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.     

Nonlinear optical behaviours in a silver nanoparticle array at different wavelengths

The optical nonlinearities of an Ag nanoparticle array are investigated by performing the Z-scan measurements at the selected wavelengths (400, 600, 650, and 800 nm). The nonlinear refraction index in the resonant region (around 400 nm) exhibits a significant enhancement by two orders compared with that in the off-resonant region (around 800 nm)), and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region (600 and 650 nm), which is attributed to the competition of the saturated absorption and the two-photon absorption processes.     

Nonlinear optical behaviors in a silver nanoparticle array at different wavelengths

The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths (400, 600, 650, and 800 nm). The nonlinear refraction index in the resonant region (around 400 nm) exhibits a significant enhancement by two orders compared with that in the off-resonant region (around 800 nm)), and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region (600 and 650 nm), which is attributed to the competition of the saturated absorption and the two-photon absorption processes.     

Shifting of Fluorescence Peak in CdS Nanoparticles by Excitation Wavelength Change

CdS nanoparticles with different size are prepared by chemical bath deposition method. These particles show strong fluorescence at emission wavelength of 507 nm. It has been observed that this emission peak changes through a range of 147 nm, by varying the excitation wavelengths through 370–480 nm.The emission peak can thus be tuned by varying the excitation wavelengths. This peak emission wavelength shift is due to the selective excitation of vibronic levels in the surface state of the CdS nanoparticles.     

Synchrotron and laser excitation of luminescence in PbWO<Subscript>4</Subscript>:Tb crystals at different temperatures

The effect of temperature on the spectral luminescence characteristics of PbWO₄:Tb³⁺ crystals with synchrotron and laser excitation is studied. If PbWO₄:Tb³⁺ is excited by synchrotron radiation with λ = 88 nm at 300 K, a faint recombination luminescence of the impurity terbium is observed against the matrix luminescence. When the temperature is reduced to 8 K, the luminescence intensity of PbWO₄:Tb³⁺ increases by roughly an order of magnitude and the characteristic luminescence of the unactivated crystal is observed. Excitation of PbWO₄:Tb³⁺ by a nitrogen laser at 300 K leads to the appearance of emission from Tb³⁺ ions. At 90 K, a faint matrix luminescence is observed in addition to the activator emission. The formation of the luminescence excitation spectra for wavelengths of 60–320 nm is analyzed and the nature of the emission bands is discussed.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

Luminescence Enhancement from Silica-Coated Gold Nanoparticle Agglomerates Following Multi-photon Excitation

Multi-photon absorption induced luminescence (MAIL) from bare gold nanoparticles, silica-coated particles, as well as silica-coated agglomerated gold nanoparticles suspended in aqueous solution was studied by using time-resolved and steady-state luminescence spectroscopy. The nanoparticles were excited by femtosecond pulses of wavelengths ranging from 630 nm to 900 nm. The luminescence from the particles exhibits a broad spectrum in the UV and VIS region. The time-resolved measurements indicate a luminescence lifetime of a few ps, limited by the response of the experimental system. The studied dependence of the MAIL efficiency on the excitation wavelength showed that the luminescence from silica-coated agglomerates was enhanced over the whole range of excitation wavelengths, when compared to the luminescence from individual gold nanoparticles. The agglomerates show an almost excitation wavelength independent efficiency of the MAIL, while for individual nanoparticles a rapid decrease of the MAIL efficiency was observed with increasing excitation wavelength. The observed enhancement of the MAIL from the agglomerated nanostructures can be attributed to the presence of localized surface plasmon resonances in the spectral region corresponding to the excitation wavelengths. The high MAIL efficiency from the agglomerated nanoparticle structures in the near-infrared could be an advantage in the expanding field of luminescence-based-imaging, as well as in biosensor technology.     

Fluorescence properties of Ag nanoparticles in water, methanol and hexane

Ag nanoparticles, synthesized employing the electro-exploding wire technique, are reported. Absorption in the UV-visible region by these particles is characterized by the features reported in the literature, namely, a possible plasmon peak at ∼404 nm. For Ag nanoparticles dispersed in water, photo-excitation in the ranges 210-235 and 255-280 nm produces similar fluorescence emission at ∼300 nm, whose corresponding resonant absorption takes place at 215 and 270 nm in the excitation spectra. Further, we study the effect of the surrounding medium (solvent effect) on fluorescence from these nanoparticles by comparing fluorescence emission in methanol and hexane for photo-excitation in the same range. Compared to water, fluorescence emission in methanol is observed red-shifted at ∼310 nm, which further red-shifts to ∼325 nm in hexane. The corresponding resonant absorptions in methanol are at 225 and 275 nm. Consequence of this red-shift in a less polar solvent is discussed.     

Enhanced UV-excited luminescence of europium ions in silver/tin-doped glass

Glasses containing silver, tin and europium were prepared by the melt-quenching technique with silver nanoparticles (NPs) being embedded upon heat treatment (HT). An intensification of Eu³⁺ ions emission was observed for non-resonant excitation around 270 nm, corresponding to UV absorption in the material. Optical measurements suggest that light absorption occurs at single Ag⁺ ions and/or twofold-coordinated Sn centers followed by energy transfer to europium which results in populating the ⁵D₀ emitting state in Eu³⁺. After HT at 843 K, a quenching effect is observed on Eu³⁺ luminescence with increasing holding time in the 350–550 nm excitation range. The quenching effect shows with the presence of Ag NPs which may provide multipole radiationless pathways for excitation energy loss in europium ions.     

Luminescence properties of Eu3+ and Sm3+ coactivated Gd(III) tungstate phosphor for light-emitting diodes

Rare-earth ions coactivated red phosphors Gd_0.2RE_1.8(WO₄)₃ (RE=Eu³⁺ and Sm³⁺) were synthesized by conventional solid-state reaction using boric acid as a flux agent. The samples were characterized by X-ray diffractometer (XRD), energy-dispersive X-ray spectrometer (EDS) and luminescence spectrometer (LS). The results showed that the Eu–Sm system exhibits higher emission intensity than those of the Eu single-doped system and Sm separate-doped system under ultraviolet (UV) radiation. Samarium(III) ions are effective in broadening and strengthened absorptions around 400 nm. Furthermore, it exhibits enhanced luminescence emission. when the mole ratio of boric acid is about 0.16, the luminescence capability is optimum. Two strongest lines at ultraviolet (394 nm) and blue (465 nm) in excitation spectra of these phosphors match well with the output wavelengths of UV and blue GaN-based light-emitting diodes (LEDs) chips.     

Preparation and Time-Resolved Luminescence Bioassay Application of Multicolor Luminescent Lanthanide Nanoparticles

Because highly luminescent lanthanide compounds are limited to Eu³⁺ and Tb³⁺ compounds with red (Eu, ~615 nm) and green (Tb, ~545 nm) emission colors, the development and application of time-resolved luminescence bioassay technique using lanthanide-based multicolor luminescent biolabels have rarely been investigated. In this work, a series of lanthanide complexes covalently bound silica nanoparticles with an excitation maximum wavelength at 335 nm and red, orange, yellow and green emission colors has been prepared by co-binding different molar ratios of luminescent Eu³⁺–Tb³⁺ complexes with a ligand N,N,N¹,N¹-(4′-phenyl-2,2′:6′,2′′-terpyridine-6,6′′-diyl)bis(methylenenitrilo) tetrakis (acetic acid) inside the silica nanoparticles. The nanoparticles characterized by transmission electron microscopy and luminescence spectroscopy methods were used for streptavidin labeling, and time-resolved fluoroimmunoassay (TR-FIA) of human prostate-specific antigen (PSA) as well as time-resolved luminescence imaging detection of an environmental pathogen, Giardia lamblia. The results demonstrated the utility of the new multicolor luminescent lanthanide nanoparticles for time-resolved luminescence bioassays.     

Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Core–shell nanophosphor with enhanced NIR–visible upconversion as spectrum modifier for enhancement of solar cell efficiency

A distinct enhancement of upconversion luminescence from core to core/shell (C/S) structure under low flux near infrared (NIR) excitation at 976 nm has been achieved in lanthanide (Er³⁺, Yb³⁺)-doped NaYF₄ core with undoped NaYF₄ shell nanoparticles (NP). A green chemistry approach has been taken to synthesize monodisperse monophasic C/S NP with the core (~20 nm) and shell (~5 nm) crystallizing into cubic phase. Hydrophobic C/S NP have been further made hydrophilic by coating a transparent SHMP layer without affecting luminescence. C/S (NaYF₄: Er, Yb/NaYF₄) NP integrated dye-sensitized solar cell indicated 11.9% enhancement in overall conversion efficiency under AM 1.5 conditions, due to NIR–visible spectrum modification by fluorescent NPs. The results indicate great potential of such upconverting C/S nanophosphor in solar cell applications.     

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.     

Study of VUV emission and γ-ray responses of Nd:BaF2 scintillaotor

Nd³⁺ 1%, 5% and 10% doped BaF₂ single crystals were grown by the micro-pulling down method. Photoluminescence properties, including excitation and emission spectra and luminescence decay were measured under synchrotron radiation excitation at the Superlumi station in HASYLAB at DESY (Hamburg, Germany). The Nd³⁺ related 5d-4f emission lines peaking around 180 nm, 230 nm, and 260 nm, identified as the 5d–⁴I_j, 5d–⁴F_j, and 5d–²G_j transitions, were observed under 140–168 nm excitation. In photoluminescence decay under the 160 nm excitation, the dominant component decay time is about 12, 2.5 and 1.2 ns for Nd³⁺ 1%, 5% and 10% concentration, respectively. The decay time shortening is explained by the concentration quenching effect. Transmittance of Nd1% sample is about 80% for wavelengths above 185 nm. Finally, gamma-ray responses, non-proportionality and energy resolution of Nd1% sample were compared with the undoped BaF₂ scintillator. The light yield of the Nd1%:BaF₂ is about 93% of that of undoped BaF₂. ^©2009 Elsevier Ltd. All rights reserved.     

硼酸盐玻璃中Eu掺杂对Ag纳米颗粒的析出机制及其发光性质研究

采用高温熔融法制备了Eu-Ag共掺的硼酸盐玻璃,利用吸收光谱和发射光谱等研究了玻璃中网络形成体B₂O₃含量变化和Eu离子共掺对于Ag在基质中赋存状态的影响。在Eu-Ag共掺玻璃的吸收光谱中发现,随着B₂O₃含量的增加,Ag纳米颗粒在4 10 nm附近的宽带吸收强度逐渐下降;玻璃在340 nm光源激发下,位于350～600 nm的蓝绿光区出现一个Ag分子团簇的宽带发光,且其发光强度随B₂O₃含量的增加逐渐增强。在Eu或Ag单掺的玻璃中可分别观测到微弱的Eu3+或Ag分子团簇的本征发射,而Eu-Ag共掺样品中Eu3+和Ag分子团簇的发光都得到了显著的增强。并且Eu离子浓度的增加促进了Ag纳米颗粒在410 nm附近的宽带吸收。对Eu离子的添加促进Ag纳米颗粒析出的机理进行了讨论。同时,由于Eu3+的5D₀→7F_J的电子跃迁发射为橙红光,Ag纳米团簇可发射蓝绿光甚至黄光,因此通过玻璃结构的调控和Eu离子掺杂浓度的调节可以实现玻璃的白光发射,这有望成为潜在的白光LED用玻璃照明材料。     

Surface‐enhanced Raman scattering studies of carbon nanotubes using Ag‐core Au‐shell nanoparticles

Surface‐enhanced Raman scattering from carbon nanotube bundles adsorbed with plasmon‐tunable Ag‐core Au‐shell nanoparticles (Ag@Au nps) was carried out for the first time. By utilizing nanoparticles whose plasmon resonance peak (541, 642 nm) closely matches the commonly used Raman excitation sources (532, 632.81 nm), we can observe a large enhancement in the Raman signatures of carbon nanotubes. We obtain greater enhancement in the Raman signal for the above case when compared to nanotubes adsorbed with conventional Ag, Au or other ‘off resonant’ Ag@Au nps. The power‐dependent SERS experiment on single‐walled nanotubes (SWNTs) with resonant Ag@Au nps reveals a linear behavior between the G‐band intensity and the photon flux density, which is in agreement with the vibrational pumping model of SERS. The observed enhancement by resonance matching is pronounced for carbon nanotubes and may lead to insights into understanding nanotube–nanoparticle interaction. Copyright © 2009 John Wiley & Sons, Ltd.     

Numerical synthesis of metallic nanostructures for enhancing the emission of a dipole through surface plasmon coupling

In this study, we numerically synthesize a two-dimensional metallic nanostructure consisting of a Au half-space and two separate Ag elliptical cylinders by the simulated annealing (SA) method. The simulated nanostructure is so designed that the surface plasmon polariton (SPP) and the localized surface plasmon (LSP) are simultaneously excited at their common resonant wavelength (535 nm), leading to the enhancement of emission of a nearby dipole source. This enhancement effect is more significant than that of the case where only one of the SPP and LSP is excited. In numerically synthesizing a metallic nanostructure, we try to maximize both the downward emission (in the direction away from the metallic structure) and the emission efficiency. A cost function is defined as some combination of the downward emission and the emission efficiency. We adjust the simulated structure by SA to minimize the cost function at a designated resonant wavelength, and calculate and analyze the spectra of downward emission and emission efficiency for the optimal structure. Other structures are also investigated for comparison. From numerical simulations, it is demonstrated that the enhancement of dipole emission is better for optimization at wavelength 535 nm than at other wavelengths. Note that the downward emission and the emission efficiency can reach maxima almost simultaneously when the SPP and the LSP couple effectively at a common resonant wavelength. This implies that the lighting efficiency of green light-emitting diodes (LEDs) can be increased by the coupling effect at a common resonant wavelength of SPP and LSP.     

SERS active Ag nanoparticles in mesoporous silicon: detection of organic molecules and peptide–antibody assays

Ag nanoparticles synthesized on porous silicon samples were studied and applied as substrates for surface‐enhanced Raman scattering (SERS). The metallic nanostructures prepared by immersion plating were characterized by UV–Vis reflectance spectroscopy and scanning electron microscopy. SERS activity of the substrates was tested using Cyanine dye 1,3,3,1′,3′,3′‐esamethyl‐5,5′‐dimethoxyindodicarbocyanine iodide (Cy5‐OCH₃) as a probe molecule. The Raman spectra obtained for different excitation wavelengths indicate amplifications ascribed to plasmonic resonances with an enhancement factor up to 10⁷. CGIYRLRS peptides were chemisorbed on the Ag nanoparticles with the plasmonic resonance tuned at the excitation energy. Such oligopeptides were used as baits for a specific polyclonal antibody. The overall Raman enhancement allowed to evidence a good selectivity to the target analyte as required by most of the SERS applications on biological assays. Copyright © 2011 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.