无机固体材料中的忆阻效应

缺陷调控是固体化学中的基本问题,也是决定材料性能的核心要素。基于缺陷调控的忆阻效应将给未来电子信息领域带来全新的变革。本文综述了无机固体材料中忆阻效应的研究进展,主要总结了忆阻效应的产生机制和忆阻材料的类型,结合原子级p-n结的相关工作,提出深入明确电场下缺陷迁移机制将是从无机固体化学角度研究忆阻效应的重要方向。     

基于氧化铟锡电极的透明忆阻器件工作机制研究进展

随着电子技术的发展,兼具透明、柔性等特性的功能电子器件得到了广泛关注。作为新型电子存储器件,忆阻器在新一代信息技术领域(包括低功耗类脑计算、非易失逻辑、数据存储等)有着广阔的应用前景,成为近年来备受关注的新型纳米器件。氧化铟锡是一种常用的透明导电材料,因其优异的光学透明度、稳定的物理、化学特性等优点,成为制备新型透明忆阻器件的理想电极。本文首先简略介绍了忆阻器件的结构,接着综述了基于氧化铟锡材料的忆阻器件的研究和应用,包括其作为存储器、电子突触和痛觉感受器等。然后针对氧化铟锡忆阻器的阻变机制,特别是近年来新发现的铟扩散机制进行了进一步介绍,最后总结展望了氧化铟锡忆阻器的发展前景。     

稀土基氧化物忆阻器的研究进展

忆阻器是一种将电荷和磁通量关联起来的电路学基本元器件，在量纲上它与电阻相同，表现为随电压电流变换的非线性电阻变换行为。作为一种新型的非易失性存储器件，忆阻器具有结构简单、存储密度高和能够模拟生物神经突触等特性。因其独特的“记忆特性”，在阻变存储器、人工神经网络和非线性运算电路设计等领域被广泛的研究。其中，稀土基氧化物忆阻器因其更加稳定的性能和多元的应用前景，成为忆阻器研究关注的热门材料。但目前对于稀土氧化物材料，尤其对重稀土元素并没有较为全面的总结和归纳。因此，文章从忆阻器的结构、组成和电阻转换机理进行了论述。以元素为分类标准，系统地梳理从Y元素到Lu元素，国内外每种稀土氧化物以及稀土掺杂氧化物忆阻器在阻变存储器，人工神经网络等方面应用的重点工作。最后，对目前稀土基忆阻器研究遇到的问题和挑战进行了分析，总结了稀土基氧化物忆阻器优缺点，提出了目前可行的方法，并展望了发展趋势和应用潜力。     

高分子忆阻材料的设计、制备和神经突触仿生研究进展

自从1971年加州大学伯克利分校电子理论家蔡少棠教授提出忆阻器(又称"记忆电阻",第四种电路元件)假设后,引起了材料科学家和固体物理学家的极大的研究兴趣。作为一种在计算机数据存储和神经运行领域具有广泛潜在应用价值的非线性动态电子器件,其影响可以追溯到发明电阻器、电容器、电感器之前。与生物大脑的神经突触类似,忆阻器兼具记忆和逻辑运算的功能。本文综述了近年来高分子忆阻材料的合成和生物神经突触模拟研究进展。利用不同的前、后突触刺激可以模拟神经突触展现的一些诸如短期/长期可塑性(STP/LTP)、尖峰时间相关的可塑性(STDP)、穗率相关塑性(SRDP)和"学习-记忆-遗忘"等基本功能。大量研究结果已经表明:材料体系的电荷转移与传输、分子间弱相互作用、材料分子结构、聚集态结构、薄膜微结构和电输运特性等因素对材料忆阻效应有显著影响。     

新型Ti3C2 MXene的化学制备及基于MXene忆阻器特性与机理

阻变器件是一种微电子器件,具有阻值可在两个甚至两个以上的阻态之间重复变化的特点。忆阻器作为新型的阻变器件,具有可连续变化的丰富阻态。近年来因其具备简单的二端结构、高集成度以及低工作电压等特性,在新型非易失性存储以及构建神经形态系统等方面被广泛研究。但其在实现应用的过程中仍存在着稳定性较差等问题。近期一些工作证明了二维材料如氧化石墨烯在优化忆阻器性能方面具备良好的应用潜力。MXene是一种具备类似石墨烯结构的新型二维过渡金属碳/氮化物,因其具备二维层状结构显现出特殊的力学以及电学特性,有望应用于忆阻器中以提高器件的电学性能。在本文中,我们通过化学湿法刻蚀制备了Ti₃C₂粉末,通过旋涂工艺在忆阻器结构中引入Ti₃C₂薄膜。Ti₃C₂ MXene与SiO₂同时作为忆阻器阻变层,制备了Cu/Ti₃C₂/SiO₂/W结构的忆阻器,并且对其相关电学特性进行了探究。在该器件上,通过实验测得忆阻器典型的开关特性曲线并在双向直流电压下针对高、低阻态的可重复性、稳定性进行了实验。结果表明该器件能够在100个扫描循环过程中保持稳定的高、低阻态达到10⁴ s以上。同时,该器件状态能够受脉冲电压调节,实现突触间典型的双脉冲易化行为。实验结果表明基于Ti₃C₂ MXene的忆阻器将有望应用于构建新兴存储设备以及人工神经形态系统。     

基于Cu2S电阻开关器件的光电记忆效应

硫化亚铜由于其独特的电和光学特性，被广泛应用于电阻开关存储和光伏器件.本文通过脉冲激光沉积/化学气相沉积两步法合成Cu₂S薄膜，该膜由纳米颗粒构成，结晶度高，在近红外区有较好的光吸收特性.蒸镀铜电极构成Cu/Cu₂S/P-Si结构忆阻器件后，器件表现出电子型双极阻变行为，其阻变机制由空间电荷限制电流和肖特基发射机制协同主导.此外，还探究了光对器件阻变行为的响应及机理.结果表明，在光照下，最大电流响应增加至暗态时的5倍.分析认为，光照使Cu/Cu₂S界面处的肖特基势垒减小，在高阻态下，阻变机制由肖特基发射机制转变为空间电荷限制电流机制，并使器件电导率增加.本工作为Cu₂S基光电协同响应忆阻器的研发提供了新思路.     

溶胶凝胶法制备TiO2@Cf柔性忆阻器交叉开关

以碳纤维作为柔性衬底和电极材料,通过溶胶凝胶法在其表面镀覆TiO₂阻变活性层,进而通过“十”字搭接制备成柔性纤维忆阻器（TiO₂@C_f）。采用X射线衍射、扫描电子显微镜、X射线光电子能谱等测试手段对TiO₂@C_f结构进行表征并对其忆阻特性及阻变机理进行研究。结果表明：碳纤维上的TiO₂涂层为锐钛矿型晶体结构,其氧空位的浓度约为19.5%;制备的TiO 2@C_f柔性忆阻器为突变型忆阻器,其高低阻态阻值开关比可达10⁴;经过疲劳耐受性测试,忆阻器件的高低阻态开关比稳定在2个数量级左右。TiO₂@C_f忆阻器的机理表现为：在高阻态和低阻态时是以欧姆导电为主导的载流子输运机制,其阻态转变机制与氧空位导电细丝的形成和断裂有关。制备的TiO₂@C_f柔性忆阻器在一定程度上具有柔性弯曲变形,同时满足可编织、穿戴等功能。     

共价有机框架薄膜的界面生长策略及其在忆阻器中的研究进展

随着大数据和物联网时代数字通信技术的飞速发展,忆阻器在高密度数据存储技术和神经形态计算等应用中扮演着越来越重要的角色.得益于共价有机框架(COF)材料优异的可设计性及独特的光电特性,同时,伴随着液体界面辅助的制备策略不断发展与完善, COF材料在存储器件中的应用得到了极大推广.为了开发更高性能的基于COF材料的存储器件,需要全面地了解从材料设计、制备到器件应用的不断发展.因此,本综述系统地总结了COF薄膜的制备策略及其在忆阻器中应用的进展.最后,我们对基于COF存储器件的当前挑战及未来发展进行了总结与展望.     

无机固体功能材料的水热合成化学

综述了无机固体功能材料的水热合成化学进展。重点强调强关联系固体、无机-有机杂化材料、缺陷与混合价态固体、三重价态与原子尺度p-n结以及水热生物化学。     

第二届全国无机固体化学和合成化学学术会议通知

中国化学会无机专业委员会拟定于1988年7月4日至了月9日在合肥中国科学技术大学召开第二届个国无机固体化学和合成化学会议。1.征文内容:缺陷化学、固相反应、固体表面和界面化学、固相中的扩散、无机固体新材料、复合金属氧化物、极端条件下的无机合成。固体化学中的制备方法、固态初质的分析和表征等。2.将论文详细摘要(1500字左右)一式二份寄北京大学化学系苏勉曾、或合肥中国科技大学材料系     

Advances in Ordered Architecture Design of Composite Solid Electrolytes for Solid-State Lithium Batteries

Solid electrolyte lithium batteries are the next generation of advanced energy devices. The incorporation of solid electrolytes can significantly improve the safety issue of lithium-ion batteries. Organic-inorganic composite solid electrolytes (CSE) are promising candidates for solid-state batteries, but their application is mainly limited by low ionic conductivity. Many studies have shown that the architecture of ordered inorganic fillers in CSE can act as fast lithium-ion transfer channels by auxiliary means, thus significantly improving the ionic conductivities. This review summarises the recent advances in CSE with different dimensional inorganic fillers. Various effective strategies for the construction of ordered structures in CSE are then presented. The review concludes with an outlook on the future development of CSE. This review aims to provide researchers with an in-depth understanding of how to achieve ordered architectures in CSE for advanced solid state lithium batteries.     

Role of self-assembly in construction of inorganic nanostructural materials

Understanding the evolution process and formation mechanism of nanoscale structures is crucial to controllable synthesis of inorganic nanomaterials with well-defined geometries and unique functionalities. In addition to the conventional Ostwald ripening process, oriented aggregation has been recently found to be prevalent in nanocrystal growth. In this new mechanism, primary small nanocrystals firstly spontaneously aggregate in the manner of oriented attachment, and then the large crystalline materials are formed via the process of interparticle recrystallization. Furthermore, controllable fabrication of the ordered nanocrystal solid materials that has shown specific collective properties will promote the application of inorganic nanocrystal in devices. Therefore, investigation of the mechanism of oriented aggregation is essential to controllable synthesis of nanocrystals and ordered nanocrystal solid materials. In this review, we summarize recent advances in the preparation of nanocrystal materials, which are mostly focused on our work about the role of self-assembly in construction of inorganic nanostructural materials.     

Solid state 17O NMR-an introduction to the background principles and applications to inorganic materials

Oxygen is a key chemical element and solid state NMR can provide unique insight into the its local environment. In the last decade there have been significant advances (sensitivity, resolution) in the NMR methodology for non-integer spin quadrupole nuclei such as oxygen and the background to these techniques is presented in this tutorial review. The information that the NMR parameters can provide about the local environment is explained through a series of illustrations from different areas of solid state chemistry and structural science of inorganic materials.     

Crystal Chemistry of Ternary and Quaternary Transition Metal Nitrides

Nitrides are fascinating materials. Although the air we breathe is 78% nitrogen, essentially 100% of the land we walk upon are made of oxides. It would take an encyclopaedia to review oxide crystal chemistry, on the other hand we can present here a comprehensive review of ternary and quaternary solid state nitrides. In the ternary and quaternary solid state nitrides (IA,IIA)-M-N, unusual low valence M⁺ were found for copper, nickel, cobalt, iron and manganese, and various MN_n transition metal-nitrogen coordination polyhedra with CN=2(linear), 3(trigonal-planar), 4(tetrahedral and square planar), 5(square pyramidal), and 6(octahedral and trigonal prismatic) and different fashions of connection make nitrides an important family of inorganic solid state materials. A suitable classification is made on the basis of the correlation between coordination numbers (CN), the connection fashions and oxidation states of the anionic principal structures.     

New approach to evaluation of the stress-strain properties of nanolayers of solid materials

The review focuses on results obtained in the development of a new approach to determination of the stress-strain properties (tensile strength, yield point, plastic deformation under uniaxial stretching) of nanolayers of solid materials. The approach is based on analysis of parameters of the microrelief generated by strains in polymer films with hard thin coatings. A significant increase in the tensile strength and ductility of noble metal coatings under uniaxial stretching at the metal layer thickness less than 30 nm is demonstrated for the first time. This substantiates the assumption of a specific state of nanolayers of solid materials. The developed method also enables evaluation of the effect of characteristic defects in solids on their stress-strain behavior. It was found that the stress-strain properties of nanocoatings depend on the physical state of the polymer substrate. A possible mechanism of the revealed phenomena is suggested.     

Calixarene/pillararene-based supramolecular selective binding and molecular assembly

This review mainly summarized the recent researches on the supramolecular selective binding and molecular assembly based on calixarene and pillararene. Several representative examples were provided to expound the progress in the area of recognition and sensing, multi-functional assembly and crosslinked multi-dimensional materials.     

Molecular manipulation of solid state structure: influences of organic components on vanadium oxide architectures

Among the inorganic materials enjoying widespread contemporary interest, the metal oxide based solid phases occupy a prominent position by virtue of their applications to catalysis, sorption, molecular electronics, energy storage, optical materials and ceramics. The diversity of properties associated with these materials reflects the chemical composition, which allows variations in covalency, geometry and oxidation states, and the crystalline architecture, which may provide different pore structures, coordination sites, or juxtapositions of functional groups. Despite such fundamental and practical significance, the design of the structure of such materials remains a challenge in solid state chemistry. While organic materials have been synthesized which self-assemble into ordered arrays at low temperature and which exhibit molecular recognition and biomimetic activity, the ability to synthesize inorganic materials by rational design remains elusive. Small, soluble molecular building blocks with well-defined reaction chemistries which allow their low-temperature assembly into crystalline solid state inorganic materials are not well known. However, the existence of naturally occurring, structurally complex minerals establishes that hydrothermal synthesis can provide a low temperature pathway to produce open-framework and layered metastable structures utilizing inorganic starting materials. Thus, hydrothermal conditions have been used to prepare microporous tetrahedral framework solids that are capable of shape-selective absorption, like zeolites and aluminophosphates, and more recently in the preparation of complex solid arrays of the M/O/PO³⁻₄ and M/O/RPO²⁻₃ systems (M=V and Mo). The hydrothermal technique may be combined with the introduction of organic components which may act as charge compensating groups, space-filling units, structure directing agents, templates, tethers between functional groups, or conventional ligands in the preparation of inorganic/organic composites.In the past decade, this general strategy has been exploited in the evolution of a family of vanadium oxides incorporating structure-directing organic or secondary-metal organic subunits, which are the topic of this review. The synthetic approach to novel vanadium oxide solids occupies the interface between materials science and coordination chemistry. The emerging theme focuses on the association of an organic component, acting as a ligand, tether, or structure directing moiety, with the inorganic framework of the solid to provide unique composites. While some organic components may limit the size of inorganic cluster subunits of a solid by passivating the surface of an aggregate through capping, such ligands may also serve to link inorganic subunits into complex networks. In other cases, the organic subunit, rather than participating as a covalently bound unit of the framework, acts in a structure directing role, producing amphiphilic materials whose structures are determined by hydrophobic–hydrophilic interactions. This latter feature is reminiscent of the factors influencing biomineralization, a field which may prove relevant to the development of new strategies for the controlled synthesis of organized inorganic and organic/inorganic composite materials. These various approaches to the “design” of inorganic solids are discussed and assessed in terms of the new structural types recently observed in the vanadium oxide chemistry.     

Solid-state polymerization of butadienes. Polymerization of salts of 6-amino-2,4-trans,trans-hexadienoic acid

The polymerization of 6-amino-2,4-trans,trans-hexadienoic acid and various of its salts was studied in the solid state. Crystals of the hydrochloride and organic inorganic double halides with cadmium chloride, manganese (II) chloride, and iron(II) chloride were found to polymerize rapidly upon UV or γ irradiation. An erythro-diisotactic polymer is obtained in the form of extended chain crystals. The polymer behaves as an amphoteric polyelectrolyte. The kinetics and the mechanism of the polymerization as well as morphological changes during the solid state reaction are discussed.