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.

Conductive-bridge memory cells based on a nanoporous electrodeposited GeSbTe alloy.

We report on the fabrication of memory devices based on a nanoporous GeSbTe layer electrodeposited inbetween TiN and Ag electrodes. It is shown that devices can operate along two distinct electrical modes consisting of a volatile or a non-volatile resistance switching mode upon appropriate preconditioning procedures. Based on electrical measurements conducted in both switching modes and physical analysis performed on a device after electrical stress, resistance switching is attributed to the formation/dissolution of a conductive filament from the Ag electrode into the GST layer whereas the volatile/non-volatile resistance switching is attributed to the presence of an interface layer between the GST and the Ag top electrode. Due to their simple, low-cost and low-temperature fabrication procedure, these devices could be advantageously exploited in flexible electronic applications or embedded into the back-end of line CMOS technology.

Tunable Neuromorphic Switching Dynamics via Porosity Control in Mesoporous Silica Diffusive Memristors.

In response to the growing need for efficient processing of temporal information, neuromorphic computing systems are placing increased emphasis on the switching dynamics of memristors. While the switching dynamics can be regulated by the properties of input signals, the ability of controlling it via electrolyte properties of a memristor is essential to further enrich the switching states and improve data processing capability. This study presents the synthesis of mesoporous silica (mSiO2) films using a sol-gel process, which enables the creation of films with controllable porosities. These films can serve as electrolyte layers in the diffusive memristors and lead to tunable neuromorphic switching dynamics. The mSiO2 memristors demonstrate short-term plasticity, which is essential for temporal signal processing. As porosity increases, discernible changes in operating currents, facilitation ratios, and relaxation times are observed. The underlying mechanism of such systematic control was investigated and attributed to the modulation of hydrogen-bonded networks within the porous structure of the silica layer, which significantly influences both anodic oxidation and ion migration processes during switching events. The result of this work presents mesoporous silica as a unique platform for precise control of neuromorphic switching dynamics in diffusive memristors.

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.

Film before aggregates: an operando GISAXS study on electrochemically assisted surfactant assembly.

The process of electrochemically assisted surfactant assembly was followed in real time by grazing incidence small angle X-ray scattering with the aim to deconvolute the formation of mesoporous silica film and unwanted porous particles. The X-ray technique proved to be useful for the characterisation of this process, as it takes place at a very dynamic, solid/liquid interface. This paper shows the electrochemically driven onset and evolution of silica/surfactant structures. Additional control experiments indicate the formation of vertically aligned structures without the use of an electric field, although it seems to be beneficial for increased pore ordering.

Fractal-like gold nanonetworks formed by templated electrodeposition through 3D-mesoporous silica films.

Fractal-like networks of gold nanoparticles created by templated electrodeposition are described. Templated electrodeposition is a powerful and efficient technique for the bottom-up fabrication of nanostructures which can effectively control the size and shape of the electrodeposits. In this work, mesoporous silica films with highly ordered mesopores and three-dimensional mesostructure are synthesised and are used as templates for the electrodeposition of gold nanoparticles. The mesoporous silica films have small mesopores (∼8 nm) and complex mesopore channels (Fmmm structure with the [0 1 0] axis perpendicular to the substrate). A variety of nucleation conditions were applied to investigate their effect on the nanoparticles' arrangement and growth in templated electrodeposition. The electrodeposited gold particles are characterised by electron microscopy and grazing incidence small-angle X-ray scattering (GISAXS). GISAXS shows changes in the lattice parameters of the mesostructure after gold electrodeposition that relate to dimensional changes in directions linked to the shortest distances between the main spherical pores. Top-view SEM shows large areas of gold nanoparticles were deposited into the film and they were growing towards the surface. After removing the silica film templates, the gold nanoparticles display interesting fractal morphologies: the linked gold nanonetworks form a branched structure. The lengths of branches vary from the applied nucleation deposition conditions. Generally, with increasing nucleation time, fractal gold nanoparticles with longer branches are more likely to be obtained.

Tungsten(VI) selenide tetrachloride, WSeCl4 - synthesis, properties, coordination complexes and application of [WSeCl4(SenBu2)] for CVD growth of WSe2 thin films.

WSeCl4 was obtained in good yield by heating WCl6 and Sb2Se3in vacuo. Green crystals grown by sublimation were shown by single crystal X-ray structure analysis to contain square pyramidal monomers with apical WSe, and powder X-ray diffraction (PXRD) analysis confirmed this to be the only form present in the bulk sample. Density functional theory (DFT) calculations using the B3LYP-D3 functional replicated the structure, identified the key bonding orbitals, and were used to aid assignment of the IR spectrum of WSeCl4. Reaction of WSeCl4 with ligands L gave [WSeCl4(L)] (L = MeCN, DMF, thf, py, OPPh3, 2,2'-bipy, SeMe2, SenBu2), whilst the dimers [(WSeCl4)2(µ-L-L)] were formed with L-L = Ph2P(O)CH2P(O)Ph2, 1,4-dioxane and 4,4'-bipyridyl. The complexes were characterised by microanalysis, IR and 1H NMR spectroscopy, and single crystal X-ray structures determined for [WSeCl4(L)] (L = OPPh3, MeCN, DMF) and [(WSeCl4)2(µ-L-L)] (L-L = 1,4-dioxane, 4,4'-bipyridyl). All except the 2,2'-bipy complex, which is probably seven-coordinate, contain six-coordinate tungsten with the neutral donor trans to WSe. Alkylphosphines, including PMe3 and PEt3, decompose WSeCl4 upon contact, forming phosphine selenides (SePR3). In contrast, the selenoether complexes [WSeCl4(SeMe2)] and [WSeCl4(SenBu2)] were isolated and characterised. The crystal structure of the minor W(VI) by-product, [(WSeCl4)2(µ-SeMe2)], was determined and using SMe2, a few crystals of the W(V) species, [{WCl3(SMe2)}2(µ-Se)(µ-Se2)], were obtained and structurally characterised. The isolated W(VI) complexes are compared with those of WOCl4 and WSCl4 and the combination of experimental and computational data are consistent with WSeCl4 being a weaker Lewis acid and its complexes significantly less stable than those of the lighter analogues, especially in solution. Low pressure chemical vapour deposition (LPCVD) using [WSeCl4(SenBu2)] in the range 660-700 °C (0.1 mmHg) produced highly reflective thin films, which were identified to be WSe2 by grazing incidence X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XRD analysis of the thinner films revealed them to be highly oriented in the <00l> direction.

AC-assisted deposition of aggregate free silica films with vertical pore structure.

Silica thin films with vertical nanopores are useful to control access to electrode surfaces and may act as templates for growth of nanomaterials. The most effective method to produce these films, electrochemically assisted surfactant assembly, also produces aggregates of silica particles. This paper shows that growth with an AC signal superimposed onto the potential avoids the aggregates and only very small numbers of single particles are found. This finding is linked to better control of the diffusion field of hydroxide ions that are responsible for particle growth. The resultant films are smooth, with very well-ordered hexagonal pore structures.

3D-structured mesoporous silica memristors for neuromorphic switching and reservoir computing.

Memristors are emerging as promising candidates for practical application in reservoir computing systems that are capable of temporal information processing. Here, we experimentally implement a physical reservoir computing system using resistive memristors based on three-dimensional (3D)-structured mesoporous silica (mSiO2) thin films fabricated by a low cost, fast and vacuum-free sol-gel technique. The in situ learning capability and a classification accuracy of 100% on a standard machine learning dataset are experimentally demonstrated. The volatile (temporal) resistive switching in diffusive memristors arises from the formation and subsequent spontaneous rupture of conductive filaments via diffusion of Ag species within the 3D-structured nanopores of the mSiO2 thin film. Besides volatile switching, the devices also exhibit a bipolar non-volatile resistive switching behavior when the devices are operated at a higher compliance current level. The implementation of mSiO2 thin films opens the route to fabricate a simple and low cost dynamic memristor with a temporal information process functionality, which is essential for neuromorphic computing applications.

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.

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.

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.

Poly(N-isopropylacrylamide) based thin microgel films for use in cell culture applications.

Poly(N-isopropylacrylamide) (PNIPAm) is widely used to fabricate cell sheet surfaces for cell culturing, however copolymer and interpenetrated polymer networks based on PNIPAm have been rarely explored in the context of tissue engineering. Many complex and expensive techniques have been employed to produce PNIPAm-based films for cell culturing. Among them, spin coating has demonstrated to be a rapid fabrication process of thin layers with high reproducibility and uniformity. In this study, we introduce an innovative approach to produce anchored smart thin films both thermo- and electro-responsive, with the aim to integrate them in electronic devices and better control or mimic different environments for cells in vitro. Thin films were obtained by spin coating of colloidal solutions made by PNIPAm and PAAc nanogels. Anchoring the films to the substrates was obtained through heat treatment in the presence of dithiol molecules. From analyses carried out with AFM and XPS, the final samples exhibited a flat morphology and high stability to water washing. Viability tests with cells were finally carried out to demonstrate that this approach may represent a promising route to integrate those hydrogels films in electronic platforms for cell culture applications.

Thioether complexes of WSCl4, WOCl4 and WSCl3 and evaluation of thiochloride complexes as CVD precursors for WS2 thin films.

The red-brown [(WSCl4)2{µ-RS(CH2)2SR}] (R = Me, Ph, iPr) and [(WSCl4)2{µ-MeS(CH2)3SMe}] have been made by reaction of WSCl4 with the thioether in a 2 : 1 molar ratio, in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR, UV/Vis and 1H NMR spectroscopy. The X-ray structures of the four dithioether complexes reveal square pyramidal WSCl4 units and bridging dithioethers with W[double bond, length as m-dash]S trans to thioether sulfur. Paramagnetic W(v) complexes, [WSCl3{RS(CH2)2SR}] (R = Me, iPr), have been made similarly using a 1 : ≥1 ratio of reactants or longer reaction times. The W(vi) complexes, [WSCl4(SMe2)] and [WSCl4(SeMe2)], are also described. Analogous complexes of WOCl4, [(WOCl4)2{RS(CH2)2SR}] (R = Ph, iPr), have been made similarly from WOCl4, but reactions using MeS(CH2)nSMe (n = 2, 3) led to reduction to W(v), forming [WOCl3{MeS(CH2)nSMe], both of which were identified crystallographically. Curiously, they are geometric isomers: [WOCl3{MeS(CH2)3SMe}] has the dithioether trans Cl/Cl whereas in [WOCl3{MeS(CH2)2SMe}] it is trans O/Cl. Remarkably, low pressure chemical vapour deposition (CVD) experiments using the dinuclear W(vi) species, [(WSCl4)2{iPrS(CH2)2SiPr}], as a single source precursor produced thin films of 4H-WS2, identified by grazing incidence X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy; the tungsten thiochloride complex is the first single source low pressure CVD precursor for WS2. In contrast, the mononuclear W(v) complex, [WSCl3{iPrS(CH2)2SiPr}], does not deposit WS2 under similar conditions.

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.

[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.

Tin(iv) chalcogenoether complexes as single source precursors for the chemical vapour deposition of SnE2 and SnE (E = S, Se) thin films.

The molecular Sn(iv) complexes, [SnCl4{nBuS(CH2)3SnBu}] (2), [SnCl4(nBu2S)2] (3) and [SnCl4(nBu2Se)2] (4) have been prepared in good yield from reaction of SnCl4 with the appropriate chalcogenoether ligand in anhydrous hexane and, together with the known [SnCl4{nBuSe(CH2)3SenBu}] (1), employed as single source precursors for the low pressure chemical vapour deposition of the corresponding tin dichalcogenide thin films. At elevated temperatures the bidentate ligand precursors, (1) and (2), also form the tin monochalcogenides, SnSe and SnS, respectively. In contrast, (3) gave a mixture of phases, SnS2, Sn2S3 and SnS and (4) gave SnSe2 only. The morphologies, elemental compositions and crystal structures of the resulting films have been determined by scanning electron microscopy, energy dispersive X-ray spectroscopy, grazing incidence X-ray diffraction and Raman spectroscopy. Van der Pauw measurements on the SnS2, SnS and SnSe2 films confirm their resistivities to be 2.9(9), 266(3) and 4.4(3) Ω cm, respectively.