SPR and SERS characteristics of gold nanoaggregates with different morphologies

In this study, surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS) characteristics of gold nanoaggregates with different morphologies are examined to elucidate the correlation between SPR and SERS of the object. Nanoaggregates, defined as random aggregates (hereafter RA), elongated aggregates (hereafter EA) and two-dimensional layered aggregates (hereafter 2DLA) are fabricated by immobilizing colloidal gold nanoparticles on glass substrates. The color variation observed in the RA and EA samples indicates the variation in localized SPR excitations excited on the samples. The RA sample mostly shows a broadened and shifted SPR peak centered at 570 nm in addition to another peak in the longer wavelength region (∼700 nm), whereas in the EA sample a weak blue-shifted peak is observed near 450 nm in addition to a broadened peak centered at 570 nm covering a trail for another one near 700 nm. In the case of the 2DLA sample, more than one SPR peaks are observed in the longer wavelength region. The SERS observation confirms million times higher enhancement at least in Raman intensity using the gold nanoaggregates adsorbed by dye molecules. The EA sample of gold nanoparticles shows ∼5 times higher enhancement in Raman signal compared to that of the RA and 2DLA sample.     

Sensitivity enhancement based on application of multi-pass interferometry in phase-sensitive surface plasmon resonance biosensor

A novel design of multi-pass surface plasmon resonance (SPR) biosensor with differential phase interrogation based on multi-pass interferometry is presented. This new configuration provides an intrinsic phase amplification effect of over twofold by placing the SPR sensor head in a signal arm of the interferometer so that the interrogating optical beam will traverse the sensor surface infinite number of times. Experimental interferometers based on the Michelson and Fabry–Perot configurations have been employed to experimentally verify this amplification effect when they were compared with Mach–Zehnder configuration, results obtained from salt–water mixtures, antibody–antigen, and protein–DNA binding reaction confirmed the expected phase measurement enhancement, thus leading to the possibility of direct detection of small sized bio-molecules using SPR.     

银纳米链状材料的制备及近红外吸收性质

报道了利用水/油相界面反应,采用湿化学法合成银纳米链状材料的方法,并对这种材料的近红外吸收性质和光热转换性质进行了研究。TEM分析表明,银纳米材料为链状结构,直径约为50nm,长度分布范围较宽,从几十纳米至几百纳米。这种材料具有强的近红外吸收特性,随着还原剂加入量的增加,吸收带逐渐展宽(800～1300nm),而且平坦。这种材料具有优异光热转换性质,一经808nm激光照射,温度迅速提高。该材料优异的近红外吸收和光热转换性质,使其在红外断层成像和近红外热疗等领域具有广阔的应用前景。     

Experimental study of sensitivity enhancement in surface plasmon resonance biosensors by use of periodic metallic nanowires

We have experimentally confirmed sensitivity enhancement of a nanowire-based surface plasmon resonance (SPR) sensor structure. Gold nanowires with periods of 200 and 500 nm were fabricated, respectively, by electron-beam and interference lithography on a gold/SF10 substrate. Sensitivity enhancement was measured to be 44% compared with a conventional thin-film-based SPR structure for nanowires of 200 nm period and 31% for 500 nm when evaluated using ethanol at a varied concentration. This result is consistent with numerical data. Surface roughness is responsible for sensitivity reduction by more than 10%. More significant sensitivity improvement can be achieved by inducing strong localized plasmon coupling with finer nanowires.     

纳米金表面修饰与表面等离子体共振传感器的相互作用研究

为了分析纳米金表面修饰对表面等离子体共振(SPR)的放大作用,以及其对传感器本身的影响,首先,基于色散介质的吸收理论,通过建立波长型SPR生物传感器四层膜结构的数学模型,理论分析了传感器表面所吸附纳米金对传感器的影响:纳米金的表面修饰,改变了表面等离子体传感器中棱镜表面各介质层内电磁场的能量分布,削弱了金属膜在共振吸收中的作用,从而使SPR曲线的半波宽度增加,最小反射系数增大,金膜的最优膜厚度也随之改变.其次,通过不同厚度的金膜外吸附纳米金的对比试验,验证了此理论.金膜厚45nm、表面修饰10nm纳米金颗 关键词： 表面等离子体共振 生物传感器 纳米金 金属膜     

Shape tailoring of hexagonally ordered triangular gold nanoparticles with nanosecond-pulsed laser light

In this contribution recent results on selective and precise tailoring of triangular gold nanoparticles (NPs) using ns-pulsed laser light are presented. The NPs were prepared by nanosphere lithography and subsequently tailored with ns-pulsed laser light using different fluences and wavelengths. The method is based on the size and shape dependent localized surface plasmon polariton resonance (SPR) of the NPs. We will demonstrate that the gap size between triangular NPs can be tuned from approximately 102±14 nm to 122±11 nm, due to a shape change of the NP from triangular to oblate. These morphological changes are accompanied by a significant shift of the surface plasmon resonance from λ_SPR=730 nm to λ_SPR=680 nm. Most importantly if the laser wavelength is chosen such that the dipolar SPR is excited, the hexagonal order of the NPs remains intact after irradiation, in contrast to excitation via the quadrupole SPR or within the interband transition. A tuneable gap size and the conservation of the hexagonal order of the NP array is the precondition for applications, where the NPs should serve as anchor points, e.g. for functional molecular nanowires, which can be used to utilize molecular devices.     

Investigation of the surface properties of gold nanowire arrays

Gold nanowire arrays with diameters ranging from 45 to 200 nm were obtained via electrochemical deposition within the ion-track templates. The morphology of gold nanowires was imaged by scanning electron microscopy (SEM). The surface properties were investigated by surface plasmon resonance (SPR) and X-ray photoelectron spectroscopy (XPS). The SPR peaks were observed as the gold nanowire arrays embedded in the templates and their intensity decreased after the sample exposed to the air for a certain time due to the formation of chemisorbed oxygen on nanowire surface. The positive binding energy shifts in Au core level was found when the gold nanowire arrays embodied in template and the initial- and finial-state effects were introduced to explain this phenomenon.     

Nanostars on a fiber facet with near field enhancement for surface-enhanced Raman scattering detection

A 4-pointed gold nanostar is proposed to form the array on a fiber facet to achieve a greatly enhanced near field intensity for Surface-Enhanced Raman Scattering (SERS) detection. The proposed gold nanostar array has a Surface Plasmon Resonance (SPR) peaked at a wavelength of ～650 nm with up to 45 times electric field intensity enhancement compared with the state-of-the-art nanorod design. It has a wideband SPR field enhancement spanned from 600 to 720 nm, which covers the wavelengths for both the excitation light (632.8 nm) and the Raman signal of the analytes (675–706 nm); With symmetrical structure it forms four hot spots in every unit cell and can detect best for light polarized horizontal or perpendicular to the waist of the nanostars. It also could be altered to tune the SPR and allows the fiber sensor to resonate at different wavelengths, as demonstrated by an example at 533 nm. All the above features make the gold nanostar-based compact and portable fiber sensor an attractive solution for SERS detection.     

Nanostructuring of thin Au films by means of short UV laser pulses

The particle size distribution, morphology and optical properties of the Au nanoparticle (NP) structures for surface enhanced Raman signal (SERS) application are investigated in dependence on their preparation conditions. The structures are produced from relatively thin Au films (10–20 nm) sputtered on fused silica glass substrate and irradiated with several pulses (6 ns) of laser radiation at 266 nm and at fluencies in the range of 160–412 mJ/cm². The SEM inspection reveals nearly homogeneously distributed, spherical gold particles. Their initial size distribution of the range of 20–60 nm broadens towards larger particle diameters with prolonged irradiation. This is accompanied by an increase in the uncovered surface of the glass substrate and no particle removal is observed. In the absorption profiles of the nanostructures, the broad peak centred at 546 nm is ascribed to resonant absorption of surface plasmons (SPR). The peak position, halfwidth and intensity depend on the shape, size and size distribution of the nanostructured particles in agreement with literature. From peak intensities of the Raman spectra recorded for Rhodamine 6G in the range of 300–1800 cm⁻¹, the relative signal enhancement by factor between 20 and 603 for individual peaks is estimated. The results confirm that the obtained structures can be applied for SERS measurements and sensing.     

Formation of gold nanoparticles in heat-treated reactive co-sputtered Au-SiO2 thin films

In this work, formation of gold nanoparticles in radio frequency (RF) reactive magnetron co-sputtered Au-SiO₂ thin films post annealed at different temperatures in Ar + H₂ atmosphere has been investigated. Optical, surface topography, chemical state and crystalline properties of the prepared films were analyzed by using UV-visible spectrophotometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD) techniques, respectively. Optical absorption spectrum of the Au-SiO₂ thin films annealed at 800 °C showed one surface plasmon resonance (SPR) absorption peak located at 520 nm relating to gold nanoparticles. According to XPS analysis, it was found that the gold nanoparticles had a tendency to accumulate on surface of the heat-treated films in the metallic state. AFM images showed that the nanoparticles were uniformly distributed on the film surface with grain size of about 30 nm. Using XRD analysis average crystalline size of the Au particles was estimated to about 20 nm.     

Synthesis of colloidal gold nanobones with tunable negative curvatures at end surface and their application in SERS

In this work, gold nanobones with the length from 50 to 70 nm were synthesized by a seed-mediated method. The plasmonic optical properties and the roles of gold seed amount in regulating the negative curvatures of the end surfaces of the gold nanobones have also been studied. Compared with the gold nanorods, a new middle surface plasmon resonance (SPR) peak appears in the absorption spectra due to the negative curvatures on the end surfaces of the gold nanobones. What is more, the surface enhanced Raman scattering (SERS) activities of gold nanobones are much stronger than that of gold nanorods. By controlling the amount of the gold seed, the wavelength of the middle SPR peak can be adjusted between 560 and 650 nm, and the corresponding negative curvature of the end surfaces could also be fine tuned. When the amount of gold seed reaches saturation, the end surfaces of nanobones have the strongest negative curvature, which results in the greatest SERS activity. This improved SERS has been attributed to the negative curvature-induced formation of the antenna dimers. The orientation of plasmon coupling between the antenna dimers is perpendicular to the nanobones. Thus, the hot spots at the ends of nanobones could always be created when the excitation beam polarization is either parallel or perpendicular to the nanobones. This negative curvature-dependent SERS enhancement lays the foundation for the extensive application of gold nanobones in SERS.     

金和银纳米粒子二维周期阵列的光学性质

本文利用离散点偶极子近似方法(DDA)研究了金和银纳米粒子二维周期阵列的光学性质。研究结果表明二维周期阵列的消光性质及其表面等离子共振(SPR)波长受到阵列内粒子组成材料、粒子形状尺寸、阵列周期和阵列排布方式等因素的影响。对于二维正方阵列,当周期较小时(一般小于300 nm),阵列的共振波长主要取决于粒子组成材料和形状尺寸;当周期与阵列单体的共振波长附近时,阵列的消光谱中会出现极窄且锐的SPR共振峰,峰位只与阵列的周期值相关。改变阵列在平行和垂直于入射光偏振方向的周期,可以方便地调节二维长方阵列的共振峰的峰位和峰宽。     

Bimetallic Silver–Gold Film Waveguide Surface Plasmon Resonance Sensor

Abstract

It is desirable that a surface plasmon resonance (SPR) sensor is highly sensitive to binding interactions within the sensing region, generate evanescent fields with long penetration depths, and utilize a metal film that is very stable even in extreme environmental conditions. In this study, we present the first example of a wavelength-modulated waveguide SPR sensor with a bimetallic silver–gold film for surface plasmon excitation. The underlying silver yields better evanescent field enhancement of the sensing surface, while the overlying gold ensures that the stability of the metallic film is not compromised. It is shown experimentally that in terms of dλ/dn, the bimetallic film waveguide SPR configuration has a sensitivity of 1232 nm/RIU, greater than two times improvement from the 594 nm/RIU achievable with single gold film waveguide SPR sensor. The higher sensitivity, compact nature, and better evanescent field enhancement of this configuration provides the potential to biosensing applications.     

偏振控制光强调制型点阵SPR传感器研究

介绍了一种偏振控制光强调制型点阵表面等离子体共振(SPR)传感器,分析了入射角度、金膜厚度、起偏器设置、光源波长及数据处理方式对传感器灵敏度和线性范围的影响,并对632.8 nm与740 nm两种光源传感器系统进行了实验测试与分析.结果表明,偏振控制光强调制型点阵SPR传感器可将光经过表面等离子体共振所产生的偏振态变化...     

Rapid synthesize of gold nanoparticles by microwave irradiation method and its application as an optical limiting material

We present rapid synthesis of gold nanoparticles by microwave irradiation method. Sample with average particle size 7.7 nm is obtained from TEM. Linear and nonlinear optical studies of the prepared samples are discussed. Reverse saturable absorption (RSA) at longitudinal surface plasmon resonance (SPR) in gold nanoparticles (Au NPs) have been observed using Z-scan and transient absorption techniques with 532 nm laser pulses. Such RSA behavior makes Au NPs an ideal candidate for optical limiting applications.     

Preparation of gold tetrananocages and their photothermal effect

A gold tetrahedral nanocage, i.e., a tetrananocage, that converts near-infrared （NIR） light into heat was fabricated by using a simple method. Silver tetrahedra with good homogeneity and dispersity were synthesized by a hydrothermal route. Gold tetrananocages were obtained using a galvanic replacement reaction between Ag tetrahedra and HAuC14 solution. The surface plasmon resonance （SPR） of gold tetrananocages was tuned from 412 nm to 850 nm through controlling the volume of HAuC14 solution added. This Au tetrananocage can effectively convert NIR light into heat when the SPR couples with the exciting light. When cancer cells are cultured with the gold tetrananocages for several hours and irradiated, the gold tetrananocages destroy the cancer cells effectively and demonstrate themselves to be a good candidate for combating cancer.     

Highly sensitive differential phase-sensitive surface plasmon resonance biosensor based on the Mach-Zehnder configuration

A high-sensitivity surface plasmon resonance (SPR) biosensor based on the Mach-Zehnder interferometer design is presented. The novel feature of the new design is the use of a Wollaston prism through which the phase quantities of the p and s polarizations are interrogated simultaneously. Since SPR affects only the p polarization, the signal due to the s polarization can be used as the reference. Consequently, the differential phase between the two polarizations allows us to eliminate all common-path phase noise while keeping the phase change caused by the SPR effect. Experimental results obtained from glycerin-water mixtures indicate that the sensitivity limit of our scheme is 5.5 x 10(-8) refractive-index units per 0.01 degrees phase change. To our knowledge, this is a significant improvement over previously obtained results when gold was used as the sensor surface. Such an improvement in the sensitivity limit should allow SPR biosensors to become a possible replacement for conventional biosensing techniques based on fluorescence. Monitoring of the bovine serum albumin (BSA) binding reaction with BSA antibodies is also demonstrated.     

Bimetallic Silver-Gold Film Waveguide Surface Plasmon Resonance Sensor

It is desirable that a surface plasmon resonance (SPR) sensor is highly sensitive to binding interactions within the sensing region, generate evanescent fields with long penetration depths, and utilize a metal film that is very stable even in extreme environmental conditions. In this study, we present the first example of a wavelength-modulated waveguide SPR sensor with a bimetallic silver-gold film for surface plasmon excitation. The underlying silver yields better evanescent field enhancement of the sensing surface, while the overlying gold ensures that the stability of the metallic film is not compromised. It is shown experimentally that in terms of dλ/dn, the bimetallic film waveguide SPR configuration has a sensitivity of 1232 nm/RIU, greater than two times improvement from the 594 nm/RIU achievable with single gold film waveguide SPR sensor. The higher sensitivity, compact nature, and better evanescent field enhancement of this configuration provides the potential to biosensing applications.     

Shape and size dependence of the surface plasmon resonance of gold nanoparticles studied by Photoacoustic technique

We report on the optical absorption properties of as prepared gold naoparticles of different shapes and sizes measured by photoacoustic (PA) method. The gold nanoparticles of two different shapes (dots, rods) have been prepared using the seed mediated growth method. The shape and the size of these different nanoparticles were determined by STM measurements. PA spectra show the splitting of the surface plasmon resonance (SPR) into two modes (transverse and longitudinal) in case of gold nanorods. The increase in the aspect ratio of the nanorods leads to clear redshifts of the longitudinal SPR. These shifts were used to determine the dielectric constant of the surrounding medium and its variation with the aspect ratios.     

内置调制层型光纤表面等离子体波共振传感器研究

研究了一种基于内置调制层结构的光纤表面等离子体波共振(SPR)传感器。通过在金膜与纤芯的内侧增覆具有不同厚度和属性的光学透明薄膜作为内调制层,构成了性能独特的光电复合薄膜,起到调节倏逝波矢量和金膜表面等离子体振荡波矢量的双重作用,进而控制共振效应,为调节灵敏度提供依据。采用时域有限差分方法对内置调制层结构光纤SPR共振激励模型属性进行数值仿真。在此基础上,研制了用于液体折射率测量的内置调制层型光纤SPR传感探针。实验结果表明,该传感器在1.335～1.392折射率范围内,随着待测液体折射率的增大,SPR共振光谱向长波方向偏移,且灵敏度达到2263.1nm/RIU,与基于纤芯-金膜-环境介质三层结构的常规光纤SPR传感器相比提高一倍,能够更好地满足环境折射率检测的需求。