有机自旋光电子学的基本过程

有机自旋光电子学的研究方向分为磁场效应和自旋注入两个方面.研究表明,外加低磁场能够显著改变非磁性有机半导体材料的光致发光、注入电流、电致发光和光电流.这称为有机半导体材料的磁场效应.近年来,非磁性有机半导体材料的磁场效应引起了广泛的关注和研究兴趣.首先,有机半导体材料的磁场效应是强有力的实验手段,用以研究有机电学、光学和光电器件中电荷传输和激发态中的有用和无用过程,为解决电荷传输和激发态过程中的瓶颈问题提供有效的实验手段,为实现磁-光-电多功能集成提供科学原理,尤其是磁场效应能够为提高能量转换效率、探测和传感光电子学器件的响应频谱范围和灵敏度提供新思路.同时利用磁电极,有机半导体材料和器件中自旋注入及其对电荷传输和激发态过程的调控可以用于发展新型功能化的自旋光电子学器件.本文综述并讨论了有机半导体材料和器件中的磁场效应和自旋注入的光电子学效应.     

有机微纳晶场效应晶体管

有机单晶中分子排列长程有序、无晶界且杂质和缺陷很少,是揭示有机半导体材料本征性能和制备高迁移率器件的最佳选择。因此,有机单晶材料对于构筑高性能电子器件和电路等方面具有无可比拟的优势。同时,有机单晶材料也为揭示半导体材料微观分子堆积与宏观电性能关系提供了重要手段。有机分子间以弱的范德华力相结合,因此,有机半导体单晶多以微纳晶形式存在。目前,种类繁多的有机微纳晶半导体材料被广泛应用于高性能场效应晶体管器件,这些器件的研究不仅可以筛选出高性能的有机半导体材料,也为科研人员提供更多的机会来理解有机半导体中电荷传输的物理内涵。本综述介绍了有机单晶场效应晶体管的基本结构和运行机理;微纳晶制备、表征方法以及器件构筑方法;总结了近三年来有机微纳晶半导体材料与器件取得的最新研究进展;探讨了当前有机微纳晶研究的热点和趋势并分析了面临的挑战。     

自旋阀多层膜的电化学制备及其巨磁电阻效应

采用双槽控电位电沉积法在n-Si(111)基体上以NiFe 薄膜为缓冲层制备了[Ni80Fe20/Cu/Co/Cu]n自旋阀多层膜, 并确定了电沉积的工艺条件. 利用X射线衍射(XRD)表征了自旋阀多层膜的超晶格结构, 研究了NiFe缓冲层对自旋阀生长取向的影响. 采用四探针法研究了各子层厚度对自旋阀巨磁电阻效应的影响, 通过振动样品磁强计(VSM)测试了自旋阀的磁滞回线. 自旋阀的巨磁电阻(GMR)值最初随着铜层厚度的变化并发生周期性振荡, Cu 层厚度为3.6 nm时, GMR 达到最大值,随后逐渐减小. 随着Co层和NiFe 层厚度的增大, GMR 值的变化趋势均为先增大后减小. 当自旋阀的结构为NiFe(25 nm)/[Cu(3.6 nm)/Co(1.2 nm)/Cu(3.6 nm)/NiFe(2.8 nm)]30时, GMR 值可达5.4%, 对应的磁电阻灵敏度(SV)为0.2%·Oe-1, 饱和磁场仅为350 Oe.     

可蒸镀自旋交叉配合物的薄膜与器件

自旋交叉配合物在温度、压力、光照和磁场等刺激下可以发生高低自旋态之间的可逆转变, 通常还伴随着颜色、体积和电导率变化以及热滞等效应, 因此这类材料在光热开关、传感器、显示和存储等领域具有潜在的应用. 由于可以获得高质量的超洁净薄膜, 高真空蒸镀工艺常用于分子电子学与分子磁学等的器件制备, 目前报道的可蒸镀自旋交叉配合物种类较少, 大大限制了自旋交叉配合物的器件应用. 针对可蒸镀自旋交叉配合物的薄膜与器件进行了系统的综述, 介绍了几种主要的适于高真空蒸镀的自旋交叉配合物, 结合不同的表征手段分析了衬底对分子薄膜自旋转变特性的影响, 并针对相关的概念性器件进行了讨论, 最后对自旋交叉配合物在器件应用中存在的难点和未来的发展趋势进行了展望和评述, 希望能够为自旋交叉领域的器件应用提供一些借鉴.     

有机神经形态机器视觉器件及系统

随着有机半导体材料及其器件的快速发展,有机电子学在可穿戴设备、人工智能等发面取得快速发展.有机半导体材料具有成本低、生物相容性好、光谱响应可调、柔性度好等优势,在光电器件等新兴智能感知领域显示出巨大的商业应用潜力,同时也是制造柔性仿生视觉传感器不可或缺的组成部分.本文从有机光电材料分类及用于视觉仿生感知的光电器件层面重点介绍了近年来人工神经形态视觉智能传感系统的研究进展,包括应用较多的视觉触觉多感集成系统.最后阐述了发展有机仿生视觉系统的重要意义与现存挑战以及展望,为将来有机视觉感知应用及多感集成提供可行的研究方向.     

有机发光晶体管的关键材料和器件研究※

有机发光晶体管(organic light-emitting transistor, OLET)是一种变革性的小型化有机光电器件, 其在同一器件中集成了场效应晶体管和发光二极管的两种器件功能, 在材料的基础物性研究、新型柔性显示/照明、有机电泵浦激光以及片上集成光电子器件等方面都具有着重要的研究意义. OLET独特的器件结构及工作模式使其对核心的关键材料和器件制备提出了新的要求, 而高性能OLET器件的构筑需要从材料和器件两个方面同时进行优化与改善. 近五年作者课题组和合作者在全面调研和分析OLET领域整体研究背景和存在基本科学问题基础上, 聚焦于高迁移率发光有机半导体关键材料的开发和高效OLET器件(线光源和面光源发光模式)的构筑两个方面开展了初步的探索性研究, 发展了系列特别是基于蒽和芴的高迁移率发光/激光有机半导体材料, 构筑了高性能的单组分有机单晶OLET器件和新型平面OLET面光源发射显示器件, 为进一步推动OLET及其相关领域发展奠定了重要的材料和器件研究基础.     

自旋电子学-光催化产氢交叉学科研究中的测试表征技术进展

清洁能源的研究和开发为解决化石燃料的日益枯竭问题带来了希望.氢能燃烧热值高,产物零污染,是理想的清洁能源.利用太阳能,通过光催化反应从水中制取氢气,是一条极有发展前景的制氢途径.然而,太阳能光催化制氢的发展受到许多因素的限制,特别是光电子传输过程中的电子-空穴复合及能量损失导致的电子输运效率低以及高的产氢产氧过电位导致水分解过程的势垒增大.自旋电子学的发展,为太阳能光催化制氢中的这些问题提供了解决之道.通过将自旋电子学的思路及原理应用于太阳能光催化制氢,借助自旋输运及电子隧穿可有效提高电子的输运效率,光电子的自旋极化还可降低产氢产氧过电位并抑制副产物的生成.测试表征技术的发展为揭示自旋电子学-太阳能光催化制氢交叉科学的内秉机理做出了重要贡献.然而,目前尚无相关文籍对此类测试表征技术的发展进行总结和评述.考虑到这些测试表征技术在自旋电子学-太阳能光催化制氢交叉科学研究中的重要作用,对它们进行归纳和总结,评述其发展面临的问题与挑战,探索并合理预测其未来的发展方向.     

疏水基底表面可控生长有机单晶阵列用于高性能晶体管

有机场效应晶体管(OFETs)、有机发光二极管等光电器件有望实现低成本柔性光电子应用,但低成本潜力取决于基于溶液法大面积沉积有机半导体单晶(OSSC)阵列的能力.然而,差的表面润湿行为和复杂的流体动力学过程限制了溶液沉积大面积OSSC阵列.本文中,我们通过添加微量的表面活性剂改善了润湿性能和流体干燥动力学,并增强了有机...     

硼氮杂稠环化合物的合成与电子学应用

有机半导体材料的开发为有机电子学的发展提供了材料基础。杂原子的引入进一步丰富了材料的种类和数量。作为CC单元的等电子体,BN单元对有机半导体材料的性能调节受到了科学家们的关注。本文主要介绍了有机共轭体系中BN单键的构筑方法,以及这类硼氮杂稠环分子在有机电子学领域的应用。     

酰胺与酰亚胺类n型有机半导体材料的研究进展

有机半导体材料具有来源丰富、化学结构可裁剪、柔韧性较高、器件制备温度低和塑料衬底兼容性好等优点, 极大地拓展了电子器件的功能与应用. 然而, 电子传输型(n型)有机半导体在分子多样性、载流子迁移率和空气稳定性方面远远落后于空穴传输型(p型)半导体, 从而阻碍了双极晶体管、p-n结和有机互补电路的发展. 酰胺或酰亚胺功能化能显著提高有机材料的电子亲和势, 是构建高性能n型有机半导体的重要策略. 本综述总结了近年来萘二酰亚胺类、苝二酰亚胺类、吡咯并吡咯二酮类、异靛蓝类和其他酰胺/酰亚胺类小分子和聚合物n型有机半导体材料的研究进展, 从分子设计角度出发, 深入讨论了分子结构如何改变分子前线轨道能级、分子间相互作用力、聚集态结构、器件稳定性和电学性能, 最后对其未来的发展方向和面临的挑战进行了展望.     

Formation of radicals during dimethyldioxirane decomposition

Thermal decomposition of dimethyldioxirane is followed by the formation of radicals registered by ESR spectroscopy using aC-phenyl-N-tert-butylnitronc spin trap. The intensity of the ESR signal increases linearly with increasing temperature; the dependence is extreme in character.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1552–1554, June, 1996.     

2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves

2D conductive metal–organic frameworks (2D c‐MOFs) feature promising applications as chemiresistive sensors, electrode materials, electrocatalysts, and electronic devices. However, exploration of the spin‐polarized transport in this emerging materials and development of the relevant spintronics have not yet been implemented. In this work, layer‐by‐layer assembly was applied to fabricate highly crystalline and oriented thin films of a 2D c‐MOF, Cu₃(HHTP)₂, (HHTP: 2,3,6,7,10,11‐hexahydroxytriphenylene), with tunable thicknesses on the La_0.67Sr_0.33MnO₃ (LSMO) ferromagnetic electrode. The magnetoresistance (MR) of the LSMO/Cu₃(HHTP)₂/Co organic spin valves (OSVs) reaches up to 25 % at 10 K. The MR can be retained with good film thickness adaptability varied from 30 to 100 nm and also at high temperatures (up to 200 K). This work demonstrates the first potential applications of 2D c‐MOFs in spintronics.     

Thermo-oxidative degradation of ultrahigh molecular weight poly(ethylene oxide) in volatile organic solvents

The degradation of ultrahigh molecular weight poly(ethylene oxide) (UHMWPEO) was investigated in three volatile organic solvents, methanol, chloroform, and tetrahydrofuran. Particularly, degradation rate was determined by means of Ubbelohde viscometry and degradation products were characterized by using electron spin resonance spectroscopy (ESR) and Fourier transform infrared spectroscopy (FTIR). The highest degradation rate was observed for UHMWPEO in tetrahydrofuran, with the lowest one in methanol. The ESR results showed that PEO-C• and •OH radicals were produced during the degradation process. Among these selected solvents, tetrahydrofuran was found to generate free radicals through an autoxidation mechanism. This would accelerate the degradation of UHMWPEO, resulting in the observed highest degradation rate in the UHMWPEO/tetrahydrofuran solution. Esters were also detected in the degradation products of these UHMWPEO solutions, while formates and formate ions were generated in the solutions of UHMWPEO/tetrahydrofuran and UHMWPEO/cloroform except for PEO/methanol. Furthermore, the degradation mechanism of UHMWPEO was deduced. This work enabled an in-depth understanding on the thermo-oxidative degradation mechanism of UHMWPEO in representative organic solvents, which would be instructive for developing optimal solution-based processing technique of UHMWPEO.     

ESR study of the molecular orientation and dynamics of stable organic radicals included in the 1‐D organic nanochannels of 2,4,6‐tris‐4‐(chlorophenoxy)‐1,3,5‐triazine

The molecular orientation and dynamics of the organic stable radicals such as 2,2,6,6‐tetramethyl‐1‐piperidinyl‐1‐oxyl (TEMPO) or 4‐hydroxy‐TEMPO (TEMPOL) included in the one‐dimensional (1‐D) organic nanochannels of 2,4,6‐tris‐4‐(chlorophenoxy)‐1,3,5‐triazine (CLPOT) were investigated by examining the inclusion compounds (ICs) diluted by the co‐inclusion of non‐radicals using ESR spectroscopy. Spectral simulation showed that the axial rotation of TEMPO or TEMPOL molecules is excited in the nanochannels with activation energies of 8 and 7 kJ mol^?1, respectively. The rotation axis was estimated to be tilted towards the principal x direction in the axis system of the g ‐tensor of the respective radicals. This is quite different from that for similar ICs in the nanochannels of tris(o‐phenylenedioxy)cyclotriphosphazene (TPP), in which the radicals are axially rotating around the principal axis y of the g‐tensor. The difference is attributed to the larger nanospace of the CLPOT nanochannels. Copyright © 2012 John Wiley & Sons, Ltd.     

Halogen Bonding between an Isoindoline Nitroxide and 1,4‐Diiodotetrafluorobenzene: New Tools and Tectons for Self‐Assembling Organic Spin Systems

Radical assembly : Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which N? O^.???I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems.

     

Hybrid polystyrene based electrospun fibers with spin‐crossover properties

We have succeeded in the preparation of electrospun fibers of polystyrene incorporating a metallo‐organic polymer of [Fe (II) (4‐octadecyl‐1,2,4‐triazole)₃(ClO₄)₂]n. The obtained fibers have diameters in the range 2–4 µm and show the characteristic spin‐crossover transition associated with the metallo‐organic polymer. The structure of both, polystyrene and the metallo‐organic polymer, in the fibers was also studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 814–821     

Photo‐ and Electronically Switchable Spin‐Crossover Iron(II) Metal–Organic Frameworks Based on a Tetrathiafulvalene Ligand

A major challenge is the development of multifunctional metal–organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4‐pyridyl)tetrathiafulvalene (TTF(py)₄) and spin‐crossover Fe^II centers. The materials exhibit redox activity, in addition to thermally and photo‐induced spin crossover (SCO). A crystal‐to‐crystal transformation induced by I₂ doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo‐magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest‐induced redox‐state switching.     

Charge‐induced modulation of magnetic interactions in a [2 × 2] metal‐organic grid complex

We investigate the magnetic state of a recently synthesized [2 × 2]‐metal‐organic grid complex as a function of its redox state. Our analysis of a phenomenological model for the relevant molecular orbitals reveals that additional electrons on the ligands can couple their spins via the bridging metal sites. We find that at certain stages of the reduction of the complex cation, a maximal total spin ground state of the complex (S = 3/2) can be stabilized by the Nagaoka mechanism. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Thermochromic Meltable Materials with Reverse Spin Transition Controlled by Chemical Design

We report a series of meltable Fe^II complexes, which, depending on the length of aliphatic chains, display abrupt forward low-spin to high-spin transition or unprecedented melting-triggered reverse high-spin to low-spin transition on temperature rise. The reverse spin transition is perfectly reproducible on thermal cycling and the obtained materials are easily processable in the form of thin film owing to their soft-matter nature. We found that the discovered approach represents a potentially generalizable new avenue to control both the location in temperature and the direction of the spin transition in meltable compounds.     

无自旋混杂的耦簇理论

本文用APCCSD(T)，自旋投影方法消除CCSD中的自旋混杂，自旋投影算符^P用自旋湮灭算符^As 1和^As 2的乘积近似表出，提高了计算精度。