Evidence for compliance controlled oxygen vacancy and metal filament based resistive switching mechanisms in RRAM

We present electrical evidence on asymmetric metal-insulator-semiconductor (MIS) based test structures in support of the presence of two different independent switching mechanisms in a resistive random access memory (RRAM) device. The valid mechanism for switching depends on the compliance capping (I_gl) for forming/SET transition. Our results convincingly show that low compliance based switching only involves reversible oxygen ion drift to and from oxygen gettering gate electrodes, while high compliance switching involves formation and rupture of conductive metallic nanofilaments, as verified further by our physical analysis investigations. We have observed this unique dual mode switching mechanism only in NiSi-based gate electrodes, which have a moderate oxygen solubility as well as relatively low melting point.     

Low voltage bipolar resistive switching in self-assembled PVDF nanodot network in capacitor like structures on Au/Cr/Si with Hg as a top electrode

In this letter, resistive switching phenomena in self-assembled nanodot network of Polyvinylidene fluoride (PVDF) polymer in a capacitor geometry of Hg/PVDF/Au/Cr/Si is investigated. A stable & bipolar resistive switching with a set voltage ranging from 0.35 V to 0.9 V & reset voltage with a range of −0.08 V to −0.25 V is detected. A practical resistance ratio between HRS and LRS of 10–25 may have great potential in organic memories. Possible mechanism for the bipolar switching is discussed with the filament type conduction mechanism. Furthermore, the low voltage switching is elucidated with the high current density associated filament formation and it is explicated using the parallel resistor model.     

Sol-gel法制备SrTiO_3薄膜的电阻开关性能研究

采用sol-gel法制作了28nm厚的SrTiO3薄膜和Au/SrTiO3/LaNiO3/Si(100)三明治结构的器件,并研究其物理性能。结果显示:室温下,用直流电压可以使薄膜的电阻在高低阻态间进行转换。最大的电阻变化率约为10309。对I-V特性的分析,发现在高阻态时,有空间电荷限制电流机制(SCLC)和肖特基势垒导电机制存在。应用在高场区有非对称电子陷阱中心的空间电荷限制电流理论,解释了这种电阻开关现象。     

Effect of the oxygen vacancy gradient in titanium dioxide on the switching direction of bipolar resistive memory

Resistive memory switching behavior depending on voltage sweep direction is studied by intentionally creating oxygen vacancies within titanium dioxide (TiO₂). By inserting a reactive Ti layer on the TiO₂, oxygen deficient TiO_2−x layer is created, which then causes TiO_2−x/TiO₂ which has an oxygen vacancy gradient. This gradient of oxygen vacancy makes it possible to create an insulating TiO₂ layer on the bottom electrode during the first reset with a negative bias at the top electrode. This insulating layer makes counterclockwise directional bipolar switching more stable. On the other hand, under the clockwise directional voltage sweeping, the first set switching is prevented by the insulating TiO₂ layers created during the first and second reset, which leads to a short circuit due to local heating eventually.     

脉冲激光沉积制备NiO(111)外延薄膜及其结构研究

采用脉冲激光沉积法(PLD)在具有六方纤锌矿结构的蓝宝石衬底上制备了NiO外延薄膜,研究了沉积温度、氧分压对薄膜结构和形貌的影响。在650℃、20Pa氧分压的条件下制得了高结晶质量的单晶NiO薄膜。高能电子衍射分析发现,该NiO薄膜沿Al2O3[11–20]方向入射的衍射图像为清晰的斑点,说明NiO薄膜的生长模式为岛状模式,薄膜与衬底的外延匹配关系为:(111)[11–2]NiO//(0001)[11–20]Al2O3。     

(Pb0.76Ca0.24)TiO3薄膜电畴反转行为的压电力显微镜研究

用溶胶-凝胶法在（Pt／Ti／SiO2/Si）衬底制备了（Pb0.76Ca0.24）TiO3（PCT）薄膜。利用扫描力显微镜（SFM）的压电响应模式（PFM）观测了PCT薄膜的纳米尺度畴结构。畴结构和晶粒尺寸相关,尺寸在100nm左右的晶粒表现为单畴,尺寸较大的晶粒表现为多畴。利用压电力显微镜研究了PCT薄膜中电畴的极化反转行为。通过SFM探针对畴施加一系列直流偏压极化,在每次极化后,利用压电响应模式扫描进行压电力成像,获得了与极化电压相关的畴反转信息。用探针施加电压对薄膜极化后,在不同的时间进行压电力成像,研究了电畴的退极化行为。     

Study of the interfaces in resistive switching NiO thin films deposited by both ALD and e-beam coupled with different electrodes (Si, Ni, Pt, W, TiN)

Thin NiO films, included in a metal/resistive oxide/metal (MRM) stack, are receiving great interest, as they exhibit resistive switching when subjected to an external applied field, and can thus be implemented in a resistive random access memory (ReRAM). The electrical switching characteristic is seen to depend on the NiO/metal coupling. Therefore a characterization of the interface between NiO and the electrode is vital to optimize and get insights on the switching phenomena. In this work we deposited NiO thin films by atomic layer deposition (ALD) at 300 °C and electron beam deposition (e-beam) at 40 °C on Si, Ni, Pt, W and TiN substrates and we characterized them with X-ray reflectivity (XRR), grazing incidence X-ray diffraction (GIXRD) and time of flight secondary ion mass spectrometry (ToF-SIMS). Depending on the growth process, we found an influence of the substrate on the NiO film roughness, which exhibits values in the 1.2-6.2 nm range. NiO electron density was 1.35-1.96 e⁻Å⁻³ spread around the nominal value of 1.83 e⁻ Å⁻³ for bulk cubic polycrystalline NiO. X-ray diffraction showed that NiO is polycrystalline in the cubic phase. ToF-SIMS profiles confirm NiO/Metal interface sharpness and the optimal uniformity of NiO layers. Intermixing phenomena are limited or absent and the presence of contaminants, such as C, F, and Cl is very low.     

The source of negative capacitance and anomalous peak in the forward bias capacitance-voltage in Cr/p-si Schottky barrier diodes (SBDs)

The frequency and voltage dependence of capacitance–voltage (C–V) and conductance-voltage (G/ω−V) characteristics of the Cr/p-Si metal semiconductor (MS) Schottky barrier diodes (SBDs) were investigated in the frequency and applied bias voltage ranges of 10 kHz to 5 MHz and (−4 V)−(+4 V), respectively, at room temperature. The effects of series resistance (R_s) and density distribution of interface states (N_ss), both on C–V and G/ω−V characteristics were examined in detail. It was found that capacitance and conductance, both, are strong functions of frequency and applied bias voltage. In addition, both a strong negative capacitance (NC) and an anomalous peak behavior were observed in the forward bias C–V plots for each frequency. Contrary to the behavior of capacitance, conductance increased with the increasing applied bias voltage and there happened a rapid increase in conductance in the accumulation region for each frequency. The extra-large NC in SBD is a result of the existence of R_s, N_ss and interfacial layer (native or deposited). In addition, to explain the NC behavior in the forward bias region, we drew the C–I and G/ω−I plots for various frequencies at the same bias voltage. The values of C decrease with increasing frequency at forward bias voltages and this decrease in the NC corresponds to an increase in conductance. The values of N_ss were obtained using a Hill–Coleman method for each frequency and it exhibited a peak behavior at about 30 kHz. The voltage dependent profile of R_s was also obtained using a Nicollian and Brews methods.     

Rectifying,giant magnetoresistance,spin-filtering,newgative differential resistance,and switching effects in single-molecule magnet Mn(dmit)2-based molecular device with graphene nanoribbon electrodes

By applying the density functional theory and the nonequilibrium Green’s function formalism, we investigate the spin transport properties of a single-molecule magnet Mn(dmit)₂ sandwiched between two ferromagnetic zigzag-edge graphene nanoribbon electrodes. The results show that the system can present large rectifying, giant magnetoresistance, spin-filtering and negative differential resistance effects with the help of magnetic field modulation. Moreover, an improved switching effect can also be realized by changing the orientation between planes of two dmit ligands. Therefore, the system will provide the possibilities for a multifunctional molecular device design.     

钙钛矿型外延薄膜中两种分解失配位错的HRTEM研究

在（001）LaAlO3上生长钙钛矿型Ba0.3Sr0.7TiO3外延薄膜近界面层,用HRTEM观察到多种新型的分解失配位错,其中两种较复杂的分解失配位错已见报道。本文介绍在该薄膜中观察到的另外两种有趣的分解失配位错。这两种失配位错都分解成两个柏格斯矢量b=（1／2）（110）的不全位错,都与（1／2）（110）层错相伴。这些不全位错对薄膜应变松弛都有贡献,其发生与Ba0.3Sr0.7TiO3薄膜的岛状成核和莫扎克生长有关。     

Si(001)外延ZnSe薄膜界面原子的结合与成键

基于密度泛函理论的第一性原理计算,通过对Si(001)和氮化Si(001)表面单层Zn/Se原子结合的方式,模拟ZnSe外延薄膜的二维生长模式,从单层原子结合能、界面原子电子得失、共价结合成键的角度解释了Zn/Se原子在衬底表面的黏附性问题,阐述了薄膜生长初期界面无定形Se出现等现象,分析了氮化Si(001)表面对薄膜二维均匀生长的作用,结果显示N的引入缓和了Si衬底的非极性共价结合与ZnSe原子间的极性离子键结合之间的异质差异。     

The effect of frequency and temperature on capacitance/conductance–voltage (C/G–V) characteristics of Au/n-GaAs Schottky barrier diodes (SBDs)

The capacitance–voltage (C–V) and conductance–voltage (G/ω–V) characteristics of the Au/n-GaAs Schottky barrier diodes (SBDs) have been investigated for 10, 100 and 500 kHz at 80 and 280 K. To evaluate the reason of non-ideal behavior in C–V and G/ω–V plots, the measured C and G/ω values were corrected by taking into accounts series resistance effect. Experimental results show that the values of C and G/ω were found to be a strong function of interface states (N_ss) at inverse and depletion regions especially at low frequencies, but R_s is effective only at the accumulation region especially at high frequencies. Such behavior of the C and G/ω values may be attributed to an increase in polarization especially at low frequencies and the existence of N_ss or dislocations between metal and semiconductor. It can be concluded that the increase in C and G/ω at low frequencies especially at weak and depletion regions results from the existence of N_ss. The values of doping concentration (N_d) and barrier height (BH) between metal and semiconductor were also obtained from the linear part of high frequency (500 kHz) C⁻² vs. V plots at 80 and 280 K, respectively.     

Epitaxial growth of Dy2O3 thin films on epitaxial Dy-germanide films on Ge(0 0 1) substrates

Ultra-thin films of Dy are grown on Ge(0 0 1) substrates by molecular beam deposition near room temperature and immediately annealed for solid phase epitaxy at higher temperatures, leading to the formation of DyGe_x films. Thin films of Dy₂O₃ are grown on the DyGe_x film on Ge(0 0 1) substrates by molecular beam epitaxy. Streaky reflection high energy electron diffraction (RHEED) patterns reveal that epitaxial DyGe_x films grow on Ge(0 0 1) substrates with flat surfaces. X-ray diffraction (XRD) spectrum suggests the growth of an orthorhombic phase of DyGe_x films with (0 0 1) orientations. After the growth of Dy₂O₃ films, there is a change in RHEED patterns to spotty features, revealing the growth of 3D crystalline islands. XRD spectrum shows the presence of a cubic phase with (1 0 0) and (1 1 1) orientations. Atomic force microscopy image shows that the surface morphology of Dy₂O₃ films is smooth with a root mean square roughness of 10 Å.     

退火工艺对La-Nb共掺杂Bi_4Ti_3O_(12)薄膜结构的影响

采用sol-gel法制备了Si基Bi3.25La0.75Ti2.94Nb0.06O12.03(BLTN)铁电薄膜,研究了退火温度、升温速率和退火时间对BLTN薄膜微观结构的影响。结果表明:制备的BLTN薄膜具有单一的钙钛矿结构,且为随机取向,表面平整致密;退火温度由550℃升高到750℃时,薄膜的衍射峰强度增强,晶粒尺寸由65 nm增大到110 nm;退火升温速率由10℃/min提高为20℃/min时,薄膜的晶化程度降低;退火时间对薄膜的晶相结构影响不大,但时间超过30 min会造成薄膜表面孔洞增多、致密性下降。     

Effect of bottom electrodes on resistance degradation and breakdownof (Ba,Sr)TiO3 thin films

The influence of bottom electrodes (Pt, Ir, Ru) on the degradation of (Ba,Sr)TiO₃ (BST) thin films under dc stress conditions was investigated. The current-time (I-t) and current-voltage (I-V) measurement results indicated that the BST thin films deposited on Ru have faster degradation than those deposited on Pt and Ir. The degradation was considered to be caused by the deterioration of the Schottky-barrier. Under dc stress conditions, the dielectric relaxation current in the BST dielectric films probably enhances the deterioration. The breakdown time was found to be approximated by an exponential function of an electric field [t_B=α exp(-βE)] for dc stress. The value of the exponential factor β for BST deposited on Pt and Ir was about a quarter of that for BST deposited on Ru. The different value of β observed under dc stress indicates that the degradation of BST on Ru would be more serious than on Pt and Ir. The ten years lifetime of time-dependent dielectric breakdown (TDDB) studies indicate that BST on Pt, Ir and Ru have longer lifetime over ten years for operation at the voltage bias of 1 V     

Rapid thermal annealing of cerium dioxide thin films sputtered onto silicon (111) substrates: Influence of heating rate on microstructure and electrical properties

The impact of the heating rate (HR) of a Rapid Thermal Annealing (RTA) on the crystallinity and on the morphology of CeO₂ thin films has been investigated by Raman Spectroscopy (RS), Photoluminescence (PL), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and tapping mode Atomic Force Microscopy (AFM). The electrical properties of CeO₂ thin films have also been studied with the Conductive AFM mode. This paper highlights the importance of the heating rate value used during an RTA on crystalline quality, morphology and on the electrical properties of the CeO₂ layer. In fact, the best crystallinity with a good morphology and a high resistivity has been obtained for a CeO₂ layer sputtered on (111) Si substrate and post-annealed at 1000 °C for 30 s with an HR of 25 °C/s.     

Antimony sulfide (Sb2S3) thin films by pulse electrodeposition: Effect of thermal treatment on structural,optical and electrical properties

Antimony sulfide films have been deposited by pulse electrodeposition on Fluorine doped SnO₂ coated glass substrates from aqueous solutions containing SbCl₃ and Na₂S₂O₃. The crystalline structure of the films was characterized by X-ray diffraction, Raman spectroscopy and TEM analysis. The deposited films were amorphous and upon annealing in nitrogen/sulfur atmosphere at 250 °C for 30 min, the films started to become crystalline with X-ray diffraction pattern matching that of stibnite, Sb₂S₃, (JCPDS 6-0474). AFM images revealed that Sb₂S₃ films have uniformly distributed grains on the surface and the grain agglomeration occurs with annealing. The optical band gap calculated from the transmittance and the reflectance studies were 2.2 and 1.65 eV for as deposited and 300 °C annealed films, respectively. The annealed films were photosensitive and exhibited photo-to-dark current ratio of two orders of magnitude at 1 kW/m² tungsten halogen radiation.     

Effect of series resistance on the electrical characteristics and interface state energy distributions of Sn/p-Si (MS) Schottky diodes

In this study, electrical characteristics of the Sn/p-type Si (MS) Schottky diodes have been investigated by current-voltage (I-V) and capacitance-voltage (C-V) measurements at room temperature. The barrier height obtained from C-V measurement is higher than obtained from I-V measurement and this discrepancy can be explained by introducing a spatial distribution of barrier heights due to barrier height inhomogeneities, which are available at the nanostructure Sn/p-Si interface. A modified Norde’s function combined with conventional forward I-V method was used to extract the parameters including barrier height (Φ_b) and the series resistance (R_S). The barrier height and series resistance obtained from Norde’s function was compared with those from Cheung functions. In addition, the interface-state density (N_SS) as a function of energy distribution (E_SS-E_V) was extracted from the forward-bias I-V measurements by taking into account the bias dependence of the effective barrier height (Φ_b) and series resistance (R_S) for the Schottky diodes. While the interface-state density (N_SS) calculated without taking into account series resistance (R_S) has increased exponentially with bias from 4.235 × 10¹² cm⁻²eV⁻¹ in (E_SS - 0.62) eV to 2.371 × 10¹³ cm⁻²eV⁻¹ in (E_SS - 0.39) eV of p-Si, the N_SS obtained taking into account the series resistance has increased exponentially with bias from of 4.235 × 10¹² to 1.671 × 10¹³ cm⁻²eV⁻¹ in the same interval. This behaviour is attributed to the passivation of the p-doped Si surface with the presence of thin interfacial insulator layer between the metal and semiconductor.     

Physical investigations on (In2S3)x(In2O3)y and In2S3−xSex thin films processed through In2S3 annealing in air and selenide atmosphere

In₂S_3−xSe_x and (In₂S₃)_x(In₂O₃)_y thin films have been prepared on glass substrates using appropriate heat treatments of In evaporated thin films. X-ray analysis shows that In thin films which were annealed under sulfur atmosphere at 350 °C were mainly formed by In₂S₃. A heat treatment of this binary in air at 400 °C during one hour leads to (In₂S₃)_x(In₂O₃)_y ternary material which has a tetragonal structure with a preferred orientation of the crystallites along the (109) direction. Similarly, a heat treatment of In₂S₃ in selenium atmosphere at 350 °C during six hours leads to a new In₂S_3−xSe_x ternary material having tetragonal body centered structure with a preferred orientation of the crystallites along the (109) direction. Optical band gap, refractive index and extinction coefficient values of In₂S_3−xSe_x and (In₂S₃)_x(In₂O₃)_y thin films have been reached. Moreover, correlations between optical conductivity, XRD, AFM and Urbach energy of such ternary thin films have been discussed. Finally, the recorded formation disparity between the quaternary (In₂S₃)_x(In₂O₃)_y and ternary In₂S_3−xSe_x compounds has been discussed in terms of the Simha–Somcynsky and Lattice Compatibility theories.