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.     

Effect of defect content on the unipolar resistive switching characteristics of ZnO thin film memory devices

In this study, unipolar resistive switching (URS) characteristics in ZnO thin film memory devices were systematically investigated with variable defect content. ZnO films displayed typically URS behavior while oxygen-deficient ZnO_1?x films did not show resistive switching effects. The devices with two intentional Ohmic interfaces still show URS. These results show that appearance of URS behavior can be dominated by initial oxygen vacancy content in ZnO thin films. Modest increase in oxygen vacancy content in ZnO films will lead to forming-free and narrower distributions of switching parameters (set and reset voltage, high and low resistance states). It indicates that controlling the initial oxygen vacancy content was an effective method to enhance the URS performance.     

N空位对Cu掺杂AlN电磁性质的影响的第一性原理研究

利用基于密度泛函理论的平面波超软赝势法研究了N空位对Cu掺杂AlN的电子结构和磁学性质的影响。结果表明,与Cu最近邻的N原子更易失去形成N空位。N空位的引入减小了Cu掺杂AlN体系的半金属能隙;减弱了Cu及其近邻N原子的自旋极化的强度以及Cu3d与N2p轨道间的杂化,因而减小了体系的半金属铁磁性。因此,制备Cu掺杂AlN稀磁半导体时应尽可能地避免产生N空位。     

过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器性能的影响

实验表明掺杂是一种改善阻变存储器性能的有效手段,但其物理机理鲜有研究.本文采用第一性原理方法系统研究了过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器中氧空位迁移势垒和形成能的影响.计算结果表明Ni掺杂可同时有效降低+1和+2价氧空位在掺杂原子附近的迁移势垒,X掺杂均减小了氧空位的形成能,特别是掺杂Ni时氧空位的形成能减小最为显著(比未掺杂时减少了64%).基于该结果制备了未掺杂和Ni掺杂ZnO阻变存储器,研究表明通过掺杂控制体系中氧空位的迁移势垒和形成能,可以有效改善器件的初始化过程、操作电压、保持性等阻变性能.研究结果有助于理解探究影响阻变的微观机制,并可为掺杂提高阻变存储器性能提供一定的理论指导.     

Effects of oxygen vacancy concentration and temperature on memristive behavior of SrRuO_3/Nb:SrTiO_3 junctions

Metal/semiconductor memristive heterostructures have potential applications in nonvolatile memory and computing devices. To enhance the performance of the memristive devices, it requires a comprehensive engineering to the metal/semiconductor interfaces. Here in this paper, we discuss the effects of oxygen vacancies and temperature on the memristive behaviors of perovskite-oxide Schottky junctions, each consisting of SrRuO_3 thin films epitaxially grown on Nb:SrTiO_3 substrates. The oxygen partial pressure and laser fluence are controlled during the film growth to tune the oxygen defects in SrRuO_3 films, and the Schottky barrier height can be controlled by both the temperature and oxygen vacancies. The resistive switching measurements demonstrate that the largest resistance switching ratio can be obtained by controlling oxygen vacancy concentration at lower temperature. It suggests that reducing Schottky barrier height can enhance the resistive switching performance of the SrRuO_3/Nb:SrTiO_3 heterostructures. This work can conduce to the development of high-performance metal-oxide/semiconductor memristive devices.     

First-principles study of the formation and electronic structure of a conductive filament in ZnO-based resistive random access memory

Oxygen vacancy plays a crucial role in resistive switching. To date, a quantitative study about the distribution of the oxygen vacancies and its effect on the resistive switching has not yet been reported. In this study, we report our first-principles calculations in ZnO-based resistive switching memory grown on a Pt substrate. We show that the oxygen vacancies prefer to be located in the ZnO (0001) plane, i.e. in the direction parallel to the film surface in the preparation process. These oxygen vacancies drift easily in the film when a voltage is applied in the SET process and prefer to form a line defect perpendicular to the film surface. An isolated oxygen vacancy makes little contribution to the conductivity of ZnO, whereas the ordering of oxygen vacancies in the direction perpendicular to the film surface leads to a dramatic enhancement of the conductivity and thus forms conductive filaments. The semiconducting characteristics of the conductive filaments are confirmed experimentally.     

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.     

Resistive switching behavior and mechanism of room-temperature-fabricated flexible Al/TiS2-PVP/ITO/PET memory devices

The mixture of two-dimensional (2D) TiS₂ nanoflakes and polyvinylpyrrolidone (PVP) exhibits a nonvolatile, bipolar resistive switching behavior with a low resistance state (LRS)/high resistance state (HRS) current ratio of ～10² in the devices with a flexible Al/TiS₂-PVP/indium tin oxide (ITO)/polyethylene terephthalate (PET) structure. The polymer-assistant liquid-phase exfoliation of 2D nanoflakes from TiS₂ bulk material is processed in low-boiling solvent. And the fabrication process of these devices is performed entirely at room temperature. Such an energy-saving and scalable production process indicates a huge potential of large-scale industrial application. The AFM and TEM characterizations showed that the exfoliated 2D TiS₂ are flakes at micrometer scale with a layer-number of mostly 7 or 8. Both the HRS and the LRS can be kept for more than 10⁴ s. The endurance of devices was obtained over 100 direct current (DC) sweeping cycles with remarkable separations between different resistive states. The distributions of writing (set) and erasing (reset) voltages show that set and reset voltages are small (<2 V). Also, the resistive switching characteristics of the devices are stable during 1000 bending cycles. The switching behavior is explained by the thinning and recovery of Schottky barriers within devices.     

基于HfO2的阻变存储器中Ag导电细丝方向和浓度的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 研究了基于HfO₂的阻变存储器中Ag 导电细丝浓度以及方向性. 通过计算Ag杂质5种方向模型的分波电荷态密度等势面图、形成能、 迁移势垒和分波电荷态密度最高等势面值, 发现[-111]方向最有利于Ag导电细丝的形成, 这对器件的开启电压、形成电压和开关比有很大影响. 本文基于最佳的[-111]导电细丝方向, 设计了4 种Ag 浓度结构. 计算4种Ag浓度结构的分波电荷态密度等势面图, 得出Ag浓度低于4.00 at.% 时晶胞结构中无导电细丝形成且无阻变现象. 当Ag浓度从4.00 at.%增加到4.95 at.% 时, 晶胞结构中发现有导电细丝形成, 表明Ag浓度高于4.00 at.%时, 晶胞中可以发生阻变现象. 然而, 通过进一步对比计算这两种晶胞结构中Ag的形成能、分波电荷态密度最高等势面值、总态密度与Ag的投影态密度发现, Ag浓度越大, 导电细丝却不稳定, 并且不利于提高阻变存储器的开关比. 本文的研究结果可为改善基于HfO₂的阻变存储器的性能提供一定理论指导.     

Zinc Oxide Thin Films for Memristive Devices: A Review

Zinc Oxide (ZnO) thin films have been addressed as promising candidates for the fabrication of Resistive Random Access Memory devices, which are alternative to conventional charge-based flash memories. According to the filamentary conducting model and charge trapping/detrapping theory developed in the last decade, the memristive behavior of ZnO thin films is explained in terms of conducting filaments formed by metallic ions and/or oxygen vacancies, and their breaking through electrochemical redox reactions and/or recombination of oxygen vacancies/ions. A comparative review of the memristive properties of ZnO thin films grown by sputtering, atomic layer deposition (ALD), pulsed laser deposition (PLD), and sol-gel methods is here proposed. Sputtered ZnO thin films show promising resistive switching behaviors, showing high on/off ratios (10–10⁴), good endurance, and low operating voltages. ALD is also indicated to be useful for growing conformal ZnO layers with atomic thickness control, resulting in important resistive switching characteristics, such as relatively high on/off ratios and low operating voltages. High insulating epitaxial ZnO thin films can be obtained by PLD, showing reliable switching properties at low voltages and with good retention. On the contrary, the sol-gel approach generally results in ZnO thin films with poor resistive switching behaviors. Nevertheless, thin films derived from ZnO NPs show improved switching performances, with higher on/off ratios and lower operating voltages. Independently of the synthetic approach, doped ZnO thin films exhibit better resistive switching behaviors than pristine ones, coupling a strong increase of the on/off ratio with a more stable switching response.     

铜掺杂氧化锌薄膜阻变特性的研究

以 ZnO：Al为底电极,Cu为顶电极,在同种工艺条件下分别制备了类电容结构的纯ZnO 阻变器件和ZnO：2%Cu阻变器件,分析比较了两种器件的典型I-V特性曲线、置位电压（V_Set）和复位电压（V_Reset）的分布范围、器件的耐久性。结果显示,ZnO：Cu阻变器件较纯ZnO阻变器件有更大的开关比和更稳定的循环性能。另外,研究了 ZnO：Cu阻变器件的阻变机理,通过对其I-V特性曲线分析得出以下结论：ZnO：Cu阻变器件在高阻态遵循空间电荷限制电流效应,低阻态符合欧姆定律。     

电泳沉积法制备的Zn1-xCxO薄膜的结构及阻变性能

采用电泳沉积法在FTO导电玻璃基片上制备Zn_1-xCu_xO薄膜,并对其微观结构、光致发光谱、伏安特性、保持特性和转换电压分布进行探讨。PL谱表明,Cu掺杂在禁带中引入深受主能级,降低氧空位浓度,导致ZnO薄膜的紫外发光、蓝光发光和绿光发光峰强度降低。所得薄膜的晶粒细小、致密、均匀,具有稳定的双极性阻变特性,开关比R_off/R_on最高达到10⁵,其低阻态（LRS）和高阻态（HRS）的阻变机理分别符合欧姆定律和空间电荷限制传导理论。器件经100次循环测试后开关比无明显变化,呈现出较为良好的抗疲劳特性。Cu掺杂对LRS影响不大,但显著改善了HRS的分散性以及转换电压V_SET的分散性。当Cu掺杂量x=0.04时,器件表现出良好的综合性能：R_off≈10⁶ Ω,R_off/R_on≈10⁴,V_SET介于0.4~3.03 V之间。     

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.     

缺陷分布对Ag-SiO2薄膜电阻翻转效应的影响

通过改变制备条件,研究了Ag-SiO₂薄膜中的缺陷对电阻翻转效应的影响.对比不同的热处理实验条件, 发现在120 ℃退火的样品经forming过程后具有稳定的电阻转变特性;另一方面, 在Ar/O₂混合气氛下生长的SiO₂具有比在纯Ar下生长的样品更加稳定、重复的电阻转变特性. 通过实验分析,表明热处理、电场作用和样品制备气氛可以改变、调节样品中的缺陷分布 (Ag填隙原子和氧空位缺陷),从而导致Ag-SiO₂中基于缺陷的导电通道结构的形成和湮灭, 提出了提高电阻翻转稳定性的必要条件.     

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.     

Dynamic resistive switching in a three-terminal device based on phase separated manganites

A three-terminal device based on electronic phase separated manganites is suggested to produce high performance resistive switching. Our Monte Carlo simulations reveal that the conductive filaments can be formed/annihilated by reshaping the ferromagnetic metal phase domains with two cross-oriented switching voltages. Besides, by controlling the high resistance state(HRS) to a stable state that just after the filament is ruptured, the resistive switching remains stable and reversible, while the switching voltage and the switching time can be greatly reduced.     

Rectifying resistance switching behaviors of SnO2 microsphere films modulated by top electrodes

Based on the bipolar resistive switching (RS) characteristics of SnO₂ films, we have fabricated a new prototypical device with sandwiched structure of Metal/SnO₂/fluorine-doped tin oxide (FTO). The SnO₂ microspheres film was grown on FTO glass by template-free hydrothermal synthesis, which was evaporated with various commonly used electrodes such as aluminium (Al), silver (Ag), and gold (Au), respectively. Typical self-rectifying resistance switching behaviors were observed for the RS devices with Al and Au electrodes. However, no obvious rectifying resistance switching behavior was observed for the RS device with Ag electrode. Above results were interpreted by considering the different interface barriers between SnO₂ and top metal electrodes. Our current studies pave the ways for modulating the self-rectifying resistance switching properties of resistive memory devices by choosing suitable metal electrodes.     

Metal-substitution strategy to control the conductive path in titanium dioxide: ab initio calculations

Revealing the atomic-nature of the conductive path in TiO₂ layer based resistive-switching devices still remains a critical challenge. Metal atoms doping in TiO₂ layer are always considered as an effective way to improve the electronic properties in resistive random access memory. Efforts to clarify the effects of metal atom substitution on the conductive path in rutile TiO₂ have been done by using first-principles calculation. The dependence of the conductive path on the substitution of Ag/Cu/Al/Hf/Ta/V adjacent to the ordering oxygen vacancies or away from them has been studied in detail to elucidate the formation mechanism of conductive path. Theoretical investigation demonstrates that Hf or V substitution where it occurs adjacent to the oxygen vacancies benefits electrons aggregation among Ti-ions. Such electrons aggregation, which is one type of the conductive path in TiO₂, will be prompted by Ti-t2g orbital electron. The dependent relation of the conductive path on the substitution of Ag/Cu/Al/Hf/Ta/V will be an important factor to optimize future resistive random access memory.     

Effects of oxygen partial pressure on resistive switching characteristics of ZnO thin films by DC reactive magnetron sputtering

Cu/ZnO/n⁺-Si structures were prepared by magnetron sputtering of a layer of ZnO thin film onto heavily doped silicon substrate, followed by thermal evaporation of a thin layer of metallic Cu. The resistive switching characteristics of Cu/ZnO/n⁺-Si structures were investigated as a function of oxygen partial pressure during ZnO deposition. Reproducible resistive switching characteristics were observed in ZnO thin films deposited at 20%, 33% and 50% oxygen partial pressure ratios while ZnO thin film deposited at 10% oxygen partial pressure ratio did not show resistive switching behavior. The conduction mechanisms in high and low resistance states are dominated by space-charge-limited conduction and ohmic behavior respectively, which suggests that resistive switching behaviors in such structures are related to filament formation and rupture. It is also found that the reset current decreases as oxygen partial pressure increases, due to the variation of oxygen vacancy concentration in the ZnO thin films.     

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.