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At least 1,081 records · Page 60

Optimizing TaO{sub x} memristor performance and consistency within the reactive sputtering “forbidden region”

Standard deposition processes for depositing ReRAM oxides utilize mass flow of reactive gas to control stoichiometry and have difficulty depositing a precisely defined sub-stoichiometry within a “forbidden region” where film properties are discontinuous with mass flow. We show that by maintaining partial pressure within this discontinuous “forbidden region,” instead of by maintaining mass flow, we can optimize tantalum oxide device properties and reduce or eliminate the electroforming step. We also show that defining the partial pressure set point as a fraction of the “forbidden region” instead of as an absolute value can be used to improve wafer-to-wafer consistency with minimal recalibration efforts.

36 MATERIALS SCIENCE↗

Stimulated electroluminescence emission from n-ZnO/p-GaAs:Zn heterojunctions fabricated by electro-deposition

In this study, n-ZnO thin films were electrochemically deposited on p-GaAs:Zn substrates. The XRD results of ZnO thin films deposited on p-GaAs:Zn substrates at potentials varied from −0.9 V to −1.2 V show a strong c-axis (002) orientation and homogeneity. The current-voltage characteristics exhibit rectification, proving a low turn-on voltage and an ideality factor of 4.71. The n-ZnO/p-GaAs heterostructures show blue-white electroluminescence (EL) emission, which is composed of broad emission bands. In addition to these broad peaks, stimulated emission also appear on the top of the spectra due to the multiple reflections from the mirror like surfaces of ZnO-ZnO and ZnO-GaAs interfaces. Besides, three broad photoluminescence (PL) emission peaks have also been observed peaking at respectively around 3.36 eV, 3.28 eV and 3.07 eV generally attributed to the near bandedge emission, the residual donor level and deep level emission due to the localized defects, respectively.

36 MATERIALS SCIENCE↗

Optical microcavities and enhanced electroluminescence from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes

Electroluminescence (EL) and electron emission into vacuum (EM) occur when a non-destructive dielectric breakdown of Al-Al{sub 2}O{sub 3}-Ag diodes, electroforming, results in the development of a filamentary region in which current-voltage (I-V) characteristics exhibit voltage-controlled negative resistance. The temperature dependence of I-V curves, EM, and, particularly, EL of Al-Al{sub 2}O{sub 3}-Ag diodes with anodic Al{sub 2}O{sub 3} thicknesses between 12 nm and 30 nm, has been studied. Two filters, a long-pass (LP) filter with transmission of photons with energies less than 3.0 eV and a short-pass (SP) filter with photon transmission between 3.0 and 4.0 eV, have been used to characterize EL. The voltage threshold for EL with the LP filter, V{sub LP}, is ∼1.5 V. V{sub LP} is nearly independent of Al{sub 2}O{sub 3} thickness and of temperature and is 0.3–0.6 V less than the threshold voltage for EL for the SP filter, V{sub SP}. EL intensity is primarily between 1.8 and 3.0 eV when the bias voltage, V{sub S} ≲ 7 V. EL in the thinnest diodes is enhanced compared to EL in thicker diodes. For increasing V{sub S}, for diodes with the smallest Al{sub 2}O{sub 3} thicknesses, there is a maximum EL intensity, L{sub MX}, at a voltage, V{sub LMX}, followed by a decrease to a plateau. L{sub MX} and EL intensity at 4.0 V in the plateau region depend exponentially on Al{sub 2}O{sub 3} thickness. The ratio of L{sub MX} at 295 K for a diode with 12 nm of Al{sub 2}O{sub 3} to L{sub MX} for a diode with 25 nm of Al{sub 2}O{sub 3} is ∼140. The ratio of EL intensity with the LP filter to EL intensity with the SP filter, LP/SP, varies between ∼3 and ∼35; it depends on Al{sub 2}O{sub 3} thickness and V{sub S}. Enhanced EL is attributed to the increase of the spontaneous emission rate of a dipole in a non-resonant optical microcavity. EL photons interact with the Ag and Al films to create surface plasmon polaritons (SPPs) at the metal-Al{sub 2}O{sub 3} interfaces. SPPs generate large electromagnetic fields in the filamentary region of the electroformed Al-Al{sub 2}O{sub 3}-Ag diode, which then acts as an optical microcavity. A model is proposed for electronic processes in electroformed Al-Al{sub 2}O{sub 3}-Ag diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Patterned electrochemical deposition of copper using an electron beam

We describe a technique for patterning clusters of metal using electrochemical deposition. By operating an electrochemical cell in the transmission electron microscope, we deposit Cu on Au under potentiostatic conditions. For acidified copper sulphate electrolytes, nucleation occurs uniformly over the electrode. However, when chloride ions are added there is a range of applied potentials over which nucleation occurs only in areas irradiated by the electron beam. By scanning the beam we control nucleation to form patterns of deposited copper. We discuss the mechanism for this effect in terms of electron beam-induced reactions with copper chloride, and consider possible applications.

36 MATERIALS SCIENCE↗

Towards forming-free resistive switching in oxygen engineered HfO{sub 2−x}

We have investigated the resistive switching behavior in stoichiometric HfO{sub 2} and oxygen-deficient HfO{sub 2−x} thin films grown on TiN electrodes using reactive molecular beam epitaxy. Oxygen defect states were controlled by the flow of oxygen radicals during thin film growth. Hard X-ray photoelectron spectroscopy confirmed the presence of sub-stoichiometric hafnium oxide and defect states near the Fermi level. The oxygen deficient HfO{sub 2−x} thin films show bipolar switching with an electroforming occurring at low voltages and low operating currents, paving the way for almost forming-free devices for low-power applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Post magnetic field annealing effect on magnetic and structural properties of Co{sub 80}Pt{sub 20} nanowires and nanotubes fabricated by electrochemical method

Highly ordered Co{sub 80}Pt{sub 20} nanowires (NWs) and nanotubes (NTs) have been synthesized by low cost DC electrochemical deposition method with constant stirring during the fabrication process in anodic aluminum oxide nano-templates with average pore diameter of about 200 nm. The structural and magnetic properties of nanostructures have been investigated before and after simple and magnetic field annealing. Magnetic field of 1 T has been applied during annealing process in the direction perpendicular to NWs and NTs axis. X-Ray Diffraction analysis shows face centered cubic (fcc) as the dominant phase for Co{sub 80}Pt{sub 20} NWs and post annealing led to better crystallinity with retained fcc phase. Furthermore, magnetic properties, including saturation magnetization (M{sub s}), squareness ratio (M{sub r}/M{sub s}), and coercivity (H{sub c}), have been investigated as a function of annealing temperature by Vibrating Sample Magnetometer.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electrochemical deposition of iron sulfide thin films and heterojunction diodes with zinc oxide

Iron sulfide thin films were fabricated by the electrochemical deposition method from an aqueous solution containing FeSO{sub 4} and Na{sub 2}S{sub 2}O{sub 3}. The composition ratio obtained was Fe:S:O = 36:56:8. In the photoelectrochemical measurement, a weak negative photo-current was observed for the iron sulfide films, which indicates that its conduction type is p-type. No peaks were observed in X-ray diffraction pattern, and thus the deposited films were considered to be amorphous. For a heterojunction with ZnO, rectification properties were confirmed in the current-voltage characteristics. Moreover, the current was clearly enhanced under AM1.5 illumination.

36 MATERIALS SCIENCE↗

Design for reliability of BEoL and 3-D TSV structures – A joint effort of FEA and innovative experimental techniques

Copper-TSVs for 3D-IC-integration generate novel challenges for reliability analysis and prediction, e.g. the need to master multiple failure criteria for combined loading including residual stress, interface delamination, cracking and fatigue issues. So, the thermal expansion mismatch between copper and silicon leads to a stress situation in silicon surrounding the TSVs which is influencing the electron mobility and as a result the transient behavior of transistors. Furthermore, pumping and protrusion of copper is a challenge for Back-end of Line (BEoL) layers of advanced CMOS technologies already during manufacturing. These effects depend highly on the temperature dependent elastic-plastic behavior of the TSV-copper and the residual stresses determined by the electro deposition chemistry and annealing conditions. That’s why the authors pushed combined simulative/experimental approaches to extract the Young’s-modulus, initial yield stress and hardening coefficients in copper-TSVs from nanoindentation experiments, as well as the temperature dependent initial yield stress and hardening coefficients from bow measurements due to electroplated thin copper films on silicon under thermal cycling conditions. A FIB trench technique combined with digital image correlation is furthermore used to capture the residual stress state near the surface of TSVs. The extracted properties are discussed and used accordingly to investigate the pumping and protrusion of copper-TSVs during thermal cycling. Moreover, the cracking and delamination risks caused by the elevated temperature variation during BEoL ILD deposition are investigated with the help of fracture mechanics approaches.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Impact of composition and crystallization behavior of atomic layer deposited strontium titanate films on the resistive switching of Pt/STO/TiN devices

The resistive switching (RS) properties of strontium titanate (Sr{sub 1+x}Ti{sub 1+y}O{sub 3+(x+2y)}, STO) based metal-oxide-metal structures prepared from industrial compatible processes have been investigated focusing on the effects of composition, microstructure, and device size. Metastable perovskite STO films were prepared on Pt-coated Si substrates utilizing plasma-assisted atomic layer deposition (ALD) from cyclopentadienyl-based metal precursors and oxygen plasma at 350 °C, and a subsequent annealing at 600 °C in nitrogen. Films of 15 nm and 12 nm thickness with three different compositions [Sr]/([Sr] + [Ti]) of 0.57 (Sr-rich STO), 0.50 (stoichiometric STO), and 0.46 (Ti-rich STO) were integrated into Pt/STO/TiN crossbar structures with sizes ranging from 100 μm{sup 2} to 0.01 μm{sup 2}. Nano-structural characterizations revealed a clear effect of the composition of the as-deposited STO films on their crystallization behavior and thus on the final microstructures. Local current maps obtained by local-conductivity atomic force microscopy were in good agreement with local changes of the films' microstructures. Correspondingly, also the initial leakage currents of the Pt/STO/TiN devices were affected by the STO compositions and by the films' microstructures. An electroforming process set the Pt/STO/TiN devices into the ON-state, while the forming voltage decreased with increasing initial leakage current. After a RESET process under opposite voltage has been performed, the Pt/STO/TiN devices showed a stable bipolar RS behavior with non-linear current-voltage characteristics for the high (HRS) and the low (LRS) resistance states. The obtained switching polarity and nearly area independent LRS values agree with a filamentary character of the RS behavior according to the valence change mechanism. The devices of 0.01 μm{sup 2} size with a 12 nm polycrystalline stoichiometric STO film were switched at a current compliance of 50 μA with voltages of about ±1.0 V between resistance states of about 40 kΩ (LRS) and 1 MΩ (HRS). After identification of the influences of the films' microstructures, i.e., grain boundaries and small cracks, the remaining RS properties could be ascribed to the effect of the [Sr]/([Sr] + [Ti]) composition of the ALD STO thin films.

36 MATERIALS SCIENCE↗

Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Joint contributions of Ag ions and oxygen vacancies to conducting filament evolution of Ag/TaO{sub x}/Pt memory device

The electroforming and resistive switching behaviors in the Ag/TaO{sub x}/Pt trilayer structure are investigated under a continual change of temperatures between 300 K and 100 K to distinguish the contributions of Ag ions and oxygen vacancies in developing of conducting filaments. For either electroforming or resistive switching, a significantly higher forming/set voltages is needed as the device is operated at 100 K, as compared to that observed when operating at 300 K. The disparity in forming/set voltages of Ag/TaO{sub x}/Pt operating at 300 K and 100 K is attributed to the contribution of oxygen vacancies, in addition to Ag atoms, in formation of conducting filament at 100 K since the mobilities of oxygen vacancies and Ag ions become comparable at low temperature. The presence of oxygen vacancy segment in the conducting filament also modifies the reset current from a gradually descending behavior (at 300 K) to a sharp drop (at 100 K). Furthermore, the characteristic set voltage and reset current are irreversible as the operation temperature is brought from 100 K back to 300 K, indicating the critical role of filament constituents on the switching behaviors of Ag/oxide/Pt system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spectra of surface plasmon polariton enhanced electroluminescence from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes

Narrow band-pass filters have been used to measure the spectral distribution of electroluminescent photons with energies between 1.8 eV and 3.0 eV from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes with anodic Al{sub 2}O{sub 3} thicknesses between 12 nm and 18 nm. Electroforming of metal-insulator-metal (MIM) diodes is a non-destructive dielectric breakdown that results in a conducting channel in the insulator and changes the initial high resistance of the MIM diode to a low resistance state. It is a critical step in the development of resistive-switching memories that utilize MIM diodes as the active element. Electroforming of Al-Al{sub 2}O{sub 3}-Ag diodes in vacuum results in voltage-controlled negative resistance (VCNR) in the current-voltage (I-V) characteristics. Electroluminescence (EL) and electron emission into vacuum (EM) develop simultaneously with the current increase that results in VCNR in the I-V characteristics. EL is due to recombination of electrons injected at the Al-Al{sub 2}O{sub 3} interface with radiative defect centers in Al{sub 2}O{sub 3}. Measurements of EL photons between 1.8 eV and 3.0 eV using a wide band-pass filter showed that EL intensity is exponentially dependent on Al{sub 2}O{sub 3} thickness for Al-Al{sub 2}O{sub 3}-Ag diodes between 12 nm and 20 nm thick. Enhanced El intensity in the thinnest diodes is attributed to an increase in the spontaneous emission rate of recombination centers due to high electromagnetic fields generated in Al{sub 2}O{sub 3} when EL photons interact with electrons in Ag or Al to form surface plasmon polaritons at the Al{sub 2}O{sub 3}-Ag or Al{sub 2}O{sub 3}-Al interface. El intensity is a maximum at 2.0–2.2 eV for Al-Al{sub 2}O{sub 3}-Ag diodes with Al{sub 2}O{sub 3} thicknesses between 12 nm and 18 nm. EL in diodes with 12 nm or 14 nm of Al{sub 2}O{sub 3} is enhanced by factors of 8–10 over EL from a diode with 18 nm of Al{sub 2}O{sub 3}. The extent of EL enhancement in the thinnest diodes can vary significantly between samples. A narrow band of recombination centers was found in one Al-Al{sub 2}O{sub 3}-Ag diode with 12 nm of Al{sub 2}O{sub 3}; it had EL intensity 100 times greater at 2.15 eV than the diode with 18 nm of Al{sub 2}O{sub 3}. EL intensity for photons with energies greater than 2.6 eV is nearly the same for all diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Design of the new extraction grid for the NIO1 negative ion source

NIO1 is a compact source of negative ions jointly developed by RFX and INFN, to study the physics of production and acceleration of H{sup −} beams. Negative ions, up to 120 mA of current, are extracted from a radiofrequency driven plasma, by means of a gridded electrode (plasma grid, PG) featuring 9 apertures arranged in a 3x3 square lattice. The same aperture pattern is replicated in the following electrodes, allowing ion acceleration up to 60 keV. All electrodes are realized in copper, by electro-deposition technique, leaving empty slots in the metal to place magnets and to flow water for the grid cooling. The first set of electrodes was completed, installed in the source and tested. At the same time, an upgrade of the extraction system was carried out, in order to optimize the beam optics and to explore alternative electrostatic configurations. In particular, the accelerator will be modified by completely replacing the EG grid, exploiting the modularity of NIO1. The new electrode will feature other slots in between apertures, to place additional magnets. This allows testing different magnetic configurations, to optimize electron filtering and residual ion deflection. The present paper describes the theoretical activities driving the design of these new extractors, carried out with most updated numerical codes, and exploiting the synergy with the refined modeling of the 40 A ITER negative ion sources, under development at Consorzio RFX. Beam simulations are performed both with tracing codes (SLACCAD and OPERA) and with particle in cell codes (ACCPIC)

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Atomic-scale electrochemistry on the surface of a manganite

The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La 0.625 Ca 0.375 MnO 3 grown on (001) SrTiO 3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunnelling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A reconfigurable liquid metal antenna driven by electrochemically controlled capillarity

We describe a new electrochemical method for reversible, pump-free control of liquid eutectic gallium and indium (EGaIn) in a capillary. Electrochemical deposition (or removal) of a surface oxide on the EGaIn significantly lowers (or increases) its interfacial tension as a means to induce the liquid metal in (or out) of the capillary. A fabricated prototype demonstrates this method in a reconfigurable antenna application in which EGaIn forms the radiating element. By inducing a change in the physical length of the EGaIn, the operating frequency of the antenna tunes over a large bandwidth. This purely electrochemical mechanism uses low, DC voltages to tune the antenna continuously and reversibly between 0.66 GHz and 3.4 GHz resulting in a 5:1 tuning range. Gain and radiation pattern measurements agree with electromagnetic simulations of the device, and its measured radiation efficiency varies from 41% to 70% over its tuning range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Dielectric Breakdown Model applied to explain various morphologies of deposited metallic structures in thin gap metal electro-deposition

The phenomenon of metal electro-deposition in thin-gap geometry leads to very interesting and diverse two dimensional morphologies. This varies from dense ramified growth to thin dendritic projections. In this paper, we have proposed a stochastic model that incorporates such diversity. We carried out thin-gap electro-deposition of Copper and Zinc with varying electrolytic concentrations. A well known model, that until this work was used to explain dielectric breakdown patterns, was employed to explain the variation in deposition morphology with concentration. The sole parameter in the model was varied and the numerically obtained patterns was seen to correlate well with those obtained from electro-deposition. A linear relationship between the parameter and molar concentration was established. The established relationship was then analysed and interpreted.

36 MATERIALS SCIENCE↗

Abnormal bipolar resistive switching behavior in a Pt/GaO{sub 1.3}/Pt structure

A stable and repeatable abnormal bipolar resistive switching behavior was observed in a Pt/GaO{sub 1.3}/Pt sandwich structure without an electroforming process. The low resistance state (LRS) and the high resistance state (HRS) of the device can be distinguished clearly and be switched reversibly under a train of the voltage pulses. The LRS exhibits a conduction of electron tunneling, while the HRS shows a conduction of Schottky-type. The observed phenomena are considered to be related to the migration of oxygen vacancies which changes the space charge region width of the metal/semiconductor interface and results in a different electron transport mechanism.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗