Search

Phase change memories (PCM) is an emerging type of non-volatile memory that has shown a strong presence in the data-storage market. This technology has recently attracted significant research interest in the development of non-Von Neumann computing architectures such as in-memory and neuromorphic computing. Research in these areas has been primarily motivated by the scalability potential of phase change materials and their compatibility with industrial nanofabrication processes. In this work, we are presenting our development of crossbar phase change memory arrays through the electrodeposition of GeSbTe (GST). We show that GST can be electrodeposited in microfabricated TiN crossbar arrays using a scalable process. Our phase switching test of the electrodeposited materials have shown that a SET/RESET resistance ratio of 2-3 orders of magnitude is achievable with a switching endurance of around 80 cycles. These results represent the first phase switching of electrodeposited GeSbTe in microfabricated crossbar arrays. Our work paves the way towards developing large memory arrays involving electrodeposited materials for passive selectors and phase switching devices. It also opens opportunities for developing a variety of different electronic devices using electrodeposited materials., Comment: 9 pages, 5 figures

To reduce the amount of chalcogen needed in the post-annealing process, we demonstrate significantly increased sulfur incorporation into pure sulfide CZTS films achieved by increasing the thiourea content of DMSO-based precursor solution. The increase of sulfur content was confirmed by thermogravimetric analyses (TGA). To understand how the elemental distribution across the CZTS layer is affected by extra thiourea, a systematic compositional study was carried out using X-ray photoelectron spectroscopy (XPS). XPS depth profiling reveals increased sulfur incorporation in the final CZTS films when more thiourea is added to the solution. The grain size was reduced slightly with increased sulfur content and the surface morphology was changed significantly. The effect on the surface of the CZTS film has been investigated using scanning electron microscopy (SEM), Raman spectroscopy, and XPS. External-quantum-efficiency (EQE) measurements with an electrolyte contact were used to investigate the optoelectronic properties of the deposited CZTS films.

Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: General discussion

Valence change ReRAMs (VCM) - Experiments and modelling: General discussion

This paper presents a method for the electrodeposition of stoichiometric, crystalline HgTe, which provides advantages over conventional HgTe preparation techniques, such as physical and chemical vapor deposition, in a number of ways; e.g. fast deposition rates (2 mm/hr) and the ability to reliably produce stoichiometric or near-stoichiometric material. The HgTe is prepared in a dichloromethane based plating bath using [NnBu4]2[TeCl6] and [NnBu4]2[HgCl4] as the precursors for Te and Hg, respectively. The paper details the electrochemical behavior of the plating bath and its components, together with a detailed characterization of the morphology, crystallinity and composition of the prepared HgTe.

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.

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.

Transparent nano-structured hematite (α-Fe2O3) films of approximately 550 nm thickness on tin-doped indium oxide (ITO) have been obtained conveniently by ink-jet printing of a Fe(NO3)3/Brij® O10 precursor ink and subsequent annealing at 500 °C in air. When illuminated with a blue LED (λ = 455 nm, ca. 100 mW cm−2), the hematite films exhibited photocurrents of up to 70 μA cm−2 at 0.4 V vs. SCE in 0.1 M NaOH electrolyte. Thermal annealing in vacuum at 500 °C for 2 h increased photocurrents more than three times to 230 μA cm−2 in agreement with previous literature reports for pure hematite materials. These results suggest that a simple ink-jetting process with surfactants is viable. The effects of vacuum-annealing on the photoelectrical properties of α-Fe2O3 films are discussed in terms of a sub-surface state templating hypothesis based on data gathered from photo-transients, field emission scanning electron microscopy, X-ray photoelectron spectroscopy analysis, X-ray diffraction, photocurrent spectra, and cyclic voltammetry.

Single crystals of Cu2ZnSnS4 (CZTS) have been grown by iodine vapor transport with and without addition of NaI. Crystals with tin-rich copper-poor and with zinc-rich copper-poor stoichiometries were obtained. The crystals were characterized by single crystal X-ray diffraction, energy-dispersive X-ray spectroscopy, photocurrent spectroscopy and electroreflectance spectroscopy using electrolyte contacts as well as by spectroscopic ellipsometry, Raman spectroscopy and photoluminescence spectroscopy (PL)/decay. Near-resonance Raman spectra indicate that the CZTS crystals adopt the kesterite structure with near-equilibrium residual disorder. The corrected external quantum efficiency of the p-type crystals measured by photocurrent spectroscopy approaches 100% close to the bandgap energy, indicating efficient carrier collection. The bandgap of the CZTS crystals estimated from the external quantum efficiency spectrum measured using an electrolyte contact was found to be 1.64-1.68 eV. An additional sub-bandgap photocurrent response (Urbach tail) was attributed to sub bandgap defect states. The room temperature PL of the crystals was attributed to radiative recombination via tail states, with lifetimes in the nanosecond range. At high excitation intensities, the PL spectrum also showed evidence of direct band to band transitions at ∼1.6 eV with a shorter decay time. Electrolyte electroreflectance spectra and spectra of the third derivative of the optical dielectric constant in the bandgap region were fitted to two optical transitions at 1.71 and 1.81 eV suggesting a larger valence band splitting than predicted theoretically. The high values of the EER broadening parameters (192 meV) indicate residual disorder consistent with the existence of tail states.

CdSe1–xTex quantum dot (QD) alloys are characterized by high luminescence quantum yields and a strong band gap bowing as a function of the Se:Te ratio, featuring longer emission wavelengths than CdTe or CdSe dots of identical size. In this contribution, these properties are rationalized by examining the structure and band edge energy of CdSe1–xTex as functions of x. The QDs were synthesized employing the “hot-injection” method, in the presence of either trioctylphosphine oxide (TOPO) or octadecene (ODE) as the Cd precursor solvent. Elementary analysis of the QDs indicated that TOPO plays a crucial role in tuning the content of Se in the alloys, as only traces of this element were found when using ODE. Detailed studies based on X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) revealed a high degree of complexity in the structure of the alloyed dots. The analysis concluded that the structure of the QDs was essentially wurtzite, a...

A novel approach to tuning electrochemical rectification using 2D assemblies of quantum dots (QDs) is presented. Asymmetric enhancement of the oxidation and reduction currents in the presence of the Fe(CN)(6)(3-/4-) redox couple is observed upon adsorption of QDs at thiol-modified Au electrodes. The extent of the electrochemical rectification is dependent on the average QD size. A molecular blocking layer is generated by self-assembling 11-mercaptoundecanoic acid (MUA) and an ultrathin film of poly(diallyldimethylammonium chloride) (PDADMAC) on the electrode. The polycationic film allows the electrostatic adsorption of 3-mercaptopropionic acid (MPA)-stabilized CdTe QDs, generating 2D assemblies with approximately 0.4% coverage. The QD adsorption activates a fast charge transfer across the blocking layer in which the reduction process is more strongly enhanced than the oxidation reaction. The partial electrochemical rectification is rationalized in terms of the relative position of the valence (VB) and conduction band (CB) edges with respect to the redox Fermi energy (ε(redox)). Quantitative analysis of the exchange current density obtained from electrochemical impedance spectroscopy demonstrates that the enhancement of charge transport across the molecular barrier is strongly dependent on the position of the QD valence band edge relative to ε(redox). The average electron tunneling rate constant through the QD assemblies is estimated on the basis of the Gerischer model for electron transfer.

edox electrolyte contacts offer a simple way of testing the photocurrent generation/collection efficiency in partially completed thin-film solar cells without the need to complete the entire fabrication process. However, the development of a reliable quantitative method can be complicated by the instability of the semiconductor/electrolyte interface. In the case of Cu(In,Ga)Se2 (CIGSe) solar cells, these problems can be overcome by using samples that have undergone the next processing step in solar cell fabrication, which involves chemical bath deposition of a thin (ca. 50 nm) CdS buffer layer. The choice of redox system is also critical. The frequently used Eu3+/2+ redox couple is not suitable for reliable performance predictions since it suffers from very slow electron transfer kinetics. This leads to the buildup of photogenerated electrons near the interface, resulting in electron–hole recombination. This effect, which can be seen in the transient photocurrent response, has been quantified using intensity-modulated photocurrent spectroscopy (IMPS). The study has demonstrated that the more oxidizing Fe(CN)63–/4– redox system can be used when a CdS buffer layer is deposited on the CIGSe absorber. The wide bandgap CdS acts as a barrier to hole injection, preventing decomposition of the CIGSe and formation of surface recombination centers. The IMPS response of this system shows that there is no recombination; i.e., electron scavenging is very rapid. It is shown that measurements of the external quantum efficiency made using the Fe(CN)63–/4– redox couple with CdS-coated CIGSe layers can provide reliable predictions of the short-circuit currents of the complete solar cells. Similar results have been obtained using CdS-coated GaAs layers, suggesting that the new approach may be widely applicable.

We report the properties of a series of electrodeposited Ge-Sb-Te alloys with various compositions. It is shown that the Sb/Ge ratio can be varied in a controlled way by changing the electrodeposition potential. This method opens up the prospect of depositing Ge-Sb-Te super-lattice structures by electrodeposition. Material and electrical characteristics of various compositions have been investigated in detail, showing up to three orders of magnitude resistance ratio between the amorphous and crystalline states and endurance up to 1000 cycles.

Electron transfer processes mediated by nanostructured materials assembled at electrode surfaces underpin fundamental processes in novel electrochemical sensors, light energy conversion systems and molecular electronics. Functionalisation of electrode surfaces with hierarchical architectures incorporating self-assembling molecular systems and materials, such as metal nanostructures, quantum dots, carbon nanotubes, graphene or biomolecules have been intensively studied over the last 20 years. Important steps have been made towards the rationalisation of the charge transfer dynamics from redox species in solution across molecular self-assembling systems to electrode surfaces. For instance, a unified picture has emerged describing the factors which determine the rate constant for electron transfer processes across rigid self-assembling molecular barriers. An increasing bulk of evidence has recently shown that the incorporation of nanomaterials into self-assembling monolayers leads to an entirely different electrochemical behaviour. This perspective rationalises some of the key observations associated with nanoparticle mediated charge transfer, such as the apparent distance independent charge transfer resistance observed for redox species in solution. This behaviour only manifests itself clearly in the case where the probability of direct charge transfer from the redox probe to the electrode is strongly attenuated by self-assembling molecular barriers. Here we will highlight specific issues concerning self-assembled monolayers as blocking barriers prior to discussing the effect of nanoparticles on the electrochemical response of the system. Selected examples will provide conclusive evidence that the extent of charge transfer mediation is determined by the overlap between the density of states of the nanostructures and the energy levels of redox species in solution. Only in the case where a strong overlap exists between the energy levels of the two components, the nanostructures behave as “electron launchers”, allowing efficient charge transfer across insulating molecular layers.

The electrochemical injection of holes into the valence band of mercaptopropionic acid stabilised CdTe quantum dots in aqueous solution was investigated employing a glassy carbon rotating disc electrode. Analysis of the first exciton peak and the electrochemical responses as a function of the particle size was performed within the framework of the effective mass approximation and tight-binding models. It is demonstrated that the energy of the quantum dot band edges can be predicted from capacitance data of bulk semiconductor electrodes modified by the same stabilising groups as on the dots. In this paper we show that the thiol binding shifts the band edges of the CdTe particles by approximately 0.7 eV with respect to the theoretical value in the absence of stabilising groups. The results also revealed a significant dependence of the hole-injection rate on the electrochemical potential.

Charge transport phenomena in opto-electronic devices featuring functional polymers and nanostructured materials critically depend on the electronic communication between the building blocks and the metal contacts. The generation of ordered multilayer structures at electrode surfaces is often a key requirement to avoid electrically isolated (inactive) areas in the devices. This issue is particularly crucial in hybrid photovoltaic, light emitting and electrochromic systems. In the present contribution, the properties of electrode surfaces modified by electrostatic layer-by-layer methods are highlighted as a versatile approach for generating two- and three-dimensional assemblies of nanostructures. The connectivity between the nanoparticles and the electrode surface is probed by a variety of techniques including Kelvin probe, electrostatic force microscopy and electrochemical methods. The main characteristics of electrode surfaces modified by electrostatic self-assembly are illustrated with several examples involving metal nanostructures and CdTe quantum dots. ? Schweizerische Chemische Gesellschaft.

A versatile electrochemical system for the non-aqueous electrodeposition of crystalline, oxide free p-block metals and metalloids is described, and it is demonstrated that by combining mixtures of these reagents, this system is suitable for electrodeposition of binary semiconductor alloys. The tetrabutylammonium halometallates, [NnBu4][InCl4], [NnBu4][SbCl4], [NnBu4][BiCl4], [NnBu4]2[SeCl6] and [NnBu4]2[TeCl6], are readily dissolved in CH2Cl2 and form reproducible electrochemical systems with good stability in the presence of a [NnBu4]Cl supporting electrolyte. The prepared electrolytes show a wide potential window and the electrodeposition of indium, antimony, bismuth, tellurium and selenium on glassy carbon and titanium nitride electrodes has been demonstrated. The deposited elements were characterised by scanning electron microscopy, energy dispersive X-ray analysis and powder X-ray diffraction. The compatibility of the reagents permits the preparation of a single electrolyte containing several halometallate species which allows the electrodeposition of binary materials, as is demonstrated for InSb. This room temperature, ‘bottom-up’ electrochemical approach should thus be suitable for the one-pot deposition of a wide range of compound semiconductor materials.