Dissertations / Theses on the topic 'Random Alloys'

The aim of the thesis is to study ordering in binary alloys on the basis of first-principles or {\it ab-initio} techniques employing density functional theory (DFT). The ordering phenomena of materials are of crucial importance for technological applications. The results of the thesis are intended to demonstrate the applicability of the first-principles calculations to provide fundamental insight to the true, namely electronic structure, nature of ordering in binary alloys. The main part of the thesis focuses on atomic short- and long-range order phenomena in binary alloys as a function of both temperature and chemical composition in FeCo and NiCr alloys. In particular, the influence of magnetism on atomic ordering in FeCo alloys is investigated using the disordered local moment.A large number of concentration dependent effective cluster interactions, derived without the use of any adjustable parameters, are obtained by the SGPM as it is implemented in the EMTO within the CPA. The SGPM interactions can subsequently be used in thermodynamic Monte-Carlo simulations or mean field approximations to determine the ordering phenomena in binary alloys. First-principles calculations of intrinsic stacking-fault energies (SFE) andanti-phase boundary energies (APBE) in Al$_{3}$Sc and the effects of temperature on SFE and APBE are investigated by using the axial Ising model and supercellapproach. Temperature effects have been taken into consideration byincluding the one-electron thermal excitations in the electronicstructure calculations, and vibrational free energy in the harmonicapproximation as well as by using temperature dependent lattice constants.The latter has been determined within the Debye-Gr{\"u}neisen model,which reproduces well the experimental data. Within the framework of the quasiharmonic approximation, the thermodynamics and elastic properties of B2- FeCo alloy are studied using first-principles calculations. The calculated thermal and elastic properties are found to be in good agreement withthe available measured values when the generalized gradientapproximations is used for the exchange correlation potential.The calculated finite temperature elastic constants show thatthe FeCo alloy is mechanically stable in the ordered phase.Meanwhile, a large elastic anisotropy exhibits a moderate dependence ontemperature.

QC 20130927

The solid, liquid, and solidification properties of Pd, Ag pure metals and especially PdxAg1-x alloys are studied by using the molecular dynamics simulation. The effects of temperature and concentration on the physical properties of Pdx$Ag1-x are analyzed. Sutton-Chen (SC) and Quantum Sutton-Chen (Q-SC) many-body potentials are used as interatomic interactions which enable one to investigate the thermodynamic, static, and dynamical properties of transition metals. The simulation results such as cohesive energy, density, elastic constants, bulk modulus, pair distribution functions, melting points and phonon dispersion curves obtained for Pd, Ag and PdxAg1-x are in good agreement with the available experimental data at various temperatures. The predicted melting points of Pd, Ag and their binary alloys by using Q-SC potential parameters are closer to experimental values than the ones predicted from SC potential parameters. The liquid properties such as diffusion constants and viscosities computed from Q-SC potentials are also in good agreement with the available experimental data and theoretical calculations. Diffusion coefficients and viscosity results calculated from simulation obey the Arrhenius equation well. The coefficients of the Arrhenius equation are given in order to calculate the self-diffusion coefficient and shear viscosity of Pd-Ag alloys at the desired temperature and concentration. Using different cooling rates, we investigate glass formation tendency and crystallization of Pd-Ag metal alloys, by analyzing pair distribution function, enthalpy, volume, and diffusion coefficient. Pd-Ag alloys show the glass structure at fast cooling rates while it crystallizes at slow cooling rates. Glass and crystallization temperatures are also obtained from the Wendt-Abraham parameter. The split of the second peak in the pair distribution function is associated with the glass transition. Glass forming ability increases with increasing concentration of Ag in Pd-Ag alloys. Thermal and mechanical properties of Cu, Au metals and their ordered intermetallic alloys Cu3 Au(L12), CuAu(L10), and CuAu3(L12) are also studied to investigate the effects of temperature and concentration on the physical properties of Cu-Au alloys. The simulation results such as cohesive energy, lattice parameter, density, elastic constants, bulk modulus, heat capacity, thermal expansion, melting points, and phonon dispersion curves are in good agreement with the available experimental and theoretical data at various temperatures. The Q-SC potential parameters are more reliable in determining physical properties of metals and their random and ordered alloys studied in this work

Nitriding and oxidising treatments of alloys for toolingpurposes have been investigated both experimentally andtheoretically. Specimens prepared by a combination of differentprocessing steps are investigated by light-optical, scanningand transmission electron microscopy and hardness measurments.The bounds of carbon and nitrogen concentration profiles duringnitriding are obtained from simulations using the DICTRA code.As a result, a new processing route to produce oxide-dispersediron-base alloys with large volume fraction of carbides issuggested. On the theoretical side the methods based on the random walktechnique have been investigated and developed further. The newmethods have been applied to study a vide range of phenomenae.g. internal oxidation, diffusion in inhomogeneous media,phase transformations and formation of porosity due to theKirkendall effect in welded joints. Probability distributionsare introduced to replace random number generators in order toincrease computational efficiency. A general method to simulatediffusional phase transformations in multicomponent systems isdeveloped and applied to ternary alloys.
QC 20100506

Ab-initio results of the core-level shift and the distribution about the average for the 3d_5/2 electrons of Ag, Pd and 2p_3/2 of Cu are presented for the face-centered-cubic AgPd and CuPd random alloys. The complete screening model, which includes both initial and final states effects in the same scheme, has been used in the investigations.

The alloys have been modeled with a supercell containing 256 atoms. Density-functional theory calculations are carried out using the locally self consistent Green's function approach.

Results from the calculations clearly shows that the core-level shift distributions characteristic is Gaussian, but the components reveals a substantial difference in the FWHM (Full-Width at Half-Maximum). Comparison between the experimental and the calculated broadening shows a remarkable agreement.

This work presents new theoretical developments of atomistic spin simulations of magnetic materials at finite temperatures. Special focus is put on the description of longitudinal magnetic fluctuations and the application in random transition metal alloys. A new computational scheme is proposed for mapping total energies from electronic structure calculations to an extended atomistic spin model. The proposed model has some new appealing features from previous models. To be more specific, the proposed model successfully eliminates the reference state dependency of the mapping that previous models have suffered from. Moreover, the proposed model includes longitudinal magnetic fluctuations that gives an improved description of the magnetic properties over a larger temperature interval. The proposed model strives to find the right compromise between accuracy and computational feasibility and it is applied not only to the elemental systems Fe, Co and Ni, but also to a number of binary transition metal alloys such as Permalloy (Fe$_{20\%}$Ni$_{80\%}$) and Fe-Co systems. Electronic structure calculations of Gilbert damping and the closely related magnetodynamic properties, the saturation magnetization and exchange stiffness, have been conducted for a number of different magnetic systems including Permalloy with additional doping of $4d$ or $5d$ transition metal impurities and the full Heusler alloy Co$_2$FeAl. Regarding the Permalloy based systems, a systematic study of the magnetodynamic properties was performed and compared with existing experimental data. In general we found good agreement and manage to explain the main trends regarding the Gilbert damping across the series with a simple model that captures the most important material properties to the damping, namely the spin orbit coupling and density of states at the Fermi level. In Co$_2$FeAl, we calculated the Gilbert damping in different existing crystal structures and compare those with new experimental data and found good agreement between them. Magnon properties of random alloys, like Permalloy, are studied using two complementory methods, the adiabatic magnon spectra valid at zero temperature and from finite temperature atomistic spin dynamics through the dynamical structure factor. The influence of chemical disorder and temperature effects on the magnon properties are investigated that hopefully could motivate new experimental studies of these materials.

QC 20170904

The overall aim of this thesis is to compare different methods for calculation of Core-Level shifts in metallic alloys. The methods compared are the Initial State model, the Complete screening and the Transition state model. Core-level shifts can give information of chemical bonding and about the electronic structure in solids.

The basic theory used is the so-called Density-Functional-Theory, in conjunction with the Local-Density Approximation and the Coherent-Potential- Approximation. The metallic alloys used are Silver-Palladium, Copper-Palladium, Copper-Gold and Copper-Platinum, all inface-centered-cubic configuration.

The complete screening- and the transition-state model are found to be in better agreement with experimental results than those calculated with the initial state model. This is mainly due to the fact that the two former models includes final-state effects, whereas the last one do not. The screening parameters within the Coherent-Potential approximation are also investigated. It is found that the Screened-Impurity Model can extend the validity of the Coherent-Potential-Approximation and increase it's accuracy.

In this study the elastic properties of a fcc Fe0.87Mn0.13 random alloy are studied by ab initio calculations. Ground state lattice parameters and elastic properties are calculated with Density Functional Theory using the Exact Muffin-Tin Orbital method and the Coherent Potential Approximation. Several magnetic models, approximations and distortion techniques are evaluated for optimized results, which are obtained by a Disordered Local Moment model with the Frozen Core and Generalized Gradient approximations using volume-conserving distortions.  Conclusively the longitudinal sound velocities are calculated from second order elastic stiffness constants and visualized by two different codes. The importance of magnetism for elastic properties is confirmed, as is the usefulness of the optimized computational scheme; all quantities obtained via the scheme is in accord with earlier theoretical and experimental results. Volume-conserving distortions are found to be more precise than volume-altering for calculation of elastic constants but also to be highly dependent on the precision of bulk modulus determination. The two sound-velocity codes are in complete agreement.

Theoretical investigations of spectroscopic and magnetic properties of metallic systems in the bulk, as well as in nanostructured materials, have been performed within the density functional theory. The major part of the present work studies the differences between binding energies of electrons tightly bound to the atoms, the so-called core electrons (in contrast with the valence electrons), that is, core-level binding energy shift (CLS).

By comparison between corresponding elemental core-levels for atoms situated in different chemical environments we obtain fundamental understanding of bonding properties of materials. The method of choice was the complete screening picture, which includes initial and final state effects on the same footing. The usefulness of CLS stems from that it is sensitive to differences in the chemical environment of an atom, which can be affected on one hand by the global composition of e.g. disordered materials, surfaces and interfaces, and on the other hand by the very local environment around an atom. Here CLSs have been obtained for both components in the fcc random alloys AgPd, CuPd, CuNi, CuPt, CuAu, PdAu, NiPd and NiPt. Moreover the model was extended to the Auger kinetic energy shift for the LMM Auger transition in AgPd alloys. Studies were also applied to the near surface and interface regions of PdMn nano structures on Pd(100), thin CuPd and AgPd films on inert Ru(0001), and at interfaces. The disorder broadening on CLS due to local environment effects was calculated in selected alloys.

A part of the thesis concern investigations related to the magnetic ordering in Invar alloys, including the influence of local environment effects. A study was made for the dependence of effective exchange parameter on the electron concentration, volume and local chemical composition.

L'objectiu de la tesi és estudiar la cinètica de les cristal·litzacions primàries en vidres metàl·lics mitjançant simulacions de tipus phase field. Una cristal·lització primària és una transició de fase sòlid-sòlid on la fase que cristal·litza (fase transformada o fase secundaria) té una composició química diferent de la fase precursora (fase no transformada o fase primària).
Les dades experimentals obtingudes a partir de l'estudi calorimètric de cristal·litzacions primàries s'analitzen generalment en el marc del model KJMA (Kolmogorov, Johnson & Mehl, Avrami). Aquest model proporciona l'evolució temporal de la fracció transformada basant-se en tres hipòtesis:
- Els nuclis de la fase secundaria estan distribuïts aleatòriament en tot l'espai.
- El creixement d'aquests nuclis és isotròpic.
- El creixement s'atura únicament per xoc directe (hard impingement).

En la cristal·lizació de vidres metàl·lics s'ha observat experimentalment un alentiment de la cinètica respecte del comportament calculat emprant la citada cinètica KJMA. Aquest alentiment s'explica a la literatura en base a que en aquest tipus de transformacions, controlades per difusió, la interacció entre els cristalls no és directa sinó que es produeix a través dels perfils de concentració (soft impingement) i, a més, l'evolució d'aquests perfils de concentració causa canvis en la concentració de la matriu amorfa, estabilitzant la i per tant fent que la nucleació de nous cristalls esdevingui no aleatòria. Diversos autors han proposat modificacions del model KJMA per tal d'intentar superar aquestes limitacions, basats bé en consideracions geomètriques, bé en aproximacions de camp mitjà. A pesar de tot, cap d'aquests models és capaç d'explicar satisfactòriament la cinètica observada en cristal·litzacions primàries. L'objectiu d'aquest treball ha estat la simulació realista de la cinètica de les transformacions primàries per trobar una explicació consistent a les diferències observades entre les dades experimentals i els models teòrics disponibles.
Per tal de poder descriure de forma realista el procés de cristal·lització primària s'ha d'estudiar el procés de nucleació i creixement de la fase secundaria alhora que es resol l'equació de difusió en la fase primària. En aquest treball s'ha emprat un model de simulació phase field que permet estudiar aquest sistema introduint una nova variable lligada al camp de concentració que pren dos valors diferents segons es tracti de fase transformada o no transformada. Amb aquest tipus de models també es poden introduir diferents protocols de nucleació i per tant estudiar independentment els efectes de la nucleació en la cinètica. D'aquesta manera s'han realitzat simulacions en 2 i 3 dimensions de cristal·litzacions primàries amb diferents graus de fracció transformada final). Els resultats de les simulacions s'ha comparat amb el model KJMA i, contra el que es preveia, s'ha obtingut un bon acord entre les fraccions transformades del model KJMA i de les simulacions. Donat que el model KJMA no reprodueix satisfactòriament el comportament experimental d'aquest resultat es dedueix que ni el soft impingement ni la nucleació no aleatòria son les responsables de l'alentiment de la cinètica obtingut en cristal·litzacions primàries.
Per tal de trobar una explicació físicament convincent del comportament observat experimentalment s'ha aprofundit en l'estudi teòric de les cristali·litzaciones primàries, incloent-hi l'efecte dels canvis composicionals que tenen lloc en la matriu a mesura que la transformació es produeix. Aquest fet, tot i ser conegut a la bibliografia, ha estat sistemàticament ignorat en l'elaboració de models cinètics. En concret, s'ha fet palès que canvis en la composició química de la fase primària han d'afectar de forma radical a la viscositat, que varia fortament a prop de la transició vitrea, i han de produir canvis en les propietats de transport atòmic. Això s'ha modelat a través de l'assumpció d'un coeficient de difusió depenent de la concentració, en base a la relació modificada d'Stokes-Einstein entre la viscositat i el coeficient de difusió. Les simulacions phase-field amb un coeficient de difusió d'aquest tipus donen lloc a una cinètica més lenta i que mostra un acord excel·lent amb la cinètica experimentalment observada en cristal·litzacions primàries de vidres metàl·lics. Per tant, les simulacions phase field confirmen que la cinètica de les cristal·litzacions primàries està controlada fonamentalment pel canvi en les propietats de transport atòmic, mentre que els efectes de soft impingement i nucleació no aleatoria, tot i estar presents, son secundaris.
El objetivo de la tesi es estudiar la cinética de las cristalizaciones primarias en vidrios metálicos mediante simulaciones de tipo phase field. Una cristalización primaria es una transición de fase sólido-sólido donde la fase que cristaliza (fase transformada o fase secundaria) tiene una composición química diferente a la fase precursora (fase no transformada o fase primaria).
Los datos experimentales obtenidos a partir del estudio calorimétrico de cristalizaciones primarias se analizan generalmente en el marco del modelo KJMA (Kolmogorov, Johnson & Mehl, Avrami). Este modelo proporciona la evolución temporal de la fracción transformada basándose en tres hipótesis:
- Los núcleos de la fase secundaria están distribuidos aleatoriamente en todo el espacio
- El crecimiento de estos núcleos es isotrópico
- El crecimiento se detiene únicamente por choque directo (hard impingement).

En la cristalización de vidrios metálicos se ha observado experimentalmente un retardo de la cinética respecto del comportamiento calculado usando la cinética KJMA. Este retardo se explica en la literatura en base a que en este tipo de transformaciones, controladas por difusión, la interacción entre los cristales no es directa sino que se produce a través de los perfiles de concentración (soft impingement) y, además, la evolución de estos perfiles de concentración causa cambios en la concentración de la matriz amorfa, estabilizándola y por tanto haciendo que la nucleación de nuevos cristales sea no aleatoria. Varios autores han propuesto modificaciones del modelo KJMA para intentar superar estas limitaciones, basados bien en consideraciones geométricas, bien en aproximaciones de campo medio. A pesar de todo, ninguno de estos modelos es capaz de explicar satisfactoriamente la cinética observada en cristalizaciones primarias. El objetivo de este trabajo ha sido la simulación realista de la cinética de las transformaciones primarias para hallar una explicación consistente a las diferencias entre los datos experimentales y los modelos teóricos disponibles.
Para describir de manera realista el proceso de cristalización primaria se tiene que estudiar el proceso de nucleación y crecimiento de la fase secundaria a la vez que se resuelve la ecuación de difusión en la fase primaria. En este trabajo se ha usado un modelo de simulación phase-field que permite estudiar este sistema introduciendo una nueva variable ligada al campo de concentración que toma dos valores diferentes según se trate de fase transformada o no transformada. Con este tipo de modelos también se pueden introducir diferentes protocolos de nucleación y por tanto estudiar independientemente los efectos de la nucleación en la cinética. De esta manera se han realizado simulaciones en 2 y 3 dimensiones de cristalizaciones primarias con diferentes grados de fracción transformada final. Los resultados de la simulaciones se han comparado con el modelo KJMA y, en contra de lo que se preveía, se ha obtenido un buen acuerdo entre las fracciones transformadas del modelo KJMA y de las simulaciones. Dado que el modelo KJMA no reproduce satisfactoriamente el comportamiento experimental, de este resultado se deduce que ni el soft impingement ni la nucleación no aleatoria son las responsables del retardo en la cinética obtenido en cristalizaciones primarias.
Para encontrar una explicación físicamente convincente del comportamiento observado experimentalmente se ha profundizado en el estudio teórico de las cristalizaciones primarias, incluyendo el efecto de los cambios composicionales que tienen lugar en la matriz a medida que la transformación se produce. Este hecho, aún y ser conocido en la bibliografía, ha sido sistemáticamente ignorado en la elaboración de modelos cinéticos. En concreto, se ha hecho patente que cambios en la composición química de la fase primaria tienen que afectar de forma radical a la viscosidad, que varía fuertemente cerca de la transición vítrea, y tienen que producirse cambios en las propiedades de transporte atómico. Esto se ha modelado a través de la asunción de un coeficiente de difusión dependiente de la concentración, en base a la relación de Stokes-Einstein modificada entre la viscosidad y el coeficiente de difusión. Las simulaciones phsae-field con un coeficiente de difusión de este tipo dan lugar a una cinética más lenta y que muestra un acuerdo excelente con la cinética experimentalmente observada en cristalizaciones primarias de vidrios metálicos. Por tanto, las simulaciones phase-field confirman que la cinética de las cristalizaciones primarias está controlada fundamentalmente por los cambios en las propiedades de transporte atómico, mientras que los efectos de soft-impingement y nucleación no aleatoria, aún y estar presentes, son secundarios.
The aim of this thesis is to study the kinetics of primary crystallization in metallic glasses by means of phase-field simulations. A primary crystallization is a solid-solid phase transformation where the crystallized phase (transformed phase or secondary phase) has a chemical composition different than the precursor phase (untransformed phase or primary phase).
Experimental data from calorimetric studies of primary crystallization are usually studied in the framework of the KJMA model (Kolmogorov, Johnson & Mehl, Avrami). This model yields the temporal evolution of the transformed fraction on the basis of three main assumptions:
- A random distribution of particle nuclei of the secondary phase
- The growth of these nuclei is isotropic
- The growth is only halted by direct collisions (hard impingement).

In the crystallization of metallic glasses, a slowing down of the kinetics respect the behavior calculated with the KJMA kinetics has been observed. This delay is explained in the literature by the fact that in this kind of transformations, that are diffusion controlled, the interaction between the crystals is not direct but through the concentration profiles (soft impingement) and moreover, the evolution of these profiles causes changes in the concentration of the amorphous matrix, stabilizing it and thus, the nucleation of new nuclei become non random. Several authors had proposed modifications to the KJMA model to try to overcome these limitations, based either on geometrical considerations or in mean field approaches. However, none of these models is able to explain the observed kinetics in primary crystallizations. The aim of this work has been the realistic simulation of the kinetics of primary crystallization to find a explanation to the differences between the experimental data and the available theoretical models.
In order to describe in a realistic way the process of a primary crystallization, the nucleation and growth process of the secondary phase has to be studied at the same time that the diffusion equation is solved in the primary phase. In this work, it has been used a phase field model for the simulations that allows to study this system introducing a new variable, coupled to the concentration field, that takes two different values in each of the existing phases. With these kinds of models, different nucleation protocols can also be introduced and thus, independently study the effects of the nucleation in the kinetics. Therefore, 2 and 3 dimensional simulations of primary crystallization have been performed with several degrees of final transformed fraction. The simulation results have been compared with the KJMA model and, unexpectedly, a good agreement between the simulations and the KJMA model has been obtained. As the KJMA model does not reproduce satisfactorily the experimental behavior, from this result can be deduced that neither the soft impingement nor the non random nucleation are the responsible of the slowing down observed in the kinetics of primary crystallization.
In order to find a physical convincing explanation of the observed experimental behavior, the theoretical study of primary crystallization has been extended, including the effects of the compositional changes that take place in the matrix as the transformation proceed. This fact, notwithstanding being known in the literature, has been systematically ignored in the development of the kinetics models. In particular, it has become clear that changes in the chemical composition of the primary phase have to radically affect the viscosity, that strongly varies near the glass transition, and some changes in the atomic transport properties must occur. This has been modeled through the assumption of a compositional dependent diffusion coefficient, on the basis of a modified Stokes-Einstein relation between viscosity and diffusion coefficient. Phase field simulations with a diffusion coefficient of this type yield a slower kinetics and show an excellent agreement with the kinetics experimentally observed in primary crystallization of metallic glasses. Thus, phase field simulations confirm that the kinetics of primary crystallization is fundamentally controlled by the changes in the atomic transport properties, while the soft impingement and non random effects, although being present, are secondary.

Kyoto University (京都大学)
0048
新制・課程博士
博士(人間・環境学)
甲第17837号
人博第658号
新制||人||158(附属図書館)
25||人博||658(吉田南総合図書館)
30652
京都大学大学院人間・環境学研究科共生人間学専攻
(主査)教授 上木 直昌, 教授 森本 芳則, 教授 髙﨑 金久
学位規則第4条第1項該当

Des monocristaux A2 de Fe0.85Al0.15 de terminaison (110), (100) et (111) ont servi de modèle pour étudier la ségrégation d'Al et l'oxydation d'aciers industriels à l'Al en combinant LEED, XPS, STM et GIXD. Toutes les surfaces propres sont sujettes à une intense ségrégation d'Al lors de recuits > 700 K. Au-delà de 1000 K, un quasi-équilibre est atteint et la couche concernée de 2-3 nm adopte une composition proche de la structure B2. Cependant, toutes les surfaces se comportent différemment en termes de reconstruction. La surface (110) développe une superstructure pseudo-hexagonale de 2nm avec une modulation incommensurable dans le plan. La surface (100) est toujours terminée (1×1) avec une apparence marbrée attri-buée à un contraste électronique et chimique. La surface (111) est locale-ment rugueuse avec des protrusions triangulaires nanométriques en raison d'un facettage induit par la ségrégation. La tendance à la ségrégation est con-firmée par des calculs ab initio. L'oxydation à haute température par O2 de ces surfaces conduit à une oxy-dation sélective de l'Al et à la formation de films d'alumine d'épaisseur 1-2nm. Des oxydes ordonnés croissent sur les faces (110) et (100) alors que des îlots apparaissent sur la face (111). Les sous-surface de (110) et (111) oxydés sont déplétées en Al et adoptent la structure D03 alors que celle de (100) ne varie pas. A la surface (110), l'alumine croit sous forme de deux domaines ayant une maille quasi-rectangulaire de (18.5 × 10.5) Å2 et un ac-cord (2×1)ox. Le film d'oxyde à la surface (100) présente deux domaines (2×1) sous la forme de bandes orthogonales; une explication plausible est la formation d'une structure distordue θ-Al2O3
A2 Fe0.85Al0.15 single crystals with low-index orientations (110), (100) and (111) have been chosen as a model system to study the Al segregation and oxidation of industrial Al-alloyed steels by using combined techniques (LEED, XPS, STM, GIXD). All clean surfaces are prone to intense Al segregation when annealed at > 700 K. After 1000 K, a quasi-equilibrium is reached and the impacted layer of 2-3 nm has a composition close to the B2 structure. But all the surfaces behave differently in terms of reconstruction. The (110) surface develops a 2 nm pseudo-hexagonal superstructure with an incommensurate in-plane modulation. The (100) surface is always (1×1) terminated with a marbled-like appearance assigned to an electronic and chemical contrast. The (111) surface is locally rough with nanometric three-fold protrusions due to seg-regation-induced faceting involving (111) vicinal surfaces. The segregation trend is confirmed through ab initio calculations. The oxidation with O2 of all surfaces at high temperature results in selective oxidation of Al and alumina formation with a 1-2 nm self-limited thick-ness. Ordered oxides are found on (110) and (100) faces while a disordered 3D oxide grows on (111). Subsurfaces of oxidised (110) and (111) are de-pleted in Al and adopt the D03 structure, while (100) subsurface composi-tion is insensitive to oxidation. At (110) surface, a two-domain alumina grows with a (18.5 × 10.5) Å2 nearly rectangular rotated unit cell with a (2×1)ox matching. The oxide film at (100) surface presents two (2×1) do-mains in the form of nanometric orthogonal stripes; a likely explanation is the formation of a distorted θ-Al2O3 structure

Over the years, people have found Quantum Mechanics to be extremely useful in explaining various physical phenomena from a microscopic point of view. Anderson localization, named after physicist P. W. Anderson, states that disorder in a crystal can cause non-spreading of wave packets, which is one possible mechanism (at single electron level) to explain metalinsulator transitions. The theory of quantum computation promises to bring greater computational power over classical computers by making use of some special features of Quantum Mechanics. The first part of this dissertation considers a 3D alloy-type model, where the Hamiltonian is the sum of the finite difference Laplacian corresponding to free motion of an electron and a random potential generated by a sign-indefinite single-site potential. The result shows that localization occurs in the weak disorder regime, i.e., when the coupling parameter λ is very small, for energies E ≤ −Cλ² . The second part of this dissertation considers adiabatic quantum computing (AQC) algorithms for the unstructured search problem to the case when the number of marked items is unknown. In an ideal situation, an explicit quantum algorithm together with a counting subroutine are given that achieve the optimal Grover speedup over classical algorithms, i.e., roughly speaking, reduce O(2n ) to O(2n/2 ), where n is the size of the problem. However, if one considers more realistic settings, the result shows this quantum speedup is achievable only under a very rigid control precision requirement (e.g., exponentially small control error).
Ph. D.

Rotundus AB är ett världsledande företag inom området för sfäriska robotar som håller på att utveckla den markbundna farkosten GroundBot(tm). För att detektera robotens translations- och rotationsrörelser används accelerometrar och hastighetsgyron. Dessutom används sensorerna för tröghetsnavigering när GPS-täckning saknas.

Målet med projektet innebär att ta fram en metod för att utvärdera precisionen hos sensorer för robotens tröghetsnavigeringsenhet. Metoden koncentrerar sig på fyra av sensorernas felkällor: Skalfaktor, bias, slumpvandring och biasinstabilitet.

För att beräkna skalfaktorn och biasen används linjära minsta kvadratmetoden där utsignalen från sensorn anpassas mot ett teoretiskt värde. Slumpvandringen och biasinstabiliteten utvärderas med Allans varians.

Comparaison du comportement des fissures courtes (inferieures a 0,3-0,4mm) et longues dans deux alliages d'aluminium 2124 et 7475 soumis a deux types de chargement : sollicitations d'amplitude constante, sollicitations incluant des surcharges uniques ou repetees periodiquement

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.

碩士
國立中山大學
材料與光電科學學系研究所
103
In the modern life, the portable electric products are indispensable. Moreover the memory plays an important role on these products. Today, the manufacturing of portable electric products tends to be small, thin, compact, and energy-saving with technological advancements. Therefore, the next generation RRAM has been greatly focused and studied. The RRAM is known for the most potential next generation non-volatile memories, due to the advantages of simple structure, high density, low operational voltage, high read-write speed, and long storage time. In this thesis, the Au70Ag30 and Au30Ag70 alloy thin film and the SiO2 thin film are coated on the TiN electrode which was provided from Industrial Technology Research Institute (ITRI) via Lithography Electroforming Micro Molding technique. The results show that the Au-Ag alloy thin film owns comparably higher operational speed and is more energy-saving than the pure Ag thin film. The current conductive mechanisms and the metal filament models in the insulator layer of Au30Ag70/SiO2/TiN RRAM device are study and discussed. The other section is the fabrication of nanoporous Au-Ag alloy for the bottom electrode of RRAM devices. This section is talking about using the chemical dealloying method to control the surface morphology of the bottom electrode of RRAM devices. The results show that the surface morphology, roughness and composition can be controlled via immersing in HNO3 for different periods of time.

碩士
逢甲大學
電子工程學系
107
Resistive random-access memory (RRAM)is one of the most promising candidates for the next generation nonvolatile memory due to the simple metal-insulator-metal structure, fast program speed, and compatibility with CMOS technology. Conductive bridging random access memory (CBRAM) is one type of RRAM device, it’s switching mechanism is control by metallic ions to form the metal filament between device electrodes, typical CBRAM uses active metal elements as a source of metal ions, such as Copper (Cu) and Silver (Ag). In this study, a bottom electrode of a different proportions Cu-Ag alloy made by chemical displacement technique (CDT) was compared in terms of resistance switching properties for a silicon dioxide based RRAM device. The result shows the process voltage decrease, stability increase and at least an order of memory window and only a very small percentage of silver is needed as a catalyst to trigger this mechanism.

碩士
國立臺灣大學
光電工程學研究所
107
In this thesis, a full 3D simulation model is applied to analyze the alloy fluctuation, QW thickness or composition fluctuation in the green LEDs. Recently, studies show that alloy fluctuation could influence electric property due to localized state or the percolation due to the fluctuation potential. Furthermore, we found that in order to make the prediction more accurately, the QW thickness fluctuation or large scale QW composition fluctuation will be needed. After we compare the structure with and without thickness fluctuation, we have found that models with (thickness fluctuation/or composition fluctuation) can make the turned-on voltage obtained by the simulation smaller and match well to the experimental result. The thinner of QW provides a smaller barrier induced by polarization field and it allows carriers to be injected at this low barrier side so that the turn-on voltage will be smaller. However, the drawback for thickness fluctuation is the reduction of active volume size so that local carrier density at the same current is much larger than the case without thickness fluctuation. Therefore, a smaller IQE and a stronger droop was observed if the ratio of thin QW to thick QW region was too large. Finally, we tried to under the influence of lateral carrier diffusion to the potential fluctuation through the diffusion model. We compared the differences between the QW with or without random alloy fluctuation, QW with thickness fluctuation. Our studies show that the fluctuation reduce the diffusion length of electron and holes by 2 or 3 times. Electrons are limited to be less than 1um and holes to be less than 100nm. However, if the thickness fluctuation is further considered, the diffusion length was observed to be limited by the periods of thickness fluctuation.

Brutalist architecture, popularized in Britain in the late 1950s and heralded as a progressive form of Modernism in the United States until the 1970s, now presents a conundrum to preservationists as it ages. Once critically acclaimed, many Brutalist buildings have lost their appeal over time. The unpolished materials have proven unpopular with many who live and work in these structures, and key examples of the style are now facing demolition. Though “Brutalism” has become a nebulous architectural designation in the preservation community, this paper focuses on a specific subset of late Modernist architecture that primarily utilizes unfinished concrete to promote the philosophy of material truth and unapologetic permanence. While artistry of form and overall functionality affect preservation of Brutalist buildings in the United States, an important factor in the decision to demolish is often overlooked: the interplay of public opinion with critical acclaim, both in the past and within current architectural climates. This project examines the Brutalist approach to architecture and chronicles the shifts in critical and public perspective of several key case studies, focusing on university structures (the Yale Art and Architecture Building, Harry Ransom Center, and the University of Texas School of Nursing), theaters (Morris Mechanic Theater and Alley Theater), and civic buildings (Orange County Government Center, Boston City Hall, and Prentice Women’s Hospital). Understanding how and why shifts in opinion took place is critical in making informed preservation decisions about Brutalist architecture.
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