Direct Observation of Oxygen Ion Dynamics in a WO3-x based Second-Order Memristor with Dendritic Integration Functions

Direct observation of oxygen dynamics in an oxide-based second-order memristor can provide the valid evidence to clarify the memristive mechanism, however, which is still limited for now. In this study, the migration and diffusion of oxygen ions in the region of Pt/WO_3-x Schottky interface are observed in the WO_3-x second-order memristor by using the technique of in situ transmission electron microscopy (TEM) and the electron energy loss spectroscopy. Interestingly, the coexistence of memristive and memcapacitive switching can be implemented in this memristor. Combined with the analysis of depth-profile X-ray photoelectron spectroscopy (XPS), an interface-barrier-modulation second-order memristive model is proposed based on the above results. Notably, temporally correlative oxygen dynamics in the memristor offers the platform to integrate signals from multiple inputs, enabling the realization of the dendritic functions of synchronous and asynchronous integration for the application of logic operations with fault-tolerance capability and associative learning. These findings provide the experimental evidence to in-depth understanding of oxygen dynamics and switching mechanism in second-order memristor, which can support the optimization of memristive performance and the achievement of biorealistic synaptic functions.     

Blocking of Conducting Channels Widens Window for Ferroelectric Resistive Switching in Interface‐Engineered Hf0.5Zr0.5O2 Tunnel Devices

Films of Hf_0.5Z_0.5O₂ (HZO) contain a network of grain boundaries. In (111) HZO epitaxial films on (001) SrTiO₃, for instance, twinned orthorhombic (o‐HZO) ferroelectric crystallites coexist with grain boundaries between o‐HZO and a residual paraelectric monoclinic (m‐HZO) phase. These grain boundaries contribute to the resistive switching response in addition to the genuine ferroelectric polarization switching and have detrimental effects on device performance. Here, it is shown that, by using suitable nanometric capping layer deposited on HZO film, a radical improvement of the operation window of the tunnel device can be achieved. Crystalline SrTiO₃ and amorphous AlO_x are explored as capping layers. It is observed that these layers conformally coat the HZO surface and allow to increase the yield and homogeneity of ferroelectric junctions while strengthening endurance. Data show that the capping layers block ionic‐like transport channels across grain boundaries. It is suggested that they act as oxygen suppliers to the oxygen‐getters grain boundaries in HZO. In this scenario it could be envisaged that these and other oxides could also be explored and tested for fully compatible CMOS technologies.     

One‐Pot Synthesis of Framework Porphyrin Materials and Their Applications in Bifunctional Oxygen Electrocatalysis

Organic framework materials constructed by covalently linking organic building blocks into framework structures are highly regarded as paragons to precisely control the material structure at the atomic level. Herein, a direct synthesis methodology is proposed as a guidance for the bulk synthesis of organic framework materials. Framework porphyrin (POF) materials are one‐pot synthesized to demonstrate the advances of the direct synthesis methodology. The as‐synthesized POF materials are intrinsically 2D and exhibit impressive versatility in composition, structure, morphology, and function, delivering a free‐standing POF film, hybrids of POF and nanocarbon, and cobalt‐coordinated POF. When applied as electrocatalysts for oxygen reduction reaction and oxygen evolution reaction, the cobalt‐coordinated POF exhibits excellent bifunctional electrocatalytic performances comparable with noble‐metal‐based electrocatalysts. The direct synthesis methodology and resultant POF materials demonstrate the ability of controlling materials at the atomic level for energy electrocatalysis.     

Opportunities and Challenges in Precise Synthesis of Transition Metal Single-Atom Supported by 2D Materials as Catalysts toward Oxygen Reduction Reaction

Transition metal single-atom catalysts (SACs) are currently a hot area of research in the field of electrocatalytic oxygen reduction reaction (ORR). In this review, the recent advances in transition metal single-atom supported by 2D materials as catalysts for ORR with high performance are reported. Due to their large surface area, uniformly exposed lattice plane, and adjustable electronic state, 2D materials are ideal supporting materials for exploring ORR active sites and surface reactions. The rational design principles and synthetic strategies of transition metal SACs supported by 2D materials are systematically introduced while the identification of active sites, their possible catalytic mechanisms as well as the perspectives on the future of transition metal SACs supported by 2D materials for ORR applications are discussed. Finally, according to the current development trend of ORR catalysts, the future opportunities and challenges of transition metal SACs supported by 2D materials are summarized.     

Oxygen Vacancies and Ordering of d‐levels Control Voltage Suppression in Oxide Cathodes: the Case of Spinel LiNi0.5Mn1.5O4‐δ

This study presents a microscopic model for the correlation between the concentration of oxygen vacancies and voltage suppression in high voltage spinel cathodes for Li‐ion batteries. Using first principles simulations, it is shown that neutral oxygen vacancies in LiNi_0.5Mn_1.5O_4‐δ promote substitutional Ni/Mn disorder and the formation of Ni‐rich and Ni‐poor regions. The former trap oxygen vacancies, while the latter trap electrons associated with these vacancies. This leads to the creation of deep and shallow Mn³⁺ states and affects the stability of the lattice Li ions. Together, these two factors result in a characteristic profile of the voltage dependence on Li content. This insight provides guidance for mitigating the voltage suppression in LiNi_0.5Mn_1.5O₄ and other cathodes.     

ACO结合P2P信任模型的无线传感器网络Sinkhole攻击检测

针对无线传感器网络中的Sinkhole攻击问题,提出了一种基于蚁群优化(ACO)结合P2P信任模型的Sinkhole攻击检测(P-ACO)算法.首先,使用蚁群优化算法检测路由中是否存在Sinkhole攻击,并生成传感器节点的警报信息;然后,利用布尔表达式进化标记生成算法为群组警报节点分发密钥,并使用密钥标记可疑节点;最后,计算可疑节点列表中各节点的信任值,将信任值低于预设阈值的节点视为攻击节点.分析表明,相比二分查找算法与基于规则匹配的神经网络(RMNN)算法,该算法在匹配过程中需要更少的匹配搜索次数,提高了算法执行效率.实验结果显示,相比RMNN算法,该算法可以更加准确地检测Sinkhole攻击.