La mémoire NAND Flash représente une part importante dans le marché des circuits intégrés et a bénéficié de la traditionnelle miniaturisation de l’industrie des sémiconducteurs lui permettant un niveau d’intégration élevé. Toutefois, cette miniaturisation semble poser des sérieux problèmes au-delà du noeud 22 nm. Dans un souci de dépasser cette limite, des solutions mémoires alternatives sont proposées parmi lesquelles la mémoire résistive (RRAM) se pose comme un sérieux candidat pour le remplacement de NAND Flash. Ainsi, dans cette thèse nous essayons de répondre à des nombreuses questions ouvertes sur les dispositifs RRAM à base d’oxyde d’hafnium (HfO2) en particulier en adressant le manque de compréhension physique détaillée sur leur fonctionnement et leur fiabilité. L’impact de la réduction de taille des RRAM, le rôle des électrodes et le processus de formation et de diffusion des défauts sont étudiés. L’impact de l’alliage/dopage de HfO2 avec d’autres matériaux pour l’optimisation des RRAM est aussi abordé. Enfin, notre étude tente de donner quelques réponses sur la formation du filament conducteur, sa stabilité et sa possible composition. / Among non-volatile memory technologies, NAND Flash represents a significant portion in the IC market and has benefitted from the traditional scaling of semiconductor industry allowing its high density integration. However, this scaling seems to be problematic beyond the 22 nm node. In an effort to go beyond this scaling limitation, alternative memory solutions are proposed among which Resistive RAM (RRAM) stands out as a serious candidate for NAND Flash replacement. Hence, in this PhD thesis we try to respond to many open questions about RRAM devices based on hafnium oxide (HfO2), in particular, by addressing the lack of detailed physical comprehension about their operation and reliability. The impact of scaling, the role of electrodes, the process of defects formation and diffusion are investigated. The impact of alloying/doping HfO2 with other materials for improved RRAM performance is also studied. Finally, our study attempts to provide some answers on the conductive filament formation, its stability and possible composition.

Resistive random access memory (RRAM) is a non-volatile memory technology based on resistive switching in a dielectric or semiconductor sandwiched between two different metals. Also known as memristors, these devices are potential candidates for a next-generation replacement for flash memory. In this thesis, bipolar resistive switching is reported for the first time in solution-deposited zinc-tin-oxide (ZTO). The impact of the compliance current on device operation, including the SET and RESET voltages, pre-SET, RESET and post-RESET currents, the resistance ratio between the low and high resistance states, retention, and the endurance, is investigated for an isolated Al dot/ZTO/Ir blanket device and for Al/ZTO/Pt crossbar RRAM devices. A gradual forming process is devised to improve device stability and performance. It is found that the device performance depends critically on the compliance current density that is used to limit the breakdown conduction during the SET operation. In addition, it was found that the conduction and switching mechanisms are consistent with the filament model of formation and rupture of conductive filaments. / Graduation date: 2012

Les mémoires vives à changement de résistance (ReRAM de l'anglais Resistive Random Access Memories) attirent fortement l'attention car elles sont considérées comme unes des plus prometteuses pour la prochaine génération de composants. Ceci est du à leurs basse consommation de puissance, leurs vitesse de commutation élevée et leurs potentiel pour devenir une mémoire à haute densité compatible avec la technologie CMOS. Ces mémoires se basent sur l'effet de commutation résistive (RS de l'anglais resistive switching) qui est un changement réversible de la résistivité contrôlé par un champ électrique externe. Il a été proposé que le RS soit couplé avec la migration de lacunes d'oxygène qui permet de générer, de façon réversible, un canal de conduction dans l'oxyde. Plusieurs expériences ont été menées pour élucider les mécanismes de la commutation pendant les dernières années sans aucune conclusion définitive sur le mécanisme sous jacent au RS. Le principal objectif de ce travail est de comprendre les mécanismes physiques qui contrôlent le RS et de pointer quels sont les paramètres clés qui pourraient améliorer la performance des dispositifs d'un point de vue technologique. Dans cette mémoire nous présentons des études de RS dans différentes interfaces métal/oxyde en utilisant de l'or, de l'argent et du platine comme métaux et des oxydes complexes : YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) et La0.7Sr0.3CoO3 (LSCO). Ces oxydes ont été choisis car ce sont des systèmes à électrons fortement corrélés ayant des propriétés physiques qui dépendent fortement de la Stœchiométrie d'oxygène. Ils ont une structure similaire (type pérovskite) et une haute mobilité d'oxygène. Nous avons réalisé la validation du principe de fonctionnement pour chaque type de jonction et expliqué le RS en utilisant un modèle de diffusion de lacunes d'oxygène assisté par champ électrique. Nous avons caractérisé ensuite le mécanisme de conduction des jonctions qui suit une conduction dominé par un effet Poole-Frenkel dans YBCO et par un mécanisme type SCLC dans LSCO. La faisabilité des dispositifs de mémoire dans ces jonctions a été testée atteignant des répétitivités élevées avec une consommation de puissance optimale avec plus de 103 commutations RS réussies. Nous avons également étudié l'effet d'accumulation d'impulsions électriques cycliques d'amplitude croissante sur l'état de résistance de la mémoire non-volatile de la jonction. On a trouvé une relation entre l'amplitude du RS et le nombre d'impulsions appliquées pour une amplitude et une température fixées. Cette relation est similaire à l'équation de Basquin qui décrit la loi d'endommagement dans les essais mécaniques de fatigue reliant la contrainte appliquée au nombre de répétitions de la sollicitation (temps de vie). Ceci fait ressortir la similarité de la physique du RS et de la propagation de défauts dans les matériaux soumis à des contraintes mécaniques cycliques. Finalement, nous avons analysé l'évolution temporelle de l'état résistif rémanent dans l'interface oxyde-métal. Le temps de relaxation peut se décrire par une loi exponentielle étendue qui est caractérisée par un exposant d'étirement près de 0.5. Nous trouvons que les temps caractéristiques augmentent avec la température et la puissance appliquée ce qui veut dire que ce n'est pas un phénomène classique d'activation thermique. Les résultats mettent clairement en évidence la relation entre le RS et la diffusion de lacunes d'oxygène dans une surface avec une densité de pièges dépendante de la température et qui peut correspondre physiquement à la diffusion aux joints de grains. / Resistive Random Access Memories (RRAM) have attracted significant attention recently, as it is considered as one of the most promising candidates for the next generation of non-volatile memory devices. This is due to its low power consumption, fast switching speed and the ability to become a high density memory compatible with the conventional CMOS processes. The working principle of this kind of memories is the resistive switching (RS) which is simply the controlled reversible change in the resistivity of a junction generated by an external electric field. It has been proposed that the RS is coupled with the migration of oxygen vacancies generating a reversible conduction path inside the oxide. Many experiments have been done to address the switching mechanism during the last decade without any conclusive answer of what is the physical mechanism beneath the RS. The main goal of the present work it's to understand the physical mechanism that control the RS and to point out which are the key parameters that can help improve the performance of the memory devices from a technological point of view. In this dissertation we report on the studies of the RS in different interfaces metal/oxide where we have utilized gold, silver and platinum as metal and as complex oxides: YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) y La0.7Sr0.3CoO3 (LSCO). This oxides have been chosen because all of them are strongly correlated compounds with physical properties strongly dependent of their oxygen stoichiometry. They also have a similar crystalline structure (perovskite type) and a high oxygen mobility. We realized the proof of concept for each type of junction successfully and explain the RS effect and explained the RS utilizing an electric assisted diffusion of oxygen vacancies model. We characterized them the conduction mechanism of the junctures with a conduction dominated by the Poole-Frenkel effect in the YBCO and by the SCLC mechanism in the LSCO. The feasibility of the memory devices in this junctions have been tested reaching high repeatability with optimize power consumption with more than 103 successful switching events. We have also studied the effects of accumulating cyclic electrical pulses of increasing amplitude on the non-volatile resistance state of the junctions. We have found a relation between the RS amplitude and the number of applied pulses, at a fixed amplitude and temperature. This relation remains very similar to the Basquin equation use to describe the stress-fatigue lifetime curves in mechanical tests. This points out to the similarity between the physics of the RS and the propagation of defects in materials subjected to repeated mechanical stress. This relation can be used as the basis to build an error correction scheme. Finally, we have analyzed the time evolution of the remnant resistive state in the oxide-metal interfaces. The time relaxation can be described by a stretched exponential law that is characterized by a power exponent close to 0.5. We found that the characteristic time increases with increasing temperature and applied power which means that this is not a standard thermally activated process. The results are a clear evidence of the relation between RS and the diffusion of oxygen vacancies on a two-dimensional surface with a temperature-dependent density of trapping centers, which may correspond, physically, to the diffusion along grain boundaries. / Las memorias resistivas están entre los principales candidatos a ser utilizados como elementos en una nueva generación de memorias no volátiles. Esto se debe a su bajo consumo energético, una alta velocidad de lectura/escritura y a la posibilidad de lograr memorias de alta densidad compatibles con los procesos de la tecnología CMOS actual (por sus siglas en inglés: Complementary Metal–Oxide–Semiconductor).El funcionamiento de estas memorias se basa en la conmutación resistiva (CR), que consiste en el cambio controlado de la resistencia de una interfase metal-óxido a través de estímulos eléctricos. Si bien hasta el presente no se ha podido determinar con certeza el mecanismo físico que controla la CR, se piensa que está basado en el movimiento de vacancias de oxígeno que formarían de manera reversible zonas de alta/baja conducción dentro del óxido.La presente tesis tiene como objetivo principal entender los mecanismos físicos que gobiernan a la CR y poner en evidencia algunos de los aspectos esenciales que pueden contribuir a lograr dispositivos útiles desde el punto de vista tecnológico.Para ello se han realizado estudios de las características principales de la CR para distintas interfases metal-óxido a distintas condiciones de temperatura. Se han utilizado Au, Pt y Ag como metales y los siguientes óxidos complejos YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) y La0.7Sr0.3CoO3 (LSCO). Se han elegido estos óxidos complejos debido a que presentan características similares, como ser materiales fuertemente correlacionados con una estructura cristalina tipo perovskita y una alta movilidad de oxígenos, lo que afecta muchas de sus propiedades físicas, ya que dependen fuertemente de la estequiometría.Nuestros resultados han demostrado la existencia de una CR bipolar en todos estos sistemas. Ésta es explicada satisfactoriamente a través de un modelo de difusión de vacancias de oxígeno asistidas por campo eléctrico.Se han caracterizado las interfases como dispositivos de memoria, estudiando sus mecanismos de conducción, encontrándose una conducción dominada por un mecanismo del tipo Poole-Frenkel para la muestra de YBCO y una conducción del tipo SCLC para el LSCO y el LSMO. Adicionalmente, se ha conseguido una alta durabilidad y repetitividad en el funcionamiento de estas junturas como dispositivos de memoria,vgracias a la optimización en el protocolo utilizado para escribir/borrar, lográndose más de 103 conmutaciones consecutivas sin fallas en dispositivos bulk.También se ha estudiado el efecto de la acumulación de pulsos idénticos en las interfases obteniéndose una relación entre la amplitud de la CR y el número de pulsos aplicado a amplitud y temperatura fijas. Luego de someter la interfase a ciclos de fatiga eléctrica, se ha encontrado una similitud entre la evolución de la resistencia remanente en esta con la propagación de defectos en un metal sometido a pruebas de fatiga mecánica. Esta relación puede ser usada como base para generar un algoritmo de corrección de errores y para mejorar la efectividad y el consumo de energía de estos dispositivos de memoria.Finalmente, se han realizado estudios sobre la evolución temporal de cada estado de resistencia. Hemos demostrado que sigue una ley exponencial estirada con un exponente cercano a 0.5 y un tiempo característico dado, que depende tanto de la temperatura como de la potencia utilizada. Estos resultados implican que la evolución temporal no está dominada por un proceso estándar de difusión térmicamente activado. La difusión de vacancias de oxígeno ocurre en una superficie con una densidad de trampas que depende de la temperatura, donde dicha superficie correspondería físicamente a los bordes de grano del óxido.

Thin-film transistors (TFTs) are primarily used as a switching element in liquid crystal displays. Currently, amorphous silicon is the dominant TFT technology for displays, but higher performance TFTs will become necessary to enable ultra-definition resolution high-frequency large-area displays. Amorphous zinc tin oxide (ZTO) TFTs were fabricated by RF magnetron sputter deposition. In this study, the effect of both deposition and post annealing conditions have been evaluated in regards to film structure, composition, surface contamination, and device performance. Both the variation of oxygen partial pressure during deposition and the temperature of the post-deposition annealing were found to have a significant impact on TFT properties. X-ray diffraction data indicated that the ZTO films remain amorphous even after annealing to 600° C. Rutherford backscattering spectrometry indicated that the Zn:Sn ratio of the films was ~1.7:1 which is slightly tin rich compared to the sputter target composition. X-ray photoelectron spectroscopy data indicated that the films had significant surface contamination and that the Zn:Sn ratios changed depending on sample annealing conditions. Electrical characterization of ZTO films using TFT test structures indicated that mobilities as high as 17 cm² V⁻¹ s⁻¹ could be obtained for depletion mode devices. It was determined that the electrical properties of ZTO films can be precisely controlled by varying the deposition conditions and annealing temperature. It was found that the ZTO electrical properties could be controlled where insulating, semiconducting and conducting films could be prepared. This precise control of electrical properties allowed us to incorporate sputter deposited ZTO films into resistive random access memory (RRAM) devices. RRAM are two terminal nonvolatile data memory devices that are very promising for the replacement of silicon-based Flash. These devices exhibited resistive switching between high-resistance states to low-resistance states and low-resistance states to high-resistance states depending on polarity of applied voltages and current compliance settings. The device switching was fundamentally related to the defect states and material properties of metal and insulator layers, and their interfaces in the metalinsulator-metal (MIM) structure. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 6, 2012 - Jan. 6, 2013

The promising role resistive random-access memory (RRAM) plays in the imminent reality of wearable electronics calls for a new, updated physical model of their operating mechanism. Their high applicability as the next-generation flexible non-volatile memory (NVM) devices has promoted the recent emergence of a novel ultra-thin (< 5nm) organic/inorganic hybrid dielectric RRAM. A deep understanding of their resistive switching (RS) behavior is required to unlock their suitability in future electronics applications. However, the extremely reduced thicknesses bring about new challenges in terms of material characterization sample processing, while the RS observations through electrical characterization techniques lack uniformity in the key switching parameters, thus hindering the identification of any clear trends.  This work studies the RS mechanism in ultra-thin Al/Hf-hybrid/Ni RRAM devices through uniformity-improved electrical observations. First, the focus is to implement a ramped-pulse train method during the reset process to reduce the dispersion of the voltage and resistance fluctuations at different starting voltage amplitudes and pulse widths. After finding the optimal electrical programming conditions for reduced parameter dispersions, a temperature test was performed to study the contributions of the metal ions and oxygen vacancies (V2+) in the switching layer. Finally, a physical model describing the operating mechanism in flexible RRAM is proposed after the close observation and study of the processed devices. The model is based on the coexistence of a hetero-metallic portion composed of Al and Hf3Al2, and a V2+ portion connected to form the hybrid conducting filament (CF) and turning the device on. The CF forming processes emphasize the strong presence of these vacancies partaking in RS, as the temperature dependence results suggest the majority of their concentration to be generated during this step. Also, the different electrical potential, temperature, and concentration gradients influencing the V2+ migration during RS may explain some of the failure mechanisms in the rupture and the re-forming of the filament. Additionally, the possible presence of a thin Al-oxide layer in the Al/Hf-hybrid interface may give a reason for leaky on-states. A detailed physical model of the RS mechanism in next-generation flexible RRAMs is key to learn to unlock a range of emerging technologies fitted to today’s needs. / Den senaste introduktionen av ultratunn (<5 nm) organisk-oorganisk hybrid dielektrisk RRAM som nästa generations icke-flyktiga minnesenheter kräver en djup förståelse för hybridskiktresistiv växling (RS). Den extremt reducerade tjockleken hindrar emellertid deras bearbetbarhet för materialkarakteriseringstekniker. Dessutom hindrar den dåliga enhetligheten i viktiga omkopplingsparametrar fortfarande i RRAM att alla trender kan definieras tydligt genom elektrisk karakterisering. Detta arbete använder elektrisk manipulation genom en RPS-metod (ramped-pulse series) för att förbättra spännings- och motståndsfluktuationerna i återställningsprocessen för ultratunna Al/Hf-hybrid/Ni-enheter vid olika spänningsamplitud, pulsbredd och temperaturförhållanden. Från de erhållna RPS-optimerade resultaten föreslås en ny och detaljerad fysisk modell som beskriver driftsmekanismen. Samexistensen i den ledande filamenten (CF) av en hybridmetalldel, sammansatt av Al och Hf3Al2, och en syrevakansdel bekräftas. Vår modell betonar vakansbidraget i RS, där majoriteten genereras under CF-formningsprocessen och deltar i olika grad i filamentbrottet för RPS och ingen RPS-bearbetade enheter via Joule-uppvärmning, drift och Fick-krafter. Dessutom förklaras kopplingsfelhändelser baserat på närvaron av ett Al2O3-lager i Al/Hf-hybridgränssnittet.

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