A new high-k dielectric material, i.e., zirconium-doped tantalum oxide (Zr-doped TaOx), in the form of a sputter-deposited thin film with a thickness range of 5-100 nm, has been studied. Important applications of this new dielectric material include the gate dielectric layer for the next generation metal-oxide-semiconductor field effect transistor (MOSFET). Due to the aggressive device scaling in ultra-large-scale integrated circuitry (ULSI), the ultra-thin conventional gate oxide (SiO2) is unacceptable for many practical reasons. By replacing the SiO2 layer with a high dielectric constant material (high-k), many of the problems can be solved. In this study, a novel high-k dielectric thin film, i.e., TaOx doped with Zr, was deposited and studied. The film’s electrical, chemical, and structural properties were investigated experimentally. The Zr dopant concentration and the thermal treatment condition were studied with respect to gas composition, pressure, temperature, and annealing time. Interface layer formation and properties were studied with or without an inserted thin tantalum nitride (TaNx) layer. The gate electrode material influence on the dielectric properties was also investigated. Four types of gate materials, i.e., aluminum (Al), molybdenum (Mo), molybdenum nitride (MoN), and tungsten nitride (WN), were used in this study. The films were analyzed with ESCA, XRD, SIMS, and TEM. Films were made into MOS capacitors and characterized using I-V and C-V curves. Many promising results were obtained using this kind of high-k film. It is potentially applicable to future MOS devices.

A new high-k dielectric material, i.e., zirconium-doped tantalum oxide (Zr-doped TaOx), in the form of a sputter-deposited thin film with a thickness range of 5-100 nm, has been studied. Important applications of this new dielectric material include the gate dielectric layer for the next generation metal-oxide-semiconductor field effect transistor (MOSFET). Due to the aggressive device scaling in ultra-large-scale integrated circuitry (ULSI), the ultra-thin conventional gate oxide (SiO2) is unacceptable for many practical reasons. By replacing the SiO2 layer with a high dielectric constant material (high-k), many of the problems can be solved. In this study, a novel high-k dielectric thin film, i.e., TaOx doped with Zr, was deposited and studied. The film’s electrical, chemical, and structural properties were investigated experimentally. The Zr dopant concentration and the thermal treatment condition were studied with respect to gas composition, pressure, temperature, and annealing time. Interface layer formation and properties were studied with or without an inserted thin tantalum nitride (TaNx) layer. The gate electrode material influence on the dielectric properties was also investigated. Four types of gate materials, i.e., aluminum (Al), molybdenum (Mo), molybdenum nitride (MoN), and tungsten nitride (WN), were used in this study. The films were analyzed with ESCA, XRD, SIMS, and TEM. Films were made into MOS capacitors and characterized using I-V and C-V curves. Many promising results were obtained using this kind of high-k film. It is potentially applicable to future MOS devices.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Objectives: (1) Compare the effects of grinding on a Y-TZP ceramic executed by diamond discs and diamond burs (with similar grit sizes) in the micromorphology of surface, phase transformation (t®m), flexural strength and structural reliability (Weibull analysis), (2) evaluate the effect of LTD (low-temperature degradation) in the outcomes mentioned above. Methods: Three hundred and sixty discs (15mm x 1,2 mm) of Y-TZP were made according to ISO 6872 2008 for flexural strength determination on ceramic materials and sintered according to the manufacturer`s instructions, than they were divided into groups according to two factors in study: surface treatment - 5 levels (without treatment, extra-fine diamond bur, 600-grit diamond disc, coarse diamond bur and 120-grit diamond disc) and LTD on 2 levels (with and without). For grinding with diamond discs a polishing machine was employed, while for grinding with diamond burs a device was employed to assure the perpendicularity between diamond tip and abrading surface, that way the abrasion movements and the applied pressure were standardized. The LTD was induced in an autoclave at 134ºC under 2 bar for 20 hours. Results: Our findings support that LTD although promoted increase in mphase content and micromorphological alterations did not promoted decrease in zirconia s mechanical properties, grinding at a first moment did not affected too, but when ground Y-TZP was submitted to the LTD effects, the defects introduced by grinding could be detrimental to the material`s resistance. From a methodological point of view, diamond discs should not be employed to simulate clinical abrasion performed with diamond burs on Y-TZP ceramics. Conclusion: Thus grinding of zirconia should be avoided and when it was really necessary tools with low grit sizes should be employed. / Objetivos: (1) Comparar os efeitos do desgaste da cerâmica Y-TZP gerados por lixas e pontas diamantadas (com granulações semelhantes) na micromorfologia da superfície, na transformação de fase (t®m), na resistência à flexão biaxial e confiabilidade estrutural (análise de Weibull), (2) Avaliar o efeito da LTD nos desfechos citados acima. Métodos: Trezentos e sessenta discos (15 mm x 1,2 mm) de Y-TZP foram confeccionados segundo as instruções da ISO 6872 2008 para ensaios de flexão em material cerâmico e sinterizados de acordo com as recomendações do fabricante, posteriormente foram divididos em grupos, de acordo com dois fatores em estudo: tratamento de superfície da cerâmica - 5 níveis (sem tratamento, disco de granulação 120, ponta diamantada de granulação super grossa, disco de granulação 600, ponta diamantada extra fina) e LTD - 2 níveis (sem e com). Para abrasão com lixas de diferentes granulações foi utilizada uma politriz, enquanto que para a abrasão com as pontas diamantadas foi utilizado um dispositivo que garantiu a perpendicularidade da ponta diamantada à superfície da amostra, padronizando os movimentos de abrasão e a pressão aplicada. A LTD foi realizada em autoclave sob 134° C à 2 bar por 20 horas. Resultados: Nossos achados suportam que a LTD embora promovesse aumento de fase monoclínica e alterações micromorfológicas não causou perda de propriedades mecânicas da zircônia, o desgaste em primeiro momento também não promoveu, mas quando esta superfície foi submetida aos efeitos da LTD, os defeitos introduzidos pelo desgaste podem ser prejudiciais a resistência do material. Sob um ponto de vista metodológico o uso de discos diamantados não deve ser empregado para simular o desgaste executado clinicamente com pontas diamantadas. Conclusão: Dessa forma o desgaste da superfície da zircônia deve ser evitado e quando necessário deve ser realizado com instrumentos de menor granulação.

This study aimed to determine the effects of grinding and low temperature aging on the surface micromorphology (roughness measurement, Scanning Electron Microscopy and Atomic Force Microscopy), phase transformation (t→m), biaxial flexural strength and structural reliability (Weibull analysis) of an yttrium-stabilized tetragonal zirconia polycrystalline ceramic. One hundred and eighty ceramic discs (15.0 × 1.2 ± 0.2 mm, VITA In-Ceram YZ) were prepared and randomly assigned into six groups according to 2 factors (n = 30): grinding (Ctrl without treatment, as-sintered; Xfine grinding with extra fine diamond bur - 30 μm; Coarse grinding by coarse diamond bur - 151 μm), and aging (without or with aging: CtrlLTD; XfineLTD; CoarseLTD). Grinding was performed in an oscillatory motion with a contra-angle handpiece under constant water-cooling. Low temperature degradation (LTD) was simulated in an autoclave at 134 °C, under 2 bar pressure, for 20 h. The roughness (Ra and Rz parameters) significantly increased after grinding in accordance with bur grit-size (Coarse > Xfine > Ctrl), and aging promoted distinct effects (Ctrl = CtrlLTD; Xfine > XfineLTD; Coarse = CoarseLTD). Grinding increased the m-phase, and aging led to an increase in the m-phase in all groups. However, different susceptibilities to LTD were observed. Weibull analysis showed a significant increase in the characteristic strength after grinding (Coarse = Xfine > Ctrl), while aging did not lead to any deleterious impact. Neither grinding nor aging resulted in any deleterious impact (no statistical decrease in the Weibull moduli) on material reliability. Thus, neither grinding nor aging led to a deleterious effect on the mechanical properties of the evaluated Y-TZP ceramic although a high m-phase content and roughness were observed. / Este estudo avaliou o efeito do desgaste com brocas diamantadas de diferentes granulações (Grossa G e Extrafina FF), associado ou não ao envelhecimento em autoclave (LTD) na micromorfologia superficial, na transformação de fase (tetragonal para monoclínica, t→m), e nas propriedades mecânicas de uma zircônia policristalina parcialmente estabilizada por óxido de ítrio. Foram confeccionados 180 discos (15,0 Ø x 1,2 mm de espessura) conforme a ISO 6872-2008, que foram divididos em 6 grupos (n=30) de acordo com dois fatores em estudo: desgaste da superfície (controle C - sem desgaste; desgaste com broca G ou FF); e envelhecimento em autoclave (CLTD, GLTD FFLTD); Os desgastes foram executados por um operador treinado sob refrigeração constante; e a LTD em autoclave a 134ºC, sob 2 bar de pressão, por 20 horas. Os resultados indicam que o envelhecimento em autoclave associado ou não ao desgaste não foram prejudiciais às propriedades mecânicas da zircônia. Entretanto cabe ressaltar que estes estímulos promoveram grande aumento de fase monoclínica, o que pode ser um indício de degradação do material. A análise de Weibull (Módulo de Weibull) demonstrou que os tratamentos avaliados (desgaste, envelhecimento em autoclave) não promoveram efeitos deletérios, não resultando em maior variabilidade da resistência mecânica. Logo, não há indícios de que os diferentes tratamentos realizados impactem negativamente na resistência à flexão biaxial da Y-TZP. Adicionalmente, nota-se que as superfícies desgastadas com brocas diamantadas têm uma menor susceptibilidade à LTD (menor aumento de fase m).

Made available in DSpace on 2014-08-20T14:30:13Z (GMT). No. of bitstreams: 1 Dissertacao_Guilherme_Zdradk_ Guimaraes.pdf: 689162 bytes, checksum: bf7171adce4262e2641a3db4c51d4cd3 (MD5) Previous issue date: 2011-08-12 / In this study the effect of concentration and type of acidic monomer on the bond strength (BS) of experimental primers to zirconia before and after aging simulation was investigated. Primers were formulated from the mixture of the monomers urethane dimethacrylate and 2-hidroxyethyl methacrylate with the phosphate monomer (PAM) 1,3-glycerol dimethacrylate phosphate or the carboxylic monomer (CAM)mono-2-(methacryloyloxy)ethyl maleate, and ethanol. In each primer, PAM or CAM were be added at concentrations of 10, 20, 40 or 60 mass%. Degree of conversion (DC) of the primers was evaluated by infrared spectroscopy (n=5). For the BS test, sintered yttria-stabilized zirconia blocks (Zircon-CAD, Angelus) were used. The primers were applied to the ceramic and cylinders of dual-cure resin cement (Eco-Link, Ivoclar Vivadent) built-up on the surfaces for the shear BS test (n=20). In the control group, adhesion of the cylinders will be carried out without using primer. In half the number of specimens in each group, the BS test was carried out after 24h on a mechanical testing machine. In order to simulate aging and evaluate the stability of the zirconia bonds, the other half the number of specimens was submitted to 3000 thermal cycles before the BS test. The failure modes were classified under a 40× magnification.DC data were submitted to one-way ANOVA for each monomer; BS data were submitted to two-way ANOVA for each storage condition. The Student-Newman-Keuls post-hoc test was used. BS comparison between 24h and after thermalcycling was carried out using t-tests. (Non-)linear regression analyses were used to investigate the relationship between acidic monomer concentration and DC or BS (α=0.05 for all analyses). Increase in acidic monomers concentration was associated with a linear decrease in DC. The BS for PAM-based primers was higher than CAM-based materials for all groups except 10% at 24h. For PAM, the primer with 40% of acidic monomers yielded higher BS than all the other primers, either at 24h or after thermalcycling. For CAM, the BS results were at 24h were 10% > 60% > 40% > 20%, while after thermalcycling the primer with 60% of acidic monomers generally showed higher BS. All PAM groups except 10% showed lower BS after the thermal cycles, while 10% was the only concentration that showed lower BS after thermalcycling for CAM. Increased PAM concentration had a significant relationship with the zirconia bonds according to a peak model, while increase in CAM content had a polynomial inverse relationship. Regression models after thermalcycling were not significant. The only group that showed mixed failures was PAM 40%, while the other groups failed adhesively. In conclusion, both the acidic monomer type and concentration have a significant role on the adhesion to zirconia. The primer with 40% of PAM showed the best performance on bonding to zirconia / Neste estudo avaliou-se o efeito da concentração e tipo de monômero ácido na resistência de união (RU) de primers experimentais à zircônia antes e após simulação de envelhecimento. Primers foram formulados a partir da mistura dos monômeros dimetacrilato de uretano e metacrilato de 2-hidroxietila com o monômero ácido fosfórico (MAF) dimetacrilato de glicerol-fosfato ou o monômero ácido carboxílico (MAC) maleato de mono(2-metacriloiloxi)etila, além de etanol. Em cada primer, MAF ou MAC foram adicionados nas concentrações 10, 20, 40 ou 60% em massa. O grau de conversão (GC) dos primers foi avaliado por espectroscopia infravermelha (n=5). Para o teste de RU, blocos sinterizados de zircônia estabilizada por ítria (Zircon-CAD, Angelus) foram utilizados. Os primers foram aplicados na superfície da cerâmica e nesta obtidos cilindros de cimento resinoso dual (Eco-Link, Ivoclar Vivadent) para teste de RU ao cisalhamento (n=20). Em metade do número de espécimes de cada grupo, o teste de RU foi realizado após 24h, em máquina de ensaios mecânicos.Para simular envelhecimento e avaliar a estabilidade da união à zircônia, a outra metade do número de espécimes foi submetida a 3000 ciclos térmicos antes do teste de RU. Os modos de falha foram classificados sob aumento de 40×. Os dados de GC foram submetidos a Análise de Variância de 1 critério para cada monômero; os dados de RU foram submetidos a Análise de Variância de 2 critérios para cada condição de armazenamento. O teste post-hoc de Student-Newman-Keuls foi utilizado. Comparação de RU entre 24h e após termociclagem foi realizada com testes-t. Análises de regressão (não-)linear foram utilizadas para investigar a relação entre concentração de monômero ácido e GC ou RU (α=0,05 para todas as análises). Aumento na concentração de monômeros ácidos foi associado a diminuição linear no GC. A RU de primers à base de MAF foi maior que materiais à base de MAC para todos os grupos exceto 10% a 24h. Para o MAF, o primer com 40% de monômeros ácidos gerou RU maior que todos os demais, a 24h ou após termociclagem. Para o MAC, os resultados de RU a 24h foram 10% > 60% > 40% > 20%, enquanto após ciclagem o primer com 60% de monômeros ácidos em geral mostrou maior RU. Todos os grupos do MAF exceto 10% mostraram RU menor após os ciclos térmicos, enquanto 10% foi a única concentração que apresentou menor RU após a ciclagem para o MAC. Aumento na concentração de MAF teve relação significativa com a adesão á zircônia de acordo com um modelo de pico, enquanto aumento no conteúdo de MAC teve uma relação polinomial inversa.Os modelos de regressão após termociclagem não foram significativos. O único grupo que teve falhas mistas foi o MAF 40%, enquanto todos os outros falharam adesivamente. Como conclusão, tanto o tipo quanto a concentração de monômeros ácidos têm papel significativo na adesão de primers à zircônia. O primer com 40% de MAF mostrou o melhor desempenho na adesão à zircônia

Abstract Exhaust gas emissions, e.g. nitrogen oxides (NOx), hydrocarbons (HCs) and carbon monoxide (CO), are harmful to human health and the environment. Catalysis is an efficient method to decrease these emissions. Unfortunately, the fuels and lubricant oils may contain chemical impurities that are also present in exhaust gases. Thus, catalytic materials with high activity and chemical resistance towards impurities are needed in the abatement of exhaust gas emission. In this thesis, the aim was to gain new knowledge about the effects of chemical impurities on the behaviour and activity of the catalysts. To find out these effects, the impurities existing in the exhaust gas particulate matter after combustion of biofuels and fossil fuels were analysed. The studied zeolite (ZSM-5), cerium-zirconium mixed oxides (CeZr and ZrCe) and silicon-zirconium oxide (SiZr) based catalysts were also treated with impurities to simulate the poisoning of the catalysts by, e.g. potassium, sodium, phosphorus and sulphur, using gas or liquid phase treatments. Several characterization techniques were applied to find out the effects of impurities on catalysts’ properties. The activity of catalysts was tested in laboratory-scale measurements in CO and HC oxidation and NOx reduction using ammonia (NH3) and hydrogen (H2) as reductants. The results revealed that the CeZr based catalysts had a high activity in NOx reduction by NH3 and moderate activity by H2. Sulphur was proven to enhance the activity of CeZr catalysts in NOx reduction. This is due to an increase in chemisorbed oxygen after the sulphur treatment on the catalyst surface. Instead, in HC and CO oxidation reactions, sulphur had a negligible impact on the activity of the SiZr based diesel oxidation catalyst. Thus, both CeZr and SiZr based catalysts can be utilized in exhaust gas purification when sulphur is present. ZSM-5 based catalysts were proven to be resistant to potassium and sodium. Alternatively, the activity of SiZr based catalysts decreased due to phosphorus. Thus, the removal of biomaterial-based impurities from the exhaust gases is needed to retain high catalyst activity in the exhaust gas after-treatment system. / Tiivistelmä Pakokaasupäästöissä olevat typen oksidit (NOx), hiilivedyt (HCs) ja hiilimonoksidi (CO) ovat haitallisia ihmisten terveydelle ja ympäristölle. Katalyysi on tehokas menetelmä vähentää näitä päästökomponentteja. Polttoaineet ja voiteluöljyt sisältävät epäpuhtauksia, jotka siirtyvät myös pakokaasuihin. Tästä johtuen pakokaasupäästöjen hallinnassa tarvitaan katalyyttimateriaaleja, joilla on hyvä vastustuskyky myrkyttymistä vastaan. Tavoitteena oli saada uutta tietoa kemiallisten epäpuhtauksien vaikutuksesta katalyyttien toimintaan. Biopolttoaineiden sisältämät mahdolliset epäpuhtaudet selvitettiin analysoimalla fossiilisen ja biopolttoaineen palamisessa muodostuvia partikkeleita ja vertaamalla niitä polttoaineiden hivenaineanalyysiin. Tutkimuksessa käytetyt zeoliitti (ZSM-5), cerium-zirkonium-sekaoksidi (CeZr) ja pii-zirkonium-oksidipohjaiset (SiZr) katalyytit käsiteltiin epäpuhtauksilla (kalium, natrium, fosfori ja rikki) kaasu- ja nestefaasissa. Tutkimuksessa käytettiin useita karakterisointitekniikoita, joiden avulla selvitettiin epäpuhtauksien vaikutuksia katalyyttien ominaisuuksiin. Katalyyttien toimintaa testattiin laboratoriomittakaavan kokeissa CO:n ja HC-yhdisteiden hapetuksessa sekä NOx:ien pelkistyksessä käyttäen ammoniakkia (NH3) tai vetyä (H2) pelkistimenä. Tulokset osoittavat, että CeZr-pohjaisten katalyyttien aktiivisuus NOx:ien pelkistyksessä oli hyvä käytettäessä pelkistimenä NH3:a ja kohtalainen käytettäessä vetyä. Rikki paransi CeZr-katalyyttien aktiivisuutta NOx:ien pelkistyksessä, mikä johtui kemiallisesti sitoutuneen hapen osuudesta katalyyttien pinnoilla. Vastaavasti hiilivetyjen ja CO:n hapetusreaktioissa rikki ei vaikuttanut SiZr-pohjaisten dieselhapetuskatalyyttien aktiivisuuteen. Sekä CeZr- ja SiZr-pohjaisia katalyytteja voidaan siten käyttää rikkiä sisältävien pakokaasujen puhdistuksessa. SiZr-pohjaisten katalyyttien aktiivisuus laski fosforin vuoksi. ZSM-5-pohjaiset katalyytit olivat vastustuskykyisiä kaliumille ja natriumille. Kestäviä katalyyttejä on siten kehitettävä, mikäli biopolttoaineiden sisältämien epäpuhtauksien poistaminen polttoaineista ei ole mahdollista.

Despite increasing attention for the recently found ferro- and antiferroelectric properties, the polymorphism in hafnia- and zirconia-based thin films is still not sufficiently understood. In the present work, we show that it is important to have a good quality X-ray absorption spectrum to go beyond an analysis of the only the first coordination shell. Equally important is to analyze both EXAFS and XANES spectra in combination with theoretical modelling to distinguish the relevant phases even in bulk materials and to separate structural from chemical effects. As a first step toward the analysis of thin films, we start with the analysis of bulk references. After that, we successfully demonstrate an approach that allows us to extract high-quality spectra also for 20 nm thin films. Our analysis extends to the second coordination shell and includes effects created by chemical substitution of Hf with Zr to unambiguously discriminate the different polymorphs. The trends derived from X-ray absorption spectroscopy agree well with X-ray diffraction measurements. In this work we clearly identify a gradual transformation from monoclinic to tetragonal phase as the Zr content of the films increases. We separated structural effects from effects created by chemical disorder when ration of Hf:Zr is varied and found differences for the incorporation of the substitute atoms between powders and thin films, which we attribute to the different fabrication routes. This work opens the door for further in-depth structural studies to shine light into the chemistry and physics of these novel ferroelectric thin films that show high application relevance.

Metal-insulator-metal (MIM) capacitors are used for analog, RF, and DRAM applications in ICs. The International Technology Roadmap for Semiconductors (ITRS) specifies continuing increase in capacitance density (> 7 fF/ m2), lower leakage current density (< 10 8 A/cm2), very low effective oxide thickness (EOT < 1 nm, for DRAM applications), and better capacitance density-voltage (C-V) linearity ( < 100 ppm/V2, for analog/RF applications). In addition, the maximum fabrication/processing temper-ature should not be greater than 400 0C, in order to be compatible with the thermal budget of back-end fabrication steps. Low dielectric constants of conventional SiO2 and Si3N4 capacitors limit the capacitance densities of these devices. Although scaling down of dielectric thickness increases the capacitance density, it results in large leakage current density and poor C-V linearity. In this work, the effects of high-k materials (Eu2O3, Gd2O3, TiO2) on the device performance of MIM capacitors are studied. The performance of multi-dielectric stack, and doped-dielectric stack devices are also investigated. The effects of anneal temperature, anneal ambient, anneal mode, and dielectric thickness on device performance are evaluated. C-V, current density-voltage (J-V), and reliability measurements are performed to benchmark the electrical performance, and this is correlated to the structural and material properties of the films through ellipsometry, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) measurements. High-performance MIM capacitors are fabricated by using (RF sputtered) Eu2O3 dielectric. The fabricated devices are subjected to different anneal conditions, to study their device performance. Forming gas (FG) and argon (Ar) annealed devices are shown to have higher capacitance densities (7 fF/ m2jF G), lower leakage current densities (3.2 10 8 A/cm2jAr at -1 V), and higher , compared to oxygen (O2) annealed de-vices ( 100kHz = 193 ppm/V2jO2). The electrical characterization results are correlated with the surface chemical states of the films through XPS measurements. The annealing ambient is shown to alter the surface chemical states, which, in turn, modulate the electrical characteristics. High-density MIM capacitors are fabricated by using (RF sputtered) Gd2O3, and Gd2O3-Eu2O3 stacked dielectrics. The fabricated Gd2O3 capacitors are also subjected to different anneal conditions, to study their device performance. Although Gd2O3 capacitors provide high capacitance density (15 fF/ m2), they suffer from high leakage current density, high , and poor reliability. Therefore, stacked dielectrics of Gd2O3 and Eu2O3 (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) are fabricated to reduce leakage current density, improve , and improve reliability, with only a marginal reduction in capacitance density, compared to Gd2O3 capacitors. Density of defects and barrier/trap heights are extracted for the fabricated capacitors, and correlated with the device characteristics. High-performance MIM capacitors with bilayer dielectric stacks of (ALD-deposited) TiO2-ZrO2, and Si-doped ZrO2 are characterized. Devices with (ALD-deposited) TiO2/ ZrO2/TiO2 (TZT) and AlO-doped TZT stacks are also characterized. The influence of doping on the device performance is studied. The surface chemical states of the deposited films are analyzed by high-resolution XPS. The structural analysis of the samples is performed by XRD measurements, and this is correlated to the electrical characteristics of the devices. Reliability measurements are performed to study the effects of constant voltage and current stress on device performance. High capacitance density (> 45 fF/ m2), low leakage current density (< 5 10 8 A/cm2 at -1 V, for most devices), and sub-nm EOT are achieved. These parameters exceed the ITRS specifications for DRAM storage capacitors.

Ionic conductivity of solid polymer electrolytes (SPEs) can be enhanced by the addition of fillers, while maintaining good chemical stability, and compatibility with popular cathode and anode materials. Additionally, polymer composite electrolytes can replace the flammable organic liquid in a lithium-ion battery design and are compatible with lithium metal. Compatibility with Li-metal is a key development towards a next-generation rechargeable Li-ion battery, as a Li-metal anode has a specific capacity an order of magnitude higher than LiC6 anodes used today in everyday devices. The addition of fillers is understood to suppress the crystalline fraction in the polymer phase, increasing the ionic conductivity, as Li-ion conduction is most mobile through the amorphous phase. A full model for a conduction mechanism has not yet constructed, as there is evidence that a semi-crystalline PEO-based electrolyte performs better than a fully amorphous electrolyte. Furthermore, it is not yet fully understood why the weight load of fillers in PCEs can range from 2.5%wt to 52.5%wt, in order to achieve high ionic conductivity (~10-4S/cm). This work seeks to investigate the conduction mechanism in the PCE through the use of doped-Li7La3Zr2O12 as a filler and analysis of the PCE microstructure. In this work, a solid-state electrolyte, doped-Li7La3Zr2O12 (LLZO) was synthesized via a sol-gel method, and characterized. The effect of doping and co-doping the Li, La and Zr sites in the LLZO garnet was investigated. A PEO-based polymer composite electrolyte (PCE) was prepared by adding bismuth doped LLZO (Li7-xLa3Zr2-xBixO12) as a filler. The bismuth molar ratio was changed in value to study the dopant role on the bulk PCE ionic conductivity, polymer phase crystallinity and microstructure. Results suggest that small variations in dopant can determine the optimal weight load of filler at which the maximum ionic conductivity is reached. By understanding the relationship between filler properties and electrochemical properties, higher performance can be achieved with minimal filler content, lowering manufacturing costs a solid-state rechargeable Li-ion battery.<br>

Indiana University-Purdue University Indianapolis (IUPUI) / Zirconia (ZrO2) is an important ceramic material with a broad range of applications. Due to its high melting temperature, low thermal conductivity, and high-temperature stability, zirconia based ceramics have been widely used for thermal barrier coatings (TBCs). When TBC is exposed to thermal cycling during real applications, the TBC may fail due to several mechanisms: (1) phase transformation into yttrium-rich and yttrium-depleted regions, When the yttrium-rich region produces pure zirconia domains that transform between monoclinic and tetragonal phases upon thermal cycling; and (2) cracking of the coating due to stress induced by erosion. The mechanism of erosion involves gross plastic damage within the TBC, often leading to ceramic loss and/or cracks down to the bond coat. The damage mechanisms are related to service parameters, including TBC material properties, temperature, velocity, particle size, and impact angle. The goal of this thesis is to understand the structural and mechanical properties of the thermal barrier coating material, thus increasing the service lifetime of gas turbine engines. To this end, it is critical to study the fundamental properties and potential failure mechanisms of zirconia. This thesis is focused on investigating the structural and mechanical properties of zirconia. There are mainly two parts studied in this paper, (1) ab initio calculations of thermodynamic properties of both monoclinic and tetragonal phase zirconia, and monoclinic-to-tetragonal phase transformation, and (2) image-based finite element simulation of the indentation process of yttria-stabilized zirconia. In the first part of this study, the structural properties, including lattice parameter, band structure, density of state, as well as elastic constants for both monoclinic and tetragonal zirconia have been computed. The pressure-dependent phase transition between tetragonal (t-ZrO2) and cubic zirconia (c-ZrO2) has been calculated using the density function theory (DFT) method. Phase transformation is defined by the band structure and tetragonal distortion changes. The results predict a transition from a monoclinic structure to a fluorite-type cubic structure at the pressure of 37 GPa. Thermodynamic property calculations of monoclinic zirconia (m-ZrO2) were also carried out. Temperature-dependent heat capacity, entropy, free energy, Debye temperature of monoclinic zirconia, from 0 to 1000 K, were computed, and they compared well with those reported in the literature. Moreover, the atomistic simulations correctly predicted the phase transitions of m-ZrO2 under compressive pressures ranging from 0 to 70 GPa. The phase transition pressures of monoclinic to orthorhombic I (3 GPa), orthorhombic I to orthorhombic II (8 GPa), orthorhombic II to tetragonal (37 GPa), and stable tetragonal phases (37-60 GPa) are in excellent agreement with experimental data. In the second part of this study, the mechanical response of yttria-stabilized zirconia under Rockwell superficial indentation was studied. The microstructure image based finite element method was used to validate the model using a composite cermet material. Then, the finite element model of Rockwell indentation of yttria-stabilized zirconia was developed, and the result was compared with experimental hardness data.