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.     

金纳米结构表面二次电子发射特性

使用低气压蒸发工艺制备了金纳米结构,研究了金纳米结构的二次电子发射特性及其对表面形貌的依赖规律,表征了金纳米结构表面出射二次电子能量分布.实验结果表明:蒸发气压升高时,金纳米结构孔隙率增大,表面电子出射产额降低;能量分布表明金纳米结构仅对低能真二次电子有明显抑制作用,对背散射电子的作用效果则依赖于表面形貌.使用由半球和沟槽构成的复合结构,并结合二次电子发射唯象概率模型,对金纳米结构进行模型等效及电子发射特性仿真,模拟结果表明:纳米结构中的半球状纳米颗粒对两种电子产额均有增强作用;沟槽对真二次电子产额有强抑制作用,而对背散射电子产额仅有微弱抑制作用.本工作深入研究了金纳米结构表面电子发射机理,对于开发空间微波系统中纳米级低电子产额表面有重要参考价值.     

金纳米粒子的电化学合成及光谱表征

采用电化学方法合成各种形状的金纳米粒子,生成的金纳米粒子形貌与施加电流有关,通过匀速递增电流电解的方法,可制备得到哑铃形,球形以及棒状金纳米粒子,采用恒电流电解方法主要获得球形及哑铃形纳米粒子。利用透射电镜、紫外-可见光谱及拉曼光谱对金纳米粒子进行相关表征。紫外-可见光谱研究发现金纳米棒出现位于近红外区间的吸收峰(985 nm),由此推测棒的长径比约为6。以结晶紫为探针分子,研究了金纳米粒子的表面增强拉曼光谱(SERS)效应,并分析得出其平躺的吸附模式。根据形貌表征的结果推断了纳米粒子的生长机理。     

不同形貌金纳米粒子的制备及其表面增强拉曼散射效应的研究

不同形状的金纳米粒子在表面增强拉曼散射(surface enhanced Raman scattering,SERS)中有不同的增强效果,多面体金纳米粒子具有多角结构,显示出比金纳米板更为明显的增强效果,近年来对其合成和性质的研究备受关注。该研究探究了十二面体,二十面体,三角板,球形四种形状的金纳米粒子在SERS中不同的增强效果。分别采用硼氢化钠还原法和以N,N-二甲基甲酰胺(DMF)为还原剂制备金三角纳米片和二十面体金纳米粒子,又以二十面体金纳米粒子为种子制备出十二面体金纳米粒子,并分别以以上三种不同形貌的金纳米粒子及球形金溶胶为基底,4-巯基吡啶,对巯基苯甲酸为探针分子检测了其在不同激发波长下的增强效果。透射电子显微镜结果表明金三角纳米板的平均边长为130nm,二十面体和十二面体金纳米粒子的粒径分别为100和120nm。三者的紫外可见吸收峰分别在589,598和544nm处。表面增强拉曼散射结果表明金多面体比金三角纳米板表现出更好的增强效果。     

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.     

应用平行隔板增强纳米球表面电场

球形纳米粒子已经被广泛地应用于表面增强拉曼散射.为进一步提高纳米球表面电场,从而提高表面增强拉曼散射信号强度,本文设计了平行隔板纳米球结构.离散偶极子近似计算结果表明,应用平行隔板后,纳米球表面电场得到了大幅度增强,故平行隔板纳米球结构更适合作为表面增强拉曼散射衬底,用于生物分子探测.另外,本文还系统地研究了平行隔板结构参数对整个平行隔板纳米球结构光学性质的影响. 关键词： 银纳米球 平行隔板 表面等离子体 离散偶极子近似     

飞秒激光所致金纳米粒子析出的玻璃非线性吸收

依据Z-scan技术,使用波长532nm的纳秒脉冲,研究了通过聚焦的飞秒脉冲诱导并辅以热处理得到的金纳米粒子析出的玻璃的非线性吸收.观察到金纳米粒子析出的玻璃具有饱和吸收特性.根据局域场效应,对实验结果拟合,得到在接近表面等离子体共振激发情况下,金纳米粒子三阶极化率虚部分别为Imχ(3)m=57×10-7esu.玻璃样品中金纳米粒子的非线性响应主要起源于热电子贡献. 关键词： 带内跃迁 带间跃迁 热电子贡献     

分子层次的金纳米棒-表面活性剂-磷脂自组装复合体形貌

金纳米粒子表面修饰剂的组分和形貌影响其物理化学性质.本文采用隐式溶剂耗散粒子动力学模拟的方法,研究了金纳米棒、溴化十六烷基三甲基铵和二肉豆蔻酰磷脂酰胆碱的自组装形貌.结果表明,复合体组装形貌主要与溴化十六烷基三甲基铵和二肉豆蔻酰磷脂酰胆碱这两种修饰剂的摩尔比有关,而金纳米棒与修饰剂的相互作用强度以及金纳米棒的直径对形貌的影响不明显.当作用强度和直径一定时,随着摩尔比增加,修饰剂在金纳米棒表面会形成完整的双层膜、有裂痕的双层膜、长片状胶束、以及以螺旋形式缠绕在金纳米棒上的蠕虫状胶束.进一步分析发现,金纳米棒直径越小、摩尔比越大、或作用强度越大时,金纳米棒两端的覆盖程度越高,同时修饰剂吸附层的厚度越薄.这些结果直接表征了溴化十六烷基三甲基铵和二肉豆蔻酰磷脂酰胆碱混合物在金纳米棒表面的形态,在分子水平上加深了对金纳米棒自组装行为的理解,有助于实现金纳米棒的可控自组装.     

掺金玻璃在电场热处理中的形核过程

利用电场热处理工艺,成功制备出含纳米尺寸金颗粒掺杂的硼硅酸盐玻璃，采用x射线衍射、扫描电子显微镜和吸收光谱分析了在不同工艺条件下制备得到的玻璃样品的相成分、微观形貌和光学性能.然后在理论上分析了外电场对掺杂玻璃热处理过程的影响，提出了适合掺金玻璃的电场热处理热力学模型.模型中的关键因素是电场能量变化量，对此采用两种方法计算，一种是在一定简化后的理论计算；另一种是利用计算机有限元方法计算.两种方法的结果比较相近，并且都能解释前面的实验现象. 关键词： 掺金玻璃 形核 电场     

Semiconductor Nanoparticle in an Electric Field

The distributions of electrons and positive charges within a spherical semiconductor nanoparticle with surface electron traps in a uniform applied electric field are studied. The minimization of the total free energy gives the resulting effective electric field, which depends on the densities of donors and surface traps, as well as on the distance from the center of the nanoparticle. It is shown that the near-surface field at a relatively low donor density in the region of its entrance to the nanoparticle significantly differs from that in the region of its departure from the nanoparticle. The induced dipole moment of the nanoparticle is calculated and different contributions to it are determined. The ranges of applicability of the results are indicated.     

金纳米颗粒等离激元对不同形貌氧化锌薄膜发光性能的调控

采用化学气相沉积法制备了纳米棒状的氧化锌纳米结构薄膜和没有纳米棒的氧化锌薄膜,通过直流溅射在所制备的有纳米棒和没有纳米棒的氧化锌薄膜上淀积约3 nm厚的金纳米颗粒薄膜,研究了金纳米颗粒对不同表面形貌氧化锌薄膜的发光特性的影响。实验发现金纳米颗粒的存在使具有纳米棒的氧化锌薄膜的紫外发射增强,但使来自缺陷的可见光发射受到很大的抑制。通过比较有纳米棒和没有纳米棒的氧化锌薄膜在镀金纳米颗粒前后的发光特性,发现金表面等离激元对氧化锌发光的调控取决于氧化锌的表面形貌,纳米棒的存在更有利于金纳米颗粒等离激元调控氧化锌的发光特性。     

Local fields close to the surface of nanoparticles and aggregates of nanoparticles

A refined discussion of the near-field scattering of spherical nanoparticles and the electromagnetic fields close to the particle surface is given. New results for the dependence on the distance from the surface and the angular distribution of the scattered light in the near-field are given. It will be shown that the radial component of the electric field leads to striking differences in the phase functions in the near-field and the far-field. Exemplary computations are presented for Ag and Au particles with different size. In a second part the discussion is extended to assemblies of spherical Ag and Au nanoparticles. It will be shown that large near-fields at wavelengths commonly used in SERS experiments are obtained for aggregates. In the near-field scattering intensity “hot spots” mark regions between particles in the aggregate where the near-field is particularly high. Received: 4 May 2001 / Revised version: 20 July 2001 / Published online: 19 September 2001     

Angular distribution of electron emission from atomic hydrogen by bare ion impact

A series of silver nanoparticle embedded in erbium-doped tellurite glasses were synthesized using a one step melt-quenching method. Density and refractive index of glasses were measured. Thermal and optical characterizations were performed and plasmon bands of elliptical nanoparticles were observed. An enhancement of green (525 and 550 nm) and red (632 nm) lines in luminescence spectra of Er³⁺-doped silver-embedded tellurite glass was recorded and explained by energy transfer mechanism from silver nanoparticles to erbium ion in addition to enhanced local field in vicinity of metallic nanoparticles in the glass. The presence of nanoparticles was confirmed by transmission electron microscopy imaging and reduction of silver ions to silver neutral particles discussed through the redox potential estimation in probable reactions. Silver-erbium co-doped tellurite glass exhibits strong novel optical properties which nominate it as the promising glass for laser, color displays, and photonic applications.     

The color of finely dispersed nanoparticles

We discuss the dependence of the color of low-concentrated nanoparticle systems on particle size and mass concentration for Ag, Au and TiN nanoparticles, which exhibit a surface plasmon polariton resonance in extinction spectra. Comparison is made with color data obtained for Ag and Au colloidal suspensions. When particles lump into aggregates, the splitting of the surface plasmon resonance into new resonances affects the extinction of light and, hence, the color of the particle assembly. This is demonstrated for aggregated colloidal suspensions of Ag and Au nanoparticles. Finally, for highly concentrated assemblies such as pigment films, we discuss the dependence of the color in diffuse reflectance and transmittance according to Kubelka and Munk (P. Kubelka, F. Munk: Z. Techn. Phys. 12, 593 (1931)), and extend this model by using optical properties of aggregates of spheres. Received: 2 July 2001 / Published online: 10 October 2001     

Local Surface-Plasmons in Nonspherical Metal Nanoparticles

When a small metallic nanoparticle.is irradiated by incident light, the oscillating electric field can cause the conduction electrons to oscillate coherently, which excites the local surface plasmons （LSPs）. As is well known, excited LSPs can gather the energy of incident light to the surface of metallic nanoparticle. Recently, some nonspherical particles, e.g. tetrahedron, are suggested to obtain stronger localized electric field. We employ the discrete dipole approximation method to calculate the optical response of the tetrahedron nanoparticle, including the extinction and distribution of the electric field around the particle. The influences of some parameters, including the nanoparticle size, incident direction and polarization, are investigated to analyse the response modes and to obtain stronger localized electric field.     

Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.     

Behaviour of nematic liquid crystals doped with ferroelectric nanoparticles in the presence of an electric field

A planar nematic liquid crystal cell (NLC) doped with spherical ferroelectric nanoparticles is considered. Polarisation of the nanoparticles are assumed to be along the NLC molecules parallel and antiparallel to the director with equal probability. The NLC molecules anchoring to the cell walls are considered to be strong, while soft anchoring at the nanoparticles surface is supposed. Behaviour of the NLC molecules and nanoparticles in the presence of a perpendicular electric field to the NLC cell is theoretically investigated. The electric field of the nanoparticles is taken into account in the calculations. Freedericksz transition (FT) threshold field in the presence of nanoparticles is found. Then, the director and particles reorientations for the electric fields larger than the threshold field are studied. Measuring the onset of the nanoparticles reorientation is proposed as a new method for the FT threshold measurement.     

Localization of the electromagnetic field in the vicinity of gold nanoparticles: Surface modification of different substrates

Theoretical predictions and experimental results for nanosized modification of metal (Au), semiconductor (Si), or dielectric (soda lime glass) substrates using near-electromagnetic field enhancement in the vicinity of gold nanoparticles are presented. The near field properties for the system consisting of an isolated gold nanoparticle or nanoparticle aggregate deposited on the substrates, which is irradiated by electromagnetic wave, are investigated using Finite Difference Time Domain Simulation technique. The influence of the substrate material on the near field distribution characteristics is predicted. The results reveal that the field on the substrate surface is enhanced in the three investigated cases, but its spatial distribution and magnitude depend on the substrate material. In the case of the metal and semiconductor substrate the enhanced near field is strongly localized in the vicinity of the contact point with the particle, in an area with diameter smaller than the particle's one. The intensity of the enhanced field on the glass is more than an order of magnitude lower than the case of using silicon substrate. The properties of the near field on the substrate surface also depend on the particle arrangement. For a two-dimensional gold nanoparticle array, when the particles are closely arrayed, the intensity of the enhanced field on the substrate surface is minimal. With the increase of the interparticle distance the near field intensity increases. The validity of the obtained theoretical results is confirmed experimentally.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.