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     

纳米Ag颗粒复合薄膜的制备及其吸收特性

利用磁控溅射分层制备Ag和SiO₂薄膜,通过快速热处理,使Ag颗粒富集在复合薄膜的表面.研究了Ag膜层厚度、退火时间、退火温度和退火方式对Ag颗粒形貌的影响,以及Ag颗粒致密度对其共振吸收的影响.结果表明:通过控制每层Ag膜的厚度,可有效控制Ag颗粒形貌.当每层金属为2 nm、退火温度为500 ℃时,形成的颗粒粒径大小均匀且致密度较高.通过间断退火可有效降低Ag颗粒的粒径.发现Ag颗粒表面等离子共振吸收并没有随颗粒粒径的减小而明显降低,甚至提高.这和以往的报道不同.通过深入研究金属颗粒表面等离子体产生机理,发现其表面等离子共振吸收增强的原因是致密度较高的颗粒表面能级与费米能级差值较大,Ag颗粒内部的电子向颗粒表面迁移越多,形成新的费米能级E'_F的电子数就越多,表面等离子共振吸收就越强.最终得出了金属颗粒共振吸收不单纯依赖于金属粒径、和颗粒的致密度也有很大关系的结论.     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

Interaction between localized and propagating surface plasmons: Ag fine particles on Al surface

Samples consisting of Ag fine particles 4nm in size placed near to an Al surface were prepared by depositing Ag-SiO₂ composite films by a rf cosputtering method onto vacuum-evaporated Al films. Angle-scan attenuated total reflection (ATR) measurements were performed over a wide wavelength range (λ=350-630nm) covering the resonance region (λ-410nm) of localized surface plasmon (LSP) in the Ag particles. It was found that the existence of Ag fine particles near to the Al surface led to a deformation of the dispersion curve of the surface plasmon polariton (SPP) propagating on the Al surface, in particular, in the LSP resonance region. The interaction between LSP and SPP was found to become much stronger as the distance between the particles and the surface decreases. The theoretical calculations based on the effective medium theory, which gave an effective dielectric function of the Ag-SiO₂ composite film, reproduced the deformation of the dispersion curve of the SPP. The deformation of the dispersion observed experimentally was qualitatively explained by the behavior of the effective dielectric function of the Ag-SiO₂ composite film.     

Te/TeO2-SiO2复合薄膜的吸收和非线性光学特性研究

应用分光光度计测量Te/TeO₂-SiO₂复合薄膜的透射光谱和吸收光谱, 在480nm附近观察到Te颗粒引起的等离子体共振吸收峰; 采用Z扫描技术研究了共振(激发波长为532 nm)和非共振情况下(激发波长1064 nm) 不同电位制备薄膜的Te颗粒状态与复合薄膜的三阶非线性极化率的关系. 基于有效介质理论对复合薄膜的三阶非线性效应进行分析, 研究Te颗粒大小对Te/TeO₂-SiO₂复合薄膜的非线性光学性质的影响及其产生机理. 结果表明薄膜制备过电位增大, Te的粒径减小, 颗粒数量多, 颗粒分布趋于均匀, 使得金属颗粒的表面等离子体共振峰红移, 吸收强度增强, 导致三阶非线性光学效应增强, χ⁽³⁾由1064 nm的5.12×10^-7 esu增大为532 nm的8.11×10^-7 esu. 关键词： 碲 二氧化碲 复合薄膜 三阶非线性     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO₂ medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO₂ medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO₂ pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.     

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.     

Nanosphere Templated Metallic Grating Assisted Enhanced Fluorescence

In this paper, enhanced fluorescence from a silver film coated nanosphere templated grating is presented. Initially, numerical simulation was performed to determine the plasmon resonance wavelength by varying the thickness of the silver film on top of a monolayer of 400 nm nanospheres. The simulation results are verified experimentally and tested for enhancing fluorescence from fluorescein isothiocyanate whose excitation wavelength closely matches with the plasmon resonance wavelength of the substrate with 100 nm silver film over nanosphere. The 12 times enhancement in the intensity is attributed to the local field enhancement in addition to the excitation of surface plasmon polaritons along the surface.     

IR absorption enhancement for ionized p -nitrobenzoic acid on silver island films epitaxially grown on the 7 × 7 reconstructed Si(111) surface

An enhanced infrared absorption is reported for p-nitrobenzoic acid (PNBA) adsorbed on molecular-beam-epitaxially grown silver films at room temperature on 7×7 reconstructed Si(111) substrates. Reflection high-energy electron diffraction reveals the formation of Ag(111) islands even for 82-monolayer-thick silver deposition on the substrate. The NO₂ symmetric stretch of the surface-ionized species (PNBA^-) is a maximum in intensity at a thickness of 64 monolayers and is one order of magnitude stronger than the same mode of PNBA deposited at a thickness of 5 nm on a Si wafer. Based on the change in film morphology and in light transmittance with silver film thickness, this absorption enhancement is ascribed to the excitation of transverse collective electron resonance of the silver islands. The thickness dependence of the enhancement and of the film morphology will be compared with those observed for silver films deposited on oxidized Si(111) substrates. PACS 61.14.Hg; 68.37.Hk; 78.30.-J     

Pulsed laser deposition of nanostructured Ag films

Ultra-thin (0.5-5 nm) films of Ag have been prepared by pulsed laser deposition in vacuum using a 26 ns KrF excimer laser at 1 J cm⁻². The deposition was controlled using a Langmuir ion probe and a quartz crystal thickness monitor. Transmission electron microscopy showed that the films are not continuous, but are structured on nanometer size scales. Optical absorption spectra showed the expected surface plasmon resonance feature, which shifted to longer wavelength and increased in strength as the equivalent film thickness was increased. It is shown that Maxwell Garnett effective medium theory can be used to calculate the main features of optical absorption spectra.     

掺Ag纳米颗粒的BaTiO3复合薄膜的非线性光学特性

通过准分子激光(XeCl, 308 nm, 20 ns)在MgO(100)单晶衬底上制备了不同掺杂浓度的Ag:BaTiO₃纳米复合薄膜,通过X射线衍射和X射线光电子能谱对薄膜的结构和组分进行了表征.在430 nm和470 nm附近观测到了不同浓度Ag纳米颗粒引起的等离子体吸收峰,通过z扫描技术对复合薄膜的三阶非线性光学特性进行了测量,并对其光学非线性的增强机制进行了讨论. 关键词： 金属纳米复合薄膜 激光沉积 非线性光学     

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     

金属纳米团簇复合薄膜Au/BaTiO3与Fe/BaTiO3的PLD制备及其光吸收特征

用脉冲激光沉积技术制备了掺杂纳米金属颗粒Au或Fe的BaTiO₃复合薄膜.用透射电子显微镜和x射线光电子能谱表征了金属颗粒的形态和化学态.330—800nm范围的吸收谱研究表明，掺Au颗粒的BaTiO₃薄膜在580nm附近有一个明显的共振吸收峰，而掺Fe颗粒的BaTiO₃薄膜没有这样的吸收峰.用Mie散射理论对结果进行了分析. 关键词： 复合薄膜 金属颗粒 脉冲激光沉积 吸收谱     

Magnetron and pulsed laser deposition of silver and gold nanoparticles and discontinuous films and their optical properties

Ag and Au nanoparticles are obtained by magnetron sputtering and pulsed laser deposition under different conditions, and the features of their absorption spectra associated with plasmon resonances are investigated. Optimal deposition conditions for obtaining small (5?C10 nm) silver nanoparticles with a high density of surface distribution include an increased argon pressure (2.5 × 10^?2 Torr) and a low discharge voltage (100 V). Gold nanoparticle arrays obtained by pulsed laser deposition at a temperature of 200°C in vacuum are more uniformly distributed on the substrates than those deposited at room temperature in argon. It is shown that the maximum of the plasmon absorption shifts toward shorter wavelengths with a decrease in the equivalent thickness of metal films and depends not only on this thickness but also on the type of substrate, which is responsible for the morphology of nanoparticle arrays.     

Dielectric layer-dependent surface plasmon effect of metallic nanoparticles on silicon substrate

The electromagnetic interaction between Ag nanoparticles on the top of the Si substrate and the incident light has been studied by numerical simulations. It is found that the presence of dielectric layers with different thicknesses leads to the varied resonance wavelength and scattering cross section and consequently the shifted photocurrent response for all wavelengths. These different behaviours are determined by whether the dielectric layer is beyond the domain where the elcetric field of metallic plasmons takes effect, combined with the effect of geometrical optics. It is revealed that for particles of a certain size, an appropriate dielectric thickness is desirable to achieve the best absorption. For a certain thickness of spacer, an appropriate granular size is also desirable. These observations have substantial applications for the optimization of surface plasmon enhanced silicon solar cells.     

Optical properties of ZnO and Al2O3 implanted with silver ions

ZnO and Al₂O₃ samples implanted with 30-keV silver ions with fluences in the interval (0.25–1.00) × 10¹⁷ ions/cm² are studied by the method of optical photometry in the visible part of the spectrum. The optical transmission spectra of the implanted samples exhibit a selective band associated with surface plasmon resonance absorption of silver nanoparticles. The intensity of this band nonmonotonically depends on the implantation fluence. The silver ion depth distribution in the samples is calculated. It is shown that the non-monotonicity observed in experiments is due to an increase in the substrate sputtering ratio with increasing implantation fluence. It is found that vacuum thermal annealing of the implanted Al₂O₃ layers up to 700°C causes a considerable narrowing of the plasmon absorption bandwidth without a tangible change in its intensity. At higher annealing temperatures, the plasmon absorption band broadens and its intensity drops. Annealing of the ZnO films under such conditions causes their complete vaporization.     

Preparation of monodisperse bimetallic nanorods with gold nanorod core and silver shell and their plasmonic property and SERS efficiency

In this study, monodisperse bimetallic nanorods with gold (Au) nanorod core and silver (Ag) shell (Au@AgNRs) were synthesized through seed‐mediated growth process by reduction of AgNO₃ using Au nanorods with narrow size and shape distribution as seeds. With increasing the used amount of AgNO₃, the Ag shell thickness of their lateral facets is raised faster than that of their two tips, leading to a decrease of their aspect ratios. Four plasmon bands are observable on the extinction spectra of Au@AgNRs, which are attributed to the longitudinal dipolar plasmon mode, transverse dipolar plasmon mode, and octupolar plasmon mode of the core‐shell structured bimetallic nanorods, respectively. As their Ag shell thickness increases, their longitudinal plasmon band blue‐shifts notably with the transverse plasmon band blue‐shifting and the two octupolar plasmon bands red‐shifting slightly, due to the decrease of their aspect ratios and enhancement of Ag plasmon resonance contribution. When used as surface‐enhanced Raman scattering (SERS) substrate for probing minute amounts of 4‐mercaptobenzoic acid in aqueous solution, Au@AgNRs have much stronger SERS activity than Au nanorods, and the obtained Raman signals are highly reproducible arising from their excellent monodispersity. Their SERS activity is remarkably increased with their Ag shell thickness thanks to the enhancing surface electric field and the chemical enhancement associated with electronic ligand effect. Copyright © 2014 John Wiley & Sons, Ltd.     

Ag-SiO2复合薄膜形貌和吸收特性的研究

通过分层镀膜的方式制备Ag和SiO₂的分层结构，经过快速热退火后，Ag颗粒扩散到复合薄膜的表面附近. 通过改变Ag颗粒扩散的距离(SiO₂的膜厚)，可很好地控制Ag颗粒在复合薄膜表面附近的大小，浓度和形貌，进而对共振吸收特性产生影响. 在实验中，根据Ag颗粒扩散的长度来调节退火的时间. 发现经过足够长的时间(17.5min)后，Ag颗粒会形成平行于衬底的平面团簇. 由于Ag原子在平面团簇之间容易扩散，使得Ag颗粒的粒径平均值变小并趋于某一特定的半径，且粒径分布范围变小，导致吸收谱发生蓝移，吸收带变窄，且强度增加. 关键词： 复合薄膜 共振吸收 平面团簇