Laser fabrication of periodic microstructures from silver nanoparticles in polymer films

The fabrication of photoand thermostable periodic structures from silver nanoparticles in polymer plates (cross-linked oligourethanemethacrylate impregnated with silver precursors Ag(hfac) and Ag(fod) dissolved in the supercritical carbon dioxide) is studied. The process is based on the local (depending on the irradiated spot size) photochemical decomposition of the silver precursors in the polymer matrix that initiates the atomic aggregation and creation of silver nanoparticles with the plasmon resonance in absorption in the spectral range 420–430 nm. The third-harmonic radiation of a Nd:YAG laser (355 nm) and the Kr⁺-laser (521 nm) radiation are employed for the recording of periodic structures with submillimeter and micron resolutions. The photosensitivity of the polymer matrices impregnated with the silver precursors to the UV and visible radiation is discussed.     

Optical spectroscopy of the Eu(FOD)<Subscript>3</Subscript> complex impregnated into the free volume of nanoporous glass and polymethylmethacrylate using supercritical carbon dioxide

The absorption and photoluminescence spectra of Eu(FOD)₃ molecules (FOD = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) impregnated into samples of nanoporous Vycor glass and polymethylmethacrylate using supercritical carbon dioxide were measured. The influence of the matrix on the shape and intensity of the absorption bands of Eu(FOD)₃ molecules and the photoluminescence bands of Eu³⁺ ions was analyzed.     

Spectra of copper and europium β-diketonates in alcoholic solutions and transparent dielectrics

We have used optical and EPR spectroscopy to study the mechanisms for color center formation in nanoporous glasses, polymethylmethacrylate, and alcoholic solutions containing ?-diketonate molecules: Cu(hfac)₂, Ba(hfac)₂, Pr(hfac)₃, and Eu(fod)₃. We have observed and studied the complex structure of the absorption bands in the 300 nm region belonging to the intraligand π-π* transition. Analogous results were obtained when studying the photoluminescence spectra of ⁵D₀ → ⁷F₀ transitions of Eu³⁺ ions and the EPR spectra of Cu²⁺ ions in matrices doped with Cu(hfac)₂. We propose a model according to which for β-diketonate molecules (except for basic diketonates), a hydrolyzed form exists that is formed during synthesis of the polycrystalline powder due to the presence of water molecules. The model allows us to explain the spectral manifestations of β-diketonates in different matrices.     

铋化物发光玻璃中银表面等离激元对铒离子的发光增强作用

局域表面等离激元可以由自由空间的光直接激发,这也是局域表面等离激元的优点所在。研究铋化物发光玻璃中纳米银颗粒的表面等离激元对铒离子发光的增强效应、进一步的提高铋化物发光玻璃中铒离子的发光性能很有意义。首先,测量了(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃与(B)Er 3+(0.5%):铋化物发光玻璃样品的吸收谱,发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃在约600.0 nm处有一个较弱的宽的银表面等离激元共振吸收峰。同时发现两者都有典型的铒离子的吸收峰,它们的吸收几乎完全一样:在波峰形状、峰值强度和峰值波长等方面都很相近。测量了(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃和(B)Er 3+(0.5%):铋化物发光玻璃样品的激发谱,发现有位于379.0,406.0,451.0,488.0和520.5 nm的5个550.0 nm可见光的可见激发谱峰,和位于379.0,406.5,451.0,488.5,520.5,544.0,651.5和798.0 nm的8个1531.0 nm红外光的红外激发谱峰,容易指认出依次为Er 3+的4I 15/2→4G 11/2,4I 15/2→2H 9/2,4I 15/2→(4F 3/2,4F 5/2),4I 15/2→4F 7/2,4I 15/2→2H 11/2,4I 15/2→4S 3/2,4I 15/2→4F 9/2和4I 15/2→4I 9/2跃迁的吸收峰,通过测量发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃相对于(B)Er 3+(0.5%):铋化物发光玻璃样品的可见和红外激发谱的最大增强依次分别是238%和133%。最后,测量了它们的发光谱,发现有位于534.0,547.5和658.5 nm的三组可见发光峰,容易指认出依次为Er 3+的2H 11/2→4I 15/2,4S 3/2→4I 15/2,4F 9/2→4I 15/2荧光跃迁。还发现红外发光峰位于978.0和1531.0 nm,依次为Er 3+的4I 11/2→4I 15/2和4I 13/2→4I 15/2的荧光跃迁。通过测量发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃相对于(B)Er 3+(0.5%):铋化物发光玻璃样品的可见和红外发光谱的最大增强依次分别是215%和138%。对于银表面等离激元增强铒离子发光的机理,认为主要为纳米银颗粒的局域表面等离激元共振,造成金属纳米结构附近产生的局域电场的强度要远大于入射光的电场强度,从而导致了金属纳米结构对入射光产生强烈的吸收和散射,进而导致了荧光的增强;即局域表面等离子体共振局域场的场增强效应。     

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.     

Dynamics of formation and decay of supercritical fluid silver colloid under pulse laser ablation conditions

The effect of the density of supercritical carbon dioxide (SC-CO₂) on the dynamics of formation of supercritical fluid (SCF) silver colloids during pulse laser ablation and their post-pulse degradation was studied by in situ UV/vis absorption spectroscopy. Laser irradiation of a silver target in SC-CO₂ caused ablative formation of Ag nanoparticles of different shapes and sizes: quasi-spherical particles (~4 nm) and larger Ag nanoparticles (hundreds of nanometers). A change in the colloid density from 0.24 to 0.82 g/cm³ caused significant changes in the dynamics of ablative formation of large and small particles, the rate of aggregation of small Ag particles into large particles, and the rate of gravitation-induced sedimentation of nanoparticles in the SCF colloid.     

Formation of sub-surface silver nanoparticles in silver-doped sodium–lead–germanate glass

The formation of silver nanoparticles in 60GeO₂–20PbO–20Na₂O bulk glass doped with 0.15 wt% of Ag has been studied by optical methods in the near ultraviolet-to-near infrared and mid-infrared ranges. A clear optical absorption band, which grows when increasing the annealing temperature, is observed around 460 nm, as a consequence of the surface plasmon resonance in the Ag nanoparticles. From the simultaneous analysis of optical transmittance and spectroscopic ellipsometry spectra in the near ultraviolet-to-near infrared range, it is demonstrated that the nanoparticles are surprisingly formed only in a thin layer (some tens of nm thick) underneath the sample surfaces. The potential of such a simultaneous optical analysis for determining the localization of the nanoparticles in glasses of any nature is underlined. Based on the results of a complementary mid-infrared spectroscopy characterization, the processes involved in silver migration to the surfaces and further aggregation to form nanoparticles are discussed.     

Fabrication and optical study of Ag@SnO<Subscript>2</Subscript> core-shell structure nanoparticle thin films

Ag@SnO₂ core-shell nanoparticles dispersed in poly-(vinyl) alcohol films were fabricated on glass substrate by employing a dip-coating technique. Synthesis of Ag@SnO₂ nanoparticles with core-shell morphology is carried out by a soft-chemical technique in aqueous phase at 60°C. Formation of core-shell structure is monitored by the red-shift of the surface plasmon band of Ag nanoparticles (from 390 to 410 nm) in the UV-visible spectrum. These nanoparticles are deposited on the glass substrate. The structure and morphology of these films were investigated by X-ray diffraction technique and field-emission transmission electron microscopy, respectively. Optical properties of these pseudo-solids were studied by UV-visible spectroscopy. Surface plasmon spectrum of the core-shell nanoparticles film remained unaltered with increase in the number of layers. However, silver nanoparticles films have shown peak broadening and development of additional peaks with increase in the number of layers. Our investigations showed that the surface plasmon band of the silver nanoparticles could be preserved by controlled deposition of the tin dioxide shell.     

A novel method for synthesis of colloidal silver nanoparticles by arc discharge in liquid

This paper presents a novel, inexpensive and one-step approach for synthesis of silver nanoparticles (Ag NPs) using arc discharge between titanium electrodes in AgNO₃ solution. The resulting nanoparticles were characterized using UV–Vis spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Silver nanoparticles of 18 nm diameter were formed during reduction of AgNO₃ in plasma discharge zone. Optical absorption spectroscopy of as prepared samples at 15 A arc current in AgNO₃ solution shows a surface plasmon resonance around 410 nm. It was found that sodium citrate acts as a stabilizer and surface capping agent of the colloidal nanoparticles. SEM images exhibit the increase of reduced nanoparticles in 6 min arc duration compared with 1 min arc duration. TEM image of the sample prepared at 6 min arc duration shows narrow size distribution with 18 nm mean particle size. Antibacterial activities of silver nanoparticles were investigated at the presence of Escherichia coli (E-coli) bacteria.     

Electron microscopy and EXAFS studies on oxide-supported gold-silver nanoparticles prepared by flame spray pyrolysis

Gold and gold-silver nanoparticles prepared by flame spray pyrolysis (FSP) were characterized by electron microscopy, in situ X-ray absorption spectroscopy (XANES and EXAFS), X-ray diffraction (XRD) and their catalytic activity in CO oxidation. Within this one-step flame-synthesis procedure, precursor solutions of dimethyl gold(III) acetylacetonate and silver(I) benzoate together with the corresponding precursor of the silica, iron oxide or titania support, were sprayed and combusted. In order to prepare small metal particles, a low noble metal loading was required. A loading of 0.1-1 wt.% of Au and Ag resulted in 1-6 nm particles. The size of the noble metal particles increased with higher loadings of gold and particularly silver. Both scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDXS) and X-ray absorption spectroscopy (XAS) studies proved the formation of mixed Au-Ag particles. In case of 1% Au-1% Ag/SiO₂, TEM combined with electron spectroscopic imaging (ESI) using an imaging filter could be used in addition to prove the presence of silver and gold in the same noble metal particle. CO oxidation in the presence of hydrogen was chosen as a test reaction sensitive to small gold particles. Both the influence of the particle size and the alloying of gold and silver were reflected in the CO oxidation activity.     

采用紫外光照法在磷酸盐玻璃中合成CdS/Ag复合微粒

掺杂有Ⅱ-Ⅵ族半导体纳米颗粒(如CdS)或者过渡金属(如Ag)的玻璃由于其较大的非线性光学效应而引起人们的极大兴趣,而同时掺杂有半导体/金属的复合微粒则可以进一步增强玻璃的三阶非线性效应,因此成为目前的研究热点。我们利用玻璃沉淀技术及随后的热处理和紫外光还原技术制备了含高浓度(1%)Ag微粒的玻璃,并采用X射线衍射分析了其物相,用高分辨扫描电镜分析了其形貌,以及测试了其吸收和发光性能。从CdS/Ag复合微粒的扫描照片可以发现晶粒均匀分布在玻璃中,尺寸约为1μm。X射线衍射发现经过热处理和紫外光照的样品衍射峰中含有CdS和Ag,而只进行热处理的样品则只含有CdS,未处理的样品则显非晶态。CdS/Ag复合微粒的吸收峰呈现典型的表面等离子共振峰(420nm)以及CdS的峰(600nm),只含有CdS微粒的样品的吸收峰则在480nm附近,未处理的样品在320nm附近有一个吸收峰,这可能是由于样品在快速冷却过程中的微小晶化造成的。只含有CdS微粒的样品有三个明显的发光峰,然而CdS/Ag复合微粒的发过峰则消失。我们提出了共振能量转移机制来解释该现象。讨论了紫外光照还原Ag微粒的机制。可以认为通过紫外光照,CdS表面的电子被激发出来还原Ag+,从而形成银颗粒,伴随着空穴则被表面缺陷所捕获。     

Silver aggregates and twofold-coordinated tin centers in phosphate glass: A photoluminescence study

The optical properties of silver species in various oxidation and aggregation states and of tin centers in melt-quenched phosphate glasses have been assessed by optical absorption and photoluminescence (PL) spectroscopy. Glasses containing silver and tin, or either dopant, were studied. Emission and excitation spectra along with time-resolved and temperature-dependent PL measurements were employed in elucidating the different emitting centers observed and investigating on their interactions. In regard to silver, the data suggests the presence of luminescent single Ag⁺ ions, Ag⁺-Ag⁺ and Ag⁺-Ag⁰ pairs, and nonluminescent Ag nanoparticles (NPs), where Ag⁺-Ag⁰→Ag⁺-Ag⁺ energy transfer is indicated. Tin optical centers appear as twofold-coordinated Sn centers displaying PL around 400 nm ascribed to triplet-to-singlet electronic transitions. The optically active silver centers were observed in glasses where 8 mol% of both Ag₂O and SnO, and 4 mol% of Ag₂O were added. Heat treatment (HT) of the glass with the high concentration of silver and tin leads to chemical reduction of ionic silver species resulting in a large volume fraction of silver NPs and the vanishing of silver PL features. Further characterization of such heat-treated glass by transmission electron microscopy and X-ray photoelectron spectroscopy appears consistent with silver being present mainly in nonoxidized form after HT. On the other hand, HT of the glass containing only silver results in the quenching of Ag⁺-Ag⁰ pairs emission that is ascribed to nonradiative energy transfer to Ag NPs due to the positioning of the pairs near the surface of NPs during HT. In this context, an important finding is that a faster relaxation was observed for this nanocomposite in relation to a heat-treated glass containing both silver and tin (no silver pairs) as revealed by degenerate four-wave mixing spectroscopy. Such result is attributed to Ag NP→Ag⁺-Ag⁰ plasmon resonance energy transfer. The data thus indicates that energy transfer between Ag⁺-Ag⁰ pairs and NPs is bi-directional.     

Tunable surface-plasmon-resonance wavelength of silver island films

This paper experimentally and theoretically investigates the effect of the underlayer medium on tuning of the surface plasmon resonance (SPR) wavelength of silver island films,and the effect of substrate temperature on the morphologies and optical properties of the films.From the absorption spectra of single Ag with various thickness and overcoated (Ag/TiO 2) films deposited on glass substrates at various substrate temperatures by RF magnetron sputtering,we demonstrate that the surface plasmon resonance wavelength can be made tunable by changing the underlayer medium,the thickness of metal layer and the substrate temperature.By varying substrate temperatures,the interparticle coupling effects on plasmon resonances of nanosilver particles enhance as the spacing between the particles reduces.When the substrate temperature is up to 500 C,the absorption peak decreases sharply and shifts to shorter wavelength side due to the severe coalescence between silver islands in the film.     

银镜法制备具有表面增强红外活性Ag纳米粒子的探讨

利用银镜法在玻璃基底上沉积金属银制得表面增强红外材料,扫描电镜显示,沉积在基片上的银为球状颗粒,且平均直径在100nm左右,银纳米粒子形成一个个不相连的金属岛。以邻硝基苯胺为探针分子,用衰减全反射法(ATR)考察了邻硝基苯胺在银镜基底上的表面增强红外光谱。结果表明:邻硝基苯胺的最小检出质量约为40ng,增强因子约为70。制备银膜的最佳条件为:A gNO3质量分数为1%,反应温度为60℃,且加入表面活性剂可使银纳米粒子分散均匀。     

Amplification of raman scattering by localized plasmons in silver nanoparticles on the surface of zinc oxide nanorods

The magnetron sputtering of Ag nanoparticles onto ZnO nanorod arrays is studied. The lateral faces of the nanorods are coated with nanoparticles at a much lower density as compared to the flat faces at comparable sputtering times. The silver density is high on the edges of the lateral faces of the nanorods. The plasmon absorption in the synthesized arrays of nanorods coated with individual Ag nanoparticles is maximal at 450?C500 nm. The appearance of local plasmon excitations increases the intensity of the multiphonon processes with the participation of ZnO polar modes in Raman spectra. The cross section of resonance Raman scattering for A ₁(LO) phonon overtones increases with the equivalent Ag film thickness.     

Formation of silver nanoclusters in transparent polyimides by Ag-K ion-exchange process

Silver nanoclusters embedded in two transparent fluorinated polyimides, 4,4'-hexafluoroisopropylidene diphthalic anhydride – 2,3,5,6-tetramethyl paraphenylene diamine (6FDA-DAD) and 3,3',4,4' – biphenyltetracarboxylic acid dianhydride – 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (BPDA-3F), have been produced by surface modification with KOH aqueous solution followed by K-assisted Ag doping and thermal reduction in hydrogen atmosphere. The reaction rate of the nucleophilic hydrolysis in KOH, studied by Fourier transform infrared spectroscopy (FT-IR) and Rutherford backscattering spectrometry (RBS), depends on the polyimide chemical structure. After ion-exchange in AgNO₃ solution and subsequent annealing, the polyimide structure recovery was monitored by FT-IR whereas the characteristic surface plasmon absorption band of silver nanoparticles was evidenced by optical absorption measurements. The structure of silver nanoclusters as related to size and size distribution in the different polyimide matrices was thoroughly investigated by Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The collected data evidenced a uniform distribution of Ag clusters of nanometric size after thermal treatment at 300 ^○C in both polyimides. For the same ion-exchange treatment parameters and annealing temperature, XRD analyses evidenced the presence of crystallites with similar sizes.     

A facile strategy to synthesize bimetallic Au/Ag nanocomposite film by layer-by-layer assembly technique

A facile strategy has been developed for the preparation of bimetallic gold–silver (Au–Ag) nanocomposite films by alternating absorption of poly-(ethyleneimine)–silver ions and Au onto substrates and subsequent reduction of the silver ions. The composition, micro-structure and properties of the {PEI–Ag/Au}_n nanocomposite films were characterized by ultraviolet visible spectroscopy (UV–vis), transmisson electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), surface enhanced Raman scattering (SERS) and cyclic voltammetry (CV). The UV–vis characteristic absorbances of {PEI–Ag/Au}_n nanocomposite thin film increase almost linear with the number of bilayers, which indicates a process of uniform assembling. Appearance of a double plasmon bands in the visible region and the lack of apparent core–shell structures in the TEM images confirm the formation of bimetallic Au–Ag nanoparticles. The result of XPS also demonstrates the existence of Ag and Au nanoparticles in the nanocomposite films. TEM and FESEM images show that these Ag and Au nanoparticles in the films possess sphere structure with the size of 20–25 nm. The resulting {PEI–Ag/Au}_n films inherit the properties from both the metal Ag and Au, which exhibits a unique performance in SERS and electrocatalytic activities to the oxidation of dopamine. As a result, the {PEI–Ag/Au}_n films are more attractive compared to {PEI–Ag/PSS}_n and {PEI/Au}_n films.     

脉冲激光沉积Ag:BaTiO3纳米复合薄膜及其光学特性

在MgO(100)基片上利用脉冲激光沉积技术制备了掺有Ag纳米颗粒的BaTiO₃复合薄膜.通过X射线衍射对薄膜的结构进行了表征,利用透射电子显微镜对Ag纳米颗粒的尺寸、形态进行了观测,X射线光电子能谱结果表明Ag呈金属态.在410—500nm范围内观测到了Ag纳米颗粒引起的等离子振荡峰,随着后处理温度和Ag颗粒浓度的增加,吸收峰发生红移,并出现了双峰现象. 关键词： 金属纳米复合薄膜 激光沉积 光吸收     

Observation of simultaneous reverse saturation absorption and saturation absorption in silver nanoparticles incorporated into europium oxide thin film

In this work, nano silver clusters incorporated into europium oxide thin films at a level of 3.8% and 12.5% have been prepared by a vacuum evaporation method on glass and silicon substrates. Samples were investigated by X-ray fluorescence, X-ray diffraction, and linear and nonlinear optical absorption methods. The X-ray diffraction reveals that the Eu oxide of these samples remains amorphous after pre-annealing at 400 °C. The linear optical absorption of the samples shows surface plasmon resonance (SPR) phenomena, which varies with the Ag content of the samples. The optical nonlinear absorption properties of the prepared films were investigated using an open Z-scan technique with cw laser at wavelengths 476 nm and 514 nm. A changeover from reverse saturation absorption (RSA) to saturation absorption (SA) was observed. RSA is attributed to interband transition via two photon absorption. SA is attributed to plasmon bleach.     

On the fluorescence enhancement mechanism of Er3+ in germanate glass containing silver particles

The spectral properties of trivalent erbium ions(Er3+) are systematically studied in a melt-quenched germanate glass(60 GeO2-20PbO-10BaO-10K2O-0.1Ag2O) containing silver(Ag) particles.Thermal treatment of the material leads to the precipitation of Ag particles as observed by transmission electron microscopy and confirmed by absorption spectrum for the obvious surface plasmon resonance peak of Ag particles.The fluorescence from Er3+ in the 10-min-annealed sample with Ag particles is found to be 4.2 times enhanced compared with the unannealed sample excited by 488-nm Ar+ laser.A comparison is made between a spectral study performed on the unannealed Er3+-doped sample and the one annealed for 20 min.The data of absorption cross section and Judd-Ofelt intensity parameters show the agreement between the two samples no matter whether there are Ag particles,indicating that the introduction of Ag particles by post-heat treatment has no effect on the crystal field environment of Er3+ ions.The fluorescence enhancement is attributed to the surface plasmon oscillations of Ag particles in germanate glass.