Bottom-up fabrication approaches to novel plasmonic materials

Recent research effort towards developing novel metal nanoparticles (NPs) and their ordered arrays have been motivated by the emergence of plasmonics. In particular, tuning the size, morphology, composition and the separation of metal NPs has allowed us to engineer the collective properties of plasmonic crystals for specific applications. Here we present our recent development of bottom-up growth methods and demonstrate convenience for the preparation of such plasmonic materials. By implementation of physical, chemical, or electrochemical deposition of a metal in combination with micromolding on two-dimensional colloidal crystals, metallic NPs with a variety of morphologies can be created in an ordered lattice. The prepared novel plasmonic crystals could find applications in optics, optoelectronics, materials science, sensing and biophysics.     

A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups

So-called bottom-up fabrication methods aim to assemble and integrate molecular components exhibiting specific functions into electronic devices that are orders of magnitude smaller than can be fabricated by lithographic techniques. Fundamental to the success of the bottom-up approach is the ability to control electron transport across molecular components. Organic molecules containing redox centres-chemical species whose oxidation number, and hence electronic structure, can be changed reversibly-support resonant tunnelling and display promising functional behaviour when sandwiched as molecular layers between electrical contacts, but their integration into more complex assemblies remains challenging. For this reason, functionalized metal nanoparticles have attracted much interest: they exhibit single-electron characteristics (such as quantized capacitance charging) and can be organized through simple self-assembly methods into well ordered structures, with the nanoparticles at controlled locations. Here we report scanning tunnelling microscopy measurements showing that organic molecules containing redox centres can be used to attach metal nanoparticles to electrode surfaces and so control the electron transport between them. Our system consists of gold nanoclusters a few nanometres across and functionalized with polymethylene chains that carry a central, reversibly reducible bipyridinium moiety. We expect that the ability to electronically contact metal nanoparticles via redox-active molecules, and to alter profoundly their tunnelling properties by charge injection into these molecules, can form the basis for a range of nanoscale electronic switches.     

Programmed self-assembly of DNA origami nanoblocks into anisotropic higher-order nanopatterns

Anisotropic nanopatterns have potentials in constructing novel plasmonic structures which have various applications in such as super-resolution microscopy, medicine, and sensors. However, it remains challenging to build big anisotropic nanopatterns that are suitable for big noble metal nanoparticles. Herein, we report a simple and reliable strategy for constructing DNA origami-based big anisotropic nanopatterns with controlled size and shape, nanoscale resolution, and fully addressability. Two kinds of basic DNA origami nanoblocks-cross-shaped and rectangular DNA origami units were used. We have demonstrated that by encoding nanoblocks’ edges, anisotropic higher-order nanopatterns, such as dimer, trimer, tetramer and mini "windmill" like pentamer nanopatterns could be constructed. To show the potential use as template to direct the assembly of anisotropic nanoparticles arrays, a proof of concept work was conducted by anchoring streptavidin nanoparticles on the "windmill" template to form a chiral array. Significantly, these nanopatterns have the sizes of hundreds of nanometers, which are in principle also suitable for big noble metal nanoparticles arrays.     

Channel plasmon subwavelength waveguide components including interferometers and ring resonators

Photonic components are superior to electronic ones in terms of operational bandwidth, but the diffraction limit of light poses a significant challenge to the miniaturization and high-density integration of optical circuits. The main approach to circumvent this problem is to exploit the hybrid nature of surface plasmon polaritons (SPPs), which are light waves coupled to free electron oscillations in a metal that can be laterally confined below the diffraction limit using subwavelength metal structures. However, the simultaneous realization of strong confinement and a propagation loss sufficiently low for practical applications has long been out of reach. Channel SPP modes--channel plasmon polaritons (CPPs)--are electromagnetic waves that are bound to and propagate along the bottom of V-shaped grooves milled in a metal film. They are expected to exhibit useful subwavelength confinement, relatively low propagation loss, single-mode operation and efficient transmission around sharp bends. Our previous experiments showed that CPPs do exist and that they propagate over tens of micrometres along straight subwavelength grooves. Here we report the design, fabrication and characterization of CPP-based subwavelength waveguide components operating at telecom wavelengths: Y-splitters, Mach-Zehnder interferometers and waveguide-ring resonators. We demonstrate that CPP guides can indeed be used for large-angle bending and splitting of radiation, thereby enabling the realization of ultracompact plasmonic components and paving the way for a new class of integrated optical circuits.     

基于磁光材料的磁可调石墨烯多带吸收特性

为了改善石墨烯的吸收性能,基于石墨烯的磁光效应,提出了一种采用磁性材料构成的光子晶体异质结构。该光学结构可使石墨烯实现多带吸收。吸收带的数目可通过改变光子晶体的周期数来调节。利用4×4传输矩阵法数值研究了该光子晶体异质结构的相关参数对石墨烯吸收率的影响。结果表明:石墨烯的吸收特性表现出一定的磁圆二色性。但通过调节费米能量,在外磁场的作用,左旋圆偏振光和右旋圆偏振光均可具有较高的吸收率。研究结果为偏振光学领域石墨烯基新型光子学器件的设计制作提供了理论依据。     

Ag纳米粒子增强CdS白光量子点器件的研制

在十八烯体系中合成Cd S量子点,用光诱导法制备银纳米粒子,并将两者复合,制备成4种复合样品,分析复合样品的荧光谱,在银纳米颗粒的表面等离子体共振峰分别对应于富含缺陷的硫化镉量子点的带边荧光峰和表面态荧光峰时,发生了带边荧光淬灭而表面态荧光增强的现象.结果表明,通过控制金属和量子点之间的距离,能够控制带边荧光辐射和缺陷带荧光辐射的比例,从而控制白光量子点的色温.采用395 nm紫光LED作为激发光源,将涂有荧光样品的玻片与激发光源组装成银纳米颗粒/量子点复合结构白光照明器件原型,银纳米粒子能够改变Cd S量子点样品发光颜色,荧光效应的增强程度随着量子点样品的厚度减小而加强.该研究为认识荧光物质和金属之间的相互作用提供了新途径,同时探讨了该器件在变色发光材料方向的应用前景.     

Selection of peptides with semiconductor binding specificity for directed nanocrystal assembly

In biological systems, organic molecules exert a remarkable level of control over the nucleation and mineral phase of inorganic materials such as calcium carbonate and silica, and over the assembly of crystallites and other nanoscale building blocks into complex structures required for biological function. This ability to direct the assembly of nanoscale components into controlled and sophisticated structures has motivated intense efforts to develop assembly methods that mimic or exploit the recognition capabilities and interactions found in biological systems. Of particular value would be methods that could be applied to materials with interesting electronic or optical properties, but natural evolution has not selected for interactions between biomolecules and such materials. However, peptides with limited selectivity for binding to metal surfaces and metal oxide surfaces have been successfully selected. Here we extend this approach and show that combinatorial phage-display libraries can be used to evolve peptides that bind to a range of semiconductor surfaces with high specificity, depending on the crystallographic orientation and composition of the structurally similar materials we have used. As electronic devices contain structurally related materials in close proximity, such peptides may find use for the controlled placement and assembly of a variety of practically important materials, thus broadening the scope for 'bottom-up' fabrication approaches.     

等离子体太阳电池的研究进展

 高效太阳电池是近年太阳电池产业发展的目标,等离子体太阳电池技术则是近年来研究的比较活跃的高效太阳电池技术之一。该文对等离子体太阳电池,从原理,材料到技术的最新研究进展做了比较全面的论述。等离子体太阳电池主要是利用贵金属纳米颗粒的表面等离子体效应增强太阳电池的光吸收。该技术既可以用在传统的硅电池上也可以用在薄膜电池上,尤其适用于作为薄膜电池的陷光结构,并且易于和传统的电池制造工艺相结合,有实现商业化的潜力。     

Single scattering particles based analytical techniques

Single scattering particles,especially noble metal(plasmonic) nanoparticles,based analytical techniques are attractive recently and becoming the research focus of the light scattering analytical techniques.In this mini review,we summarize the single scattering particles based analytical techniques in the past decade including single scattering particles counting,single plasmonic nanoparticles sensing,and single plasmonic nanoparticles tracking/imaging.We emphasize the discussion on the single plasmonic nanoparticles sensing that combines with dark-field microscopy and resonant Rayleigh scattering spectroscopy.     

Multifunctional artificial nacre via biomimetic matrix-directed mineralization

Natural nacre, one of the most studied biological structural materials with delicate hierarchical structures and extraordinary performance, has inspired the design and fabrication of artificial structural ceramics with high fracture toughness. However, to meet the diverse requirements of different applications, future structural materials must be multifunctional with superior mechanical properties, such as strength, hardness, and toughness. Herein, based on the matrix-directed mineralization method for producing biomimetic structural materials, we introduce nanoparticles with different inherent functions into the platelets of artificial nacre via the co-mineralization of aragonite and the nanoparticles. Besides their enhanced mechanical properties, the obtained artificial nacre materials also exhibit different functions depending on the type of the nanoparticles. To extend the versatility of this strategy, the effects of nanoparticles of different sizes and zeta potentials on mineralization are also analyzed. This universal strategy can be applied to the fabrication of other types of functionalized biomimetic structural ceramics that have potential applications in various fields, such as biomedical science.     

Liquid crystal 'blue phases' with a wide temperature range

Liquid crystal 'blue phases' are highly fluid self-assembled three-dimensional cubic defect structures that exist over narrow temperature ranges in highly chiral liquid crystals. The characteristic period of these defects is of the order of the wavelength of visible light, and they give rise to vivid specular reflections that are controllable with external fields. Blue phases may be considered as examples of tuneable photonic crystals with many potential applications. The disadvantage of these materials, as predicted theoretically and proved experimentally, is that they have limited thermal stability: they exist over a small temperature range (0.5-2 degrees C) between isotropic and chiral nematic (N*) thermotropic phases, which limits their practical applicability. Here we report a generic family of liquid crystals that demonstrate an unusually broad body-centred cubic phase (BP I*) from 60 degrees C down to 16 degrees C. We prove this with optical texture analysis, selective reflection spectroscopy, K?ssel diagrams and differential scanning calorimetry, and show, using a simple polarizer-free electro-optic cell, that the reflected colour is switched reversibly in applied electric fields over a wide colour range in typically 10 ms. We propose that the unusual behaviour of these blue phase materials is due to their dimeric molecular structure and their very high flexoelectric coefficients. This in turn sets out new theoretical challenges and potentially opens up new photonic applications.     

Manipulation of light in MIM plasmonic waveguide systems

Plasmonic waveguides that allow deeply subwavelength confinement of light provide an effective platform for the design of ultracompact photonic devices.As an important plasmonic waveguide,metal-insulator-metal(MIM)structure supports the propagation of light in the nanoscale regime at the visible and near-infrared ranges.Here,we focus on our work in MIM plasmonic waveguide devices for manipulating light,and review some of the recent development of this topic.We introduce MIM plasmonic wavelength filtering and demultiplexing devices,and present the electromagnetic induced transparency(EIT)-like and Fano resonance effects in MIM waveguide systems.The slow-light and rainbow trapping effects are demonstrated theoretically.These results pave a way toward dynamic control of the special and useful optical responses,which actualize some new plasmonic waveguide-integrated devices such as nanoscale filters,demultiplexers,sensors,slow light waveguides,and buffers.     

Detection of magnetic circular dichroism using a transmission electron microscope

A material is said to exhibit dichroism if its photon absorption spectrum depends on the polarization of the incident radiation. In the case of X-ray magnetic circular dichroism (XMCD), the absorption cross-section of a ferromagnet or a paramagnet in a magnetic field changes when the helicity of a circularly polarized photon is reversed relative to the magnetization direction. Although similarities between X-ray absorption and electron energy-loss spectroscopy in a transmission electron microscope (TEM) have long been recognized, it has been assumed that extending such equivalence to circular dichroism would require the electron beam in the TEM to be spin-polarized. Recently, it was argued on theoretical grounds that this assumption is probably wrong. Here we report the direct experimental detection of magnetic circular dichroism in a TEM. We compare our measurements of electron energy-loss magnetic chiral dichroism (EMCD) with XMCD spectra obtained from the same specimen that, together with theoretical calculations, show that chiral atomic transitions in a specimen are accessible with inelastic electron scattering under particular scattering conditions. This finding could have important consequences for the study of magnetism on the nanometre and subnanometre scales, as EMCD offers the potential for such spatial resolution down to the nanometre scale while providing depth information--in contrast to X-ray methods, which are mainly surface-sensitive.     

有机手性分子器件的光电特性

目前多种有机手性分子器件虽已研制成功,但其内在的物理机理仍有许多未解之谜,其中手性分子的圆二色性精细结构、手性诱导的自旋选择效应等是有机手性分子研究的核心.为设计基于手性的新型有机功能器件提供理论指导,考虑有机手性分子螺旋势场诱导的自旋-轨道耦合,围绕分子的光电特性及其调控展开了系列研究.根据光致跃迁理论,得到手性分子...     

Plasmonic coupling in single flower-like gold nanoparticle assemblies

Localized surface plasmon resonance (LSPR) arises when light interacts with metallic nanoparticles (NPs). When nanoparticles (NPs) assemble together, the plasmon coupling effect between the NPs often leads to new features in the LSPR of the assembled structure. Understanding the plasmon coupling in the complex assemblies will greatly benefit the development of new plasmonic devices. Here we demonstrate the fabrication of a 3D structure using two different sized Au NPs as building blocks. This 3D structure was achieved by manipulating the binding efficiency of ligands linking the NPs, and proper choice of the NP size. The assembled structure is flower-like structure, with one 130 nm Au NP in the center, and several 40 nm Au NPs attaching as “petals”. Single particle dark-field scattering measurements of the individual assemblies were performed, together with electrodynamics simulations. The experimental and theoretical studies show that, the plasmonic coupling lead to broadening of the LSPR and additional peaks, depending on the number and 3D arrangement of the 40 nm NPs around the center 130 nm NP.     

DNA-guided crystallization of colloidal nanoparticles

Many nanometre-sized building blocks will readily assemble into macroscopic structures. If the process is accompanied by effective control over the interactions between the blocks and all entropic effects, then the resultant structures will be ordered with a precision hard to achieve with other fabrication methods. But it remains challenging to use self-assembly to design systems comprised of different types of building blocks-to realize novel magnetic, plasmonic and photonic metamaterials, for example. A conceptually simple idea for overcoming this problem is the use of 'encodable' interactions between building blocks; this can in principle be straightforwardly implemented using biomolecules. Strategies that use DNA programmability to control the placement of nanoparticles in one and two dimensions have indeed been demonstrated. However, our theoretical understanding of how to extend this approach to three dimensions is limited, and most experiments have yielded amorphous aggregates and only occasionally crystallites of close-packed micrometre-sized particles. Here, we report the formation of three-dimensional crystalline assemblies of gold nanoparticles mediated by interactions between complementary DNA molecules attached to the nanoparticles' surface. We find that the nanoparticle crystals form reversibly during heating and cooling cycles. Moreover, the body-centred-cubic lattice structure is temperature-tuneable and structurally open, with particles occupying only approximately 4% of the unit cell volume. We expect that our DNA-mediated crystallization approach, and the insight into DNA design requirements it has provided, will facilitate both the creation of new classes of ordered multicomponent metamaterials and the exploration of the phase behaviour of hybrid systems with addressable interactions.     

Activator-assisted electroless deposition of copper nanostructured films

This paper showed simple and effective synthesis of copper nanoparticles within controlled diameter using direct electroless deposition on glass substrates, following the sensitization and activation steps. Electroless-deposited metals, such as Cu, Co, Ni, and Ag, and their alloys had many advantages in micro- and nanotechnologies. The structural, morphological, and optical properties of copper deposits were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-Vis spectroscopy. The structural data was further analyzed using the Rietveld refinement program. Structural studies reveal that the deposited copper prefers a (111) orientation. AFM studies suggest the deposited materials form compact, uniform, and nanocrystalline phases with a high tendency to self-organize. The data show that the particle size can be controlled by controlling the activator concentration. The absorption spectra of the as-deposited copper nanoparticles reveal that the plasmonic peak broadens and exhibits a blue shift with decreasing particle size.     

Biomimetic self-templating supramolecular structures

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres, distinctively coloured skin tissues from cholesteric phase fibre bundles, and mineralized tissues from hierarchically organized fibres. Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.     

Free-standing mesoporous silica films with tunable chiral nematic structures

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.