As the semiconductor industry grapples with escalating scaling challenges associated with the floating gate MOSFET, alternative memory technologies like Resistive Random Access Memory (ReRAM) are gaining prominence in the scientific community. Boasting a straightforward device structure, ease of fabrication, and compatibility with CMOS (Complementary Metal-oxide Semiconductor) Back-end of Line (BEOL), ReRAM stands as a leading candi- date for the next generation of non-volatile memory (NVM). ReRAM devices feature nanoionics-based filamentary switching, outperforming flash memory in terms of power consumption, scalability, retention, ON/OFF ratio, and endurance. Furthermore, integrating ReRAMs within the CMOS BEOL/low-k Cu interconnect system not only reduces latency between the connectivity constraints of logic and memory modules but also minimizes the chip footprint. However, investigations have revealed a significant concern surrounding ReRAMs—specifically, their electro-thermal reliability. This research provides evidence highlighting the critical influence of material properties, deposition effects, and thermal transport on the device's performance and reliability. Various material systems have undergone in this work scrutiny to comprehend the impact of intrinsic material properties such as thermal conductivity, specific heat capacity, thermal diffusivity, and deposition effects like surface roughness on the electroforming voltages of ReRAM devices. The reference device structure considered in this work is Cu/TaOx/Pt, which has been compared with alternative configurations involving metals like Ru and Co as potential substitutes for Pt. Additionally, a new vehicle has been introduced to quantify cell degradation resulting from thermal cross-talk in crossbar Resistive Random Access Memory (ReRAM) arrays. Furthermore, a novel methodology has been presented to predict cell degradation due to remote heating, taking into account the cell's location, the material properties of the device, and geometry of its electrodes. The experimental results presented in this study showcase filament rupture caused by remote heating, along with spontaneous filament restoration ensuing from the subsequent cooling of the ReRAM cell. / Doctor of Philosophy / As the demand for compact, high-speed logic-memory modules continues to surge, the diminishing silicon real estate in our gadgets poses a challenge in extending Moore's law to meet the scaling needs of the semiconductor device industry. To tackle this challenge, emerging memory technologies like Resistive Random Access Memory (ReRAM) are positioned as promising successors to flash memory. ReRAM devices offer distinct advantages over flash memory, showcasing superior power consumption, scalability, long retention, a high ON/OFF ratio, and good endurance. Their compatibility with current CMOS (Complementary Metal-oxide Semiconductor) technology facilitates seamless integration. However, a significant concern associated with ReRAMs is their electro-thermal reliability. This research delves into how material properties comprising a ReRAM device and fabrication factors, such as the surface roughness of the material, can impact the electrical and thermal reliability of a ReRAM cell. In this context, a novel methodology has been introduced to predict cell degradation within ReRAM crossbar arrays induced by thermal cross-talk, considering material properties and the geometry of the device. The new methodology has been thoroughly verified on manufactured ReRAM arrays with various composite electrodes. The study also presents experimental results demonstrating the rupture of cell filaments due to remote heating, along with instances of spontaneous filament restoration due to subsequent cooling.

Emerging memory technologies are being intensively investigated for extending Moore\'s law in the next decade. The conductive bridge random access memory (CBRAM) is one of the most promising candidates. CBRAM shows unique nanoionics-based filamentary switching mechanism. Compared to flash memory, the advantages of CBRAM include excellent scalability, low power consumption, high OFF-/ON-state resistance ratio, good endurance, and long retention. Besides the nonvolatile memory applications, resistive switching devices implement the function of memristor which is the fourth basic electrical component. This research presents the characterization and modeling of Cu/TaOx/Pt resistive switching devices. Both Cu and oxygen vacancy nanofilaments can conduct current according to the polarity of bias voltage. The volatile resistive switching phenomenon has been observed on Cu/TaOx/delta-Cu/Pt devices and explained by a flux balancing model. The resistive devices are also connected in series and in anti-parallel manner. These circuit elements are tested for chaotic neural circuit. The quantum conduction has been observed in the I-V characteristics of devices, evidencing the metallic contact between the nanofilament and electrodes. The model of filament radial growth has been developed to explain the transient I-V relation and multilevel switching in the metallic contact regime. The electroforming/SET and RESET processes have been simulated according to the mechanism of conductive filament formation and rupture and validated by experimental results. The Joule and Thomson heating effects have also been investigated for the RESET processes. / Ph. D.

While the scaling of conventional memories based on floating gate MOSFETs is getting increasingly difficult, novel type of non-volatile memories, such as resistive switching memories, have lately found increased attention by both industry and academia. Resistive switching memory (ReRAM) is being considered one of the prime candidates for next-generation non-volatile memory due to relatively high switching speed, superior scalability, low power consumption, good retention and simplicity of its structure which does not require the expensive real estate structure of the silicon substrate. Furthermore, integration of ReRAM directly into a CMOS low-k/Cu interconnect module would not only reduce latency in connectivity constrained devices, but also would reduce chip's footprint by stacking memory layers on top of the logic circuits. One good candidate is the well-behaved Cu/TaOx/Pt resistive switching device. However, since platinum (Pt) acting as the inert electrode is not an economic choice for industrial production, a Back End of Line (BEOL)-compatible replacement of Pt is highly desirable. A systematic investigation has been conducted and metals such as Ru, Rh and Ir are found to be the best potential candidates to supplant Pt. The device properties of Ru, Rh and Ir based resistive switching devices have been explored in this work. However, the challenges of implementing ReRAM cell into BEOL of CMOS encompass not only the choice of materials of a CBRAM cell proper, but also the way the cell is embedded within BEOL. In case of the inert electrode, the metal interfacing the solid electrolyte (e.g. TaOx) has to be supplanted by a glue layer, and heat transport layer, leading to an engineering task of a composite electrode beyond the requirements of low miscibility with, and low surface diffusivity of the inert electrode with respect of the active metal atoms released by the active electrode (here Cu). The metal of the active electrode (Cu, Ag, Ni) is required to allow for a copious redox reaction but simultaneously preventing reactions with the dielectric. Finally, for the solid electrolyte, a dielectric with a moderate level of defects is preferred which may be controlled, for example by the deposition processes modulating the stoichiometry of the material. This research study begins with exploration of several devices derived from the benchmark device Cu/TaOx/Pt and manufacturing those in Micron nanofabrication and characterization laboratory at Virginia Tech with the latter device used as a benchmark for performance assessment. Electric characterization of the manufactured Cu/TaOx/Ru devices has shown some notable differences between them due to the different formation, shape and rupture of the conductive filament. The inferior switching properties of the Ru device have been attributed to the substantially degraded inertness properties of the Ru electrode as a stopping barrier for Cu as compared to the Pt electrode. To study this degradation effect further, two nominally identical devices however differently embedded on the Si wafer have been fabricated. The electric behavior of the two devices are found to be markedly different and is attributed to the difference in high local temperatures in the device during the switching that cause species interlayer diffusion and trigger undesired chemical reactions. Thus, the embedment of the device has a foremost impact on the intrinsic device performance. To investigate the impact of inert electrode on the endurance of ReRAM memory cells, baseline device Cu/TaOx/Pt/Ti is compared with six devices manufactured with different inert electrode constructions: Pt/Cr, Rh/Cr, Rh/Ti, Rh/Al2O3, Ir/Ti, and Ir/Cr, while the Cu electrode and the TaOx dielectric are identical. Although the glue layers Ti, Cr or Al2O3 are not an inherent part of the device proper, they have a tangible impact on the device endurance as well. It is experimentally demonstrated that inert electrodes with high thermal conductivities have superior endurance properties over an electrode with low thermal conductivity and the heat conductivity of inert electrode has a substantial impact on ReRAM cell performance. Since reset operation is a thermally driven process, frequent switching of resistive memory cell leads to a local accumulation of Joules heat, especially when the switching rate is faster than the heat removal rate. This investigation of local heating effects led to the exploration of non-local heat transfer within a memory array. In a crossbar arranged ReRAM cell array, heat generated in one device spreads via common electrode metal lines to the neighboring cells causing their performance degradation constituting non-local heat transfer mechanism leading to performance deterioration of neighboring cells. In addition to the electrical characterization of devices affected by the remote heat transfer, novel cell array architectures have been proposed and investigated with the goal to significantly mitigate the cell-to-cell thermal crosstalk. One of the possible mitigation measures would be modified cell erasure algorithm. / Doctor of Philosophy / Emerging memory technologies are being intensively investigated for extending Moore's scaling law in the next decade. The resistive random-access memory (ReRAM) is one of the most propitious contenders to replace the current ubiquitous FLASH memory. ReRAM shows unique nanoionics based filamentary switching mechanism. Compared to the current nonvolatile memory based on floating gate MOSFET transistor, the advantages of ReRAM include superior scalability, low power consumption, high OFF-/ON-state resistance ratio, excellent endurance, and long retention of the logic bit states. Besides the nonvolatile memory applications, resistive switching devices implement the function of a memristor which is the fourth basic electrical component and can be used for neuromorphic computing. A ReRAM device is in essence a metal-insulator-metal structure. One of the metal electrodes is called the active electrode and provides the building material for the filamentary connection between the electrodes. An important requirement of the second electrode, called the inert electrode, is to be immiscible with the metal atoms of the active electrode and to exhibit a minimum of susceptibility to structural changes and chemical reactions. This research presents a thorough investigation of the role and properties of the inert electrode and offers guideline for the optimal selection of the inert electrode in a commercially viable product. It has been found out that one important property of the inert electrode is its heat conductivity and also the way the inert electrode is embedded on a substrate. Consequently, the concept of the inert electrode has been replaced by the concept of engineered inert electrode module which evolved from a single metal layer to a multilayer stack displaying glue layers, high thermal conductivity layers dissipating the heat quickly, and diffusion stop layers eliminating unwanted chemical reactions. The investigation of the electro-thermal effects led to the discovery of the cell-to-cell thermal cross talk within the memory array which can seriously affect the performance of cells impacted by the remote heat transfer. When a memory cell is switched repeatedly a considerable amount of heat is dissipated in the cell and the heat may spread to neighboring cells that share the same metal lines. This heat transfer causes degradation of electrical performance of the neighboring cells. A method has been developed to characterize quantitatively how the electrical performance is affected by the thermal cross-talk impacting the electric performance of neighboring cells. Several novel mitigation strategies of new memory array architectures have been proposed and investigated.

付記する学位プログラム名: 京都大学卓越大学院プログラム「先端光・電子デバイス創成学」 / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第24622号 / 工博第5128号 / 新制||工||1980(附属図書館) / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 木本 恒暢, 教授 白石 誠司, 准教授 小林 圭 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Recently, the resistance switching random access memory (ReRAM) in several MIM systems has been studied extensively for applications to the next generation non-volatile memory (NVM) devices and memristors since the scaling of conventional memories based on floating gate MOSFETs is getting increasingly difficult. ReRAM is being considered one of the most promising candidates for next generation non-volatile memory due to its relatively high switching speed, superior scalability, low power consumption, good retention and simple fabrication method. Cu/TaOX/Pt resistive switching device is a very good candidate due to its well performance and well characterization. However, since platinum (Pt) acting as the inert electrode is not economical efficient for industrial production, a compatible replacement of Pt is highly desirable. The device property of Co based resistive switching devices has been explored in this work. Compared with Pt devices, electric characterization of the fabricated Cu/TaOX/Co devices exhibits very similar FORM, SET and RESET voltages for Cu conductive filaments. However, for the oxygen vacancy (VO) filament the Co device has a significant smaller FORM, SET and RESET voltages of VO filament, which can be partly attributed to the work function difference between Pt and Co of 1.35 V and partly to the impaired integrity properties of Co vs Pt inert electrode. The limit of SET-RESET operations is mainly due to the geometrical shape of the Cu conductive filament is more cylindered rather than Cone-like shape as well as the high Joules heat dissipation. What’s more, ReRAM is also the most promising candidate for a flexible memory, as a variety of materials can be used both inorganics, organics and even hybrid nanocomposites. Besides inorganic ReRAM device, we also fabricated an organic ReRAM device with the structure Cu doped PANI-CSA/O-AA/Al. We have manufactured ReRAM based on Cu-doped PANI-CSA polymer electrode, O-AA as the polymer solid electrolyte and Al as the bottom electrode for the first time. This polymer device shows a significantly lower forming voltage than inorganic ReRAM devices such as Cu/TaOX/Pt. Our results also demonstrate that our organic ReRAM is a promising candidate for inexpensive candidate for inexpensive and environmentally friendly memory devices. We have demonstrated that the FORM operation of the polymer devices depends on the concentration of Cu+ ions as well as the thickness of the polymer electrode. / M.S. / Although the scaling of conventional memories such as volatile dynamic random access memory (DRAM) and non-volatile flash technology is becoming increasingly difficult, new types of non-volatile memories, such as resistive switching memories, have recently attracted the attention of both industry and academia. Resistive switching memory is considered as the next generation non-volatile memory because of its excellent scalability, high switching speed, simple structure and low power consumption. What’s more, ReRAM is also a promising candidate for a flexible memory, as a variety of materials can be used both inorganics, organics and even hybrid nanocomposites. ReRAM shows unique nanoionics based filamentary switching mechanism. Besides the nonvolatile memory applications, resistive switching devices implement the formation of a memristor, which is the fourth basic electrical component and can be used for neuromorphic computing. First, we report the device property of Co based resistive switching devices with a structure of Cu/TaOX/Co layers. The I-V characteristics of the manufactured Cu/TaOX/Co devices shows very similar FORM, SET and RESET voltages for Cu conductive filaments compared with Pt device. However, the Co device has a significant smaller FORM, SET and RESET voltages for oxygen vacancy (VO) filaments, which can be partly attributed to the work function difference between Pt and Co of 13.5 eV and partly to the impaired integrity properties of Co vs Pt inert electrode. The main reason for the limit of SET-RESET operations is that high Joules heat dissipation. With high Joules heat accumulation, the maximum switching cycles of Co devices is up to 8 times, while in the case of Pt cases, it is almost unlimited. Secondly, we fabricated an organic ReRAM device with the structure Cu-doped PANI-CSA/O-AA/Al. Cu-doped PANI-CSA polymer electrode has been introduced for the first time as the top polymer electrode of a ReRAM device. Compared to inorganic ReRAM device, this polymer device can be operated at a significantly lower forming voltage than inorganic devices such as Cu/TaOX/Pt. We have demonstrated that our organic ReRAM is a promising candidate for environmentally friendly and flexible memory devices. Our results demonstrate the FORM operation of the polymer devices depend on the concentration of Cu+ ions as well as the thickness of the polymer top layer.

Das Konzept neuartiger, resistiv schaltender Langzeitspeicherzellen sieht eine enorme Erhöhung der Speicherdichte bei gleichzeitig geringem Energieverbrauch und hoher Skalierbarkeit vor. In diesem Zusammenhang sind unterschiedlichste Übergangsmetalloxide Gegenstand der aktuellen Forschung, die zwischen Metallelektroden in einer Metall-Isolator-Metall-Struktur eingebettet sind. Ein anerkanntes Modell zur Klärung der lokalen Struktur innerhalb des Schaltmechanismus beschreibt die Änderung des resistiven Zustandes in der wechselnden Ausbildung und Auflösung eines leitfähigen Pfades in der Oxidschicht, der beide Elektroden miteinander verbindet. Die vorliegende Arbeit befasst sich auf dieser Grundlage mit der Untersuchung solcher Speicherzellen, wobei anhand der gewählten Elektrodenmaterialien Speichereffekte rein auf Änderungen im Oxid zurückzuführen sind. Die sich daraus ergebende Möglichkeit der gezielten Änderung des efekthaushaltes und des resistiven Schaltverhaltens der Oxidschichten durch deren Ausheizung oder Modifikation mittels Ionenimplantation stand im Fokus der Arbeit. Dementsprechend muss für eine genaue Lokalisierung des Schaltmechanismus die gewählte Oxidstruktur nicht nur genauestens bekannt, sondern auch möglichst rein sein. Zur Vereinigung all diese Faktoren wird das Modellsystem SrO-TiO2 mit den beiden Vertretern TiO2 und SrTiO3 untersucht, da seine Eigenschaften in der Literatur bereits rege diskutiert wurden. Zur Gewährleistung der Reinheit der Schichten wird die Herstellung der Isolatorschichten durch Atomlagenabscheidung eingesetzt und deren Optimierung, sowie Schichtcharakterisierung im ersten Teil der Arbeit vorgestellt. Mittels einer Vielzahl optischer und struktureller Analysemethoden lassen sich definierte Rückschlüsse über die Eigenschaften der Oxide ziehen. Sämtliche Veröffentlichungen zur Herstellung von SrTiO3 mittels Atomlagenabscheidung beziehen sich entweder auf eigens hergestellte Anlagensysteme oder Präkursormaterialien, wodurch die Schichten industriell nicht reproduzierbar sind. Eines der Ergebnisse der vorliegenden Arbeit ermöglicht eben dies durch die erstmalige Kombination einer kommerziell erhältlichen Anlage mit kommerziellen Präkursormaterialien. Nach deren Optimierung werden die Oxidschichten zwischen den beiden Metallelektroden Au und TiN integriert und die daraus resultierenden Speicherzellen elektrisch charakterisiert. Es kann bipolares, nichtflüchtiges, resistives Schaltverhalten in amorphen und ex situ kristallisierten Oxiden nachgewiesen werden. Anhand von Struktur-Eigenschaft-Korrelationen gelingt es, die Leitungsmechanismen in den untersuchten Speicherzellen als Schottky-Emission und bei ausreichend hohen Spannungen als volumendominierte Poole-Frenkel-Emission zu charakterisieren. Bei den dafür notwendigen Defekten handelt es sich um flache Donatorzustände. Die Annahme des resistiven Schaltens über einen reversiblen leitfähigen Pfad basierend auf Defektzuständen wird durch die Änderung der Coulomb-Barrierenhöhe bei konstanter Schottky-Barrierenhöhe innerhalb derselben Mikrostruktur bestätigt. Besonders das untersuchte TiO2 amorpher Struktur mit Schalt- und Lesegeschwindigkeiten von wenigen Millisekunden, aber auch polykristallines SrTiO3 zeigen ein hohes Potential für deren zukünftige Anwendung auf dem Gebiet resistiv schaltender Speicherzellen. Durch Kr+-Ionenimplantation ändern sich nachweislich sowohl die elektrischen als auch die strukturellen Eigenschaften in TiO2 und SrTiO3. XRD-Messungen an polykristallinen TiO2-Schichten bestätigen die mittels SRIM durchgeführten Simulationsdaten und zeigen für Implantationen ausreichend hoher Fluenzen eine Amorphisierung der kristallinen Strukturen durch atomare Umverteilung im Oxid. Dadurch bilden sich zusätzlich intrinsische, tiefe Defektniveaus in den Oxidschichten, welche das resistive Schalten modifizieren. Die Implantation polykristalliner TiO2-Schichten führt nachweislich zur Umwandlung flüchtiger in nichtflüchtige Schaltkurven, die im Vergleich zu amorphen Ausgangsproben stabilere Widerstandswerte bei geringerem Energieaufwand zeigen. / The concept of novel, longterm resistive switching memories is based on an enormous increase of the storage density with a simultaneous low energy consumption and a high scalability. In this context, different transition metal oxides, which are embedded between metal electrodes in a metal-insulatormetal structure, are part of the ongoing research. A widely recognized model for an explanation of the local structure within the switching mechanism discribes the alteration of the resistive state as a result of an alternating forming and interruption of a conducting path inside an oxide layer. The presence of such a filament acts like a linkage between the electrodes. Based on that, the present study deals with the investigation of such memory storages. In the wake of this the chosen electrode materials enables the determination of memory effects due to pure modifications inside the oxide layers. Thus, a targeted manipulation of defects and the resistive switching mechanism becomes possible by annealing of the layer or its modification by ion implantation which was the central challenge. Therefore the used oxide structures have to be well reputed and, additionally, almost free of defects to be able to localize changes in the switching mechanism exactly. To combine all this facts, the model system SrO-TiO2 is investigated with the two compounds TiO2 und SrTiO3. The properties of this system are already well discussed in literature. To ensure the purity of the layers, they are created by atomic layer deposition. The optimisation of the deposition process and layer characterization is presented in the first part of this study. Using a variety of optical and structural analysis methods allows defined conclusions about the oxide properties. All publications concerning the atomic layer deposition of SrTiO3 deal with self-made devices or precursor materials foreclosing an industrial reproduction. One of the results of this thesis enables exactly that by a combination of a commerically available device and commercial precursor materials. After its optimisation, the oxide layers are integrated between the two electrode materials Au and TiN in order to characterize the electrical properties of the resulting memory cells. Bipolar, nonvolatile resistive switching can be proved for amorphous and ex situ crystallised oxides. Based on structure-property correlations the conduction mechanism within the investigated cells can be identified as Schottky emission and for sufficiently high voltage as volume-dominated Poole Frenkel emission. The necessary defects therefore are determined to be shallow donor states. The assumption of resistive switching based on a reversible conducting filament consisting of defect states is confirmed by a changing Coulomb barrier high during the high of the Schottky barrier remains contant. Especially amorphous TiO2 with switching and reading speeds up to a few milliseconds, but also polycrystalline SrTiO3 showing high potential for future implementation in resistive switching memory cells. By use of Kr+ ion implantation the electrical and structural properties of TiO2 and SrTiO3 are changed. XRD measurements at crystalline TiO2 layers verify simulation data carried out by SRIM. For high enough fluences it shows an amorphisation of the crystalline structures by atomic redistribution inside the oxids. Thus, additionally intrinsic deep defects are created inside the oxide layers which modify the resistive switching character. A special focus is on the transformation of crystalline volatile switching TiO2 layers into amorphous non-volatile memory devices which shows more stable resistance values combined with lower energy input compared to initial amorphous layers.

abstract: Programmable Metallization Cell (PMC) devices are, in essence, redox-based solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

Sneak path current is a significant remaining obstacle to the utilization of large crossbar arrays for non-volatile memories and other applications of memristors. A two-terminal selector device with an extremely large current-voltage nonlinearity and low leakage current could solve this problem. We present here a Ag/oxide-based threshold switching (TS) device with attractive features such as high current-voltage nonlinearity (~1010), steep turn-on slope (less than 1 mV/dec), low OFF-state leakage current (~10-14 A), fast turn ON/OFF speeds (<75/250 ns), and good endurance (>108 cycles). The feasibility of using this selector with a typical memristor has been demonstrated by physically integrating them into a multilayered 1S1R cell. Structural analysis of the nanoscale crosspoint device suggests that elongation of a Ag nanoparticle under voltage bias followed by spontaneous reformation of a more spherical shape after power off is responsible for the observed threshold switching of the device. Such mechanism has been quantitatively verified by the Ag nanoparticle dynamics simulation based on thermal diffusion assisted by bipolar electrode effect and interfacial energy minimization.

Táto práca sa zaoberá technikou výroby samousporiadaných nanoštruktúr pre elektrické aplikácie. Prototypy boli pripravené anodickou oxidáciou v dvoch dĺžkach a tromi rôznymi tepelnými úpravami. Štrukturálna charakterizácia bola spravená pomocou techniky SEM, TEM a EDX a vyhodnotenie nielen z štrukturálneho, ale aj z materiálového hľadiska. Jedinečná koreňová štruktúra samousporiadaných nanotyčiniek bola vyhodnotená a porovnaná po troch rôznych tepelných úpravách: po anodizácii, po vákuovom žíhaní, a po žíhaní vo vzduchu. Všetky prototypy obsahujú nanotyčinky s amorfnou štruktúrou, ale našli sa však aj nanokryštály pod koreňovými štruktúrami. Elektrická charakterizácia prototypov ukázala: odporové spínacie správanie (RS), diódové charakteristiky a charakteristiku podobnú pre diódy s kapacitorom. Aktívny povrch pre spínací mechanizmus je v hornej časti nanoštruktúr na rozhraní nanotyčiniek a zlatej elektródy. Výška Schottkyho bariéry na rozhraní Ti / TiO2 bola vypočítaná dvoma spôsobmi a pre všetky tri zariadenia bola nižšia ako 1,11 eV.

Объектом исследования являются структуры металл/полупроводник/металл на основе анодированных слоев диоксида титана толщиной от 60 до 500 нм с диаметром нанотрубок от 30 до 60 нм, полученных во фторсодержащем растворе. Цель работы – исследование влияния толщины оксидного слоя, материала электрода и его площади на процессы резистивного переключения сэндвич-структур Ti/TiO2/Ме на основе нанотубулярного диоксида титана. Синтезированы сэндвич-структуры Ti/TiO2-НТ/Au и Ti/TiO2-НТ/Ag с диаметрами мемристивных элементов ≈ 100 мкм и ≈ 5,5 мм. Аттестация образцов проведена методами растровой электронной и оптической микроскопии, рентгенофазового анализа и спектроскопии комбинационного рассеяния. Исследованы ВАХ сфабрикованных структур в полных циклах резистивного переключения и в процессах, симулирующих многократное считывание информации. Получено, что микромемристор Ti/TiO2-НТ/Au с толщиной оксидного слоя 160 нм имеет наилучшие характеристики биполярного переключения среди исследованных. Продемонстрирована работоспособность структуры на протяжении 17 тыс. циклов переключения. Сделан вывод о возможности использования микромемристоров Ti/TiO2-НТ/Au в качестве перспективных элементов резистивной памяти. / The object of investigation of metal/semiconductor/metal structures based on the anodized layer of titanium dioxide. Ones are 60 – 500 nm thick with 30 – 60 nm diameter of nanotubes obtained in fluorine-containing solution. The goal of this paper is to investigate the effect of oxide layer thickness, its electrode material and the area on resistive switching processes in sandwich Ti/TiO2/Me nanotubular structures based on titanium dioxide. Sandwich structures of Ti/TiO2-NT/Au and Ti/TiO2-NT/Ag with diameters of memristive elements about 5.5 mm and 100 µm have been synthesized. Characterization of samples was carried out by scanning electron and optical microscopy, X-ray diffraction and Raman spectroscopy. CVC fabricated structures in the full cycle of the resistive switching and processes simulating multiple reading of information were studied. It was found that Ti/TiO2-NT/Au micromemristor with a thickness of the oxide layer about 160 nm has the best bipolar switching characteristics among studied samples. Structure performance within 17 thousands switching cycles was demonstrated. It is concluded that Ti/TiO2-NT/Au micromemristors were proved to be promising resistive memory elements.