Enhanced Computational Study with Experimental Correlation on I-V Characteristics of Tantalum Oxide (TaOx) Memristor Devices in a 1T1R Configuration.

Memristors, non-volatile switching memory platform, has recently attracted significant interest, offering unique potential to enable the realization of human brain-like neuromorphic computing efficiency. Memristors also demonstrate excellent temperature tolerance, long-term durability, and high tunability with nanosecond pulses, making them highly attractive for neuromorphic computing applications. To better understand the material processing, microstructure, and property relationship of switching mechanisms in memristor devices, computational methodologies, and tools are developed to predict the I-V characteristics of memristor devices based on tantalum oxide (TaOx) resistive random-access memory (ReRAM) integrated with an n-channel metal-oxide-semiconductor (NMOS) transistor. A multiphysics model based on coupled partial differential equations for electrical and thermal transport phenomena is solved for the high- and low-resistance states during the formation, growth, and destruction of a conducting filament through SET and RESET stages. These stages effectively represent the migration of oxygen vacancies within an oxide exchange layer. A series of parametric studies and energy minimization calculations are conducted to determine probable ranges for key material and model parameters accounting for the experimental data. The computational model successfully predicted the measured I-V curves across various gate voltages applied to the NMOS transistor in the one transistor one resistance (1T1R) configuration.

Conductive filament shape in HfO2 electrochemical metallization cells under a range of forming voltages.

The development of neuromorphic computing architectures based on two terminal filamentary resistance switching devices is limited in part by the high degree of variability in resistance states and switching voltages. Because of the large role filament shape plays in directing thermal and electric fields around the filament (and thus switching parameters), unambiguous knowledge of filament morphology resulting from direct characterization of filament shape is essential to solve critical ongoing challenges of device switching variability. Here, we have utilized a conductive atomic force microscopy scalpel technique to simultaneously scribe through a polycrystalline dielectric layer in formed Cu/HfO2/p+Si electrochemical metallization cell devices. Filament tomograms reveal that when conductive filaments are formed at typical bias conditions (4 V, 100 µA), a variety of filament shapes result, which deviate from the inverse conical shape predicted by the phenomenological electrochemical model. Furthermore, the observation of an increasing spectrum of damage which scales with forming voltage (associated with compliance current overshoot), and which is uncorrelated with electric field or oxide microstructure, supports the role of thermal pulses in expanding filaments, leading to irreversible dielectric breakdown structures at the extreme. Overall, these findings suggest that the original conductive filament shape can be highly varied as a result of thermally driven expansion from joule heating during the forming step, which is not explicitly accounted for in the widely accepted electrochemical model.

Density functional tight binding study of ß-Ga2O3: Electronic structure, surface energy, and native point defects.

A new parameter set to model monoclinic gallium oxide, ß-Ga2O3, with the density functional tight binding (DFTB) method is developed. Using this new parameter set, DFTB calculations of bulk electronic band structure, surface energy of low-index surfaces, and formation energy of native point vacancy defects are performed and compared with the state-of-the-art density functional theory (DFT) calculations using the advanced hybrid exchange correlation functional. DFTB calculates the bandgap energy of 4.87 eV around the Fermi energy with the conduction band approximately following the DFT study by Peelaers and Van de Walle [Phys. Status Solidi B 252, 828 (2015)]. The surface energies calculated feature the correct order of stability among low index surfaces with surface energies in semiquantitative agreement with Bermudez' report [Chem. Phys. 323, 193 (2006)]. Oxygen and gallium vacancy defect formation energies and respective transition levels calculated using DFTB with a new parameter set are in semiquantitative agreement with the previous DFT reports by Varley et al. and Zacherle et al. [Appl. Phys. Lett. 97, 142106 (2010); Phys. Rev. B 87, 235206 (2013)]. This new semiempirical parameter set for ß-Ga2O3, validated in bulk, surface, and point properties, would be useful for large spatiotemporal quantum chemical calculations regarding ß-Ga2O3.

Effect of oxygen vacancy and Si doping on the electrical properties of Ta2O5 in memristor characteristics.

The resistive switching behavior in Ta2O5 based memristors is largely controlled by the formation and annihilation of conductive filaments (CFs) that are generated by the migration of oxygen vacancies (OVs). To gain a fundamental insight on the switching characteristics, we have systematically investigated the electrical transport properties of two different Ta2O5 polymorphs ([Formula: see text]-Ta2O5 and λ-Ta2O5), using density functional theory calculations, and associated vacancy induced electrical conductivity using Boltzmann transport theory. The projected band structure and DOS in a few types of OVs, (two-fold (O2fV), three-fold (O3fV), interlayer (OILV), and distorted octahedral coordinated vacancies (OεV)) reveal that the presence of OILV would cause Ta2O5 to transition from a semiconductor to a metal, leading to improved electrical conductivity, whereas the other OV types only create localized mid-gap defect states within the bandgap. On studying the combined effect of OVs and Si-doping, a reduction of the formation energy and creation of defect states near the conduction band edge, is observed in Si-doped Ta2O5, and lower energy is found for the OVs near Si atoms, which would be advantageous to the uniformity of CFs produced by OVs. These findings can serve as guidance for further experimental work aimed at enhancing the uniformity and switching properties of resistance switching for Ta2O5-based memristors.

Memristive Field-Programmable Analog Arrays for Analog Computing.

The increasing interests in analog computing nowadays call for multipurpose analog computing platforms with reconfigurability. The advancement of analog computing, enabled by novel electronic elements like memristors, has shown its potential to sustain the exponential growth of computing demand in the new era of analog data deluge. Here, a platform of a memristive field-programmable analog array (memFPAA) is experimentally demonstrated with memristive devices serving as a variety of core analog elements and CMOS components as peripheral circuits. The memFPAA is reconfigured to implement a first-order band pass filter, an audio equalizer, and an acoustic mixed frequency classifier, as application examples. The memFPAA, featured with programmable analog memristors, memristive routing networks, and memristive vector-matrix multipliers, opens opportunities for fast prototyping analog designs as well as efficient analog applications in signal processing and neuromorphic computing.

Metalized nanotube tips improve through thickness thermal conductivity in adhesive joints.

The through-thickness thermal conductivity in conventional adhesive joints (of approximately 0.3 W/m-K) fails to meet the thermal load transfer requirement in numerous applications to enable lean manufacturing and improve system reliability to thermal load. Carbon nanotubes are known to possess extremely high thermal conductivity along the longitudinal axis. According to molecular dynamics simulations, the value can be as high as 3500 W/m-K at room temperature for multi-walled carbon nanotubes (MWCNT). Meanwhile, the transverse thermal conductivity perpendicular to the longitudinal axis of the MWCNTs is known to be relatively low, approximately 10-15 W/m-K. Existing studies of mixing the MWCNTs in polymers for adhesive joints only achieved minimal enhancement in the thermal conductivity and failed to satisfy the thermal property requirement for the adhesive joints. In order to properly utilize the superior axial thermal conductivity of the MWCNTs, vertically aligned MWCNTs have been used in this study and incorporated in the adhesive joint configuration. Analytical parametric study was conducted to identify critical parameters that affect the overall thermal conductivity of the joint and to provide guidelines for the process development. The process development involved growing the vertically aligned MWCNTs on silicon wafers. The aligned nanotube array was partially infused with epoxy adhesive. Selective reactive ion etching of the epoxy revealed the nanotube tips. In order to reduce the impedance mismatch and phonon scattering at the interface between the nanotube tips and the adherends, gold was thermally evaporated on the nanotube tips. The measured thermal conductivity of the adhesive joint device incorporating the MWCNTs was 262 W/m-K, which is significantly larger compared to that of less than 1 W/m-K without the MWCNTs.

Vertically-aligned carbon nanotubes infiltrated with temperature-responsive polymers: smart nanocomposite films for self-cleaning and controlled release.

We have demonstrated that the infiltration of temperature-responsive polymers (e.g., PNIPAAm) into vertically-aligned carbon nanotube forests created synergetic effects, which provided the basis for the development of smart nanocomposite films with temperature-induced self-cleaning and/or controlled release capabilities.

Carbon nanotube dry adhesives with temperature-enhanced adhesion over a large temperature range.

Conventional adhesives show a decrease in the adhesion force with increasing temperature due to thermally induced viscoelastic thinning and/or structural decomposition. Here, we report the counter-intuitive behaviour of carbon nanotube (CNT) dry adhesives that show a temperature-enhanced adhesion strength by over six-fold up to 143 N cm-2 (4 mm × 4 mm), among the strongest pure CNT dry adhesives, over a temperature range from -196 to 1,000 °C. This unusual adhesion behaviour leads to temperature-enhanced electrical and thermal transports, enabling the CNT dry adhesive for efficient electrical and thermal management when being used as a conductive double-sided sticky tape. With its intrinsic thermal stability, our CNT adhesive sustains many temperature transition cycles over a wide operation temperature range. We discover that a 'nano-interlock' adhesion mechanism is responsible for the adhesion behaviour, which could be applied to the development of various dry CNT adhesives with novel features.

Covalently interconnected three-dimensional graphene oxide solids.

The creation of three-dimensionally engineered nanoporous architectures via covalently interconnected nanoscale building blocks remains one of the fundamental challenges in nanotechnology. Here we report the synthesis of ordered, stacked macroscopic three-dimensional (3D) solid scaffolds of graphene oxide (GO) fabricated via chemical cross-linking of two-dimensional GO building blocks. The resulting 3D GO network solids form highly porous interconnected structures, and the controlled reduction of these structures leads to formation of 3D conductive graphene scaffolds. These 3D architectures show promise for potential applications such as gas storage; CO2 gas adsorption measurements carried out under ambient conditions show high sorption capacity, demonstrating the possibility of creating new functional carbon solids starting with two-dimensional carbon layers.

Importance of interfaces in governing thermal transport in composite materials: modeling and experimental perspectives.

Thermal management in polymeric composite materials has become increasingly critical in the air-vehicle industry because of the increasing thermal load in small-scale composite devices extensively used in electronics and aerospace systems. The thermal transport phenomenon in these small-scale heterogeneous systems is essentially controlled by the interface thermal resistance because of the large surface-to-volume ratio. In this review article, several modeling strategies are discussed for different length scales, complemented by our experimental efforts to tailor the thermal transport properties of polymeric composite materials. Progress in the molecular modeling of thermal transport in thermosets is reviewed along with a discussion on the interface thermal resistance between functionalized carbon nanotube and epoxy resin systems. For the thermal transport in fiber-reinforced composites, various micromechanics-based analytical and numerical modeling schemes are reviewed in predicting the transverse thermal conductivity. Numerical schemes used to realize and scale the interface thermal resistance and the finite mean free path of the energy carrier in the mesoscale are discussed in the frame of the lattice Boltzmann-Peierls-Callaway equation. Finally, guided by modeling, complementary experimental efforts are discussed for exfoliated graphite and vertically aligned nanotubes based composites toward improving their effective thermal conductivity by tailoring interface thermal resistance.

Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions.

The establishment of covalent junctions between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize nanotube-based three-dimensional (3D) frameworks exhibiting superior material properties. Engineering such 3D structures in scalable synthetic processes still remains a challenge. This work pioneers the bulk synthesis of 3D macroscale nanotube elastic solids directly via a boron-doping strategy during chemical vapour deposition, which influences the formation of atomic-scale "elbow" junctions and nanotube covalent interconnections. Detailed elemental analysis revealed that the "elbow" junctions are preferred sites for excess boron atoms, indicating the role of boron and curvature in the junction formation mechanism, in agreement with our first principle theoretical calculations. Exploiting this material's ultra-light weight, super-hydrophobicity, high porosity, thermal stability, and mechanical flexibility, the strongly oleophilic sponge-like solids are demonstrated as unique reusable sorbent scaffolds able to efficiently remove oil from contaminated seawater even after repeated use.