High-refractive index acrylate polymers for applications in nanoimprint lithography

The development of polymeric optical materials with a higher refractive index,transparency in the visible spectrum region and easier processability is increasingly desirable for advanced optical applications such as microlenses,image sensors,and organic light-emitting diodes.Most acrylates have a low refractive index(around 1.50)which does not meet the high perfo rmance requirements of advanced optical materials.In this research,three novel acrylates were synthesized via a facile one-step approach and used to fabricate optical transparent polymers.All of the polymers reveal good optical properties including high transparency(≥90%)in the visible spectrum region and high refractive index values(1.6363)at 550 nm.Moreover,nanostructures of these acrylate polymers with various feature sizes including nanogratings and photonic crystals were successfully fabricated using nanoimprint lithography.These results indicate that these acrylates can be used in a wide range of optical and optoelectronic devices where nanopatterned films with high refractive index and transparency are required.     

Facile fabrication of metallic nanostructures by tunable cracking and transfer printing

You crack me up: A topographically patterned PDMS stamp was coated with thin metal film and swelled under organic vapor to induce the tunable cracking of the brittle film into metallic nanostructures (see SEM images, scale bars 1?μm). UV/Vis spectra, OLED efficiency, and SERS spectra demonstrate the fine controllability of the metallic nanostructures, the well-ordered and highly regulable surface plasmons, and the facile fabrication process.     

Synthesis and characterization of hyperbranched polymers with increased chemical versatility for imprint lithographic resists

Hyperbranched polymers were prepared from a variety of mono‐ and difunctional monomers and used in the development of novel UV‐imprint lithography (UV‐IL) resists. The unique physical and chemical properties of these hyperbranched materials significantly increase the range of molecular systems that could be imprinted. Traditional challenges, such as the use of monomers that have low boiling points or the use of insoluble/highly crystalline momomers, are overcome by the preparation of hyperbranched polymers that incorporate these repeat units. In addition, the low viscosity of the hyperbranched macromolecules and the large number of reactive chain ends overcome many difficulties that are traditionally associated with the use of polymeric materials as imprint resists. Hyperbranched polymers containing up to 12 mol % pendant vinyl groups, needed for secondary crosslinking during imprinting, were prepared with a wide range of repeat unit structures and successfully imprinted with features from tens of microns to ∼ 100 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6238–6254, 2008     

Materials for the preparation of polymer pen lithography tip arrays and a comparison of their printing properties

Polymer Pen Lithography (PPL) uses an array of polymeric tips, typically composed of poly(dimethyl siloxane), to transfer ink onto a surface and create patterns of soft molecules with micrometer to nanometer feature dimensions. In this study, tip arrays were fabricated from poly(methyl methacrylate), poly([methyl methacrylate]‐co‐[butyl methacrylate]), and poly(3‐mercaptopropylmethylsiloxane), and used to pattern 1‐mercaptohexadecanoic acid onto Au surfaces to determine the fidelity of pattern transfer by PPL as a function of the mechanical properties of the materials. It was found that the dependence between the applied force and feature edge length correlates directly to the mechanical properties of each of the polymers used to fabricate the tip arrays, where stiffer polymers have a reduced dependence between the applied force and feature size. This study demonstrates that PPL tip arrays can be composed of a wide variety of materials whose choice is determined by the desired printing application. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

A mild etch for the fabrication of three-dimensional nanostructures in gold

A novel mild etch is reported for the fabrication of three-dimensional structures in gold films when used in conjunction with an alkylthiol resist. This etch consists of a solution of mercaptoethylamine in ethanol to which a small amount of ammonium hydroxide has been added. Using mask-based photolithography, micron-scale features have been created that exhibit good edge definition. For long-chain thiols, there is little tendency for the regions protected by thiols to be eroded on extended exposure to the etch solution. In conjunction with scanning near-field photolithography, the new etch solution enables the fabrication of nanoscale structures with dimensions significantly smaller than the conventional diffraction limit.     

Advances in polymer and polymeric nanostructures for protein conjugation

Linear polymers have been considered the best molecular structures for the formation of efficient protein conjugates due to their biological advantages, synthetic convenience and ease of functionalization. In recent years, much attention has been dedicated to develop synthetic strategies that produce the most control over protein conjugation utilizing linear polymers as scaffolds. As a result, different conjugate models, such as semitelechelic, homotelechelic, heterotelechelic and branched or star polymer conjugates, have been obtained that take advantage of these well-controlled synthetic strategies. Development of protein conjugates using nanostructures and the formation of said nanostructures from protein–polymer bioconjugates are other areas in the protein bioconjugation field. Although several polymer–protein technologies have been developed from these discoveries, few review articles have focused on the design and function of these polymers and nanostructures. This review will highlight some recent advances in protein-linear polymer technologies that employ protein covalent conjugation and successful protein-nanostructure bioconjugates (covalent conjugation as well) that have shown great potential for biological applications.     

A mechanism for the electron beam lithography of solvent-soluble photosensitive polyimides

Solvent-soluble and intrinsically photosensitive polyimides were prepared, and their electron beam reaction was investigated. Negative tone patterns were formed by the electron beam irradiation of PI(BTDA/DEDPM) and PI(BEDA/DEDPM). The mechanism for the pattern formation of PI(BTDA/DEDPM) was determined from transient absorption measurements, changes in the molecular weights, and IR spectrum measurements to be crosslinking via hydrogen abstraction by the triplet excited state benzophenone moiety. For the case of PI(BEDA/DEDPM), the pattern was formed by insolubilization due to chemical change in the polymer. These reactions are found to be so inhomogeneous that insolubilization of the polymer occurs at an early stage of gelation.     

Soft-graphoepitaxy using nanoimprinted polyhedral oligomeric silsesquioxane substrates for the directed self-assembly of PS-b-PDMS

We report here the fabrication of periodic sub-25 nm diameter size cylinder structures using block copolymer (BCP) directed self-assembly on nanoimprinted topographically patterned substrates. Tailored polyhedral oligomeric silsesquioxanes (POSSs) films were spin coated onto silicon substrates and were patterned by nanoimprint lithography to produce topographies commensurable with the BCP domain spacing. The chemistry of the POSS was tuned to control the alignment and orientation of the BCP films. The substrates were used to direct the microphase separation (following toluene solvent annealing) of a hexagonal structure forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) having a domain spacing of 42.6 nm and PDMS cylinder widths of 23.7 nm. On more hydrophilic POSS substrates the cylinders were obtained parallel to the substrate plane and aligned with the topography. In contrast, in more hydrophobic POSS patterns, the cylinders align perpendicular to the substrate plane. The use of these methods for the nanofabrication of vias, nanofluidic devices or interconnect structures of sub-25 nm feature size is discussed.     

Emerging methods for the fabrication of polymer capsules

Hollow polymer capsules are attracting increasing research interest due to their potential application as drug delivery vectors, sensors, biomimetic nano- or multi-compartment reactors and catalysts. Thus, significant effort has been directed toward tuning their size, composition, morphology, and functionality to further their application. In this review, we provide an overview of emerging techniques for the fabrication of polymer capsules, encompassing: self-assembly, layer-by-layer assembly, single-step polymer adsorption, bio-inspired assembly, surface polymerization, and ultrasound assembly. These techniques can be applied to prepare polymer capsules with diverse functionality and physicochemical properties, which may fulfill specific requirements in various areas. In addition, we critically evaluate the challenges associated with the application of polymer capsules in drug delivery systems.     

高分子结晶的新进展、新模型

回顾了高分子结晶经典模型－成核与生长模型，讨论了近年来高分子结晶研究的新结果，新进展，特别介绍了德国著名高分子物理学家Strobl提出的高分子结晶是从熔体先形成中间相，中间相转变为小晶块，最后小晶块融合为均匀为片晶的全新模型。     

Use of thin sectioning (nanoskiving) to fabricate nanostructures for electronic and optical applications

This Review discusses nanoskiving--a simple and inexpensive method of nanofabrication, which minimizes requirements for access to cleanrooms and associated facilities, and which makes it possible to fabricate nanostructures from materials, and of geometries, to which more familiar methods of nanofabrication are not applicable. Nanoskiving requires three steps: 1) deposition of a metallic, semiconducting, ceramic, or polymeric thin film onto an epoxy substrate; 2) embedding this film in epoxy, to form an epoxy block, with the film as an inclusion; and 3) sectioning the epoxy block into slabs with an ultramicrotome. These slabs, which can be 30 nm-10 μm thick, contain nanostructures whose lateral dimensions are equal to the thicknesses of the embedded thin films. Electronic applications of structures produced by this method include nanoelectrodes for electrochemistry, chemoresistive nanowires, and heterostructures of organic semiconductors. Optical applications include surface plasmon resonators, plasmonic waveguides, and frequency-selective surfaces.     

高分子的良溶剂和不良溶剂的两种定义辩析

介绍了目前国际学术界存在的对高分子溶液体系的溶剂优劣性的两种判断标准 ,即相互作用参数χ=1 /2和χ=0 ,前者基于混合自由能 ,后者基于混合热。作者阐明了其倾向于采用后者的观点 ,而后者在目前国内所有高分子物理学教科书中均未被介绍。     

测定高聚物结晶动力学参数的非等温理论和方法

对测定高聚物结晶动力学参数的非等温结晶理论和等速变温ＤＳＣ方法进行了讨论，文中包含了作者在此领域研究工作的最新进展。     

高性能聚合物光伏材料的设计与应用

高性能聚合物光伏材料对于推动聚合物太阳能电池领域的发展具有十分重要的作用.随着研究的深入,聚合物光伏材料从早期的聚噻吩体系逐步发展到具有推拉电子作用的给体-受体(D-A)交替共聚物,其相应的器件光伏效率也从最初的1%左右提升到如今超过11%.近十年来,种类繁多的给受体单元被开发并应用于聚合物材料的构建中,其中基于苯并二噻吩(BDT)单元的聚合物材料因为具有良好的光伏性能,得到了十分广泛的应用.近年来,非富勒烯受体的迅速发展给聚合物太阳能电池的研究注入了新的活力,BDT类聚合物在基于非富勒烯受体的聚合物太阳能电池中也展现出重要的作用,已经获得了超过11%的光电转化效率.本文简要介绍了我们在高性能聚合物光伏材料的设计与应用中的相关工作,主要分为聚噻吩和苯并二噻吩材料的设计与应用、活性层形貌调控以及非富勒烯聚合物太阳能电池的相关研究.     

Simple procedure for the fabrication of flexible NMR shim coils

Photolithography allows simple fabrication of flexible NMR shim coils. Here we demonstrate this procedure by fabricating optimized first-order shim coils for a transverse field orientation “Halbach” permanent magnet cylinder.     

A facile and environment-friendly method for fabrication of polymer brush

A novel environment-friendly system is proposed tofabricate polymer brush, which has the advantages including non-toxic and inexpensive initiator(eosin Y), visible-light exposure(λ= 515 nm), water medium and ambient environment. The experimental results from UV-Vis spectroscopy, AFM-based single molecule force spectroscopy(SMFS) and other measurements indicate thata polymer brush with a living nature is fabricated via free radical polymerization. This polymer brush may find applications incoatings, bio-interfaces and so forth.     

Advances in square arrays through self‐assembly and directed self‐assembly of block copolymers

This review covers recent advances in developing square arrays in thin films using block copolymers. Theoretical and experimental results from self‐assembly of block copolymers in bulk and thin films, directed self‐assembly of block copolymers confined in small wells, on substrates with arrays of posts, and on chemically nanopatterned substrates, as well as applications as nanolithography are reviewed. Some future work and hypothesis are discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Two-step colloidal synthesis of micron-scale Bi2O2Se nanosheets and their electrostatic assembly for thin-film photodetectors with fast response

Recently discovered bismuth oxychalcogenide (Bi₂O₂Se) has aroused great interest due to its ultrahigh carrier mobility, tunable band gap and good environmental stability, making it a promising candidate for high-performance electronics and optoelectronics. Their synthesis by colloidal approaches represents a cost-effective alternative to well-established chemical vapor deposition methods, and the resulting electronic-grade inks are important for large-area printed or wearable electronics. However, it is still challenging to control the colloidal growth of Bi₂O₂Se nanosheets in solution in addition to their assembly into high-performance thin films. Here, we report a two-step colloidal synthesis of Bi₂O₂Se nanosheets by separating the seeding and growth steps, thereby achieving controllable production of nanosheets with a lateral size of 1.4 μm and a thickness of 10 nm at optimized reaction conditions. These Bi₂O₂Se nanosheets are electrostatically assembled into large-area thin films, from which a photodetector is fabricated with a responsivity of 6.1 A/W and a short response time of 368 μs under the 520-nm laser illumination. The device exhibits fast response to modulations as high as 100 kHz, along with a −3 dB bandwidth of 1 kHz. This work provides an important understanding of the controlled colloidal synthesis of Bi₂O₂Se nanosheets, and demonstrates their potential applications in fast photodetectors.     

两性高分子作为保护剂的贵金属胶体的制备及其催化氢化活性

在金属催化领域,近年来人们对于高分子保护金属胶体的研究表现出很大的兴趣。高分散、窄分布金属胶体的制备研究成为众多工作者努力的目标。这在沟通分子催化与凝聚相物质催化间的联系有着重要的理论意义和应用价值。人们作出了种种努力设法获得高分散、窄分布的金属胶体。如:Bradley等报导用金属蒸汽冷凝法,Schmid等用水溶性三苯膦磺酸钠小分子配位体作为稳定剂,Esumi等用在有机溶剂中热解金属化合物的方法,Toshima等利用表面活性剂形成胶束的方法,Nagy的工作也很相似。这些工作在一定程度上取得进展。     

The fabrication of a colloidal gold-carbon nanotubes composite film on a gold electrode and its application for the determination of cytochrome c

Colloid Au (Au_nano) with a diameter of about 20 nm was prepared and used in combination with the multi-wall carbon nanotubes (MWNTs) to modify a gold electrode. Dihexadecylphosphate (DHP) dispersed in Au_nano aqueous solution was used to solubilize MWNTs. Deposition of Au_nano on MWNTs was realized as illustrated by TEM micrographs. The DHP formed a network that connected Au_nano and MWNTs to the gold electrode surface. The Au_nano–MWNTs–DHP composite film on the gold electrode surface was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammmetry (CV). The composite film modified gold electrode was used to detect cytochrome c and a pair of well-defined redox waves was obtained. It was found that the composite film promoted the redox of horse heart cytochrome c and its effect was developed for the determination of cytochrome c.