Unipolar resistive switching behavior of BiFeO3 thin films prepared by chemical solution deposition

Bismuth ferrite (BiFeO₃, BFO) thin films were spin-coated on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method. The ferroelectric BFO films annealed at 500 °C and 550 °C were found to possess unipolar resistive switching behaviors. The resistance ratio of the high resistance state (HRS) to the low resistance state (LRS) of the unipolar resistance switching is about 10³ for the ferroelectric BFO films. The conduction mechanisms are concluded to be space charge-limited conduction for the initial state and Ohmic conduction for the LRS. As for the HRS, the Poole-Frenkel emission fits well in the whole voltage region. Traps composed of oxygen vacancies are considered to play a key role in forming conducting paths. The relaxation time of electronic carriers is much shorter than that of ionic oxygen vacancies; therefore, the resistance switching is considered more probably due to carrier injection and emission through the Poole-Frenkel model after forming.     

Forming-Free Unipolar Resistive Switching in BiFe0.95Co0.05O3 Films

We report the forming-free unipolar resistive switching effects in polycrystalline BiFe_0.95Co_0.05O₃ films which were spin-coated on ITO/glass substrates by a chemical solution deposition method. The resistive ratio of the high resistive state (HRS) to the low resistive state (LRS) is more than 2 orders of magnitude. The conduction of the HRS is dominated by the space-charge-limited conduction mechanism, while Ohmic behavior dominates the LRS, which suggests a filamentary conduction mechanism. The oxygen vacancies are considered to play an important role in forming the conducting filaments.     

Mechanisms of current conduction in Pt/BaTiO3/Pt resistive switching cell

The 80-nm-thickness BaTiO₃ (BT) thin film was prepared on the Pt/Ti/SiO₂/Si substrate by the RF magnetron sputtering technique. The Pt/BT/Pt/Ti/SiO₂/Si structure was investigated using X-ray diffraction and scanning electron microscopy. The current-voltage characteristic measurements were performed. The bipolar resistive switching behavior was found in the Pt/BT/Pt cell. The current-voltage curves were well fitted in different voltage regions at the high resistance state (HRS) and the low resistance state (LRS), respectively. The conduction mechanisms are concluded to be Ohmic conduction and Schottky emission at the LRS, while space-charge-limited conduction and Poole-Frenkel emission at the HRS. The electroforming and switching processes were explained in terms of the valence change mechanism, in which oxygen vacancies play a key role in forming conducting paths.     

Low power and stable resistive switching in graphene oxide-based RRAM embedded with ZnO nanoparticles for nonvolatile memory applications

The present study reports the role of zinc oxide nanoparticles (ZnO NPs) embedded in graphene oxide (GO)-based RRAM for non-volatile memory applications. GO thin film embedded with different concentrations of ZnO NPs was deposited on bottom electrode, i.e., indium tin oxide (ITO) coated glass. Thermal evaporation technique was used for the fabrication of top electrodes for electrical measurements. Structural and morphological studies of synthesized GO and ZnO NPs were done by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Switching characteristics of the RRAM devices were investigated using electrical measurements. It has been observed that the optimized concentration of ZnO NPs (20%) shows stable switching behavior with low SET (??0.61 V) and RESET (+?0.65 V) voltages as compared to pure GO devices. The switching of the fabricated memory devices from high resistance state (HRS) to low resistance state (LRS) has been found due to conductive filament formed between top and bottom electrodes. This conductive filament has been confirmed by the change in resistance as a function of temperature. The Al/GO-ZnO(20%)/ITO devices show stable endurance behavior for >?50 cycles and retention behavior for >?4?×?10³ s. In HRS, the dominated conduction mechanism was found to be space-charge limited conduction (SCLC), whereas in LRS, the Ohmic conduction mechanism was observed. The incorporation of ZnO NPs increased the number of oxygen vacancies in switching layer which eventually enhanced the formation of conductive filament. This phenomenon has been confirmed using XPS characterization of the switching layer. These optimized concentrations of ZnO embedded in GO switching layers provide a way for future low power non-volatile memory devices.

     

退火温度对TiO2基电阻开关器件性能的影响

采用直流磁控溅射法在n+-Si上制备了TiO2薄膜,采用电子束蒸发镀膜仪在TiO2薄膜上沉积Au电极,获得了Au/TiO2/n+-Si结构的器件.研究了退火温度对薄膜结晶性能及器件电阻开关特性的影响.Au/TiO2/n+-Si结构的器件具有单极性电阻开关特性,置位(set)电压,复位(reset)电压、reset电流及功率的大小随退火温度的不同而不同,并基于灯丝理论对器件的电阻开关效应的工作机理进行了探讨.研究结果表明,500℃退火的器件具有良好的非易失性.器件高低阻态的阻值比大于103,其信息保持特性可达10年之久.在读写次数为100次时,器件仍具有电阻开关效应.     

Studies on nonvolatile resistance memory switching in ZnO thin films

Six decades of research on ZnO has recently sprouted a new branch in the domain of resistive random access memories. Highly resistive and c-axis oriented ZnO thin films were grown by us using d.c. discharge assisted pulsed laser deposition on Pt/Ti/SiO₂/Si substrates at room temperature. The resistive switching characteristics of these films were studied in the top-bottom configuration using current-voltage measurements at room temperature. Reliable and repeated switching of the resistance of ZnO thin films was obtained between two well defined states of high and low resistance with a narrow dispersion and small switching voltages. Resistance ratios of the high resistance state to low resistance state were found to be in the range of 2–5 orders of magnitude up to 20 test cycles. The conduction mechanism was found to be dominated by the Ohmic behaviour in low resistance states, while Poole-Frenkel emission was found to dominate in high resistance state. The achieved characteristics of the resistive switching in ZnO thin films seem to be promising for nonvolatile memory applications.     

Influence of carrier injection on resistive switching of CaCu3Ti4O12 thin films with Ni electrode

The influence of electron injection on the electric-pulse-induced resistive switching of perovskite CaCu₃Ti₄O₁₂ (CCTO) films was studied by current-voltage (I-V) measurements. The electron injection was reduced by annealing the sample in an O₂ atmosphere. The switching from the high-resistance state HRS to the low-resistance state LRS by a filamentary mechanism was suppressed when the carrier injection occurs by Poole-Frenkel emission. The interfacial potential barrier plays a crucial role in determining the carrier injection.     

室温下制备非晶ZnO薄膜及其电阻开关特性研究

室温下采用紫外固化的方法取代溶胶-凝胶方法中的高温退火制备了氧化锌薄膜, XRD分析结果表明薄膜为非晶的, XPS分析结果表明薄膜的主要成分是ZnO。在深紫外固化后的薄膜表面溅射Al作为顶电极获得Al/a-ZnO/FTO结构的器件,研究深紫外照射时间对器件电阻转变性能的影响, 进一步解释了深紫外固化的机制。研究表明: 经过充足时间(12 h)照射的器件表现出双极性电阻开关特性,阈值电压分布集中(-3.7 V<V_set<-2.9 V, 3.4 V< V_reset<4.3 V)且符合低电压工作的要求, 至少在4000 s内器件的高低阻态都没有发生明显的退化, 表现出了良好的存储器特性。Al/a-ZnO/FTO器件的这种电阻转变特性可以用空间电荷限制电流传导机制解释。     

Improvement of resistive switching in Cu/ZnO/Pt sandwiches by weakening the randomicity of the formation/rupture of Cu filaments

We report an improvement in minimizing the dispersion of resistive switching (RS) parameters such as ON/OFF state resistances and switching voltages of Cu/ZnO/Pt structures in which ZnO films have been deposited at elevated temperature with N doping. This deposition process can enlarge the ZnO grain size and lessen grain boundaries while maintaining a high initial resistance since ZnO naturally shows n-type conductivity and N is a p-type dopant but with a low solubility. Cu filaments with a diameter of 15?nm are found to form at the ZnO grain boundaries. Therefore, fewer grain boundaries could depress the randomicity of the formation/rupture of Cu filaments and result in more stable RS performances. Such memory devices show a fast programming speed of 10?ns.     

Reproducible resistance switching for BaTiO3 thin films fabricated by RF-magnetron sputtering

BaTiO₃ (BTO) thin film was fabricated to investigate its non-volatile and reversible resistance switching phenomena by RF-sputtering method. The reversible resistance switching phenomenon was observed by DC voltage sweep and Pt/BTO/Pt metal-insulator-metal structure devices showed the bipolar resistance switching such as Pr_0.7Ca_0.3MnO₃ and Cr-doped SrTiO₃. The typical leakage current-voltage characteristic measurements were performed. High resistance state (HRS) and low resistance state (LRS) were maintained without power supply. The margin of the resistance between HRS and LRS is considerable during 120th cycles. The current emission mechanisms were suggested by double logarithm plot of leakage current vs. voltage. The comparison of the spreading current mapping images for two different resistance states showed that local conduction path was formed at LRS and was destroyed at HRS.     

The Bipolar Resistive Switching in BiFeO3 Films

Pure-phase polycrystalline BiFeO₃ films have been successfully prepared by pulsed-laser deposition on surface oxidized Si substrates using LaNiO₃ buffer layer with substrate temperature (T _s) ranging from 550?°C to 800?°C and a laser frequency of 5?Hz and 10?Hz. Bipolar resistive switching has been observed in all the films using LaNiO₃ as bottom electrodes and silver glue dots as top electrodes, the resistivity switches from a high-resistance state (HRS) to a low-resistance state (LRS) with positive voltage applied on the top Ag electrodes, and from LRS to HRS with positive voltage applied on the bottom LaNiO₃ electrodes. The mechanism of the resistive switching has been confirmed to be due to the voltage polarity dependent formation/rupture of the conducting filaments formed by the O vacancies. The highest resistive ratio of HRS to LRS, of more than 2 orders of magnitude, has been achieved in the highest resistive BiFeO₃ film prepared at T _s of 650?°C and laser frequency of 10?Hz.     

铋掺杂对SrTiO3薄膜微观结构及阻变行为的影响

采用溶胶-凝胶及快速退火工艺在p+-Si上制备了Bi掺杂SrTiO_3薄膜,构建了Ag/Sr_(1-x)Bi_xTiO_3/p+-Si结构阻变器件,研究了Bi掺杂量对薄膜微观结构、器件阻变行为及特性的影响。结果表明:Bi掺杂量较低时并未改变Sr_(1-x)Bi_xTiO_3薄膜的相结构,但随着掺杂比例的增大,晶粒尺寸也明显增大,当掺杂量x=0.16时,有Bi4SrTi4O15及TiO2相形成;不同Bi掺杂量的Ag/Sr_(1-x)Bi_xTiO_3/p+-Si器件均呈现出双极性阻变特性,且有明显的多级阻变行为。随Bi掺杂量的增加,器件的阻变性能逐步提高,当x=0.12时器件的高、低阻态电阻比值最大,达到105左右,并且在2 000次可逆循环测试下,高、低阻态电阻比未出现衰减,表现出良好的抗疲劳特性,但当掺杂量x达到或超过0.16后,器件的性能呈下降趋势。Bi掺杂量的增大会导致器件高阻态时的导电机制从空间电荷效应(SCLC)导电机制(x0.16)转变为肖特基势垒发射(x=0.16)。器件在低阻态下均遵循欧姆导电机制。     

Complementary Resistive Switching Using Metal–Ferroelectric–Metal Tunnel Junctions

Complementary resistive switching (CRS) devices are receiving attention because they can potentially solve the current‐sneak and current‐leakage problems of memory arrays based on resistive switching (RS) elements. It is shown here that a simple anti‐serial connection of two ferroelectric tunnel junctions, based on BaTiO₃, with symmetric top metallic electrodes and a common, floating bottom nanometric film electrode, constitute a CRS memory element. It allows nonvolatile storage of binary states (“1” = “HRS+LRS” and “0” = “LRS+HRS”), where HRS (LRS) indicate the high (low) resistance state of each ferroelectric tunnel junction. Remarkably, these states have an identical and large resistance in the remanent state, characteristic of CRS. Here, protocols for writing information are reported and it is shown that non‐destructive or destructive reading schemes can be chosen by selecting the appropriate reading voltage amplitude. Moreover, this dual‐tunnel device has a significantly lower power consumption than a single ferroelectric tunnel junction to perform writing/reading functions, as is experimentally demonstrated. These findings illustrate that the recent impressive development of ferroelectric tunnel junctions can be further exploited to contribute to solving critical bottlenecks in data storage and logic functions implemented using RS elements.     

Bi2O3薄膜的制备及其电阻开关特性的研究

电阻式存储器由于具有众多的优点有望成为最有前景的下一代高速非挥发性存储器的选择之一.实验利用射频磁控溅射法在重掺硅上沉积了Bi2O3薄膜,并对该薄膜的结晶状态和Au/Bi2O3/n+Si/Al结构的电阻开关特性进行了研究.XRD分析结果表明,射频磁控溅射法沉积所得的Bi2O3薄膜结晶性能好,(201)取向明显.I-V曲线测试结果表明,Au/Bi2O3/n+Si/Al结构具有单极性电阻开关特性.通过对不同厚度Bi2O3薄膜的Au/Bi2O3/n+Si/Al结构I-V特性比较发现,随着薄膜厚度的增加,电阻开关的Forming、Set和Reset阈值电压均随之增加.对于Bi2O3薄膜厚度为31.2 nm的Au/Bi2O3/n+Si/Al结构,其Forming、Set和Reset阈值电压均低于4 V,符合存储器低电压工作的要求.     

Schottky barrier mediated single-polarity resistive switching in Pt layer-included TiO(x) memory device

A distinct unipolar but single-polarity resistive switching behavior is observed in a TiO(x)/Pt/TiO(x) trilayer structure, formed by thermal oxidation of a Ti/Pt/Ti stack. As a comparison, a memory device with a single TiO(x) active layer (without addition of Pt midlayer) is also fabricated but it cannot perform resistive switching. Energy band diagrams are illustrated to realize the modulation of Schottky barrier junctions and current conduction in TiO(x)-based devices under various biasing polarities. Introduction of the Pt midlayer creates two additional Schottky barriers, which mediate the band bending potential at each metal-oxide interface and attains a rectifying current conduction at the high-resistance state. The rectifying conduction behavior is also observed with an AFM-tip as the top electrode, which implies the rectifying property is still valid when miniaturizing the device to nanometer scale. The current rectification consequently leads to a single-polarity, unipolar resistive switching and electrically rewritable performance for the TiO(x)/Pt/TiO(x) device.     

Phenomenological analysis of random telegraph noise in amorphous TiOx-based bipolar resistive switching random access memory devices

As dimensions of resistive random access memories (RRAMs) devices continue to shrink, the low-frequency noise of nanoscale devices has become increasingly important in evaluating the device reliability. Thus, we investigated random telegraph noise (RTN) caused by capture and emission of an electron at traps. We physically analyzed capture and emission processes through systematic measurements of amorphous TiOx (alpha-TiOx)-based bipolar RRAMs. RTNs were observed during high-resistance state (HRS) in most devices. However, discrete switching behavior was scarcely observed in low-resistance state (LRS) as most of traps in the alpha-TiOx were filled with mobile ions such as O2- in LRS. The capture and emission processes of an electron at traps are largely divided into two groups: (1) both capture and emission processes are mainly affected by electric field; and (2) one of the capture and emission processes is only influenced by the thermal process. This paper provides fundamental physics required to understand the mechanism of RTNs in alpha-TiOx-based bipolar RRAMs.     

Electrode effect on resistive switching of Ti-added amorphous SiOx films

Ti-added amorphous SiO_x films were sputter-deposited into stacks of Pt/SiO_x/Pt and Cu/SiO_x/Pt. Optimally prepared Pt/SiO_x/Pt exhibits unipolar resistive switching over 10² cycles, resistance ratio ∼ 10³, yet wide voltage distribution (2 ∼ 7 V for SET, 0.5 ∼ 1.5 V for RESET). Cu/SiO_x/Pt exhibit similar endurance, resistance ratio up to 10⁷, and SET and RESET voltages reduced to 1.8 ∼ 4.2 V and 0.5 ∼ 1 V, respectively. Cu diffusion into SiO_x at the virgin state may play a role in resistive switching of Cu/SiO_x/Pt stack besides of filament conduction. Ti-added amorphous SiO_x films incorporating Cu electrode shows potential for resistive memory.     

Rectifying switching characteristics of Pt/ZnO/Pt structure based resistive memory

40 nm thick amorphous ZnO thin films were deposited by radio frequency magnetron sputtering at room temperature and asymmetric electrical switching characteristics are observed in the macroscopic symmetric Pt/ZnO/Pt structure. The crystal structure was examined by X-ray diffraction (XRD). The chemical bonding states of ZnO resistive switching layer was investigated by X-ray photoelectron spectroscopy (XPS). Keithley 4200 semiconductor characterization system was used to measure the current-voltage (I-V) characteristics of the fabricated devices. The results reveal that a reversible resistive switching behavior between the high resistance state and the low resistance state with rectifying effects can be repeated for more than 100 dc cycles. This asymmetric electrical behavior is thought to be related to the naturally self-formed PtOx between ZnO film and the Pt bottom electrode, which introduces an energy barrier when electrons flow from top electrode towards the bottom electrode. The model of Pt/ZnO/Pt memory cell is expected to be able to alleviate the misreading error in cross-point array for high density integrations.     

Fabrication and resistive switching characteristics of high compact Ga-doped ZnO nanorod thin film devices

This study investigates the resistive switching behavior of Ga-doped ZnO (GZO) nanorod thin films with various Ga/Zn molar ratios. Vertically well-aligned and uniform GZO nanorod thin films were successfully grown on Au/Ti/SiO(2)/p-Si substrates using an aqueous solution method. X-ray diffraction (XRD) results indicate that GZO nanorods have [0001] highly preferred orientation. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show the formation of highly ordered and dense nanorod thin films. These compact GZO nanorod thin films can be used to make resistive switching memory devices. Such memory devices can be reversibly switched between ON and OFF states, with a stable resistance ratio of ten times, narrow dispersion of ON and OFF voltages, and good endurance performance of over 100 cycles. The resistive switching mechanism in these devices is related to the formation and rupture of conducting filaments consisting of oxygen vacancies, occurring at interfaces between GZO nanorods (grain boundaries). Results show that the resulting compact GZO nanorod thin films have a high potential for resistive memory applications.     

Full Electric Control of Exchange Bias at Room Temperature by Resistive Switching

Electric control of exchange bias (EB) is of vital importance in energy‐efficient spintronics. Although many attempts have been made during the past decade, each has its own limitations for operation and thus falls short of full direct and reversible electrical control of EB at room temperature. Here, a novel approach is proposed by virtue of unipolar resistive switching to accomplish this task in a Si/SiO₂/Pt/Co/NiO/Pt device. By applying certain voltages, the device displays obvious EB in the high‐resistance‐state while negligible EB in the low‐resistance state. Conductive filaments forming in the NiO layer and rupturing near the Co–NiO interface are considered to play dominant roles in determining the combined resistive switching and EB phenomena. This work paves a new way for designing multifunctional and nonvolatile magnetoelectric random access memory devices.