Cu12Sb4S13量子点的光照增强阻变性能

采用热注入法制备了粒径为7.9 nm的Cu₁₂Sb₄S₁₃量子点（CAS QDs）,并利用旋涂法在室温下制备了结构为FTO/CAS QDs/Au（其中FTO为导电玻璃）的阻变存储器（RRAM）.在光照条件下,该三明治结构的RRAM呈现典型的双极性阻变开关特征,具有-0.38 V/0.42 V的低工作电压和10⁵的高阻变开关比,并表现出优异的数据保持性和耐久性.在持续工作1.4×10⁶ s和经过10⁴次快速读取后,器件阻变性能变化率小于0.1%.在光照和电场共同作用下,S^2-导电通道的形成与破坏和FTO/CAS QDs界面肖特基势垒高度的调制是FTO/CAS QDs/Au在高阻态与低阻态之间转变的原因.     

脉冲激光沉积制备非晶La0.75Sr0.25MnO3薄膜用于半透明阻变存储器

用脉冲激光沉积方法制备非晶La_0.75Sr_0.25MnO₃（a-LSMO）薄膜作为阻变器件（Ag/a-LSMO/ITO）的中间层,所得器件具有良好的非易失性和双极阻变行为。ITO衬底及超薄a-LSMO薄膜具有很高的可见光透过率,从而可制备半透明阻变器件。通过高分辨透射电镜直接观测到了在银电极与ITO电极间的银导电细丝。器件的阻变特性归因于在非晶镧锶锰氧层中的银导电细丝的生长与断裂。     

脉冲激光沉积制备非晶La0.75Sr0.25MnO3薄膜用于半透明阻变存储器

用脉冲激光沉积方法制备非晶La_0.75Sr_0.25MnO₃（a-LSMO）薄膜作为阻变器件（Ag/a-LSMO/ITO）的中间层,所得器件具有良好的非易失性和双极阻变行为。ITO衬底及超薄a-LSMO薄膜具有很高的可见光透过率,从而可制备半透明阻变器件。通过高分辨透射电镜直接观测到了在银电极与ITO电极间的银导电细丝。器件的阻变特性归因于在非晶镧锶锰氧层中的银导电细丝的生长与断裂。     

Charge transport through Geobacter sulfurreducens biofilms grown on graphite rods

Biofilms of the electroactive bacterium Geobacter sulfurreducens were induced to grow on graphite-rod electrodes under a potential of 0 V (vs Ag/AgCl) in the presence of acetate as an electron donor. Increased anodic currents for bioelectrocatalytic oxidation of acetate were obtained when the electrodes were incubated for longer periods with periodic electron-donor feeding. The maximum current density for acetate oxidation increased 2.8-fold, and the biofilm thickness increased by 4.25-fold, over a time period of 83-147 h. Cyclic voltammetry in the presence of acetate supports a model of heterogeneous electron transfer, one electron at time, from biofilm to electrode through a dominant redox species centered at -0.41 V vs Ag/AgCl. Voltammetry performed under nonturnover conditions provided an estimate of the surface coverage of the redox species of 25 nmol/cm(2). This value was used to estimate a redox species concentration of 7.3 mM within the 34-μm-thick biofilm and a charge-transport diffusion coefficient of 3.6 × 10(-7) cm(2)/s. This value of diffusion coefficient is greater than that observed in traditional thin-film voltammetric studies with redox polymer films containing much higher surface concentrations of redox species and might be associated with proton transport to ensure electroneutrality within the biofilm upon electrolysis.     

Impact of Top Electrodes (Cu,Ag, and Al) on Resistive Switching behaviour of Cu-rich Cu2ZnSnS4 (CZTS) Ideal Kesterite

Cu₂ZnSnS₄ (CZTS) active material-based resistive random-access memory (RRAM) devices are investigated to understand the impact of three different Cu, Ag, and Al top electrodes. The dual resistance switching (RS) behaviour of spin coated CZTS on ITO/Glass is investigated up to 10² cycles. The stability of all the devices (Cu/CZTS/ITO, Ag/CZTS/ITO, and Al/CZTS/ITO) is investigated up to 10³ sec in low- (LRS) and high- (HRS) resistance states at 0.2 V read voltage. The endurance up to 10² cycles with 30 msec switching width shows stable write and erase current. Weibull cumulative distribution plots suggest that Ag top electrode is relatively more stable for set and reset state with 33.61 and 25.02 shape factors, respectively. The charge carrier transportation is explained by double logarithmic plots, Schottky emission plots, and band diagrams, substantiating that at lower applied electric field intrinsic copper ions dominate in Cu/CZTS/ITO, whereas, at higher electric filed, top electrodes (Cu and Ag) dominate over intrinsic copper ions. Intrinsic Cu⁺ in CZTS plays a decisive role in resistive switching with Al electrode. Further, the impedance spectroscopy measurements suggest that Cu⁺ and Ag⁺ diffusion is the main source for the resistive switching with Cu and Ag electrodes.     

The Old Polyoxometalates in New Application as Molecular Resistive Switching Memristors

The coming big-data era has created a huge demand for next-generation memory technologies with characters of higher data-storage densities, faster access speeds, lower power consumption and better environmental compatibility. In this field, the design of resistive switching active materials is pivotal but challengeable. Polyoxometalates (POMs) are promising candidates for next-generation molecular memristors due to their versatile redox characters, excellent electron reservoirs and good compatibility/convenience in microelectronics processing. In this review, five kinds of POM-based active materials in nonvolatile memories (inorganic POMs, crystalline organic-inorganic hybrid POMOFs, polymer modified POMs, POM/transition metal oxides composites and the deposition of POM on metal surfaces) were described. The components of POMs active materials, device fabrications, device parameters, and resistive switching mechanisms relative to their structures were summarized. Finally, challenges and future perspectives of POMs-based memristors were also presented.     

新型Ti3C2 MXene的化学制备及基于MXene忆阻器特性与机理

阻变器件是一种微电子器件,具有阻值可在两个甚至两个以上的阻态之间重复变化的特点。忆阻器作为新型的阻变器件,具有可连续变化的丰富阻态。近年来因其具备简单的二端结构、高集成度以及低工作电压等特性,在新型非易失性存储以及构建神经形态系统等方面被广泛研究。但其在实现应用的过程中仍存在着稳定性较差等问题。近期一些工作证明了二维材料如氧化石墨烯在优化忆阻器性能方面具备良好的应用潜力。MXene是一种具备类似石墨烯结构的新型二维过渡金属碳/氮化物,因其具备二维层状结构显现出特殊的力学以及电学特性,有望应用于忆阻器中以提高器件的电学性能。在本文中,我们通过化学湿法刻蚀制备了Ti₃C₂粉末,通过旋涂工艺在忆阻器结构中引入Ti₃C₂薄膜。Ti₃C₂ MXene与SiO₂同时作为忆阻器阻变层,制备了Cu/Ti₃C₂/SiO₂/W结构的忆阻器,并且对其相关电学特性进行了探究。在该器件上,通过实验测得忆阻器典型的开关特性曲线并在双向直流电压下针对高、低阻态的可重复性、稳定性进行了实验。结果表明该器件能够在100个扫描循环过程中保持稳定的高、低阻态达到10⁴ s以上。同时,该器件状态能够受脉冲电压调节,实现突触间典型的双脉冲易化行为。实验结果表明基于Ti₃C₂ MXene的忆阻器将有望应用于构建新兴存储设备以及人工神经形态系统。     

Simple electrochemical method for deposition and voltammetric inspection of silver particles at the liquid-liquid interface of a thin-film electrode

A novel experimental methodology for depositing and voltammetric study of Ag nanoparticles at the water-nitrobenzene (W-NB) interface is proposed by means of thin-film electrodes. The electrode assembly consists of a graphite electrode modified with a thin NB film containing decamethylferrocene (DMFC) as a redox probe. In contact with an aqueous electrolyte containing Ag(+) ions, a heterogeneous electron-transfer reaction between DMFC((NB)) and Ag(+)((W)) takes place to form DMFC(+)((NB)) and Ag deposit at the W-NB interface. Based on this interfacial reaction, two different deposition strategies have been applied. In the uncontrolled potential deposition protocol, the electrode is immersed into an AgNO(3) aqueous solution for a certain period under open circuit conditions. Following the deposition step, the Ag-modified thin-film electrode is transferred into an aqueous electrolyte free of Ag(+) ions and voltammetrically inspected. In the second protocol the deposition was carried out under controlled potential conditions, i.e., in an aqueous electrolyte solution containing Ag(+) ions by permanent cycling of the electrode potential. In this procedure, DMFC((NB)) is electrochemically regenerated at the electrode surface, hence enabling continuation and voltammetric control of the Ag deposition. Hence, the overall electrochemical process can be regarded as an electrochemical reduction of Ag(+)((W)) at the W-NB interface, where the redox couple DMFC(+)/DMFC acts as a mediator for shuttling electrons from the electrode to the W-NB interface. Ag-particles deposited at the W-NB interface affect the ion transfer across the interface, which provides the basis for voltammetric inspection of the metal deposit at the liquid-liquid interface with thin-film electrodes. Voltammetric properties of thin-film electrodes are particularly sensitive to the deposition procedure, reflecting differences in the properties of the Ag deposit. Moreover, this methodology is particularly suited to inspect catalytic activities of metal particles deposited at the liquid-liquid interface toward heterogeneous electron-transfer reactions occurring at the at the liquid-liquid interface.     

Amphiphilic Carbazole‐Containing Compounds with Lower Critical Solution Temperature Behavior for Supramolecular Self‐Assembly and Solution‐Processable Resistive Memories

The self‐organization and resistive memory performances of a series of newly synthesized water‐soluble amphiphilic carbazole derivatives have been explored. Temperature‐dependent UV/Vis absorption spectroscopy has been conducted to study the isodesmic self‐assembly mechanism of the carbazole‐containing compounds. This class of compounds also exhibits interesting lower critical solution temperature properties, which are sensitive to concentration and ionic additives. One of the compounds has been solution‐processed and utilized as an active material in the engineering of resistive memory devices, exhibiting a switching voltage of about 3.9 V, a constant ON/OFF current ratio of 10⁶, and a long retention time of 10⁴ s. The present work demonstrates the versatile potential applications of water‐soluble amphiphilic carbazole‐containing compounds in supramolecular chemistry and resistive memory devices.     

Evaluation of an amperometric glucose biosensor based on a ruthenium complex mediator of low redox potential

An amperometric glucose ring-disk biosensor based on a ruthenium complex mediator of low redox potential was fabricated and evaluated. This thin-layer radial flow microsensor (10 μl) with ring-disk working electrode displayed remarkable amperometric sensitivity. For Ru₃(μ₃-O)(AcO)₆(Py)₃(ClO₄) (Ru-Py), a trinuclear oxo-acetate bridged cluster, a reversible redox curve of low redox potential and narrow potential window (redox potentials were −0.190 and −0.106 V versus Ag/AgCl wire, respectively) was observed, which is comparable to many reported mediators such as ferrocene derivatives and other ruthenium complexes. The glucose and hydrogen peroxide assays were carried out with this complex-modified electrode Ru-Py-HRP-GOx/Nafion. The sensitivity was obtained 24 nA (15.4 mA M⁻¹ cm⁻²) for 10 μM glucose and 126 nA (160 mA M⁻¹ cm⁻²) for 5 μM H₂O₂, respectively with a working potential at 0 V versus Ag/AgCl. Ascorbic acid was studied as interference to the glucose assay. The application of 0 V potential versus Ag/AgCl did not avoid the occurrence of the oxidation of ascorbic acid, however, the pre-coating of ascorbate oxidase on the disk part of the ring-disk working electrode efficiently pre-oxidized the ascorbic acid and hence eliminated its interference on the glucose response. The practical reliability was also evaluated by assaying the dialysate from the prefrontal cortex of Wistar rats.     

Spatial nonuniformity in resistive-switching memory effects of NiO

Electrically driven resistance change phenomenon in metal/NiO/metal junctions, so-called resistive switching (RS), is a candidate for next-generation universal nonvolatile memories. However, the knowledge as to RS mechanisms is unfortunately far from comprehensive, especially the spatial switching location, which is crucial information to design reliable devices. In this communication, we demonstrate the identification of the spatial switching location of bipolar RS by introducing asymmetrically passivated planar NiO nanowire junctions. We have successfully identified that the bipolar RS in NiO occurs near the cathode rather than the anode. This trend can be interpreted in terms of an electrochemical redox model based on ion migration and p-type conduction.     

MoTe2-based low energy consumption artificial synapse for neuromorphic behavior and decimal arithmetic

Two-dimensional material-based memristors have shown attractive research prospects as brain-like devices for neuromorphic computing. Among them, transition metal dichalcogenides–based memristors have proved to be one of the most promising competitors. In this work, a two-dimensional memristor based on MoTe₂ nanosheets was fabricated and demonstrated. The experimental results illustrate that the two-terminal synaptic based on the Ag/MoTe₂/ITO structure exhibits stable bipolar and non-volatile resistive switching characteristics attributed to the controllable formation and rupturing of silver conductive filaments. The device can be successively modulated by a pulse train with a minimum pulse width of 40 ns. More interestingly, the energy consumption of the device to complete one write event is only 74.2 pJ. In addition, biological synaptic behaviors, such as excitatory postsynaptic current gain properties, long-term potentiation (LTP)/long-term depression, spike-timing-dependent- plasticity, short-term plasticity, long-term potentiation (LTP), paired-pulse facilitation, post-tetanic potentiation, and learning-experimental behaviors were mimicked faithfully. Finally, the decimal arithmetic application was introduced to the device, and it is confirmed that addition and multiplication functions can be performed. Therefore, the artificial synapse based on MoTe₂ nanosheets not only exhibits the stable non-volatile resistive switching behavior but also facilitates the development of low-energy consumption neuromorphic computing chips based on transition metal dichalcogenides.     

Control of Interfacial Potentials and Redox Reactions on Bipolar Electrodes Using Ag/AgCl

The interfacial potential difference on the surface of bipolar electrodes was controlled by placing Ag/AgCl on part of the electrode. Oxygen reduction on the cathodic pole was coupled with an electrochemiluminescence (ECL) reaction on the anodic pole. In an open bipolar system, the ECL intensity depended on the location of Ag/AgCl and the concentration of Cl⁻ ions. A current flowed through Ag/AgCl and the ratio of currents generated at the anodic and cathodic poles was affected by the position of Ag/AgCl. Further, the effect of Ag/AgCl placement was also demonstrated in a closed bipolar system using hydrogen peroxide (H₂O₂) and glucose as analytes. Ag/AgCl was also effective in adjusting the sensitivity to these analytes to achieve the best performance. This method of interfacial potential control is expected to contribute toward the development of reliable sensing devices and applications such as redox cycling, which require precise potential control.     

The instructive redox behaviour of 4‐ferrocenylcatechol on nanocrystalline titanium dioxide electrodes

An investigation into the redox behaviour of 4‐ferrocenylcatechol bound to nanocrystalline TiO₂ electrodes identified a limitation to the use of catechol as an electron‐transfer facilitating anchoring group. 4‐Ferrocenylcatechol was adsorbed to transparent nanocrystalline TiO₂ electrodes. UV–visible spectra of the modified electrode were recorded in an acetonitrile‐electrolyte solution. At an applied potential of + 0.45 mV (vs Ag/AgCl/Cl^?) the ferrocenyl group oxidized to the ferrocenium cation and the catecholate group oxidized to the benzoquinone form. Subsequent application of a potential of 0 V reduced the ferrocenium to ferrocene but, owing to the irreversibility of the catechol oxidation in aprotic solvents, benzoquinone is not reduced to catecholate and subsequently desorbs and is lost due into solution. Electrochromic switching of the ferrocenyl electrochromophore on TiO₂ with aprotic electrolyte is, therefore, irreversible. Copyright © 2006 John Wiley & Sons, Ltd.     

Opportunity of spinel ferrite materials in nonvolatile memory device applications based on their resistive switching performances

The opportunity of spinel ferrites in nonvolatile memory device applications has been demonstrated by the resistive switching performance characteristics of a Pt/NiFe(2)O(4)/Pt structure, such as low operating voltage, high device yield, long retention time (up to 10(5) s), and good endurance (up to 2.2 × 10(4) cycles). The dominant conduction mechanisms are Ohmic conduction in the low-resistance state and in the lower-voltage region of the high-resistance state and Schottky emission in the higher-voltage region of the high-resistance state. On the basis of measurements of the temperature dependence of the resistances and magnetic properties in different resistance states, we explain the physical mechanism of resistive switching of Pt/NiFe(2)O(4)/Pt devices using the model of formation and rupture of conducting filaments by considering the thermal effect of oxygen vacancies and changes in the valences of cations due to the redox effect.     

Silver UPD ultra-thin film modified nanoporous gold electrode with applications in the electrochemical detection of chloride

Nanoporous noble metals are usually expected to exhibit much higher surface areas than smooth ones, making them of particular importance in many electrochemical applications. This paper describes a simple electrochemical method to modify a nanoporous Au (NPG) surface by using an under potentially deposited (UPD) Ag adlayer. The NPG electrode was obtained by the dealloying of Zn from Au_xZn_1−x in a 40-60 mol% zinc chloride-1-ethyl-3-methylimidazolium chloride (ZnCl₂-EMIC) ionic liquid. The Ag UPD modified nanoporous gold (NPG/Ag(UPD)) electrode possessed dual properties, including an intrinsic high surface area from the nanoporous structure and the characteristics of the Ag UPD adlayer. The potential utility of using NPG/Ag(UPD) for sensors was demonstrated by its excellent sensitivity and selectivity in the electrochemical determination of chloride ions. An atomic scale metal monolayer obtained in the UPD process was selected as a sensing agent. The long-term storability and operational stability of the electrode were strongly demonstrated. Specifically, two couples of redox waves at ∼552 mV and ∼272 mV, respectively, were observed in the cyclic voltammograms (CVs) of the NPG/Ag(UPD) after the adsorption of chloride ions. The first couple of redox waves was related to the UPD and silver stripping and the second couple of redox waves was induced by the adsorption of Cl⁻. The Cl⁻ adsorption process on the NPG/Ag(UPD) electrode followed the transient Langmuir adsorption kinetic model. The ratio of the integrated charges for these two anodic stripping peaks was selectively used to determine dilute chloride ion levels. The calibration curve was linear in the Cl⁻ concentration range of 0.5-30.0 μM.     

Influence of Poly (methyl metacrylate) Addition on Resistive Switching Performance of P3HT/P(VDF-TrFE) Blend Films

Organic semiconducting/ferroelectric blend films attracted much attention due to their elec-trical bistability and rectification properties and thereof the potential in resistive memory devices. Blend films were usually deposited from solution, during which phase separation oc-curred, resulting in discrete semiconducting phase whose electrical property was modulated by surrounding ferroelectric phase. However, phase separation resulted in rough surface and thus large leakage current. To further improve electrical properties of such blend films, poly(methyl metacrylate) (PMMA) was introduced as additive into P3HT/P(VDF-TrFE) semiconducting/ferroelectric blend films in this work. It indicated that small amount of PMMA addition could effectively enhance the electrical stability to both large electrical stress and electrical fatigue and further improve retention performance. Overmuch PMMA addition tended to result in the loss of resistive switching property. A model on the con-figuration of three components was also put forward to well understand our experimental observations.     

Self‐assembled Azobenzenethiol Monolayer on Electrode Surfaces: Effect of Photo‐switching on the Surface and Electrical Property

Azobenzenethiol molecules carrying different para‐substituents were used to form mixed monolayers with n‐alkanethiol molecules on Au and Ag surfaces. UV‐ and visible light irradiation of the surfaces resulted in reversible alternation of contact angle and characteristic infrared absorption peak intensities, as well as the work function of the metal surfaces. The alternations can be correlated with the cis‐trans isomerization of the azobenzene moieties at the surface. Electron transport from the metal electrode to a redox center in a contacting solution was measured and analyzed based on the change in the work function of the electrode as well as the monolayer film structure upon isomerization.     

Spatially resolved Raman spectroelectrochemistry of solid-state polythiophene/viologen memory devices

A three terminal molecular memory device was monitored with in situ Raman spectroscopy during bias-induced switching between two metastable states having different conductivity. The device structure is similar to that of a polythiophene field effect transistor, but ethylviologen perchlorate was added to provide a redox counter-reaction to accompany polythiophene redox reactions. The conductivity of the polythiophene layer was reversibly switched between high and low conductance states with a "write/erase" (W/E) bias, while a separate readout circuit monitored the polymer conductance. Raman spectroscopy revealed reversible polythiophene oxidation to its polaron form accompanied by a one-electron viologen reduction. "Write", "read", and "erase" operations were repeatable, with only minor degradation of response after 200 W/E cycles. The devices exhibited switching immediately after fabrication and did not require an "electroforming" step required in many types of memory devices. Spatially resolved Raman spectroscopy revealed polaron formation throughout the polymer layer, even away from the electrodes in the channel and drain regions, indicating that thiophene oxidation "propagates" by growth of the conducting polaron form away from the source electrode. The results definitively demonstrate concurrent redox reactions of both polythiophene and viologen in solid-state devices and correlate such reactions with device conductivity. The mechanism deduced from spectroscopic and electronic monitoring should guide significant improvements in memory performance.