京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第13240号 / 論工博第4178号 / 新制||工||1720(附属図書館) / (主査)教授 木本 恒暢, 教授 藤田 静雄, 教授 山田 啓文 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第19091号 / エネ博第315号 / 新制||エネ||64(附属図書館) / 32042 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 岸本 泰明, 教授 前川 孝, 教授 中村 祐司 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

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The easiest and most effective way to influence the separation process in gas chromatography (GC) is achieved by controlling the temperature of the chromatographic column. In conventional GC, the temperature along the length of the column is constant at any given time, T(t). In my research, I investigated the effects of temperature gradients on GC separations as a function of time and position, T(t,x), along the column. This separation mode is called thermal gradient GC (TGGC). The research reported in this dissertation highlights the fundamental principles of axial temperature gradients and the separation potential of the TGGC technique. These goals were achieved through the development of mathematical models and instrumentation that allowed study of the effects of axial temperature gradients. The use of mathematical models and computer simulation facilitated evaluation of different gradient profiles and separation strategies prior to development of the instrumentation, providing theoretical proof of concept. Three instruments capable of generating axial temperature gradients, based on convective cooling and resistive heating, were developed and evaluated. Unique axial temperature gradients, such as nonlinear and moving sawtooth temperature gradients with custom profiles were generated and evaluated. The results showed that moving sawtooth temperature gradients allowed continuous analysis and were well-suited for comprehensive GCxGC separations. The use of custom temperature profiles allowed unique control over the separation power of the system, improving separations, as well as selectively increasing the peak capacity and signal-to-noise. A direct comparison of TGGC with conventional GC methods showed that TGGC produces equivalent separations to temperature programmed GC. This technology holds great promise for performing smart separations in which the column volume is most efficiently utilized and optimum separations can be quickly achieved. Moreover, precise control of the elution of compounds can be used to greatly reduce method development time in GC. This feature can be automated using feedback to develop efficient separations with minimum user intervention. This technology is of special interest in micro-GC systems, which allows relatively easy incorporation of resistive heating elements in the micro-column design.

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.