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.     

Effect of cation and anion defects on the resistive switching polarity of ZnO x thin films

In this paper, we achieve the resistive switching (RS) polarity from unipolar to bipolar in a simple Al/ZnO _x /Al structure by moderating the oxygen content in the ZnO sputtering process. In a pure Ar sputtering, Al/ZnO _x /Al shows unipolar behavior, as oxygen partial pressure increases, the RS polarity changes to bipolar, and the switch current decreases by about five orders of magnitude. The current transport properties of unipolar device show ohmic behavior under both high resistance (HRS) and low resistance states (LRS), but the bipolar device shows Schottky barrier modulated current transport properties. We study the defect types in the unipolar and bipolar devices through photoluminescence (PL) spectra. The PL results show that the interstitial zinc (Zn_i) and interstitial oxygen (O_i) are dominant in unipolar and bipolar devices, respectively. We attribute this phenomenon to Zn_i and O_i playing important role in unipolar (URS) and bipolar resistive switching (BRS), respectively.     

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.     

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.     

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.     

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.     

Solution-processed high-k thin films as a resistive switching for ReRAM applications

Resistive switching characteristics of solution-processed high-k thin films (HfO_x and TaO_x) were investigated for ReRAM applications. The thickness of solution-processed high-k thin films can be easily controlled by simple spin coating. We optimized the critical thickness of solution-processed HfO_x and TaO_x thin films, for reliable ReRAM operations. A similar bipolar resistive switching behavior was observed from both solution-processed and sputter-processed HfO_x films. Furthermore, it was found that the solution-processed HfO_x and TaO_x films have a uniform resistive switching characteristic. The dominant conduction of these solution-processed films is described by Ohmic conduction in the low-resistance state. On the other hand, Ohmic conduction at low voltage and Poole–Frenkel emission at high voltage dominate in the high-resistance state. It was verified that the solution-processed HfO_x and TaO_x films have superior endurance and retention characteristics. Therefore, ReRAM devices based on solution-processed high-k materials are expected to be a promising candidate, for usage of resistive memory in glass substrate or flexible substrate based electronic devices.     

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.     

下电极对ZnO薄膜电阻开关特性的影响

本文采用直流磁控溅射法在三种不同的下电极(BEs)上制备了ZnO薄膜, 获得了W/ZnO/BEs存储器结构. 研究了不同的下电极材料对器件电阻开关特性的影响. 研究结果表明, 以不同下电极所制备的器件都具有单极性电阻开关特性. 在低阻态时, ZnO薄膜的导电机理为欧姆传导, 而高阻态时薄膜的导电机理为空间电荷限制电流. 不同下电极与ZnO薄膜之间的肖特基势垒高度对电阻开关过程中的操作电压有较大的影响, 并基于导电细丝模型对不同下电极上ZnO薄膜的低阻态阻值及reset电流的变化进行了解释. 关键词： ZnO薄膜 电阻开关 下电极     

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.     

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)     

Resistive switching of in situ and ex situ oxygen plasma treated ZnO thin film deposited by atomic layer deposition

In situ and ex situ oxygen plasma treatment (OPT) were applied to treat ZnO thin films deposited by thermal atomic layer deposition (T-ALD), and the resistive switching (RS) behaviors of the films were investigated. For the in situ OPT, the treatment was applied after each T-ALD cycle. For the ex situ OPT, the treatment was applied on the as-grown film. The T-ALD-grown ZnO films were defect-rich and conductive with no RS behavior. After the OPT process, the resistivity of the films increased drastically, which is believed to be mainly due to the removal of hydrogen impurities, and the films showed bipolar RS characteristics. The dominant conduction mechanisms are the trap-controlled space charge limited current and ohmic behavior at different field regions. The RS behavior was induced upon the formation/disruption of the conducting filaments. Owing to the homogeneous chemical composition and fewer defects, the resistance ratio of the in situ OPT ZnO film is higher than that of the ex situ OPT film, implying that the in situ OPT method is an efficient way to fabricate resistive random access memory devices using the ALD-grown ZnO films.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

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.     

The electrical and magnetic properties of epitaxial orthorhombic YMnO3 thin films grown under various oxygen pressures

Orthorhombic YMnO₃ thin films were epitaxially grown on bare and LaNiO₃ buffered (0 0 1)-SrTiO₃ substrates by pulsed laser deposition under various oxygen pressures from 5 to 30 Pa. The crystal structure and microstructure of these films have been characterized by both X-ray diffractions and transmission electron microscopy. The leakage current, modeled as the space charge limited current (SCLC) mechanism, decreased significantly with the increase of oxygen content. It is further found that the magnetic property of films is greatly enhanced in YMnO₃ films grown under high oxygen pressure, which can be explained decreased oxygen vacancies. In addition, bipolar switching behavior was obtained only in the films grown under 30 Pa oxygen pressure, which is attributed to the decrease of voltage-driven oxygen vacancy migration.     

Effects of different dopants on switching behavior of HfO_2-based resistive random access memory

In this study the effects of doping atoms(Al, Cu, and N) with different electro-negativities and ionic radii on resistive switching of HfO2-based resistive random access memory(RRAM) are systematically investigated. The results show that forming voltages and set voltages of Al/Cu-doped devices are reduced. Among all devices, Cu-doped device shows the narrowest device-to-device distributions of set voltage and low resistance. The effects of different dopants on switching behavior are explained with deferent types of CFs formed in HfO2 depending on dopants: oxygen vacancy(Vo) filaments for Al-doped HfO2 devices, hybrid filaments composed of oxygen vacancies and Cu atoms for Cu-doped HfO2 devices,and nitrogen/oxygen vacancy filaments for N-doped HfO2 devices. The results suggest that a metal dopant with a larger electro-negativity than host metal atom offers the best comprehensive performance.     

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)     

The effects of substrate temperature on ZnO-based resistive random access memory devices

Ag/ZnO/Zn/Pt structure resistive switching devices are prepared by radio frequency magnetron sputtering.The ZnO thin films are grown at room temperature and 400 C substrate temperature,respectively.By comparing the data,we find that the latter device displayed better stability in the repetitive switching cycle test,and the resistance ratio between a high resistance state and a low resistance state is correspondingly increased.After 104-s storage time measurement,this device exhibits a good retention property.Moreover,the operation voltages are very low:-0.3 V/-0.7 V(OFF state) and 0.3 V(ON state).A high-voltage forming process in the initial state is not required,and a multistep reset process is demonstrated.     

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.     

Study on ferroelectric polarization induced resistive switching characteristics of neodymium-doped bismuth ferrite thin films for random access memory applications

The present work reports on resistive switching (RS) characteristics of Neodymium (Nd)-doped bismuth ferrite (BFO) layers. The Nd (2–10 at%) doped BFO thin film layers were deposited using a spray pyrolysis method. The structural analysis reveals that a higher Nd doping concentration in BFO leads to significant distortion of the prepared Nd:BFO thin films from rhombohedral to tetragonal characteristics. The morphological analysis shows that all the deposited Nd:BFO thin films have regularly arranged grains. The X-ray photoelectron spectroscopy (XPS) analysis reveals that the prepared Nd:BFO thin films have a higher Fe ³⁺/Fe ²⁺ratio and less oxygen vacancy (V_O) defects which enriches the ferroelectric characteristics in Nd:BFO layers. The polarization-electric field (P-E) and RS characteristics of the fabricated Nd:BFO-based RS device were examined. It was observed that the Nd (7 at%) doped BFO RS device shows large remnant polarization (P _r) of 0.21 μC/cm² and stable RS characteristics.