Patterning organic single-crystal transistor arrays

Field-effect transistors made of organic single crystals are ideal for studying the charge transport characteristics of organic semiconductor materials. Their outstanding device performance, relative to that of transistors made of organic thin films, makes them also attractive candidates for electronic applications such as active matrix displays and sensor arrays. These applications require minimal cross-talk between neighbouring devices. In the case of thin film systems, simple patterning of the active semiconductor layer minimizes cross-talk. But when using organic single crystals, the only approach currently available for creating arrays of separate devices is manual selection and placing of individual crystals-a process prohibitive for producing devices at high density and with reasonable throughput. In contrast, inorganic crystals have been grown in extended arrays, and efficient and large-area fabrication of silicon crystalline islands with high mobilities for electronic applications has been reported. Here we describe a method for effectively fabricating large arrays of single crystals of a wide range of organic semiconductor materials directly onto transistor source-drain electrodes. We find that film domains of octadecyltriethoxysilane microcontact-printed onto either clean Si/SiO(2) surfaces or flexible plastic provide control over the nucleation of vapour-grown organic single crystals. This allows us to fabricate large arrays of high-performance organic single-crystal field-effect transistors with mobilities as high as 2.4 cm(2) V(-1) s(-1) and on/off ratios greater than 10(7), and devices on flexible substrates that retain their performance after significant bending. These results suggest that our fabrication approach constitutes a promising step that might ultimately allow us to utilize high-performance organic single-crystal field-effect transistors for large-area electronics applications.     

Increasing the conductivity of crystalline polymer electrolytes

Polymer electrolytes consist of salts dissolved in polymers (for example, polyethylene oxide, PEO), and represent a unique class of solid coordination compounds. They have potential applications in a diverse range of all-solid-state devices, such as rechargeable lithium batteries, flexible electrochromic displays and smart windows. For 30 years, attention was focused on amorphous polymer electrolytes in the belief that crystalline polymer:salt complexes were insulators. This view has been overturned recently by demonstrating ionic conductivity in the crystalline complexes PEO6:LiXF6 (X = P, As, Sb); however, the conductivities were relatively low. Here we demonstrate an increase of 1.5 orders of magnitude in the conductivity of these materials by replacing a small proportion of the XF6- anions in the crystal structure with isovalent N(SO2CF3)2- ions. We suggest that the larger and more irregularly shaped anions disrupt the potential around the Li+ ions, thus enhancing the ionic conductivity in a manner somewhat analogous to the AgBr(1-x)I(x) ionic conductors. The demonstration that doping strategies can enhance the conductivity of crystalline polymer electrolytes represents a significant advance towards the technological exploitation of such materials.     

Rapid and reversible shape changes of molecular crystals on photoirradiation

The development of actuators based on materials that reversibly change shape and/or size in response to external stimuli has attracted interest for some time. A particularly intriguing possibility is offered by light-responsive materials, which allow remote operation without the need for direct contact to the actuator. The photo-response of these materials is based on the photoisomerization of constituent molecules (typically trans-cis isomerization of azobenzene chromophores), which gives rise to molecular motions and thereby deforms the bulk material. This effect has been used to create light-deformable polymer films and gels, but the response of these systems is relatively slow. Here we report that molecular crystals based on diarylethene chromophores and with sizes ranging from 10 to 100 micrometres exhibit rapid and reversible macroscopic changes in shape and size induced by ultraviolet and visible light. We find that on exposure to ultraviolet light, a single crystal of 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene changes from a square shape to a lozenge shape, whereas a rectangular single crystal of 1,2-bis(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene contracts by about 5-7 per cent. The deformed crystals are thermally stable, and switch back to their original state on irradiation with visible light. We find that our crystals respond in about 25 microseconds (that is, about five orders of magnitude faster than the response time of the azobenzene-based polymer systems) and that they can move microscopic objects, making them promising materials for possible light-driven actuator applications.     

Rapid growth of ZnO hexagonal tubes by direct microwave heating

Zinc oxide hexagonal tubular crystals were synthesized by direct microwave heating from ZnO powders within 5 min without any metal catalysts or transport agents. ZnO source materials were evaporated from the high-temperature zone in an enclosure, and crystals were grown on the self-source substrate in an appropriate condition. The ZnO vapor formed in the high-temperature zone can deposit and grow on the powders located in the low-temperature zone to form crystals. The scanning electron microscopy (SEM) reveals that these products are hexagonal tube crystals with 80 μm in diameter and 250 μm in length, having a well faceted end and side surface. A possible growth mechanism and the influence of reaction temperature on the formation of crystalline ZnO hexagonal tubes were presented. The photoluminescence (PL) exhibits strong ultraviolet emission at room temperature, indicating the potential applications in short-wave light-emitting photonic devices.     

Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals

Polar liquid crystalline materials can be used in optical and electronic applications, and recent interest has turned to formation strategies that exploit the shape of polar molecules and their interactions to direct molecular alignment. For example, banana-shaped molecules align their molecular bent within smectic layers, whereas conical molecules should form polar columnar assemblies. However, the flatness of the conical molecules used until now and their ability to flip have limited the success of this approach to making polar liquid crystalline materials. Here we show that the attachment of five aromatic groups to one pentagon of a C(60) fullerene molecule yields deeply conical molecules that stack into polar columnar assemblies. The stacking is driven by attractive interactions between the spherical fullerene moiety and the hollow cone formed by the five aromatic side groups of a neighbouring molecule in the same column. This packing pattern is maintained when we extend the aromatic groups by attaching flexible aliphatic chains, which yields compounds with thermotropic and lyotropic liquid crystalline properties. In contrast, the previously reported fullerene-containing liquid crystals all exhibit thermotropic properties only, and none of them contains the fullerene moiety as a functional part of its mesogen units. Our design strategy should be applicable to other molecules and yield a range of new polar liquid crystalline materials.     

稀土晶体材料与应用

稀土是我国重要的战略资源,在永磁体、合金、催化剂、石油精炼、精细抛光、发光材料、玻璃陶瓷等高新技术领域具有重要的应用。稀土晶体是一类重要的高端光学材料,是指稀土元素可以完整占据结晶学结构中某一格点的晶体,作为核心工作物质在激光技术与电离辐射探测技术中得到了广泛应用。以稀土激光晶体、稀土闪烁晶体、稀土倍频晶体、稀土单晶光纤为代表,综述了近年来面向不同应用领域的高端稀土晶体材料在组成设计与性能优化方面的研究进展。在生长技术方面,结晶生长的化学键合理论能够为多尺度稀土晶体生长提供精细化的关键因素控制技术,有利于获得高品质稀土晶体材料。     

A titanosilicate molecular sieve with adjustable pores for size-selective adsorption of molecules

Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.     

低腐蚀隧道密度压电石英晶体

小型化高频器件的发展 ,需要一些低隧道密度压电石英晶体 .本文分析了低隧道密度石英晶体的特点 ,用水热法生长了低隧道密度石英晶体 .报道了生长这种晶体的工艺条件 ,对产品的性能进行了测试 .讨论了工艺和技术条件对产品质量的影响 .     

A robust DNA mechanical device controlled by hybridization topology.

Controlled mechanical movement in molecular-scale devices has been realized in a variety of systems-catenanes and rotaxanes, chiroptical molecular switches, molecular ratchets and DNA-by exploiting conformational changes triggered by changes in redox potential or temperature, reversible binding of small molecules or ions, or irradiation. The incorporation of such devices into arrays could in principle lead to complex structural states suitable for nanorobotic applications, provided that individual devices can be addressed separately. But because the triggers commonly used tend to act equally on all the devices that are present, they will need to be localized very tightly. This could be readily achieved with devices that are controlled individually by separate and device-specific reagents. A trigger mechanism that allows such specific control is the reversible binding of DNA strands, thereby 'fuelling' conformational changes in a DNA machine. Here we improve upon the initial prototype system that uses this mechanism but generates by-products, by demonstrating a robust sequence-dependent rotary DNA device operating in a four-step cycle. We show that DNA strands control and fuel our device cycle by inducing the interconversion between two robust topological motifs, paranemic crossover (PX) DNA and its topoisomer JX2 DNA, in which one strand end is rotated relative to the other by 180 degrees. We expect that a wide range of analogous yet distinct rotary devices can be created by changing the control strands and the device sequences to which they bind.     

Co2+: CaAl2S4吸收光谱的理论解释

MgAl2Sd，CaAl2S4，CO^2 MgAl2S4和Co^2 CaAl2S4晶体是典型的三重复合半导体材料，由化学输运反应的方法可以成功制备而得出，具有宽的能隙结构，因而在光电方面有着非常重要的应用而备受广泛的关注．采用Sugano-Tallabe强场近似理论，引入平均共价因子Ⅳ，利用经典晶场能量矩阵公式，在D2对称模型下计算出的结果较好符合了实验事实，从而纠正了S．K．Oh等人对Co^2 ：CaAl2S4吸收光谱的不合理解释。     

液晶聚合物分子排列调控的研究进展

液晶的应用不仅仅局限于电视或电脑,具有光响应性的液晶在许多领域都存在应用,如平板显示、光学领域、光驱动设备以及许多正在发展的微科技领域. 液晶作为一种中间相的物质,既表现出了液体的流动性,又具有晶态的分子规整排列的性质. 液晶软物质材料具有许多有趣的性质,如自组装性质;长程有序的流动性;分子协同作用;双折射性质和物理性质（光、力、和电）的各向异性;外场诱导的表面分子取向;以及液晶弹性体的刺激响应性形变. 文中综述了具有不同液晶分子取向排列的液晶聚合物的刺激响应性形变,着重介绍了光取向技术诱导液晶分子取向的液晶聚合物的刺激响应性形变行为,并展望了未来液晶材料的设计在微流体和微型机器人领域的潜在应用.     

胆甾相液晶光学性质的研究

胆甾相液晶具有特殊的光学性质,因此在液晶显示和光电子器件方面有特殊的应用.实验制备出稳定的平面态和焦锥态织构样品,用偏光显微镜观察织构并拍摄了各个织构的照片.研究发现,大晶畴焦锥态样品也有比较好的透光性,可作为光延迟器件使用,这对胆甾相液晶的应用具有重要的意义.     

钢渣基高碱度微晶玻璃的一步法制备及工艺参数研究

为了提高微晶玻璃原料中高钙冶金渣的掺量,需要制备出碱度更高的微晶玻璃. 本文采用一步法,以钢渣为主要原料,制备碱度( CaO与SiO2的质量比)为0. 9的钢渣基高碱度微晶玻璃. 通过X射线衍射分析、扫描电镜和性能测试等手段,研究热处理条件对微晶玻璃微观形貌及线收缩率、体积密度和抗折强度等性能的影响规律. 研究表明,高碱度微晶玻璃适合采用一步法制备工艺,当在1100℃保温120 min时,微晶玻璃烧结过程基本完成,此时获得最大体积密度2. 4 g·cm-3 ,最高抗折强度56. 4 MPa. 微晶玻璃的主晶相为钙铝黄长石,副晶相为辉石. 基础玻璃颗粒在升温过程中完成了成核和析晶过程,而在保温过程中主要进行的是基础玻璃颗粒的烧结致密化和晶体的进一步发育. 升温至1100℃保温30 min,微晶玻璃的抗折强度超过45 MPa,微晶玻璃内部晶体呈方柱状交织排列并构成晶体骨架分布在残余的玻璃基体中;随着保温时间的增加,微晶玻璃的线性烧结收缩率、体积密度和抗折强度均逐渐增大,而晶相的含量基本保持不变,晶体逐渐由球形颗粒状和短柱状发育为长柱状. 晶体的形状以及与残余玻璃相构成的整体致密结构是导致高碱度微晶玻璃力学性能提高的主要因素.     

一种新的晶体定向切割方法

发展了一种新的晶体定向切割方法，此法利用Ｘ光定向仪，在只须知道晶体某一晶面的情况下，借助于该晶体的标准极图，即可定向切割出该晶体的任意所需晶面（或晶向）。理论分析表明，此法对立方晶系、六方（含三方）晶系、四方晶系、正交晶系均正确、可靠，定向切割操作快速、准确、简捷，具有很高的实用性。     

Two-substrate vertical deposition for stable colloidal crystal chips

By combining vertical deposition with micromolding in capillaries method, we have demonstrated the two-substrate vertical deposition, an alternative and versatile procedure for fabricating high-quality stable colloidal crystal chips. Apparent bright colors, special UV-vis spectra, scanning electron microscopy (SEM) and atomic force microscopy (AFM) images all prove that high-quality colloidal crystal structures are formed in between the two substrates.During the two-substrate vertical deposition for colloidal crystal chips, capillary force and evaporation of the medium are critical to the formation of the colloidal crystals; while the confinement in between two close substrates makes the resulting colloidal crystal chips more stable. Due to the excellent stability, these colloidal crystal chips can be used to construct some composite optical devices via a simpler and more flexible process. Meanwhile, they can also be further used as the templates for ordered multiporous materials.     

从FGD残渣中制备高强型α半水石膏的研究

探索了溶液结晶法从烟气脱硫残渣中制备α半水石膏的机理及过程晶形的控制,结果表明:pH值、温度和盐溶液是影响α型半水石膏产品性能的最重要因素。由于α型半水石膏的强度取决于制浆需水量,而制浆需水量又取决于其晶体形态,当晶形从针状向短柱状转化时,其制品强度逐渐增大,这是制备高强α型半水石膏的必要条件,本研究借助了差示微分扫描量热仪等分析手段,得出了溶液结晶法从烟气脱硫残渣中制备α半水石膏的机理。     

A novel high-efficiency crystal/polymer composite material for nonlinear optics

FOR practical applications in optoelectronic devices, nonlinear optical materials should ideally combine appropriate optical properties (that is, a nonlinear response to an electric field, characterized by second-harmonic generation) with the mechanical properties, such as strength and rigidity, required for ease of processibility. As reported here, we have developed a new class of material that combines these attributes, by growing aligned crystals of an optically nonlinear organic compound in a transparent polymer matrix. The host conveys desirable mechanical characteristics to the otherwise fragile organic crystals. The composites are transparent and non-scattering, with a refractive index that can be varied by modification of the polymer host. Given, in addition, the high chemical stability of these materials, we believe that they will have an important part to play in the development of optoelectronic devices.     

Thin-film thermoelectric devices with high room-temperature figures of merit

Thermoelectric materials are of interest for applications as heat pumps and power generators. The performance of thermoelectric devices is quantified by a figure of merit, ZT, where Z is a measure of a material's thermoelectric properties and T is the absolute temperature. A material with a figure of merit of around unity was first reported over four decades ago, but since then-despite investigation of various approaches-there has been only modest progress in finding materials with enhanced ZT values at room temperature. Here we report thin-film thermoelectric materials that demonstrate a significant enhancement in ZT at 300 K, compared to state-of-the-art bulk Bi2Te3 alloys. This amounts to a maximum observed factor of approximately 2.4 for our p-type Bi2Te3/Sb2Te3 superlattice devices. The enhancement is achieved by controlling the transport of phonons and electrons in the superlattices. Preliminary devices exhibit significant cooling (32 K at around room temperature) and the potential to pump a heat flux of up to 700 W cm-2; the localized cooling and heating occurs some 23,000 times faster than in bulk devices. We anticipate that the combination of performance, power density and speed achieved in these materials will lead to diverse technological applications: for example, in thermochemistry-on-a-chip, DNA microarrays, fibre-optic switches and microelectrothermal systems.     

新型介晶光致液晶取向剂的合成与性质

为了开发新型光致取向剂 ,通过硅氢化反应合成了一种新型的液晶高分子光致取向材料——对烯丙氧基肉桂酸对丙氧基苯酚酯接枝聚硅氧烷 (PSPAC)。并用示差扫描量热分析和偏光显微镜进行表征 ,确定其相变温度和液晶织构。热降解机理的红外研究表明这是一种热稳定性远远优于传统光致取向材料聚乙烯醇肉桂酸酯的新型液晶光致取向剂。线性偏振光聚合 (L PP)取向法实现了液晶分子良好的垂直和平行取向 ,实验结果同时也表明曝光后不同的液晶分子取向状态并不相同。     

Intercalation of alkylamines into an organic polymer crystal

Organic solid-state synthesis allows formation of products that are difficult or impossible to produce by conventional methods. This feature, and the high degree of reaction selectivity that can be achieved, is a direct result of the control over the relative orientation of the reactants afforded by the solid state. But as the successful development of 'topochemical reactions' requires the careful design of suitable reactant crystals, the range of both reactions and products amenable to this approach has been limited. However, recent advances in organic crystal engineering, particularly the rational design of complex solid architectures through supramolecular preorganization, have renewed interest in topochemical reactions. Previously, we have orientated muconate monomers--diene moieties with a carboxylate group on each end--using long-chain n-alkylammonium ions, such that the topochemical photopolymerization of the solid-state reactants produces layered crystals of stereoregular and high-molecular-mass polymers. Here we show that these polymer crystals are capable of repeated, reversible intercalation by conversion to the analogous poly(carboxylic acid), followed by transformation into a number of poly(alkylammonium muconate)s upon addition of the appropriate amine. Introduction of functional groups into these crystals may allow the design of organic solids for applications such as molecular recognition, separation and catalysis, thereby extending the range and practical utility of current intercalation compounds.