利用纳米金局域表面等离子体共振散射方法检测痕量汞(Ⅱ)

在Britton-Robinson(BR)(pH为9.0)缓冲介质中,微量Hg(Ⅱ)离子能诱使被巯基乙酸钠包被的AuNPs发生聚集,以此诱发局域表面等离子体共振(localized surface plasmon resonance, LSPR)散射峰的出现,随着Hg(Ⅱ)浓度的不断增加,体系在548 nm的LSPR散射信号显著增强,其散射强度与Hg(Ⅱ)的浓度具有相关性,且在0.08～0.8 μmol·L-1范围内呈现一定的线性关系,由此构建了以Hg(Ⅱ)为目标分析物的LSPR散射分析检测方法,检测限为8 nmol·L-1。研究了体系的LSPR散射光谱以及吸收光谱,利用扫描电镜考察了AuNPs与Hg(Ⅱ)反应前后粒径的变化情况,发现单独的AuNPs呈现良好的分散状态,当加入Hg(Ⅱ)后,AuNPs呈现聚集状态。同时探讨了体系反应机理,结果表明Hg(Ⅱ)的加入与AuNPs表面的羧基发生螯合作用诱导了AuNPs的聚集。考察了体系对金属离子Hg(Ⅱ)的选择性,实验中选择了一系列的金属离子与AuNPs作用,其结果表明Hg(Ⅱ)与AuNPs作用的LSPR散射信号增强效果最为明显,而其余离子即使在浓度较高时其LSPR散射强度依然较弱,说明了实验设计方案对Hg(Ⅱ)具有优异的选择性。此外,研究了体系酸度,离子强度以及稳定剂对体系的影响。实验所建立起来的方法操作简单,分析速度快速,检测灵敏度较高。该方法已经成功用于环境水样中痕量Hg(Ⅱ)的检测。     

内嵌圆饼空心方形银纳米结构的光学性质

采用离散偶极子近似方法计算了内嵌圆饼空心方形银纳米结构的消光光谱以及其近场的电场强度分布,并进一步与空心方形纳米结构的消光光谱和表面电场做比较.结果表明,在耦合作用下内嵌圆饼空心方形银纳米结构不仅产生了新的共振模式,而且新的共振模式在传统表面增强拉曼散射的激发波长范围内,进而可以弥补由于实验上运用纳米切片法所制备的空心方形纳米结构尺寸较大导致其共振吸收峰在远红外波长范围的不足.此外,可以通过改变内嵌圆饼空心方形银纳米结构的形貌参数调节其表面等离子体共振峰的共振波长,以满足在表面增强拉曼散射、生物分子或化学分子探测上的应用.     

Profile calculation of gold nanostructures by dispersed-nanosphere lithography through oblique etching for LSPR applications

Nanosphere lithography is an inexpensive method used to fabricate gold nanostructures on a substrate. Using dispersed-nanosphere lithography, in which the nanospheres are dispersed on a substrate, 2D or 3D nanostructures can be fabricated by obliquely depositing a gold film on the nanospheres and etching the gold film afterward. These nanostructures are tunable and acute, and are thus good emitting elements for the localized surface plasmon resonance applications. So far, for the fabrication of nanostructures on a substrate with dispersed nanospheres, only 2D nanostructures have been reported through perpendicular etching. We report in this paper that the 3D nanostructures fabricated by dispersed-nanosphere lithography are rigid non-conformal structures, and perpendicular gold etching can be expanded to oblique etching, which provides more possibilities for fabricating the gold nanostructures in various shapes. The profiles of gold nanostructures after several varying angle depositions, and their final profiles after perpendicular or oblique etching, are calculated in this paper. Our profile simulations are applicable for nanospheres (or microspheres) within the range of tens of nanometers to tens of micrometers, and are consistent with our fabricated nanostructures observed using scanning electron and atomic force microscopy. Electronic Supplementary Material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Resonant light absorption and plasmon tunability of lateral triangular Au nanoprisms array

Optical characteristics and electric field distribution of triangular Au nanoprism in a unit and units array under polarized light irradiation were systematically studied by numerical simulation with finite difference time domain method. It is found that the plasmonic properties of the triangular nanoprism are dominated by the electric polarization rather than the wave propagation. The triangular nanoprism presents similar optical response with a strong dipole band under different wave propagations if the electric polarization vectors are parallel to the triangular cross section. The lateral triangular Au nanoprisms array possesses a large tunability of the plasmonic properties contributed from the combined influence of inter-particle distance, particles size, polarization angle and even environmental medium. From the plasmon band shift versus the refractive index, ultra-high local surface plasmon resonance sensitivity (509.96 nm/RIU, figure of $\text{merit}=5.55$) is reached at $\sim 850\text{nm}$, making this array promising for biochemical sensing applications.     

Ag-Al纳米球二聚体的光学性质研究

金属纳米材料因其表面等离子体共振特性而备受关注。异质结构的金属纳米材料的光学特性相比于同质结构因其材料的不同破坏了原有结构的对称性,对称性的破坏将引起光学性质的改变,相邻两个颗粒之间的相互作用会产生Fano共振。Fano共振是由异质纳米结构的表面等离子体共振耦合引起的,通过合理地调控表面等离子体共振的耦合,将进一步调控Fano共振的强度同时促使异质结构的电场增强特性和辐射特性得到进一步优化。受金银等贵金属的带间跃迁影响,金属铝纳米材料成为研究紫外-近紫外光区的表面等离子体共振研究最佳选择。采用有限时域差分方法研究了Ag-Al纳米球二聚体的光学特性。研究了Ag和Al纳米球组成的二聚体的吸收光谱与入射光偏振方向、纳米球半径、颗粒间距和介质折射率等几何结构及物理参数的关系,并深入讨论了二聚体的局域场分布规律;讨论了获取更高效的Fano共振光谱的方法。由于材料的对称性被破坏,异质二聚体的光学性质与同质二聚体明显不同,Ag-Al异质纳米球二聚体呈现出在紫外和可见光区的双Fano共振现象。Ag-Al二聚体表面等离子体互相耦合引起Fano共振从而导致表面等离子体的共振抑制和增强。研究结果对在紫外-可见光区的表面等离子体应用、纳米光学器件的设计与开发及基于表面等离子体共振的表面增强光谱、生物传感和检测研究等有一定参考价值。     

Transmission properties of periodically patterned triangular prisms

Transmission properties of plasmonic structure arrays are simulated by finite element method. The array unit is composed of two combined triangular prisms. Results reveal that several resonant modes are found in the transmission spectra, which are due to the resonance of the surface plasmon polariton in the metal slit or to the localized surface plasmon resonance of the combined prisms. The resonant wavelengths can be tuned by changing the structural parameters of the combined prisms. In addition, the resonant modes are sensitive to small refractive index changes of the surrounding media, revealing potential detection applications in nanophotonic systems.     

基于芯片实验室技术的表面增强光谱学在分析科学中的应用

集成具有一序列微流控操作单元的芯片实验室技术,在微流控通道内铺陈金属纳米粒子(尤其是金、银以及铜纳米粒子)作为衬底,泵入多通道微纳升分析物,用于联用表面增强光谱在痕量、实时、原位、过程反应等检测中具有重要的意义。这种联用检测技术集成了芯片实验室和表面光谱两种技术的优点：芯片实验室技术集成流程式分步操作,实现筛选取样,分段、实时反应检测,减小样品量,稳定测试环境等优势以及表面增强光谱的光谱响应快,灵敏性和选择性强、原位检测等优点。借助于Drude模型以及适当的边界条件,外电场引发金属颗粒价电子的局域等离子振荡,并推导了产生共振的局域表面等离子增强以及受激感应偶极子振荡产生表面拉曼增强的物理电磁增强机制。综述了芯片实验室表面局域等离子检测在生物、医药、食品安全等方面的应用,检测通道的增加促使检测效率有较大的提高,同时检测限能力获得较大的突破。综述了芯片实验室技术结合表面增强拉曼光谱公共安全、生物医学、电化学和生物传感器等领域的应用, 表面增强拉曼光谱的高度灵敏性以及指纹性应用于痕量检测。根据芯片实验室技术在研究开发和应用已经获得不断的进展,结合3D打印技术,精准控制多通道结构尺寸,更好地满足设计的需求。表面等离子增强光谱以及表面增强拉曼光谱等表面光谱检测技术在应用上日趋成熟,获得突破传统显微镜的光学极限的分辨能力。这种联用技术在实际定性或者半定量痕量分析检测应用中具有光明的前景。     

Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance

The specific optical characteristics which can be observed from noble metal nanostructured materials such as nanoparticles and nanoislands have wide variety of applications such as biosensors, solar cells, and optical circuit. Because, these noble metal nanostructures induce the increment of light absorption efficiency by the enhancing effect of electrical field from localized surface plasmon resonance (LSPR) excitation. However, the enhancing effects of electrical field from LSPR using simple structured noble metal nanostructures for several applications are not satisfactory. To realize the more effective light absorption efficiency by the enhancing effect of electrical field, quite different noble metal nanostructures have been desired for applying to several applications using LSPR. In this study, to obtain the more effective enhancing effect of electrical field, conditions for LSPR excitation using a gold-capped nanoparticle layer substrate are computationally analyzed using finite-difference time-domain (FDTD) method. From the previous research, LSPR excitation using such gold-capped nanoparticle layer substrates has a great potential for application to high-sensitive label-free monitoring of biomolecular interactions. For understanding of detailed LSPR excitation mechanism, LSPR excitation conditions were investigated by analyzing the electrical field distribution using simulation software and comparing the results obtained with experimental results. As a result of computational analysis, LSPR excitation was found to depend on the particle alignment, interparticle distance, and excitation wavelength. Furthermore, the LSPR optical characteristics obtained from the simulation analysis were consistent with experimentally approximated LSPR optical characteristics. Using this gold-capped nanoparticle layer substrate, LSPR can be excited easily more than conventional noble metal nanoparticle-based LSPR excitation without noble metal nanoparticle synthesis. Hence, this structure is detectable a small change of refractive index such as biomolecular interactions for biosensing applications.     

十字形银纳米结构的表面等离子体光子学性质

本文应用离散偶极子近似方法计算了十字形银纳米结构的消光光谱及其近场电场强度分布. 研究表明相比于单根纳米棒, 十字形纳米结构能够提供更强的表面电场; 由于相邻凸起间的电场耦合作用, 当入射光的偏振方向改变时, 在十字形纳米结构的侧表面总能激发出较强的电场.另外, 本文还系统地研究了十字形纳米结构的形貌参数对其表面等离子体共振峰的影响. 这些结果将会指导十字形纳米结构的制备, 以满足其在表面增强拉曼散射中的应用.     

Deviating from the nanorod shape: Shape-dependent plasmonic properties of silver nanorice and nanocarrot structures

Noble metallic nanostructures exhibit special optical properties resulting from excitation of surface plasmons. Among the various metallic nanostructures, nanorods have attracted particular attention because of their unique and intriguing shape-dependent plasmonic properties. Nanorods can support transverse and longitudinal plasmon modes, the latter ones depending strongly on the aspect ratio of the nanorod. These modes can be routinely tuned from the visible to the near-infrared spectral regions. Although nanorods have been investigated extensively, there are few studies devoted to nanostructures deviating from the nanorod shape. This review provides an overview of recent progress in the development of two kinds of novel quasi-one-dimensional silver nanostructures, nanorice and nanocarrot, including their syntheses, crystalline characterizations, plasmonic property analyses, and performance in plasmonic sensing applications.     

Confocal white light reflection imaging for characterization of metal nanostructures

A simple far-field confocal white light reflection imaging system was proposed using a xenon (Xe) lamp as the incident light source. The best spatial resolution was determined to be about 410 nm. Localized surface plasmons (LSPs) of isolated single and dimer gold nanospheres were studied and the resonance energy difference between their LSPs was extracted. Polarization dependent reflection imaging and contrast spectrum of single silver nanowires were also investigated, which correlate closely with the polarization dependent excitation of their LSP.     

有序金纳米颗粒阵列的制备及光吸收特性研究

采用纳米球刻蚀技术中漂移法在玻璃基片上制备较大 面积不同直径的聚苯乙烯小球掩模板, 采用磁控溅射技术在掩模板上沉积不同厚度的金薄膜, 去除聚苯乙烯小球后, 通过扫描电子显微镜观察到周期排列的三角状金纳米颗粒点阵. 通过紫外-可见分光光度计测试所制备样品的光吸收特性, 发现表面等离子体共振峰随粒径增大发生红移, 随金纳米颗粒高度增加发生蓝移. 基于Mie理论, 利用Matlab软件编程对不同粒径的金阵列光吸收特性进行理论模拟, 并与实验结果进行对比. 关键词： 纳米球刻蚀 金纳米颗粒阵列 表面等离子体共振     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒(Au nanorods)作为种子,借助形成核/壳结构,诱导了Ag, Pd, Pt棒状纳米结构的形成,并实现了对杂化纳米结构光学和催化性能的调控,进一步扩展了贵金属纳米结构的应用范围.作者的研究结果表明,形成杂化纳米结构是性能调控的一种有效方式.     

Fano resonances in complex plasmonic super-nanoclusters: The effect of environmental modifications on the LSPR sensitivity

In this study, gold nanodisk clusters in heptamer orientations as clusters were used to design a super-heptamer consisting of one central and six peripheral heptamers. We examined the position and movement of the plasmon and Fano resonances by sketching the spectral response of the superstructure for various nanodisk dimensions. The quality of the interference between the superradiant and subradiant plasmon resonance modes of the nanodisk clusters was found to depend strongly on the structural configuration and the refractive index of the environmental medium. We replaced the central heptamer with a nanodisk and probed the position of the Fano resonance by geometrically altering the nanodisk structure. Finally, the effect of the dielectric environment on the plasmon response of both of the studied structures was examined numerically and theoretically. The localized surface plasmon resonance sensitivity of the finite plasmonic structures to the presence of liquid substances was investigated and shown by plotting the linear figure of merit. The finite-difference time-domain method was used as a numerical tool to investigate the plasmon response of the structure.     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒（Au nanorods）作为种子,借助形成核/壳结构,诱导了Ag...     

多层金属纳米点阵的制备及其光学性质的研究

采用纳米球刻蚀法结合热蒸发技术制备了银和氧化硅交替层叠的纳米颗粒阵列. 扫描隧道显微镜测量结果表明, 该纳米阵列呈锥形多层结构. 分光光度计测量样品表明, 该纳米阵列在近红外波段存在明显的透射谷, 该透射谷来源于金属纳米颗粒局域等离激元的激发, 随着金属/介质层数的增多, 透射谷的位置向短波方向移动. 利用HFSS软件对该纳米阵列进行了仿真, 并分析了透射谷蓝移的原因. 关键词： 纳米球刻蚀技术 金属/介质纳米颗粒 表面等离子激元     

Au:TiO2和Au:Al2O3纳米颗粒复合膜的线性和非线性光学特性

主要从实验和理论两个方面,探讨了不同Au颗粒尺寸和不同基质对Au：TiO₂和Au：Al₂O₃复合膜线性和非线性光学性质的影响.用吸收光谱研究了Au颗粒尺寸和基质与Au复合膜表面等离子体共振带之间的关系;用皮秒Z扫描技术研究了共振和非共振情况下(激发光波长分别为532nm和1064nm),Au颗粒尺寸和基质与复合膜三阶非线性极化率的关系.基于表面等离子体共振理论和局域场增强理论对复合膜进行了分析,得到了不同Au颗粒大小和不同基质时Au复合膜的 关键词： 金属纳米颗粒 复合膜 三阶非线性 表面等离子体共振     

Aqueous phase Ag nanoparticles with controlled shapes fabricated by a modified nanosphere lithography and their optical properties

We have developed a modified nanosphere lithography (NSL) process to fabricate surface-confined Ag nanoparticles (NPs) with controlled shapes. NPs with different shapes, such as triangular, quadrilateral, pentagon or trapezoidal with rounded tips or edges, can be fabricated by this process. These Ag NPs can be dislodged into water forming NPs in an aqueous environment. The developed process results in better NP shape retaining than those obtained using the routine NSL process. The UV-vis absorption of the surface-confined Ag NPs show distinct blue shift and reduced intensity after surface modification. The NPs produced by the modified NSL and dislodged in water have significantly less density of debris as observed by transmission electron microscopy and UV-vis absorption spectrum.     

Investigation of optical properties of modulation doped GaN/AlGaN MQWS nanostructures

Due to many important applications, the group III-nitride semiconductors have recently attracted remarkable attention among the semiconductor researchers and engineers. In this paper, we report on the impact of the extrinsic and temporal carriers on the screening of the polarization internal fields. The optical efficiency of GaN/AlGaN multiple quantum well (MQW) nanostructures were studied by means of photoluminescence (PL) and time-resolved PL measurements. Extrinsic carriers come from Si doping in the barriers while temporal carriers originate when the samples are excited by the laser beam. The emission peaks of MQWs in PL spectra of the undoped and low-doped samples show a shift towards higher energy levels as excitation intensity increases, while the other samples do not exhibit such a phenomenon due to the dominance of the extrinsic carriers. The transient data confirm the results of the PL measurements.