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.     

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.     

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     

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.     

Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

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.     

原子层沉积方法制备核-壳型纳米材料研究

采用原子层沉积方法在碳黑纳米颗粒表面分别沉积Al₂O₃, ZnO, TiO₂和Pt, 成功制备出核-壳型纳米材料. 通过高分辨率透射电子显微镜、X射线光电子能谱仪、 能谱仪对材料的表面形貌、晶体结构、薄膜成分进行了表征和分析. 结果表明, 原子层沉积方法是制备核壳型纳米材料的理想方法. 此外, 还分析了采用原子层沉积方法沉积不同材料, 所生长的薄膜材料有单晶、多晶、非晶等多种存在形式的形成原因. 关键词： 原子层沉积 核-壳型纳米材料 碳黑纳米颗粒     

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.     

脉冲激光沉积方法制备ZnO薄膜生长参量对发光特性的影响

用脉冲激光沉积（PLD）方法在Si（111）衬底上制备了ZnO薄膜。以325nmHe-Cd激光器为光源对薄膜进行了荧光光谱分析,用X射线衍射仪（XRD）和原子力显微镜（AFM）分别对薄膜的结构和形貌进行了分析。脉冲激光沉积方法的主要生长参量为氧压、激光重复频率、生长温度和激光能量。通过控制这些参量变量,研究了这些参量对ZnO薄膜发光特性的影响,得到了用于紫外发光的ZnO薄膜生长的优化条件：发现在温度为650℃左右、氧压50Pa左右、频率5Hz左右的范围内能得到半峰全宽较窄,强度较大的紫外发光峰。分析认为紫外峰主要是由激子辐射复合发光形成的,绿光带主要和Ozn的存在密切相关,氧空位是蓝光发射的重要原因。     

Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by x-ray absorption spectroscopy

We report a comprehensive study of the defects in room-temperature ferromagnetic (RTFM) Cu-doped ZnO thin films using x-ray absorption spectroscopy. The films are doped with 2 at.% Cu, and are prepared by reactive magnetron sputtering (RMS) and pulsed laser deposition (PLD), respectively. The results reveal unambiguously that atomic point defects exist in these RTFM thin films. The valence states of the Cu ions in both films are 2(+). In the film prepared by PLD, the oxygen vacancies (V(O)) form around both Zn ions and Cu ions in the hexagonal wurtzite structure. Upon annealing of the film in O(2), the V(O) population reduces and so does the RTFM. In the film prepared by RMS, the V(O)s around Cu ions are not detected, and the V(O) population around Zn ions is also smaller than in the PLD-prepared film. However, zinc vacancies (V(Zn)) are evidenced. Given the low doping level of spin-carrying Cu ions, these results provide strong support for defect-mediated ferromagnetism in Cu-doped ZnO thin films.     

Nanoscale imaging of ferroelectric domain and resistance switching in hybrid improper ferroelectric Ca3Ti2O7 thin films

Hybrid improper ferroelectrics have their electric polarization generated by two or more combined non-ferroelectric structural distortions such as the rotation and tilting of Ti-O octahedral in Ca₃Ti₂O₇ (CTO) family. In this work, we prepared different thickness CTO thin films on Pt substrates by pulsed laser deposition, and investigated their ferroelectric polarization reversal and the current transport properties by using the piezoresponse force microscopy and conducting atomic force microscopy, respectively. It is found that the CTO films exhibit clear ferroelectric domain switching and ferroelectric resistance switching behaviors, and the maximum resistive ratios of CTO film reaches ∼1750. These results demonstrate that hybrid improper ferroelectrics CTO films are promising materials for being employed in non-volatile memory and logic devices.     

Growth and characterization of pulsed laser deposited ZnO thin films

One of the most important and promising materials from metal oxides is ZnO with specific properties for near UV emission and absorption optical devices. The properties of ZnO thin films strongly depend on the deposition method. Among them, pulsed laser deposition (PLD) plays an important role for preparing various kinds of ZnO films, e.g. doped, undoped, monocrystalline, and polycrystalline. Different approaches — ablation of sintered ZnO pellets or pure metallic Zn as target material are described. This contribution is comparing properties of ZnO thin films deposited from pure Zn target in oxygen atmosphere and those deposited from sintered ZnO target. There is a close connection between final thin film properties and PLD conditions. The surface properties of differently grown ZnO thin films are measured by secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, different approaches — ablation of sintered ZnO pellet or pure metallic Zn as target materials are described. The main results characterize typical properties of ZnO films versus technological parameters are presented. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

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.     

原子层沉积法 生长ZnO的性质与前驱体源量的关系研究

介绍了新型材料ZnO的各项性能,并采用原子层沉积方法制备新型材料ZnO. 实验中采用二乙基锌(DEZn) 和水作为生长ZnO的前驱体源, 在蓝宝石衬底上生长ZnO; 采用氮气作为载气, 生长温度为180℃. 通过改变在实验中的通入锌源的时间, 探索不同的DEZn的源的量对薄膜的成分(Zn/O)、薄膜的厚度、生长速率、晶型、 表面形貌、三维形貌以及粗糙度的影响. 关键词： 氧化锌 原子层沉积 Zn/O     

生长条件对脉冲激光沉积制备ZnO：Al薄膜光电性能的影响

本文研究了脉冲激光沉积(PLD)生长过程中, 铝掺量、氧压及衬底温度等实验参数对ZnO:Al(AZO)薄膜生长的影响, 并利用扫描电子显微镜、原子力显微镜、X射线衍射、霍尔效应、光透射光谱等实验手段对其透明导电性能进行了探讨. 变温霍尔效应和光透射测量表明, 当靶材中铝掺量大于0.5 wt%时, 所制备AZO薄膜中铝施主在80 K时已完全电离, 因Bernstein-Moss (BM) 效应其带隙变大, 均为重掺杂简并半导体. 进一步系统研究了氧压和衬底温度对AZO薄膜透明导电性能的影响, 实验发现当氧压为1 Pa, 衬底温度为200 ℃时, AZO 导电性能最好, 其霍尔迁移率为28.8 cm²/V·s, 薄膜电阻率最小可达2.7×10^-4 Ω·cm, 且在可见光范围内光透过率超过了85%. 氧压和温度的增加, 都会导致薄膜电阻率变大. 关键词： 脉冲激光沉积法 ZnO：Al薄膜 透光性 导电性     

Pulsed laser deposition of ZnO grown on glass substrates for realizing high-performance thin-film transistors

We report characterization of ZnO thin-film transistors (TFTs) on glass substrates fabricated by pulsed laser deposition (PLD). ZnO films were characterized by X-ray diffraction (XRD), atomic force microscopy and Hall effect measurements. The XRD results showed high c-axis-oriented ZnO(0002) diffraction corresponding to the wurtzite phase. Moreover, the crystallization and the electrical properties of ZnO thin films grown at room temperature are controllable by PLD growth conditions such as oxygen gas pressure. The ZnO films are very smooth, with a root-mean-square roughness of 1 nm. From the Hall effect measurements, we have succeeded in fabricating ZnO films on glass substrates with an electron mobility of 21.7 cm²/V s. By using the ZnO thin film grown by two-step PLD and a HfO₂ high-k gate insulator, a transconductance of 24.1 mS/mm, a drain current on/off ratio of 4.4×10⁶ and a subthreshold gate swing of 0.26 V/decade were obtained for the ZnO TFT.     

Carrier storage in Ge nanoparticles produced by pulsed laser deposition

In this work, we report on the electrical characterization of Ge nanoparticles (NPs) produced by pulsed laser deposition (PLD) at room temperature (RT) in Ar gas inert atmosphere using a shadowed off‐axis deposition geometry. Our results show that functional thin films of crystalline Ge NPs embedded between thin alumina films can be obtained on p‐type Si(100) substrates following a low temperature and short rapid thermal annealing (RTA) treatment. Metal–oxide–semiconductor (MOS) structures with and without Ge NPs embedded in the alumina were prepared for the electrical measurements. The results indicate a strong memory effect at relatively low programming voltages (±4 V) due to the presence of Ge NPs. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Coexistence of unipolar and bipolar modes in Ag/ZnO/Pt resistive switching memory with oxygen-vacancy and metal-Ag filaments

In this study, the unipolar resistive switching(URS) and bipolar resistive switching(BRS) are demonstrated to be coexistent in the Ag/Zn O/Pt memory device, and both modes are observed to strongly depend on the polarity of forming voltage. The mechanisms of the URS and BRS behaviors could be attributed to the electric-field-induced migration of oxygen vacancies(VO) and metal-Ag conducting filaments(CFs) respectively, which are confirmed by investigating the temperature dependences of low resistance states in both modes. Furthermore, we compare the resistive switching(RS)characteristics(e.g., forming and switching voltages, reset current and resistance states) between these two modes based on VO- and Ag-CFs. The BRS mode shows better switching uniformity and lower power than the URS mode. Both of these modes exhibit good RS performances, including good retention, reliable cycling and high-speed switching. The result indicates that the coexistence of URS and BRS behaviors in a single device has great potential applications in future nonvolatile multi-level memory.     

基于SSCVD方法的a-b轴取向ZnO薄膜制备

以Zn₄(OH)₂(O₂CCH₃)₆·2H₂O为单一固相有机源,采用单源化学气相沉积法(Single sour cechem icalvapor deposition,SSCVD)在Si(100)衬底上制备ZnO薄膜,用X射线衍射(XRD)、原子力显微镜(AFM)分析ZnO薄膜样品的晶体结构和微观形貌,并用X射线光电子能谱(XPS)对薄膜的锌氧化学计量比进行了分析。研究结果表明:在非平衡条件下所得到的ZnO薄膜沿a-b轴取向生长,基片温度对ZnO薄膜生长过程影响较大,随着基片温度的升高,薄膜呈现c轴生长趋势;晶粒成柱状、尺寸均匀、膜层结构致密;薄膜样品中n_Zn:n_O=0.985。     

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.