Dielectric Breakdown in Chemical Vapor Deposited Hexagonal Boron Nitride

Insulating films are essential in multiple electronic devices because they can provide essential functionalities, such as capacitance effects and electrical fields. Two-dimensional (2D) layered materials have superb electronic, physical, chemical, thermal, and optical properties, and they can be effectively used to provide additional performances, such as flexibility and transparency. 2D layered insulators are called to be essential in future electronic devices, but their reliability, degradation kinetics, and dielectric breakdown (BD) process are still not understood. In this work, the dielectric breakdown process of multilayer hexagonal boron nitride (h-BN) is analyzed on the nanoscale and on the device level, and the experimental results are studied via theoretical models. It is found that under electrical stress, local charge accumulation and charge trapping/detrapping are the onset mechanisms for dielectric BD formation. By means of conductive atomic force microscopy, the BD event was triggered at several locations on the surface of different dielectrics (SiO2, HfO2, Al2O3, multilayer h-BN, and monolayer h-BN); BD-induced hillocks rapidly appeared on the surface of all of them when the BD was reached, except in monolayer h-BN. The high thermal conductivity of h-BN combined with the one-atom-thick nature are genuine factors contributing to heat dissipation at the BD spot, which avoids self-accelerated and thermally driven catastrophic BD. These results point to monolayer h-BN as a sublime dielectric in terms of reliability, which may have important implications in future digital electronic devices.Fil: Jiang, Lanlan. Soochow University; ChinaFil: Shi, Yuanyuan. Soochow University; China. University of Stanford; Estados UnidosFil: Hui, Fei. Soochow University; China. Massachusetts Institute of Technology; Estados UnidosFil: Tang, Kechao. University of Stanford; Estados UnidosFil: Wu, Qian. Soochow University; ChinaFil: Pan, Chengbin. Soochow University; ChinaFil: Jing, Xu. Soochow University; China. University of Texas at Austin; Estados UnidosFil: Uppal, Hasan. University of Manchester; Reino UnidoFil: Palumbo, Félix Roberto Mario. Comisión Nacional de Energía Atómica; Argentina. Universidad Tecnológica Nacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Lu, Guangyuan. Chinese Academy of Sciences; República de ChinaFil: Wu, Tianru. Chinese Academy of Sciences; República de ChinaFil: Wang, Haomin. Chinese Academy of Sciences; República de ChinaFil: Villena, Marco A.. Soochow University; ChinaFil: Xie, Xiaoming. Chinese Academy of Sciences; República de China. ShanghaiTech University; ChinaFil: McIntyre, Paul C.. University of Stanford; Estados UnidosFil: Lanza, Mario. Soochow University; Chin

Polycrystallization effects on the nanoscale electrical properties of high-k dielectrics

In this study, atomic force microscopy-related techniques have been used to investigate, at the nanoscale, how the polycrystallization of an Al2O3-based gate stack, after a thermal annealing process, affects the variability of its electrical properties. The impact of an electrical stress on the electrical conduction and the charge trapping of amorphous and polycrystalline Al2O3 layers have been also analyzed

Molecular Bridges Link Monolayers of Hexagonal Boron Nitride during Dielectric Breakdown

We use conduction atomic force microscopy (CAFM) to examine the soft breakdown of monocrystalline hexagonal boron nitride (h-BN) and relate the observations to the defect generation and dielectric degradation in the h-BN by charge transport simulations and density functional theory (DFT) calculations. A modified CAFM approach is adopted, whereby 500 7 500 nm2 to 3 7 3 μm2 sized metal/h-BN/metal capacitors are fabricated on 7 to 19 nm-thick h-BN crystal flakes and the CAFM tip is placed on top of the capacitor as an electrical probe. Current-voltage (I-V) sweeps and time-dependent dielectric breakdown measurements indicate that defects are generated gradually over time, leading to a progressive increase in current prior to dielectric breakdown. Typical leakage currents are around 0.3 A/cm2 at a 10 MV/cm applied field. DFT calculations indicate that many types of defects could be generated and contribute to the leakage current. However, three defects created from adjacent boron and nitrogen monovacancies exhibit the lowest formation energy. These three defects form molecular bridges between two adjacent h-BN layers, which in turn "electrically shorts"the two layers at the defect location. Electrical shorting between layers is manifested in charge transport simulations, which show that the I-V data can only be correctly modeled by incorporating a decrease in effective electrical thickness of the h-BN as well as the usual increase in trap density, which, alone, cannot explain the experimental data. An alternative breakdown mechanism, namely, the physical removal of h-BN layers under soft breakdown, appears unlikely given the h-BN is mechanically confined by the electrodes and no change in AFM topography is observed after breakdown. High-resolution transmission electron microscope micrographs of the breakdown location show a highly localized (<1 nm) breakdown path extending between the two electrodes, with the h-BN layers fractured and disrupted, but not removed

Resistive Switching in Silicon-rich Silicon Oxide

Over the recent decade, many different concepts of new emerging memories have been proposed. Examples of such include ferroelectric random access memories (FeRAMs), phase-change RAMs (PRAMs), resistive RAMs (RRAMs), magnetic RAMs (MRAMs), nano-crystal floating-gate flash memories, among others. The ultimate goal for any of these memories is to overcome the limitations of dynamic random access memories (DRAM) and flash memories. Non-volatile memories exploiting resistive switching – resistive RAM (RRAM) devices – offer the possibility of low programming energy per bit, rapid switching, and very high levels of integration – potentially in 3D. Resistive switching in a silicon-based material offers a compelling alternative to existing metal oxide-based devices, both in terms of ease of fabrication, but also in enhanced device performance. In this thesis I demonstrate a redox-based resistive switch exploiting the formation of conductive filaments in a bulk silicon-rich silicon oxide. My devices exhibit multi-level switching and analogue modulation of resistance as well as standard two-level switching. I demonstrate different operational modes (bipolar and unipolar switching modes) that make it possible to dynamically adjust device properties, in particular two highly desirable properties: non-linearity and self-rectification. Scanning tunnelling microscopy (STM), atomic force microscopy (AFM), and conductive atomic force microscopy (C-AFM) measurements provide a more detailed insight into both the location and the dimensions of the conductive filaments. I discuss aspects of conduction and switching mechanisms and we propose a physical model of resistive switching. I demonstrate room temperature quantisation of conductance in silicon oxide resistive switches, implying ballistic transport of electrons through a quantum constriction, associated with an individual silicon filament in the SiOx bulk. I develop a stochastic method to simulate microscopic formation and rupture of conductive filaments inside an oxide matrix. I use the model to discuss switching properties – endurance and switching uniformity

Electrical spin injection, transport, and detection in graphene-hexagonal boron nitride van der Waals heterostructures: progress and perspectives

The current research in graphene spintronics strives for achieving a long spin lifetime, and efficient spin injection and detection in graphene. In this article, we review how hexagonal boron nitride (hBN) has evolved as a crucial substrate, as an encapsulation layer, and as a tunnel barrier for manipulation and control of spin lifetimes and spin injection/detection polarizations in graphene spin valve devices. First, we give an overview of the challenges due to conventional SiO$_2$ substrate for spin transport in graphene followed by the progress made in hBN based graphene heterostructures. Then we discuss in detail the shortcomings and developments in using conventional oxide tunnel barriers for spin injection into graphene followed by introducing the recent advancements in using the crystalline single/bi/tri-layer hBN tunnel barriers for an improved spin injection and detection which also can facilitate two-terminal spin valve and Hanle measurements, at room temperature, and are of technological importance. A special case of bias induced spin polarization of contacts with exfoliated and chemical vapour deposition (CVD) grown hBN tunnel barriers is also discussed. Further, we give our perspectives on utilizing graphene-hBN heterostructures for future developments in graphene spintronics.Comment: Review, Author submitted manuscript - draft; 25 pages, 8 figure

Local Characterization of Resistance Switching Phenomena in Transition Metal Oxides

The development of neuromorphic computing systems that emulate the analog charge states and plasticity of the brain’s neuron-synapse architecture has been a major driver of resistance switching materials exploration. Materials that demonstrate changes in conductance with tunable ratios and volatility of resistance states within a single layer are highly desirable. Although excellent resistance switching device performance has been demonstrated in a range of transition metal oxides, a lack of understanding of the fundamental microscale evolution of a material during resistance switching presents a key limitation to controlling switching parameters. Here, we examine the role of materials defects on local resistance switching structures in two representative transition metal oxide materials: HfOv2 thin films and hydrothermally synthesized VOv2 single crystals. In each material, we seek to clarify the structure of resistance switching domains and the kinetics of domain formation resulting from intentional defect introduction. This thesis is therefore divided into two main parts concerning (1) the introduction of planar defects in HfOv2 filamentary resistance switching devices, and (2) the impact of introduction of point defects on the metal-insulator transition in VOv2 single crystals. Part I (Sections 2 – 3) details investigation of Cu ion migration rates in Cu/HfOv2/p+Si and Cu/HfOv2/TiN devices in which oxide microstructure varies between amorphous, polycrystalline, and oriented polycrystalline. Ion migration across the oxide layer is shown to be rate limiting and faster in polycrystalline layers than in amorphous HfO2 layers at equivalent electric field. Moreover, the 3D shape of conductive filaments is investigated by a scribing atomic force microscopy experiment in Cu/HfOv2/p+Si devices and reveals a broad range of filament shapes under identical electrical stress conditions. Thermal dissipation is interpreted as the principal determinant of filament area, while oxide microstructure is shown to direct the location of filaments within the device. In part II (Sections 4 – 5), the hysteresis of the metal-insulator transition (switching volatility) in VOv2 is shown to intrinsically derive from nucleation limited transformations in individual particles. Here, hysteresis is a strong function of particle size, but may be increased or decreased by synthesis techniques that affect the concentration and potency of intrinsic point defects. Upon chemical doping with boron at interstitial lattice sites, a unique kinetic effect on the hysteresis of the current driven metal-insulator transition in two terminal BxVOv2 devices is observed. Dependence of the critical switching current on thermal relaxation time and temperature is characterized and recommendations for further kinetic testing are made. Finally, a few experimental extensions of the work presented in this thesis are made in Section 6

Nanoelectronic Materials

This thesis explores fabrication methods and characterization of novel materials used in field effect transistors, including metallic nanowires, carbon nanotubes, and graphene. Networks of conductive nanotubes are promising candidates for thin film electrode alternatives due to their desirable transparency, flexibility, and potential for large-scale processing. Silver nanowire and carbon nanotube networks are evaluated for their use as thin film electrode alternatives. Growth of silver nanowires in porous alumina membranes, dispersion onto a variety of substrates, and patterning is described. Metallic carbon nanotubes are suspended in aqueous solutions, airbrushed onto substrates, and patterned. The conductivity and transparency of both networks is evaluated against industry standards. Graphene is a two dimensional gapless semimetal that demonstrates outstanding room temperature mobilities, optical transparency, mechanical strength, and sustains large current densities, all desirable properties for semiconductors used in field effect transistors. Graphene's low on/off ratio and low throughput fabrication techniques have yet to be overcome before it becomes commercially viable. Silicon oxide substrates are common dielectrics in field effect transistors and instrumental in locating mechanically exfoliated graphene. The morphology of two different silicon oxides have been studied statistically with atomic force microscopy and scaling analysis. Tailoring the physical properties of these substrates may provide a control of graphene's electrical properties. A silicon oxide substrate may also be chemically altered to control the properties of graphene. I have modified silicon oxide with self-assembled monolayers with various terminal groups to control the field near the graphene. I characterize the monolayers with atomic force microscopy, x-ray photospectroscopy, and contact angles. I characterize graphene on these substrates using Raman microscopy and transport measurements. Finally, I examine low frequency noise in graphene field effect transistors on conventional silicon oxide substrates. As devices become smaller, the signal to noise ratio of these devices becomes important. Low frequency noise occurs on long time scales and must be controlled for device stability. I measure novel behavior of low frequency noise in multiple graphene devices. The noise may be described electron-hole puddles in the graphene that are caused by trapped charges near the surface of silicon oxide

2D materials and van der Waals heterostructures

The physics of two-dimensional (2D) materials and heterostructures based on such crystals has been developing extremely fast. With new 2D materials, truly 2D physics has started to appear (e.g. absence of long-range order, 2D excitons, commensurate-incommensurate transition, etc). Novel heterostructure devices are also starting to appear - tunneling transistors, resonant tunneling diodes, light emitting diodes, etc. Composed from individual 2D crystals, such devices utilize the properties of those crystals to create functionalities that are not accessible to us in other heterostructures. We review the properties of novel 2D crystals and how their properties are used in new heterostructure devices