Self-organization of supramolecular helical dendrimers into complex electronic materials

The discovery of electrically conducting organic crystals and polymers has widened the range of potential optoelectronic materials, provided these exhibit sufficiently high charge carrier mobilities and are easy to make and process. Organic single crystals have high charge carrier mobilities but are usually impractical, whereas polymers have good processability but low mobilities. Liquid crystals exhibit mobilities approaching those of single crystals and are suitable for applications, but demanding fabrication and processing methods limit their use. Here we show that the self-assembly of fluorinated tapered dendrons can drive the formation of supramolecular liquid crystals with promising optoelectronic properties from a wide range of organic materials. We find that attaching conducting organic donor or acceptor groups to the apex of the dendrons leads to supramolecular nanometre-scale columns that contain in their cores pi-stacks of donors, acceptors or donor-acceptor complexes exhibiting high charge carrier mobilities. When we use functionalized dendrons and amorphous polymers carrying compatible side groups, these co-assemble so that the polymer is incorporated in the centre of the columns through donor-acceptor interactions and exhibits enhanced charge carrier mobilities. We anticipate that this simple and versatile strategy for producing conductive pi-stacks of aromatic groups, surrounded by helical dendrons, will lead to a new class of supramolecular materials suitable for electronic and optoelectronic applications.     

石墨烯在光电器件中的应用

 讨论了近年来石墨烯在太阳能电池、有机发光二极管以及场致发射器件方面的应用研究。石墨烯是碳的同素异形体的一种,是二维的薄膜材料,具有独特的导电特性及机械弯曲性能,可以作为太阳能电池、有机发光器件的柔性电极;石墨烯与有机聚合物材料复合可以形成大的给体受体界面,有利于太阳能电池中激子的扩散速率、载流子迁移率的提高,可以作为有机太阳能电池的电子受体材料;石墨烯具有一维尖锐的刀口状边缘,具有大的电场增强系数,同时由于石墨烯自身的良好导电能力,可以作为场致发射器件中的电子传导与电场发射材料。石墨烯在光电器件中应用的深入研究有望突破目前光电技术的发展瓶颈,是一个极具前景的新研究领域。     

Electroluminescence from single monolayers of nanocrystals in molecular organic devices

The integration of organic and inorganic materials at the nanometre scale into hybrid optoelectronic structures enables active devices that combine the diversity of organic materials with the high-performance electronic and optical properties of inorganic nanocrystals. The optimization of such hybrid devices ultimately depends upon the precise positioning of the functionally distinct materials. Previous studies have already emphasized that this is a challenge, owing to the lack of well-developed nanometre-scale fabrication techniques. Here we demonstrate a hybrid light-emitting diode (LED) that combines the ease of processability of organic materials with the narrow-band, efficient luminescence of colloidal quantum dots (QDs). To isolate the luminescence processes from charge conduction, we fabricate a quantum-dot LED (QD-LED) that contains only a single monolayer of QDs, sandwiched between two organic thin films. This is achieved by a method that uses material phase segregation between the QD aliphatic capping groups and the aromatic organic materials. In our devices, where QDs function exclusively as lumophores, we observe a 25-fold improvement in luminescence efficiency (1.6 cd A(-1) at 2,000 cd m(-2)) over the best previous QD-LED results. The reproducibility and precision of our phase-segregation approach suggests that this technique could be widely applicable to the fabrication of other hybrid organic/inorganic devices.     

Ultrafast holographic nanopatterning of biocatalytically formed silica

Diatoms are of interest to the materials research community because of their ability to create highly complex and intricate silica structures under physiological conditions: what these single-cell organisms accomplish so elegantly in nature requires extreme laboratory conditions to duplicate-this is true for even the simplest of structures. Following the identification of polycationic peptides from the diatom Cylindrotheca fusiformis, simple silica nanospheres can now be synthesized in vitro from silanes at nearly neutral pH and at ambient temperatures and pressures. Here we describe a method for creating a hybrid organic/inorganic ordered nanostructure of silica spheres through the incorporation of a polycationic peptide (derived from the C. fusiformis silaffin-1 protein) into a polymer hologram created by two-photon-induced photopolymerization. When these peptide nanopatterned holographic structures are exposed to a silicic acid, an ordered array of silica nanospheres is deposited onto the clear polymer substrate. These structures exhibit a nearly fifty-fold increase in diffraction efficiency over a comparable polymer hologram without silica. This approach, combining the ease of processability of an organic polymer with the improved mechanical and optical properties of an inorganic material, could be of practical use for the fabrication of photonic devices.     

Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound

Crystal engineering--the planning and construction of crystalline supramolecular architectures from modular building blocks--permits the rational design of functional molecular materials that exhibit technologically useful behaviour such as conductivity and superconductivity, ferromagnetism and nonlinear optical properties. Because the presence of two cooperative properties in the same crystal lattice might result in new physical phenomena and novel applications, a particularly attractive goal is the design of molecular materials with two properties that are difficult or impossible to combine in a conventional inorganic solid with a continuous lattice. A promising strategy for creating this type of 'bi-functionality' targets hybrid organic/inorganic crystals comprising two functional sub-lattices exhibiting distinct properties. In this way, the organic pi-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and its derivatives, which form the basis of most known molecular conductors and superconductors, have been combined with molecular magnetic anions, yielding predominantly materials with conventional semiconducting or conducting properties, but also systems that are both superconducting and paramagnetic. But interesting bulk magnetic properties fail to develop, owing to the discrete nature of the inorganic anions. Another strategy for achieving cooperative magnetism involves insertion of functional bulky cations into a polymeric magnetic anion, such as the bimetallic oxalato complex [MnIICrIII(C2O4)3]-, but only insoluble powders have been obtained in most cases. Here we report the synthesis of single crystals formed by infinite sheets of this magnetic coordination polymer interleaved with layers of conducting BEDT-TTF cations, and show that this molecule-based compound displays ferromagnetism and metallic conductivity.     

蛋白基柔性材料的介观重构及其光电子器件

自然界中的蛋白质材料具有天然丰度、多种化学成分、可调控的性能、优异的生物相容及可降解性能等特点,为柔性光电子器件的发展提供了新的机遇.然而,蛋白质化学稳定性差、机械柔性不可控等缺点使得传统加工技术难以应用在其表面,严重制约了其在柔性电子领域的应用.本文首先以丝蛋白和角蛋白为例介绍了天然蛋白材料的介观重构以及加工技术,阐述了天然蛋白质材料的多级网络结构与其物理性能的关系.在此基础上,侧重介绍它们在柔性传感、发光、晶体管及存储等器件中的应用,最后展望了蛋白基柔性材料在光电子器件发展中所面临的挑战以及发展机遇.     

Progress in photonic and optoelectronic active polymers and organic solids

The progress of the researches in photonic and optoelectronic active polymers and organic solids in recent two decades is reviewed with particular attention to the excellent achievements of Chinese scientists. The recent progress in the areas of conducting polymers, organic light-emitting diodes, photoelectric conversion material, material for information storage, and nonlinear optical polymers is introduced. The peculiarities of organic photonic and optoelectronic active materials are briefly compared with those of inorganic photonic and optoelectronic materials.     

Growth dynamics of pentacene thin films

The recent demonstration of single-crystal organic optoelectronic devices has received widespread attention. But practical applications of such devices require the use of inexpensive organic films deposited on a wide variety of substrates. Unfortunately, the physical properties of these organic thin films do not compare favourably to those of single-crystal materials. Moreover, the basic physical principles governing organic thin-film growth and crystallization are not well understood. Here we report an in situ study of the evolution of pentacene thin films, utilizing the real-time imaging capabilities of photoelectron emission microscopy. By a combination of careful substrate preparation and surface energy control, we succeed in growing thin films with single-crystal grain sizes approaching 0.1 millimetre (a factor of 20-100 larger than previously achieved), which are large enough to fully contain a complete device. We find that organic thin-film growth closely mimics epitaxial growth of inorganic materials, and we expect that strategies and concepts developed for these inorganic systems will provide guidance for the further development and optimization of molecular thin-film devices.     

二维材料偏振响应光电探测

各向异性二维材料由于其晶体结构的特殊性,在电学或者光学性质(如光致发光光谱、拉曼光谱、光吸收谱和电导率等)上表现出各向异性。这些性质引起了研究人员的广泛关注,特别是在光电探测方面的研究进展非常迅速,为其在光电器件的设计和开发中提供了巨大的应用潜力。文章从本征偏振探测和结构改进两方面综述了近几年来各向异性二维材料在偏振光电探测领域的发展和成果。首先阐述了各向异性二维材料的晶体结构特点和各向异性的来源,然后介绍了基于这类材料制备的多种偏振敏感光电探测器,接着提出了各向异性二维材料在光电探测应用上的重要性,最后基于现状提出了其所面临的挑战及机遇。     

2022年纳米颗粒精确自组装热点回眸

构筑具有特定功能的复杂物质是纳米颗粒自组装的重要目标之一。聚焦于纳米颗粒自组装的基本原则,讨论了纳米粒子间的相互作用力驱动自组装具有理想性能的纳米结构和材料,精确制备从零维到三维的高质量结构,如胶体分子、纳米链、胶体晶体和光子晶体等;回顾了2022年纳米颗粒组装体在传感、光电器件、显示、药物递送和生物医疗诊断领域所取得的重要进展,并提出了该领域在构筑新物质方面面临的挑战。     

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.     

A guest-free germanium clathrate

The challenges associated with synthesizing expanded semiconductor frameworks with cage-like crystal structures continue to be of interest. Filled low-density germanium and silicon framework structures have distinct properties that address important issues in thermoelectric phonon glass-electron crystals, superconductivity and the possibility of Kondo insulators. Interest in empty framework structures of silicon and germanium is motivated by their predicted wide optical bandgaps of the same magnitude as quantum dots and porous silicon, making them and their alloys promising materials for silicon-based optoelectronic devices. Although almost-empty Na(1-x)Si136 has already been reported, the synthesis of guest-free germanium clathrate has so far been unsuccessful. Here we report the high-yield synthesis and characteristics of germanium with the empty clathrate-II structure through the oxidation of Zintl anions in ionic liquids under ambient conditions. The approach demonstrates the potential of ionic liquids as media for the reactions of polar intermetallic phases.     

Sensitivity gains in chemosensing by lasing action in organic polymers

Societal needs for greater security require dramatic improvements in the sensitivity of chemical and biological sensors. To meet this challenge, increasing emphasis in analytical science has been directed towards materials and devices having highly nonlinear characteristics; semiconducting organic polymers (SOPs), with their facile excited state (exciton) transport, are prime examples of amplifying materials. SOPs have also been recognized as promising lasing materials, although the susceptibility of these materials to optical damage has thus far limited applications. Here we report that attenuated lasing in optically pumped SOP thin films displays a sensitivity to vapours of explosives more than 30 times higher than is observed from spontaneous emission. Critical to this achievement was the development of a transducing polymer with high thin-film quantum yield, a high optical damage threshold in ambient atmosphere and a record low lasing threshold. Trace vapours of the explosives 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT) introduce non-radiative deactivation pathways that compete with stimulated emission. We demonstrate that the induced cessation of the lasing action, and associated sensitivity enhancement, is most pronounced when films are pumped at intensities near their lasing threshold. The combined gains from amplifying materials and lasing promise to deliver sensors that can detect explosives with unparalleled sensitivity.     

柔性显示基板材料研究进展

随着显示技术的不断发展,柔性显示以其质轻、可轻薄化、耐用和可收卷等优点,成为最具发展潜力的下一代显示技术. 柔性显示技术的实现除了要求现有的设计和制造工艺进行改进之外,更加对加工和使用过程中材料的性能提出了新的要求,其中,柔性基板作为柔性显示器件的重要组成部分,基板材料要求具有良好的光学透明度、柔韧性、热稳定性和阻水阻氧等特性,因此,开发出具有优异的综合性能的基板材料成为实现柔性显示的关键环节. 目前,可以作为柔性显示基板的材料包括聚合物基板、超薄玻璃基板、不锈钢基板、纸质基板和生物复合薄膜基板,以前3种最常用. 文中针对近年来柔性显示基板材料的研究状况,从光学透明度、热稳定性、机械性能、阻水阻氧性能和表面平坦性等方面对这5种基板材料的性能进行了比较,聚合物基板相较于超薄玻璃基板和不锈钢基板,不仅具有透明、柔性、质轻的优点,而且耐用性优良,被公认为具有非常广阔的应用前景,并对聚合物基板的研究进行了展望.     

Doping-free carbon nanotube optoelectronic devices

Semiconducting carbon nanotubes (CNTs) possess outstanding electrical and optical properties because of their special one-dimensional (1D) structure. CNTs are direct bandgap materials, which makes them ideal for use in optoelectronic devices, e.g. light emitters and light detectors. Excitons determine their light absorption and light emission processes due to the strong Coulomb interactions between electrons and holes in CNTs. In this paper, we review recent progress in CNT photodetectors, photovoltaic devices and light emitters. In particular, we focus on the doping-free CNT optoelectronic devices developed by our group in recent years.     

A general strategy for nanocrystal synthesis

New strategies for materials fabrication are of fundamental importance in the advancement of science and technology. Organometallic and other organic solution phase synthetic routes have enabled the synthesis of functional inorganic quantum dots or nanocrystals. These nanomaterials form the building blocks for new bottom-up approaches to materials assembly for a range of uses; such materials also receive attention because of their intrinsic size-dependent properties and resulting applications. Here we report a unified approach to the synthesis of a large variety of nanocrystals with different chemistries and properties and with low dispersity; these include noble metal, magnetic/dielectric, semiconducting, rare-earth fluorescent, biomedical, organic optoelectronic semiconducting and conducting polymer nanoparticles. This strategy is based on a general phase transfer and separation mechanism occurring at the interfaces of the liquid, solid and solution phases present during the synthesis. We believe our methodology provides a simple and convenient route to a variety of building blocks for assembling materials with novel structure and function in nanotechnology.     

共轭高分子非线性光学材料结构与性能关系的研究

探讨了共轭高分子材料的非线性光学性能与其化学结构之间的关系,确证共轭高分子非线性光学性能与共轭高分子的主链骨架结构、侧链取代基结构、掺杂物质的结构和浓度有密切关系。     

n-type colloidal semiconductor nanocrystals

Colloidal semiconductor nanocrystals combine the physical and chemical properties of molecules with the optoelectronic properties of semiconductors. Their colour is highly controllable, a direct consequence of quantum confinement on the electronic states. Such nanocrystals are a form of 'artificial atoms' (ref. 4) that may find applications in optoelectronic systems such as light-emitting diodes and photovoltaic cells, or as components of future nanoelectronic devices. The ability to control the electron occupation (especially in n-type or p-type nanocrystals) is important for tailoring the electrical and optical properties, and should lead to a wider range of practical devices. But conventional doping by introducing impurity atoms has been unsuccessful so far: impurities tend to be expelled from the small crystalline cores (as observed for magnetic impurities), and thermal ionization of the impurities (which provides free carriers) is hindered by strong confinement. Here we report the fabrication of n-type nanocrystals using an electron transfer approach commonly employed in the field of conducting organic polymers. We find that semiconductor nanocrystals prepared as colloids can be made n-type, with electrons in quantum confined states.     

Mechanism of hydrogen-induced crystallization of amorphous silicon

Hydrogenated amorphous and nanocrystalline silicon films manufactured by plasma deposition techniques are used widely in electronic and optoelectronic devices. The crystalline fraction and grain size of these films determines electronic and optical properties; the nanocrystal nucleation mechanism, which dictates the final film structure, is governed by the interactions between the hydrogen atoms of the plasma and the solid silicon matrix. Fundamental understanding of these interactions is important for optimizing the film structure and properties. Here we report the mechanism of hydrogen-induced crystallization of hydrogenated amorphous silicon films during post-deposition treatment with an H(2) (or D(2)) plasma. Using molecular-dynamics simulations and infrared spectroscopy, we show that crystallization is mediated by the insertion of H atoms into strained Si-Si bonds as the atoms diffuse through the film. This chemically driven mechanism may be operative in other covalently bonded materials, where the presence of hydrogen leads to disorder-to-order transitions.     

有机聚合物条波导的制备和耦合

介绍了三种有机电光聚合物体系：分散红（ＤＲ１）和聚甲基丙烯酸甲酯（ＰＭＭＡ）的掺杂型体系、ＤＲ１与聚酰亚胺（ＰＩ）掺杂型体系、ＤＲ１和ＰＭＭＡ侧链型体系。描述了用它们制备光波导的过程。用导波法表征聚合物波导薄膜的光学特性，并分析了它们在有机电光器件制备方面的应用前景。