No description available.

Les nanostructures de semiconducteurs II-VI ont de nombreuses applications en microélectronique, optoélectronique et photonique. Notamment, les boites quantiques II-V peuvent servir de source de photons uniques. Dans cette étude, nous nous sommes intéressés à la caractérisation chimique et structurale des nanostructures de semiconducteurs II-VI (boites quantiques (BQs) auto-organisées, nanofils II-VI et III-V …) par sonde atomique tomographique (SAT). Dans un premier temps, nous avons optimisé les conditions d’analyse des semiconducteurs III-V et II-VI par SAT. Ensuite, nous avons étudié les compositions chimiques des interfaces II-VI/III-V en montrant la formation d’un composé Ga2.7Se3 à l’interface ZnSe/GaAs et un mélange de cations (Ga, Zn) à l’interface ZnTe/InAs. Les mesures de compositions chimiques et des tailles des boites quantiques en trois dimensions par SAT ont permis de faire une corrélation avec les mesures optiques. Nous nous sommes aussi intéressés à l’étude des mécanismes de croissance des nanofils GaAs et ZnTe ainsi que des BQs (CdTe) insérés dans des nanofils ZnTe en analysant la composition chimique des catalyseurs, les BQs dans les nanofils aussi que la base des nanofils. Ces mesures montrent que les boites quantiques sont formées d’un fort mélange CdxZn1-xTe. Un scénario basé sur la diffusion de surface a été proposé pour expliquer la croissance ainsi que le mélange entre Zn/Cd pour les BQs insérées dans les nanofils. / Nanostructures of II-VI nanostructure have many applications in microelectronics, optoelectronics and photonics. For example, II -V quantum dots have shown the ability to be a source of single photons. In this work, we performed in the chemical and structural characterization of nanostructures of II-VI semiconductors (self- organized quantum dots (QDs), nanowires II-VI and III- V ...) by atom probe tomography (APT). Firstly, the analysis conditions of III-V and II- VI semiconductors by APT were optimized. Then, we studied the chemical composition of II-VI/III-V interfaces and showed the formation of a Ga2.7Se3 compound at the ZnSe/GaAs interface and the (Ga, Zn) cations mixing at the ZnTe/InAs interface. The measurements of the chemical composition and the sizes of quantum dots in three dimensions by APT allowed making a correlation with optical measurements. We studied also growth mechanisms of GaAs, ZnTe nanowire and the CdTe QDs inserted in ZnTe nanowires by analyzing the chemical composition of the catalysts QDs and nanowires basis. These measurements show that the quantum dots are formed of a strong mixing of CdxZn1-xTe. A scenario based on surface diffusion has been proposed to explain the growth and the mixing between Zn/Cd for the QDs.

No description available.

Within this work, bonding technologies based upon the alloying of gallium with other metals to assemble semiconductor substrates for the possible application of encapsulation and 3D-integration of micro systems and devices have been researched. Motivated by the important demand to achieve low temperature processes, methods with bonding temperatures below 200°C were investigated. Necessary technologies like the deposition of gallium as thin film and subsequent micro structuring have been developed. The alloying between gallium and gold as well as gallium and copper was analysed in detail. A good correlation between the elemental composition of the interface and its mechanical and electrical parameters was established, particularly regarding its thermal dependence. It emerged that in case of combination Au/Ga Kirkendall void are extensively formed whereby serious problems with mechanical strength as well as hermeticity emerged. In case of Cu/Ga, this problem is existent to a much lesser degree; it was possible to create hermetic tight bonds. For the necessary pre-treatment of copper, several methods could be successfully demonstrated. In summary, the development of bonding technologies based upon metallic interfaces that exhibit electric conductance, high strength and hermetic seal could be demonstrated. / In dieser Arbeit werden Bondverfahren zum Fügen von Halbleitersubstraten für mögliche Anwendungen für die Verkapselung und 3D-Integration von Bauelementen der Mikrosystemtechnik erforscht, die auf der Legierungsbildung von Gallium mit anderen Metallen beruhen. Motiviert von der zentralen Anforderung an niedrige Prozesstemperaturen wurden Methoden mit Fügetemperaturen deutlich unter 200°C untersucht. Dafür nötige Technologien zum Abscheiden von Gallium als Dünnschicht und das anschließende Mikrostrukturieren wurden entwickelt. Die Legierungsbildung zwischen Gallium und Gold sowie zwischen Gallium und Kupfer wurde im experimentell im Detail analysiert. Dabei konnte eine gute Korrelation zwischen der stofflichen Zusammensetzung und den mechanischen bzw. elektrischen Parametern der Zwischenschicht, auch und insbesondere hinsichtlich ihrer Temperaturabhängigkeit gefunden werden. Es stellte sich heraus, dass im Falle der Kombination Au/Ga Kirkendall Hohlräume in einer Menge entstehen, die zu erheblichen Problemen bezüglich mechanischer Festigkeit und Dichtheit der Fügeverbindung führen. Bei der Materialkombination Cu/Ga hingegen trat dieses Problem nur begrenzt auf; es war möglich hermetisch dichte Verbindungen herzustellen. Für die bei Kupfer nötige Vorbehandlung wurden mehrere Methoden erfolgreich getestet. Insgesamt konnte die Entwicklung von Fügetechnologien gezeigt werden, die metallische Zwischenschichten verwenden, elektrisch leitfähig sind, sehr gute Festigkeiten aufweisen und hermetisch dicht sind.

The knowledge of diffusion parameters provides important understanding of many physical and mechanical properties of materials. In most of the applications silicides are grown by a diffusion controlled process mainly in thin film condition. Because of this reason, most of the studies till date are available in thin film condition. Although more than one phase is present in all these systems, mainly disilicides were found at the interface. In this thesis bulk interdiffusion studies are conducted by coupling pure refractory metals (group IVB, VB and VIB elements) with single crystal Si. Several phase layers grow between binary refractory metal and Si systems. The layer thicknesses of the phases are measured from the microstructures. Composition profiles were measured in electron probe microanalyzer. Different diffusion parameters are estimated such as parabolic growth constants, integrated diffusion coefficients, activation energy for diffusion and ratio of tracer diffusivities of the components are estimated. Growth mechanisms of the phases are discussed with the help of diffusion parameters. The atomic mechanism of the diffusion is discussed considering crystal structure of the phases along with possible defects present. Solid diffusion couple experiments are conducted to analyse the growth mechanism of the phases and the diffusion mechanism of the components in the Ti-Si system. The calculation of the parabolic growth constant and of the integrated diffusion coefficients substantiates that the analysis is intrinsically prone to erroneous conclusions if it is based just on the parabolic growth constants determined for a multiphase interdiffusion zone. The location of the marker plane is detected based on the uniform grain morphology in the TiSi2 phase, which indicates that this phase grows mainly because of Si diffusion. The growth mechanism of the phases and morphological evolution in the interdiffusion zone are explained with the help of imaginary diffusion couples. The activation enthalpies for the integrated diffusion coefficient of TiSi2 and the Si tracer diffusion are calculated as 190±9 and 170±12 kJ/mol, respectively. The crystal structure, details on the nearest neighbours of the elements and the relative mobilities of the components indicate that the vacancies are mainly present on the Si sublattice. Diffusion controlled growth of the phases in the Hf-Si and Zr-Si are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane detected based on the grain morphology indicates that the disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 ± 37 and 346 ± 34 kJ/mol, respectively. The same is calculated for the HfSi phase as 485±42 kJ/mol. The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 ± 36 and 348 ± 34 kJ/mol, respectively. We conducted interdiffusion studies to understand the atomic mechanism of the diffusing species and the growth mechanism of the phases. Integrated diffusion coefficients and the ratio of tracer diffusion coefficients were estimated for these analyses. The activation energies for the integrated diffusion coefficients were calculated as 550 ± 70 and 410 ± 39 kJ/mol in the TaSi2 and the Ta5Si3 phases, respectively. In the TaSi2 phase, Ta has a slightly lower but comparable diffusion rate with respect to Si, although no TaTa bonds are present in the crystal. In the Ta5Si3 phase, Si has higher diffusion rate, which is rather unusual, if we consider the atoms in the nearest-neighbor positions for both the elements. The ratio of Si to Ta tracer diffusion coefficients is found to be lower in the Si-rich phase, TaSi2, compared to the Si-lean phase, Ta5Si3, which is also unusual. This indicates the type of structural defects present. An analysis on the growth mechanism of the phases indicates that duplex morphology and the Kirkendall marker plane should only be present in the TaSi2 phase. This is not present in the Ta5Si3 phase because of the very high growth rate of the TaSi2 phase, which consumes most of the Ta5Si3 phase layer. The problems in the calculation method used previously by others in this system are also explained. Experiments are conducted in the W-Si system to understand the diffusion mechanism of the species. The activation energies for integrated diffusion are found to be 152±7 and 301±40 kJ/mol in the WSi2 and W5Si3 phases, respectively. In both the phases, Si has a much higher diffusion rate compared to W. The result found in the WSi2 phase is not surprising, if we consider the nearest neighbors in the crystal. However, it is rather unusual to find that Si has higher diffusion rate in the W5Si3 phase, indicating the presence of high concentration of Si antisites in this phase. In the group IVB, VB and VIB M-Si systems are considered to show an interesting pattern in diffusion of components with the change in atomic number in a particular group. MSi2 and M5Si3 are considered for this discussion. Except in the Ta-Si system, activation energy for integrated diffusion of MSi2 is always lower than M5Si3. Interestingly, in both the phases, the relative mobilities measured by the ratio of tracer D* diffusion coefficients, S i decreases with the increase in atomic number in both the DM* groups. Both the phases have similar crystal structures in a particular group in which these parameters are calculated. In both the phases Si has higher diffusion rate compared to M. Absence of any M-M bonds in MSi2 and increase in the diffusivities of M with the increase in atomic number substantiates the increasing concentration of M anti-sites and higher interactions of M with vacancies. Only one or two Si-Si bonds are present in M5Si3, however, the higher diffusion rate of Si indicates the presence of vacancies mainly D* on its sublattice. On the other hand, increase in S i with increasing atomic number in DM* Both the groups substantiates increasing interactions of M and vacancies.

Advances in wide-bandgap semiconductor devices have increased the allowable operating temperature of power electronic systems. High-temperature devices can benefit applications such as renewable energy, electric vehicles, and space-based power electronics that currently require bulky cooling systems for silicon power devices. Cooling systems can typically be reduced in size or removed by adopting wide-bandgap semiconductor devices, such as silicon carbide. However, to do this, semiconductor device packaging with high reliability at high temperatures is necessary. Transient liquid phase (TLP) die-attach has shown in literature to be a promising bonding technique for this packaging need. In this work TLP has been comprehensively investigated and characterized to assess its viability for high-temperature power electronics applications. The reliability and durability of TLP die-attach was extensively investigated utilizing electrical resistivity measurement as an indicator of material diffusion in gold-indium TLP samples. Criteria of ensuring diffusive stability were also developed. Samples were fabricated by material deposition on glass substrates with variant Au–In compositions but identical barrier layers. They were stressed with thermal cycling to simulate their operating conditions then characterized and compared. Excess indium content in the die-attach was shown to have poor reliability due to material diffusion through barrier layers while samples containing suitable indium content proved reliable throughout the thermal cycling process. This was confirmed by electrical resistivity measurement, EDS, FIB, and SEM characterization. Thermal and mechanical characterization of TLP die-attached samples was also performed to gain a newfound understanding of the relationship between TLP design parameters and die-attach properties. Samples with a SiC diode chip TLP bonded to a copper metalized silicon nitride iv substrate were made using several different values of fabrication parameters such as gold and indium thickness, Au–In ratio, and bonding pressure. The TLP bonds were then characterized for die-attach voiding, shear strength, and thermal impedance. It was found that TLP die-attach offers high average shear force strength of 22.0 kgf and a low average thermal impedance of 0.35 K/W from the device junction to the substrate. The influence of various fabrication parameters on the bond characteristics were also compared, providing information necessary for implementing TLP die-attach into power electronic modules for high-temperature applications. The outcome of the investigation on TLP bonding techniques was incorporated into a new power module design utilizing TLP bonding. A full half-bridge inverter power module for low-power space applications has been designed and analyzed with extensive finite element thermomechanical modeling. In summary, TLP die-attach has investigated to confirm its reliability and to understand how to design effective TLP bonds, this information has been used to design a new high-temperature power electronic module.

Ce travail de thèse, de nature théorique, présente quatre axes de recherche portant sur la dynamique d'interfaces molles. (1) Gouttes et films de liquide sur substrats poreux : Nous avons étudié la déformation d'une goutte soumise simultanément à une aspiration de liquide et à un ancrage de sa ligne de contact avec le substrat. Nous nous sommes aussi intéressés au problème de l'entraînement d'un film de liquide sur une surface poreuse tirée hors d'un bain : le film a une hauteur finie, que nous avons calculée, et présente une structure non-triviale à l'approche de la ligne de contact. (2) Réticulation et interdiffusion à l'interface entre deux polymères : La formation de joints entre deux pièces de polymère nécessite une bonne interdiffusion des chaînes, qui peut cependant être considérablement contrariée lorsqu'un agent réticulant est introduit (dans le but de renforcer le matériau final). Nous avons modélisé la compétition qui s'installe, en montrant qu'il existait un paramètre de contrôle simple permettant d'optimiser le système et en donnant des prédictions sur l'énergie d'adhésion attendue dans deux régimes-limites. (3) Ecoulements granulaires : Nous donnons le scénario analytique complet du déroulement d'une avalanche sur un tas de sable, en tenant compte de l'effet d'un profil de vitesse linéaire dans la couche roulante. Parmi les prédictions, nous avons trouvé que l'épaisseur maximale devait varier comme la racine carrée de la taille de l'empilement. (4) Dynamique de films de savon verticaux : Les propositions actuelles concernant le mécanisme du drainage de ces films font appel à des instabilités hydrodynamiques se développant au bord du film ("régénération marginale"). Nous avons cherché à en déterminer précisément l'état précurseur : de manière générique, le profil forme une zone de striction, dont nous avons calculé analytiquement les dimensions typiques ; celle-ci pourrait rassembler les caractéristiques nécessaires à l'émergence des instabilités.

Metal silicon systems have a wide range of applications, ranging from the use in electronic industry, as superconductors, protective coatings and as high temperature structural materials. Mo- and Nb-based silicides have emerged as suitable high temperature materials and extensive studies are being conducted make it suitable for various applications. Because of very good strength to density ratio, Nb-based silicides have attracted maximum attention. This is basically a mixture of Nb solid solution and Nb5Si3 intermetallic compound. A very small amount of NbCr2 Laves phase could also be present because of Cr addition. Incorporation of other alloying elements, which are mainly partitioned to these phases, helps to achieve a property balance like, high temperature strength, high fracture toughness, high creep and oxidation resistance. The knowledge on diffusion parameters is useful to understand many physical and mechanical properties. In this thesis, diffusion couple technique is used in different temperature ranges to study the growth kinetics and diffusion of the phases in an interdiffusion zone in binary silicides, Nb/Si, Mo/Si and V/Si, binary solid solutions, Nb/Mo, Nb/Ti, Nb/Zr and ternary silicides, Nb-Mo/Si, Nb-Ti/Si, Nb-Zr/Si. The parabolic growth constant, the integrated diffusion coefficients and the tracer diffusion coefficients are calculated from the experimental results obtained in this study and also from the results already available in the literature on the binary silicides. The activation energy for growth kinetics and the diffusion coefficients are also calculated to gain knowledge on the diffusion mechanism. The atomic mechanism of the diffusing species in all the phases of Nb and Mo silicide are discussed with the help of crystal structure and possible defects present. Also, a detailed analysis is done on the growth mechanism of the phases in Nb/Si and Mo/Si systems. In the Nb/Si system, Si is found to have higher diffusion rate in both the NbSi2 and Nb5Si3 phases. The number of nearest neighbour Si bonds is higher than nearest neighbour Nb bonds and hence one may predict high concentration of Nb antisites to be present in the NbSi2 phase. The growth mechanism analysis following the physico chemical approach explains the absence of the Kirkendall plane in the Nb5Si3 phase and duplex morphology in the NbSi2 phase in the Nb/Si couple. In the Mo/Si system, Si diffusion is faster than Mo in all the three phases. In the MoSi2 phase, Mo is practically immobile due to the absence of vacancies on the Mo sublattice. Similar defect structure is expected in the Mo5Si3 and Mo3Si phases also with additional Si antisite defects to assist Si diffusion. The growth mechanism analysis explains the absence of the Kirkendall plane in the Mo5Si3 and Mo3Si phases and continuous columnar grains in the MoSi2 phase in the Mo/Si couple. In the V/Si system, the activation energy for integrated diffusion coefficient of the VSi2 phase is found to be reasonably lower than the other phases which could happen because of very high concentration of defects, and/or because of contribution from the grain boundary diffusion as it shows the presence of columnar grains. Problems associated with the analysis done in literature are also discussed. A diffusion study is performed in different temperature ranges for the three binary metallic solid solution systems to determine the interdiffusion coefficients over the entire composition range using the relation developed by Wagner. The change in activation energy for interdiffusion with composition is also determined. It is found that activation energy for interdiffusion in Nb/Mo system is much higher than that for Nb/Ti and Nb/Zr system. Further the impurity diffusion coefficients of the species are determined and compared with the available data in literature. It is found that the activation energy for the impurity diffusion of Nb in Ti, Zr and Mo is higher than that of Ti, Zr and Mo in Nb. Interdiffusion study is done in the ternary silicides with the aim to examine the role of alloying additions, such as, Ti, Mo and Zr on the growth kinetics and diffusion behaviour of the phases in the Nb/Si system. The average interdiffusion (or integrated) coefficients are calculated when possible. The reaction and dissociation of the species at the interfaces are considered to understand the growth mechanism of the phases. An attempt is made to understand the change in diffusion mechanism because of the presence of third element. It is found that none of the alloying elements participate in the diffusion process although they do alter the growth kinetics and diffusion rate in both the phases, NbSi2 and Nb5Si3. It is also found that Nb becomes immobile in the NbSi2 phase in the presence of the alloying elements. Mo reduces the growth of both the phases while Ti addition does not cause any change in the growth but affects the diffusivity. Zr addition also reduces growth of the Nb5Si3 phase. It however complicates the interdiffusion zone in the Nb(Zr)/Si couple, which limits to qualitative study only. The Growth and consumption rate of the end members become very significant in many practical applications. Hence, relations for the growth and consumption rate in systems with finite end member thickness is developed considering single and double phase layer in the interdiffusion zone. Two different methodologies are used, the diffusion based and the physico-chemical approach to develop the same relations. We have shown that the diffusion based approach is rather straightforward; however, the physico-chemical approach is much more versatile than the other method. It is found that the position of the marker plane becomes vague in the second stage of the interdiffusion process in such a system, where two phases grow simultaneously.

Within this work, bonding technologies based upon the alloying of gallium with other metals to assemble semiconductor substrates for the possible application of encapsulation and 3D-integration of micro systems and devices have been researched. Motivated by the important demand to achieve low temperature processes, methods with bonding temperatures below 200°C were investigated. Necessary technologies like the deposition of gallium as thin film and subsequent micro structuring have been developed. The alloying between gallium and gold as well as gallium and copper was analysed in detail. A good correlation between the elemental composition of the interface and its mechanical and electrical parameters was established, particularly regarding its thermal dependence. It emerged that in case of combination Au/Ga Kirkendall void are extensively formed whereby serious problems with mechanical strength as well as hermeticity emerged. In case of Cu/Ga, this problem is existent to a much lesser degree; it was possible to create hermetic tight bonds. For the necessary pre-treatment of copper, several methods could be successfully demonstrated. In summary, the development of bonding technologies based upon metallic interfaces that exhibit electric conductance, high strength and hermetic seal could be demonstrated. / In dieser Arbeit werden Bondverfahren zum Fügen von Halbleitersubstraten für mögliche Anwendungen für die Verkapselung und 3D-Integration von Bauelementen der Mikrosystemtechnik erforscht, die auf der Legierungsbildung von Gallium mit anderen Metallen beruhen. Motiviert von der zentralen Anforderung an niedrige Prozesstemperaturen wurden Methoden mit Fügetemperaturen deutlich unter 200°C untersucht. Dafür nötige Technologien zum Abscheiden von Gallium als Dünnschicht und das anschließende Mikrostrukturieren wurden entwickelt. Die Legierungsbildung zwischen Gallium und Gold sowie zwischen Gallium und Kupfer wurde im experimentell im Detail analysiert. Dabei konnte eine gute Korrelation zwischen der stofflichen Zusammensetzung und den mechanischen bzw. elektrischen Parametern der Zwischenschicht, auch und insbesondere hinsichtlich ihrer Temperaturabhängigkeit gefunden werden. Es stellte sich heraus, dass im Falle der Kombination Au/Ga Kirkendall Hohlräume in einer Menge entstehen, die zu erheblichen Problemen bezüglich mechanischer Festigkeit und Dichtheit der Fügeverbindung führen. Bei der Materialkombination Cu/Ga hingegen trat dieses Problem nur begrenzt auf; es war möglich hermetisch dichte Verbindungen herzustellen. Für die bei Kupfer nötige Vorbehandlung wurden mehrere Methoden erfolgreich getestet. Insgesamt konnte die Entwicklung von Fügetechnologien gezeigt werden, die metallische Zwischenschichten verwenden, elektrisch leitfähig sind, sehr gute Festigkeiten aufweisen und hermetisch dicht sind.

Magnesium alloys are being developed as advanced materials for structural applications where reduced weight is a primary motivator. Alloying can enhance the properties of magnesium without significantly affecting its density. Essential to alloy development, inclusive of processing parameters, is knowledge of thermodynamic, kinetic, and mechanical behavior of the alloy and its constituents. Appreciable progress has been made through conventional development processes, but to accelerate development of suitable wrought Mg alloys, an integrated Materials Genomic approach must be taken where thermodynamics and diffusion kinetic parameters form the basis of alloy design, process development, and properties-driven applications. The objective of this research effort is twofold: first, to codify the relationship between diffusion behavior, crystal structure, and mechanical properties; second, to provide fundamental data for the purpose of wrought Mg alloy development. Together, the principal deliverable of this work is an advanced understanding of Mg systems. To that end, the objective is accomplished through an aggregate of studies. The solid-to-solid diffusion bonding technique is used to fabricate combinatorial samples of Mg-Al-Zn ternary and Mg-Al, Mg-Zn, Mg-Y, Mg-Gd, and Mg-Nd binary systems. The combinatorial samples are subjected to structural and compositional characterization via Scanning Electron Microscopy with X-ray Energy Dispersive Spectroscopy, Electron Probe Microanalysis, and analytical Transmission Electron Microscopy. Interdiffusion in binary Mg systems is determined by Sauer-Freise and Boltzmann-Matano methods. Kirkaldy*s extension of the Boltzmann-Matano method, on the basis of Onsager*s formalism, is employed to quantify the main- and cross-interdiffusion coefficients in ternary Mg solid solutions. Impurity diffusion coefficients are determined by way of the Hall method. The intermetallic compounds and solid solutions formed during diffusion bonding of the combinatorial samples are subjected to nanoindentation tests, and the nominal and compositionally dependent mechanical properties are extracted by the Oliver-Pharr method. In addition to bolstering the scantly available experimental data and first-principles computations, this work delivers several original contributions to the state of Mg alloy knowledge. The influence of Zn concentration on Al impurity diffusion in binary Mg(Zn) solid solution is quantified to impact both the pre-exponential factor and activation energy. The main- and cross-interdiffusion coefficients in the ternary Mg solid solution of Mg-Al-Zn are reported wherein the interdiffusion of Zn is shown to strongly influence the interdiffusion of Mg and Al. A critical examination of rare earth element additions to Mg is reported, and a new phase in thermodynamic equilibrium with Mg-solid solution is identified in the Mg-Gd binary system. It is also demonstrated that Mg atoms move faster than Y atoms. For the first time the mechanical properties of intermetallic compounds in several binary Mg systems are quantified in terms of hardness and elastic modulus, and the influence of solute concentration on solid solution strengthening in binary Mg alloys is reported. The most significant and efficient solid solution strengthening is achieved by alloying Mg with Gd. The Mg-Nd and Mg-Gd intermetallic compounds exhibited better room temperature creep resistance than intermetallic compounds of Mg-Al. The correlation between the concentration dependence of mechanical properties and atomic diffusion is deliberated in terms of electronic nature of the atomic structure.