Miniaturiser les composants impose des changements radicaux pour l'élaboration des dispositifs micro électroniques du futur. Dans ce cadre, les oxydes de grille MOS atteignent des épaisseurs limites qui les rendent perméables aux courants de fuite. Une solution est de remplacer le SiO2 par un matériau de permittivité plus élevée permettant l'utilisation de couches plus épaisses pour des performances comparables. Dans ce travail nous présentons une modélisation multi-échelle de la croissance par couche atomique (ALD) d'HfO2 sur Si permettant de relier la nano-structuration d'une interface au procédé d'élaboration. Nous montrons que la connaissance de processus chimiques élémentaires, via des calculs DFT, permet d'envisager une simulation procédé qui repose sur le développement d'un logiciel de type Monte Carlo Cinétique nommé "HIKAD". Au delà des mécanismes les plus évidents, adsorption, désorption, décomposition et hydrolyse des précurseurs sur la surface, nous introduirons la notion de mécanismes de densification des couches d'oxyde déposées. Ces mécanismes sont l'élément clé permettant de comprendre comment s'effectue la croissance de la couche en termes de couverture. Mais au delà de cet aspect ils nous permettent d'appréhender comment, à partir de réactions de type moléculaire le système évolue vers un matériau massif. Nous discuterons ces divers éléments à la lumière de résultats de caractérisations obtenus récemment sur le plan expérimental du dépôt d'oxydes d'hafnium.

<p>Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy.</p><p>This thesis describes atomic layer deposition of Ta₂O₅, HfO₂ and SnO₂ thin films and chemical vapour deposition of SnO₂ thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined.</p><p>The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.</p>

<p>Materials prepared on the nanoscale often exhibit many different properties compared to the same materials in their bulk-state. Interest in nanostructured materials has increased because of these properties in fields such as microelectronics, catalysis, optics and sensors. This increased interest in nanostructured materials calls for new and more precise fabrication techniques.</p><p>This thesis describes how to use the porous anodic aluminium oxide as a template for the fabrication of a variety of nanostructured materials. Palladium and copper nanoparticles were deposited along the pore walls in anodic aluminum oxide using electroless deposition and atomic layer deposition. In both cases, it was possible to control the size of the nanoparticles by carefully monitoring the deposition parameters. The thesis also describes how Prussian blue nanoparticles and nanotubes can be fabricated using the anodic aluminium oxide as a template. The deposition of Prussian blue was performed by a sequential wet-chemical method. By using atomic layer deposition, it was also possible to deposit thin films of amorphous Nb2O5 on the pore walls. When the template was removed by etching, freestanding nanotubes were obtained. The anodic aluminium oxide membrane was also used as a mask for high energy (MeV) ion irradiation of an underlying substrate. The tracks produced were etched away with hydrogen fluoride. In this way, it was possible to transfer the highly ordered porous pattern from the mask onto other oxides such as SiO2 and TiO2.</p><p>All fabricated structures were characterized using a variety of analysis techniques: scanning electron microscopy for evaluating sample morphology; transmission electron microscopy for better resolved investigations of the morphology; X-ray diffraction to assess crystallinity; energy dispersive spectroscopy and X-ray fluorescence spectroscopy to determine the elemental composition and identify possible contaminants.</p><p>The general aim of the work described in this thesis has been to create a set of tools for use in the fabrication of a variety of nanostructured materials, whose dimensions composition can be tailored by selecting appropriate fabrication methods and parameters.</p>

The continuous and aggressive dimensional miniaturization ofthe conventional complementary-metal-oxide semiconductor (CMOS)architecture has been the main impetus for the vast growth ofIC industry over the past decades. As the CMOS downscalingapproaches the fundamental limits, unconventional materials andnovel device architectures are required in order to guaranteethe ultimate scaling in device dimensions and maintain theperformance gain expected from the scaling. This thesisinvestigates both unconventional materials for the gate stackand the channel and a novel notched-gate device architecture,with the emphasis on the challenging issues in processintegration. High-κ gate dielectrics will become indispensable forCMOS technology beyond the 65-nm technology node in order toachieve a small equivalent oxide thickness (EOT) whilemaintaining a low gate leakage current. HfO2and Al2O3as well as their mixtures are investigated assubstitutes for the traditionally used SiO2in our MOS transistors. These high-κ filmsare deposited by means of atomic layer deposition (ALD) for anexcellent control of film composition, thickness, uniformityand conformality. Surface treatments prior to ALD are found tohave a crucial influence on the growth of the high-κdielectrics and the performance of the resultant transistors.Alternative gate materials such as TiN and poly-SiGe are alsostudied. The challenging issues encountered in processintegration of the TiN or poly-SiGe with the high-k are furtherelaborated. Transistors with TiN or poly-SiGe/high-k gate stackare successfully fabricated and characterized. Furthermore,proof-of-concept strained-SiGe surface-channel pMOSFETs withALD high-κ dielectrics are demonstrated. The pMOSFETs witha strained SiGe channel exhibit a higher hole mobility than theuniversal hole mobility in Si. A new procedure for extractionof carrier mobility in the presence of a high density ofinterface states found in MOSFETs with high-κ dielectricsis developed. A notched-gate architecture aiming at reducing the parasiticcapacitance of a MOSFET is studied. The notched gate is usuallyreferred to as a local thickness increase of the gatedielectric at the feet of the gate above the source/drainextensions. Two-dimensional simulations are carried out toinvestigate the influence of the notched gate on the static anddynamic characteristics of MOSFETs. MOSFETs with optimizednotch profile exhibit a substantial enhancement in the dynamiccharacteristics with a negligible effect on the staticcharacteristics. Notched-gate MOSFETs are also experimentallyimplemented with the integration of a high-κ gatedielectric and a poly-SiGe/TiN bi-layer gate electrode. Key words:CMOS technology, MOSFET, high-κ, gatedielectric, ALD, surface pre-treatment, metal gate, poly-SiGe,strained SiGe, surface-channel, buried-channel, notchedgate.

Materials prepared on the nanoscale often exhibit many different properties compared to the same materials in their bulk-state. Interest in nanostructured materials has increased because of these properties in fields such as microelectronics, catalysis, optics and sensors. This increased interest in nanostructured materials calls for new and more precise fabrication techniques. This thesis describes how to use the porous anodic aluminium oxide as a template for the fabrication of a variety of nanostructured materials. Palladium and copper nanoparticles were deposited along the pore walls in anodic aluminum oxide using electroless deposition and atomic layer deposition. In both cases, it was possible to control the size of the nanoparticles by carefully monitoring the deposition parameters. The thesis also describes how Prussian blue nanoparticles and nanotubes can be fabricated using the anodic aluminium oxide as a template. The deposition of Prussian blue was performed by a sequential wet-chemical method. By using atomic layer deposition, it was also possible to deposit thin films of amorphous Nb2O5 on the pore walls. When the template was removed by etching, freestanding nanotubes were obtained. The anodic aluminium oxide membrane was also used as a mask for high energy (MeV) ion irradiation of an underlying substrate. The tracks produced were etched away with hydrogen fluoride. In this way, it was possible to transfer the highly ordered porous pattern from the mask onto other oxides such as SiO2 and TiO2. All fabricated structures were characterized using a variety of analysis techniques: scanning electron microscopy for evaluating sample morphology; transmission electron microscopy for better resolved investigations of the morphology; X-ray diffraction to assess crystallinity; energy dispersive spectroscopy and X-ray fluorescence spectroscopy to determine the elemental composition and identify possible contaminants. The general aim of the work described in this thesis has been to create a set of tools for use in the fabrication of a variety of nanostructured materials, whose dimensions composition can be tailored by selecting appropriate fabrication methods and parameters.

Most electrical, magnetic or optical devices are today based on several, usually extremely thin layers of different materials.  In this thesis chemical synthesis processes have been developed for growth of less stable and metastable layers, and even multilayers, of nickel containing compounds. A chemical vapor deposition (CVD) method for deposition of metastable Ni3N has been developed.  The deposition process employs ammonia as nitrogen precursor. An atomic layer deposition (ALD) process for deposition of both polycrystalline and epitaxial NiO and using low oxygen activity, has also been developed. Both deposition processes utilizes bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (Ni(thd)2) as the metal precursor. The Ni3N deposition proceeds via surface reactions. The growth rate is very sensitive to the partial pressure of ammonia, why adsorbed –NHx species are believed to be of importance for the film growth. Similar reactions can be expected between the metal precursor and H2O. For ALD of NiO a large excess of water was needed For the multilayered structures of Ni3N/NiO, growth processes, working at low activities of oxygen and hydrogen, are needed to avoid oxidation or reduction of the underlying layer. Chemical vapor growth methods such as CVD and ALD are often suffering from using high activities of hydrogen or oxygen to deposit metals and oxides. An alternative deposition pathway for metal deposition, without any hydrogen in the vapor, has been demonstrated. The metal has been formed by decomposition of the metastable nitride Ni3N in a post-annealing process.  Ni3N decomposes via different mechanisms, depending on environment in the annealing process. The different mechanisms result in different degrees of ordering in the resulting Ni films. From the knowledge gained about the chemical growth of NiO and Ni3N as well as the decomposition of Ni3N, well-defined multilayer structures have been produced in different combinations of NiO, Ni3N and Ni.

Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy. This thesis describes atomic layer deposition of Ta2O5, HfO2 and SnO2 thin films and chemical vapour deposition of SnO2 thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined. The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.

The objective of the research was to develop high quality GaN epitaxial growth on alternative substrates that could result in higher external quantum efficiency devices. Typical GaN growth on sapphire results in high defect materials, typically 10⁸⁻¹⁰cm⁻², due to a large difference in lattice mismatch and thermal expansion coefficient. Therefore, it is useful to study epitaxial growth on alternative substrates to sapphire such as ZnO which offers the possibility of lattice matched growth. High-quality metalorganic chemical vapor deposition (MOCVD) of GaN on ZnO substrate is hard to grow due to the thermal stability of ZnO, out-diffusion of Zn, and H₂back etching into the sample. Preliminary growths of GaN on bare ZnO substrates showed multiple cracks and peeling of the surface. A multi-buffer layer of LT-AlN/GaN was found to solve the cracking and peeling-off issues and demonstrated the first successful GaN growth on ZnO substrates. Good quality InGaN films were also grown showing indium compositions of 17-27% with no indium droplets or phase separation. ZnO was found to to sustain a higher strain state than sapphire, and thereby incorporating higher indium concentrations, as high as 43%, without phase separation, compared to the same growth on sapphire with only 32%. Si doping of InGaN layers, a known inducer for phase separation, did induce phase separation on sapphire growths, but not for growths on ZnO. This higher strain state for ZnO substrates was correlated to its perfect lattice match with InGaN at 18% indium concentration. Transmission electron microscopy results revealed reduction of threading dislocation and perfectly matched crystals at the GaN buffer/ZnO interface showing coherent growth of GaN on ZnO. However, Zn diffusion into the epilayer was an issue. Therefore, an atomic layer deposition of Al₂O₃was grown as a transition layer prior to GaN and InGaN growth by MOCVD. X-ray and PL showed distinct GaN peaks on Al₂O₃/ZnO layers demonstrating the first GaN films grown on Al₂O₃/ZnO. X-ray photoelectron spectroscopy showed a decrese in Zn diffusion into the epilayer, demonstrating that an ALD Al₂O₃layer was a promising transition layer for GaN growth on ZnO substrates by MOCVD.

Thin films and coatings of oxides are used in various fields of science and technology, such as semiconductor and optoelectronic devices, gas sensors, protective and wear resistant coatings etc. Of late, there has been a tremendous interest in pure and doped vanadium dioxide as thermoelectric switch material. VO2 has been doped with hetero-atoms such as W, Mo, Nb, Ti etc. and effects of doping have been correlated with feasibility of being used as a smart window material. The oxide Al2O3 has been studied as an alternative gate dielectric. Ga2O3 is also a contender for replacing SiO2 as a dielectric material. Atomic layer deposition (ALD) is a technique for the deposition of thin films of various materials and is found to be of considerable scientific and technological importance. In particular, using β-diketonate complexes as precursors is very useful in preparing thin films of oxides, as these precursors already contain a metal-oxygen bond. In this thesis, β-diketonate complexes have been used as precursors for deposition of thin films. The thesis has been divided into two parts: First part deals with deposition and characterization of thin films of VO2 on glass and fused quartz. The second part deals with synthesis and chemical and thermal characterization of bimetallic Al-Ga acetylacetonates along with thin film deposition using the same. Chapter 1 presents a brief introduction to application of thin films of oxides in various fields of science and technology. A brief introduction to the ALD reactor used for the current work is also presented. The importance of thermal analysis of precursors for CVD is briefly reviewed. Chapter 2 deals with the instruments and methods used for the work done for this thesis. In Chapters 3 and 4 of the thesis, a detailed study of deposition of VO2 films on glass and fused quartz has been presented. The films deposited have been analyzed using a host of techniques, for their texture, microstructure and electrical properties. In spite of chemical similarities, considerable differences in structure and properties have been observed between the films deposited on the two substrates. These differences have been explained on the basis of the small chemical differences between the two substrates. Chapters 5, 6 and 7 deal with synthesis, thermal characterization and use of bimetallic Al-Ga precursors, respectively. The bimetallic acetylacetonates have been synthesized using ‘homogenization in solution’ approach. Chemical characterization of the precursors revealed that nominal percentages of Al and Ga are retained in the solid precursors. Single crystal structure confirmed the observation. Thermal analysis of the precursors showed that the precursors, which are solid solutions of Al and Ga acetylacetonates, show negative deviation from the Raoult’s Law. Films were deposited using these precursors and were found to near completely retain the composition of the precursors. Chapter 8 of the thesis presents the conclusions of the current work and proposes future directions.

<p>The continuous and aggressive dimensional miniaturization ofthe conventional complementary-metal-oxide semiconductor (CMOS)architecture has been the main impetus for the vast growth ofIC industry over the past decades. As the CMOS downscalingapproaches the fundamental limits, unconventional materials andnovel device architectures are required in order to guaranteethe ultimate scaling in device dimensions and maintain theperformance gain expected from the scaling. This thesisinvestigates both unconventional materials for the gate stackand the channel and a novel notched-gate device architecture,with the emphasis on the challenging issues in processintegration.</p><p>High-κ gate dielectrics will become indispensable forCMOS technology beyond the 65-nm technology node in order toachieve a small equivalent oxide thickness (EOT) whilemaintaining a low gate leakage current. HfO₂and Al₂O₃as well as their mixtures are investigated assubstitutes for the traditionally used SiO₂in our MOS transistors. These high-κ filmsare deposited by means of atomic layer deposition (ALD) for anexcellent control of film composition, thickness, uniformityand conformality. Surface treatments prior to ALD are found tohave a crucial influence on the growth of the high-κdielectrics and the performance of the resultant transistors.Alternative gate materials such as TiN and poly-SiGe are alsostudied. The challenging issues encountered in processintegration of the TiN or poly-SiGe with the high-k are furtherelaborated. Transistors with TiN or poly-SiGe/high-k gate stackare successfully fabricated and characterized. Furthermore,proof-of-concept strained-SiGe surface-channel pMOSFETs withALD high-κ dielectrics are demonstrated. The pMOSFETs witha strained SiGe channel exhibit a higher hole mobility than theuniversal hole mobility in Si. A new procedure for extractionof carrier mobility in the presence of a high density ofinterface states found in MOSFETs with high-κ dielectricsis developed.</p><p>A notched-gate architecture aiming at reducing the parasiticcapacitance of a MOSFET is studied. The notched gate is usuallyreferred to as a local thickness increase of the gatedielectric at the feet of the gate above the source/drainextensions. Two-dimensional simulations are carried out toinvestigate the influence of the notched gate on the static anddynamic characteristics of MOSFETs. MOSFETs with optimizednotch profile exhibit a substantial enhancement in the dynamiccharacteristics with a negligible effect on the staticcharacteristics. Notched-gate MOSFETs are also experimentallyimplemented with the integration of a high-κ gatedielectric and a poly-SiGe/TiN bi-layer gate electrode.</p><p><b>Key words:</b>CMOS technology, MOSFET, high-κ, gatedielectric, ALD, surface pre-treatment, metal gate, poly-SiGe,strained SiGe, surface-channel, buried-channel, notchedgate.</p>