gaas utilisant l'irradiation électronique. L'irradiation induit une légère variation du niveau de fermi, qui doit favoriser l'effet photorefractif a 1,3 m. Les résultats obtenus ont montre que l'effet attendu était fortement contrebalance par la création au milieu de la bande interdite, d'un défaut d'irradiation. L'influence directe de ce défaut a été établie grâce au développement d'un modèle théorique de l'effet photorefractif prenant en compte deux niveaux de pièges profonds. En parallèle a cette étude de l'effet d'irradiation, nous avons travaille sur les composes ii-vi, comme le CdTe. Les premiers cristaux étudiés présentent des gains photorefractifs intéressants avec des faisceaux de faible puissance. Ces résultats confirment les promesses de ces cristaux pour une extension de l'effet photorefractif vers 1,5 m. Pour finir, nous présentons une technique d'amplification du gain photorefractif qui utilise l'application d'un champ alternatif carre. une augmentation du gain d'un ordre de grandeur est obtenue.