An ultra high-endurance memristor using back-end-of-line amorphous SiC.

Integrating resistive memory or neuromorphic memristors into mainstream silicon technology can be substantially facilitated if the memories are built in the back-end-of-line (BEOL) and stacked directly above the logic circuitries. Here we report a promising memristor employing a plasma-enhanced chemical vapour deposition (PECVD) bilayer of amorphous SiC/Si as device layer and Cu as an active electrode. Its endurance exceeds one billion cycles with an ON/OFF ratio of ca. two orders of magnitude. Resistance drift is observed in the first 200 million cycles, after which the devices settle with a coefficient of variation of ca. 10% for both the low and high resistance states. Ohmic conduction in the low resistance state is attributed to the formation of Cu conductive filaments inside the bilayer structure, where the nanoscale grain boundaries in the Si layer provide the pre-defined pathway for Cu ion migration. Rupture of the conductive filament leads to current conduction dominated by reverse bias Schottky emission. Multistate switching is achieved by precisely controlling the pulse conditions for potential neuromorphic computing applications. The PECVD deposition method employed here has been frequently used to deposit typical BEOL SiOC low-k interlayer dielectrics. This makes it a unique memristor system with great potential for integration.

Flexible Memristor Devices Using Hybrid Polymer/Electrodeposited GeSbTe Nanoscale Thin Films.

We report on the development of hybrid organic-inorganic material-based flexible memristor devices made by a fast and simple electrochemical fabrication method. The devices consist of a bilayer of poly(methyl methacrylate) (PMMA) and Te-rich GeSbTe chalcogenide nanoscale thin films sandwiched between Ag top and TiN bottom electrodes on both Si and flexible polyimide substrates. These hybrid memristors require no electroforming process and exhibit reliable and reproducible bipolar resistive switching at low switching voltages under both flat and bending conditions. Multistate switching behavior can also be achieved by controlling the compliance current (CC). We attribute the switching between the high resistance state (HRS) and low resistance state (LRS) in the devices to the formation and rupture of conductive Ag filaments within the hybrid PMMA/GeSbTe matrix. This work provides a promising route to fabricate flexible memory devices through an electrodeposition process for application in flexible electronics.

Confining the growth of mesoporous silica films into nanospaces: towards surface nanopatterning.

The combination of lithographic methods and sol gel bottom-up techniques is a promising approach for nanopatterning substrates. The integration and scalable fabrication of such substrates are of great interest for the development of nanowire-based materials opening potentialities in new technologies. We demonstrate the deposition of ordered mesoporous silica into nanopatterned silica substrates by dip coating. Using scanning electron microscopy and grazing incidence small angle X-ray scattering, the effect of the sol composition on the pore ordering was probed. Optimising the sol composition using anodic alumina membranes as confined spaces, we showed how the pH controlled the transformation from circular to columnar mesophase. Vertical mesopores were obtained with very good repeatability. The effect of the sol chemistry on the surfactant curvature was then shown to be similar in nanopatterned substrates made by e-beam lithography.

The Effects of Hydrogen Annealing on Carbon Nanotube Field-Effect Transistors.

We have systematically investigated the effects of hydrogen annealing on Ni- and Al-contacted carbon nanotube field-effect transistors (CNTFETs), whose work functions have not been affected by hydrogen annealing. Measured results show that the electronic properties of single-walled carbon nanotubes are modified by hydrogen adsorption. The Ni-contacted CNTFETs, which initially showed metallic behavior, changed their p-FET behavior with a high on-current over 10 µA after hydrogen annealing. The on-current of the as-made p-FETs is much improved after hydrogen annealing. The Al-contacted CNTFETs, which initially showed metallic behavior, showed unipolar p-FET behavior after hydrogen annealing. We analyzed the energy band diagrams of the CNTFETs to explain experimental results, finding that the electron affinity and the bandgap of single-walled carbon nanotubes changed after hydrogen annealing. These results are consistent with previously reported ab initio calculations.

Low-Pressure CVD of GeE (E = Te, Se, S) Thin Films from Alkylgermanium Chalcogenolate Precursors and Effect of Deposition Temperature on the Thermoelectric Performance of GeTe.

The homologous series [GenBu3(EnBu)] (E = Te, Se, S; (1), (3) and (4)) and [GenBu2(TenBu)2] (2) have been synthesized as mobile oils in excellent yield (72-93%) and evaluated as single-source precursors for the low-pressure chemical vapor deposition (LPCVD) of GeE thin films on silica. Compositional and structural characterizations of the deposits have been performed by grazing-incidence X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, and Raman spectroscopy, confirming the phase purity and stoichiometry. Electrical characterization via variable-temperature Hall effect measurements is also reported. Given the strong interest in GeTe and its alloys for thermoelectric applications, variable-temperature Seebeck data were also investigated for a series of p-type GeTe films. The data show that it is possible to tune the thermoelectric response through intrinsic Ge vacancy regulation by varying the deposition temperature, with the highest power factor (40 µW/K2cm@629 K) and effective ZT values observed for the films deposited at higher temperatures.

Tungsten disulfide thin films via electrodeposition from a single source precursor.

We report a simple process for the electrodeposition of tungsten disulfide thin films from a CH2Cl2-based electrolyte using a tailored single source precursor, [NEt4]2[WS2Cl4]. This new precursor incorporates the 1 : 2 W : S ratio required for formation of WS2, and eliminates the need for an additional proton source in the electrolyte to remove excess sulfide. The electrochemical behaviour of [NEt4]2[WS2Cl4] is studied by cyclic voltammetry and electrochemical quartz crystal microbalance techniques, and the WS2 thin films are grown by potentiostatic electrodeposition.

Direct observation of surface charge redistribution in active nanoscale conducting channels by Kelvin Probe Force Microscopy.

Surface-exposed uniformly doped silicon-on-insulator channels are fabricated to evaluate the accuracy of Kelvin Probe Force Microscopy (KPFM) measured surface potential and reveals the role of surface charge on the exposed channel operated in the ambient environment. First, the quality of the potential profile probed in the vacuum environment is assessed by the consistency of converted resistivity from KPFM result to the resistivity extracted by the other three methods. Second, in contrast to the simulated and vacuum surface potential profile and image, the ambient surface potential is bent excessively at the terminals of the channel. The excessive bending can be explained by the movement of surface charge under the drive of geometry induced strong local electric field from the channel and results in non-uniform distribution. The dynamic movement of surface charges is proved by the observation of time-dependent potential drift in the ambient measurement. The result suggests the surface charge effect should be taken into account of the measurement of the surface potential in the ambient environment and the design of charge sensitive devices whose surfaces are exposed to air or in ambient conditions in their operation.

Low temperature CVD of thermoelectric SnTe thin films from the single source precursor, [nBu3Sn(TenBu)].

This work has demonstrated that the single source precursor [nBu3Sn(TenBu)], bearing n-butyl groups and containing the necessary 1 : 1 Sn : Te ratio, facilitates growth of continuous, stoichiometric SnTe thin films. This single source CVD precursor allows film growth at significantly lower temperatures (355-434 °C at 0.01-0.05 Torr) than required for CVD from SnTe powder. This could be advantageous for controlling the surface states in topological insulators. The temperature-dependent thermoelectric performance of these films has been determined, revealing them to be p-type semiconductors with peak Seebeck coefficient and power factor values of 78 µV K-1 and 8.3 µW K-2 cm-1, respectively, at 615 K; comparing favourably with data from bulk SnTe. Further, we have demonstrated that the precursor facilitates area selective growth of SnTe onto the TiN regions of SiO2/TiN patterned substrates, which is expected to be beneficial for the fabrication of micro-thermoelectric generators.

Large-Area Electrodeposition of Few-Layer MoS2 on Graphene for 2D Material Heterostructures.

Heterostructures involving two-dimensional (2D) transition metal dichalcogenides and other materials such as graphene have a strong potential to be the fundamental building block of many electronic and optoelectronic applications. The integration and scalable fabrication of such heterostructures are of the essence in unleashing the potential of these materials in new technologies. For the first time, we demonstrate the growth of few-layer MoS2 films on graphene via nonaqueous electrodeposition. Through methods such as scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, energy- and wavelength-dispersive X-ray spectroscopies, and X-ray photoelectron spectroscopy, we show that this deposition method can produce large-area MoS2 films with high quality and uniformity over graphene. We reveal the potential of these heterostructures by measuring the photoinduced current through the film. These results pave the way toward developing the electrodeposition method for the large-scale growth of heterostructures consisting of varying 2D materials for many applications.

Thermoelectric Properties of Bismuth Telluride Thin Films Electrodeposited from a Nonaqueous Solution.

We report the thermoelectric properties of Bi2Te3 thin films electrodeposited from the weakly coordinating solvent dichloromethane (CH2Cl2). It was found that the oxidation of porous films is significant, causing the degradation of its thermoelectric properties. We show that the morphology of the film can be improved drastically by applying a short initial nucleation pulse, which generates a large number of nuclei, and then growing the nuclei by pulsed electrodeposition at a much lower overpotential. This significantly reduces the oxidation of the films as smooth films have a smaller surface-to-volume ratio and are less prone to oxidation. X-ray photoelectron spectroscopy (XPS) shows that those films with Te(O) termination show a complete absence of oxygen below the surface layer. A thin film transfer process was developed using polystyrene as a carrier polymer to transfer the films from the conductive TiN to an insulating layer for thermoelectrical characterization. Temperature-dependent Seebeck measurements revealed a room-temperature coefficient of -51.7 µV/K growing to nearly -100 µV/K at 520 °C. The corresponding power factor reaches a value of 88.2 µW/mK2 at that temperature.

Embedded Metal Oxide Plasmonics Using Local Plasma Oxidation of AZO for Planar Metasurfaces.

New methods for achieving high-quality conducting oxide metasurfaces are of great importance for a range of emerging applications from infrared thermal control coatings to epsilon-near-zero nonlinear optics. This work demonstrates the viability of plasma patterning as a technique to selectively and locally modulate the carrier density in planar Al-doped ZnO (AZO) metasurfaces without any associated topographical surface profile. This technique stands in strong contrast to conventional physical patterning which results in nonplanar textured surfaces. The approach can open up a new route to form novel photonic devices with planar metasurfaces, for example, antireflective coatings and multi-layer devices. To demonstrate the performance of the carrier-modulated AZO metasurfaces, two types of devices are realized using the demonstrated plasma patterning. A metasurface optical solar reflector is shown to produce infrared emissivity equivalent to a conventional etched design. Second, a multiband metasurface is achieved by integrating a Au visible-range metasurface on top of the planar AZO infrared metasurface. Independent control of spectral bands without significant cross-talk between infrared and visible functionalities is achieved. Local carrier tuning of conducting oxide films offers a conceptually new approach for oxide-based photonics and nanoelectronics and opens up new routes for integrated planar metasurfaces in optical technology.

Strongly coupled evenly divided disks: a new compact and tunable platform for plasmonic Fano resonances.

Plasmonic artificial molecules are promising platforms for linear and nonlinear optical modulation at various regimes including the visible, infrared and terahertz bands. Fano resonances in plasmonic artificial structures are widely used for controlling spectral lineshapes and tailoring of near-field and far-field optical response. Generation of a strong Fano resonance usually relies on strong plasmon coupling in densely packed plasmonic structures. Challenges in reproducible fabrication using conventional lithography significantly hinders the exploration of novel plasmonic nanostructures for strong Fano resonance. In this work, we propose a new class of plasmonic molecules with symmetric structure for Fano resonances, named evenly divided disk, which shows a strong Fano resonance due to the interference between a subradiant anti-bonding mode and a superradiant bonding mode. We successfully fabricated evenly divided disk structures with high reproducibility and with sub-20 nm gaps, using our recently developed sketch and peel lithography technique. The experimental spectra agree well with the calculated response, indicating the robustness of the Fano resonance for the evenly divided disk geometry. Control experiments reveal that the strength of the Fano resonance gradually increases when increasing the number of split parts on the disk from three to eight individual segments. The Fano-resonant plasmonic molecules that can also be reliably defined by our unique fabrication approach open up new avenues for application and provide insight into the design of artificial molecules for controlling light-matter interactions.

Towards a 3D GeSbTe phase change memory with integrated selector by non-aqueous electrodeposition.

We have recently reported a new method for the electrodeposition of thin film and nanostructured phase change memory (PCM) devices from a single, highly tuneable, non-aqueous electrolyte. The quality of the material was confirmed by phase cycling via electrical pulsed switching of both 100 nm nano-cells and thin film devices. This method potentially allows deposition into extremely small confined cells down to less than 5 nm, 3D lay-outs that require non-line-of-sight techniques, and seamless integration of selector devices. As electrodeposition requires a conducting substrate, the key condition for electronic applications based on this method is the use of patterned metal lines as the working electrode during the electrodeposition process. In this paper, we show the design and fabrication of a 2D passive memory matrix in which the word lines act as the working electrode and nucleation site for the growth of confined cells of Ge-Sb-Te. We will discuss the precursor requirement for deposition from non-aqueous, weakly coordinating solvents, show the transmission electron microscopy analysis of the electrodeposition growth process and elemental distribution in the deposits, and show the fabrication and characterisation of the Ge-Sb-Te memory matrix.

[Ge(TenBu)4] - a single source precursor for the chemical vapour deposition of germanium telluride thin films.

Reaction of activated germanium with nBu2Te2 in THF solution was shown to be more effective for the preparation of the germanium(iv) tellurolate compound, [Ge(TenBu)4], than reaction of GeCl4 with LiTenBu in a 1 : 4 molar ratio in THF. The product was characterised by 1H, 13C{1H} NMR spectroscopy and microanalysis and evaluated as a single source precursor for the low pressure chemical vapour deposition of GeTe thin films. Depending upon deposition conditions, either dull grey films (predominantly elemental Te) or highly reflective (GeTe) films were obtained from the pure precursor. Grazing incidence X-ray diffraction shows that the highly reflective films are comprised of the rhombohedral α-GeTe phase, while scanning electron microscopy and energy dispersive X-ray analysis reveal rhomb-shaped crystallites with a 49(1) : 51(1)% Ge : Te ratio. This structure is also confirmed from Raman spectra. Van der Pauw measurements show ρ = 3.2(1) × 10-4 Ω cm and Hall electrical measurements indicate that the GeTe thin films are p-type, with a mobility of 8.4(7) cm2 V-1 s-1 and carrier concentration of 2.5(2) × 1021 cm-3. The high p-type concentration is most likely a result of the substantial Ge vacancies in its sub-lattice, in line with the EDX elemental ratios.

Fermi Level Tuning of ZnO Films Through Supercycled Atomic Layer Deposition.

A novel supercycled atomic layer deposition (ALD) process which combines thermal ALD process with in situ O2 plasma treatment is presented in this work to deposit ZnO thin films with highly tunable electrical properties. Both O2 plasma time and the number of thermal ALD cycles in a supercycle can be adjusted to achieve fine tuning of film resistivity and carrier concentration up to six orders of magnitude without extrinsic doping. The concentration of hydrogen defects are believed to play a major role in adjusting the electrical properties of ZnO films. Kelvin probe force microscopy results evidently show the shift of Fermi level in different ZnO films and are well associated with the changing of carrier concentration. This reliable and robust technique reported here clearly points towards the capability of using this method to produce ZnO films with controlled properties in different applications.

Compliance-Free ZrO2/ZrO2 - x /ZrO2 Resistive Memory with Controllable Interfacial Multistate Switching Behaviour.

A controllable transformation from interfacial to filamentary switching mode is presented on a ZrO2/ZrO2 - x /ZrO2 tri-layer resistive memory. The two switching modes are investigated with possible switching and transformation mechanisms proposed. Resistivity modulation of the ZrO2 - x layer is proposed to be responsible for the switching in the interfacial switching mode through injecting/retracting of oxygen ions. The switching is compliance-free due to the intrinsic series resistor by the filaments formed in the ZrO2 layers. By tuning the RESET voltages, controllable and stable multistate memory can be achieved which clearly points towards the capability of developing the next-generation multistate high-performance memory.

Nanoscale modeling of electro-plasmonic tunable devices for modulators and metasurfaces.

The interest in plasmonic electro-optical modulators with nanoscale footprint and ultrafast low-energy performance has generated a demand for precise multiphysics modeling of the electrical and optical properties of plasmonic nanostructures. We perform combined simulations that account for the interaction of highly confined nearfields with charge accumulation and depletion on the nanoscale. Validation of our numerical model is done by comparison to a recently published reflective meta-absorber. The simulations show excellent agreement to the experimental mid-infrared data. We then use our model to propose electro-optical modulation of the extinction cross-section of a gold dimer nanoantenna at the telecom wavelength of 1550 nm. An ITO gap-loaded nanoantenna structure allows us to achieve a normalized modulation of 45% at 1550 nm, where the gap-load design circumvents resonance pinning of the structure. Resonance pinning limits the performance of simplistic designs such as a uniform coating of the nanoantenna with a sheet of indium tin oxide, which we also present for comparison. This large value is reached by a reduction of the capacitive coupling of the antenna arms, which breaks the necessity of a large volume overlap between the charge distribution and the optical nearfield. A parameter exploration shows a weak reliance on the exact device dimensions, as long as strong coupling inside the antenna gap is ensured. These results open the way for a new method in electro-optical tuning of plasmonic structures and can readily be adapted to plasmonic waveguides, metasurfaces and other electro-optical modulators.

A systematic method for simulating total ionizing dose effects using the finite elements method.

Simulation of total ionizing dose effects in field isolation of FET technologies requires transport mechanisms in the oxide to be considered. In this work, carrier transport and trapping in thick oxides using the finite elements method in the Synopsys Sentaurus platform are systematically simulated. Carriers are generated in the oxide and are transported out through a direct contact with the gate and thermionic emission to the silicon. The method is applied to calibrate experimental results of 400 nm SiO 2 capacitors irradiated at total doses of 11.6 kRad ( SiO 2 ) and 58 kRad ( SiO 2 ). Drift-diffusion-enabled trapping as well as other issues that arise from the involved physics are discussed. Effective bulk trap densities and activation energies of the traps are extracted.

Nanoscale arrays of antimony telluride single crystals by selective chemical vapor deposition.

Arrays of individual single nanocrystals of Sb2Te3 have been formed using selective chemical vapor deposition (CVD) from a single source precursor. Crystals are self-assembled reproducibly in confined spaces of 100 nm diameter with pitch down to 500 nm. The distribution of crystallite sizes across the arrays is very narrow (standard deviation of 15%) and is affected by both the hole diameter and the array pitch. The preferred growth of the crystals in the <1 1 0> orientation along the diagonal of the square holes strongly indicates that the diffusion of adatoms results in a near thermodynamic equilibrium growth mechanism of the nuclei. A clear relationship between electrical resistivity and selectivity is established across a range of metal selenides and tellurides, showing that conductive materials result in more selective growth and suggesting that electron donation is of critical importance for selective deposition.

Antenna-assisted picosecond control of nanoscale phase transition in vanadium dioxide.

Nanoscale devices in which the interaction with light can be configured using external control signals hold great interest for next-generation optoelectronic circuits. Materials exhibiting a structural or electronic phase transition offer a large modulation contrast with multi-level optical switching and memory functionalities. In addition, plasmonic nanoantennas can provide an efficient enhancement mechanism for both the optically induced excitation and the readout of materials strategically positioned in their local environment. Here, we demonstrate picosecond all-optical switching of the local phase transition in plasmonic antenna-vanadium dioxide (VO2) hybrids, exploiting strong resonant field enhancement and selective optical pumping in plasmonic hotspots. Polarization- and wavelength-dependent pump-probe spectroscopy of multifrequency crossed antenna arrays shows that nanoscale optical switching in plasmonic hotspots does not affect neighboring antennas placed within 100 nm of the excited antennas. The antenna-assisted pumping mechanism is confirmed by numerical model calculations of the resonant, antenna-mediated local heating on a picosecond time scale. The hybrid, nanoscale excitation mechanism results in 20 times reduced switching energies and 5 times faster recovery times than a VO2 film without antennas, enabling fully reversible switching at over two million cycles per second and at local switching energies in the picojoule range. The hybrid solution of antennas and VO2 provides a conceptual framework to merge the field localization and phase-transition response, enabling precise, nanoscale optical memory functionalities.