Silver nanoparticles produced by PLD in vacuum: role of the laser wavelength used

In this work we report the results of investigation of silver (Ag) nanoparticles prepared on a silica substrate by laser ablation. Our attention was focused on the mean diameter, size distribution and optical absorption properties of nanoparticles prepared in vacuum by using different laser wavelengths. The fundamental wavelength and the second, third, and fourth harmonics of a nanosecond Nd:YAG laser were used for nanoparticles fabrication. The corresponding values of the laser fluence for each wavelength were: 0.6 J/cm² at 266 nm, 0.8 J/cm² at 355 nm, 2.8 J/cm² at 532 nm, and 2 J/cm² at 1064 nm. The Ag nanoparticles produced have mean diameters in the range from 2 nm to 12 nm as the nanoparticles’ size decreases with the decrease of the wavelength used. The presence of the Ag nanoparticles was also evidenced by the appearance of a strong optical absorption band in the measured UV-VIS spectra associated with surface plasmon resonance (SPR). A redshift and widening of the absorption peak were observed as the laser wavelength was increased. Some additional investigations were performed in order to clarify the structure of the Ag nanoparticles.     

Ag:Bi2O3复合膜的线性和非线性光学性质

从实验和理论两个方面，探讨了金属Ag不同掺杂浓度对Ag:Bi₂O₃复合膜线性和非线性光学性质的影响. 用吸收光谱研究了Ag浓度与Ag:Bi₂O₃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)，金属Ag浓度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Ag浓度时Ag:Bi₂O₃复合膜的三阶非线性效应，研究了激发波长和金属浓度对复合膜线性和非线性光学性质的影响. 结果表明，等离子体共振增强和合适的金属掺杂浓度使得三阶极化率增强二个量级，在Ag浓度为35％左右和接近等离子体共振频率(相应吸收带位于560nm—622nm)的532nm激发时，χ⁽³⁾具有最大值2.4×10^-9esu. 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     

Self-assembled silver nanoparticles: correlation between structural and surface plasmon resonance properties

We report a facile method for controllable fabrication of high-density silver nanoparticle films with a widely adjustable surface plasmon resonance (SPR) frequency, based on the gas phase cluster beam deposition. On the one hand, we can control the particle size by depositing clusters on silica substrate. Light extinction spectra of the self-assembled Ag nanoparticles with various particle sizes are characterized and show two SPRs, in which a SPR exhibits a redshift from less 400 nm to more than 570 nm with an increase in the particle size, whereas the other shows a slight position shifting. On the other hand, the inter-particle distance of the self-assembled Ag nanoparticles can also be controlled by depositing clusters on silica glass coated with Formvar film, and the SPR wavelength shows a redshift from <400 nm to more than 560 nm, which can be attributed to the increase of the fraction of closely spaced nanoparticle pairs that are near-field coupled with the deposition mass. The size and coverage-dependent SPR properties are also compared with the results from the discrete dipole approximation calculations. The present method of tailoring metallic microstructures could find important applications in plasmonics.     

Calculation of curvature dependent surface plasmon resonance in gold nanospheroid and nanoshell

In this paper, theoretical calculations based on dipole-limit are performed to investigate the effects of curvature on the surface plasmon resonance (SPR) properties of nanometer size gold spheroid and shell. By comparing the aspect ratio with the shell thickness, we demonstrated that the curvature radius is a common better factor that can be used to predict the SPR wavelength and shift fashion. For nanospheroid, increasing the ratio of curvature radius corresponding to the climaxes leads to an increase in the ratio of SPR wavelength, whereas increasing the ratio of curvature radius of outer and inner surface in nanoshell leads to an decrease in the ratio of SPR wavelength. As a morphologic factor, curvature radius plays an important role in affecting the distribution of electron density, and consequently controlling the SPR frequency.     

Laser sintering of silver nanoparticle thin films: microstructure and optical properties

We present a method for the sintering of silver (Ag) nanoparticle thin films by millisecond pulsed laser irradiation. The microstructure of sintered thin films and sintering behaviors of nanoparticles were systematically investigated in this paper. Absorption spectra of sintered thin films showed blue-shifted surface plasmon resonances (SPR) from 500 nm to 480 nm and red-shifted from 480 nm to 550 nm when laser power was varied from 100 W to 140 W and from 140 W to 200 W, respectively. This indicates a new technique to control light absorption through joining nanoparticles with laser sintering. According to theoretical calculations based on a heat diffusion model, the melting temperature of these Ag nanoparticles was estimated to be 440 °C during laser irradiation.     

Optical properties of the Au–Ag alloy nanowire coated with an anisotropic shell

The optical properties of the Au–Ag alloy nanowire coated with a cylindrical shell with radial dielectric anisotropy are investigated based on quasistatic theory. Numerical results show that the surface plasmon resonance (SPR) peak is redshifted with increasing the component ratio of Au in the alloy, while the intensity of extinction section at the SPR increases with increasing the component ratio of Ag in the alloy. In addition, as the extent of anisotropy of the shell increases, the extinction section at SPR wavelength decreases and the SPR wavelength is redshifted, but compared with the isotropic shell consisting of comparable dielectric constant materials, the SPR has a distinct blueshift for anisotropic shell. We also find that the field enhancement can be completely concentrated inside the anisotropic shell and the electromagnetic transparency can be exhibited.     

基于银/二氧化钛复合膜的表面等离子共振气体传感器

表面等离子体共振是一种免标记的传感技术,当介质周围的介电常数发生改变时,则SPR谐振光谱特性也会随之改变.因此表面等离子体共振传感技术已广泛应用于生物化学和环境监测等领域.由于二氧化钛(TiO2)覆盖层不仅可以保护金属层,还能调谐SPR谐振的光谱强度和谐振波长于近红外波段,应用于1550 nm的光纤传感,其氧化还原反应...     

波长调制型表面等离子体共振的传感特性研究

表面等离子体共振(SPR)光学传感器能实现生物医学的快速、 无标记、 高精度检测,是生物化学分析的重要方法。 研制了基于波长调制型的Kretschmann结构表面等离子体共振(SPR)生物传感系统,研究了在体溶液传感方式下的传感性能。 利用不同浓度的乙醇和乙二醇溶液进行体溶液传感测试。 实验结果表明,在折射率低时共振波长对折射率变化响应的灵敏度低,但响应的线性度高;随着折射率增大,共振波长对折射率的响应变化的灵敏度提高。 在1.407 0～1.430 RIU折射率范围内,灵敏度高达11 487 nm·RIU-1。 传感器的共振波长的稳定性为0.213 8 nm,可分辨最小折射率趋近10-6 RIU。 所研制的波长调制型表面等离子共振传感器操作简单、 灵敏度高、 检测范围大,可实现浓度极低生物标记物的有效检测,在化学、 生物传感领域有重要的应用。     

Influence of amount of CTAB and ascorbic acid concentration on localized surface plasmon resonance property of gold nanorod

Gold nanorods (AuNRs) are prepared through seeded growth approach. Synthesis parameters of the amount of cetyltrimethylammonium bromide (CTAB), and concentration of ascorbic acid (AA) were studied. We were aiming for an aspect ratio of 3 which could be achieved by a nanorod feature in the range of 45 nm length and 15 nm width. The absorption spectra are observed with an UV–visible NIR spectrophotometer and analysed theoretically. It is known that there are two plasmon resonance peaks for gold nanorod corresponding to transverse surface plasmon resonance (TSPR) and longitudinal surface plasmon resonance (LSPR), respectively. It is found that as the concentration of CTAB increases, the yield of NRs increases. As the concentration of AA increased from 0.05 to 0.2 M, LSP shifts to longer wavelength but upon further increasing the concentration, LSP shifts back to shorter wavelength. A linear relationship between LSPR wavelength and surrounding medium dielectric constant is obtained, which is in good agreement with the theoretical results.     

Optical,structural, and antibacterial properties of biosynthesized Ag nanoparticles at room temperature using Azadirachta indica leaf extract

We report an enhancement of antibacterial properties of Ag nanoparticles (NPs) synthesized at room temperature using leaf extract of Azadirachta indica (Neem) following green synthesis route. To study such antibacterial properties Ag NPs of sizes within 9 nm to 17 nm were synthesized by varying the concentration of Neam leaf extract (NLE). The NP size and size distribution were seen to increase and decrease, respectively, with increase in NLE concentration. Also Ag NPs having a fixed size (~26 nm) was also synthesized by varying the precursor (AgNO₃) concentration. It is noticed that concentration of NLE has significant effects on the control of NP size as well as size distribution whereas there is almost no role of precursor concentration of the NP size. All the Ag NPs are found to have face-centred-cubic crystal structure with preferential growth along (111) plane which is stable one. The peak of X-ray diffraction at ~32.4° (2θ value), which is prominent for low concentrations of NLE and precursor, is identified as (101) plane of Ag crystal. The generation and growth of Ag NPs had also been confirmed using electron microscopic studies. These Ag NPs show prominent surface plasmon resonance (SPR) absorption at ~ 420 nm confirming again the genesis of Ag NPs. The SPR peak shifts towards longer wavelength (redshift) with a corresponding reduction in full width at half maximum with increase in NP size. All of the samples containing Ag NPs show a broad blue photoluminescence (PL) emission at ~ 471 nm. Emission peak is seen to redshift with increase in NP size and is consistent with the optical absorption data. Such PL emission is argued as due to interband transition or plasmon luminescence. Being biocompatible of the green synthesis process, antibacterial properties of these Ag NPs were studies in details considering all the samples (with varied NP size for one set and with fixed NP size for other set of samples). As per our knowledge this is the first report of size related total study of Ag NPs, showing increased antibacterial effect as size decreased and equal antibacterial effect as size equals. It is found that smaller Ag NPs has enhanced antibacterial effects due to large surface area to volume ratio in comparison with bigger sized Ag NPs.     

Fabrication of Ag nanodot array over large area for surface-enhanced Raman scattering using hybrid nanoimprint mold made from AAO template

We demonstrated the fabrication of dense hexagonal arrays of Ag nanodots over a large area using a novel nanoimprint-based fabrication technique for surface-enhanced Raman spectroscopy. Flexible imprint molds with sub-10 nm features were duplicated from AAO templates using a novel hybrid mold technique. This method solves the nonflatness-induced defect issue in the conventional thermal nanoimprint technique, and allows high-quality duplications of nanometer features from rigid nonflat templates. Moreover, with the help of the excellent tunability of the size of nanoholes on AAO templates, we were able to tune the size of Ag nanodots, and consequently to tailor the resonance frequency of the Ag nanodot arrays. Finally, surface-enhanced Raman scattering of Rhodamine-123 on Ag nanodot arrays was measured, and large signal enhancement was observed on the 70 nm Ag nanodots. We numerically simulated the optical properties of those Ag nanodot arrays, and excellent agreement was found with the experimental results.     

Efficient fabrication of transparent antimicrobial poly(vinyl alcohol) thin films

We have explored in situ synthesis of Ag nanoparticles in transparent PVA films in view of increasing areas of application of those films. The two-step procedure consists of ion incorporation in the matrix and subsequent thermal reduction. Smooth and transparent PVA films containing Ag nanoparticles of 5–20 nm were fabricated by this approach. The optical property of the films and the size of metal nanoparticles could be controlled by changing the reaction conditions. By increasing heating temperature, the absorbance and wavelength of surface plasmon resonance (SPR) of the composite film increased, and nanoparticles with larger particle sizes and broader size distributions were obtained. In the temperature range of 130–170 °C, the wavelength of SPR increased with increasing the AgNO₃ concentration. At 190 °C, however, the wavelenght of SPR blue-shifted initially when the AgNO₃ concentration increased from 10 to 80 mmol/L, and red-shifted thereafter. The composite films showed excellent antimicrobial performance toward bacteria such as Escherchia coli. Such hybrids afford very effective and environment-friendly antimicrobial surface coatings.     

Adjustable surface plasmon resonance with Au,Ag, and Ag@Au core-shell nanoparticles

We report an experimental study on the synthesis of metal nanoparticles （NPs） with adjustable optical density based on surface plasmon resonance （SPR）. Metal NPs prepared by laser ablation in liquid method and the effect of laser parameters on the size, distribution, wavelength of SPR of Ag, Au, and mixture of Ag-Au, and Ag core/Au shell NPs are investigated. Our results show that the adjustable SPR band can be achieved in each class of NPs which is suitable for adjustable optical window applications.     

Design of a silicon-based plasmonic optical sensor for magnetic field monitoring in the infrared

Surface plasmon resonance (SPR) sensor chip is proposed for magnetic field monitoring in the infrared wavelength region. The structure is based on silicon substrate and gold as SPR-active metal used with an appropriate magnetic fluid film. The angular interrogation method has been used to study the sensor’s performance in terms of large shift and small width of the SPR curve for a wide range of magnetic field between 30 and 220 Oe. The effect of field incidence angle is also studied on the proposed sensor’s performance, and it is observed that the field should be incident as parallel to the magnetic fluid surface as possible. Any possibility of oxidation problem to the proposed SPR sensor is addressed by using a stable buffer layer. All the performance parameters were found to be significantly large for the above field incidence condition. The proposed sensor is able to achieve a resolution of the order as high as 0.18 Oe for magnetic field detection.     

Surface Plasmon Resonance and Field Enhancement of Au/Ag Alloyed Hollow Nanoshells

We investigate the nanostructure, surface plasmon resonance （SPR） absorption and nonlinear enhancement of Au/Ag alloyed hollow nanoshells prepared by the replacement reaction of Ag nanoparticles in a HAuCI4 aqueous solution. As the volume of HAuCl4 increases from OmL to 0.S mL, the SPR band of the Au/Ag alloyed nanoshells is tuned from 430nm to 780nm, and the third-order nonlinear optical susceptibility is enhanced nearly by an order of magnitude, which indicates a large enhancement of local field in the Au/Ag alloyed hollow nanoshells with hole defects.     

Highly Luminescent Material Based on Alq3:Ag Nanoparticles

Tris (8-hydroxyquinoline) aluminum (Alq₃) is an organic semiconductor molecule, widely used as an electron transport layer, light emitting layer in organic light-emitting diodes and a host for fluorescent and phosphorescent dyes. In this work thin films of pure and silver (Ag), cupper (Cu), terbium (Tb) doped Alq₃ nanoparticles were synthesized using the physical vapor condensation method. They were fabricated on glass substrates and characterized by X-ray diffraction, scanning electron microscope (SEM), energy dispersive spectroscopy, atomic force microscope (AFM), UV-visible absorption spectra and studied for their photoluminescence (PL) properties. SEM and AFM results show spherical nanoparticles with size around 70–80 nm. These nanoparticles have almost equal sizes and a homogeneous size distribution. The maximum absorption of Alq₃ nanoparticles is observed at 300 nm, while the surface plasmon resonant band of Ag doped sample appears at 450 nm. The PL emission spectra of Tb, Cu and Ag doped Alq₃ nanoparticles show a single broad band at around 515 nm, which is similar to that of the pure one, but with enhanced PL intensity. The sample doped with Ag at a concentration ratio of Alq₃:Ag?=?1:0.8 is found to have the highest PL intensity, which is around 2 times stronger than that of the pure one. This enhancement could be attributed to the surface plasmon resonance of Ag ions that might have increased the absorption and then the quantum yield. These remarkable result suggest that Alq₃ nanoparticles incorporated with Ag ions might be quite useful for future nano-optoelectronic devices.     

Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.     

Tuning the number of plasmon band in silver ellipsoidal nanoshell: refractive index sensing based on plasmon blending and splitting

Because of the geometric features of both rod and shell, dielectric-silver core–shell ellipsoidal nanostructure with 12–40 nm semi-major axis may bring forth four surface plasmon resonance (SPR) absorption peaks at most. Theoretical calculations based on quasi-static approximation show that there is surrounding refractive index-dependent plasmon blending and splitting in the absorption spectra, which makes the number of plasmon band of the silver ellipsoidal nanoshell is tunable. The sensitivity of the plasmon blending and splitting to the surrounding refractive index may be improved by increasing the shell thickness, aspect ratio or core refractive index. This local refractive index dependent-plasmon blending and splitting presents a new sensing picture based on tuning the number of SPR absorption peaks.     

Numerical study of a highly sensitive surface plasmon resonance sensor based on circular-lattice holey fiber

A new design of surface plasmon resonance (SPR) sensor employing circular-lattice holey fiber to achieve high-sensitivity detection is proposed. The sensing performance of the proposed sensor is numerically investigated and the results indicate that our proposed SPR sensor can be applied to the near-mid infrared detection. Moreover, the maximum wavelength sensitivity of our proposed sensor can reach as high as 1.76×10⁴ nm/refractive index unit (RIU) and the maximum wavelength interrogation resolution can be up to 5.68×10^-6 RIU when the refractive index (RI) of analyte lies in (1.31, 1.36). Thanks to its excellent sensing performance, our proposed SPR sensor will have great potential applications for biological analytes detection, food safety control, bio-molecules detection and so on.     

Surface plasmon optical sensor with enhanced sensitivity using top ZnO thin film

Surface plasmon resonance (SPR) is one of the most sensitive label-free detection methods and has been used in a wide range of chemical and biochemical sensing. Upon using a 200 nm top layer of dielectric film with a high value of the real part ε′ of the dielectric function, on top of an SPR sensor in the Kretschmann configuration, the sensitivity is improved. The refractive index effect of dielectric film on sensitivity is usually ignored. Dielectric films with different refractive indices were prepared by radio frequency magnetron (RF) sputtering and measured with spectroscopic ellipsometry (SE). The imaginary part ε′′ of the top nanolayer permittivity needs to be small enough in order to reduce the losses and get sharper dips. The stability of the sensor is also improved because the nanolayer is protecting the Ag film from interacting with the environment. The response curves of the Ag/ZnO chips were obtained by using SPR sensor. Theoretical analysis of the sensitivity of the SPR sensors with different ZnO film refractive indices is presented and studied. Both experimental and simulation results show that the Ag/ZnO films exhibit an enhanced SPR over the pure Ag film with a narrower full width at half maximum (FWHM). It shows that the top ZnO layer is effective in enhancing the surface plasmon resonance and thus its sensitivity.