Pulse Electrodeposition of Lead-Free Tin-Based Composites for Microelectronic Packaging

This chapter provides a detailed overview of the various Sn-based composites solders reinforced with ceramic nanoparticles. These solders are lead free in nature and are produced by various process like powder metallurgy, ball milling, casting as well as simple and economic pulse co-electrodeposition technique. In this chapter, various electrodeposited composite solders, their synthesis, characterization, and evaluation of various properties for microelectronic packaging applications, such as microstructure, microhardness, density and porosity, wear and friction, electrochemical corrosion, melting point, electrical resistivity, and residual stress of the monolithic Sn-based and (nano)composite solders have been presented and discussed. This chapter is divided into the following sections: such as introduction to microelectronic packaging, synthesis routes for solders and composites, various nanoreinforcement, and the mechanism of incorporation in solder matrix, the pulse co-electrodeposition technique, the various factors affecting composite deposition, and the improved properties of composite solders over monolithic solders for microelectronic packaging applications are also summarized here

Probing resistive switching in HfO2/Al2O3 bilayer oxides using in-situ transmission electron microscopy

In this work, we investigate the resistive switching in hafnium dioxide (HfO2) and aluminum oxide (Al2O3) bilayered stacks using in-situ transmission electron microscopy and X-ray energy dispersive spectroscopy. Conductance of the HfO2/Al2O3 stack changes gradually upon electrical stressing which is related to the formation of extended nanoscale physical defects at the HfO2/Al2O3 interface and the migration and re-crystallization of Al into the oxide bulk. The results suggest two competing physical mechanisms including the redistribution of oxygen ions and the migration of Al species from the Al electrode during the switching process. While the HfO2/Al2O3 bilayered stack appears to be a good candidate for RRAM technology, the low diffusion barrier of the active Al electrode causes severe Al migration in the bi-layered oxides leading to the device to fail in resetting, and thereby, largely limiting the overall switching performance and material reliability

Research Institute for Physical Chemical Problems of the Belarusian State University

Edition contains information about the history of Research Institute for Physical Chemical Problems of the Belarusian State University, contact data and institute`s structure. The main developments of the institute are described also.Edition contains information about the history of Research Institute for Physical Chemical Problems of the Belarusian State University, contact data and institute`s structure. The main developments of the institute are described also

Defect Engineering in HfO2/TiN-based Resistive Random Access Memory (RRAM) Devices by Reactive Molecular Beam Epitaxy

Recently, there has been huge interest in emerging memory technologies, spurred by the ever increasing demand for storage capacities in various applications like Internet of Things (IoT), Big Data, etc. CMOS based flash memory, the current mainstay of the memory technology, has been able to increase its density by scaling down to a 16 nm node and further implementation of 3D architectures. However, flash memory is expected to soon run into disadvantage due to challenges in further scaling. Therefore, extensive efforts are being made towards developing new devices for the next generation of non-volatile memories with the combined advantages of flash memory like non-volatility, high density, low cost and low power consumption as well as high speed performance of DRAM. Among the many competitors, resistive random access memories (RRAM) based on resistive switching in oxides are promising due to its simple metal-insulator-metal (MIM) structure, fast switching speeds (<10 ns), excellent scalability (<10 nm) and potential for multi-level switching. RRAM devices based on the popular dielectric-metal gate combination of hafnium oxide (HfO2) and titanium nitride (TiN), which is the subject of research in this work, are particularly interesting due to its compatibility with existing CMOS technology in addition to the aforementioned advantages. Though prototype RRAM chips have already been demonstrated, key problems for commercial realization of RRAM include large variability and insufficient understanding of the complex switching physics. Resistive switching mechanism in oxides is generally understood to be mediated via the transport of oxygen ions leading to the formation of a conductive filament composed of oxygen vacancy defects. Appropriate defect engineering approaches offer potential towards tailoring the switching behavior as well as improving the performance and yield of HfO2-RRAM. In this thesis, the impact of pre-induced defects on the resistive switching behavior of HfO2-RRAM is investigated in detail and our results are presented. Defect engineered oxide thin films were deposited using reactive molecular beam epitaxy (RMBE) to fabricate metal oxide/TiN based devices. RMBE technique offers the unique possibility to precisely and reproducibly control the oxygen stoichiometry of the thin films in a wide range. Using RMBE, defects were introduced in polycrystalline HfOx thin films intrinsically by oxygen stoichiometry engineering and extrinsically via impurity doping (trivalent lanthanum and pentavalent tantalum). Both the studies were performed at at CMOS compatible deposition temperatures (< 450 °C) with an eye on practical applications. Prior to tantalum doping in HfO2, oxygen stoichiometry engineering studies were also performed in amorphous tantalum oxide (TaOx) thin films to identify the oxidation conditions of tantalum metal. The density of oxygen stoichiometry engineered thin films of HfOx and TaOx could be tuned in a wide range from that of the bulk oxide density to close to metallic density. High degree of oxygen deficiency in oxides led to the formation of defect states near the Fermi level as well as multiple oxidation states of the metal, as observed by X-ray photoelectron spectroscopy (XPS). The pure stoichiometric hafnium oxide films crystallize as expected in a stable monoclinic structure (m-HfO2) whereas, oxygen deficient HfOx thin films were found to crystallize in vacancy stabilized tetragonal like structure (t-HfO2-x). Impurity doping also led to the stabilization of higher symmetry tetragonal (t-Ta:HfOx) or cubic structures (c-La:HfOx) depending on the ionic radii of the dopant. The growth of TiN thin films was also investigated using RMBE. The devices used for electrical studies in this work mostly involved deposition of oxides by RMBE on polycrystalline TiN/Si electrodes after ex-situ transfer for further deposition. Therefore, RMBE grown TiN thin film electrodes with similar or better quality would allow in-situ uninterrupted deposition of subsequent oxide layers in future to form cleaner interfaces. Optimized conditions for growth of epitaxial TiN films on the commercially relevant (001) oriented silicon and c-cut sapphire substrates were established, with focus on achieving smooth surfaces and low resistivity. High quality epitaxial TiN(111)||Al2O3(0001) and TiN(001)||Si(001) films with a low resistivity (20-200 uOhm.cm) were achieved, in spite of the large lattice mismatch. Very low surface roughness, characterized by a streaky reflection high energy electron diffraction (RHEED) pattern during TiN film growth was additionally obtained, by tuning the Ti/N flux ratios. Oxygen engineered HfOx/TiN devices were further electrically characterized to obtain I-V characteristics during quasi-static DC switching. Usually, an initial electroforming step (high voltages) is required to obtain further reproducible switching operation (at lower voltages). High device to device variability in RRAM is typically associated with the stochastic nature of electroforming process which increases at higher forming voltages. Using highly oxygen deficient HfOx and TaOx films, the forming voltages were found to be reduced to levels close to operating voltages, paving the way for forming-free devices. However, the use of high defect concentration adds to increasing the complexity of the switching mechanism. This is reflected in the rather complex and dissimilar switching behaviors observed in the myriad of similar RRAM devices reported in the rapidly growing literature. Using model Pt/HfOx/TiN-based device stacks; it is shown that a well-controlled oxygen stoichiometry governs the filament formation and the (partial) occurrence of multiple resistive switching modes (bipolar, unipolar, threshold, complementary). These findings fuel a better fundamental understanding of the underlying phenomena for future theoretical considerations. The oxygen vacancy concentration is found to be the key factor in manipulating the balance between electric field and Joule heating during formation, rupture (reset), and reformation (set) of the conductive filaments in the dielectric. While a bipolar switching occurs in all the devices irrespective of defect concentration, switching modes like unipolar and threshold switching is favored only at higher oxygen stoichiometry. This suggests the suppression of thermal effects via higher heat dissipation and lowered concentration gradient of oxygen vacancies in oxygen deficient devices. A qualitative switching model based on the drift, diffusion and thermophoresis of oxygen ions is suggested to account for the partial occurrence of various switching modes depending on the oxygen stoichiometry. Further, the evolution or drift of high resistance states during endurance test of the common bipolar operation is compared for HfO2 and HfO1.5 based devices and interpreted using the quantum point contact (QPC) model. Similar observations regarding switching modes were also obtained in oxygen engineered Pt/TaOx/TiN devices, therefore allowing the findings to be generalized to other filamentary resistive switching oxides and contributing towards developing a unified switching model. Besides finding application as non-volatile memory, RRAM devices are also promising for hardware implementation of neuromorphic computing. This is motivated by the possibility of multi-level switching or gradual (analog) modulation of resistance in an RRAM device which can emulate biological synapses. Defect engineering approaches have thus been investigated in Pt/hafnium oxide/TiN devices for tuning the DC I-V switching dynamics to achieve multi-level or gradual switching electronic synapses. Higher contribution of thermal effects in pure stoichiometric HfO2 typically results in a single sharp set process and abrupt sharp current jumps during the reset process during a conventional bipolar operation. By using ~18% La-doped HfOx based device, a completely gradual reset behavior with a higher ON/OFF ratio could be achieved during the bipolar reset operation. This is likely related to filament stabilization around the dopant sites allowing a uniform rupture during reset. More interestingly, in oxygen deficient HfO1.5 based devices, intermediate conductance states corresponding to integer or half-integer multiples of quantum conductance (G0) was observed during both the set and reset operations at room temperature. These are related to the better stabilization of intermediate atomic size filament constrictions during the switching process. Occurrence of these intermediate quantum conductance states, especially during the typically abrupt set process, is likely aided by a weaker filament and better thermal dissipation in the highly oxygen deficient devices. These results suggest that a combination of doping and high oxygen vacancy concentration may lead to improved synaptic functionality with concurrent gradual set and reset behaviors

Microstructure and Functionalities in Epitaxial Manganites Based Vertically Aligned Nanocomposite Thin Films

Vertically aligned nanocomposite (VAN) presents as a novel material platform for creating high-quality self-assembled, nano-pillars of one phase in matrix of another structures. In the past decade, extensive efforts have been devoted and demonstrated the great potential of VAN thin films in enabling novel and enhanced functionalities. Mixed valence La1-xSrxMnO3 (LSMO) exhibits unique magnetic and transport properties, promising for spintronic device applications. In this dissertation, novel and enhanced magnetic and electrical functionalities including low-field magnetoresistance (LFMR), magnetic exchange bias (EB), etc., are explored using VAN design, with a focus on the LSMO based materials. By selecting CeO2 and CuO as the secondary phases and optimizing the growth conditions, large and tunable LFMR in a wide temperature region has been achieved in LSMO: CeO2 and LSMO: CuO VAN films. Detailed analysis indicate that the phase boundaries, the secondary phase domain size, and the strain states in the films contribute to the enhanced LFMR in different temperature regions. Perpendicular exchange bias (PEB) is desired in next-generation memories to offer perpendicular unidirectional magnetic anisotropy. By confining ferromagnetic (FM) and antiferromagnetic (AFM) hetero-interfaces coupling in the vertical direction, strong PEB effect are demonstrated in the LSMO: LaFeO3 VAN films. The microstructures, PEB behavior correlated with the composition variation, strain tuning and cooling field effect are analyzed. A spin-glass (SG) state at the vertical interfaces is ascribed to be responsible for the remarkable PEB here. Conventional VAN films tend to present random distributed pillars in matrix structure. Achieving spatial ordering is timely demanded. Here, a novel approach are introduced for one-step self-organization growth of VAN films with long range ordering by substrate nano-templating. The SrTiO3 (001) substrates with surface nanopatterns of alternating chemical terminations developed by thermal treatment are demonstrated to be effective for selective growth of well-ordered VAN structures, using LSMO: CeO2 as a prototype. Remarkable enhanced magnetic and transport properties is achieved for the templated films. The studies in this dissertation exploited the capability of the unique VAN structures in enhancing the magnetic and transport performance of LSMO based nanocomposite materials. Great enhanced LFMR, PEB as well as well-ordered nanostructures have been achieved. The VAN design provide a powerful way in enabling novel and enhanced functionalities, promising for spintronic devices applications

Nuclear Fusion Programme: Annual Report of the Association Karlsruhe Institute of Technology (KIT)/EURATOM ; January 2009 - December 2009 (KIT Scientific Reports ; 7548)

The Karlsruhe Institute of Technology (KIT) is working in the framework of the European Fusion Programme on key technologies in the areas of superconducting magnets, microwave heating systems (Electron-Cyclotron-Resonance-Heating, ECRH), the deuterium-tritium fuel cycle, He-cooled breeding blankets, a He-cooled divertor and structural materials, as well as refractory metals for high heat flux applications including a major participation in the preparation of the international IFMIF project

Towards Oxide Electronics:a Roadmap

At the end of a rush lasting over half a century, in which CMOS technology has been experiencing a constant and breathtaking increase of device speed and density, Moore's law is approaching the insurmountable barrier given by the ultimate atomic nature of matter. A major challenge for 21st century scientists is finding novel strategies, concepts and materials for replacing silicon-based CMOS semiconductor technologies and guaranteeing a continued and steady technological progress in next decades. Among the materials classes candidate to contribute to this momentous challenge, oxide films and heterostructures are a particularly appealing hunting ground. The vastity, intended in pure chemical terms, of this class of compounds, the complexity of their correlated behaviour, and the wealth of functional properties they display, has already made these systems the subject of choice, worldwide, of a strongly networked, dynamic and interdisciplinary research community. Oxide science and technology has been the target of a wide four-year project, named Towards Oxide-Based Electronics (TO-BE), that has been recently running in Europe and has involved as participants several hundred scientists from 29 EU countries. In this review and perspective paper, published as a final deliverable of the TO-BE Action, the opportunities of oxides as future electronic materials for Information and Communication Technologies ICT and Energy are discussed. The paper is organized as a set of contributions, all selected and ordered as individual building blocks of a wider general scheme. After a brief preface by the editors and an introductory contribution, two sections follow. The first is mainly devoted to providing a perspective on the latest theoretical and experimental methods that are employed to investigate oxides and to produce oxide-based films, heterostructures and devices. In the second, all contributions are dedicated to different specific fields of applications of oxide thin films and heterostructures, in sectors as data storage and computing, optics and plasmonics, magnonics, energy conversion and harvesting, and power electronics

Nuclear Fusion Programme: Annual Report of the Association Karlsruhe Institute of Technology/EURATOM ; January 2012 - December 2012 (KIT Scientific Reports ; 7647)

The Karlsruhe Institute of Technology (KIT) is working in the framework of the European Fusion Programme on key technologies in the areas of superconducting magnets, microwave heating systems (Electron-Cyclotron-Resonance-Heating, ECRH), the deuterium-tritium fuel cycle, He-cooled breeding blankets, a He-cooled divertor and structural materials, as well as refractory metals for high heat flux applications including a major participation in the preparation of the international IFMIF project

Elevated temperature mechanical properties of zirconium diboride based ceramics

Research presented in this dissertation focused on the mechanical behavior of ZrB₂ based ceramic at elevated temperatures. Flexure strength, fracture toughness, and elastic modulus were measured at temperatures up to 2300ºC for three compositions: monolithic ZrB₂ (Z); ZrB₂ - 30 vol% SiC - 2 vol% B₄ C (ZS); and ZrB₂ - 10 vol% ZrC (ZC). In argon, Z, ZS, and ZC had strengths of 210 (at 2300ºC), 260 (at 2200ºC), and 295 MPa (at 2300ºC), the highest temperatures tested for each composition. Fractography was used extensively to characterize the strength limiting flaws as a function of temperature. Strength of ZS in argon was controlled by the SiC cluster size up to 1800ºC, and the formation of B-O-C-N phases that bridged SiC clusters above 2000ºC. For ZC, surface flaws introduced during specimen preparation were the source of critical flaws in the material up to 1400ºC, sub-critical crack growth of surface flaws between 1600 and 2000ºC, and microvoid coalescence above 2000ºC. It was also shown that thermal annealing at either 1400, 1500, or 1600ºC improves the strength and modulus of ZS at temperatures between 800ºC and 1600ºC. Heat treatment at 1400ºC for 10 hours produced the largest improvement in strength, 430 MPa at 1600ºC versus 380 MPa for the as processed material. As a whole, the research pointed to several key microstructural features currently limiting the mechanical properties at the highest temperatures. In particular, removal of unfavorable secondary phases, and improved control over microstructure, should be promising methods to improve the elevated temperature properties of ZrB₂ ceramics. --Abstract, page iv