Thesis (M.S.)--Boise State University, 2009. / Includes abstract. Includes bibliographical references (leaves 124-131).

Thesis (M.S.)--Boise State University, 2009. / Title from t.p. of PDF file (viewed June 1, 2010). Includes abstract. Includes bibliographical references (leaves 124-131).

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Ionic liquids (ILs) are nowadays a large and widely explored class of ionic compounds that melt below 100 °C. Due to their attractive properties, ILs are now of growing interests in a variety of inorganic materials preparation. However, most studies have put much focus on the description of new synthetic strategies. The chemical reactivity of ILs in the reactions is often neglected. In this dissertation, a series of metal chalcogenides were synthesized using the decompositions of ILs. The role or chemical reactivity of ILs in the reactions was demonstrated in detail. The hierarchical desert-rose-like SrTiO3 particles have been successfully prepared based on an ethylene glycol (EG) mediated one-pot IL-assisted solvothermal synthetic route. The used basic ionic liquid tetrabutylammonium hydroxide (TBAH) serves as an alkaline source and can also replace EG as the sole solvent to synthesize polyhedral SrTiO3, showing “all-in-one” solvent and reactant. A series of metal sulfides, such as Sb2S3, Bi2S3, PbS, CuS, Ag2S, ZnS, and CdS have been obtained from a choline chloride/thioacetamide based deep eutectic solvent (DES, an IL analog solvent) by a simple and general synthetic method. The reaction mainly proceeds in two steps: i) the dispersion of metal salts in the DES and the formation of a metal-DES complex, and ii) the decomposition of the metal-DES complex and formation of the final products. In addition, the chemical reactivity of phosphonium based ILs with selenium and tellurium at above 220 °C was systematically investigated by a series of dissolution experiments, tracking the solute selenium and tellurium species by nuclear magnetic resonance (NMR). NMR results clearly indicate some common decomposition mechanisms for quaternary phosphonium ILs at a relatively high temperature in the presence of selenium or tellurium. The decomposition of the quaternary phosphonium cations should proceed by an elimination of one alkyl substituent via an SN2 reaction, forming the respective trialkylphosphane selenides or tellurides in the presence of selenium or tellurium, which is then responsible for the genuine dissolution of selenium or tellurium. However, in the case of tellurium, the dissolution behavior is much more complicated compared to that of selenium. The coupling of P and Te which indicates a P–Te bond formation is only observed in the NMR spectra when a sufficient amount of tellurium (e.g. Te : IL = 1 : 1) is provided. The existence of a parallel-competitive IL decomposition route besides the SN2 reaction is regarded as the side reaction for the dissolution of tellurium. This may at least partially explain the relatively lower solubility of tellurium in phosphonium based ILs compared to that of selenium.

The structure, magnetic behaviour and chemistry of layered oxychalcogenides of composition A₂MO₂X₂Ch₂ (where A = Sr, Ba; M = Mn, Co, Ni, Cu, Zn; X = Cu, Ag and Ch = S, Se, Te) has been investigated by the synthesis of new compounds of this type and control of the properties of these compounds by oxidative deintercalation of Cu/Ag. I₂ can be used to oxidatively deintercalate Cu from Sr₂MnO₂Cu_1.5S₂, forming Sr₂MnO₂Cu_1.33S₂, an incommensurately modulated compound, with a completely different Cu/vacancy ordering and antiferromagnetic ordering structure to the parent. This reaction is also probed in real-time, using in situ powder X-ray diffraction. Sr₂MnO₂Ag_1.5Se₂ was found to have an A-type magnetic ordering structure, similar to Sr₂MnO₂Cu_1.5Se₂. Sr₂MnO₂Cu_1.8Te₂ on the other hand with a lower Mn oxidation state shows only two-dimensional magnetic correlations, rather than long-range order. Extending the reaction with I₂ to several Co-containing analogues revealed that ~ 25% Ag could be removed from Sr₂CoO₂Ag₂Se₂, sufficient to observe a change in magnetic behaviour, from antiferromagnetic to ferromagnetic. By contrast only ~11% Cu can be deintercalated from Sr₂CoO₂Cu₂S₂ and even less (~5%) from Sr₂CoO₂Cu₂Se₂. Neutron diffraction was used to examine the resultant changes in magnetic ordering. The novel compounds Sr₂CuO₂Cu₂Se₂ and Ba₂CuO_2-xCu₂Se₂ are related by substitution of the alkali-earth metal, but while Sr₂CuO₂Cu₂Se₂ is a stoichiometric compound with metal-like character, Ba₂CuO_2-xCu₂Se₂ is an oxygen-deficient semiconductor, with tuneable oxygen content. Unusual features are observed in the magnetic susceptibility measurements of Sr₂NiO₂Cu₂Se₂ that appear unrelated to this compound's long-range magnetic ordering, as probed by neutron diffraction. Furthermore, unusual peak splitting is observed in low-temperature powder X-ray diffraction patterns of this compound; this may plausibly be due to a photon-induced effect arising from the use of a high-energy beamline; although further measurements are required to examine this. Overall the work shows the flexibility and range of behaviour exhibited by a series of the transition metal oxide chalcogenides.

L'intérêt porté au développement de matériaux thermoélectriques est grandissant car ils permettent de créer des sources d'énergie renouvelable, dites « vertes », ce qui s'inscrit pleinement dans la stratégie de lutte contre le réchauffement climatique. A ce jour le rendement de tels systèmes reste faible, le coût de développement élevé, et les plages de températures d'utilisation sont limitées. Dans ces travaux de thèse différentes pistes sont explorées pour développer des matériaux innovants à base de chalcogènes, principalement le tellure. Les principaux résultats portent sur les points suivants. (i) Une étude par spectroscopies couplée à des calculs théoriques a permis de mieux comprendre les phénomènes de conduction dans les verres du système Cu-As-Te. (ii) La recristallisation complète de verres de formulation Ge20Te77Se3 dopés a été réalisée pour pousser à son terme la logique dite du Phonon Glass Electron Crystal (PGEC).(iii) Différents modes de synthèses ont été mis en œuvre pour suivre les propriétés thermoélectriques de matériaux de formulation CuPb18SbTe20 (frittage, SPS, flash-SPS, hybrid flash-SPS). (iv) Accroissement de 170% des performances d'alliage du système Pb-Sb-Te en générant des vacances de sites (composés non-stœchiométriques). (v) Le suivi des conséquences du dopage de GeTe par un seul élément a montré la nécessité d'un co-dopage pour simultanément accroître la conductivité électronique et le Seebeck. (vi) Le co-dopage In-Bi de GeTe a permis de créer des niveaux résonants (In) et d'accroitre la diffusion thermique (Bi). (vii) Enfin, le résultat le plus remarquable porte sur le co-dopage Ga-Sb de GeTe qui permet d'effectuer de l'ingénierie de structure de bandes. Couplé à une synthèse par hybrid flash SPS ces matériaux prometteurs permettent d'obtenir un zT 2 sur une large gamme de température (600–773 K). / With the performance of direct conversion between thermal and electrical energy, thermoelectric materials, which are crucial in the renewable energy conversion roadmap, provide an alternative for power generation and refrigeration to solve the global energy crisis. But the low efficiency of the current materials, their usual costs, availability, and limited working temperatures, drastically constrain their application. Hence, the search for new and more efficient thermoelectric materials is one of the most dynamic objectives of this thesis. The key milestones achieved from this thesis work includes: (i) elucidating the mechanism for hole conductivity in Cu-As-Te glasses by X-ray absorption spectroscopy and quantum simulations; (ii) formulating a novel approach to achieve phonon-glass electron-crystal mechanism by crystallizing the Ge20Te77Se3 glasses by excess doping with metals or semi-metals (glass-ceramics); (iii) demonstrating the effect of processing route on the thermoelectric performance of CuPb18SbTe20 and highlighting the advantage of hybrid-flash spark plasma sintering technique, i.e., better optimization of electrical and thermal transport properties and achieving multi-scale hierarchical architectures; (iv) improving the thermoelectric performance of Pb-Sb-Te alloys (enhancement by 170%) by tuning their cation vacancies (Pb deficiencies); (v) understating the impact of doping just a group-11 coinage metal, or group-13 element on GeTe solid-state solution and recapitulating the need for pair substitution; (vi) substantially enhancing the average zT of In-Bi codoped GeTe; (vii) achieving a remarkably high and stable zT of close to 2 over a wide temperature range (600 – 773 K) by manipulating the electronic bands in Ga-Sb codoped GeTe, which has been processed by hybrid flash-spark plasma sintering, thus making it a serious candidate for energy harvesting systems.

In today's "silicon age" in which we live, field-effect transistors (FET) are the workhorse of virtually all modern-day electronic gadgets. Although silicon currently dominates most of these electronics, layered 2D transition metal dichalcogenides (TMDCs) have great potential in low power optoelectronic applications due to their indirect-to-direct band gap transition from bulk to few-layer and high on/off switching ratios. TMDC WSe2 is studied here, mechanically exfoliated from CVT-grown bulk WSe2 crystals, to create a few-layered ambipolar FET, which transitions from dominant p-type behavior to n-type behavior dominating as temperature decreases. A high electron mobility μ>150 cm2V-1s-1 was found in the low temperature region near 50 K. Temperature-dependent photoconduction measurements were also taken, revealing that both the application of negative gate bias and decreasing the temperature resulted in an increase of the responsivity of the WSe2 sample. Besides TMDCs, Group III-VI van der Waals structures also show promising anisotropic optical, electronic, and mechanical properties. In particular, mechanically exfoliated few-layered InSe is studied here for its indirect band gap of 1.4 eV, which should offer a broad spectral response. It was found that the steady state photoconduction slightly decreased with the application of positive gate bias, likely due to the desorption of adsorbates on the surface of the sample. A room temperature responsivity near 5 AW-1 and external quantum efficiency of 207% was found for the InSe FET. Both TMDC’s and group III-VI chalcogenides continue to be studied for their remarkably diverse properties that depend on their thickness and composition for their applications as transistors, sensors, and composite materials in photovoltaics and optoelectronics.

Pour que l'énergie photovoltaïque devienne compétitive, les coûts de production doivent être baissés et l'efficacité des cellules augmentée. Les cellules solaires à base de nanocristaux semi-conducteurs constituent une approche prometteuse pour remplir ces objectifs combinant une mise en œuvre par voie liquide avec la possibilité d'ajuster précisément la largeur de bande interdite et les niveaux électroniques. Aujourd'hui, les rendements de conversion des cellules constituées de nanocristaux de sulfure de plomb approchent les 7%. Seulement, à cause des normes européennes destinées à l'affranchissement du plomb du fait de ses risques pour la santé et l'environnement, de nouveaux matériaux doivent être trouvés. Cette thèse concerne la synthèse de nouveaux types de nanocristaux semi-conducteurs et leur application dans des cellules solaires. La synthèse des nanocristaux de CuInSe2 et de SnS de taille et de forme contrôlées a été effectuée, notamment par des voies de synthèses reproductibles dont le passage à grande échelle est facilement possible. Une analyse approfondie de la structure des nanocristaux de SnS par spectroscopie Mössbauer a montré que ces nanocristaux avaient une forte tendance à s'oxyder, ce qui limite leur utilisation dans des dispositifs électroniques après exposition à l'air. La constitution de couches minces continues ayant de bonnes propriétés électriques a été effectuée par le dépôt contrôlé de nanocristaux ainsi que l'échange de leurs ligands de surface. En particulier, un nouveau type de ligand inorganique a été utilisé qui a montré une augmentation de la conductivité des films multiplié par quatre ordres de grandeurs par rapport aux ligands initiaux. Enfin, la préparation de cellules solaires basées sur ces couches minces de nanocristaux a montré des résultats encourageants et notamment un clair effet photovoltaïque lorsque le dépôt est effectué sous atmosphère inerte. / In order to be cost-effective, photovoltaic energy conversion needs to improve the solar cell efficiencies while decreasing the production costs. Nanocrystal based solar cells could fulfil these requirements through solution-processing, band gap and energy level engineering. PbS nanocrystal thin films already proved their potential for use as solar cell active materials with power conversion efficiencies approaching 7%. However, since lead based compounds are not compatible with European regulations and present high risks for health and environment, semiconductor nanocrystals of alternative materials have to be developed. This thesis focuses on novel types of semiconductor nanocrystals and their application in photovoltaics. The first part of the study deals with the synthesis of size- and shape-controlled CuInSe2 and SnS nanocrystals. An in-depth investigation of the structure of SnS nanocrystals using Mössbauer spectroscopy revealed their high oxidation sensitivity, which limits their usability in optoelectronic devices after air exposure. The second part deals with the thin film preparation and the surface ligand exchange of the obtained nanocrystals. Using a fully inorganic nanocrystal-surface ligand system, the deposited films exhibited a current density improved by four orders of magnitude as compared to the initial ligands. Finally, solar cell devices based on nanocrystal thin films were fabricated, which showed encouraging results with a clear photovoltaic effect when processed under inert atmosphere.

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. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

Neste trabalho foram estudados os fenômenos fotoinduzidos apresentados pelos vidros calcogenetos de composições: Ga IND.10Ge IND.25S IND.65 e Ga IND.5Ge IND.25As IND.5S IND.65. Estes vidros ao serem iluminados com luz que possui energia próxima a do bandgap apresentam vários fenômenos fotoinduzidos. Sendo assim um estudo sistemático em função da potência, tempo de iluminação e do comprimento de onda foi efetuado. Para energias acima da banda proibida ocorre a fotoexpansão, variação do índice de refração e fotoclareamento. Por outro lado, para energias abaixo da banda proibida não foi observada nenhuma variação do volume; no entanto foi detectado um fotoescurecimento. Estes fenômenos mostraram ser irreversíveis, visto que ao serem levados a tratamento térmico a temperatura próxima a temperatura de transição vítrea, os vidros não recuperaram sua forma original. Várias técnicas experimentais foram usadas tais como: microscopia de força atômica, perfilometria, espectro de absorção óptica, espectroscopia na região do infravermelho, espalhamento Raman, EDX, EXAFS e RBS para caracterização dos fenômenos fotoinduzidos e elucidar o mecanismo envolvido. Os resultados obtidos a partir de EXAFS, Infravermelho, RBS e EDX indicaram a incorporação de oxigênio na superfície dos vidros quebrando assim as ligações Ge-S. Foi observado que a magnitude da fotoexpansão depende da atmosfera usada durante a irradiação. Um estudo comparativo entre o vidro e o filme depositado foi realizado. Foi mostrado através de espalhamento Raman e Infravermelho que os tipos de ligações presente no filme depositado é diferente daquela do vidro original. Os mesmos fenômenos fotoinduzidos foram também detectados nos filmes depositados, os quais foram estudados e caracterizados também de maneira sistemática. Como aplicação destes fenômenos fotoinduzidos, a fotoexpansão foi usada para a produção de redes de difração. ) As medidas de eficiência de difração e as imagens de microscopia de força atômica demonstraram que a fotoexpansão cria uma rede de relevo na superfície do vidro / We report the photoinduced phenomena observed in two chalcogenide glass compositions: Ga IOGe2SS6eSGasGe2sAssS6s. These glasses present several photoinduced phenomena when exposed to light having energy comparable to bandgap energy. Systematic study has been carried out in function of power density, exposure time and wavelength. Samples exposed to energy above the bandgap the photoexpansion, photorefraction and photobleaching has been observed. Otherwise, to energy below the bandgap a photodarkening was detected without volume variation. These phenomena are irreversible since the surface does not restore the original structure when annealing to the glass transition temperature. To Characterize and understand the mechanism processes of the photoexpansíon effect, atomíc force mícroscopy, perfilometry, absorption spectra, ínfrared absorption, Raman, EDX, EXAFS and RBS has been used before and after illumination of the glass samples. The EXAFS, infrared, RBS and EDX data showed that íllumínatíon leads to an introduction of oxygen ín the glass structure breaking Ge-S intermolecular bonds followed by the formatíon of Ge-O bonds. We observed that the magnitude of the photoínduced expansíon of the GaGeS glass ís strongly dependent on the atmosphere used. Comparative study has been performed between glass and filmo Infrared and Raman data shown a different bonding behavior ín the film prepared prevíously from the glass. Under irradíation, the same photoínduced phenomenon already detected on the glass samples are observed on the thin film and also characterized systematically. As applícation of the photoinduced phenomenon, photoexpansíon effect has been used to produce díffraction gratíngs. Atomic mícroscopy images and diffractíon efficiency data indícate that photoexpansíon leads to relíef gratíng on the glass surface