Van der Waals heterostructures with photo-oxidised high- κ dielectrics

The emergence of atomically thin systems has underpinned significant discoveries in fundamental science and game changing innovation in novel technologies such as energy storage and data communication. In this thesis, different types of optoelectronic devices based on van der Waals (vdW) heterostructures are investigated. A high-dielectric (κ) material hafnium disulphide (HfS2) is embedded into these heterostructures and photo-oxidised into hafnium oxide (HfOx) by laser writing selectively and underneath the contacts. Moreover, HfOx as a gate dielectric for field-effect transistors (FET) instead of hexagonal boron nitride (h-BN) is also shown. A dielectric constant for hafnium oxide of ~15 is reported, which shows a novel way to introduce dielectrics in such complicated structures being compatible with two-dimensional 2D materials. Finally, the impact of the dielectric environment on monolayer tungsten diselenide (1L-WSe2) while been surrounded by different dielectric materials such as quartz, hexagonal boron nitride, indium selenide (In2Se3) and hafnium oxide, is demonstrated. The effect of the dielectric environment on the exciton binding energies and quasiparticle bandgap has been investigated by measuring the energy separation between the 1s and 2s states using transmission measurements. The exciton binding energy, as well as the electronic band gap, were found to decrease as the average dielectric constant increases. The largest reduction of band gap by ~300 meV is observed when WSe2 is encapsulated between HfOx compared with that of exposed WSe2 on quartz.Engineering and Physical Sciences Research Council (EPSRC

Memristive Non-Volatile Memory Based on Graphene Materials

Resistive random access memory (RRAM), which is considered as one of the most promising next-generation non-volatile memory (NVM) devices and a representative of memristor technologies, demonstrated great potential in acting as an artificial synapse in the industry of neuromorphic systems and artificial intelligence (AI), due its advantages such as fast operation speed, low power consumption, and high device density. Graphene and related materials (GRMs), especially graphene oxide (GO), acting as active materials for RRAM devices, are considered as a promising alternative to other materials including metal oxides and perovskite materials. Herein, an overview of GRM-based RRAM devices is provided, with discussion about the properties of GRMs, main operation mechanisms for resistive switching (RS) behavior, figure of merit (FoM) summary, and prospect extension of GRM-based RRAM devices. With excellent physical and chemical advantages like intrinsic Young’s modulus (1.0 TPa), good tensile strength (130 GPa), excellent carrier mobility (2.0 × 105 cm2∙V−1∙s−1), and high thermal (5000 Wm−1∙K−1) and superior electrical conductivity (1.0 × 106 S∙m−1), GRMs can act as electrodes and resistive switching media in RRAM devices. In addition, the GRM-based interface between electrode and dielectric can have an effect on atomic diffusion limitation in dielectric and surface effect suppression. Immense amounts of concrete research indicate that GRMs might play a significant role in promoting the large-scale commercialization possibility of RRAM devices

Optoelectronic devices based on atomically thin semiconductors and photo-oxidised HfOx

The direction of research in solid state physics and technology has changed since the discovery of graphene. Now, a plethora of two-dimensional materials are being thoroughly investigated for their unique properties as well as for their implementation in next-generation optoelectronic devices. Of course, much effort is needed in order to reach the current level of modern electronics which is based on decades of research and development. For example, the level of miniaturisation modern technology requires can be achieved with atomically thin materials, driving Moore's Law forward. Conventional dielectrics exhibit high leakage currents when their dimensions are reduced to the nano-scale and the need for alternative materials compatible with two-dimensional electronics arises. However, the techniques that are being used for the growth and processing of conventional semiconducting materials are not always suitable with two-dimensional materials, which need special handling. These are some of the points that will be addressed in this PhD dissertation. Here, a new method for generating a fundamentally two-dimensional high-k dielectric which can be automatically incorporated in atomically thin optoelectronics devices is presented. The photo-oxidation of hafnium disulfide, HfS2, is a straight-forward, non-invasive process that can be used to oxidise pristine few-layered HfS₂, opening new paths for applications ranging from optoelectronics to photonics. The resulting dielectric, Hafnium dioxide, HfO₂, exhibits outstanding properties that exceed those of silicon dioxide, SiO₂ and its atomically thin nature makes it an ideal insulating layer for next-generation nano-electronics. Finally, the last part of this thesis is dedicated to a novel, CVD-grown, n-type monolayer of tungsten diselenide, WSe2. This is the first time negatively doped CVD-grown WSe₂ is reported, which opens the possibility of choosing the doping of the two-dimensional semiconductor before fabrication. For investigating and characterising this novel material, field-effect transistors are fabricated and characterised optoelectronically, shining light on the carriers' behaviour and the ability of the material in light-detection applications. Vacuum and ambient annealing of the WSe2 based devices highlights a possible way to control the doping level of the material, and thus the electrical behaviour of the devices.Engineering and Physical Sciences Research Council (EPSRC

Growth and Oxidation of Graphene and Two-Dimensional Materials for Flexible Electronic Applications

The non-volatile storage of information is becoming increasingly important in our data-driven society. Limitations in conventional devices are driving the research and development of incorporating new materials into conventional device architectures to improve performance, as well as developing an array of emerging memory technologies based on entirely new physical processes. The discovery of graphene allowed for developing new approaches to these problems, both itself and as part of the larger, and ever-expanding family of 2D materials. In this thesis the growth and oxidation of these materials is investigated for implementing into such devices, exploiting some of the unique properties of 2D materials including atomic thinness, mechanical flexibility and tune-ability through chemical modification - to meet some challenges facing the community. This begins with the growth of graphene by chemical vapour deposition for a high quality flexible electrode material, followed by oxidation of graphene for use in resistive memory devices. The theme of oxidation is then extended to another 2D material, HfS2, which is selectively oxidised for use as high-k dielectric in Van der Waals heterostructures for FETs and resistive memory devices. Lastly, a technique for fabrication of graphene-based devices directly on the copper growth substrate is demonstrated for use in flexible devices for sensing touch and humidity

A walk on the frontier of energy electronics with power ultra-wide bandgap oxides and ultra-thin neuromorphic 2D materials

Altres ajuts: the ICN2 is funded also by the CERCA programme / Generalitat de CatalunyaUltra-wide bandgap (UWBG) semiconductors and ultra-thin two-dimensional materials (2D) are at the very frontier of the electronics for energy management or energy electronics. A new generation of UWBG semiconductors will open new territories for higher power rated power electronics and deeper ultraviolet optoelectronics. Gallium oxide - GaO(4.5-4.9 eV), has recently emerged as a suitable platform for extending the limits which are set by conventional (-3 eV) WBG e.g. SiC and GaN and transparent conductive oxides (TCO) e.g. In2O3, ZnO, SnO2. Besides, GaO, the first efficient oxide semiconductor for energy electronics, is opening the door to many more semiconductor oxides (indeed, the largest family of UWBGs) to be investigated. Among these new power electronic materials, ZnGa2O4 (-5 eV) enables bipolar energy electronics, based on a spinel chemistry, for the first time. In the lower power rating end, power consumption also is also a main issue for modern computers and supercomputers. With the predicted end of the Moores law, the memory wall and the heat wall, new electronics materials and new computing paradigms are required to balance the big data (information) and energy requirements, just as the human brain does. Atomically thin 2D-materials, and the rich associated material systems (e.g. graphene (metal), MoS2 (semiconductor) and h-BN (insulator)), have also attracted a lot of attention recently for beyond-silicon neuromorphic computing with record ultra-low power consumption. Thus, energy nanoelectronics based on UWBG and 2D materials are simultaneously extending the current frontiers of electronics and addressing the issue of electricity consumption, a central theme in the actions against climate chang

Standards for the Characterization of Endurance in Resistive Switching Devices

Resistive switching (RS) devices are emerging electronic components that could have applications in multiple types of integrated circuits, including electronic memories, true random number generators, radiofrequency switches, neuromorphic vision sensors, and artificial neural networks. The main factor hindering the massive employment of RS devices in commercial circuits is related to variability and reliability issues, which are usually evaluated through switching endurance tests. However, we note that most studies that claimed high endurances >106 cycles were based on resistance versus cycle plots that contain very few data points (in many cases even <20), and which are collected in only one device. We recommend not to use such a characterization method because it is highly inaccurate and unreliable (i.e., it cannot reliably demonstrate that the device effectively switches in every cycle and it ignores cycle-to-cycle and device-to-device variability). This has created a blurry vision of the real performance of RS devices and in many cases has exaggerated their potential. This article proposes and describes a method for the correct characterization of switching endurance in RS devices; this method aims to construct endurance plots showing one data point per cycle and resistive state and combine data from multiple devices. Adopting this recommended method should result in more reliable literature in the field of RS technologies, which should accelerate their integration in commercial products

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

Preparation and properties of high dose nitrogen implanted epitaxially grown gadolinium oxide on silicon

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Electronic Nanodevices

The start of high-volume production of field-effect transistors with a feature size below 100 nm at the end of the 20th century signaled the transition from microelectronics to nanoelectronics. Since then, downscaling in the semiconductor industry has continued until the recent development of sub-10 nm technologies. The new phenomena and issues as well as the technological challenges of the fabrication and manipulation at the nanoscale have spurred an intense theoretical and experimental research activity. New device structures, operating principles, materials, and measurement techniques have emerged, and new approaches to electronic transport and device modeling have become necessary. Examples are the introduction of vertical MOSFETs in addition to the planar ones to enable the multi-gate approach as well as the development of new tunneling, high-electron mobility, and single-electron devices. The search for new materials such as nanowires, nanotubes, and 2D materials for the transistor channel, dielectrics, and interconnects has been part of the process. New electronic devices, often consisting of nanoscale heterojunctions, have been developed for light emission, transmission, and detection in optoelectronic and photonic systems, as well for new chemical, biological, and environmental sensors. This Special Issue focuses on the design, fabrication, modeling, and demonstration of nanodevices for electronic, optoelectronic, and sensing applications