PS/Ag核壳结构复合微球的制备与性能

以乳液聚合法制备的平均粒径1.2~1.5μm单分散聚苯乙烯(PS)微球为核,经过超声敏化、化学镀、还原等过程制备了PS/Ag核壳结构复合微球。采用透射电镜、X射线衍射、红外光谱、紫外可见光谱对其形貌、物相、结构与光学性质进行了表征与分析。结果表明:PS/Ag复合微球粒径相对均一;通过多次敏化、控制二次银氨溶液浓度(0.002~0.006 mol/L),可实现对纳米银壳层厚度的调控;纳米银壳层沉积生长过程中,随着PS微球表面银粒子的增多、增大,复合微球的光学等离子体共振吸收峰产生显著的展宽与红移。     

空心聚苯乙烯微球电沉积金工艺

 采用自行设计的微球电沉积装置,建立了空心聚苯乙烯(PS)微球的电化学沉积金工艺。实验条件为：电源输出电压0.7~0.8 V,电流密度2.0 mA·cm^-2,镀液温度45 ℃,阴极转速250 r·min^-1,镀液流速7 mL·min^-1·cm^-2。在此工艺条件下制得的空心金微球对称性和厚度均匀性良好,表面粗糙度低于500 nm,微球表面沉积金速率约为6 μm·h^-1。     

不同能量的高电荷态Ar12+离子辐照对Au纳米颗粒尺寸的影响

报道了在兰州重离子加速器国家实验室电子回旋共振离子源原子物理实验平台上,在室温（293.15K）条件下,用固定剂量（4.3×10¹¹/cm²）的高电荷态⁴⁰Ar¹²⁺离子,辐照沉积在厚度为300nm的金膜表面上、平均直径约为35.3nm的Au纳米颗粒,使其大小发生改变的实验结果.实验中,通过改变入射离子的引出电压,选择不同的能量,利用原子力显微镜（AFM）对辐照前后颗粒的形态和大小进行表征,系统地研究了辐照后Au纳米颗 关键词： 纳米颗粒 高电荷态离子 离子辐照 临界能量     

制备集成微通道的表面增强拉曼基底

本文介绍一种集成微通道的表面增强拉曼基底。采用湿法刻蚀方法在硅片上形成微通道,然后电子束蒸发沉积金薄膜,最后在300℃温度下高真空退火30分钟,使微通道内形成均匀且高密度的金纳米颗粒结构。用场发射扫描电子显微镜(SEM)对基底表面进行表征发现:金膜厚度对基底的表面形貌影响很大,5nm厚的金膜在退火后形成了均匀的高密度的纳米颗粒结构,而10nm厚的金膜退火后没有得到高密度纳米颗粒结构。用10-6 M的罗丹明6G作为探测分子进行拉曼实验测试结果同样表明:5nm厚的金膜退火后形成高密度的金纳米颗粒显著地增强了R6G拉曼信号。同时,对比了宽度分别为25、60、110!m三种尺寸的微通道的基底表面形貌和拉曼增强效应,微通道尺寸对表面形貌和拉曼增强效应影响均很小。     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO2纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO2的沉积时间及SiO2的沉积时间一定而改变薄膜厚度时,多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明:具有纳米层状结构的Au/SiO2多层薄膜在560nm波长附近有明显的表面等离子共振吸收峰,吸收峰的强度随Au颗粒的浓度增加而增强,在Au颗粒浓度相同的情况下,复合薄膜光学吸收强度随薄膜厚度的增加而增强.但当金属颗粒的浓度增加到一定程度时,金属颗粒相互接触,没有观察到纳米层状结构,薄膜不显示共振吸收峰特征.用修正后的M-G(Maxwell-Garnett)理论对吸收光谱进行了模拟,得到了与实验一致的结果.     

单晶Si表面离子束溅射沉积Co纳米薄膜的研究

采用离子束溅射沉积法，在单晶Si基片上制备了不同厚度(1—100nm)的Co纳米薄膜.利用原子力显微镜、X射线光电子能谱(XPS)仪和X射线衍射仪对不同厚度的Co纳米薄膜进行了分析和研究.结果表明：当薄膜厚度为1—10nm时，沉积颗粒形态随薄膜厚度增加将由二维生长的细长胞状过渡到多个颗粒聚集成的球状.当膜厚大于10nm时，小颗粒球聚集成大颗粒球，颗粒球呈现三维生长状态.表面粗糙度随膜厚的增加呈现先增加后减小的趋势，在膜厚为3nm时出现极值.XPS全程宽扫描和窄扫描显示：薄膜表面的元素成分为Co，化学态分别 关键词： 离子束沉积 纳米薄膜 X射线光电子能谱 X射线衍射     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO₂纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO₂的沉积时间及SiO₂的沉积时间一定而改变薄膜厚度时，多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明：具有纳米层状结构的Au/SiO₂多层薄膜在560 nm波长附近有明显的表面等离子共振吸收峰，吸收峰的强度随Au颗粒的浓度增加而增强，在Au颗粒浓度相同的情况下，复合薄膜 关键词： 2纳米复合薄膜')" href="#">Au/SiO₂纳米复合薄膜 多靶磁控溅射 吸收光谱 有效介质理论     

蓝宝石基底上制备蠕虫状ZnO及强紫外发光性能研究

选用纳米球刻蚀技术在蓝宝石（Al₂O₃）基底上制备350 nm聚苯乙烯（PS）微球密排掩模版,然后采用反应射频磁控溅射方法分别在PS/Al₂O₃和Al₂O₃基底上沉积氧化锌（ZnO）薄膜,去除掩模版的PS微球后,对经退火处理的两种样品进行X射线衍射分析、扫描电子显微镜观察和荧光光谱测试。结果表明,在PS/Al₂O₃上生长的ZnO薄膜（样品1）的晶粒呈明显的蠕虫状,而直接在Al₂O₃基底上生长的ZnO薄膜（样品2）表面晶粒为不完全六棱台形状。样品2的结晶性能优于样品1,但是在362 nm附近样品1的近带边缘荧光发射峰强度比样品2的发射峰强43倍。     

Au/SiO2纳米复合薄膜的微结构及光吸收特性研究

用多靶磁控溅射技术制备了Au/SiO2纳米多层薄膜.利用透射电子显微镜以及吸收光谱对Au/SiO2复合薄膜的微观结构、表面形貌及光学性能进行了表征和测试.研究结果表明:单层Au/SiO2薄膜中Au沉积时间小于10s时,分散在SiO2中的Au颗粒随Au的沉积时间的延长而增大;当沉积时间超过10s后,Au颗粒的尺寸几乎不随沉积时间变化,但Au颗粒的形状由网络状结构变为薄膜状结构.[Au(t1)SiO2(600)]×5多层薄膜在540-560nm波长附近有明显的表面等离子共振吸收峰,且吸收峰的强度随Au的沉积时间增加而增强.基于修正后的Maxwell-Garnett (M-G)有效媒质理论,讨论了金属颗粒的形状对等离子共振吸收峰的峰位和强度的影响.模拟的吸收光谱与实验吸收光谱形状、趋势及吸收峰位相符合.     

Au/TiN复合薄膜制备及其表面增强拉曼光谱研究

表面增强拉曼散射光谱(SERS)已用于环境监测、生物医药、食品卫生等领域,而高活性SERS基底是表面增强拉曼散射光谱技术应用的关键。TiN作为新型等离子材料具有较强的SERS性能,同时化学稳定性及生物相容性较好,但其SERS性能不如贵金属金强。该研究采用氨气还原氮化法和电化学沉积法,在TiN薄膜表面沉积贵金属Au纳米颗粒制备出Au/TiN复合薄膜。在Au/TiN复合薄膜中单质Au和TiN两种物相共存;随着电化学沉积时间延长,TiN薄膜表面单质金纳米颗粒数量逐渐增多,金纳米颗粒尺寸增大,颗粒间距减小。由于金与TiN两者的本征表面等离子共振耦合作用,Au/TiN复合薄膜的共振吸收峰发生了偏移。利用罗丹明6G为拉曼探针分子,对Au/TiN复合薄膜进行SERS性能分析,发现Au/TiN复合薄膜上的R6G探针分子的拉曼峰信号强度随沉积时间延长呈现先增大后减小的规律;当电化学沉积时间为5 min时,R6G拉曼信号峰较高,复合薄膜样品的SERS活性最大。将Au/TiN复合薄膜和Au薄膜分别浸泡在10-3,10-5,10-7,10-8及10-9 mol·L-1 R6G溶液5 min,进行检测限分析,发现Au/TiN复合薄膜检测极限达10-8 mol·L-1,增强因子达到8.82×105,与Au薄膜和TiN薄膜相比,Au/TiN复合薄膜上对R6G探针分子SERS活性最高。这得益于Au/TiN复合膜中表面等离子体产生的耦合效应,使得局域电磁场强度增强,从而引起R6G探针分子拉曼信号增强。通过2D-FDTD模拟电场分布发现Au/TiN,Au及TiN薄膜具有电场增强作用,其中Au/TiN复合薄膜的增强作用尤为显著,这也证实了氮化钛与金纳米颗粒之间存在耦合效应。另外发现TiN与Au之间可能存在电荷转移,促进了4-氨基苯硫酚氧化反应,进而证实了TiN与Au薄膜的协同作用。此外,Au/TiN复合薄膜均匀性较好,相对平均偏差仅为7.58%。由此可见,采用电化学沉积制备的Au/TiN复合薄膜具有作为SERS基底材料的应用潜力。     

Large-scale protein/antibody patterning with limiting unspecific adsorption

A simple synthetic route based on nanosphere lithography has been developed in order to design a large-scale nanoarray for specific control of protein anchoring. This technique based on two-dimensional (2D) colloidal crystals composed of polystyrene spheres allows the easy and inexpensive fabrication of large arrays (up to several centimeters) by reducing the cost. A silicon wafer coated with a thin adhesion layer of chromium (15 nm) and a layer of gold (50 nm) is used as a substrate. PS spheres are deposited on the gold surface using the floating-transferring technique. The PS spheres were then functionalized with PEG-biotin and the defects by self-assembly monolayer (SAM) PEG to prevent unspecific adsorption. Using epifluorescence microscopy, we show that after immersion of sample on target protein (avidin and anti-avidin) solution, the latter are specifically located on polystyrene spheres. Thus, these results are meaningful for exploration of devices based on a large-scale nanoarray of PS spheres and can be used for detection of target proteins or simply to pattern a surface with specific proteins.     

一种用于LSPR传感器的准正方型银纳米颗粒阵列制备

首先控制聚苯乙烯纳米球(PS球)乳液在基片上的干燥温度,采用自组装方法,使用单一粒径的PS球制备出单层的PS球亚稳态正方排列结构模板。然后,在模板上通过磁控溅射法沉积一层银膜。利用纳米球光刻技术,去掉PS球模板得到二维正方点阵排列的准正方形银纳米颗粒阵列结构。     

基于直接胶体晶体刻蚀技术的高度有序纳米硅阵列的尺寸及形貌控制

以自组装单层胶体小球阵列为掩模，采用直接胶体晶体刻蚀技术在硅表面制备二维有序尺寸可控的纳米结构.在样品制备过程中，首先通过自组装法在硅表面制备了直径200nm的单层聚苯乙烯(PS)胶体小球的二维有序阵列；然后对样品直接进行反应离子刻蚀(RIE)，以氧气为气源，利用氧等离子体对聚苯乙烯小球和对硅的选择性刻蚀作用，通过改变刻蚀时间，制备出不同尺寸的PS胶体小球的有序单层阵列；接着以此二维PS胶体单层膜为掩模，以四氟化碳为气源对样品进行刻蚀；最后去除胶体球后得到二维有序的硅柱阵列.SEM和AFM的测量结果表明：改变氧等离子体对胶体球的刻蚀时间和四氟化碳对硅的刻蚀时间，可以控制硅柱的尺寸以及形貌，而硅柱阵列的周期取决于原始胶体球的直径. 关键词： 胶体晶体刻蚀 纳米硅柱阵列     

Plasmonics properties of trimetallic Al@Al2O3@Ag@Au and Al@Al2O3@AuAg nanostructures

Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric–metal–metal (DMM) system consisting of a particle with a dielectric core (Al@Al₂O₃), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al₂O₃@Ag@Au and Al@Al₂O₃@AgAu triple-layered core–shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core–shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core–shell Al@Al₂O₃. The Al@Al₂O₃ particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al₂O₃@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al₂O₃@Ag@Au core–shell or Al@Al₂O₃@AgAu alloy. The formation of core–shell and alloy nanostructure was confirmed by UV–visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400–520 nm with increasing ablation time suggesting formation of Ag–Au alloy in the presence of alumina particles in the solution.     

The effect of the size,shape, and structure of metal nanoparticles on the dependence of their optical properties on the refractive index of a disperse medium

The effect of the size, shape, and structure of gold and silver nanoparticles on the dependence of their extinction and integral scattering spectra on the dielectric environment has been investigated. Calculations were performed using the Mie theory for spheres and nanoshells and the T-matrix method for chaotically oriented bispheres, spheroids, and s cylinders with hemispherical ends. The sensitivity of plasmon resonances to variations in the refractive index of the environment in the range 1.3–1.7 for particles of different equivolume size, as well as to variations in the thickness of the metal layer of nanoshells, was studied. For nanoparticles with an equivolume diameter of 15 nm, the maximal shifts of plasmon resonances due to variation in the refractive index of the environment are observed for bispheres and the shifts decrease in the series nanoshells, s cylinders or spheroids, and spheres. For particles 60 nm in diameter, the largest shifts of plasmon resonances occur for nanoshells and the shifts decrease in the series bispheres, s cylinders or spheroids, and spheres. All other conditions being the same, silver nanoparticles are more sensitive to the resonance tuning due to a change in the dielectric environment.     

The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

二维氧化锌纳米阵列的制备及光学吸收特性研究

采用漂移法,在玻璃衬底上制备出粒径分别为117,350和500 nm单层、大面积的聚苯乙烯胶体球掩膜板,在已制得的掩膜板上用射频磁控溅射的方法沉积一层氧化锌薄膜,最后用有机溶液四氢呋喃(THF)浸泡去除聚苯乙烯胶体球,获得不同粒径的二维氧化锌纳米团簇。通过扫描电子显微镜和能量色散X射线光谱仪对样品的形貌及成份进行表征,表明所制得样品为有序分布的蜂窝网状氧化锌纳米阵列。在室温下,通过吸收光谱仪测试样品在300～800 nm波长范围内的吸收光谱,结果表明对于具有不同尺寸晶粒的氧化锌纳米团簇样品,随着所采用的聚苯乙烯胶体球粒径的增大,即氧化锌纳米团簇粒径的增加,光吸收峰出现了宽化和红移;随着溅射时间的延长,即氧化锌薄膜膜厚的增加,光吸收率提高。此外,对氧化锌纳米团簇阵列的光吸收特性进行了基于离散偶极子近似的理论计算从而获得任意形状和尺寸粒子的吸收。目前,文献报道中用此理论计算各种形状的纳米金、银等金属的结果与实验结果相符,但是应用离散偶极子的近似理论计算氧化锌纳米颗粒的报道很少。应用此理论计算三角棱台形状的氧化锌光学吸收特性,根据氧化锌薄膜介电常数和膜厚的变化进行光吸收特性的模拟,并解释了实验结果。     

Composition distributions in FePt(Au) nanoparticles

Ternary alloy FePt(Au) nanoparticles were prepared by the co-reduction of platinum(II) acetylacetonate and gold(III) acetate and the thermal decomposition of iron pentacarbonyl in hot phenyl ether in the presence of oleic acid and oleylamine ligands. This gave spherical particles with an average diameter of 4.4 nm with a range of diameters from approximately 1.6–9 nm. The as-synthesized particles had a solid solution, face-centered-cubic structure. Though the average composition of the particles was Fe₄₄Pt₄₅Au₁₁, individual particle analysis by Scanning Transmission Electron Microscopy–X-ray Energy Dispersive Spectroscopy showed a broad distribution in composition. In general, smaller-sized particles tended to have a lower amount of Au as compared to larger-sized particles. As the Au content increased, the ratio of Fe/Pt widened.     

Attenuation,scattering, and depolarization of light by gold nanorods with silver shells

Gold nanoparticles with silver nanoshells are obtained by synthesizing gold nanorods in a growing solution containing cetyltrimethylammonium bromide, subsequent separation in a concentration gradient of glycerol, and reduction of silver nitrate by ascorbic acid under alkaline conditions in the presence of polyvinylpyrrolidone. The formation of silver nanoshells was monitored by the shift of plasmon resonances of extinction and differential light scattering, by the appearance of characteristics peaks of silver in the energy dispersive X-ray (EDX) spectra of samples, by the data of transmission electron microscopy, and by visual changes in the color of colloids. The spectrum of the intensity ratio of the co- and cross-polarized compo- nents of light scattered by gold-silver nanorods is measured for the first time, and it is observed that the maximum is shifted by 80–100 nm compared to previously published spectra of gold nanorods (Khlebtsov et al., J. Phys. Chem. C 112, 12760 (2008)). The extinction and light scattering spectra are calculated by the method of separation of variables using the model of a confocal two-layer spheroid and these calculations are found to agree with spectral measurements. A method for determining the thickness of a silver nanolayer by the spectral shift of an extinction longitudinal resonance is described. The obtained data of optical spectroscopy and transmission electron microscopy and estimations of the mass of the deposited metal show that the aver-age thickness of the silver layer varies from 0.12 to 4 nm as the Ag/Au ratio changes from 2/80 to 90/80 μg/μg.     

Surface plasmon sensor with gold film deposited on a two-dimensional colloidal crystal

A sensor based on surface plasmon resonance (SPR) of plasmonic crystals fabricated via a colloidal-crystal-assisted templating method is studied. Plasmonic crystals are prepared by depositing a thin gold (Au) layer onto a two-dimensional array of polystyrene spheres self-assembled on a quartz substrate. The enhanced transmission as a result of the SPR of Au plasmonic crystals, which are immersed in different ambient liquids, are measured and compared with that of polystyrene (PS) microsphere templates of different sizes, both before and after removal of Au nanoprisms formed on the quartz substrate through pores among the spheres. It is found that the measured sensitivities exhibit a linear dependence on the refractive index of the surrounding medium and are linked to coupling effects between SPRs on the corrugated Au film and nanoislands. The feasibility of the SPR system in molecular monolayer detection is further demonstrated through a formation of alkanethiolate self-assembled monolayers on the Au film surface, which causes a 4 nm red-shift of the main SPR. PACS  07.07.Df; 73.20.Mf; 78.66.-w; 81.16.Dn