The effect of size on the resistive switching characteristics of NiO nanodots

NiO nanodots were fabricated via a shattering process using an AFM tip, where an NiO nanodot with a diameter of approximately 90 nm was broken into very small pieces. The pieces showed diverse diameters, including three diameters of approximately 10, 20, and 30 nm. The NiO nanodots exhibited unipolar switching characteristics including bistable resistivity during 200 repeated switching cycles. Significantly, the magnitude of the “ON currents” was observed to depend on the formation of conducting filaments in the NiO nanodots. We suggest that the critical diameter of the RRAM NiO nanodots is approximately 30 nm.     

Coexistence of nonvolatile unipolar and volatile threshold resistive switching in the Pt/LaMnO3/Pt heterostructures

Coexistence of nonvolatile unipolar and volatile threshold resistive switching is observed in the Pt/LaMnO₃ (LMO)/Pt heterostructures. The nonvolatile unipolar memory is achieved by applying a negative bias, while the volatile threshold resistive switching is obtained under a positive bias. Additionally, the pristine low resistance state (LRS) could be switched to high resistance state (HRS) by the positive voltage sweeping, which is attributed to the conduction mechanism of Schottky emission. Subsequently, the insulator-to-metal transition in the LMO film due to formation of ferromagnetic metallic phase domain contributes to the volatile threshold resistive switching. However, the nonvolatile unipolar switching under the negative bias is ascribed to the formation/rupture of oxygen-vacancy conducting filaments. The simultaneously controllable transition between nonvolatile and volatile resistance switching by the polarity of the applied voltage exhibits great significance in the applications of in-memory computing technology.     

Conversion of two types of bipolar switching induced by the electroforming polarity in Au/NiO/SrTiO3/Pt memory cells

The resistive switching characteristics of Au/p-NiO/n-SrTiO₃(STO)/Pt memory cells are investigated. Two types of bipolar switching with opposite polarity coexist in the cell and can be repeatedly adjusted by the electroforming polarity. The conduction mechanisms of low resistance and high resistance states are dominated by electron tunneling and interface barrier effect, respectively. The impact of electroforming polarity on the switching mechanism and the distribution of defects are discussed. The results indicate that these two types of switching originate from a variation of interface barrier respectively at the NiO/STO p–n junction and STO/Pt Schottky contact.     

Thermochemical resistive switching: materials,mechanisms, and scaling projections

In this article, resistive switching based on the thermochemical mechanism (TCM) is reviewed. This mechanism is observed when thermochemical redox processes dominate over electrochemical processes. As the switching is based on thermal effects, it is inherently unipolar, i.e., the transitions between the resistive states can be induced by the same bias voltage polarity. NiO has emerged as a “model material” for resistive switching based on the TCM effect and the discussion of the resistance states and the switching processes are focused on this material with the appropriate electrodes, mainly Pt. Unipolar switching is unambiguously filamentary. Conductive filaments are formed during the electroforming process needed prior to memory switching. The SET operation is interpreted as a sequence of threshold switching and subsequent Joule heating which triggers local redox reactions in which oxygen deficient NiO and, if the amount of released oxygen exceeds a certain amount, also metallic Ni will form. The RESET transition can be described as a thermally activated solid-state process resulting in a local decrease of the metallic Ni species. In terms of operation and reliability, a trade-off between RESET current reduction and retention was experimentally found. This is due to the decreasing long-term stability of the filaments with decreasing size. In addition, the scaling projection of a TCM-based memory technology with NiO is directly related to RESET currents and the availability of appropriate select devices.     

Random and localized resistive switching observation in Pt/NiO/Pt

Resistive memory switching devices based on transition metal oxides are now emerging as a candidate for nonvolatile memories. To visualize nano‐sized (10 nm to 30 nm in diameter) conducting filamentary paths in the surface of NiO thin films during repetitive switching, current sensing–atomic force microscopy and ultra‐thin (<5 nm) Pt films as top electrodes were used. Some areas (or spots), which were assumed to be the beginning of the conducting filaments, appeared (formation) and disappeared (rupture) in a localized and random fashion during the switching and are thought to contribute to resistive memory switching. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanoscale formation mechanism of conducting filaments in NiO thin films

We have studied the nanoscale electrical properties of NiO thin films by using conducting atomic force microscopy (CAFM) to understand the mechanism of resistance change of the NiO thin films as we changed the applied voltage. We observed that inhomogeneous conducting filaments were generated by external voltage bias; in addition, some of the inhomogeneous conducting filaments were durable while some of them were not, and they disappeared. We deduced that the resistance change of the NiO thin films was related to inhomogeneous filamentary conducting paths generated by both Ni ions in thermodynamically unstable NiO and the existence of conducting filament segments generated by high voltage bias.     

Ferroelectric polarization and resistive switching characteristics of ion beam assisted sputter deposited BaTiO3 thin films

In this work, 150 nm thick polycrystalline BaTiO₃ (BTO) films were deposited on Pt/TiO₂/SiO₂/Si substrate by ion beam assisted sputter deposition technique. The bias voltage dependent resistive switching (RS) and ferroelectric polarization characteristics of Au/BTO/Pt devices are investigated. The devices display the stable bipolar RS characteristics without an initial electroforming process. Fittings to current–voltage (I–V) curves suggest that low and high resistance states are governed, respectively, by filamentary model and trap controlled space charge limited conduction mechanism, where the oxygen vacancies act as traps. Presence of oxygen vacancies is evidenced from the photoluminescence spectrum. The devices also display P–V loops with remnant polarization (P_r) of 5.7 μC/cm² and a coercive electric field (E_c) of 173.0 kV/cm. The coupling between the ferroelectric polarization and RS effect in BTO films is demonstrated.     

Top electrode effects on resistive switching behavior in CuO thin films

Top electrode (TE) material on the resistive switching behavior of (TE)/CuO/SnO₂:F/Si substrate has been studied. We investigated the switching properties of CuO films deposited by sol-gel process. Two kinds of top electrode (TE) material on the resistive switching behaviors have been studied. The nonpolar and bipolar resistive switching phenomenon was observed in CuO thin films with different top electrodes. The filamentary mechanism was used to explain the two kinds of resistive switching behaviors. For the Pt/CuO/ATO device, it showed the nonpolar resistive switching where conducting path is formed and disappear due to the oxygen vacancy. For the Cu/CuO/ATO device, the resistance reduction is due to the existing Cu to form conduction Cu-rich pathways. An opposite bias takes the existing Cu back to the Cu electrode to its high-resistance state. CuO thin films are also observed by XRD, AFM and XPS.     

Oxygen vacancy effects on electronic structure of Pt/NiO/Pt capacitor-like system

Oxygen vacancy effect on the electronic state of Pt/NiO/Pt capacitor-like system is theoretically investigated by density functional theory (DFT) based first-principles calculations. The potential energy profile for electrons at the interface between Pt and NiO is found to play a major role on the transport properties alternations where conduction path begin to construct. Oxygen vacancies effect is summarized in the induction of a spatially localized spin-polarized state near the Fermi level of the surrounding Ni ions. Also, electron transport through O vacancy filaments (conduction paths) is via s-orbital sub-bands. We have found that the absence or presence of a vacancy near the interface at the edges of the vacancy filament causes a conductance jump from ~0 to 1e²/h respectively which corresponds to clearly observable switching.     

Interface reaction of Ta/NiO and its effect on exchange coupling

Ta/NiO/NiFe/Ta multilayers, utilizing Ta as the buffer layer, were prepared by RF reactive and DC magnetron sputtering. The exchange coupling field between NiO and NiFe reached a maximum value of 120 Oe at a NiO film thickness of 50 nm. The composition and chemical state at the interface region of Ta/NiO/Ta were studied using the X-ray photoelectron spectroscopy (XPS) and peak decomposition technique. The results show that there is an `intermixing layer’ at the Ta/NiO (and NiO/Ta) interface due to a thermodynamically favorable reaction: 2Ta+5NiO=5Ni+Ta<sub>2</sub>O<sub>5</sub>. This interface reaction has an effect on the exchange coupling. The thickness of the `intermixing layer’ as estimated by XPS depth-profiles was about 8–10 nm.     

Photoelectrochromic properties of NiO film deposited on an N-doped TiO2 photocatalytical layer

N-doped TiO₂ film was synthesized on indium–tin oxide (ITO) conducting glass substrate by the hydrolysis method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Then high porous NiO was deposited onto the TiO_2?xN_x layer by chemical bath deposition (CBD) to prepare a double-layer TiO_2?xN_x/NiO electrode. The photoelectrochromic properties of the TiO_2?xN_x/NiO electrode were discussed through the results of UV–vis transmittance spectra, cyclic voltammogram and photocurrent transient measurements. It was found that the TiO_2?xN_x/NiO electrode was sensitive to light and exhibited a noticeable photoelectrochromism. The NiO film changed its color from colorless to brown, and the transmittance varied from 86.8% to 14.5% at 500 nm after 1 h irradiation.     

Scanning tunneling microscopy imaging of NiO(100)(1 × 1) islands embedded in Ag(100)

The imaging of NiO(100)(1 × 1) islands embedded in Ag(100) by scanning tunneling microscopy is addressed. As a function of tunneling conditions and tip termination it is possible to resolve the NiO–vacuum interface, the second oxide layer as well as the NiO-substrate interface with atomic contrast. We find that for sub-monolayer coverages of NiO the oxide islands consist of an essentially defect-free surface layer at the vacuum interface with a number of NiO second layer patches incorporated into the Ag substrate underneath. The oxide layer is surrounded by a rim of a NiO bilayer of monoatomic width. A reduction of the density of states between a NiO monolayer and local NiO bilayer stackings is suggested to be responsible for the observed appearance of mosaic patches at the island surface.     

Role of oxygen vacancies formed between top electrodes and epitaxial NiO films in bipolar resistance switching

We investigated bipolar resistance switching (RS) behavior of a top electrode/epitaxial NiO using Al and Pt as the top electrodes (TEs) and epitaxial NiO deposited at 500 °C (NiO-500) and 700 °C (NiO-700). We found that the contact between Al and Pt TEs and NiO-500 was a high resistance insulating contact, while the contact between the two TEs and NiO-700 was a low-resistance metallic contact. We also found that only NiO-500 with the Pt TE exhibited bipolar RS after an electroforming process. This study suggests that during the formation of the Pt/NiO-500 interface, the amount and behavior of oxygen at the interface seem to play the most important role in bipolar RS behavior. In order to improve the device performance, better control of oxygen content and its movement at the interface seems necessary.     

Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode

Electrochemical redox supercapacitors have been fabricated using polymeric gel electrolytes polyvinylidene fluoride co-hexafluoropropylene (PVdF-HFP)–ethylene carbonate (EC)–propylene carbonate (PC)–MClO₄: M = Li, Na, (C₂H₅)₄N and electrochemically deposited polypyrrole as conducting polymer electrode. The performance of the capacitors have been characterized using a.c impedance spectroscopy, cyclic linear sweep voltammetry and galvanostatic charge–discharge techniques. The capacitors shows larger values of overall capacitance of about 14–25 mF cm^− 2 (equivalent to a single electrode specific capacitance of 78–137 F g^− 1 of polypyrrole), which corresponds to the energy density of 11–19 W h kg^− 1 and power density of 0.22–0.44 kW kg^− 1. The values of capacitance have been found to be almost stable up to 5000 cycles and even more. A comparison indicates that the capacitive behaviour and the capacitance values are not much affected with the size of cations of the salts incorporated in gel electrolytes, rather predominant role of anions is possible at the electrode–electrolyte interfaces. Furthermore the coulombic efficiencies of all the cells were found to be nearly 100% that is comparable to the liquid electrolytes based capacitors.     

Bipolar resistive switching in BiFe_(0.95)Zn_(0.05)O_3 films

Bipolar resistive switching is studied in BiFe0.95Zn0.05O3 films prepared by pulsed laser deposition on （001） SrTiO3 substrate, with LaNiO3 as the bottom electrode, and Pt as the top electrode. Multiple steps of resistance change are ob- served in the resistive switching process with a slow voltage sweep, indicating the formation/rupture of multiple conductive filaments. A resistive ratio of the high resistance state （HRS） to the low resistance state （LRS） of over three orders of mag- nitude is observed. Furthermore, the conduction mechanism is confirmed to be space-charge-limited conduction with the Schottky emission at the interface with the top Pt electrodes in the HRS, and Ohmic in the LRS. Impedance spectroscopy demonstrates a conductive ferroelectric/interfacial dielectric 2-layer structure, and the formation/rupture of the conductive filaments mainly occurs at the interfacial dielectric layer close to the top Pt electrodes.     

In situ TEM study of reversible and irreversible electroforming in Pt/Ti:NiO/Pt heterostructures

Experimental verification of the microscopic origin of resistance switching in metal/oxide/metal heterostructures is needed for applications in non‐volatile memory and neuromorphic computing. Numerous reports suggest that resistance switching in NiO is caused by local reduction of the oxide layer into nanoscale conducting filaments, but few reports have shown experimental evidence correlating electroforming with site‐specific changes in composition. We have investigated the mechanisms of reversible and irreversible electroforming in 250–500 nm wide pillars patterned from a single Ta/Ti/Pt/Ti‐doped NiO/Pt/Ta heterostructure and have shown that these can coexist within a single sample. We performed in situ transmission electron microscopy (TEM) electroform‐ ing and switching on each pillar to correlate the local electron transport behavior with microstructure and composition in each pillar. DFT calculations fitted to electron energy loss spectroscopy data showed that the Ti‐doped NiO layer is partially reduced after reversible electroforming, with the formation of oxygen vacancies ordered into lines in the 〈110〉 direction. However, under the same probing conditions, adjacent pillars show irreversible electroforming caused by electromigration of metallic Ta to form a single bridge across the oxide layer. We propose that the different electroforming behaviors are related to microstructural variations across the sample and may lead to switching variability. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Coexistence of unipolar and bipolar modes in Ag/ZnO/Pt resistive switching memory with oxygen-vacancy and metal-Ag filaments

In this study, the unipolar resistive switching(URS) and bipolar resistive switching(BRS) are demonstrated to be coexistent in the Ag/Zn O/Pt memory device, and both modes are observed to strongly depend on the polarity of forming voltage. The mechanisms of the URS and BRS behaviors could be attributed to the electric-field-induced migration of oxygen vacancies(VO) and metal-Ag conducting filaments(CFs) respectively, which are confirmed by investigating the temperature dependences of low resistance states in both modes. Furthermore, we compare the resistive switching(RS)characteristics(e.g., forming and switching voltages, reset current and resistance states) between these two modes based on VO- and Ag-CFs. The BRS mode shows better switching uniformity and lower power than the URS mode. Both of these modes exhibit good RS performances, including good retention, reliable cycling and high-speed switching. The result indicates that the coexistence of URS and BRS behaviors in a single device has great potential applications in future nonvolatile multi-level memory.     

Hybrid inorganic–organic proton conducting membranes for fuel cells and gas sensors

We developed new fast proton conducting membranes based on a hybrid inorganic–organic phosphosilicate polymer synthesized from othophosphoric acid, dichlorodimethylsilane, and tetraethoxysilane. The membranes were amorphous, translucent, and flexible. A high concentration of –OH groups and short distances between them promoted fast proton conductivity in dry atmosphere at increased temperatures. The proton conductivity was measured using the electrochemical impedance spectroscopy. Its value increased with rising temperature following the Arrhenius dependence with the activation energy 20 kJ/mol. In dry conditions at 120 °C, the conductivity was 1.6 S/m. The tests in a H₂/O₂ fuel cell confirmed that the membrane was able to operate at temperatures from 100 to 130 °C using dry input gas streams. The cell performance significantly improved with increasing temperature. The membrane was also tested in a potentiometric gas sensor with the TiH_x reference electrode and the Pt sensing electrode. The sensor exhibited fast, stable, and reproducible response to dry H₂ and O₂ gases at temperatures above 100 °C. We expect the application of our membrane in intermediate temperature fuel cells and gas sensors operating in dry conditions.     

Nonvolatile Resistive Switching and Physical Mechanism in LaCrO_3 Thin Films

Polycrystalline LaCrO_3(LCO) thin films are deposited on Pt/Ti/SiO_2/Si substrates by pulsed laser deposition and used as the switching material to construct resistive random access memory devices. The unipolar resistive switching(RS) behavior in the Au/LCO/Pt devices exhibits a high resistance ratio of ~104 between the high resistance state(HRS) and low resistance state(LRS) and exhibits excellent endurance/retention characteristics.The conduction mechanism of the HRS in the high voltage range is dominated by the Schottky emission, while the Ohmic conduction dictates the LRS and the low voltage range of HRS. The RS behavior in the Au/LCO/Pt devices can be understood by the formation and rupture of conducting filaments consisting of oxygen vacancies,which is validated by the temperature dependence of resistance and x-ray photoelectron spectroscopy results.Further analysis shows that the reset current I_R and reset power P_R in the reset processes exhibit a scaling law with the resistance in LRS(R_0), which indicates that the Joule heating effect plays an essential role in the RS behavior of the Au/LCO/Pt devices.     

Reversible alternation between bipolar and unipolar resistive switching in La-SrTiO_3 thin films

The alternation from bipolar to unipolar resistive switching is observed in perovskite La0.01Sr0.99TiO3thin films.These two switching modes can be activated separately depending on the compliance current(Icomp)during the electroforming process:with a higher Icomp(5 mA)the unipolar resistance switching behavior is measured,while the bipolar resistance switching behavior is observed with a lower Icomp(1 mA).On the basis of I–V characteristics,the switching mechanisms for the URS and BRS modes are considered as being a change in the Schottky-like barrier height and/or width at the Pt/La-SrTiO3interface and the formation and disruption of conduction filaments,respectively.