Self-compliance-improved resistive switching using Ir/TaOx/W cross-point memory

Resistive switching properties of a self-compliance resistive random access memory device in cross-point architecture with a simple stack structure of Ir/TaO _x /W have been investigated. A transmission electron microscope and atomic force microscope were used to observe the film properties and morphology of the stack. The device has shown excellent switching cycle uniformity with a small operation of ±2.5 V and a resistance ratio of >100. The device requires neither any frorming-process nor current compliance limit for repeatable operation in contrast to conventional resistive random access memory devices. The effect of bottom electrode morphology and surface roughness is also studied. The improvement is due to the enhanced electric field at the nanotips in the bottom electrode and the defective TaO _x switching layer which enable controlled filament formation/rupture. The device area dependence of the low resistance state indicates multifilament formation. The device has shown a robust alternating current endurance of >10⁵ cycles and a data retention of >10⁴ s.     

Enhanced resistive switching phenomena using low-positive-voltage format and self-compliance IrOx/GdOx/W cross-point memories

Enhanced resistive switching phenomena of IrO_x/GdO_x/W cross-point memory devices have been observed as compared to the via-hole devices. The as-deposited Gd₂O₃ films with a thickness of approximately 15 nm show polycrystalline that is observed using high-resolution transmission electron microscope. Via-hole memory device shows bipolar resistive switching phenomena with a large formation voltage of -6.4 V and high operation current of >1 mA, while the cross-point memory device shows also bipolar resistive switching with low-voltage format of +2 V and self-compliance operation current of <300 μA. Switching mechanism is based on the formation and rupture of conducting filament at the IrO_x/GdO_x interface, owing to oxygen ion migration. The oxygen-rich GdO_x layer formation at the IrO_x/GdO_x interface will also help control the resistive switching characteristics. This cross-point memory device has also Repeatable 100 DC switching cycles, narrow distribution of LRS/HRS, excellent pulse endurance of >10,000 in every cycle, and good data retention of >10⁴ s. This memory device has great potential for future nanoscale high-density non-volatile memory applications.     

Enhanced resistive switching memory characteristics and mechanism using a Ti nanolayer at the W/TaOx interface

Enhanced resistive memory characteristics with 10,000 consecutive direct current switching cycles, long read pulse endurance of >10⁵ cycles, and good data retention of >10⁴ s with a good resistance ratio of >10² at 85°C are obtained using a Ti nanolayer to form a W/TiO_x/TaO_x/W structure under a low current operation of 80 μA, while few switching cycles are observed for W/TaO_x/W structure under a higher current compliance >300 μA. The low resistance state decreases with increasing current compliances from 10 to 100 μA, and the device could be operated at a low RESET current of 23 μA. A small device size of 150 × 150 nm² is observed by transmission electron microscopy. The presence of oxygen-deficient TaO_x nanofilament in a W/TiO_x/TaO_x/W structure after switching is investigated by Auger electron spectroscopy. Oxygen ion (negative charge) migration is found to lead to filament formation/rupture, and it is controlled by Ti nanolayer at the W/TaO_x interface. Conducting nanofilament diameter is estimated to be 3 nm by a new method, indicating a high memory density of approximately equal to 100 Tbit/in.².     

TaOx-based resistive switching memories: prospective and challenges

Resistive switching memories (RRAMs) are attractive for replacement of conventional flash in the future. Although different switching materials have been reported; however, low-current operated devices (<100 μA) are necessary for productive RRAM applications. Therefore, TaO_x is one of the prospective switching materials because of two stable phases of TaO₂ and Ta₂O₅, which can also control the stable low- and high-resistance states. Long program/erase endurance and data retention at high temperature under low-current operation are also reported in published literature. So far, bilayered TaO_x with inert electrodes (Pt and/or Ir) or single layer TaO_x with semi-reactive electrodes (W and Ti/W or Ta/Pt) is proposed for real RRAM applications. It is found that the memory characteristics at current compliance (CC) of 80 μA is acceptable for real application; however, data are becoming worst at CC of 10 μA. Therefore, it is very challenging to reduce the operation current (few microampere) of the RRAM devices. This study investigates the switching mode, mechanism, and performance of low-current operated TaO_x-based devices as compared to other RRAM devices. This topical review will not only help for application of TaO_x-based nanoscale RRAM devices but also encourage researcher to overcome the challenges in the future production.     

Comparison of resistive switching characteristics using copper and aluminum electrodes on GeOx/W cross-point memories

Comparison of resistive switching memory characteristics using copper (Cu) and aluminum (Al) electrodes on GeO_x/W cross-points has been reported under low current compliances (CCs) of 1 nA to 50 μA. The cross-point memory devices are observed by high-resolution transmission electron microscopy (HRTEM). Improved memory characteristics are observed for the Cu/GeO_x/W structures as compared to the Al/GeO_x/W cross-points owing to AlO_x formation at the Al/GeO_x interface. The RESET current increases with the increase of the CCs varying from 1 nA to 50 μA for the Cu electrode devices, while the RESET current is high (>1 mA) and independent of CCs varying from 1 nA to 500 μA for the Al electrode devices. An extra formation voltage is needed for the Al/GeO_x/W devices, while a low operation voltage of ±2 V is needed for the Cu/GeO_x/W cross-point devices. Repeatable bipolar resistive switching characteristics of the Cu/GeO_x/W cross-point memory devices are observed with CC varying from 1 nA to 50 μA, and unipolar resistive switching is observed with CC >100 μA. High resistance ratios of 10² to 10⁴ for the bipolar mode (CCs of 1 nA to 50 μA) and approximately 10⁸ for the unipolar mode are obtained for the Cu/GeO_x/W cross-points. In addition, repeatable switching cycles and data retention of 10³ s are observed under a low current of 1 nA for future low-power, high-density, nonvolatile, nanoscale memory applications.     

The electronic and optical properties of quaternary GaAs1-x-y N x Bi y alloy lattice-matched to GaAs: a first-principles study

First-principles calculations based on density functional theory have been performed for the quaternary GaAs_1-x-y N _x Bi _y alloy lattice-matched to GaAs. Using the state-of-the-art computational method with the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional, electronic, and optical properties were obtained, including band structures, density of states (DOSs), dielectric function, absorption coefficient, refractive index, energy loss function, and reflectivity. It is found that the lattice constant of GaAs_1-x-y N _x Bi _y alloy with y/x =1.718 can match to GaAs. With the incorporation of N and Bi into GaAs, the band gap of GaAs_1-x-y N _x Bi _y becomes small and remains direct. The calculated optical properties indicate that GaAs_1-x-y N _x Bi _y has higher optical efficiency as it has less energy loss than GaAs. In addition, it is also found that the electronic and optical properties of GaAs_1-x-y N _x Bi _y alloy can be further controlled by tuning the N and Bi compositions in this alloy. These results suggest promising applications of GaAs_1-x-y N _x Bi _y quaternary alloys in optoelectronic devices.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.     

Resistive switching memory characteristics of Ge/GeOx nanowires and evidence of oxygen ion migration

The resistive switching memory of Ge nanowires (NWs) in an IrO_x/Al₂O₃/Ge NWs/SiO₂/p-Si structure is investigated. Ge NWs with an average diameter of approximately 100 nm are grown by the vapor–liquid-solid technique. The core-shell structure of the Ge/GeO_x NWs is confirmed by both scanning electron microscopy and high-resolution transmission electron microscopy. Defects in the Ge/GeO_x NWs are observed by X-ray photoelectron spectroscopy. Broad photoluminescence spectra from 10 to 300 K are observed because of defects in the Ge/GeO_x NWs, which are also useful for nanoscale resistive switching memory. The resistive switching mechanism in an IrO_x/GeO_x/W structure involves migration of oxygen ions under external bias, which is also confirmed by real-time observation of the surface of the device. The porous IrO_x top electrode readily allows the evolved O₂ gas to escape from the device. The annealed device has a low operating voltage (<4 V), low RESET current (approximately 22 μA), large resistance ratio (>10³), long pulse read endurance of >10⁵ cycles, and good data retention of >10⁴ s. Its performance is better than that of the as-deposited device because the GeO_x film in the annealed device contains more oxygen vacancies. Under SET operation, Ge/GeO_x nanofilaments (or NWs) form in the GeO_x film. The diameter of the conducting nanofilament is approximately 40 nm, which is calculated using a new method.     

Space electric field concentrated effect for Zr:SiO2 RRAM devices using porous SiO2 buffer layer

To improve the operation current lowing of the Zr:SiO₂ RRAM devices, a space electric field concentrated effect established by the porous SiO₂ buffer layer was investigated and found in this study. The resistive switching properties of the low-resistance state (LRS) and high-resistance state (HRS) in resistive random access memory (RRAM) devices for the single-layer Zr:SiO₂ and bilayer Zr:SiO₂/porous SiO₂ thin films were analyzed and discussed. In addition, the original space charge limited current (SCLC) conduction mechanism in LRS and HRS of the RRAM devices using bilayer Zr:SiO₂/porous SiO₂ thin films was found. Finally, a space electric field concentrated effect in the bilayer Zr:SiO₂/porous SiO₂ RRAM devices was also explained and verified by the COMSOL Multiphysics simulation model.     

Formation polarity dependent improved resistive switching memory characteristics using nanoscale (1.3 nm) core-shell IrOx nano-dots

ABSTRACT: Improved resistive switching memory characteristics by controlling the formation polarity in an IrOx/Al2O3/IrOx-ND/Al2O3/WOx/W structure have been investigated. High density of 1 × 1013/cm2 and small size of 1.3 nm in diameter of the IrOx nano-dots (NDs) have been observed by high-resolution transmission electron microscopy. The IrOx-NDs, Al2O3, and WOx layers are confirmed by X-ray photo-electron spectroscopy. Capacitance-voltage hysteresis characteristics show higher charge-trapping density in the IrOx-ND memory as compared to the pure Al2O3 devices. This suggests that the IrOx-ND device has more defect sites than that of the pure Al2O3 devices. Stable resistive switching characteristics under positive formation polarity on the IrOx electrode are observed, and the conducting filament is controlled by oxygen ion migration toward the Al2O3/IrOx top electrode interface. The switching mechanism is explained schematically based on our resistive switching parameters. The resistive switching random access memory (ReRAM) devices under positive formation polarity have an applicable resistance ratio of > 10 after extrapolation of 10 years data retention at 85°C and a long read endurance of 105 cycles. A large memory size of > 60 Tbit/sq in. can be realized in future for ReRAM device application. This study is not only important for improving the resistive switching memory performance but also help design other nanoscale high-density nonvolatile memory in future.     

Photoluminescence characteristics of Cd<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te single crystals grown by the vertical Bridgman method

In this paper, we report a systematic investigation of band-edge photoluminescence for Cd_1-x Mn _x Te crystals grown by the vertical Bridgman method. The near-band-edge emissions of neutral acceptor-bound excitons (labeled as L1) were systematically investigated as a function of temperature and of alloy composition. The parameters that describe the temperature variation of the energy were evaluated by the semiempirical Varshni relation. From the temperature dependence of the full width at half maximum of the L1 emission line, the broadening factors Γ(T) were determined from the fit to the data. The activation energies of thermal quenching were obtained for the L1 peak from the temperature dependence of the bound exciton peaks and were found to decrease with increasing Mn concentration.     

Influence of embedding Cu nano-particles into a Cu/SiO2/Pt structure on its resistive switching

Cu nano-particles (Cu-NPs) were embedded into the SiO₂ layer of a Cu/SiO₂/Pt structure to examine their influence on resistive switching characteristics. The device showed a reversible resistive switching behavior, which was due to the formation and rupture of a Cu-conducting filament with an electrochemical reaction. The Cu-NPs enhanced the local electric field within the SiO₂ layer, which caused a decrease in the forming voltage. During successive switching processes, the Cu-NP was partially dissolved, which changed its shape. Therefore, the switching voltages were not reduced. Moreover, the Cu-NPs caused a non-uniform Cu concentration within the SiO₂ layer; thus, the Cu-conducting filament should be formed in a high Cu concentration region, which improves switching dispersion. The Cu-NPs within the SiO₂ layer stabilize the resistive switching, resulting in a larger switching window and better endurance characteristics.     

Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)

A series of Ni substituted spinel LiNi_xMn_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNi_xMn_2−xO₄ (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni²⁺ cations were partially oxidized to Ni³⁺. The local structures of LiNi_xMn_2−xO₄ were studied by analyzing the and A_1g Raman bands. The most compact [Mn(Ni)O₆] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi_0.2Mn_1.8O₄, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm⁻¹. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni³⁺ in the materials.     

Numerical analysis of pulverized coal combustion characteristics using advanced low-NOx burner

A three-dimensional numerical simulation is applied to a pulverized coal combustion field in a test furnace equipped with an advanced low-NO_x burner called CI-α burner, and the detailed combustion characteristics are investigated. In addition, the validities of the existing NO_x formation and reduction models are examined. The results show that a recirculation flow is formed in the high-gas-temperature region near the CI-α burner outlet, and this lengthens the residence time of coal particles in this high-temperature region, promotes the evolution of volatile matter and the progress of char reaction, and produces an extremely low-O₂ region for effective NO reduction. It is also found that, by lessening the effect of NO reduction in Levy et al.'s model and taking the NO formation from char N into account, the accuracy of the NO prediction is improved. The efficiency factor of the conversion of char N to NO affects the total NO concentration downstream after the injection of staged combustion air.     

Fabrication and characterization of Li1+x−yNb1−x−3yTix+4yO3 substrates using aqueous tape casting process

An aqueous system for tape casting Li_1+x−yNb_1−x−3yTi_x+4yO₃ (LNT) ceramics was developed using poly(vinyl alcohol) (PVA) binder, ethylene alcohol (EG) plasticizer and ammonium salt of polycarboxylate (PCA-NH₄) dispersant. The zeta potential measurement showed that the isoelectric point of the LNT particles moved slightly toward more acid region after the dispersant absorbed on the particles, while the zeta potential increased significantly. The rheological test indicated that the ceramic slurry exhibited a typical pseudoplastic behavior without thixotropy. The effect of solid loading on the properties of the green tapes was investigated. The increase in the solid loading increased the tensile strength and the green density of the tapes. TGA analysis indicated that the organic additives in the green tapes can be completely removed by heat treatment at 600 °C. SEM micrographs showed that the microstructure of the green and sintered tapes was homogeneous.     

New understanding of hardening mechanism of TiN/SiNx-based nanocomposite films

In order to clarify the controversies of hardening mechanism for TiN/SiN_x-based nanocomposite films, the microstructure and hardness for TiN/SiN_x and TiAlN/SiN_x nanocomposite films with different Si content were studied. With the increase of Si content, the crystallization degree for two series of films firstly increases and then decreases. The microstructural observations suggest that when SiN_x interfacial phase reaches to a proper thickness, it can be crystallized between adjacent TiN or TiAlN nanocrystallites, which can coordinate misorientations between nanocrystallites and grow coherently with them, resulting in blocking of the dislocation motions and hardening of the film. The microstructure of TiN/SiN_x-based nanocomposite film can be characterized as the nanocomposite structure with TiN-based nanocrystallites surrounded by crystallized SiN_x interfacial phase, which can be denoted by nc-TiN/c-SiN_x model (''c’ before SiN_x means crystallized) and well explain the coexistence between nanocomposite structure and columnar growth structure within the TiN/SiN_x-based film.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Hydrothermal synthesis of LiNixCo1−xO2 cathode materials

Ultrafine powders of LiCoO₂, nonstoichiometric LiNiO₂ and LiNi_0.9Co_0.1O₂ were prepared under mild hydrothermal conditions. The influence of the molar ratio of Li/Co, Li/Ni and Li/(Ni + Co) was studied. The final products were investigated by XRD, TEM and EDS. To synthesize a stoichiometric LiNiO₂ under mild hydrothermal conditions was found to be a big challenge. Transmission electron microscopies (TEM) revealed the formation of well-crystallized LiCoO₂ and LiNi_0.9Co_0.1O₂ with average size of 100 nm and 10 nm, respectively.     

Attempts to reduce NOx exhaust emissions by using reformulated biodiesel

Biodiesel is a renewable, domestically produced fuel that has been shown to reduce particulate, hydrocarbon, and carbon monoxide emissions from diesel engines. Under some conditions, however, biodiesel produced from certain feedstocks has been shown to cause an increase in nitrogen oxides (NO_x). This is of special concern in urban areas that are subject to strict environmental regulations. Although soy-based biodiesel may increase the emission of nitrogen oxides, it is the most easily accessible in North America. We investigated two routes to reformulate soy-based biodiesel in an effort to reduce nitrogen oxide emissions. In one of these, soy-oil methyl esters were modified by conversion of a proportion of the cis bonds in the fatty acid chains of its methyl esters to their trans isomers. In the other approach, polyol derivatives of soybean oil were transesterified to form soy methyl polyol fatty acid esters. The NO_x emissions of these modified biodiesels were then examined, using a Yanmar L100 single cylinder, four stroke, naturally aspirated, air cooled, direct injection diesel engine. Using either isomerized methyl oleate or isomerized soy biodiesel, at 20% blend level in petroleum diesel (‘B20’), nitrogen oxide emissions were elevated by between 1.5 and 3 percentage points relative to the combustion of a B20 blend of commercial biodiesel. Nitrogen oxide emissions were reduced in proportion to blend level during the combustion of polyol biodiesel, with a 20% blend in petrodiesel resulting in a reduction of about 4.5 percentage points relative to the emissions of a comparable blend of commercial soy biodiesel.     

Influence of outer secondary-air vane angle on combustion characteristics and NOx emissions of a down-fired pulverized-coal 300 MWe utility boiler

Industrial experiments were performed on a down-fired pulverized-coal 300 MWe utility boiler with swirl burners. Gas temperature, concentrations of gas components (O₂, CO, CO₂ and NO_x) in the burning region and carbon content in the fly ash were measured with outer secondary-air vane angles of 25°, 32.5° and 50°. Results indicate that with increasing vane angle, NO_x emission and boiler efficiency decrease. Overall evaluation boiler efficiency and NO_x emission, the vane angle of 32.5° is optimum. Using an IFA300 constant-temperature anemometer system, cold air experiments on a quarter-scaled burner model were also carried out to investigate the influence of various outer secondary-air vane angles on the flow characteristics in the burner nozzle region. No central recirculation zone appeared for vane angles of 25° and 32.5°. Most of the pulverized-coal was ignited in the external recirculation zone. For vane angles of 45° and 55°, a central recirculation zone could be observed, and air flow rigidity and axial velocities decreased rapidly.