氧分压对Ni/HfO_x/TiN阻变存储单元阻变特性的影响

采用射频磁控溅射的方法,基于不同氧分压制备的氧化铪构建了Ni/HfO_x/TiN结构阻变存储单元.研究发现,随着氧分压的增加,薄膜表面粗糙度略有降低;另一方面,阻变单元功耗降低,循环耐受性能可达10~3次,且转变电压分布的一致性得到改善.结合电流-电压曲线线性拟合结果及外加温度测试探究了器件的转变机理,得出在低阻态的传导机理为欧姆传导机理,在高阻态的传导机理为肖特基发射机理,并根据氧空位导电细丝理论,对高低阻态的阻变机理进行了详细的理论分析.     

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.     

Deposition and properties of B-N codoped p-type ZnO thin films by RF magnetron sputtering

B-N codoped p-type ZnO thin films have been realized by radio frequency (rf) magnetron sputtering using a mixture of argon and oxygen as sputtering gas. Types of conduction and electrical properties in codoped ZnO films were found to be dependent on oxygen partial pressure ratios in the sputtering gas mixture. When oxygen partial pressure ratio was 70%, the codoped ZnO film showed p-type conduction and had the best electrical properties. Additionally, the p-ZnO/n-Si heterojunction showed a clear p-n diode characteristic. XRD results indicate that the B-N codoped ZnO film prepared in 70% oxygen partial pressure ratio has high crystal quality with (0 0 2) preferential orientation. Meanwhile, the B-N codoped ZnO film has high optical quality and displays the stronger near band edge (NBE) emission in the temperature-dependent photoluminescence spectrum, the acceptor energy level was estimated to be located at 125 meV above the valence band.     

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.     

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     

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.     

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.     

Spectroscopic ellipsometry modeling of ZnO thin films with various O2 partial pressures

ZnO films were deposited on thermally oxidized SiO₂/p-type Si (100) substrates and glass substrates by DC magnetron sputtering using a metal Zn target. Three types of samples were prepared with various O₂/(Ar + O₂) ratios (O₂ partial pressure) of 20%, 50%, and 80%. The properties of these ZnO thin films were investigated using X-ray diffraction (XRD), optical transmittance, atomic force microscopy (AFM), and spectroscopic ellipsometry in the spectral region of 1.7–3.1 eV. The structural and optical properties of ZnO thin films were affected by O₂ partial pressure. Relationships between crystallinity, the ZnO surface roughness layer, and the refractive index (n) were investigated with varying O₂ partial pressure. It was shown that the spectroscopic ellipsometry extracted parameters well represented the ZnO thin film characteristics for different O₂ partial pressures.     

ZnO:Ag film growth on Si substrate with ZnO buffer layer by rf sputtering

ZnO buffer layers were deposited on n-Si (1 0 0) substrate by rf magnetron sputtering at a lower power of 40 W. Then Ag-doped ZnO (SZO) films were deposited on buffered and non-buffered Si at a higher sputtering power of 100 W. The effects of buffer layer on the structural, electrical and optical properties of SZO films were investigated. The three-dimensional island growth process of ZnO buffer layer was discussed. The energy band diagram of p-SZO/n-Si heterojunction was constructed based on Anderson's model. Results show the ZnO buffer layer leads to better properties of SZO film, including larger grain size, smoother surface, higher carrier mobility, better rectifying behavior, lower interface state density, and weaker deep-level emission. It is because the ZnO buffer layer effectively relaxes the partial stress induced by the large lattice mismatch between SZO and Si.     

Improved resistive switching performance in Cu-cation migrated MoS2 based ReRAM device incorporated with tungsten nitride bottom electrode

The resistive switching characteristics of sputtered deposited molybdenum disulphide (MoS₂) thin film has been investigated in Cu/MoS₂/W₂N stack configuration for Resistive Random Access Memory (ReRAM) application. The benefits of incorporating tungsten nitride (W₂N) as a bottom electrode material were demonstrate by stability in operating voltages, good endurance (10³ cycles) and long non-volatile retention (10³?s) characteristics. Resistive switching properties in Cu/MoS₂/W₂N structure are induced by the formation/disruption of Cu conducting filaments in MoS₂ thin film. Ohmic law and space charge limited current (SCLC) are observed as dominant conduction mechanism in low resistance state (LRS) and high resistance state (HRS) respectively. This study suggests the application of MoS₂ thin films with W₂N bottom electrode for next generation non-volatile ReRAM application.     

Study on oxygen source and its effect on film properties of ZnO deposited by radio frequency magnetron sputtering

The structural and optical properties of ZnO thin films deposited at various oxygen partial pressure and rf-power of rf magnetron sputtering were investigated. The sputtered ZnO films are mainly formed with the oxygen which was supplied from a sputtering gas; therefore the film stoichiometry can be controlled by the oxygen partial pressure and rf-power. From photoluminescence study, it was found that the wide emission band above 550 nm was observed due to an increase of oxygen vacancies when the ZnO film changed from O-rich to Zn-rich. The chemical stoichiometry of the film will help us to understand the formation mechanism of intrinsic defects in ZnO films.     

氧分压对磁控溅射制备ZnO薄膜的结构及光学特性的影响

采用射频反应磁控溅射法在玻璃衬底上成功制备出具有c轴高择优取向的ZnO薄膜,利用X射线衍射及紫外-可见吸收和透射光谱研究了氧分压变化对ZnO薄膜的微观结构及光吸收特性的影响。结果表明,当工作气压恒定时,用射频反应磁控溅射制备的ZnO薄膜的生长行为主要取决于成膜空间中氧的密度,合适的氧分压能够提高ZnO薄膜的结晶质量;薄膜在可见光区的平均透过率达到90%以上,且随着氧分压的增大,薄膜的光学带隙发生了一定程度的变化。采用量子限域模型对薄膜的光学带隙作了相应的理论计算,计算结果与对样品吸收谱所作的拟合结果符合较好,二者的变化趋势完全一致,表明ZnO纳米晶粒较小时,薄膜光学带隙的变化与量子限域效应有很大关系。     

Transparent conductive and near-infrared reflective Cu-based Al-doped ZnO multilayer films grown by magnetron sputtering at room temperature

Cu-based Al-doped ZnO multilayer films were deposited on glass substrates by DC magnetron sputtering at room temperature. Three kinds of multilayer structures (AZO/Cu, AZO/Cu/AZO, and Cu/AZO) were designed for comparison, and the effects of the Cu layer thickness on photoelectrical properties of the multilayer films were investigated. The results revealed that the transparent-conductive property and near-infrared reflectance of the films are closely correlated with the Cu layer thickness, and among the three structures, AZO/Cu bi-layer films exhibited preferable photoelectrical properties. The AZO/Cu bi-layer film with a Cu layer thickness of 7 nm displayed the highest figure of merit of 4.82 × 10⁻³ Ω⁻¹, with a low sheet resistance of 21.7 Ω/sq and an acceptable visible transmittance of 80%. The near infrared reflectance above 50% can be simultaneously obtained. The good performance of the coatings indicates that they are promising for coated glasses, thin film solar cells and heat-reflectors.     

The luminescence of ZnO film grown on GaAs interlayer by PA-MOCVD

ZnO film was firstly prepared by PA-MOCVD method on the substrate pre-coated with GaAs interlayer. Hall measurement found that the GaAs interlayer had important effects on the electrical behavior of the ZnO film. It could make the ZnO film convert to p-type conductivity. The XPS results confirmed that the acceptor was arsenic. And the acceptor level was 130 meV above the ZnO valence band maximum. Low-temperature PL measurement was introduced to investigate the optical properties of both as-grown n-type and arsenic doped p-type ZnO films. Then, based on this technology, ZnO homojunction light emitting device (LED) was fabricated with arsenic doped p-type ZnO and unintentionally doped n-type ZnO on GaAs/p⁺-Si substrate. Its current-voltage (I-V) character showed a typical rectification behavior, which was different from the n-ZnO/p⁺-Si structure. The UV-visible (385-580 nm) electroluminescence was detected under relatively low current injection condition from the n-ZnO/p-ZnO/p⁺-Si LED.     

Evaluation of acoustoelectric UV sensor according to ZnO thin film properties

This paper presents an improvement of the acoustoelectric effect by sensitivity and response of ultraviolet (UV) sensors by changing the argon/oxygen ratio. The acoustoelectric sensor is a delay-line type with a center frequency of 240.2625 MHz and fabricated on a piezoelectric substrate. Aluminum thin films were deposited as interdigitated transducers and patterned, and the ZnO thin film was deposited as a UV sensing layer by controlling the ratio of argon and oxygen with an RF magnetron sputtering. By increasing the oxygen partial pressure during ZnO deposition, the photoconductivity increased by 6.5 times, thereby increasing the frequency change related to the sensitivity of the sensor. The sensitivity to UV light was 110.4 Hz cm²/μW under an argon/oxygen ratio of 6:4, which is an increase of 5.1 times from 21.76 Hz cm²/μW obtained under a ratio of 10:2. In addition, the response and recovery times were improved by 2.85 times and 3.02 times, respectively.     

Effects of the oxygen partial pressure and annealing atmospheres on the microstructures and optical properties of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (1 0 0) substrates at 200 °C under various oxygen partial pressures by using radio frequency reactive magnetron sputtering. The properties of the films were characterized by the X-ray diffraction spectroscopy (XRD), energy dispersive spectrometer, X-ray photoelectron spectroscopy (XPS) and fluorescence spectrophotometer with the emphasis on the evolution of microstructures, element composition, valence state of Cu, optical properties. The results indicated that the properties of ZnO:Cu films were significantly affected by oxygen partial pressures. XRD measurements revealed that the sample prepared at the ratio of O₂:Ar of 15:10 sccm had the best crystal quality among all ZnO:Cu films. XPS analysis results suggested that the valence of Cu in the ZnO films was a mixed state of +1 and +2, and the integrated intensity ratio of Cu²⁺ to Cu⁺ increased with the increment of oxygen partial pressure. The photoluminescence measurements at room temperature revealed a violet, two blue and a green emission. We considered that the origin of green emission came from various oxygen defects when the ZnO:Cu films grew in oxygen poor and enriched environment. Furthermore, the influence of annealing atmosphere on the microstructures and optical properties of ZnO:Cu films were discussed.     

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。     

Modeling of conducting bridge evolution in bipolar vanadium oxide-based resistive switching memory

We investigate the resistive switching characteristics of a Cu/VOx/W structure. The VOx film is deposited by radio- frequency magnetron sputtering on the Cu electrode as a dielectric layer. The prepared VOx sample structure shows reproducible bipolar resistive switching characteristics with ultra-low switching voltage and good cycling endurance. A modified physical model is proposed to elucidate the typical switching behavior of the vanadium oxide-based resistive switching memory with a sudden resistance transition, and the self-saturation of reset current as a function of compliance current is observed in the test, which is attributed to the conducting mechanism is discussed in detail. growth pattern of the conducting filaments. Additionally, the related     

Characteristic modification by inserted metal layer and interface graphene layer in ZnO-based resistive switching structures

ZnO-based resistive switching device Ag/ZnO/TiN, and its modified structure Ag/ZnO/Zn/ZnO/TiN and Ag/graphene/ZnO/TiN, were prepared. The effects of inserted Zn layers in ZnO matrix and an interface graphene layer on resistive switching characteristics were studied. It is found that metal ions, oxygen vacancies, and interface are involved in the RS process. A thin inserted Zn layer can increase the resistance of HRS and enhance the resistance ratio. A graphene interface layer between ZnO layer and top electrode can block the carrier transport and enhance the resistance ratio to several times. The results suggest feasible routes to tailor the resistive switching performance of ZnO-based structure.     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.