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.     

Ag纳米颗粒增强的Ho~(3+)/Tm~(3+)共掺铋锗酸盐玻璃的2μm发光研究

采用基于传统熔融淬冷技术的热化学还原法制备了系列Ag纳米颗粒复合Ho3+/Tm3+共掺铋锗酸盐玻璃样品,研究了Ag纳米颗粒含量对玻璃2μm发光特性的影响.结果表明,Ag纳米颗粒的表面等离子体共振带位于500—900 nm,峰值位于650 nm,透射电子显微镜图像中观察到均匀分布的Ag纳米颗粒,尺寸约为5—10 nm.通过测试玻璃样品在1.7—2.3μm波段的荧光光谱发现,Ag掺杂后Ho3+离子2μm处的荧光强度得到了极大的提高,其中AgCl掺杂质量分数为0.3%时的荧光强度比未掺杂时的荧光强度增强10倍,这归因于Ag纳米颗粒的局域场增强作用.计算得到Ho3+离子的吸收截面为0.491×10-20cm-2,发射截面为1.03×10-20cm-2,当增益系数为0.2时即可实现正的增益.     

Effect of shape,height,and interparticle spacing of Au nanoparticles on the sensing performance of Au nanoparticle array

The effect of shape,height,and interparticle spacing of Au nanoparticles(NPs) on the sensing performance of Au NP array is systematically investigated. Lengthening the major axis of elliptical NPs with the minor axis kept constant will cause the redshift of the local surface plasmon(LSP) resonance mode,enhance the sensitivity,and widen the resonance peaks. Larger height corresponds to smaller LSP resonance wavelength and narrower resonance peak. With each NP size unchanged,larger interparticle spacing corresponds to larger resonance wavelength and smaller full-width at half-maximum(FWHM) . Moreover,duty cycle is important for sensitivity,which is largest when the duty cycle is 0.4.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

Green synthesis of silver-graphene nanocomposite-based transparent conducting film

In the present work, silver nanoparticles (Ag NPs)/graphene nanocomposite has been synthesized successfully by simple solvothermal method via green route. Citric acid is used as green reducing agent for the reduction of graphene oxide (GO) and Ag ions. Silver nitrate is used as a precursor material for Ag NPs. As synthesized Ag NPs/graphene nanocomposite has been characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infra-red spectroscopy, UV–vis spectroscopy, thermal gravimetric analysis, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy. Experimental results confirm the reduction of GO and the successful formation of Ag NPs decorated graphene nanosheets. In addition, spray coating technique is employed for the fabrication of transparent conducting films. Enhancement in the optoelectrical signatures has been achieved using thermal graphitization of fabricated films. Thermal graphitization at 800 °C for 1 h marks the best performance of fabricated film with sheet resistance of ~3.4 kΩ/□ and transmittance (550 nm) of ~66.40%, respectively.     

Thermal behavior of surface plasmon resonance in dynamic suprastructure multilayer

Delicate thermodynamic control at confined space has been of importance in recent nano/micro-plasmonic sensing to be more accurate and to use lower quantity of specimens than conventional devices. In our study, experimental and computational study on thermal behavior of surface plasmon resonance (SPR) was carried out using various sizes of Au nanoparticles (NPs; 4, 18, and 57 nm) and thermo-reversible polymer, poly(N-isopropylacrylamide) (PNIPAm) on SPR chip. It was interesting that SPR angle shift on temperature was dependent on NP sizes, where the smaller size the better sensitive. It is probable that both plasmonic interaction and polymer dynamicity were collaboratively affected and presumably the latter dominated in the thermal monitoring of SPR signals. The simulations clearly indicated that the interaction between the Au NPs and polymers was strengthened by increasing temperature and NP sizes, resulting in decreasing sensitivity. These results are supportive to develop further accurate devices using plasmonics and polymer dynamics, such as plasmonic sensing devices, thermo-actuators, hybrid organic solar cell, and flexible display.     

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.     

Fabrication of periodical Ag–Au compound nanostructure films with controllable Ag nanoparticle aggregate patterns: a study on surface‐enhanced Raman scattering

The Ag–Au compound nanostructure films with controllable patterns of Ag nanoparticle (NP) aggregates were fabricated. A strategy of two‐step synthesis was employed toward the target products. Firstly, the precursor Au NP (17 nm) films were synthesized as templates. Secondly, the Ag NPs (45 nm) were deposited on the precursor films. Three types of Ag NP aggregates were obtained including discrete Ag NPs (discrete type), necklace‐like Ag NP aggregates (necklace type), and huddle‐like Ag NP aggregates (huddle type). The surface‐enhanced Raman scattering (SERS) property was studied on these nanostructures by using the probing molecule of rhodamine 6G under the excitation laser of 514.5 nm. Interestingly, the different types of samples showed different enhancement abilities. A statistical method was employed to assess the enhancement. The relative enhancement factor for each Ag NP was estimated quantitatively under the ratio of 1 : 25 : 18 for the discrete‐type, necklace‐type, and huddle‐type samples at the given concentration of 10⁻⁸ mol/l. This research shows that the enhancement ability of each Ag NP is dependent on the aggregate morphology. Moreover, the different enhancement abilities displayed different limit detection concentrations up to 10⁻⁸, 10⁻¹¹, and 10⁻⁹ mol/l, separately. The understanding of the relationship between the defined nanostructures and the SERS enhancement is very meaningful for the design of new SERS substrates with better performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced blue photoluminescence and new crystallinity of Ag/organic rubrene core-shell nanoparticles through hydrothermal treatment

Light-emitting organic semiconductors have attracted considerable attention for the nanoscale fabrication of organic-based displays and their potential application in optoelectronics, plasmonics, and photonics. In this study, core-shell hybrid nanostructures of organic rubrene coated on Ag nanoparticles (NPs) have been synthesized using a chemical reduction method. The thickness of the rubrene shell was 2.6–6.0 nm and the diameter of the Ag core was 30–70 nm. The optical and structural properties of the Ag/rubrene core-shell NPs were tuned by hydrothermal (HT) treatment at 190 °C. The Ag/rubrene core-shell NPs were characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray (EDX) spectroscopy before and after the HT treatment, and their structural properties were confirmed through X-ray diffraction (XRD) analysis. XRD peaks related to an orthorhombic phase were observed along with the original triclinic crystal structure of the rubrene shell, and the triclinic crystal domain size increased from 28.2 nm to 30.8 nm owing to the HT treatment. Interestingly, the green light emission (λ_em = 550 nm) of the Ag/rubrene core-shell NPs changed to blue light emission (λ_em = 425 nm), increasing in intensity through the HT treatment. This is caused by the crystal change with H-type aggregation and enhanced energy transfer from a surface plasmon resonance.     

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.     

Plasmon-enhanced luminescence of Sm complex using silver nanoparticles in Polyvinyl Alcohol

Silver (Ag) nanoparticles (NPs) were prepared by laser ablation in water with an aim to enhance the luminescence of rare earth coordinated complex in polymer host. A fixed concentration of the complex containing Samarium (Sm), Salicylic acid (Sal) and 1, 10-phenanthroline (Phen) were combined with different concentrations of silver NPs in PolyVinyl Alcohol at room temperature. Absorption spectrum and XRD patterns of the sample show that the Sm(Sal)₃Phen complex is accompanied by Ag NPs. The luminescence from the complex was recorded in the presence and absence of Ag NPs using two different excitation wavelengths viz. 400 and 355 nm. Of these, 400 nm radiation falls in the surface plasmon resonance of Ag NPs. It was found that the Ag NPs led to a significant enhancement in luminescence of the complex. Surprisingly, a high concentration of Ag NPs tends to quench the luminescence.     

Study on Synthesis of Silver Nanoparticles Using dsDNA as Template and Detection of GSH

In this work, silver nanoparticles are synthesized using a simple and sensitive method by using double-stranded DNA (dsDNA-Ag NPs) as a template. The prepared dsDNA-Ag NPs are characterized by fluorescence spectroscopy analysis, X-ray photoelectron spectroscopy analysis, and transmission electron microscopy analysis. The excitation wavelength of the prepared silver nanoparticles is 295 nm, the emission wavelength is 377 nm, the average particle size is 11.2 nm, and the dispersion is uniform with pleasurable stability. The nanomaterials are used as fluorescent probes to detect glutathione (GSH). After adding glutathione to the dsDNA-Ag NPs fluorescent probes, the fluorescence of dsDNA-Ag NPs is burst due to electron transfer and S Ag bond generation, and the linear range of detection concentration is 0–90 mm with a detection limit of 0.37 mm .     

Plasmonic Newton's cradle for low-loss subwavelength energy transport: Homogeneous or heterogeneous nanoparticle chains?

Five closely spaced Au or Ag NPs are linearly arranged in analogy with Newton's cradle, forming various homogeneous and heterogeneous NP chains. Using small NPs, the Au–Ag–Ag–Ag–Au heterochain has the lowest propagation loss (17.6%) at short resonance wavelengths. When the NP diameter is increased to 80 nm, the dominant resonance is shifted to longer wavelengths. As low as 6% of the total energy dissipates in the intermediate NP component, and there seems to be little difference between the Au–Ag–Ag–Ag–Au heterochain and the Ag–Ag–Ag–Ag–Ag homochain. Besides the wavelength-dependent intrinsic loss (i.e., the imaginary part of the permittivity) in metals, the real part of the permittivity also plays a critical role in determining the propagation loss. Considering the high fabrication cost of the heterochain, the homochain composed of moderately large Ag NPs (<100 nm) may be an optimal choice for low-loss subwavelength energy transport in practice.     

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.     

Spectroscopic investigation and Judd–Ofelt analysis of silver nanoparticles embedded Er3+-doped tellurite glass

A series of silver nanoparticles (NPs) embedded zinc-tellurite glass is prepared by melt-quenching technique. The transmission electron microscopic images reveal spherical as well as anisotropic silver NPs having average diameter in the range of 14–48 nm. The Er³⁺-free glass sample containing AgCl exhibits surface plasmon resonance (SPR) band of Ag NPs centered at ∼ 501 nm. From Judd–Ofelt analysis, it is found that by increasing the concentration of NPs, the value of Ω₂ is enhanced suggesting increased covalency and decreased symmetry around the Er³⁺ ions. Integrated emission cross-section (IEC) is enhanced as the concentration of silver NPs is increased up to 0.5 mol% AgCl. Fourier infrared spectra show that the intensity of the vibrational band of the water molecule and fundamental stretching band of OH group are suppressed. Furthermore, under an excitation wavelength of 786 nm, three prominent upconversion emissions are observed at 520 nm, 550 nm and 650 nm which are attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 transitions, respectively. The upconversion emissions are enhanced significantly by introduction of silver NPs. The enhancement is mainly attributed to the local field effect of silver NPs. Studied nanocomposites are potential candidates for the development of solid state lasers.     

Size effects in thermal and photochemistry of (NO)2 on Ag nanoparticles

NO dimers adsorbed on alumina supported silver nanoparticles (Ag NPs, radii R approximately 1-6 nm) show decreasing desorption temperatures and complex behavior of photoinduced desorption with decreasing NP size. In particular, for resonant excitation of the (1,0) Mie plasmon at 3.5 eV the photoinduced desorption cross section increases with 1/R, showing a pronounced enhancement (40 times) at R approximately 2.5 nm compared to Ag(111). At 4.7 eV the translational temperature of photodesorbed NO increases strongly with 1/R. We discuss these trends and peculiarities in terms of the size-dependent properties of the Ag NPs.     

Antimicrobial silver nanoparticles generated on cellulose nanocrystals

We describe a new approach to the formation of silver nanoparticles (Ag NPs) using cellulose nanocrystals. The process involves periodate oxidation of cellulose nanocrystals, generating aldehyde functions which, in turn, are used to reduce Ag⁺ into Ag⁰ in mild alkaline conditions. The nanoparticles were characterized using transmission electron microscopy (TEM) and ultraviolet–visible absorption spectroscopy. From the microscope studies (TEM) we observed that Ag NPs have spherical shape with a size distribution comprise between 20 and 45 nm. The antibacterial activity was assessed using the minimum inhibitory concentration. The antibacterial assays compare favourably with most of other experiments conducted with the same species.     

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.     

Silver‐Based Nanoparticles for Surface Plasmon Resonance in Organic Optoelectronics

Organic optoelectronic devices including organic light‐emitting diodes (OLEDs) and polymer solar cells (PSCs) have many advantages, including low‐cost, mechanical flexibility, and amenability to large‐area fabrication based on printing techniques, and have therefore attracted attention as next‐generation flexible optoelectronic devices. Although almost 100% internal quantum efficiency of OLEDs has been achieved by using phosphorescent emitters and optimizing device structures, the external quantum efficiency (EQE) of OLEDs is still limited due to poor light extraction. Also, although intensive efforts to develop new conjugated polymers and device architectures have improved power conversion efficiency (PCE) up to 8%–9%, device efficiency must be improved to >10% for commercialization of PSCs. The surface plasmon resonance (SPR) effect of metal nanoparticles (NPs) can be an effective way to improve the extraction of light produced by decay of excitons in the emission layer and by absorption of incident light energy within the active layer. Silver (Ag) NPs are promising plasmonic materials due to a strong SPR peak and light‐scattering effect. In this review, different SPR properties of Ag NPs are introduced as a function of size, shape, and surrounding matrix, and review recent progress on application of the SPR effect of AgNPs to OLEDs and PSCs.     

Diamine-linked array of metal (Au,Ag) nanoparticles on glass substrates for reliable surface-enhanced Raman scattering (SERS) measurements

Metal (Au, Ag) nanoparticles (M NPs) (ca. 30–40 nm) prepared by citrate reduction method were arrayed on amine-terminated glass substrates using diamine linkers with different chain lengths. 1,4-diaminobutane (C-4 diamine) produced the uniform and densely-packed array of M NPs on glass substrates at appropriate concentration ranges, whereas diamine linkers with longer chain lengths (C-8 and C-12 diamines) produced more heterogeneous and aggregated array of M NPs. When compared to Ag NPs, Au NPs demonstrated more controllable and higher packing density due to their mono-dispersed size and higher affinity to diamine linkers. Uniformly arrayed M NPs (Au, Ag) on glass substrates exhibited high enhancement factors in SERS measurements of o-chlorothiophenol probes. Au NPs arrayed substrates exhibited an approximate power-law linearity of Raman intensity with probe concentrations (from 10⁻⁷ M to 10⁻⁴ M), demonstrating more reliable SERS substrates than Ag arrayed substrates with higher SERS activity.