Electric field induced avalanche breakdown and non-volatile resistive switching in the Mott Insulators AM4Q8

The Mott insulator compounds AM₄Q₈ exhibit a new type of volatile and non volatile resistive switchings that are of interest for RRAM application. We found that above a threshold electric field E _TH of the order of a few kV/cm these compounds undergo a volatile resistive switching based on an avalanche process. For electric field much higher than the threshold avalanche breakdown field, the resistive switching turns non volatile. Our EDXS and STEM analyses show that the non volatile resistive switching originating from the avalanche breakdown can neither be ascribed to local chemical modifications nor to a local phase change with symmetry breaking at a resolution better than a few nanometer. This is in strong contrast with non volatile resistive switching reported so far that are all based on chemical or structural changes. Conversely, our results suggest that the avalanche breakdown induce the collapse of the Mott insulating state at the local scale and the formation of a granular conductive filament formed by compressed metallic domains and expanded “superinsulating” domains.     

Enols of 2‐nitro‐ and related 2‐substituted malonamides

The structures of 2‐substituted malonamides, YCH(CONR¹R²)CONR³R⁴ (Y = Br, SO₂Me, CONH₂, COMe, and NO₂) were investigated. When Y = Br, R¹R² = R³R⁴ = HEt; Y = SO₂Me, R¹–R⁴ = H and for Y = CONH₂ or CONHPh, R¹–R⁴ = Me, the structure in solution is that of the amide tautomer. X‐ray crystallography shows solid‐state amide structures for Y = SO₂Me or CONH₂, R¹–R⁴ = H. Nitromalonamide displays an enol structure in the solid state with a strong hydrogen bond (O^…O distance = 2.3730 Å at 100 K) and d(OH) ≠ d(O^…H). An apparently symmetric enol was observed in solution, even in appreciable percentages in highly polar solvents such as DMSO‐d₆, but K_enol values decrease on increasing the solvent polarity. The N,N′‐dimethyl derivative is less enolic. Acetylmalonamides display a mixture of enol on the acetyl group and amide in non‐polar solvents, and only the amide in DMSO‐d₆. DFT calculations gave the following order of pK_enol values for Y: H > CONH₂ > COMe ≥ COMe (on acetyl) ≥ MeSO₂ > CN > NO₂ in the gas phase, CHCl₃, and DMSO. The enol on the C?O group is preferred to the aci‐nitro compound, and the N? O? H^…O?C is less favored than the C?O? H^…O?C hydrogen bond. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of AlN layer on the resistive switching properties of TiO2 based ReRAM memory devices

The present study reports the resistive switching behaviour in Titanium Dioxide (TiO₂) material, with possible implementations in non volatile memory device. The Cu/TiO₂/Pt memory device exhibit uniform and stable bipolar resistive switching behaviour. The current-voltage (I-V) analysis shows two discrete resistance states, the High Resistance State (HRS) and the Low Resistance State (LRS). The effect of an additional AlN layer in the resistive memory cell is also investigated. The Cu/TiO₂/AlN/Pt device shows a multilevel (tri-state) resistive switching. Multilevel switching is facilitated by ionic and metallic filament formation, and the nature of the formed filaments is confirmed by performing a resistance vs. temperature measurement. The bilayer device shows improved reliability over the single layer device. The formation of high thermal conductive interfacial oxy-nitride (AlON) layer is the main reasons for the enhancement of resistive switching properties in Cu/TiO₂/AlN/Pt cell. The performance of device was measured in terms of endurance and retention, which exhibits good endurance over 10⁵ cycles and long retention time of 10⁵ s at 125 °C. The above result suggests the feasibility of Cu/TiO₂/AlN/Pt devices for multilevel non volatile ReRAM application.     

Improvement of resistive switching fluctuations by using one step lift‐off process

Bipolar resistive switching characteristics are investigated in ZrO₂ containing Cu thin layer devices, particularly for the self‐isolated‐structure device fabricated by one step lift‐off process. Compared with the traditional‐structure device, the self‐isolated‐structure device shows more uniform resistive switching characteristics. This is because the isolation of each device cell has negligible influence on each other and thus mitigates possible crosstalk between each cell. These results suggest that the feasibility of good stabilization of the resistive switching parameters can be obtained through one step lift‐off process. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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)     

Why colchicine does not show mutarotation. With M05‐2X density functional in the realm of tricky natural products

It is shown here that density functional theory (DFT) calculations with the recent M05‐2X hybrid functional correctly reproduced the conformation of, and energy difference between, (R_a,7S)‐ and (S_a,7S)‐type atropisomers of isocolchicine. Interconversion of these ¹H NMR‐observable atropisomers accounts for mutarotation with this compound. In contrast, the classical B3LYP hybrid functional failed to simulate satisfactorily both the geometries and the energies involved. This extends the use of M05‐2X to natural products that embody aromatic and flexible pseudoaromatic and saturated rings, as well as cis/trans amide chains, which bring on subtle conformational problems. DFT calculations with M05‐2X also shed new light on a long‐date conundrum in organic chemistry and pharmacology, i.e., why mutarotation was never observed with colchicine. This is now best attributed to a larger energy gap between the (R_a,7S) atropisomer and the elusive (S_a,7S) atropisomer with this compound. These results solicit a rethinking of the interactions between colchicinoids and proteins. Copyright © 2007 John Wiley & Sons, Ltd.     

Electrical properties and carrier transport mechanisms of nonvolatile memory devices based on randomly oriented ZnO nanowire networks

We report reproducible bipolar resistive memory devices based on Au/ZnO nanowire networks (ZnO NWNs)/ITO, which show a high R_on/R_off ratio (～10⁴) and narrow dispersion of set and reset threshold voltages. The dominant conduction mechanisms of low resistance state and high resistance state were verified by Ohmic behavior and space charge limited current, respectively. The switching mechanism is confirmed in terms of the formation and rupture of conductive filaments, with oxygen vacancies localized on the ZnO NWNs surface involved in. The Au/ZnO NWNs/ITO devices presented in our work show potential applications in the next generation nonvolatile memory field. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Switching phenomena in CdIn2S4 thin films

Summary Two kinds of switching phenomena in CdIn₂S₄ polycrystalline and amorphous thin films which were prepared by the vacuum evaporation method and the d.c. sputtering method, respectively, were studied. One is the so-called memory switching phenomenon arising from the low resistive filament path. Another is a characteristic switching phenomenon in which the resistivity abruptly changes whenever the ambient temperature reaches a critical value. The switching time is fast and about 100 ns. This switching phenomenon is related to the native defects in the CdIn₂S₄ lattice, because they can be observed in the polycrystalline as well as in the amorphous thin films. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.     

Nanoscale resistive switching in SrTiO3 thin films

The local conductivity of SrTiO₃ thin films epitaxially grown on SrRuO₃‐buffered SrTiO₃ single crystals has been investigated in detail with an atomic force microscope equipped with a conducting tip (LC‐AFM). These experiments demonstrate that the conductivity of SrTiO₃ thin films originates from nanoscale well‐conducting filaments connecting the surface to the SrRuO₃ bottom electrode. The electrical conduction of the filaments is shown to be reversibly modulated over several orders of magnitude by application of an appropriate electrical field. We analyze the resistive switching by addressing individual filaments with the AFM tip as well as by scanning areas up to the µm scale. Temperature dependent measurements reveal that resistive switching on a macroscopic scale can be traced down to the insulator‐to‐metal transition of the independently switchable filaments. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High vertical breakdown strength in with low specific on‐resistance AlGaN/AlN/GaN HEMTs on silicon

Off‐state and vertical breakdown characteristics of AlGaN/AlN/GaN high‐electron‐mobility transistors (HEMTs) on high‐resistivity (HR)‐Si substrate were investigated and analysed. Three‐terminal off‐state breakdown (BV_gd) was measured as a function of gate–drain spacing (L_gd). The saturation of BV_gd with L_gd is because of increased gate leakage current. HEMTs with L_gd = 6 µm exhibited a specific on‐resistance R_DS[ON] of 0.45 mΩ cm². The figure of merit (FOM = BV_gd²/R_DS[ON]) is as high as 2.0 × 10⁸ V² Ω^–1 cm^–2, the highest among the reported values for GaN HEMTs on Si substrate. A vertical breakdown of ～1000 V was observed on 1.2 µm thick buffer GaN/AlN grown on Si substrate. The occurrence of high breakdown voltage is due to the high quality of GaN/AlN buffer layers on Si substrate with reduced threading dislocations which has been confirmed by transmission electron microscopy (TEM). This indicates that the AlGaN/AlN/GaN HEMT with 1.2 µm thick GaN/AlN buffer on Si substrate is promising candidate for high‐power and high‐speed switching device applications. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Composition dependence of unipolar resistance switching in TaOx thin films

Amorphous TaO_x thin films were deposited at different temperatures, and the resistance switching properties of the Pt/TaO_x/Pt structure were investigated. X‐ray photoelectron spectroscopy showed that the amount of Ta₂O₅ in the film decreased and the content of Ta suboxides increased substantially when the growth temperature was increased. Unipolar resistance switching near the anode was stable only for TaO_x film grown at room temperature. The experimental results revealed the critical effect of the film composition on the resistance switching behavior of TaO_x films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Coexistence of resistive switching and magnetism modulation in sol-gel derived nanocrystalline spinel Co3O4 thin films

We report the coexistence of resistive switching and magnetism modulation in the Pt/Co₃O₄/Pt devices, where the effects of thermal annealing and film thickness on the resistive and magnetization switching were investigated. The sol-gel derived nanocrystalline Co₃O₄ thin films obtained crack-free surface and crystallized cubic spinel structure. The 110 nm Co₃O₄ film based device annealed at 600 °C exhibited optimum resistive switching parameters. From I–V curves fitting and temperature dependent resistance, the conduction mechanism in the high-voltage region of high resistance state was dominated by Schottky emission. Magnetization-magnetic field loops demonstrated the ferromagnetic behaviors of the Co₃O₄ thin films. Multilevel saturation magnetization of the Co₃O₄ thin films can be easily realized by tuning the resistance states. Physical resistive switching mechanism can be attributed to the rejuvenation and annihilation of conductive filament consisting of oxygen vacancies. Results suggest that Pt/Co₃O₄/Pt device shows promising applications in the multifunctional electromagnetic integrated devices.     

Synthesis,structural characterization,and spectroscopic properties of the ortho,meta, and para isomers of 8‐(HOCH2‐C6H4)‐BODIPY and 8‐(MeOC6H4)‐BODIPY

Fluorescent members of the 4, 4‐difluoro‐4‐bora‐3a, 4a‐diaza‐s‐indacene (BODIPY) family are widely used for a range of markers, dyes, and sensors. The capacity to substitute the basic framework is an attractive feature permitting a range of differently substituted materials to be formed. New isomeric BODIPYs, o‐, m‐, and p‐8‐[R‐C₆H₄]‐BODIPY (R = CH₂OH, 2a (o), 2b (m), 2c (p); R = OMe, 3a (o), 3b (m), 3c (p)), have been synthesized and characterized by nuclear magnetic resonance, absorbance and emission spectroscopy, and single crystal X‐ray diffraction. The o‐isomers have a very high quantum yield emission in non‐polar solvents, while the m‐ and p‐ analogs showed weak fluorescence under the same conditions. Spectroscopic analysis, as well as X‐ray structural characterization, suggested that substitution in the ortho‐position of the phenyl ring is sufficient to increase the steric hindrance and hence impede the rotation of the phenyl moiety about the 8C‐C axis, thereby favoring radiative compared to non‐radiative relaxation. Copyright © 2013 John Wiley & Sons, Ltd.     

Investigation of light programmable non‐volatile memory in an organic phototransistor

Excellent non‐volatile memory characteristics have been demonstrated under the optoelectric conditions for organic phototransistors (OPTs). The high photosensitivity shown as reversible shifts in light‐induced V_TH exhibits a large memory window for programming caused by the excited immobile carriers (electron) trapped as a function of the electrical bias and the light intensity. The long life span of stored electrons also reveals promising behavior with respect to data retention as well as the electrical reliability to serve as a data storage medium with the non‐volatile memory characteristic in OPTs. The V_TH recovery accelerated by the reversible bias stress for the stored charges under irradiation shows that the erasing behavior is clearly brought by the discharge process of long‐lived electrons occupied in deep states. Plausible mechanisms in the energy band are discussed for the programming and erasing process, which provides a fundamental understanding of the intrinsic charge storage behavior in OPTs. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Top electrode-dependent resistance switching behaviors of lanthanum-doped ZnO film memory devices

Lanthanum-doped ZnO (Zn_0.99La_0.01O) polycrystalline thin films were deposited on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method. Metal/La-doped ZnO/Pt sandwich structures were constructed by depositing different top electrodes (Ag and Pt). Unipolar switching and bipolar switching characteristics were investigated in Pt/La-doped ZnO/Pt and Ag/La-doped ZnO/Pt structures, respectively. Compared with the undoped devices (Pt/ZnO/Pt and Ag/ZnO/Pt), the La-doped devices exhibits superior resistive switching performances, such as narrow distribution of the resistive switching properties (R _ON, R _OFF, V _Set, and V _Reset), higher R _OFF/R _ON ratio and sharp switching transition.     

Structural and sensing properties of nanocrystalline SnO<Subscript>2</Subscript> films deposited by spray pyrolysis from a SnCl<Subscript>2</Subscript> precursor

We report the fabrication and characterization of tin dioxide gas sensing layers. The tin dioxide layers were synthesized using a convenient, simple and low-cost technique of spray pyrolysis. The formation of stoichiometric SnO₂ layers with fine-grain structure is revealed by Rutherford backscattering spectroscopy. The microstructure, phase, nanoparticle size distribution and surface morphology were studied by transmission electron microscopy, electron diffraction and atomic force microscopy. Most of the grains were of 10–20 nm size; however, some particles were up to 100 nm in size and had a microtwin lamellae structure of SnO₂ phase (cassiterite) with lattice parameters a= 0.474 nm and c= 0.319 nm. The sensitivity of the layers with respect to 1000–10000 ppm CH₄ in air was obtained from both resistivity (S_R) and capacity (S_C) measurements at 330 °C and values of S_R=5–7 and S_C=22–31 were extracted. PACS 68.43.-h; 68.55.-a; 81.05.Hd; 81.07.-b; 81.15.Rs     

Self‐formed Schottky barrier induced selector‐less RRAM for cross‐point memory applications

We propose a selector‐less Pr_0.7Ca_0.3MnO₃ (PCMO) based resistive‐switching RAM (RRAM) for high‐density cross‐point memory array applications. First, we investigate the inhomogeneous barrier with an effective barrier height (Φ_eff), i.e., self‐formed Schottky barrier. In addition, a scalable 4F² selector‐less cross‐point 1 kb RRAM array has been successfully fabricated, demonstrating set, reset, and read operation for high cell efficiency and high‐density memory applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diastereofacial selectivity in some 4‐substituted (X) 2‐adamantyl derivatives: electronic versus steric effects

π‐Facial selectivity data for the reduction and methylation of some 4^ax‐substituted (X) 2‐adamantanones ( 3 , Y = O) as well as the nucleophilic trapping of secondary and tertiary 4^ax‐substituted (X)‐2‐adamantyl cations ( 4 ; R = H and CH₃, respectively) and the 4‐methylene‐2‐adamantyl radical ( 8 ) are presented. The pronounced anti‐face selectivities observed for ( 3 , Y = O and 4 , R = CH₃) emphasize the importance of the steric factor as expected for systems with a strong steric bias. However, the dominant syn‐face capture of 4 (R = H) was completely unexpected and highlights a subtle interplay between steric and electronic effects. Finally, the very high anti‐face stereoselectivity for the trapping of ( 8 ) with the trimethylstannyl anion (Me₃Sn^?) is rationalized in terms of an electrostatic effect overwhelming the steric factor. Copyright © 2007 John Wiley & Sons, Ltd.     

Multiferroic and resistive switching behaviors in BiFe0.95Cr0.05O3 thin films deposited on Pt/Ti/SiO2/Si substrates

Multiferroic and resistive switching properties of single-phase polycrystalline perovskite BiFe_0.95Cr_0.05O₃ (BFCO) thin films grown on Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering were investigated. The BFCO film shows ferroelectric and magnetic properties simultaneously at room temperature, and also exhibits a good piezoelectric property with remanent effective piezoelectric coefficient d _33,f ～55±4 pm/V. An obviously resistive switching behavior was observed in the BFCO thin film at room temperature, which was discussed by the filamentary conduction mechanism associated with the redistribution of oxygen vacancies.     

Dynamic moderation of an electric field using a SiO2 switching layer in TaOx ‐based ReRAM

ReRAMs using oxygen vacancy drift in their resistive switching are promising candidates as next generation memory devices. One remaining issue is degradation of the on/off ratio down to 10² or less with an increased number of switching cycles. Such degradation is caused by a local hard breakdown in a set process due to a very high electric field formed just before the completion of a conductive filament formation. We found that introducing an ultra‐thin SiO₂ layer prevents the hard breakdown by dynamical moderation of the electric field formed in the TaO_x matrix, resulting in repeated switching while retaining a higher on/off ratio of about 10⁵. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)