胶体金纳米颗粒的荧光光谱特性

研究了胶体金纳米颗粒的荧光激发光谱和荧光发射光谱特性.增大激发光的波长,发射峰相应红移并在629nm达到最强,对应的灵敏激发波长为473nm.增加金纳米颗粒粒径,观察到发射谱的峰值先增大然后减小.发射峰产生的原因在于电子与带间空穴的复合导致非线性共振光散射.发射峰强度和金颗粒粒径的关系可以用表面等离子体震荡引起的局域场增强来解释,数值计算结果和实验结果能较好的吻合.     

SiO_2/Ag核壳结构纳米粒子的制备及其表面荧光增强

以罗丹明B掺杂的SiO2球为核,通过化学还原的方法制备了二氧化硅/银核壳结构复合纳米粒子。采用透射电镜(TEM)、紫外-可见-近红外(UV-Vis-NIR)分光光度计和荧光分光光度计对二氧化硅/银核壳结构纳米粒子的表面形貌、表面等离子共振和表面荧光增强特性进行了研究和表征。结果表明,二氧化硅/银核壳结构纳米粒子的表面等离子共振峰具有明显的可调谐性,且其表面荧光增强强烈依赖于银壳层的表面等离子共振,随银壳层厚度的增大而增强。     

金纳米双球系统的高灵敏光学传感与其消光系数及局域场增强之关联

系统地研究了最基本的单/双金纳米球系统的共振峰移动、局域场增强和消光谱等光学响应行为.发现在双金纳米球系统中,入射光除了能激发每个金纳米球的局域表面等离激元共振模式外,调整金纳米球间隙可使共振模式间产生强烈耦合,使系统局域场增强因子进一步提升,并增强光学传感能力和消光系数.有趣的是,受限于有限的局域场增强体积,具有高局域场增强因子的间隙为2 nm的双金纳米球系统的消光系数大幅降低,其消光系数和光学传感能力均低于5 nm间隙的系统.研究表明,双金纳米球系统的光学传感灵敏度不是由局域场增强幅度直接决定的,而与系统消光系数有相似的变化行为.这些结果可指导金纳米双颗粒和多颗粒系统的设计,为表面拉曼散射增强和光学传感等方面的应用提供创新性思路和方案.     

纳米金膜及金壳表面局域等离激元对 上转换荧光波长的选择调控

基于贵金属表面局域等离子体共振(LSPR)调控上转换荧光的研究绝大部分集中于纳米颗粒或纳米棒,即使同一复合结构对上转换荧光(UCL)也有或增强或猝灭的截然相反的报道,而对于进一步提高上转换荧光材料的效率和强度以满足更广泛的应用需求则越来越引起人们高度关注。本文通过构筑两种纳米金/上转换纳米晶复合结构,系统研究了各自的表面局域等离激元对上转换荧光的增强和猝灭效应,基于微结构表征及对稳态、瞬态荧光光谱的分析,阐述了波长依赖的上转换荧光增强和猝灭机理。结果显示超薄纳米金壳结构对Ho~(3+)、Fe~(3+)共掺杂纳米晶的绿光发射选择性地增强了25倍,源于激发光能量与LSPR能量匹配的激发增强机制,而在覆盖有超薄纳米金膜的上转换纳米晶复合结构中却观察到了金膜引起的Er上转换荧光猝灭,同时红绿比随金膜厚度增加而增大,来自于金膜对激发光的散射、金膜的LSPR吸收带与绿光发射能级耦合引起无辐射跃迁几率增加,绿光上转换荧光强度下降相对显著,UCL寿命变短。     

金纳米粒子掺杂DNA-CTMA-DPFP薄膜的表面增强拉曼散射特性

采用柠檬酸三钠还原氯金酸和离子交换法制备金纳米粒子掺杂DNA-CTMA材料,利用钯催化反应合成9,9-二乙基-2,7-二-(4-吡啶)芴荧光染料(DPFP),将DPFP与DNA-CTMA混合后,旋凃制备金纳米粒子掺杂的DNA-CTMA-DPFP薄膜样品。通过吸收光谱、荧光光谱和拉曼光谱的测量,研究了薄膜样品的光学特性和表面增强拉曼散射(SERS)特性。实验结果表明,薄膜样品在300～360 nm的吸收主要来自DPFP,在500～700 nm的吸收来自样品中金纳米粒子的局域表面等离子共振;样品在370,386,408 nm处的荧光峰分别对应DPFP的S₁₀-S₀₀、S₁₀-S₀₁和S₁₀-S₀₂能级的电子振动跃迁;在785 nm激光激发下,薄膜样品的拉曼散射主要来自DPFP分子,随着金纳米粒子掺杂比的增大,DPFP分子的拉曼散射峰强度逐渐增强。因此,金纳米粒子掺杂DNA-CTMA薄膜适合作为多种染料分子的SERS基底。     

海胆状金纳米粒子表面形貌对表面增强喇曼散射特性的影响

采用改进的一步还原法合成了多种海胆状金纳米粒子,并对它们的表面增强喇曼散射特性与其表面形貌的关系进行了实验研究.实验表明,合成的海胆状金纳米粒子的直径及表面的尖刺大小可以通过改变加入到氯金酸溶液中的硝酸银的量来调节.当加入到氯金酸溶液中的硝酸银为1μL时,合成的海胆状金纳米粒子的直径最小而尖刺最长.同时测量的紫外-可见-近红外吸收光谱表明,海胆状金纳米粒子的局域表面等离子体共振带会随着加入到氯金酸溶液中的硝酸银量的增加而变宽.此外,通过喇曼标记分子对巯基苯甲酸(4MBA)的喇曼光谱测量发现,较小直径和较长尖刺的海胆状金纳米粒子具有更强的表面增强喇曼散射活性.     

海胆状金纳米粒子表面形貌对表面增强喇曼散射特性的影响（英文）

采用改进的一步还原法合成了多种海胆状金纳米粒子,并对它们的表面增强喇曼散射特性与其表面形貌的关系进行了实验研究.实验表明,合成的海胆状金纳米粒子的直径及表面的尖刺大小可以通过改变加入到氯金酸溶液中的硝酸银的量来调节.当加入到氯金酸溶液中的硝酸银为1μL时,合成的海胆状金纳米粒子的直径最小而尖刺最长.同时测量的紫外-可见-近红外吸收光谱表明,海胆状金纳米粒子的局域表面等离子体共振带会随着加入到氯金酸溶液中的硝酸银量的增加而变宽.此外,通过喇曼标记分子对巯基苯甲酸(4MBA)的喇曼光谱测量发现,较小直径和较长尖刺的海胆状金纳米粒子具有更强的表面增强喇曼散射活性.     

纳米银组装结构上罗丹明B的表面增强荧光效应

采用表面自组装技术,在玻璃表面构筑银纳米粒子的二维组装结构。银纳米粒子组装结构的表面等离子共振光谱中偶极子表面等离子体共振对组装结构更为敏感而表现出较大位移。组装银纳米粒子可极大增强罗丹明B的荧光。荧光的表面增强效应主要来自银纳米粒子对荧光分子所处区域的局部电磁场增强,银纳米粒子的表面分子修饰对其表面增强效应有较大的影响。     

银纳米颗粒对掺铒铋酸盐玻璃光谱性质的影响

采用传统熔融淬火技术制备了一系列Er3+离子掺杂复合银纳米颗粒的铋酸盐玻璃样品.研究了纳米银含量的改变对Er3+离子荧光发射特性的影响.研究发现,铒在1.53 μm处的荧光强度在银纳米颗粒质量分数为0.2%处取得最大值,为未掺杂银纳米颗粒时的4.6倍.其荧光增强的原因归结于银纳米颗粒表面等离子体共振导致局域场增强和Ag...     

金属复合纳米粒子的局域表面等离子体特性研究

提出了一种在银层上面覆盖一层金的四棱台复合纳米结构。采用离散偶极子近似(DDA)方法,针对光激发复合金属纳米粒子的局域表面等离子体共振(LSPR)进行研究,讨论了四棱台纳米粒子金银复合结构在不同尺寸、不同混合比等条件下的消光特性及折射率灵敏度。计算结果显示,在银层厚度为50 nm的四棱台纳米粒子上覆盖金层,其折射率灵敏度不变。同时,四棱台银纳米粒子厚度的增加会使其消光峰值波长蓝移。金材料比例的增加会使金银复合纳米结构的消光峰值波长红移。当金银复合结构的纳米粒子的厚度大于自由电子的平均自由程时,其局域表面等离子体激发强度不发生变化。     

表面等离子体增强氧化锌纳米带发光特性的研究

利用简单的化学气相沉积方法在低温下高产量地合成了ZnO纳米带, 并利用磁控溅射对样品进行表面修饰, 制备了Au-ZnO复合纳米带. 通过扫描电镜、透射电镜及微区拉曼等手段系统地研究了表面修饰对ZnO 纳米材料发光性能的影响.结果表明, 在ZnO纳米带上溅射Au纳米颗粒, 可有效增强其近带边发光并使可见发光强度发生淬灭, 从而增强ZnO纳米带的发光性能. ZnO纳米带发光增强因子η最大可达到85倍. 基于Au纳米颗粒的散射、吸收、Purcell增强因子, 以及Ostwald熟化理论, 又进一步探讨了Au-ZnO复合材料的发光机制. 采用表面等离子体耦合的方法可以有效地提高光电半导体器件的发光效率. 关键词： 表面等离体子 光致发光 氧化锌     

Enhanced photoluminescence of conjugated polymer thin films on nanostructured silver

Photoluminescence of a conjugated polymer in the presence of surface plasmons on metallic nanoparticles is studied. A layered device structure was constructed that enabled control over nanoparticle diameter and separation between the polymer and nanoparticles layers. The dependence of the surface plasmon evanescent field and energy transfer has been investigated with the largest enhancement in photoluminescence observed at a 40 nm distance separation between the fluorophore and the surface plasmon. A spectrum of surface plasmon resonances ranging from the emission to the absorption energies of the conjugated polymer revealed largest enhancements when the resonance was tuned to the conjugated polymer emission energy. At peak photoluminescence the maximum photoluminescent enhancement was found to be 5.6 times of the photoluminescence of the control structure and the total integrated enhancement was 5.9 times.     

Photoluminescence enhancement from hybrid structures of metallic single-walled carbon nanotube/ZnO films

We investigated the dependence of localized surface plasmon resonance (LSPR) coupled photoluminescence (PL) emission on the density of a metallic single-walled carbon nanotube (m-SWCNT). The m-SWCNTs of various densities were deposited on top of ZnO films by spin coating and filtration transfer method to form the hybrid structures. We observed PL enhancement from ZnO films deposited with spin coated m-SWCNT, comparing with pure ZnO film. The m-SWCNT acts as absorbers for the light emitted due to SPR. After resonant excitation, hot electrons in m-SWCNT are created in high energy states, which can then transfer from the m-SWCNT to the conduction band of the ZnO films. We discuss the relationship between the hot electron flow generated by internal photoemission and LSPR.     

Enhancement of photoluminescence of the CdSe/CdS quantum dots on quartz substrates in the presence of silver nanoparticles

Multilayer systems consisting of layers of hybrid quantum dots are fabricated. The quantum dots with the CdSe/CdS core/shell structure are chemically synthesized and deposited on the surface of quartz glass that contains ion-synthesized silver nanoparticles in the near-surface region. Silver nanoparticles exhibit optical absorption owing to the localized surface plasmon resonance. Variations in the photoluminescence intensity of the layer related to an increase in the distance from the quartz surface with metal nanoparticles are studied. An increase in the photoluminescence intensity is observed under excitation in the spectral region of the plasmon absorption of silver nanoparticles. An optimal distance between the layers is determined to maximize the enhancement of the photoluminescence of quantum dots in the presence of the near field of metal nanoparticles.     

Surface plasmon characteristics of tunable photoluminescence in single gold nanorods

Light emission resulting from two-photon excited gold nanoparticles has been proposed to originate from the radiative decay of surface plasmon resonances. In this vein, we investigated luminescence from individual gold nanorods and found that their emission characteristics closely resemble surface plasmon behavior. In particular, we observed spectral similarities between the scattering spectra of individual nanorods and their photoluminescence emission. We also measured a blueshift of the photoluminescence peak wavelength with decreasing aspect ratio of the nanorods as well as an optically tunable shape-dependent spectrum of the photoluminescence. The emission yield of single nanorods strongly depends on the orientation of the incident polarization consistent with the properties of surface plasmons.     

Localized surface plasmon resonance enhanced blue light-emission of polyfluorene copolymer

Polyfluorene-based blue light-emitting devices suffer from the shortcomings of low stability, drastic loss of quantum yield and poor color purity. To find out the solution, we use silver nanoparticles for enhancement of photoluminescence of polyfluorene copolymer (PCFOz) through localized surface plasmon resonance (LSPR) coupling effect. The photoluminescence from PCFOz can be concentrated down to nanoscale, realizing a high spatial selectivity of the fluorescence enhancement process. PL emission of conjugated polymer is blueshifted about 8 nm from the peak emission of 433 nm for the neat PCFOz film to around 425 nm for the Ag/PCFOz composite film. The full width at half maximum of PCFOz is reduced from 88 to 60 nm. Absorbance spectra and time resolved photoluminescence measurements further demonstrate that both absorption intensity and recombination rate of PCFOz increase due to strong LSPR-excitons coupling. Optical properties of such plasmon-enhanced organic light emitters were also studied by temperature-dependent PL spectroscopy from 10 to 200 K. In comparison with bare PCFOz, the LSPR induced emission enhancement ratio significantly increases with increasing temperature. These results are believed to be important for the development of highly efficient blue organic light-emitting devices based on all-solution processing.     

Tunable composite nanoparticle for plasmonics

We present a numerical study of the tunability properties of a plasmonic subwavelength particle deposited on a metallic slab. The particle is composed of a metallic part, supporting a localized plasmon mode, separated from the slab by a dielectric spacer. It is shown that the position of the resonance wavelength can be modified over a large spectral range by changing either the spacer thickness by a few tens of nanometers or its susceptibility within the range of usual dielectrics. A linear relation is observed between the resonance wavelength and the spacer permittivity.     

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.     

Plasmon spectroscopy of metallic nanoparticles above flat dielectric substrates

We numerically analyze the spectral properties of localized plasmon resonances in metal nanoparticles when these are above a dielectric substrate. This analysis is performed as a function of the various parameters involved in the problem (relative optical properties, particle-substrate separation, angle of incidence, etc.). It can be shown that from the spectral behavior of the resonance in the far field, information about particle near-field interactions can be obtained.     

Transmission of light through coaxial and non-coaxial double-layer gold slit arrays

We investigate numerically the transmittance of light through gold double-layer structures with periodic coaxial and non-coaxial slits. We attribute the enhanced optical transmission to the surface plasmon resonance collaborating with the localized waveguide resonance. The transmission spectra and the surface electric fields are used to characterize the resonances of both types. For the coaxial system, with the increase of the slit width of the second layer, the resonance peak values of both types increase sharply at first until the two layers have the same slit width and then decrease dramatically; additionally, the center of the localized waveguide resonance peak shifts to shorter wavelength noticeably, but the surface plasmon peak center moves negligibly. As regards the non-coaxial structure, it shows a similar behavior of the localized waveguide resonance peak to that of the coaxial one; however, the surface plasmon resonance peak behaves in a different way. These results may be associated with the surface plasmon coupling modes and the Fabry–Perot cavity modes in the double-layer structure.