Rozprawy doktorskie na temat „Chalcogenide alloys”

The emerging field of spintronics relies on the manipulation of electron spin in order to use it in spin-based electronics. Such a paradigm change has to tackle several challenges including finding materials with sufficiently long spin lifetimes and materials which are efficient in generating pure spin currents. This thesis predicts that two types of material families could be a solution to the aforementioned challenges: complex oxides and bismuth based materials. We derived a general approach for constructing an effective spin-orbit Hamiltonian which is applicable to all nonmagnetic materials. This formalism is useful for calculating spin-dependent properties near an arbitrary point in momentum space. We also verified this formalism through comparisons with other approaches for III-V semiconductors, and its general applicability is illustrated by deriving the spin-orbit interaction and predicting spin lifetimes for strained SrTiO3 and a two-dimensional electron gas in SrTiO3 (such as at the LaAIO3/SrTiO3 interface). Our results suggest robust spin coherence and spin transport properties in SrTiO3 related materials even at room temperature. In the second part of the study we calculated intrinsic spin Hall conductivities for bismuth-antimony Bi1-xSbx semimetals with strong spin-orbit couplings, from the Kubo formula and using Berry curvatures evaluated throughout the Brillouin zone from a tight-binding Hamiltonian. Nearly crossing bands with strong spin-orbit interaction generate giant spin Hall conductivities in these materials, ranging from 474 ((ћ/e)Ω-1cm-1) for bismuth to 96((ћ/e)Ω-1cm-1) for antimony; the value for bismuth is more than twice that of platinum. The large spin Hall conductivities persist for alloy compositions corresponding to a three-dimensional topological insulator state, such as Bi0.83Sb0.17. The spin Hall conductivity could be changed by a factor of 5 for doped Bi, or for Bi0.83Sb0.17, by changing the chemical potential by 0.5 eV, suggesting the potential for doping or voltage tuned spin Hall current. We have also calculated intrinsic spin Hall conductivities of Bi2Se3 and Bi2Te3 topological insulators from an effective tight-binding Hamiltonian including two nearest-neighbor interactions. We showed that both materials exhibit giant spin Hall conductivities calculated from the Kubo formula in linear response theory and the clean static limit. We conclude that bismuth-antimony alloys and bismuth chalcogenides are primary candidates for efficiently generating spin currents through the spin Hall effect.

The work described herein deals with the synthesis and characterization of lead chalcogenide thin films and nanocrystals. The first part of thesis describes the properties of semiconductors followed by an analysis on the chemical vapour deposition and nanoparticulate formation. In the next part of thesis, single-source precursors of type thioselenophosphinato, selenoureato, dithiocarbamato and dithiocarbanato complexes of lead have been synthesised and characterised. As-synthesised compounds have been utilised for the fabrication of lead sulfide and lead selenide thin films by aerosol-assisted chemical vapour deposition as well as nanocrystals by colloidal injection method. Lead sulfide thin films were also deposited by liquid-liquid interface from lead dithiocarbanato at room temperature. The as grown thin films of lead sulfide and lead selenide have been characterised by XRD, SEM and energy dispersive x-ray (EDX) analysis. In the second part of the thesis, preparation of lead sulfide and lead selenide nanocrystals in olive oil at low growth temperatures (50-60°C) is described and have shown that by controlling experimental conditions, well-defined particles with tunable emission in mid and far-infrared region can be synthesised. Furthermore, compositionally-tuned PbSxSe1-x nanocrystals has also been prepared by adding controlled amount of sulur and selenium ingredients into lead oxide. Homogenous distribution of sulfur and selenium within alloyed nanocrystals is confirmed by transmission electron microscope studies. Moreover, attempts have been made to prepare quaternary (PbTe/Se/S) nanocrystals of lead chalcogenides and depth (1.9-5.8 nm) profile analysis by x-ray photoelectron spectroscopy confirmed the formation of core/shell/shell type structure i.e. PbTe/S/Se.

La conversion thermoélectrique a suscité un regain d'intérêt en raison des possibilités d'augmenter l'efficacité tout en exploitant les effets de taille. Par exemple, les nanofils montrent théoriquement une augmentation des facteurs de puissance ainsi qu'une réduction du transport des phonons en raison d'effets de confinement et/ou de taille. Dans ce contexte, le diamètre des nanofils devient un paramètre crucial à prendre en compte pour obtenir des rendements thermoélectriques élevés. Une approche habituelle consiste à réduire la conductivité thermique phononique dans les nanofils en améliorant la diffusion sur les surfaces tout en réduisant les diamètres.Dans ce travail, la caractérisation thermique d'une forêt dense de nanofils de silicium, germanium, silicium-germanium et alliage Bi2Te3 est réalisée par une méthode 3-omega très sensible. Ces forêts de nanofils pour le silicium, le germanium et les alliages silicium-germanium ont été fabriqués selon une technique "bottom-up" suivant le mécanisme Vapeur-Liquide-Solide en dépôt chimique en phase vapeur. La croissance assistée par matrice et la croissance par catalyseurs en or des nanofils à diamètres contrôlés ont été réalisés à l'aide d'alumine nanoporeuse comme matrice. Les nanofils sont fabriqués selon la géométrie interne des nanopores, dans ce cas le profil de surface des nanofils peut être modifié en fonction de la géométrie des nanopores. Profitant de ce fait, la croissance à haute densité de nanofils modulés en diamètre a également été démontrée, où l'amplitude et la période de modulation peuvent être facilement contrôlées pendant la fabrication des matrices. Même en modulant les diamètres pendant la croissance, les nanofils ont été structurellement caractérisés comme étant monocristallins par microscopie électronique à transmission et analyse par diffraction des rayons X.La caractérisation thermique de ces nanofils a révélé une forte diminution de la conductivité thermique en fonction du diamètre, dont la réduction était principalement liée à une forte diffusion par les surfaces. La contribution du libre parcours moyen à la conductivité thermique observée dans ces matériaux "bulk" varie beaucoup, Bi2Te3 ayant une distribution en libre parcours moyen (0,1 nm à 15 nm) très faible par rapport aux autres matériaux. Même alors, des conductivités thermiques réduites (~40%) ont été observées dans ces alliages attribuées à la diffusion par les surfaces et par les impuretés. D'autre part, le silicium et le germanium ont une conductivité thermique plus élevée avec une plus grande distribution de libre parcours moyen. Dans ces nanofils, une réduction significative (facteur 10 à 15 ) a été observée avec une forte dépendance avec la taille des nanofils.Alors que les effets de taille réduisent la conductivité thermique par une meilleure diffusion sur les surfaces, le dopage de ces nanofils peut ajouter un mécanisme de diffusion par différence de masse à des échelles de longueur atomique. La dépendance en température de la conductivité thermique a été déterminée pour les nanofils dopés de silicium afin d'observer une réduction de la conductivité thermique à une valeur de 4,6 W.m-1K-1 dans des nanofils de silicium fortement dopés avec un diamètre de 38 nm. En tenant compte de la conductivité électrique et du coefficient Seebeck calculé, on a observé un ZT de 0,5. Avec l'augmentation significative de l'efficacité du silicium en tant que matériau thermoélectrique, une application pratique réelle sur les appareils n'est pas loin de la réalité<br>Thermoelectric conversion has gained renewed interest based on the possibilities of increasing the efficiencies while exploiting the size effects. For instance, nanowires theoretically show increased power factors along with reduced phonon transport owing to confinement and/or size effects. In this context, the diameter of the nanowires becomes a crucial parameter to address in order to obtain high thermoelectric efficiencies. A usual approach is directed towards reducing the phononic thermal conductivity in nanowires by achieving enhanced boundary scattering while reducing diameters.In this work, thermal characterisation of a dense forest of silicon, germanium, silicon-germanium and Bi2Te3 alloy nanowires is done through a sensitive 3ω method. These forest of nanowires for silicon, germanium and silicon-germanium alloy were grown through bottom-up technique following the Vapour-Liquid-Solid mechanism in Chemical vapour deposition. The template-assisted and gold catalyst growth of nanowires with controlled diameters was achieved with the aid of tuneable nanoporous alumina as templates. The nanowires are grown following the internal geometry of the nanopores, in such a case the surface profile of the nanowires can be modified according to the fabricated geometry of nanopores. Benefiting from this fact, high-density growth of diameter-modulated nanowires was also demonstrated, where the amplitude and the period of modulation can be easily tuned during the fabrication of the templates. Even while modulating the diameters during growth, the nanowires were structurally characterised to be monocrystalline through transmission electron microscopy and X-ray diffraction analysis.The thermal characterisation of these nanowires revealed a strong diameter dependent decrease in the thermal conductivity, where the reduction was predominantly linked to strong boundary scattering. The mean free path contribution to the thermal conductivity observed in the bulk of fabricated nanowire materials vary a lot, where Bi2Te3 has strikingly low mean free path distribution (0.1 nm to 15 nm) as compared to the other materials. Even then, reduced thermal conductivities (~40%) were observed in these alloys attributed to boundary and impurity scattering. On the other hand, silicon and germanium have higher thermal conductivity with a larger mean free path distribution. In these nanowires, a significant reduction (10-15 times) was observed with a strong dependence on the size of the nanowires.While size effects reduce the thermal conductivity by enhanced boundary scattering, doping these nanowires can incorporate mass-difference scattering at atomic length scales. The temperature dependence of thermal conductivity was determined for doped nanowires of silicon to observe a reduction in thermal conductivity to a value of 4.6 W.m-1K-1 in highly n-doped silicon nanowires with 38 nm diameter. Taking into account the electrical conductivity and calculated Seebeck coefficient, a ZT of 0.5 was observed. With these significant increase in the efficiency of silicon as a thermoelectric material, a real practical application to devices is not far from reality

Cette these est une contribution a l'etude des proprietes de transport electrique de composes d'actinides. En particulier, nous reportons les premieres mesures de resistivite electrique a haute temperature sur des monocristaux de composes de plutonium. Pour cela, nous avons mis au point un appareillage de mesure de resistivite electrique a haute temperature (entre 300k et 1000k) en boite a gants pour des echantillons de 4mm a 10mm de longueur. Nous avons developpe un nouveau type de porte-electrode afin d'etablir des contacts electriques sur l'echantillon selon une configuration quatre pointes. Nous avons etendu au domaine des hautes temperatures les mesures preexistantes de resistivite a basse temperature des monochalcogenures de plutonium. Nous observons un comportement de type kondo entre 310k et 450k pour pus, entre 250k et 400k pour puse, et entre 200k et 340k pour pute. A des temperatures plus elevees, nous observons un comportement semiconducteur non degenere entre 440k et 590k pour pus, entre 380k et 510k pour puse, et entre 330k et 460k pour pute ; avec des bandes interdites de 0. 248ev, de 0. 185ev et de 0. 175ev pour pus, puse et pute respectivement. Ces resultats sont discutes en fonction de trois modeles: semiconducteur relativiste, modele localise et modele de valence intermediaire. Une interpretation definitive du comportement observe necessite les resultats des mesures de susceptibilite magnetique a haute temperature. Nous avons etudie egalement la localisation progressive des electrons 5f entre le plutonium et l'americium metaux, au moyen des mesures de resistivite a haute et a basse temperature des alliages pu#1#-#xam#x. A partir des resultats experimentaux, nous deduisons un renforcement des fluctuations de spin du plutonium metal pour une faible dissolution avec l'americium (pu#0#. #9am#0#. #1), du a l'affaiblissement de l'hybridation des electrons 5f du plutonium. Pour des concentrations d'americium plus elevees (x entre 0. 1 et 0. 25), ces fluctuations de spin disparaissent comme consequence de la croissance distance entre les atomes de plutonium. La progressive localisation des electrons 5f du plutonium conduit a un comportement d'impuretes kondo isolees

Cette these presente une etude par des mesures galvanomagnetiques (resistivite, magnetoresistance, effet hall) des proprietes de transport electrique des monopnictures et monochalcogenures de neptunium (de structure nacl), de la solution solide pusb(1-x)te(x), et du compose intermetallique nppt3. Pour une meilleure comprehension des phenomenes physiques nos mesures sont discutees en etroite association avec les resultats obtenus par la diffraction des neutrons, l'aimantation et la spectroscopie mossbauer. L'etablissement de l'ordre antiferromagnetique triple-k de type i pour les monopnictures npas, npsb et npbi induit l'ouverture d'un gap dans la surface de fermi qui fait brusquement chuter le nombre de porteurs de charge et se traduit par une brutale augmentation de la resistivite. Dans le cas de npbi qui a la plus faible resistivite a temperature ambiante, l'ouverture du gap est si importante que ce compose devient semiconducteur. Il n'est pas aise de trancher de maniere definitive sur la nature du transport electrique des monochalcogenures de neptunium, il apparait cependant de maniere claire que ces composes sont des semi-metaux a temperature ambiante tandis qu'a basse temperature un caractere semiconducteur devient preponderant dans le cas de nps, alors que npte tendrait plutot vers un comportement metallique. Dans le cas de la solution solide pusb(1-x)te(x), il apparait que l'addition du tellure n'est pas simplement une dilution continue de pute non magnetique dans pusb, mais implique des changements fondamentaux dans les mecanismes d'echange induits par le changement de la concentration en electron. Le comportement kondo est present qu'elle que soit la concentration en tellure. Pour le compose nppt3 nous avons pu etablir son diagramme de phase magnetique a l'aide de mesures de resistivite sous champ magnetique et de fixer la temperature d'ordre antiferromagnetique t#n=30 k

On mesure l'activité du tellure en fonction de la température et de la concentration, à partir des mesures de F. E. M. On en déduit l'enthalpie libre de formation d'alliages se-te. On détermine également l'enthalpie molaire de mélange à 623, 673 et 733k. Influence de la coordinence sur ces propriétés thermodynamiques

<p>This thesis discusses the application of phase diagrams and the associated thermodynamics to semiconductor materials through theoretical computational calculations. The majority of work is focused on thermoelectric semiconducting materials that enable direct inter-conversion between electrical and thermal energy. First, one of the most efficient thermoelectric material, PbTe, is picked to demonstrate the assessment of unknown phase diagrams by combining two methods - DFT and CALPHAD. Since there had been no previous investigations of defect stability in this material using computations, DFT is used to deduce the stability of various intrinsic point defects, and in turn attribute origins of n- and p-type conductivity to the most stable defects. Then, the calculated defect formation energies are used in the Pb-Te thermodynamic model built using the CALPHAD method to compare the estimated solubility lines and non-stoichiometric range of the PbTe phase with experimental data. Next, another lead chalcogenide, PbSe, is picked to explore the phase stability of the PbSe phase upon the addition of dopants (Br, Cl, I, Na, Sb, Bi, In), which is a common strategy to make thermoelectric materials and devices more efficient. The range of efficiencies and thermoelectric properties as functions of composition and temperature that can be achieved depends on the amount of dopant that can be added without precipitating secondary phases. Also, depending on the system and its phase diagram, there can be more than one way of doping a material. To help detail which method(s) of doping into PbSe will result in maximum dopant solubility, a procedure similar to the above for PbTe is followed by using DFT in combination with Boltzmann statistics to map solvus boundaries of the PbSe phase, but now in the ternary phase space of composition and temperature. This method also helps predict electrical conductivity, n- or p-type, in each region of the phase diagrams that represent different doping methods.</p> <p>Lastly, the role of surface energy contributions in changing phase stability at nano-dimensions is explored. The CALPHAD approach is employed to investigate these changes in three systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts.</p>

GeTe and Ge2Sb2Te5 alloys are potential candidates for non-volatile phase change random access memories (PCRAM). For electrical data storage applications the materials should have stable amorphous and crystalline phases, fast crystallization time, low power to switch, and high crystallization activation energy (to be stable at normal operating temperatures). Phase change memories can be tuned through compositional variations to achieve sufficient phase change contrast and thermal stability for data retention. Selenium is one of the attractive choices to use as an additive material owing to its flexible amorphous structure and a variety of possible applications in optoelectronics and solar cells. GeSb2Te3Se alloy, in which 25 at.% of Se substituted for Te, show a higher room temperature resistance with respect to parent GeSb2Te4 alloy, but the transition temperature is lowered which will affect the thermal stability. The RESET current observed for Sb65Se35 alloys were reduced and the crystallization speed increased 25 % faster with respect to Ge2Sb2Te5. Alloys of Ga-Sb-Se possess advantages such as higher crystallization temperatures, better data retention, higher switching speed, lower thermal conductivity and lower melting point than the GST, but the resistance ratio is limited to about two orders of magnitude. This affects the resistance contrast and data readability. It is with this background a study has been carried out in GeTe and GeSbTe system with Se doping. Studies on structural, thermal and optical properties of these materials all through the phase transition temperatures would be helpful to explore the feasibility of phase change memory uses. Thin films along with their bulk counterparts such as (GeTe)1-x Sex ( 0 < x ≤ 0.50) and (GST)1-xSex (0 < x ≤ 0.50), including GeTe and GST alloys, have been prepared. The results are presented in four chapters apart from the Introduction and Experimental techniques chapters. The final chapter summarizes the results. Chapter 1 provides an introduction to chalcogenide glasses, phase change memory materials and their applications. The fundamental properties of amorphous solids, basic phase change properties of Ge2Sb2Te5 and GeTe alloys and their applications are presented in detail. Various doping studies on GeTe and Ge2Sb2Te5 reported in literatures are reviewed. The limitations, challenges, future and scope of the present work are presented. In chapter 2, the experimental techniques used for thin film preparation, electrical characterizations, optical characterization and surface characterizations etc. are explained. Chapter 3 deals entirely on Ge2Sb2Te5 films studied throughout the phase transition, by annealing at different temperatures. Changes in sheet resistance, optical transmission, morphology and surface bonding characteristics are analyzed. The crystallization leads to an increase of roughness and the resistance changes to three orders of magnitude at 125 oC. Optical studies show distinct changes in transmittance during phase transitions and the optical parameters are calculated. Band gap contrast and disorder variation with annealing temperatures are explained. The surface bonding characteristics studied by XPS show Ge-Te, Sb-Te bonds are present in both amorphous and crystalline phases. The temperature dependent modifications of the band structure of amorphous GST films at low temperatures have been little explored. The band gap increment of around 0.2 eV is observed at low temperature (4.2 K) compared to room temperature 300 K. Other optical parameters like Urbach energy and B1/2 are studied at different temperatures and are evaluated. The observed changes in optical band gap (Eopt) are fitted to Fan’s one phonon approximation, from which a phonon energy (ћω) corresponding to a frequency of 3.59 THz resulted. The frequency of 3.66 THz optical phonons has already been reported by coherent phonon spectroscopy experiment in amorphous GST. This opens up an indirect method of calculating the phonon frequency of the amorphous phase change materials. Chapter 4 constitutes comparison of optical, electrical and structural investigation of GST and (GST)1-xSex films. It is well known that GST alloys have vacancy in their structure, which leads to the possibility of switching between the amorphous and crystalline states with minimum damage. Added Se may occupy the vacancy or change the bonding characteristics which intern may manifest in the possibility of change in optical and electrical parameters. The structural studies show a direct amorphous to hexagonal transition in (GST)1-xSex, where x ≥ 0.10 at.%. Raman spectra of the as deposited and annealed (GST)1-xSex films show structural modifications. The infrared transmission spectra indicate a shift in absorption edges from low to high photon energy when Se concentration increases in GST. Band gap values calculated from Tauc plot show the band gap increment with Se doping. It is noted that a small amount of Se doping increases the resistance of the amorphous and crystalline phases and maintains the same orders of resistance contrast. This will be beneficial as it improves the thermal stability and reduces the write current in a device. Switching studies show an increasing threshold voltage as the Se doping concentration increases. Chapter 5 comprises compositional dependent investigations of the bulk GeTe chalcogenides alloys added with different selenium concentrations. The XRD investigations on bulk (GeTe)1-xSex (x = 0.0, 0.02, 0.10, 0.20 and 0.50 at.%) alloys show that the crystalline structure of GeTe alloys does not affect ≤ 0.20 at.% of Se concentration. With increasing amount of Se concentration the alloys gets modified in to a homogeneous amorphous structure. This result has been verified from the XRD, Raman, XPS, SEM and DSC measurements. The possibility that Se occupying the Ge vacancy sites in GeTe structure is explained. Since Se is an easy glass former, the amorphousness increases in the alloys due to new amorphous phases formed by the Se with other elements. It is shown from Raman and XPS analysis that the Ge-Te bonds exists up to Se 0.20 at.% alloys. Ge-Se and GeTe2 bonds are increasing with increasing Se at.%. Melting temperature has found decreases and the reduction in melting point may reduces the RESET current. Further studies on switching behavior may bring out its usefulness. Chapter 6 deals with studies on (GeTe)1-xSex films for phase change memory applications based on the insight received from their bulk study. Even at low at.% addition of Se makes the as prepared (GeTe)1-xSex film amorphous. At 200 oC, GeTe crystalline structure is evolved and the intensity of the peaks reduces in the alloys with increase of Se content. At 300 oC, more evolved GeTe crystalline structure is seen compared to 200 oC annealed films whereas 0.20 at.% Se alloy remain amorphous. Resistance and thermal studies shows increase in crystallization temperature. It is expected that Se sits in the vacancies of the GeTe crystalline structural formation. This may also account for the increased threshold voltages with increasing Se doping. The band gap increase with increase of Se at.% signifying the possibility of band gap tuning in the material. Possible explanation for the increased order in GeTe due to Se doping is presented. The modifications in the alloy with Se addition can be explained with the help of chemical bond energy approach. Those bonds having higher energy leads to increased average bond energy of the system and hence the band gap. The XPS core level spectra and Raman spectra investigation clearly shows the GeTe bonds are replaced by Ge-Se bonds and GeTe2 bonds. The 0.10 at.% Se alloy is found to have a higher thermal stability in the amorphous state and maintains a gigantic resistance contrast compared to other Se concentration alloys. This alloy can be considered as an ideal candidate for multilevel PCM applications. Chapter 7 summarizes the major findings from this work and the scope for future work.

This thesis describes a series of experimental studies of lead chalcogenide thermoelectric semiconductors, mainly PbSe. Focusing on a well-studied semiconductor and reporting good but not extraordinary zT, this thesis distinguishes itself by answering the following questions that haven’t been answered: What represents the thermoelectric performance of PbSe? Where does the high zT come from? How (and how much) can we make it better? For the first question, samples were made with highest quality. Each transport property was carefully measured, cross-verified and compared with both historical and contemporary report to overturn commonly believed underestimation of zT. For n- and p-type PbSe zT at 850 K can be 1.1 and 1.0, respectively. For the second question, a systematic approach of quality factor B was used. In n-type PbSe zT is benefited from its high-quality conduction band that combines good degeneracy, low band mass and low deformation potential, whereas zT of p-type is boosted when two mediocre valence bands converge (in band edge energy). In both cases the thermal conductivity from PbSe lattice is inherently low. For the third question, the use of solid solution lead chalcogenide alloys was first evaluated. Simple criteria were proposed to help quickly evaluate the potential of improving zT by introducing atomic disorder. For both PbTe1-xSex and PbSe1-xSx, the impacts in electron and phonon transport compensate each other. Thus, zT in each case was roughly the average of two binary compounds. In p-type Pb1-xSrxSe alloys an improvement of zT from 1.1 to 1.5 at 900 K was achieved, due to the band engineering effect that moves the two valence bands closer in energy. To date, making n-type PbSe better hasn’t been accomplished, but possible strategy is discussed.

abstract: Nanowires (NWs) have attracted many interests due to their advance in synthesis and their unique structural, electrical and optical properties. NWs have been realized as promising candidates for future photonic platforms. In this work, erbium chloride silicate (ECS), CdS and CdSSe NWs growth by vapor-liquid-solid mechanism and their characterization were demonstrated. In the ECS NWs part, systematic experiments were performed to investigate the relation between growth temperature and NWs structure. Scanning electron microscopy, Raman spectroscopy, X-ray diffraction and photoluminescence characterization were used to study the NWs morphology, crystal quality and optical properties. At low growth temperature, there was strong Si Raman signal observed indicating ECS NWs have Si core. At high growth temperature, the excess Si signal was disappeared and the NWs showed better crystal quality and optical properties. The growth temperature is the key parameter that will induce the transition from Si/ECS core-shell NWs structure to solid ECS NWs. With the merits of high Er concentration and long PL lifetime, ECS NWs can serve as optical gain material with emission at 1.5 &mu;m for communications and amplifiers. In the CdS, CdSSe NWs part, the band gap engineering of CdSSe NWs with spatial composition tuning along single NWs were demonstrated. The first step of realizing CdSSe NWs was the controlled growth of CdS NWs. It showed that overall pressure would largely affect the lengths of the CdS NWs. NWs with longer length can be obtained at higher pressure. Then, based on CdS NWs growth and by adding CdSe step by step, composition graded CdSSe alloy NWs were successfully synthesized. The temperature control over the source vapor concentration plays the key role for the growth.<br>Dissertation/Thesis<br>M.S. Electrical Engineering 2012

abstract: Layer structured two dimensional (2D) semiconductors have gained much interest due to their intriguing optical and electronic properties induced by the unique van der Waals bonding between layers. The extraordinary success for graphene and transition metal dichalcogenides (TMDCs) has triggered a constant search for novel 2D semiconductors beyond them. Gallium chalcogenides, belonging to the group III-VI compounds, are a new class of 2D semiconductors that carry a variety of interesting properties including wide spectrum coverage of their bandgaps and thus are promising candidates for next generation electronic and optoelectronic devices. Pushing these materials toward applications requires more controllable synthesis methods and facile routes for engineering their properties on demand. In this dissertation, vapor phase transport is used to synthesize layer structured gallium chalcogenide nanomaterials with highly controlled structure, morphology and properties, with particular emphasis on GaSe, GaTe and GaSeTe alloys. Multiple routes are used to manipulate the physical properties of these materials including strain engineering, defect engineering and phase engineering. First, 2D GaSe with controlled morphologies is synthesized on Si(111) substrates and the bandgap is significantly reduced from 2 eV to 1.7 eV due to lateral tensile strain. By applying vertical compressive strain using a diamond anvil cell, the band gap can be further reduced to 1.4 eV. Next, pseudo-1D GaTe nanomaterials with a monoclinic structure are synthesized on various substrates. The product exhibits highly anisotropic atomic structure and properties characterized by high-resolution transmission electron microscopy and angle resolved Raman and photoluminescence (PL) spectroscopy. Multiple sharp PL emissions below the bandgap are found due to defects localized at the edges and grain boundaries. Finally, layer structured GaSe1-xTex alloys across the full composition range are synthesized on GaAs(111) substrates. Results show that GaAs(111) substrate plays an essential role in stabilizing the metastable single-phase alloys within the miscibility gaps. A hexagonal to monoclinic phase crossover is observed as the Te content increases. The phase crossover features coexistence of both phases and isotropic to anisotropic structural transition. Overall, this work provides insights into the controlled synthesis of gallium chalcogenides and opens up new opportunities towards optoelectronic applications that require tunable material properties.<br>Dissertation/Thesis<br>Doctoral Dissertation Materials Science and Engineering 2018

abstract: In this dissertation, I described my research on the growth and characterization of various nanostructures, such as nanowires, nanobelts and nanosheets, of different semiconductors in a Chemical Vapor Deposition (CVD) system. In the first part of my research, I selected chalcogenides (such as CdS and CdSe) for a comprehensive study in growing two-segment axial nanowires and radial nanobelts/sheets using the ternary CdSxSe1-x alloys. I demonstrated simultaneous red (from CdSe-rich) and green (from CdS-rich) light emission from a single monolithic heterostructure with a maximum wavelength separation of 160 nm. I also demonstrated the first simultaneous two-color lasing from a single nanosheet heterostructure with a wavelength separation of 91 nm under sufficiently strong pumping power. In the second part, I considered several combinations of source materials with different growth methods in order to extend the spectral coverage of previously demonstrated structures towards shorter wavelengths to achieve full-color emissions. I achieved this with the growth of multisegment heterostructure nanosheets (MSHNs), using ZnS and CdSe chalcogenides, via our novel growth method. By utilizing this method, I demonstrated the first growth of ZnCdSSe MSHNs with an overall lattice mismatch of 6.6%, emitting red, green and blue light simultaneously, in a single furnace run using a simple CVD system. The key to this growth method is the dual ion exchange process which converts nanosheets rich in CdSe to nanosheets rich in ZnS, demonstrated for the first time in this work. Tri-chromatic white light emission with different correlated color temperature values was achieved under different growth conditions. We demonstrated multicolor (191 nm total wavelength separation) laser from a single monolithic semiconductor nanostructure for the first time. Due to the difficulties associated with growing semiconductor materials of differing composition on a given substrate using traditional planar epitaxial technology, our nanostructures and growth method are very promising for various device applications, including but not limited to: illumination, multicolor displays, photodetectors, spectrometers and monolithic multicolor lasers.<br>Dissertation/Thesis<br>Doctoral Dissertation Electrical Engineering 2015

Chemical Engineering<br>The successful commercialization of lithium-ion batteries is responsible for the ubiquity of personal electronics. The continued development of battery technology, as well as its application to new emerging markets such as electric vehicles, is dependent on developing safer, higher energy density, and cheaper electrode materials and battery chemistries. The focus of this dissertation is on identifying, characterizing and optimizing new materials for lithium- and sodium-ion batteries. Batteries are incredibly complex engineered systems with each electrode composed of conductive additive and polymeric binder in addition to the active material. All of these components must work together for the electrode system to function properly. In this work, glancing angle deposition (GLAD) and reactive ballistic deposition (RBD) are employed to grow thin films of novel materials with reproducible morphology for use as battery electrodes. The use of these thin film electrodes eliminated the need for conductive additives and polymer binders allowing for the active materials themselves to be studied rather than the whole electrode system. Two techniques are employed to modify the chemical properties of the electrode materials grown by RBD and GLAD: Alloying (Si-Ge alloys for Li-ion batteries and Sn-Ge alloys for Na-ion batteries) and partial chalcogenation (partial oxidation of silicon, and partial sulfidation and selenidation of germanium for Li-ion batteries). Both of these techniques are successfully employed to enhance the electrochemical properties of the materials presented in this dissertation.<br>text