Metamaterials and plasmonics: From nanoparticles to nanoantenna arrays, metasurfaces, and metamaterials

The rise of plasmonic metamaterials in recent years has unveiled the possibility of revolutionizing the entire field of optics and photonics, challenging well-established technological limitations and paving the way to innovations at an unprecedented level To capitalize the disruptive potential of this rising field of science and technology, it is important to be able to combine the richness of optical phenomena enabled by nanoplasmonics in order to realize metamaterial components, devices, and systems of increasing complexity. Here, we review a few recent research directions in the field of plasmonic metamaterials, which may foster further advancements in this research area. We will discuss the anomalous scattering features enabled by plasmonic nanoparticles and nanoclusters, and show how they may represent the fundamental building blocks of complex nanophotonic architectures. Building on these concepts, advanced components can be designed and operated, such as optical nanoantennas and nanoantenna arrays, which, in turn, may be at the basis of metasurface devices and complex systems. Following this path, from basic phenomena to advanced functionalities, the field of plasmonic metamaterials offers the promise of an important scientific and technological impact, with applications spanning from medical diagnostics to clean energy and information processing.

Surface Plasmon Resonance Enhanced Scattering of Au Colloidal Nanoparticles

Suspended gold nanoparticles have been synthesized via electrochemical method. The strongest resonance scattering peak is at 485 nm, which results from the surface plasmon resonance. When the excited wavelength is at 242 nm (12.4 × 1014 Hz), there have been a 1/2 fraction frequency scattering peak at 485 nm (1/2 × 12.4 × 1014 Hz) and a 1/3 fraction frequency scattering peak at 726 nm (1/3 × 12.4 × 1014 Hz) displayed. Emission spectra with different particle diameters were compared, the intensity of scattering light increases with the particle size. The frequency-dependent scattering average cross section of small particle was calculated from Mie theory. The model calculation is in agreement with the experimental results.

Two-thiols-regulated fabrication of plasmonic nanoparticles with co-enhanced Raman scattering and circular dichroism responses

Plasmonicnanoparticles(PNPs)with stable nanogaps are important to achieve strong,uniform and quantitative gap-enhanced Raman scattering(GERS)signals.Chiral PNPs with plasmonic circular dichroism(PCD)responses have been discovered to be suitable for applications in enantiomeric recognition,cancer therapy and activation of immune system.Herein,two-thiolsmodulated growth was demonstrated to result in the acquisition of PNPs with synergistically enhanced GERS and PCD signals.4-Aminothiophenol(4-ATP)and cysteine(Cys)played the role of Raman reporter and chiral stimulus,respectively.At a fixed 4-ATP concentration,the GERS signal of PNPs was significantly enhanced with the increase of the concentration of Cys.Simultaneously,at a fixed concentration of Cys,an increase in PCD response was observed by elevating the concentration of 4-ATP.Both aforementioned molecules acted as morphology controllers,leading to the formation of helical shell.It is suggested that the giant GERS and PCD response were contributed by the‘‘hot spots''within the PNPs and more perfect helical shells.Our research pointed out a novel synthetic guideline to obtain PNPs with multiple functionalities by incorporating multi-ligands into the growth stages.

Photothermal nonlinear scattering of shell-isolated gold nanoparticles and applications in super-resolution imaging

In this Letter,we report on the investigations of nonlinear scattering of plasmonic nanoparticles by manipulating ambient environments.We create different local thermal hosts for gold nanospheres that are immersed in oil,encapsulated in silica glass and also coated with silica shells.In terms of regulable effective thermal conductivity,silica coatings are found to contribute significantly to scattering saturation.Benefitting from the enhanced thermal stability and the reduced plasmonic coupling provided by the shell-isolated nanoparticles,we achieve super-resolution imaging with a feature size of 52 nm(λ/10),and we can readily resolve pairs of nanoparticles with a gap-to-gap distance of 5 nm.

Mercuric ions induced aggregation of gold nanoparticles as investigated by localized surface plasmon resonance light scattering and dynamic light scattering techniques

With the development of nanosciences, both localized surface plasmon resonance light scattering （LSPR-LS） and dynamic light scattering （DLS） techniques have been widely used for quantitative purposes with high sensitivity. In this contribution, we make a comparison of the two light scattering techniques by employing gold nanoparticles （AuNPs） aggregation induced by mercuric ions. It was found that citrate-stabilized AuNPs got aggregated in aqueous medium in the presence of mercuric ions through a chelation process, resulting in greatly enhanced LSPR-LS signals and increased hydrodynamic diameter. The enhanced LSPR-LS intensity （A/） is proportional to the concentration of mercuric ions in the range of 0.4-2.5 laM following the linear regression equation of A/= -84.7＋516.4c, with the correlation coefficient of 0.983 （n = 6） and the limit of determi- nation （3o-） about 0.10 gM. On the other hand, the increased hydrodynamic diameter can be identified by the DLS signals only with a concentration of Hg2＋ in the range of 1.0-2.5 gM, and a linear relationship between the average hydrodynamic diame- ters of the resulted aggregates and the concentration of Hg2＋ can be expressed as d = -6.16 ＋ 45.9c with the correlation coeffi- cient of 0.994. In such case, LSPR-LS signals were further applied to the selective determination of mercuric ions in lake water samples with high sensitivity and simple operation.

Enhancement of Perovskite Solar Cells by Plasmonic Nanoparticles

Synthetic perovskites with photovoltaic properties open a new era in solar photovoltaics. Due to high optical absorption perovskite-based thin-film solar cells are usually considered as fully absorbing solar radiation on condition of ideal blooming. However, it is not really so. The analysis of the literature data has shown that the absorbance of all photovoltaic pervoskites has the spectral hole at infrared frequencies where the solar radiation spectrum has a small local peak. This absorption dip results in the decrease of the optical efficiency of thin-film pervoskite solar cells and closes the ways of utilising them at this range for any other applications. In our work we show that to cure this shortage is possible complementing the basic structure by an inexpensive plasmonic array.

The enhancement of 21.2%-power conversion efficiency in polymer photovoltaic cells by using mixed Au nanoparticles with a wide absorption spectrum of 400 nm–1000 nm

Au nanoparticles （NPs） mixed with a majority of bone-like, rod, and cube shapes and a minority of irregu- lar spheres, which can generate a wide absorption spectrum of 400 nm-1000 nm and three localized surface plas- mon resonance peaks, respectively, at 525, 575, and 775 nrn, are introduced into the hole extraction layer poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS） to improve optical-to-electrical conversion performances in polymer photovoltaic ceils. With the doping concentration of Au NPs optimized, the cell performance is significantly improved： the short-circuit current density and power conversion efficiency of the poly（3-hexylthiophene）： [6,6]-phenyl- C60-butyric acid methyl ester cell are increased by 20.54% and 21.2%, reaching 11.15 mA.cm-2 and 4.23%. The variations of optical, electrical, and morphology with the incorporation of Au NPs in the cells are analyzed in detail, and our results demonstrate that the cell performance improvement can be attributed to a synergistic reaction, including： 1） both the local- ized surface plasmon resonanceand scattering-induced absorption enhancement of the active layer, 2） Au doping-induced hole transport/extraction ability enhancement, and 3） large interface roughness-induced efficient exciton dissociation and hole collection.

Single-molecule surface-enhanced Raman scattering： Current status and future perspective

The single-molecule surface-enhanced Raman scattering （smSERS） has been extensively studied after the initial observation in 1997, yet there still exist unsettled issues in the fundamental mechanism of smSERS. In this review, we survey some of the recent breakthroughs in the mechanism of smSERS and its application.

Fundamental studies on enhancement and blinking mechanism of surface-enhanced Raman scattering （SERS） and basic applications of SERS biological sensing

We review recent our results in the fundamental study of surface-enhanced Raman scattering （SERS） with emphasis on experiments that attempted to identify the enhancement and blinking mechanism using single Ag nanoparticle dimers attached to dye molecules. These results are quantitatively discussed in the framework of electromagnetic mechanism. We also review recent our results in basic SERS applications for biological sensing regarding detections of cell surface molecules and distinction of disease marker molecules under single cell and single molecule level.

单纳米粒子表面的甲醇电催化氧化过程

由于全球资源短缺和环境污染等问题日益加剧,开发利用洁净高效的新能源已成为当今社会研究热点.其中,直接甲醇燃料电池(DMFC)具有低温启动、无需重整制氢、洁净环保和体积小巧等特性,展现出较好的应用前景.DMFC的阳极反应为甲醇氧化反应,甲醇的完全氧化涉及到复杂的六步电子转移反应过程.揭示甲醇氧化的反应路径与机理,阐明催化剂的真实活性中心以及毒化效应,对于高效催化剂的设计和制备至关重要.随着纳米技术的发展,在单颗粒水平对纳米催化剂进行表征受到了越来越多的关注.因此,亟需发展具有高灵敏度的原位界面表征方法,实现纳米尺度的精准测量,排除催化剂平均效应,获取纳米表界面真实的催化反应信息.本文结合纳米等离子共振散射光谱与电化学技术,获得了单个纳米催化剂的同步光电响应信号,实现单颗粒水平纳米粒子表面化学、电化学反应过程(如电荷转移、分子吸附等)的高灵敏监测,揭示纳米尺度表界面催化反应机制.利用这一技术,动态监测了单个金/铂包金纳米颗粒表面的甲醇氧化过程.结果表明,在金纳米颗粒表面,甲醇氧化主要通过HCOOH路径,生成产物为HCOOH或CO_(2).其中,反应中间体与羟基离子的竞争性吸附起到重要作用,反应决速步为Au-OH和Au-CHO的共吸附.而铂催化甲醇氧化主要经过CO路径,决速步为Pt-OH和Pt-CO氧化生成Pt-COOH过程.此外,观测到金和铂氢氧化物为催化反应的活性物种,进一步证实了金属氧化物对于催化活性的钝化作用.结合密度泛函理论模拟,明确了甲醇氧化反应中间体吸附与金属氢氧化物演变之间的内在联系.综上,本文利用纳米等离子共振散射光谱,原位监测了单个纳米粒子表面的甲醇电催化氧化过程,实现了催化剂真实活性物种演变与失活过程的直接观测,揭示了不同催化剂表面的决速步骤,为提高催化反应效率提供了更加准确的反应信息.本文将有益于纳米等离子共振散射光谱在电催化反应高灵敏监测方面的广泛应用,并为高效甲醇催化剂的制备提供参考.

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.

Performance optimization of dye-sensitized solar cells by gradient-ascent architecture of SiO_2@Au@TiO_2 microspheres embedded with Au nanoparticles

Highly homogeneous, well dispersed SiO_2@Au@TiO_2(SAT) microspheres decorated with Au nanoparticles(AuNPs) were prepared and incorporated into the photoanode with an optimized concentration gradientascent. The effects of SAT microspheres and the gradient-ascent architecture on the light absorption and the photoelectric conversion efficiency(PCE) of the dye-sensitized solar cells(DSSCs) were investigated.Studies indicate that the introduction of SAT microspheres and the gradient-ascent architecture in the photoanode significantly enhance the light scattering and harvesting capability of the photoanode. The DSSC with the optimized SAT gradient-ascent photoanode has the maximum short circuit current density(J_(sc)) of 17.7 mA cm^(-2) and PCE of 7.75%, remarkably higher than those of the conventional DSSC by 23.7%and 28.0%, respectively. This significantly enhancement of the performance of the DSSC can be attributed to the excellent light reflection/scattering of SAT, the localized surface plasma resonance(LSPR) effect of AuNPs within the microspheres, and the gradient-ascent architecture of SAT microspheres inside the photoanode. This study demonstrates that the tri-synergies of the scattering of SAT microspheres, the LSPR of AuNPs and the gradient-ascent architecture can effectively improve the PCE of DSSC.

暗场显微镜下的彩色“纳米星”

具有独特局域表面等离子共振散射特性的贵金属纳米粒子,在可见光区域表现出明显的吸收和散射光谱特性。在过去的几十年中,基于纳米金和纳米银溶液的可视化颜色传感器,被广泛应用在金属离子、生物分子、农药等灵敏检测。自2000年,暗场显微镜的出现,实现了纳米尺度下等离子共振散射光谱的精准获取,将传感尺度从传统的实验试管发展到单纳米颗粒界面。单颗粒检测消除了本体溶液中大量纳米粒子产生的平均效应,可提供更加准确的反应信息。纳米粒子的散射光谱主要取决于颗粒的尺寸、形貌、成分以及颗粒间耦合作用等,因此,具有特定散射颜色的单个纳米粒子,可以作为优异的纳米探针。这篇综述聚焦于单颗粒纳米传感,首先介绍了纳米粒子局域表面等离子共振的原理和发展历史。随后,主要讨论了单个贵金属纳米粒子作为颜色编码传感器,在生物分子、环境污染物以及能源等领域的应用,尤其是基于单颗粒的原位纳米光谱电化学传感及其在电催化反应中的应用。例如,利用纳米粒子的溶出和生长过程,精巧地设计了针对不同待测物的纳米探针。另一方面,对单纳米粒子结构演变过程的原位监测,也有助于对纳米材料制备机理的理解。最后,着重探讨了纳米颜色传感器信号提取放大的检测手段,包括将肉眼识别的颜色转换为可读的三原色信息以及偏振光检测技术等,进一步扩展单颗粒颜色传感的应用范围。

Unidirectional emissions from dielectric photonic circuits decorated with plasmonic phased antenna arrays

Thanks to resonant characteristics of metallic nanoparticles, optical waves scattered from plasmonic nanoantennae can be well tailored in both amplitude and phase. We numerically demonstrate that, by varying the lengths and the lateral positions of gold nanorods in vicinity of a silicon waveguide, unidirectional emissions with typical forward-backward contrast ratio of 15 dB and directivity of 12 dB can be acquired in a plasmonic phased antenna array with sub-wavelength device length. The properties, i.e., the emission directionality and the size compactness, can be employed to control the far-field radiation pattern from a dielectric photonic circuit. Moreover, by altering the orientations of the dielectric waveguides decorated with plasmonic phased antenna arrays, we propose wireless light transportations in a layered photonic infrastructure, which may have applications in high-density photonic integrations.

帽状铜纳米粒子的制备及表面增强拉曼散射活性研究

采用真空热蒸发法在SiO2纳米粒子自组装单层膜上沉积铜薄膜制备了帽状铜纳米粒子。用扫描电镜、原子力显微镜和紫外-可见-近红外分光光度计对帽状复合纳米粒子的表面形貌和光学性质进行了表征。以亚甲基蓝和吡啶-(2-偶氮-4)间苯二酚为探针分子,研究了该复合纳米粒子的表面增强拉曼散射(SERS)活性。通过比较吸附在不同基底上的吡啶-(2-偶氮-4)间苯二酚的谱峰强度,探讨了SERS效应与表面等离子体共振(SPR)的关系。

局域表面等离子效应的新应用

评述局域表面等离子体最新研究进展,介绍近年来在金属纳米颗粒和纳米结构的表面等离子体光学理论和实验研究上取得的一些成果,包括银纳米粒子的制备以及不同形状、尺寸等因素对局域表面等离子体光谱的影响、表面等离子体共振放大拉曼散射的增强、等离子激光、等离子非线性效应及局域表面等离子光热效应等.探讨表面等离子体光学结构在纳米尺度上对光的各种性质的调控以及局域表面等离子体在纳米生物光子学方面的新应用.

金属粒子阵列共振的偏振特性

当金属纳米粒子形成规则分布且阵列周期与单粒子的共振波长近似匹配时,会形成一种特殊的阵列共振,这种共振比单粒子的局域表面等离子体共振具有更窄的共振线宽和更高的共振强度.基于修正的长波近似方法,讨论了矩形阵列的消光截面与阵列因子和单粒子的极化率之间的关系;并详细研究了在不同偏振的入射光照射下,阵列因子随着电偶极子方向的改变而产生的变化,以及这一效应对阵列共振和消光截面所产生的影响.结果表明,大型的方阵是偏振无关的;在矩形阵列中,沿着阵列两个轴向的相邻粒子之间的耦合形成了阵列因子的两个极值,并且分别对应了散射截面的最小值.

帽状金纳米结构的制备、表征及表面增强拉曼散射活性

采用真空离子溅射法在自组装的单层阵列二氧化硅纳米粒子表面沉积金薄膜,制备了以S iO2为核的帽状金纳米结构.用透射电镜、扫描电镜、原子力显微镜、X射线衍射仪和紫外-可见-近红外分光光度计对样品的表面形貌、结构及光学性质进行了表征.以亚甲基蓝作为探针分子,对金纳米帽的表面增强拉曼散射活性进行了研究,结果显示,吸附在金纳米帽上的分子拉曼散射信号得到显著增强,增强因子达到107数量级.该基底在超灵敏生物和化学检测方面具有潜在的应用前景.

基于纳米金等离子体共振光散射法测定阿米卡星

为简便、快速地对阿米卡星的注射液进行检测,基于纳米金颗粒的等离子体共振效应建立了一种检测阿米卡星的新方法。在适宜pH值的KH_2PO_4-Na_2HPO_4缓冲溶液中,利用阿米卡星与纳米金相互作用,使反应体系在640nm处共振光散射信号显著增强,且共振光散射强度增强值ΔI640nm与阿米卡星质量浓度在1.5~500ng/mL范围内线性相关,检出限为0.52ng/mL。在确定的实验条件下,阿米卡星可诱导纳米金颗粒聚集,纳米金颗粒之间距离的变化使其等离子体共振效应发生明显改变,聚集的纳米金颗粒表面等离子体耦合产生了较强的共振光散射信号,且共振光散射信号增强值与阿米卡星的浓度变化值呈现良好的线性关系。实验表明,该方法可用于快速测定阿米卡星。

金属纳米颗粒增强太阳能电池光吸收效应研究

采用Mie理论,对球形纳米金属颗粒进行数值计算,研究了金属纳米颗粒在发生表面等离激元共振时表现出的散射效应.改变金属材料类型或者颗粒尺寸大小,金属纳米球的散射效率均发生不同程度的变化.这一现象表明:金属纳米颗粒的散射效应受材料类型和尺寸大小的影响显著.计算结果表明,半径为100nm的Ag纳米颗粒在发生表面等离激元共振时,散射效率最高,吸收效应最弱.