Materials,technologies, and circuit concepts for nanocrossbar-based bipolar RRAM

The paper reports on the characterization of bipolar resistive switching materials and their integration into nanocrossbar structures, as well as on different memory operation schemes in terms of memory density and the challenging problem of sneak paths. TiO₂, WO₃, GeSe, SiO₂ and MSQ thin films were integrated into nanojunctions of 100×100 nm². The variation between inert Pt and Cu or Ag top electrodes leads to valence change (VCM) switching or electrochemical metallization (ECM) switching and has significant impact on the resistive properties. All materials showed promising characteristics with switching speeds down to 10 ns, multilevel switching, good endurance and retention. Nanoimprint lithography was found to be a suitable tool for processing crossbar arrays down to a feature size of 50 nm and 3D stacking was demonstrated. The inherent occurrence of current sneak paths in passive crossbar arrays can be circumvented by the implementation of complementary resistive switching (CRS) cells. The comparison with other operation schemes shows that the CRS concept dramatically increases the addressable memory size to about 10¹⁰ bit.     

Highly improved resistive switching performances of the self-doped Pt/HfO2:Cu/Cu devices by atomic layer deposition

Metal-oxide electrochemical metallization (ECM) memory is a promising candidate for the next generation nonvolatile memory. But this memory suffers from large dispersion of resistive switching parameters due to the intrinsic randomness of the conductive filament. In this work, we have proposed a self-doping approach to improve the resistive switching characteristics. The fabricated Pt/HfO₂:Cu/Cu device shows outstanding nonvolatile memory properties, including high uniformity, good endurance, long retention and fast switching speed. The results demonstrate that the self-doping approach is an effective method to improve the metal-oxide ECM memory performances and the self-doped Pt/HfO₂:Cu/Cu device has high potentiality for the nonvolatile memory applications in the future.     

Multilevel resistive switching performance of TiO2-based flexible memory prepared by low-temperature sol-gel method with UV irradiation

The flexible Ag/TiO₂/ITO/PET resistive switching memory is prepared by low-temperature sol-gel method with UV irradiation, and the simple method that combined the advantages of sol-gel method and low temperature can be applied to fabricate high-quality film. The flexible Ag/TiO₂/ITO/PET memory device displays good resistive behavior, for instance, the narrow distributions of switching voltages, good cycle endurance, and long retention time. Meanwhile, the multilevel resistance states of the device can be realized by controlling the compliance current or reset voltages, showing the potential of applications in neural networks and high-density storge. In addition, flexibility of the Ag/TiO₂/ITO/PET is studied, which exhibit good endurance and retention properties under bending condition. The I–V curves are replotted and fitted for analyzing the conductive mechanism of the device. The fitting results show that SCLC and Ohmic mechanism are main mechanisms of high resistance state and low resistance state respectively. The electrochemical and thermochemical modes are adopted to explain resistive switching behavior. Our results indicate the Ag/TiO₂/ITO/PET memory has potential application in wearable and foldable electronics.     

Performance improvement of amorphous indium–gallium–zinc oxide ReRAM with SiO2 inserting layer

In this study, the resistive switching performance of amorphous indium–gallium–zinc oxide (a-IGZO) resistive switching random-access memory (ReRAM) was improved by inserting a thin silicon oxide layer between silver (Ag) top electrode and a-IGZO resistive switching layer. Compared with the single a-IGZO layer structure, the SiO₂/a-IGZO bi-layer structure exhibits the higher On/Off resistance ratio larger than 10³, and the lower operation power using a smaller SET compliance current. In addition, good endurance and excellent retention characteristics were achieved. Furthermore, multilevel resistance states are obtained through adjusting SET compliance current and RESET stop voltage, which shows a promise for high-performance nonvolatile multilevel memory application.     

Investigation of resistive switching behaviours in WO3-based RRAM devices

In this paper, a WO₃-based resistive random access memory device composed of a thin film of WO₃ sandwiched between a copper top and a platinum bottom electrodes is fabricated by electron beam evaporation at room temperature. The reproducible resistive switching, low power consumption, multilevel storage possibility, and good data retention characteristics demonstrate that the Cu/WO₃/Pt memory device is very promising for future nonvolatile memory applications. The formation and rupture of localised conductive filaments is suggested to be responsible for the observed resistive switching behaviours.     

Effects of the compliance current on the resistive switching behavior of TiO2 thin films

Nanocrystalline TiO₂ thin films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by the thermal oxidation of evaporated Ti films. Effects of the compliance current on the resistive switching behavior of the Pt/TiO₂/Pt sandwich structures were studied in detail. The reset current increased when the compliance current increased from 10 mA to 20 mA. When the compliance current exceeded 20 mA, the switching behavior disappeared, which could be attributed to the change of the conducting behavior in the low-resistance state. A resistance change ratio of as high as 10² was obtained between the high-resistance state and the low-resistance state. The study of the effect of compliance current contributes to obtaining stable and reliable resistive switching behavior for nonvolatile memory applications.     

Colossal resistive switching behavior and its physical mechanism of Pt/<Emphasis Type="Italic">p</Emphasis>-NiO/<Emphasis Type="Italic">n</Emphasis>-Mg<Subscript>0.6</Subscript>Zn<Subscript>0.4</Subscript>O/Pt thin films

A heterojunction structure of p-NiO/n-Mg_0.6Zn_0.4O with an aim to tuning or improving the resistive switching properties was fabricated on Pt/TiO₂/SiO₂/Si substrates by the sol-gel spin-coating technique. The Pt/NiO/Mg_0.6Zn_0.4O/Pt heterojunction thin-film device shows excellent resistive switching properties, such as a reduced threshold current of 1 μA for device initiation, a small dispersion of reset voltage ranging from 0.54 to 0.62 V, long retention time and a high resistance ratio of high-resistance state to low-resistance state about six orders of magnitude. These results indicate that the resistive switching properties can be greatly improved by constructing the p-NiO/n-Mg_0.6Zn_0.4O heterojunction for nonvolatile memory applications. The physical mechanism responsible for colossal resistive switching properties of the heterojunction was analyzed based on interfacial defect effect and formation and rapture of conductive filaments.     

Impact of amorphous titanium oxide film on the device stability of Al/TiO2/Al resistive memory

We have investigated the role of amorphous titanium oxide film in the reliable bipolar resistive switching of Al/TiO₂/Al resistive random access memory devices. As TiO₂ deposition temperature decreased, a more stable endurance characteristic was obtained. We proposed that the degradation of the bipolar resistive switching property of Al/TiO₂/Al devices is closely related to the imperfect migration of oxygen ions between the top insulating interface layer and the oxygen-deficient titanium oxide during the set and reset operations. In addition, the dependence of the TiO₂ film thickness on the switching property was also studied. As the thickness of the film increased, a reduction in the resistance of the high resistance state rapidly appeared. We attribute the improved endurance performance of thin and low-temperature grown TiO₂ devices to the amorphous state with a low film density.     

Irradiation of glass with infrared femtosecond laser pulses

We report a novel resistive random access memory using tri-layer dielectrics of GeO _x /nano-crystal TiO₂/TaON and low cost top Ni and bottom TaN electrodes. Excellent device performance of ultra-low 720 fJ switching energy, tight distributions of set/reset currents, and exceptionally long endurance of 5×10⁹ cycles were achieved simultaneously. Such excellent endurance may create new applications such as those used for Data Centers that are ascribed to the higher-κ nano-crystal TiO₂, hopping pass via grain boundaries, and fast switching speed of 100 ns to improve the dielectric fatigue during endurance stress.     

Bipolar resistive switching of solution processed TiO2–graphene oxide nanocomposite for nonvolatile memory applications

In this study, we report the observation of memory effect in TiO₂–GO nanocomposite films. Electrical properties of the prepared Al/TiO₂–GO composite/ITO devices have shown stable and reproducible bipolar resistive switching behavior. The TiO₂–GO composite films were prepared using solution method by spin coating technique. Observed results have shown that the inclusion of GO in the TiO₂ matrix have exhibited a significant role in the resistive switching mechanism. The device has exhibited an excellent memory characteristic with low operating voltages, good endurance up to 10⁵ cycles and long retention time more than 5×10³ s$5\times {10}^3\text{s}$.     

Characteristics and mechanism of nano‐polycrystalline La2O3 thin‐film resistance switching memory

We investigated the characteristics and the mechanism of Pt/La₂O₃/Pt resistance switching memory with a set of measurements. The La₂O₃ films were determined as nano‐poly‐crystalline (diameter of the nanocrystals 5–10 nm) by XRD and HRTEM analysis. The Pt/La₂O₃/Pt device exhibited excellent resistive switching properties, including low switching voltage (<2 V), large low/high resistance ratio (>10⁸), and good cycling endurance property. The conduction mecha‐ nisms of the Pt/La₂O₃/Pt device were revealed with current–voltage characteristics, which are different in the low and high resistance states. Furthermore, XPS analysis and temperature‐dependent resistance measurement in the low resistance state showed that the conducting filaments in the Pt/La₂O₃/Pt device are mainly affected by oxygen defects rather than metallic La. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low power resistive random access memory using interface-engineered dielectric stack of SiOx/a-Si/TiOy with 1D1R-like structure

In this study, we report a resistive random access memory (RRAM) using trilayer SiO_x/a-Si/TiO_y film structure. The low switching energy of <10 pJ, highly uniform current distribution (<13% variation), fast 50-ns speed and stable cycling endurance for 10⁶ cycles are simultaneously achieved in this RRAM device. Such good performance can be ascribed to the use of interface-engineered dielectric stack with 1D1R-like structure. The SiO_x tunnel barrier in contact with top Ni electrode to form diode-like rectifying element not only lowers self-compliance switching currents, but also improves cycling endurance, which is favorable for the application of high-density 3D memory.     

Fully room‐temperature‐fabricated TiN/TaOx/Pt nonvolatile memory devices

The reliable resistive switching properties of TiN/TaO_x/Pt structures fabricated with a fully room‐temperature process are demonstrated in this letter. The devices exhibited a low operation voltage of 0.6 V as well as good endurance up to 10⁵ cycles. No data loss was reported upon continuous readout for more than 10⁴ s at 125 °C. Multilevel storage is feasible due to the dependence of the low resistance state (LRS) on the initial “SET” (switch from high to low RS) compliance current. The values of LRS showed no dependence on the size of the device, which correlated with the localized conductive filament mechanism. This nonvolatile multilevel memory effect and the fully room‐temperature fabrication process make the TiN/TaO_x/Pt memory devices promising for future nonvolatile memory application. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of fatigue fracture on the resistive switching of TiO2-CuO film/ITO flexible memory device

We fabricated the GaIn/TiO₂-CuO/ITO resistive memory and studied the effect of fatigue fracture on the switching performance. The device shows the stable bipolar resistive switching over 10⁸ s under ambient condition. The ON/OFF ratio decreases seriously with increase of bending cycles. The main fatigue fracture caused by dynamic strain includes micro defect between nanoparticles, vertical crack along the film thickness and interfacial delamination between layers. Finite element analysis indicates that channel crack plays a key role to cause the interfacial delamination between function layer and ITO electrode. The channel crack and interfacial delamination can hinder the formation of tree−like conduction filaments. Moreover, oxygen via the cracks can be easily transformed to ions and reduce the density of oxygen vacancies under the catalytic assistance of CuO. Our studies may provide some useful information for inorganic materials applied in flexible nonvolatile memory.     

Enhanced bipolar resistive switching of HfO2 with a Ti interlayer

The characteristics of resistive switching of TiN/HfO₂/Ti/HfO₂/Pt/Ti stacks on SiO₂/Si substrates were investigated and compared to TiN/HfO₂/Pt/Ti stacks in order to study Ti interlayer effects on resistive switching. The Ti interlayers were deposited in situ during the reactive sputtering of HfO₂ films. The current–voltage measurements showed that the Ti interlayers enhanced the memory window but reduced the endurance of SET/RESET operations. The energy filtered images by TEM showed asymmetric oxygen accumulation at the Ti/HfO _x interfaces. Subsequent heat treatment improved the endurance of SET/RESET operation of TiN/HfO₂/Ti/HfO₂/Pt/Ti stacks.     

Bipolar resistive switching effect and mechanism of solution-processed orthorhombic Bi2SiO5 thin films

Orthorhombic Bi₂SiO₅ thin films with dense surface were synthesized by using a chemical solution deposition method. The crystallized films were first utilized to implement resistive memory cells with Pt/Bi₂SiO₅/Pt sandwich architecture. It exhibited outstanding switching parameters including concentrated distributions of low and high resistance states, uniform switching voltages, cycling endurance, and long retention. Furthermore, the model of formation and rupture of conductive filaments consisted of oxygen vacancies was used to well explain resistive switching behavior. The results revealed that the solution-processed Bi₂SiO₅ thin film devices have great potential for forefront application in nonvolatile memory.     

Correlation between diode polarization and resistive switching polarity in Pt/TiO2/Pt memristive device

We have investigated the correlation between diode polarization and switching polarity in electroformed Pt/TiO₂/Pt memristive device. Before forming, the diode direction of the Pt/TiO₂/Pt device is reversible under the current pulses with varying current amplitude. The diode polarization arises from oxygen vacancy migration in fully depleted Pt/TiO₂/Pt films. The measurement results indicated that only the polarized diode can be electroformed and the metallic suboxide filament is created in parallel to the diode with a switching polarity dependent on the polarization of stack prior to forming. The non‐polar state inhibits field concentration at either end of the device at the specified current, preventing the electroforming. On and off state currents are measured at 0.2 V for 5 × 10⁴ s showing good retention, which is promising for non‐volatile memory application. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Resistive switching behaviors of Cu/TaOx/TiN device with combined oxygen vacancy/copper conductive filaments

Forming-free and self-compliant bipolar resistive switching is observed in Cu/TaO_x/TiN conductive bridge random access memory. Generally, Pt has been investigated as an inert electrode. However, Pt is not desirable material in current semiconductor industry for mass production. In this study, all electrodes are adapted to complementary metal-oxide-semiconductor compatible materials. The self-compliant resistive switching is achieved via usage of TiN bottom electrode. Also, dissolved Cu ions in TaO_x lead to forming-free resistive switching behavior. The resistive switching mechanism is formation and rupture of combined oxygen vacancy/metallic copper conductive filament. We propose that Cu/TaO_x/TiN is a promising candidate for a conductive bridge random access memory structure.     

Enhanced resistance switching stability of transparent ITO/TiO2/ITO sandwiches

We report that fully transparent resistive random access memory(TRRAM) devices based on ITO/TiO2/ITO sandwich structure,which are prepared by the method of RF magnetron sputtering,exhibit excellent switching stability.In the visible region(400-800 nm in wavelength) the TRRAM device has a transmittance of more than 80%.The fabricated TRRAM device shows a bipolar resistance switching behaviour at low voltage,while the retention test and rewrite cycles of more than 300,000 indicate the enhancement of switching capability.The mechanism of resistance switching is further explained by the forming and rupture processes of the filament in the TiO 2 layer with the help of more oxygen vacancies which are provided by the transparent ITO electrodes.     

Resistive switching mechanism of Ag/ZrO2:Cu/Pt memory cell

Resistive switching mechanism of zirconium oxide-based resistive random access memory (RRAM) devices composed of Cu-doped ZrO₂ film sandwiched between an oxidizable electrode and an inert electrode was investigated. The Ag/ZrO₂:Cu/Pt RRAM devices with crosspoint structure fabricated by e-beam evaporation and e-beam lithography show reproducible bipolar resistive switching. The linear I?CV relationship of low resistance state (LRS) and the dependence of LRS resistance (R _ON) and reset current (I _reset) on the set current compliance (I _comp) indicate that the observed resistive switching characteristics of the Ag/ZrO₂:Cu/Pt device should be ascribed to the formation and annihilation of localized conductive filaments (CFs). The physical origin of CF was further analyzed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). CFs were directly observed by cross-sectional TEM. According to EDS and elemental mapping analysis, the main chemical composition of CF is determined by Ag atoms, coming from the Ag top electrode. On the basis of these experiments, we propose that the set and reset process of the device stem from the electrochemical reactions in the zirconium oxide under different external electrical stimuli.