Thermal Stability of Reliable Polycrystalline Zirconium Oxide for Nonvolatile Memory Application

Thermal stability of resistive switching of stoichiometric zirconium oxide thin films is investigated for high yielding nonvolatile memory application. The A1/ZrO2/AI cell fabricated in the conventional device process shows highly reliable switching behaviour between two distinct stable resistance states. The retention capabilities are also tested under various conditions and temperatures. The excellent performance of Ai/ZrO2/AI ceil can be explained by assuming that anode/ZrO2 interface exists and by conducting filament forming/rupture mechanism. The device failure is illustrated in terms of permanent conducting filaments formation.     

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.     

Resistive switching effect in metal–oxide–metal structures with ZnO:Li oxide layer

The resistive switching effect in metal–oxide–metal (MOM) structures has been investigated, where the 10% Li-doped ZnO layer was used as an oxide layer, as well as Pt and 20% fluorine doped SnO₂ (SnO₂:F) were used as a bottom electrodes. The current–voltage (I–V) and switching (I–t) characteristics of Ag/ZnO:Li/Pt and Ag/ZnO:Li/SnO₂:F structures were investigated. The unipolar resistive switching is detected in the structures with the Pt, while the use of transparent conductive SnO₂:F electrode instead of Pt, results to the bipolar memory effect.     

Ultrasound-assisted microwave preparation of Ag-doped CdS nanoparticles

Ag-doped CdS nanoparticles were synthesized by an ultrasound-assisted microwave synthesis method. The X-ray diffraction patterns reveal a structural evolution from cubic to hexagonal with increasing molar ratios of Ag⁺/Cd²⁺ from 0% to 5%. It shows that the Ag-doped hexagonal CdS nanoparticles are polycrystal. The X-ray photoelectron spectroscopy of the CdS nanoparticles doping with 5% Ag⁺ shows that the doped Ag in CdS is metallic. Simultaneously, the characteristic Raman peaks of the CdS nanoparticles enhance with increasing Ag⁺ concentrations. The photocatalytic activity of different Ag-doped samples show a reasonable change due to different ratios of Ag which doped into CdS.     

Low power consumption bipolar resistive switching characteristics of ZnO-based memory devices

Ag/ZnO/Pt structure resistive switching devices are fabricated by radio frequency (RF) magnetron sputtering at room temperature. The memory devices exhibit stable and reversible resistive switching behavior. The ratio of high resistance state to low resistance state can reach as high as 10 2 . The retention measurement indicates that the memory property of these devices can be maintained for a long time (over 10 4 s under 0.1-V durable stress). Moreover, the operation voltages are very low, -0.4 V (OFF state) and 0.8 V (ON state). A high-voltage forming process is not required in the initial state, and multi-step reset process is demonstrated. Resistive switching device with the Ag/ZnO/ITO structure is constructed for comparison with the Ag/ZnO/Pt device.     

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.     

Mechanism analysis of switching direction transformation in an Er2O3 based RRAM device

The resistive random access memory (RRAM) based on resistive switching effect has considered to be the most advanced next generation memory, in which the switching direction determines the order of reading-writing. In this work, the rare-earth metal Er₂O₃ was used as functional layer, and Ag and indium-tin-oxide (ITO) are selected as top and bottom electrode to fabricate resistive switching device. Further, it is observed that the switching direction and memory window of resistive switching device can be regulated by exchanging top and bottom electrode. Moreover, the complementary switching memory behavior in Ag/Er₂O₃/ITO/Er₂O₃/Ag structure was also observed. Through mechanism analysis, it is expected that the barrier changes and metal-ions oxidation-reduction should be responsible for the conversion of switching direction and regulation of memory window. This work opens up a way to the development of next generation new concept memory.     

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.     

Highly reproducible large-area and double-sided pulsed laser deposition of HTSC YBCO:Ag thin films for microwave applications

Large-area pulsed laser deposition (PLD) producing high-quality YBa₂Cu₃O_7-x (YBCO) thin films on both sides of R-plane sapphire substrates with CeO₂ buffer layer is used routinely to optimize planar microwave stripline filters for satellite and mobile communication systems. A relatively simple PLD arrangement with fixed laser plume and rotating substrate, with an offset between the laser plume and the center of the substrate is employed to deposit laterally homogeneous 3-inch-diameter Ag-doped YBCO thin films. The YBCO:Ag films are about 250 nm thick and have laterally homogeneous critical current densities of more than 3.5 MA/cm² at 77 K and homogeneous maps of microwave surface resistance R_s of about 40 m Q at 145 GHz and 77 K. The R_s at 8.5 GHz and 77 K, determined in the center position of the YBCO:Ag films, remains constant at about 370 7 Q up to a microwave surface magnetic field of about 10 mT. After experience with more than 700 double-sided 3-inch-diameter films, a high degree of homogeneity and reproducibility of j_c and R_s is reached. The PLD-YBCO:Ag films are suitable for microwave applications envisaged for future communication systems.     

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.     

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)     

掺银氧化锌纳米棒的水热法制备研究

利用水热法在直流磁控溅射制备的掺铝氧化锌 (AZO) 种子层上制备了不同形貌和光学性能的掺银ZnO纳米棒, 并采用XRD、扫描电镜、透射谱、光发射谱和EDS谱详细研究了Ag离子与Zn离子的摩尔百分比 (R_Ag/Zn) 及AZO种子层对掺银ZnO纳米棒的结构和光学性质的影响. 随着R_Ag/Zn的增加, 掺银ZnO 纳米棒的微结构和光学性质的变化与银掺杂诱导的纳米棒的端面尺寸变化有关. 平均端面尺寸的变化归结于种子层颗粒大小和颗粒数密度不同导致掺入的Ag离子的相对比例不同. 溅射15 min的AZO种子层上生长的ZnO纳米棒由于缺陷增多导致在可见光区的发光峰明显强于溅射10 min 的AZO种子层上、相同R_Ag/Zn 条件下生长的ZnO纳米棒. Ag掺杂产生的点缺陷增多导致可见光区PL波包较宽. 纯ZnO纳米棒的微结构与种子层厚度导致的结晶度和颗粒大小有关. 关键词： ZnO纳米棒 水热法 Ag掺杂 直流磁控溅射     

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.     

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.     

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.     

Air Stability of Cs2CO3:Ag/Ag Cathode for Organic Light-Emitting Diodes

We report the superior stability of the composite Cs2CO3 ：Ag/Ag cathode structure, which can be used in efficient organic light-emitting diodes （OLEDs）. Devices with the Cs2CO3：Ag （1：10, 5nm）/Ag （95nm） cathode show a considerably improved lifetime compared with the control device with the Cs2CO3 （0.5 nm）/Ag （100 nm） cathode. The composite Cs2CO3 ：Ag/Ag film is proved to be stable in the atmosphere. X-ray diffraction （XRD） is applied to analyze the crystalline structure of the Cs2CO3：Ag film, and it is demonstrated that CsAg alloy is formed, leading to the improved stability of the thin film and the devices.     

Nonvolatile unipolar resistive switching in ultrathin films of graphene and carbon nanotubes

We report unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two-terminal devices with yield >99% are made at room temperature by forming continuous films of graphene of thickness ∼20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the film. These memory devices are nonvolatile, rewritable with ON/OFF ratios up to ∼ 10⁵ and switching times up to 10 μs. The devices made of MWNT films are rewritable with ON/OFF ratios up to ∼400. The resistive switching mechanism is proposed to be nanogap formation and filamentary conduction paths.     

Influence of Dopants in ZnO Films on Defects

The influence of dopants in ZnO films on defects is investigated by slow positron annihilation technique. The results show S that parameters meet S_Al>S_un>S_Ag for Al-doped ZnO films, undoped and Ag-doped ZnO films. Zinc vacancies are found in all ZnO films with different dopants. According to S parameter and the same defect type, it can be induced that the zinc vacancy concentration is the highest in the Al-doped ZnO film, and it is the least in the Ag-doped ZnO film. When Al atoms are doped in the ZnO films grown on silicon substrates, Zn vacancies increase as compared to the undoped and Ag-doped ZnO films. The dopant concentration could determine the position of Fermi level in materials, while defect formation energy of zinc vacancy strongly depends on the position of Fermi level, so its concentration varies with dopant element and dopant concentration.     

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.     

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.