Dissertations / Theses on the topic 'Hafnium oxide layers'

Cette thèse explore les propriétés ferroélectriques des films minces à base de HfO₂, en vue de leurs utilisations dans les mémoires à accès aléatoire ferroélectrique (FeRAM). Cette thèse met en avant l'intérêt croissant pour l'oxyde d'hafnium (HfO₂) en raison de sa compatibilité avec la technologie CMOS et de son potentiel pour des dispositifs ferroélectriques à échelle ultra-réduite. La recherche conduite a permis l’étude des films minces de HfO₂ dopés au Gd ou non dopés, déposés par dépôt de couches atomiques assisté par plasma (PEALD) dans une structure métal-isolant-métal (MIM) (TiN/HfO₂/TiN). Plus précisément, il s’est agi d’étudier les propriétés structurales, électriques et d'endurance.Plus précisément, ce travail a permis l’étude des films de HfO₂ dopés au Gd de moins de 10 nm, déposés par PEALD avec un pourcentage de dopage de 1,8 % et recuits à 650 °C dans une atmosphère de N₂. Ces films ont démontré de fortes propriétés ferroélectriques même à des dimensions ultra-fines, confirmées par des mesures de diffraction des rayons X et des mesures électriques, révélant un comportement ferroélectrique. La phase orthorhombique, cruciale pour la ferroélectricité, a été stabilisée à ce niveau de dopage, tandis que la phase monoclinique, non ferroélectrique, a été supprimée. À mesure que l'épaisseur des films augmentait de 4,4 nm à 8,8 nm, la phase orthorhombique se développait et les valeurs de polarisation augmentaient en conséquence. Le champ coercitif est resté autour de 2 MV/cm². Cependant, les films de moins de 4 nm se sont révélés non ferroélectriques, ce qui a été attribué à la présence d'une phase non ferroélectrique proche de la couche interfaciale. Par ailleurs, les films de HfO₂ dopés au Gd ont montré une excellente endurance, de l’ordre de 10¹⁰ cycles de commutation sans fatigue.Pour mieux comprendre l’origine de la stabilization de la phase orthorhombique (ferroélectrique) du HfO2, une comparaison entre des films de HfO2 dopé et de HfO2 non-dopé a été réalisée. Bien que le HfO₂ non dopé ait présenté un comportement ferroélectrique dans des films de moins de 14 nm, avec des niveaux de polarisation comparables à ceux du HfO₂ dopés au Gd pour une épaisseur inférieure à 7 nm, le dopage au Gd a montré de meilleures performances dans les films de plus de 7 nm. Le dopage au Gd a non seulement amélioré la polarisation, mais a également introduit un effet de "réveil" prononcé lors des cycles. Dans le HfO₂ non dopé, nous avons montré que le stress mécanique provenant des électrodes TiN était suffisant pour induire la ferroélectricité, tandis que le dopage au Gd stabilisait la phase ferroélectrique orthorhombique même en l'absence d'électrodes. Bien que le HfO₂ non dopé soit plus adapté aux couches ultra-fines en raison de son procédé de fabrication plus simple, le HfO₂ dopé au Gd offre de meilleures performances dans des films plus épais et des applications nécessitant une plus grande endurance.Une analyse supplémentaire a exploré les effets des températures de recuit et de l'épaisseur de HfO₂ sur les propriétés ferroélectriques, afin d'assurer la compatibilité de ces dispositifs avec les systèmes CMOS. L’étude a montré que le dopage au Gd permet d’abaisser la température de cristallisation de la phase orthorhombique, entraînant la formation de la ferroélectricité à des températures aussi basses que 450 °C, par rapport aux films non dopés qui nécessitaient des températures supérieures à 550 °C. Parallèlement, l'augmentation de l'épaisseur de HfO₂ a également favorisé la cristallisation ferroélectrique à des températures plus basses dans les deux cas
This thesis explores the ferroelectric properties of HfO₂-based thin films in view to their potential applications in ferroelectric random access memory (FeRAM). It highlights the growing interest in hafnium oxide (HfO₂) due to its compatibility with CMOS technology and potential for ultra-scaled ferroelectric devices. The research investigates both Gd-doped and undoped HfO₂ thin films deposited by plasma-enhanced atomic layer deposition (PEALD) in a metal-insulator-metal (MIM) structure (TiN/HfO2/TiN), evaluating their structural, electrical, and endurance properties. This work investigates the properties of sub-10 nm Gd-doped HfO₂ films deposited via PEALD with 1.8% doping and annealed at 650°C in an N₂ atmosphere. The films demonstrated strong ferroelectric properties even at ultra-thin dimensions, confirmed by X-ray diffraction and electrical measurements, revealing a clear polarization hysteresis behavior. The orthorhombic phase, crucial for ferroelectricity, was stabilized at this doping level, while the non-ferroelectric monoclinic phase was suppressed. As film thickness increased from 4.4 nm to 8.8 nm, the orthorhombic phase grew, and polarization values increased accordingly. The coercive field remained constant around 2 MV/cm². However, films thinner than 4 nm were found to be non-ferroelectric, which was attributed to the presence of a non-ferroelectric phase close to the interfacial layer. Despite this, Gd-doped HfO₂ films showed excellent endurance, withstanding 10¹⁰ switching cycles without fatigue and switching polarization at low voltages (as low as 0.9 V).To gain deeper insights into the origin of orthorhombic (ferroelectric) phase stabilization Gd-doping in stabilizing the ferroelectric phase, a comparison between Gd-doped HfO2 and undoped HfO₂, processed under the same conditions, was conducted. While undoped HfO₂ exhibited ferroelectric behavior in films under 14 nm, with polarization levels comparable to Gd-doped HfO₂ below a 7 nm thickness, Gd-doping showed superior performance in films thicker than 7 nm. Gd-doping not only enhanced polarization but also introduced a pronounced wake-up effect with cycling. In undoped HfO₂, mechanical stress from TiN electrodes was sufficient to induce ferroelectricity, whereas Gd-doping stabilized the orthorhombic ferroelectric phase even in the absence of electrodes. Although undoped HfO₂ is more suitable for ultra-thin layers due to its simpler fabrication process, Gd-doped HfO₂ offers better performance in thicker films and applications requiring greater polarization.Further analysis explored the effects of annealing temperatures and HfO₂ thickness on the ferroelectric properties, to study the compatibility of these devices with CMOS systems. Gd-doping significantly lowered the crystallization temperature for the orthorhombic phase, enabling ferroelectricity to form at temperatures as low as 450°C, compared to undoped films requiring temperatures above 550°C. In parallel, increasing the HfO₂ thickness further promoted ferroelectric crystallization at lower temperatures in both cases

In 2007 there was an important change in the architecture of nanotransistors - the building blocks of modern logic and memory devices. This change was from utilising thermally grown silicon dioxide as a dielectric to so-called high-κ hafnium oxide dielectrics grown by atomic layer deposition. The first production logic devices of this era used a hafnium oxide dielectric layer deposited by thermal atomic layer deposition; using HfCl₄ and H₂O as the precursors. Present day fabrication makes use of hafnium oxide-based atomic-layer-deposited dielectric films. The latest nanotransistor devices utilise a third generation hafnium oxide-based dielectric material. This thesis examines hafnium oxide-based thin film dielectric materials prepared by thermal atomic layer deposition on silicon substrates. Specifically the enhancement of the dielectric response of hafnium oxide by the addition of other elements is examined. Two ternary materials systems were deposited by thermal atomic layer deposition and analysed: titanium-hafnium oxide and cerium-hafnium oxide. Hafnium oxide films were deposited to be used as measurement benchmarks. Cerium oxide films were also deposited and analysed in their own right as potential dielectric layers. The hafnium oxide and both ternary deposition experiments used (MeCp)₂Hf(OMe)(Me) as the hafnium precursor. The titanium-hafnium oxide growth used Ti(ⁱOPr)₄ as a titanium source and the cerium oxide and cerium-hafnium oxide work utilised Ce(mmp)₄ as a cerium source. Post-deposition specimen sets consisted of an as-deposited sample, a sample spike-annealed in N₂ at 850°C and a sample annealed for 30 minutes at 500°C. These annealing regimes were performed to mimic typical gate-first and gate-last transistor processing steps. The compositions and thicknesses of the films were measured using medium energy ion scattering. The structure of the films was analysed by X-ray diffraction and Raman spectroscopy. Capacitance-voltage and current density-field measurements were taken from fabricated MOS capacitor specimens to assess the dielectric response of the films. X-ray diffraction and Raman measurements showed that un-doped HfO₂ had monoclinic crystallinity as-deposited and after the two annealing regimes. The dielectric constant and leakage current density, 17 and 1.7x10⁻⁷ A/cm² at -1 MV/cm respectively, are consistent with values reported in the literature for HfO₂ films. The addition of titanium suppressed the crystallinity of the material resulting in amorphous films in compositions with Ti₀_.₃Hf₀_.₇O₂ titanium and above. The optimum electrical results were recorded for the titanium-hafnium oxide material in the composition Ti₀_.₅Hf₀_.₅O₂ which had a dielectric constant of 35 as-deposited and a leakage current density of 1.0x10⁻⁷ A/cm² at -1 MV/cm. This composition of film demonstrated similar values after the 500°C/30 min anneal but both dielectric constant and leakage current density suffered after the 850°C/spike anneal; 22 and 1.8x10⁻⁶ A/cm² at -1 MV/cm respectively. Films with compositions of Ti₀_.₁Hf₀_.₉O₂ demonstrated much lower dielectric constant and higher leakage current density, especially after heat treatment. The addition of cerium in a Ce₀_.₁₁Hf⁰_.₈₉O₂ composition was found to suppress crystallinity as-deposited and then provoke a lattice-substitutional phase change to the metastable tetragonal/cubic phase after both types of heat treatment. This ceriumactivated phase change resulted in a molar volume modulation compared to un-doped HfO₂. An increased dielectric constant compared to un-doped HfO₂ of 31 was recorded for the 500 °C/30 min anneal with the 850°C/spike anneal resulting in a lower value of 21. Leakage current density was 1.3x10⁻⁷ A/cm² and 3.2x10⁻⁷ A/cm² at -1 MV/cm respectively for the same anneals. Deposition with Ce(mmp)₄ and water was found to result in cubic crystalline films across a growth temperature range 150-350 °C. The frequency dependency of the dielectric properties was found to be influenced by the crystallite size which was governed by the deposition temperature. The highest dielectric constant, 42, was measured for the 150 °C growth temperature with C-V measurements performed at 1 MHz. The two doped HfO₂-based materials systems studied have demonstrated potential as dielectric materials for use in future nanoelectronic devices.

The unprecedented ability of plasmonic metal nano-structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavors. They are used in sensing, super-resolution imaging, SPP lithography, SPP assisted absorption, SPP-based antennas, light manipulation, etc. To take full advantage of the attractive capabilities of CMOS compatible low-cost plasmonic structures based on Al and Cu, nanolaminate coatings are investigated to improve their long-term stability in corrosive physiological environments. The structures are fabricated using phase-shifting PDMS masks, e-beam deposition, RIE, Atomic Layer Deposition and Rapid Thermal Annealing. An alternate approach using Nanosphere Lithography (NSL) was also investigated. Films were examined using ellipsometry, atomic force microscopy and transmission measurements. Accelerated in-situ tests of Hafnium Oxide/Aluminum Oxide nanolaminate shells in a mildly pH environment with temperatures akin to physiological environments emulated using PBS show greatly enhanced endurance, with stable structures that last for more than one year.
Master of Science

L'objectif de ce travail est d'apporter un éclairage nouveau à la compréhension des mécanismes physico-chimiques qui contrôlent la croissance des trois oxydes d'Aluminium, de Zirconium, de Hafnium. Ces matériaux sont considérés comme les meilleurs candidats pour remplacer la silice en tant qu'oxyde de grille dans le futur composant MOS. La précision et la fiabilité de la méthode DFT associé à la fonctionnelle B3LYP, ont été testées à l'aide des résultats expérimentaux et des méthodes ab initio les plus précis telles que CCSD(T) et CISD(T), en utilisant différents ensembles des fonctions de bases. Nos résultats montrent que et la méthode hybride DFT peut prédire de façon précise les propriétés statistiques et dynamiques de la famille d'organométalliques (AlxCyHzOt) et des systèmes moléculaires à base de métaux de transition (Zr/HfxClyOzHt). Les premières études systématiques des surfaces d'énergie potentielle de TMA ont été présentes et les caractéristiques des rotors constitués des groups méthyles ont été rapportées avec une grande précision. Les mécanismes réactionnels, à plusieurs étapes, entre les molécules précurseurs de trois oxydes et les molécules d'eau résiduelle phase gazeuse ont été étudies en détail. Les mouvements internes fortement anharmoniques, des espèces moléculaires présentes touts au long du processus d'hydrolyse ont été déterminés. Les effets qualitatifs sur les cinétiques des réactions ont été discutés. La forte exothermicité de la réaction TMA/H2O a été démontrée, alors que la réaction avec les tétrachlorures de Zirconium et Hafnium ont montré un caractère plutôt endothermique. Nous avons aussi étudié les mécanismes réactionnels de la vapeur d'eau avec d'espèces moléculaires chimisorbés en surface. Les réactions interviennent dans les cycles initiales d'ALD sur en substrat de Si(001)-2x1 légèrement oxydé. Les mécanismes que nous proposons sont qualitativement proches des mécanismes d'hydrolyse discutés dans la phase gaz euse : confirmation de la forte réactivité exothermique avec les hydroxyméthyliques d'Aluminium, endothermicité des réactions avec hydroxychlorures de Zirconium et Hafnium. Les composés avec le Zirconium et le Hafnium ont des comportements similaires. Enfin, les effets de coopérativité, à la fois au niveau des molécules de vapeur d'eau, qu'au niveau des complexes en surface, sur les réactions ont été mis en évidence et discutés. Ils montrent des comportements tout à fait intéressants dans le cas des hydroxychlorures des Zirconium et Hafnium. Par contre, ces effets sont de moindre importance dans les cas de l'oxyde d'aluminium, qui est actuellement considéré comme le matériau le plus compatible avec la croissance par ALD
This work attempts to bring a new light on the understanding of some critical aspects of the physicochemical processes that control Alumina, Zirconia and Hafnia ALD growth, yet not sufficiently understood. These materials are addressed as potentially best candidates to replace gate dielectric SiO2 in the near future electronic applications. Most accurate ab initio correlated methods, like couple-cluster CCSD(T) and CISD(T), with different basis sets functions, as well as the available experimental data have been used for testing by a systematic study the accuracy and the reliability of DFT B3LYP functional. Our results have claimed this hybrid-DFT method to be chosen in predicting of high accurate static and dynamic properties throughout the family of organometallic-like (AlxCyHzOt) and transition metal-based (Zr/HfxClyOzHt) molecular systems. First systematic study of torsional potential surfaces of TMA has been performed and the related features of the hindered rotors of the methyl groups revealed with high accuracy. Laying on these accurate results we have also proposed least-squared fit methods to determine frequency scaling factors subject to different thermodynamic properties and/or thermal conditions. Many-step reaction mechanisms of ALD gas phase precursors of each of the three oxides with residual water, or regime of low pressure H2OÓALD pulses, have been studied in detail. Strong anharmonic internal movements of molecular species throughout the hydrolysis reactions have been observed and qualitatively discussed in relation with their possible effects on the reactions' kinetics. TMA/H2O reactions have been validated as strongly exothermic, while Hafnium and Zirconium tetrachlorides have founded to react endothermically with single H2O molecule. We have also studied in detail reaction mechanisms of the related on-surface ALD-complexes with water vapors. Our theoretical investigations address to the initial stage of ALD growth, more s pecifically on SiO2/Si(001)-2x1 like surfaces. The proposed many-step mechanisms, similar to those discussed for the gas phase, confirmed again the strong reactivity of H2O molecule with on-surface Aluminum hydroxymethylides, and responds strong endothemically as for the hydroxylation of Zirconium and Hafnium on-surface hydroxychlorides. The last two proved a very similar surface chemistry. Finally the cooperative effects of H2O molecules have been considered in our models of reactions, and have revealed dramatic influences on the reactivity Zirconium- and Hafnium hydroxychlorides surfaces. Our results proved the importance of both cooperative interactions of on-surface complexes and H2O molecules in the case of the Zirconia and HafniaÓALD growth, while for Aluminum oxide, presently considered ideal for ALD growth, these effects seem of secondary importance

Cette thèse examine les films minces d’oxyde de hafnium (HfO2) pour leur potentiel dans lesnanocondensateurs, répondant aux besoins en miniaturisation et haute performance del’électronique moderne. Le HfO2 est compatible avec la Déposition par Couches Atomiques(ALD), ce qui permet des dépôts minces précis et homogènes, essentiels pour garantir la fiabilitédes dispositifs électroniques. Les films minces sont soumis à différentes techniques de fabricationet de caractérisation pour analyser leur morphologie et leurs propriétés électriques, notamment laconstante diélectrique, la tension de claquage et la capacité de stockage d’énergie. Cette approchepermet de déterminer comment optimiser ces matériaux, à la fois en configurations amorphes eten structures cristallines, pour des performances maximales.Pour les diélectriques amorphes linéaires, HfO2 est combiné avec d’autres oxydes, tels quel’alumine et la silice, dans des structures de nanolaminés et de solutions solides. Ces combinaisonssont conçues pour stabiliser la constante diélectrique et offrir une résistance au claquage,améliorant l'efficacité du stockage d’énergie. La linéarité et la stabilité de ces matériaux amorphesles rendent particulièrement adaptés aux applications nécessitant une capacitance stable.L’étude approfondit aussi les propriétés des diélectriques cristallins non linéaires, dopés avec dusilicium ou de la zircone. Différentes températures de déposition et de recuit révèlent descomportements ferroélectriques et antiferroélectriques, augmentant la densité d’énergie et lastabilité. Cependant, les matériaux ferroélectriques, bien que prometteurs pour des applications àhaute densité, sont sensibles aux variations de tension, ce qui limite leur usage dans les applicationsnécessitant une capacitance constante. Les matériaux antiferroélectriques, en revanche, présententune stabilité accrue face aux variations de tension, mais ils font encore face à des défis d’efficacitéénergétique et de gestion thermique. La recherche souligne la variabilité de la constantediélectrique comme un défi majeur pour l'utilisation de ces matériaux dans des applicationsnécessitant une capacitance stable, comme le filtrage de signaux. Les matériaux nanolaminés etles solutions solides sont privilégiés pour obtenir une capacitance linéaire, mais leur efficacité restelimitée en termes de permittivité. L’exploration des phases non linéaires, cependant, ouvre la voieà des performances accrues dans certaines applications avancées.En conclusion, cette étude apporte un éclairage précieux sur les films minces d’oxyde de hafniumet leur rôle dans les nanocondensateurs, en explorant des solutions d’optimisation pour améliorerles performances diélectriques, notamment par les techniques de fabrication et les compositionsde matériaux. Les matériaux linéaires et non linéaires présentent chacun des avantages distincts,mais des recherches supplémentaires sont nécessaires pour surmonter les défis liés à la durabilité,l’efficacité électrique et la gestion thermique, afin de développer des condensateurs plusperformants pour les technologies électroniques modernes
This research investigates the use of hafnium oxide (HfO2)-based thin films in nanocapacitors, focusing on both their linear and non-linear electrical properties to meet the growing demands of high-performance and miniaturized electronic devices. Starting with the fundamental physics of energy storage capacitors, the investigation highlights the essential characteristics of effective dielectric materials, such as a high dielectric constant and a substantial band gap. Hafnium-based materials are particularly promising due to their compatibility with Atomic Layer Deposition (ALD), which allows for precise and uniform thin-film deposition—crucial for ensuring reliable performance in electronic devices.To understand the potential of these materials, various fabrication and characterization techniques were employed. This includes specific deposition processes to create the thin films and morphological tests to study the physical structure of the capacitors. Electrical testing plays a key role in evaluating critical parameters like dielectric constant, breakdown voltage, and overall energy storage capacity. By analyzing these factors, a comprehensive view of how both linear and non-linear hafnium-based dielectrics perform is provided.When exploring linear, amorphous hafnium-based dielectrics, HfO2 is combined with aluminum oxide and silicon dioxide to enhance dielectric properties. Different configurations, such as nanolaminates and solid solutions, are tested to find the optimal balance. The goal is to achieve materials that maintain a high dielectric constant and resist voltage breakdown, thereby improving their ability to store energy efficiently. On the other hand, a detailed look into non-linear, crystalline dielectrics examines the effects of doping hafnium oxide with elements like zirconia and silicon. Different deposition and annealing temperatures are assessed for their impact on crystalline structure and polarization behavior, revealing complex ferroelectric and antiferroelectric behaviors that could offer high energy density and stability.The findings suggest that while ferroelectric materials might not be suitable for applications requiring linear capacitance due to their sensitivity to voltage variations, antiferroelectric materials show promise. However, they still face challenges related to electrical efficiency and thermal management. Finding materials that can effectively stabilize voltage variations is crucial, as capacitors are increasingly used to manage these fluctuations in modern electronics.A significant challenge identified is the variability in the dielectric constant, which can limit the use of these materials in applications demanding stable capacitance, such as signal filtering. To address this issue, solid solutions and laminated materials, which provide consistent linear capacitance, are prioritized. Although these materials are effective up to a certain permittivity threshold, exploring non-linear phases opens the door to potentially higher performance under specific conditions.In summary, understanding of HfO2-based thin films and their role in nanocapacitors is advanced by this research. By examining both linear and non-linear dielectric materials, insights into how to optimize fabrication techniques and material compositions to improve dielectric properties are provided. Ongoing research into issues like material endurance, electrical efficiency, and thermal management is essential for developing reliable and high-performing capacitors that meet the evolving demands of modern electronic technologies

Die vorliegende Arbeit entstand im Rahmen einer Kooperation des Forschungszentrums Dresden-Rossendorf mit Qimonda Dresden GmbH & Co. OHG. Mithilfe der hochauflösenden Rutherford-Streuspektrometrie (HR-RBS) wurden das Diffusionsverhalten und Schichtwachstum von ZrO2 auf SiO2 und TiN im Anfangsstadium untersucht. Auf Grund der exzellenten Tiefenauflösung von 0,3 nm an der Oberfläche stand die Analyse von Konzentrationsprofilen in ultradünnen Schichten, respektive an deren Grenzflächen im Vordergrund. Zur qualitativen Verbesserung der Messergebnisse wurde erstmals ein zweidimensionaler positionsempfindlicher Halbleiterdetektor in den Aufbau der HR-RBS implementiert und charakterisiert. Außerdem wurde ein Messverfahren in Betrieb genommen, das mögliche Schädigungen durch den Ioneneintrag in die Messprobe minimiert. Durch die Optimierung der experimentellen Bedingungen und die Entwicklung eines Programmpaketes zur Unterstützung des Analysten konnte ein effizienter Routine-Messablauf erstellt werden. Im Moment einer binären Kollision zwischen einfallendem Ion und Targetelement kommt es bei kleinem Stoßparameter zu Veränderungen des Ladungszustands der gestreuten Ionen, insbesondere durch die abrupte Geschwindigkeitsänderung des Projektils und der Überlappung der Elektronenwolken. Bei der HR-RBS mit Energie separierendem Dipolmagneten muss zur Interpretation von Streuspektren die Ladungszustandsverteilung der gestreuten Projektile bekannt sein. Erstmalig konnte eine signifikante Abhängigkeit der Ladungszustandsverteilung gestreuter C-Ionen sowohl von der Schichtdicke als auch der Ordnungszahl des detektierten Targetelements, hier der vierten Nebengruppe, nachgewiesen werden. Diese gewonnen Erkenntnisse ermöglichten systematische Untersuchungen zum ZrO2-Schichtwachstum im Anfangsstadium. Zur Herstellung der ZrO2-Schichten wurde die Atomlagenabscheidung (ALD) verwendet. Anhand der nachgewiesenen Agglomeration von ZrO2 auf nativen SiO2 wurde mithilfe der Rasterkraftmikroskopie (AFM) zur Bestimmung von Oberflächenrauigkeiten eine Methode konzipiert, welche die Auswirkung lokaler Schichtdickeninhomogenitäten auf die niederenergetische Flanke eines Streuspektrums berücksichtigt. Auf dieser Grundlage durchgeführte Simulationsrechnungen ergeben, dass keine Diffusion von Zr in die darunter liegende Schicht stattfand, jedoch eine ZrSiO4-Grenzflächenschicht existiert. Für das Wachstum von ZrO2 auf TiN wird aus den hoch aufgelösten Streuspektren ein völlig anderes Verhalten abgeleitet. Messungen zu Oberflächentopografien der TiN-Schicht liefern nicht zu vernachlässigende Werte für die Rauigkeit. Um den Einfluss der Oberflächenrauigkeit auf die Form des hoch aufgelösten Spektrums erfassen zu können, wurde eine Software entwickelt. Auf Basis von AFM-Messungen ermöglicht dieses Programm das Extrahieren einer Energieverteilung aus den Weglängen von ausschließlich an der Oberfläche gestreuten Ionen. Unter Berücksichtigung des Effekts der Oberflächenrauigkeit auf die HR-RBS Spektrenform konnte die Diffusion von Zr in das polykristalline TiN erstmals verifiziert werden. Die Beobachtungen weisen daraufhin, dass bereits nach dem ersten ALD-Zyklus ein geringer Anteil der deponierten Zr-Atome bis in eine Tiefe von etwa 3 nm in das TiN diffundiert. Die vorläufigen Ergebnisse legen Korngrenzendiffusion nahe
This thesis originated from a cooperation between Research Center Dresden-Rossendorf and Qimonda Dresden GmbH & Co. OHG. By means of High Resolution Rutherford Backscattering Spectrometry (HR-RBS) the diffusion behaviour and layer growth of ZrO2 on SiO2 and TiN in the initial regime were investigated. The analysis of concentration profiles in ultrathin layers and interfaces was the focus of this work, made possible by the excellent depth resolution of less than 0.3 nm near the surface. For the first time a two-dimensional position sensitive semiconductor detector was implemented and characterized in the setup of the HR-RBS for the improvement of the quality of the measurement results. Furthermore, a measurement procedure was put into operation that allowed the reduction of ion induced damage. Through the optimization of the experimental conditions and the development of a program package for the support of the analyst, an efficient measurement procedure could be routinely ensured. At the time of a binary collision between the incident ion and the target element with a small impact factor, the charge state changes frequently, especially due to the abruptly decreasing ion velocity of the projectile and the overlapping of the electron clouds. For HR-RBS with an energy-separating dipole magnet, the charge state distribution of the scattered ions must be known for the interpretation of the measured spectra. For the first time a significant dependence of the charge state distribution of the scattered C ions on the layer thickness as well as atomic number of the detected target elements, here from the fourth subgroup, was emonstrated. This new knowledge allowed systematic investigations of the ZrO2 layer growth in the initial regime. The ZrO2 layers were produced by means of the atomic layer deposition (ALD). Based on the evidence for agglomeration of ZrO2 on SiO2 a method was introduced, which takes local thickness variations into account during the simulation of the HR-RBS spectra. An accurate statement about the ZrO2/SiO2 interface was possible due to the extraction of the thickness variation by the atomic force microscopy (AFM). The boundary surface is sharp except for a small intermediate ZrSiO4 layer and no diffusion of Zr atoms in SiO2 could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO2 on TiN. Measurements of the surface topography of the TiN layer revealed non negligible values for the surface roughness. A program was developed to capture the influence of the surface roughness on the shape of the high resolution spectrum. This software uses AFM measurements to extract an energy distribution from calculated path length differences for ions scattered at the sample surface. Diffusion of Zr into polycrystalline TiN was demonstrated for the first time taking into account the effect of the surface roughness on the shape of the spectra. This observation indicates that already after the first ALD reaction cycle a small part of the deposited Zr atoms diffuses into the TiN layer up to a depth of 3 nm. Such preliminary results suggest grain boundary diffusion

碩士
長庚大學
電子工程學研究所
96
In this thesis, we proposed the fabrication of flash memory device with high-k dielectrics, the HfGeOx, as trapping layer is formed by co-sputtering with Hf and Ge. The thermal stability and charge storage can be improved by GeOx embedding in HfOx. In this thesis, we also compared the electrical characteristic of HfGeOx trapping layer with different tunnel dielectrics: SiO2 and HfTaOx. After different rapid thermal annealing temperature, the hysteresis window does not be increased with arising temperature. It is attributed to crystallize phenomenon in HfGeOx layer with high annealing temperature on SiO2 tunnel dielectrics. On the other hand, we must consider thermal stability of HfTaOx tunnel dielectrics. We use HfTaOx tunnel dielectric due to high thermal stability. The program speed and retention time are improved obviously with RTA temperature less than 900℃.

The continuous scaling of microelectronic devices requires high permittivity (high-k) dielectrics to replace SiO₂ as the gate material. HfO₂ is one of the most promising candidates but the crystallization temperature of amorphous HfO₂ is too low to withstand the fabrication process. To enhance the film thermal stability, HfO₂ is deposited using atomic layer deposition (ALD), and incorporated with various amorphizers, such as La₂O₃, Al₂O₃, and Ta₂O₅. The incorporation is achieved by growing multiple ALD layers of HfO₂ and one ALD layer of MO[subscript x] (M = La, Al, and Ta) alternately (denoted as [xHf + 1M]), and the incorporation concentration can be effectively controlled by the HfO₂-to-MO[subscript x] ALD cycle ratio (the x value). The crystallization temperature of 10 nm HfO₂ increases from 500 °C to 900 °C for 10 nm [xHf + 1M] film, where x = 3, 3, and 1 for M = La, Al, and Ta, respectively. The incorporation of La₂O₃, and Ta₂O₅ will not compromise the dielectric constant of the film because of the high-k nature of La₂O₃, and Ta₂O₅. Angle resolved X-ray photoelectron spectroscopy (AR-XPS) reveals that when the HfO₂-to-MO[scubscript x] ALD cycle ratio is large enough (x > 3 and 4 for La and Al, respectively), periodic structures exist in films grown by this method, which are comprised of repeated M-free HfO₂ ultrathin layers sandwiched between HfM[subscript x]O[scubscript y] layers. Generally, the film thermal stability increases with thinner overall thickness, higher incorporation concentration, and stronger amorphizing capability of the incorporated elements. When the x value is low, the films are more like homogeneous films, with thermal stabilities determined by the film thickness and the amorphizer. When the x value is large enough, the periodically-repeated structure may add an extra factor to stabilize the amorphous phase. For the same incorporation concentration, films with an appropriately high periodicity may have an increased thermal stability. The manner by which the periodic structure and incorporated element affect thermal stability is explored and resolved using nanolaminates comprised of alternating layers of [scubscript y]HfO₂ and [xHf + 1M] × n, where y varied from 2 to 20, x varied from 1 to 2, and n varied from 4 to 22.
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碩士
國立臺灣大學
材料科學與工程學研究所
101
In this study, we used ALD to deposit the switching material of RRAM. RRAM has suffered from the randomness of conductive filaments which results in poor uniformity of resistive switching parameters. It has been proved that doping can overcome this problem, and ALD is a perfect process to control vertical doping by manipulating the doping layer ratio; however, due to the layer-by-layer nature, the conventional ALD process failed to control lateral doping. Here, we developed the mixed deposition process which pulses two organometallic precursors to the chamber consecutively in the same cycle, and thus created a mixed doping layer. By utilizing the mixed deposition process, we can conduct a homogeneously doped Al:HfO2 thin films with more uniform doping vertically but less doping laterally. Here, we deposited three kinds of RRAM devices with Al:HfO2 thin films of different doping distribution, which are 1:9 conventional doping, 1:4 conventional doping and 1:4 mixed doping, and the effect of doping distribution on resistive switching behavior is discussed. First, based on the filament model, hypothetical schematic images of filaments in three devices were sketched. In these images, CFs were the narrowest and most confined in the 1:4 mixed doped Al:HfO2 based device, whereas they were stronger in the 1:4 conventional doped Al:HfO2 based device and more random in the 1:9 conventional doped Al:HfO2 based device. The different shapes of CFs in three devices can explain the difference of resistive switching parameters. All three devices showed bipolar switching, and the uniformity of parameters is compared through the statistical distribution of switching parameters during 100 consecutive cycles. The 1:4 mixed doped Al:HfO2 based device displayed excellent uniformity of parameters due to homogeneous doping; besides, the reset current was also reduced due to less doping in this device. Finally, the stability of three devices was compared, and the 1:4 mixed doped Al:HfO2 based device showed excellent stability compared to the other two devices.

碩士
國立暨南國際大學
電機工程學系
102
The research topics of this thesis are: (1) To optimize atomic layer deposition hafnium oxide (HfO2) process by applying taguchi methods；(2) To investigate physical, electrical, and reliability characteristics for different gate dielectric materials. First, for the HfO2 optimization using atomic layer deposition, the variable parameters include pre-O3 pulse、O3 purge、Hf purge, and post-deposition annealing time at 750 oC；The experimental result shows that the critical effect on the HfO2 film is O3 pulse and its impact can be described as follows: The HfO2 films with pre-O3 pulse will increase the interface layer thickness, resulting in a higher equivalent oxide thickness. However, it can effectively prevent the carbon or impurities adsorption and Si element diffusion. Furthermore, due to O3 pulse can reduce the absorption of impurities so that the density and roughness of the film is improved; On the electrical properties and reliability, the experimental results shows that the film with pre O3 pulse can effectively reduce the hysteresis effect, leakage current density and has superior reliability performance due to the film with pre O3 pulse can reduce the interface defect . Second, SiO2, Al2O3, HfO2, and HfAlOx dielectric films have prepared and compared their physical, electrical characteristics, and reliability. Additionally, the HfO2 dielectric films deposited using different deposition methods ( MOCVD via ALD). The film incorporated Al atomic can reduce the interfacial layer and enhance the crystallization temperature. This phenomenon can be observed by TEM and XRD analysis. On the electrical properties, it can be found that the film incorporated Al atomic can reduce the leakage current. On the other hand, because of HfO2 film has crystallized after 750 oC annealing, it will lead to the formation of grain boundaries then the leakage current path will increase. In the comparison of reliability, the different gate dielectric materials under DC stress, the film incorporated Al atomic has a good ability to resist the charge transfer, therefore, the performance on the reliability is better than the HfO2 films. But under dynamic stress behaves, the HfO2 capacitors showed better improvement due to the more efficient charge detrapping effect .

碩士
國立臺灣大學
材料科學與工程學研究所
104
Silver nanowire is one of the most promising substitute material for indium tin oxide. However, electrode made of silver nanowires network has poor long term air stability and current operation stability, which hinder its practical application. In this thesis, to solve these problems a AgNWs-HZO composite electrode was developed by depositing ALD Hafnium-doped zinc oxide on silver nanowires film. The composite electrode showed 87.2% total transmittance at 550 nm and 26.3 Ω/□ in sheet resistance, which are comparable to commercial ITO. In addition, after 9-days storage in 85°C/85% relative humidity environment, the resistance of composite electrode was raised less than 1.2 times and after 120-hrs current operation test at 88 mA/cm2, the output voltage of composite electrode was raised only 1.13 times. Moreover, the perovskite solar cells on AgNW-HZO composite electrode showed good photovoltaic performance as much as solar cells on commercial ITO. Hence our composite electrode not only improves air stability and current operation stability of silver nanowires but also has potential to serve as transparent electrode in optoelectronic application.

Surface forces play a fundamental role in colloidal systems as they control the stability, adhesion, friction and rheology of colloids. Information on all of these can be obtained from an analysis of the normal forces measured between particles. Therefore, processing of colloidal products can be informed by knowledge of the forces between the constituent particles. For wet particles systems, the interaction forces between two particles can rarely be predicted from theory; rather, it requires experimentation or direct measurement. This requires that the surfaces used have the same surface properties as the particles. In practice this is rarely possible, as surface force measurements require surfaces with extremely low roughness and precise geometry and the majority of materials do not conform to these requirements. To address these challenges, this thesis investigates the forces measured between surfaces of low roughness and controlled chemistry produced by the use of atomic layer deposition (ALD). This thesis reports the forces between hafnia surfaces produced by ALD and shows that like ALD produced titania surfaces and silica surfaces, the expected van der Waals forces at high pH are not manifest, suggesting that most real surfaces have unexpectedly repulsive surface forces at high pH and small separations. This will fundamentally alter how these particulate systems behave when being processed, reducing the adhesion and the friction and enhancing the stability compared to the expected interaction from DLVO theory. Here, the interaction forces between very smooth Hafnia surfaces have been measured using the colloid probe technique and the forces evaluated within the DLVO framework, extended to include both hydration forces and the influence of roughness. The measured forces across a wide range of pH at different salt concentrations are well described with a single parameter for the surface roughness. These findings show that even small degrees of surface roughness significantly alter the form of the interaction force and therefore indicate that surface roughness needs to be included in the evaluation of surface forces between all surfaces that are not ideally smooth. The knowledge gained in the first part of this work as to how to account for the roughness effect, was then applied in investigating the influence of adsorbed citric acid and palmitic acid coatings on the surface forces between hafnia surfaces. The knowledge of the surface forces and citric acid adsorption that we obtained will be useful in understanding the stability and flocculation of colloids and nanoparticles which will influence the rheology of the colloidal dispersions and the distribution of colloids and nanoparticles in the environment. The measured surface force between hafnia surfaces that are hydrophobised by palmitic acid coating promises a very easy way to hydrophobise hafnia surfaces. The investigation into the forces measured between these smooth hydrophobic surfaces provides insight into the origin of the long-ranged hydrophobic force measured between surfaces covered with a monolayer of amphiphiles. A previously unrecognized interaction mechanism of interactions between single patches formed by the mobile amphiphile has been proposed based on the measured forces.

Since metal-oxide-semiconductor (MOS) devices have been adopted into integrated circuits, the endless demands for higher performance and lower power consumption have been a primary challenge and a technology-driver in the semiconductor electronics. The invention of complementary MOS (CMOS) technology in the 1980s, and the introduction of voltage and physical dimension scaling in the 1990s would be good examples to keep up with the everlasting demands. In the 2000s, technology continuously evolves and seeks for more power efficiency ways such as high-k dielectrics, metal gate electrodes, strained substrates, and high mobility channel materials. As a gate dielectric, silicon dioxide (SiO₂), most widely used in CMOS integrated circuits, has many prominent advantages, including a high quality interface (e.g. Dit ~ low 1010 cm-2eV-1), a good thermal stability in contact with silicon (Si), a large energy bandgap and the large energy band offsets in reference to Si, and a high quality dielectric itself. As the thickness of SiO₂ keeps shrinking, however, SiO₂ is facing its physical limitations from the viewpoint of gate dielectric leakage currents and reliability requirements. High-k dielectric materials have attracted extensive attention in the last decade due to their great potential for maintaining further down-scaling in equivalent oxide thickness (EOT) and a low dielectric leakage current. HfO₂ has been considered as one of the most promising candidates because of a high dielectric constant (k ~ 20-25), a large energy band gap (~ 6 eV) and the large band offsets (> 1.5 eV), and a good thermal stability. To enhance carrier mobility, strained substrates and high mobility channel materials have attracted a great deal of attention, thus III-V compound semiconductor substrates have emerged as one of possible candidates, in spite of several technical barriers, being believed as barriers so far. The absence of high quality and thermodynamically stable native oxide, like SiO₂ on Si, has been one such hurdle to implement MOS systems on III-V substrates. However, recently, there have been a number of remarkable improvements on MOS applications on them, inspiring more vigorous research activities. In this research, HfO2-based MOS capacitors and metal-oxidesemiconductor field effect transistors (MOSFETs) with a thin germanium (Ge) interfacial passivation layer (IPL) on III-V compound substrates were investigated. It was found that a thin Ge IPL could effectively passivate the surface of III-V substrate, consequently providing a high quality interface and an excellent gate oxide scalability. N-channel MOSFETs on GaAs, InGaAs, and InP substrates were successfully demonstrated and a minimum EOT of ~ 9 Å from MOS capacitors was achieved. This research has begun with GaAs substrate, and then expanded to InGaAs, InP, InAs, and InSb substrates, which eventually helped to understand the role of a Ge IPL and to guide future research direction. Overall, MOS devices on III-V substrates with an HfO₂ gate dielectric and a Ge IPL have demonstrated feasibility and potential for further investigations.
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Recently, high-κ materials have become the focus of research and been extensively utilized as the gate dielectric layer in aggressive scaled complementary metal-oxide-semiconductor (CMOS) technology. Hafnium dioxide (HfO2) is the most promising high-κ material because of its excellent chemical, thermal, mechanical and dielectric properties and also possesses good thermodynamic stability and better band offsets with silicon. Hence, HfO2 has already been used as gate dielectric in modern CMOS devices. For future technologies, it is very difficult to scale the silicon transistor gate length, so it is a necessary requirement of replacing the channel material from silicon to some high mobility material. Two-dimensional layered materials such as graphene and molybdenum disulfide (MoS2) are potential candidates to replace silicon. Due to its planar structure and atomically thin nature, they suit well with the conventional MOSFET technology and are very stable mechanically as well as chemically. HfO2 plays a vital role as a gate dielectric, not only in silicon CMOS technology but also in future nano-electronic devices such as graphene/MoS2 based devices, since high-κ media is expected to screen the charged impurities located in the vicinity of channel material, which results in enhancement of carrier mobility. So, for sustenance and enhancement of new technology, extensive study of the functional materials and its processing is required. In the present work, optimization of HfO2 thin films for gate dielectric applications in Nano-electronic devices using electron beam evaporation is discussed. HfO2 thin films have been optimized in two different thickness regimes, (i) about 35 nm physical thicknesses for back gate oxide graphene/MoS2 transistors and (ii) about 5 nm physical thickness to get Equivalent Oxide Thickness (EOT) less than 1 nm for top gate applications. Optical, chemical, compositional, structural and electrical characterizations of these films have been done using Ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford Back Scattering (RBS), X-ray Diffraction (XRD), Capacitance-Voltage and Current-Voltage characterization techniques. The amount of O2 flow rate, during evaporation is optimized for 35 nm thick HfO2 films, to achieve the best optical, chemical and electrical properties. It has been observed that with increasing oxygen flow rate, thickness of the films increased and refractive index decreased due to increase in porosity resulting from the scattering of the evaporant. The films deposited at low O2 flow rates (1 and 3 SCCM) show better optical and compositional properties. The effects of post deposition annealing (PDA) and post metallization annealing (PMA) in forming gas ambient (FGA) on the optical and electrical properties of the films have been analyzed. The film deposited at 3 SCCM O2 flow rate shows the best properties as measured on MOS capacitors. A high density film (ρ=8.2 gram/cm3, 85% of bulk density) with high dielectric constant of κ=19 and leakage current density of J=2.0×10-6 A/cm2 at -1 MV/cm has been achieved at optimized deposition conditions. Bilayer graphene on HfO2/Si substrate has been successfully identified and also transistor has been fabricated with HfO2 (35 nm) as a back gate. High transconductance compared to other back gated devices such as SiO2/Si and Al2O3/Si and high mobility have been achieved. The performance of back gated bilayer graphene transistors on HfO2 films deposited at two O2 flow rates of 3 SCCM and 20 SCCM has been evaluated. It is found that the device on the film deposited at 3 SCCM O2 flow rate shows better properties. This suggests that an optimum oxygen pressure is necessary to get good quality films for high performance devices. MoS2 layers on the optimized HfO2/Si substrate have been successfully identified and transistor has been fabricated with HfO2 (32 nm) as a back gate. The device is switching at lower voltages compared to SiO2 back gated devices with high ION/IOFF ratio (>106). The effect of film thickness on optical, structural, compositional and electrical properties for top gate applications has been studied. Also the effect of gate electrode material and its processing on electrical properties of MOS capacitors have been studied. EOT of 1.2 nm with leakage current density of 1×10-4 A/cm2 at -1V has been achieved.

Recently, high-κ materials have become the focus of research and been extensively utilized as the gate dielectric layer in aggressive scaled complementary metal-oxide-semiconductor (CMOS) technology. Hafnium dioxide (HfO2) is the most promising high-κ material because of its excellent chemical, thermal, mechanical and dielectric properties and also possesses good thermodynamic stability and better band offsets with silicon. Hence, HfO2 has already been used as gate dielectric in modern CMOS devices. For future technologies, it is very difficult to scale the silicon transistor gate length, so it is a necessary requirement of replacing the channel material from silicon to some high mobility material. Two-dimensional layered materials such as graphene and molybdenum disulfide (MoS2) are potential candidates to replace silicon. Due to its planar structure and atomically thin nature, they suit well with the conventional MOSFET technology and are very stable mechanically as well as chemically. HfO2 plays a vital role as a gate dielectric, not only in silicon CMOS technology but also in future nano-electronic devices such as graphene/MoS2 based devices, since high-κ media is expected to screen the charged impurities located in the vicinity of channel material, which results in enhancement of carrier mobility. So, for sustenance and enhancement of new technology, extensive study of the functional materials and its processing is required. In the present work, optimization of HfO2 thin films for gate dielectric applications in Nano-electronic devices using electron beam evaporation is discussed. HfO2 thin films have been optimized in two different thickness regimes, (i) about 35 nm physical thicknesses for back gate oxide graphene/MoS2 transistors and (ii) about 5 nm physical thickness to get Equivalent Oxide Thickness (EOT) less than 1 nm for top gate applications. Optical, chemical, compositional, structural and electrical characterizations of these films have been done using Ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford Back Scattering (RBS), X-ray Diffraction (XRD), Capacitance-Voltage and Current-Voltage characterization techniques. The amount of O2 flow rate, during evaporation is optimized for 35 nm thick HfO2 films, to achieve the best optical, chemical and electrical properties. It has been observed that with increasing oxygen flow rate, thickness of the films increased and refractive index decreased due to increase in porosity resulting from the scattering of the evaporant. The films deposited at low O2 flow rates (1 and 3 SCCM) show better optical and compositional properties. The effects of post deposition annealing (PDA) and post metallization annealing (PMA) in forming gas ambient (FGA) on the optical and electrical properties of the films have been analyzed. The film deposited at 3 SCCM O2 flow rate shows the best properties as measured on MOS capacitors. A high density film (ρ=8.2 gram/cm3, 85% of bulk density) with high dielectric constant of κ=19 and leakage current density of J=2.0×10-6 A/cm2 at -1 MV/cm has been achieved at optimized deposition conditions. Bilayer graphene on HfO2/Si substrate has been successfully identified and also transistor has been fabricated with HfO2 (35 nm) as a back gate. High transconductance compared to other back gated devices such as SiO2/Si and Al2O3/Si and high mobility have been achieved. The performance of back gated bilayer graphene transistors on HfO2 films deposited at two O2 flow rates of 3 SCCM and 20 SCCM has been evaluated. It is found that the device on the film deposited at 3 SCCM O2 flow rate shows better properties. This suggests that an optimum oxygen pressure is necessary to get good quality films for high performance devices. MoS2 layers on the optimized HfO2/Si substrate have been successfully identified and transistor has been fabricated with HfO2 (32 nm) as a back gate. The device is switching at lower voltages compared to SiO2 back gated devices with high ION/IOFF ratio (>106). The effect of film thickness on optical, structural, compositional and electrical properties for top gate applications has been studied. Also the effect of gate electrode material and its processing on electrical properties of MOS capacitors have been studied. EOT of 1.2 nm with leakage current density of 1×10-4 A/cm2 at -1V has been achieved.

Στη παρούσα Διατριβή διερευνήθηκε η χρήση υλικών υψηλής διηλεκτρικής σταθεράς (high-k) ως οξειδίων ελέγχου σε διατάξεις παγίδευσης φορτίου τύπου MONOS (Μetal-Οxide-Νitride-Οxide-Silicon). Τα οξείδια που εξετάστηκαν ήταν το HfO2, τo ZrO2 και το Al2O3. Η ανάπτυξή τους πραγματοποιήθηκε με χρήση της μεθόδου εναπόθεσης ατομικού στρώματος (ALD). Οι ιδιότητες των δομών μνήμης μελετήθηκαν συναρτήσει: (α) των πρόδρομων μορίων της εναπόθεσης για τα HfO2 και ZrO2, (β) του οξειδωτικού μέσου της εναπόθεσης για την περίπτωση του Al2O3 και (γ) της επακόλουθης ανόπτησης. Η ηλεκτρική συμπεριφορά των δομών εξετάστηκε με την κατασκευή πυκνωτών τύπου MOS. Τα υμένια του HfO2 αναπτύχθηκαν επί διστρωματικής στοίβας SiO2/Si3N4 με (α) αλκυλαμίδιο του χαφνίου (ΤΕΜΑΗ) και Ο3 στους 275 oC, και (β) κυκλοπενταδιενύλιο του χαφνίου (HfD-04) και Ο3 στους 350 οC. Ομοίως, τα υμένια του ZrO2 αναπτύχθηκαν επί διστρωματικής στοίβας SiO2/Si3N4 με: (α) αλκυλαμίδιο του ζιρκονίου (ΤΕΜΑΖ) και Ο3 στους 275 oC και (β) κυκλοπενταδιενύλιο του ζιρκονίου (ZrD-04) με Ο3 στους 350 oC. Ο δομικός χαρακτηρισμός, για το HfO2, φανέρωσε πως η ύπαρξη ή όχι κρυσταλλικού χαρακτήρα και η σύσταση του οξειδίου εξαρτάται τόσο από το πρόδρομο μόριο αλλά και από την ανόπτηση (600 οC, 2 min). Αντίθετα, το ZrO2 έχει σε κάθε περίπτωση κρυσταλλικότητα. Τα ηλεκτρικά χαρακτηριστικά των πυκνωτών Si/SiO2/Si3N4/high-k/Pt, δείχνουν ότι οι δομές έχουν ικανοποιητική συμπεριφορά ως στοιχεία μνήμης αφού όλες οι ιδιότητες πληρούν τις βασικές προϋποθέσεις ως στοιχεία μνήμης, παρά την ανυπαρξία ενεργειακού φραγμού μεταξύ στρώματος παγίδευσης και οξειδίου ελέγχου. Η ικανότητα παγίδευσης και η επίδοση των δομών με HfO2 και ZrO2 δεν διαφοροποιούνται σημαντικά με χρήση διαφορετικού πρόδρομου μορίου ή με την ανόπτηση. Ο έλεγχος όμως της αντοχής των δομών σε επαναλαμβανόμενους παλμούς εγγραφής/διαγραφής αναδεικνύει ότι αμφότερες οι δομές που ανεπτύχθησαν με βάση το κυκλοπενταδιενύλιο έχουν μειωμένη αντοχή ηλεκτρικής καταπόνησης. Τo Al2O3 αναπτύχθηκε χρησιμοποιώντας το μόριο ΤΜΑ και ως οξειδωτικό μέσο: (α) H2O, (β) O3 και (γ) Plasma Ο2 (μέθοδος PE-ALD) σε συνδυασμό με ΤΜΑ. Οι δομές στην αρχική κατάσταση, χωρίς ανόπτηση, χαρακτηρίζονται από ισχυρό ρεύμα έγχυσης ηλεκτρονίων από την πύλη (υπό αρνητικές τάσεις) περιορίζοντας την ικανότητα φόρτισης και την επίδοση διαγραφής. Η ανόπτηση σε φούρνο και αδρανές περιβάλλον (850 ή 1050 oC, 15 min) προκάλεσε σημαντική βελτίωση των ηλεκτρικών χαρακτηριστικών των δομών λόγω του σημαντικού περιορισμού του παραπάνω φαινομένου. Μετά το στάδιο της ανόπτησης οι συνδυασμοί ΤΜΑ/Η2Ο και ΤΜΑ/Plasma Ο2 έχουν καλύτερες χαρακτηριστικές σε σχέση με αυτές του συνδυασμού ΤΜΑ/Ο3. Το φαινόμενο της διαρροής ηλεκτρονίων από την πύλη αποδίδεται στη μεγάλη συγκέντρωση και χωρική κατανομή του υδρογόνου στο υμένιο υψηλής διηλεκτρικής σταθεράς. Τέλος, διερευνήθηκε η τροποποίηση των ιδιοτήτων μνήμης των δομών με εμφύτευση ιόντων αζώτου χαμηλής ενέργειας και υψηλής δόσης στο Al2O3 και επακόλουθη ανόπτηση υψηλής θερμοκρασίας. Η παρουσία αζώτου στο υμένιο καθώς και ο χημικός δεσμός του εμφυτευμένου αζώτου είναι συνάρτηση της θερμοκρασίας ανόπτησης. Επομένως, οι ιδιότητες μνήμης εξαρτώνται από τη μορφή σύνδεσης και την συγκέντρωση του εμφυτευμένου αζώτου στο τροποποιημένο Al2O3. Η υψηλή θερμοκρασία ανόπτησης (1050 οC, 15 min) φαίνεται να αποφέρει δομές με τις καλύτερες ιδιότητες μνήμης.
This thesis studies the functionality of high-k oxides as blocking oxide layers in SONOS type charge-trap memory devices. The oxide materials that were examined were the HfO2, the ZrO2 and the Al2O3. All these blocking oxide layers were deposited by atomic layer deposition technique (ALD). The electrical performance of the trilayer stacks was examined using Pt-gate MOS-type capacitors. The properties of the memory structures were examined as a function of: (a) precursor chemistry of HfO2 and ZrO2 deposition, (b) the deposition oxidizing agent in the case of Al2O3 and (c) subsequent high temperature annealing steps. The HfO2 films were deposited on SiO2/Si3N4 bilayer stacks using: (a) hafnium alkylamide (TEMAH) and O3 at 275 oC, and (b) hafnium cyclopentadienyl (HfD-04) and O3 at 350 oC. Similarly the ZrO2 films were deposited by (a) zirconium alkylamide (TEMAZ) and O3 at 275 oC, and (b) zirconium cyclopentadienyl (ZrD-04) and O3 at 350 oC The structural characterization of the HfO2 showed that the crystallinity of the deposited high-k material depends on the precursor choice and the post deposition annealing step (600 °C, 2 min). On the contrary ZrO2 is deposited in a crystalline phase independent of the deposition conditions and the choice of the precursors. The electrical characterization of Si/SiO2/Si3N4/high-k/Pt capacitors showed that all fabricated structures operate well as memory elements, despite the absence of an energy barrier between the trapping layer and control oxide. The trapping efficiency and the performance of structures with HfO2 or ZrO2 blocking layers do not revealed a dependence upon the precursor chemistry. However, endurance testing using continuous write/erase pulses showed that both structures deposited by cyclopentadienyl precursors cannot sustain the resulting electrical stress. The Al2O3 layers were deposited using the TMA molecule while three different oxidizing agents were used: (a) H2O, (b) O3 and (c) oxygen plasma. Electrical testing of the resulting Pt-gate trilayer capacitors showed that in the deposited condition all three samples were characterized by gate electrode induced electron leakage currents in the negative bias regime, which completely masked the substrate hole injection effects. This effect limits the performance and the functionality of the memory stacks. After a high temperature annealing step (850 or 1050 oC, 15 min) this leakage current is reduced significantly and the stacks can function as memory elements. The results point to suggest that after annealing the best performance is exhibited by the TMA/H2O and TMA/Plasma O2 samples. The effect of gate induced electron leakage current is attributed to hydrogen related contamination, which has been verified by ToF-ERDA in depth profile measurements, at least for the case of TMA/H2O samples. The modification of the memory properties of the SiO2/Si3N4/Al2O3 stacks was also investigated using low energy and high fluence nitrogen implantation into Al2O3 layer. The concentration and the chemical bonding of the implanted nitrogen is a function of annealing temperature. The memory properties of the stack depend therefore on the chemical bonding and the concentration of the remaining nitrogen in the modified Al2O3. The high temperature annealing (1050 oC, 15 min) appears to provide the structures with improved memory properties in terms of retention and fast erase performance.