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.     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

LB膜隔离层对表面增强喇曼散射的影响

本文首次利用LB膜作为分子—金属间的隔离层,考察了表面增强喇曼散射的电磁增强机理,监测了表面增强喇曼散射信号随隔离层厚度的变化。在银膜/LB膜/吡啶+氯化钾系中,实验结果表明,隔离层厚度为5nm时,表面增强喇曼散射效应仍然存在,但在15nm时已测不到其信号,实验支持了电磁增强机理。     

银三角纳米粒子的制备及其稳定性的研究

室温下,通过控制银种子胶体pH值,采用光诱导法制备出银三角纳米粒子,并对其表面增强喇曼散射活性和时间稳定性进行了实验研究.对比分析了新制备样品与在暗室中存放5个月样品的透射电子显微镜照片、紫外-可见吸收光谱和表面增强喇曼光谱.结果表明:所制备的银三角纳米粒子在室温暗室中存放5个月后其几何形状、尺寸以及相应吸收峰的位置基本不变,具有较好的时间稳定性,对罗丹明6G探针分子仍具有较好的表面增强喇曼效应.     

结晶紫、碱性品红、染料1555吸附在银胶上的表面增强喇曼散射的激发波长关系

本文通过研究在不同激发波长下吸附在银胶上的结晶紫、碱性品红、染料1555的表面增强喇曼散射散射强度的变化,分析了普通喇曼散射、表面增强喇曼散射及表面增强共振喇曼散射之间的联系与不同。     

金银双金属纳米壳层结构的SERS活性研究

利用磁控溅射技术在组装整齐的微球表面依次镀上银、金薄膜,获得双金属纳米壳层结构。以对巯基苯胺(p-ATP)为探针分子,研究了该壳层结构在不同激发线下SERS增强差异。测试结果表明,金银双金属纳米壳层结构在780nm激光下具有很好的SERS增强效果,并随着外层金膜厚度的减小而逐渐增强。对各个基底的增强因子进行计算可知,基底的表面等离子体共振(SPR)峰与激发线的匹配程度越好,其增强因子越大。由于金的高稳定性和良好的生物相容性,该基底在SERS生物传感方面具有很大应用潜力。     

内嵌圆饼空心方形银纳米结构的光学性质

采用离散偶极子近似方法计算了内嵌圆饼空心方形银纳米结构的消光光谱以及其近场的电场强度分布,并进一步与空心方形纳米结构的消光光谱和表面电场做比较.结果表明,在耦合作用下内嵌圆饼空心方形银纳米结构不仅产生了新的共振模式,而且新的共振模式在传统表面增强拉曼散射的激发波长范围内,进而可以弥补由于实验上运用纳米切片法所制备的空心方形纳米结构尺寸较大导致其共振吸收峰在远红外波长范围的不足.此外,可以通过改变内嵌圆饼空心方形银纳米结构的形貌参数调节其表面等离子体共振峰的共振波长,以满足在表面增强拉曼散射、生物分子或化学分子探测上的应用.     

光诱导转化法制备片状三角形银纳米粒子的表面增强喇曼散射

采用柠檬酸三钠化学还原法制备球形Ag纳米粒子溶胶,并用高压球形氙灯对球形Ag纳米粒子溶胶进行光诱导实验.利用透射电子显微镜、紫外-可见吸收光谱研究了不同光照时间下的银胶纳米粒子的光谱特性和表面形貌,并以结晶紫为探针分子测量了银胶纳米粒子的表面增强喇曼散射光谱.实验结果表明:随着光照时间的增多,Ag纳米粒子溶胶颜色变化显著;紫外-可见吸收光谱吸收峰从单一峰渐渐显示出多个峰;透射电子显微镜图显示Ag纳米粒子由球形逐渐转变成片状三角形银纳米粒子、截角的片状三角形银纳米粒子;表面增强喇曼散射的增强效应随着光照时间的变化先逐渐增大,然后逐渐减小.     

纳米金表面修饰与表面等离子体共振传感器的相互作用研究

为了分析纳米金表面修饰对表面等离子体共振(SPR)的放大作用,以及其对传感器本身的影响,首先,基于色散介质的吸收理论,通过建立波长型SPR生物传感器四层膜结构的数学模型,理论分析了传感器表面所吸附纳米金对传感器的影响:纳米金的表面修饰,改变了表面等离子体传感器中棱镜表面各介质层内电磁场的能量分布,削弱了金属膜在共振吸收中的作用,从而使SPR曲线的半波宽度增加,最小反射系数增大,金膜的最优膜厚度也随之改变.其次,通过不同厚度的金膜外吸附纳米金的对比试验,验证了此理论.金膜厚45nm、表面修饰10nm纳米金颗 关键词： 表面等离子体共振 生物传感器 纳米金 金属膜     

表面等离子体共振与表面增强拉曼散射相关性研究

本实验利用实验室搭建的SPR-SERS显微拉曼光谱仪同时检测了吸附在40 nm银膜上的4-amin-othiophenol(4-ATP)自组装膜的表面等离子体共振(Surface Plasmon Resonance,简称SPR)消光谱及表面增强拉曼散射(Surface-Enhanced Raman Scattering,简称SERS)光谱,研究了两者之间的相关性。实验发现随着SPR吸收的增强,SERS强度也急剧增强,在SPR共振角附近SERS强度是远离共振角处的20多倍。因此在共振角附近能够极大的提高SERS的检测灵敏度并扩展SERS的应用。     

2-氨基苯硫酚NIR-SERS光谱及其在纳米银表面吸附行为分析

本文采用静电自组装的方法制备了二维纳米银膜。UV-vis吸收光谱显示其等离子体共振吸收带位于400+900nm的光谱范围,延伸到了近红外区,可以较好的匹配785nm的近红外激发光源。以该纳米银膜为基底,对2-氨基苯硫酚(2-ATP)分子进行了近红外表面增强拉曼散射(NIR-SERS)检测,获得了重复性良好的NIR-SERS光谱图。实验表明:以2-ATP为探针分子时,该纳米银膜的NIR-SERS增强因子达到2.19×109。同时,本文采用密度泛函理论(DFT),以B3LYP/6-31G为基函数,对2-ATP分子进行结构优化和普通拉曼光谱(NR)计算,发现理论值和实验值吻合较好。此外,对2-ATP的NIR-SERS谱带进行了归属分析,发现当2-ATP分子在纳米银表面吸附时,是以-SH基团吸附到银表面,且同时-SH基团会被纳米银氧化。     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Plasma resonance — enhanced raman scattering by absorbates on gold colloids: The effects of aggregation

The excitation profile of the 1014 cm^?1 Raman band of pyridine adsorbed on colloidal gold particles, and the extinction and elastic scattering spectra of the colloids, are measured as the colloids slowly aggregate in the presence of pyridine. Transmission electron microscopy shows that the aggregates formed are predominantly strings of particles rather than compact clusters, and the dipolar plasma modes of the aggregates are therefore split into longitudinal and transverse components. It is shown that only for excitation under the longitudinal resonance extinction band is there a large Raman intensity enhancement. The Raman excitation profile maximum corresponding to excitation under this resonance moves progressively to longer wavelengths, increasing substantially in height, as the aggregation proceeds. Thus aggregation is most advantageous for the realization of large Raman signals from these colloids, the Raman intensity at a given excitation wavelength increasing approximately as the square of the absorbance at that wavelength as the aggregation proceeds. These observations are discussed in relation to the electromagnetic field enhancement contribution to the surface Raman effect, with which they are in general agreement, and the large increase in ¦?¦² for gold and silver with increase in wavelength is shown to be a significant factor in accounting for some of these effects of aggregation.     

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。     

Dependence of surface enhanced Raman scattering on the plasmonic template periodicity

Surface enhanced Raman scattering has been investigated from rhodamine 6G molecules embedded in polymethyl methacrylate (R6G+PMMA) and coated on one-dimensional and two-dimensional gold-dielectric gratings fabricated by laser interference lithographically. The Raman signals from these plasmonic templates are 200 to 400 times larger than the signal from R6G+PMMA coated on plain gold films. The enhancement of the Raman signal varies almost periodically with the period of the grating. Finite-difference time-domain simulations show that large electromagnetic near fields occur at the metallic edges due to the resonant excitation of localized surface plasmon of the gold patches by the pump laser. These give rise to large enhancements of the Raman signal. The dependence on period is due to the combined effects of the localized surface plasmon and the periodic grating that couples the pump laser to the surface plasmon polariton.     

SPR and SERS characteristics of gold nanoaggregates with different morphologies

In this study, surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS) characteristics of gold nanoaggregates with different morphologies are examined to elucidate the correlation between SPR and SERS of the object. Nanoaggregates, defined as random aggregates (hereafter RA), elongated aggregates (hereafter EA) and two-dimensional layered aggregates (hereafter 2DLA) are fabricated by immobilizing colloidal gold nanoparticles on glass substrates. The color variation observed in the RA and EA samples indicates the variation in localized SPR excitations excited on the samples. The RA sample mostly shows a broadened and shifted SPR peak centered at 570 nm in addition to another peak in the longer wavelength region (∼700 nm), whereas in the EA sample a weak blue-shifted peak is observed near 450 nm in addition to a broadened peak centered at 570 nm covering a trail for another one near 700 nm. In the case of the 2DLA sample, more than one SPR peaks are observed in the longer wavelength region. The SERS observation confirms million times higher enhancement at least in Raman intensity using the gold nanoaggregates adsorbed by dye molecules. The EA sample of gold nanoparticles shows ∼5 times higher enhancement in Raman signal compared to that of the RA and 2DLA sample.     

Photoelectron emission from granulated gold films activated by cesium and oxygen

Granulated gold films activated by cesium and oxygen are found to produce an intense photoelectron emission band about 100 nm wide at a wavelength of 530 nm with a sensitivity of about 4 mA/W in the visible range. This band is likely to be associated with excitation of surface plasmons. The results obtained indicate that, owing to surface photoeffect, gold films activated by Cs and O can be used as fast photocathodes with a time constant of several femtoseconds.     

金纳米粒子自组装薄膜的光谱学研究

采用柠檬酸钠还原氯金酸制备了金胶体，通过静电自组装制备了金纳米粒子薄膜，利用紫外-可见光吸收光谱等对金纳米粒子薄膜进行了光谱学研究，紫外-可见光吸收光谱表明所制备的金溶胶为单分散体系，根据自组装薄膜的X-射线衍射谱，由谢乐公式估算金纳米粒子的粒径约为21nm；X-射线光电子能谱显示氯金酸的还原反应比较完全，金主要以Au^0的价态存在，金胶体粒子通过静电吸引机制组装到PDDA改性的衬底表面；紫外-可见光吸收光谱和表面增强拉曼光谱显示，由于粒子间的电磁耦合，自组装金纳米粒子薄膜表现出协同等离子体共振吸收行为和表面增强拉曼散射效应。     

Suppressed Thermal Conductivity in Polycrystalline Gold Nanofilm: The Effect of Grain Boundary and Substrate

We investigate the electrical conductivity and thermal conductivity of polycrystalline gold nanofilms,with thicknesses ranging from 40.5nm to 115.8 nm,and identify a thickness-dependent electrical conductivity,which can be explained via the Mayadas and Shatzkes(MS)theory.At the same time,a suppressed thermal conductivity is observed,as compared to that found in the bulk material,together with a weak thickness effect.We compare the thermal conductivity of suspended and supported gold films,finding that the supporting substrate can effectively suppress the in-plane thermal conductivity of the polycrystalline gold nanofilms.Our results indicate that grain boundary scattering and substrate scattering can affect electron and phonon transport in polycrystalline metallic systems.