基于电泳法和磁控溅射技术制备金纳米阵列

采用纳米球刻蚀技术中的电泳法设计了3组对照实验,通过控制电压、悬浮液的体积分数和基板正负极性,得到电泳法制备纳米球掩膜板的最佳条件,制备出排布均匀的纳米球单层密堆积结构的掩膜板.采用磁控溅射技术在掩膜板上沉积金薄膜,去除纳米球掩模板,通过扫描电子显微镜观察到周期排列的三角形棱台状金纳米颗粒阵列.测量其吸收光谱,可观察到表面等离子体共振吸收峰.     

利用单层密排的纳米球提高发光二极管的出光效率

在发光二极管(LED)的透明电极层上制作单层六角密排的聚苯乙烯(polystyrene, PS) 纳米球, 研究提高GaN基蓝光LED的出光效率. 采用自组装的方法在透明电极铟锡氧化物层上制备了直径分别约为250, 300, 450, 600和950 nm的PS纳米球, 并且开展了电致发光的研究. 结果表明, 在LED的透明电极层上附有PS纳米球能有效地提高LED的出光效率; 当PS纳米球的直径与出射光的波长比较接近时, LED的出光效率最优. 与参考样品相比, 在20 mA和150 mA工作电流下, 附有PS纳米球的样品的发光效率分别增加1.34倍和1.25倍. 三维时域有限差分方法计算表明, 该出光增强主要归因于附有PS纳米球的LED结构可以增大LED结构的光输出临界角, 从而提高LED的出光效率. 因此, 这是一种低成本的实现高效率LED的方法.     

电阻热蒸发镀膜与电子束蒸发镀膜对纳米球刻蚀方法制备二维银纳米阵列结构的影响

在使用纳米球刻蚀法制备二维银纳米点阵的过程中,使用不同的镀膜方法在同样的模板上得到了不同形貌的银纳米阵列结构.使用电阻热蒸发镀膜方法获得了六角排列的银纳米三角形阵列结构,使用电子束蒸发镀膜方法则获得了六角排列的银纳米环阵列结构.研究表明,沉积纳米粒子的粒径、表面纳米曲率效应和热能是形成不同结构形貌的纳米阵列结构的关键因素. 关键词： 银纳米阵列 电阻热蒸发 电子束蒸发 纳米球刻蚀     

铬过渡层对纳米球刻蚀法制备二维银纳米结构的影响

研究了铬过渡层对纳米球刻蚀法制备二维银纳米点阵结构的影响。首先利用自组装的方法在玻璃基底上制备出单层排列的聚苯乙烯纳米球阵列,然后使用物理气相沉积的方法在二维聚苯乙烯纳米球阵列上沉积一层铬层作过渡层和银层,最后将玻璃基底在乙醇溶液中超声移除聚苯乙烯纳米球,得到二维的银纳米点阵。实验发现,随着铬过渡层厚度的增加,制得的二维银纳米点阵阵列趋于完整,单个的银纳米颗粒由椭圆状转变为三角形形状。实验中测量了所得到的二维银纳米结构的吸收光谱。     

海胆状ZnO纳米线阵列的制备及其光学性能

采用一种低成本的有效方法制备出了有序排列的海胆状ZnO纳米线阵列。首先利用自组装的方法得到了单层的聚苯乙烯(PS)小球,以其为模板用水热法在小球表面生长ZnO纳米线,得到了由PS小球和ZnO纳米线构成的海胆状结构。纳米线的直径均一,长度可通过水热反应时间进行控制。利用这种方法制备的一维ZnO纳米结构在传感器、太阳能电池及光催化领域有潜在的应用价值。     

氧等离子体处理对GaAs表面单层自组装SiO2纳米球薄膜的影响

二维纳米阵列结构因其重要的光学性能被广泛应用于各类光电子器件。本文对自组装单层SiO2纳米球掩模刻蚀法制备GaAs纳米柱二维阵列结构的关键工艺技术进行了研究。采用旋涂法在GaAs表面制备自组装单层SiO2纳米球,重点研究了GaAs表面氧等离子体亲水处理工艺对纳米球排列特性的影响,获得最佳工艺条件为功率配比100 W+80 W、腔室压力4 Pa、氧气流量20 mL/min、处理时间1200 s,并最终得到排列紧密的大面积单层纳米球薄膜。以单层纳米球为掩模,采用感应耦合等离子体刻蚀技术在GaAs表面制备了纳米柱阵列并测试了其表面光反射谱。测试结果表明,GaAs纳米柱阵列在特定波段的反射率降低至5%,远低于表面无纳米结构的薄膜材料表面高达40%的光反射。分析表明纳米柱可以激发米氏散射共振效应,从而有效降低反射率并提升光吸收。     

铬过渡层位置及金属沉积角度对纳米球刻蚀法制备二维银纳米点阵结构的影响

利用纳米球刻蚀法制备了二维六角密排三角形银纳米阵列, 通过加入铬过渡层并改变其位置和改变金属沉积角度, 研究它们对点阵结构的影响. 实验发现, 加入铬过渡层所形成的银纳米点阵结构较无铬层有很大改善, 三角形角部更加尖锐, 更能满足传感器对信号检测的要求. 同时, 该过渡层应蒸镀在模板球排列之后, 才能获取更大面积的二维银纳米点阵结构. 在沉积角度对制备二维银纳米点阵的实验中, 基片没有旋转, 采用垂直镀膜方式更容易得到结构完整、结合较牢固、且面积较大、角部尖锐的二维银纳米点阵. 吸收光谱测量进一步验证了铬过渡层对二维银纳米点阵形貌结构的改善作用. 这些为下一步的生物修饰以及生物化学传感器的制备提供了先决条件.     

有序金纳米颗粒阵列的制备及光吸收特性研究

采用纳米球刻蚀技术中漂移法在玻璃基片上制备较大 面积不同直径的聚苯乙烯小球掩模板, 采用磁控溅射技术在掩模板上沉积不同厚度的金薄膜, 去除聚苯乙烯小球后, 通过扫描电子显微镜观察到周期排列的三角状金纳米颗粒点阵. 通过紫外-可见分光光度计测试所制备样品的光吸收特性, 发现表面等离子体共振峰随粒径增大发生红移, 随金纳米颗粒高度增加发生蓝移. 基于Mie理论, 利用Matlab软件编程对不同粒径的金阵列光吸收特性进行理论模拟, 并与实验结果进行对比. 关键词： 纳米球刻蚀 金纳米颗粒阵列 表面等离子体共振     

纳米球刻蚀法制备的二维有序的CdS纳米阵列及其光学性质的研究

采用纳米球刻蚀(nanosphere lithography)技术,以自组装的聚苯乙烯纳米小球(polystyrene,PS小球)的单层膜为掩模,制备出二维有序的CdS纳米阵列.利用扫描电子显微镜(SEM)对样品结构进行了表征,用紫外—可见分光光度计对样品光学性质进行了分析.结果表明：制备的二维CdS纳米阵列是高度有序的,且与作为掩模的纳米小球的原始尺寸及排布结构一致;禁带宽度为2.60eV,相对于体材料的2.42eV,向短波长蓝移了0.18eV,表现出CdS材料在纳米结构点阵中的量子尺寸效应;CdS纳米 关键词： 纳米球刻蚀 二维CdS纳米有序阵列     

Au诱导形成有序Si纳米孔阵列及其应用

以自组装聚苯乙烯小球(PS)单层膜为掩膜,利用Au对Si表面的催化氧化作用以及KOH溶液对单晶Si的各向异性腐蚀特性,在Si(100)面上制备了一系列尺寸小于100 nm有序可控的Si纳米孔阵列.扫描电镜(SEM)和原子力显微镜(AFM)等的测试结果显示:当PS小球溶液与甲醇溶液的体积比为9:11时,可形成大面积无缺陷的单层膜;但当体积比过大时,会导致类似双层膜结构的形成;而当体积比过小时,会诱导形成点缺陷和线缺陷.对PS小球及溅射Au处理过的Si晶片进行KOH溶液腐蚀,随着腐蚀时间变长,纳米孔的横向尺寸和深度增大,其形貌由圆形逐渐变为倒金字塔型,当腐蚀时间超过10 min,纳米孔阵列的有序性遭到破坏.采用离子束溅射技术在倒金字塔型纳米孔衬底上获得了有序Ge/Si纳米岛,而在圆形纳米孔衬底上获得了有序Ge/Si纳米环.进一步对有序Ge/Si纳米岛及纳米环的形成机理进行了解释.     

空心微球结构Au/Ag合金泡沫块体的制备

将平均晶粒尺寸为4.6 nm的金粒子通过静电作用粘附于聚苯乙烯（PS）微球表面用于化学镀,化学镀金后PS表面的金沉积层几乎达到完全包覆,厚度70~90 nm;在Au/PS表面进行化学镀银,沉积的银颗粒堆积紧密,颗粒大小较先前沉积的金颗粒大,镀覆层厚度增厚至200~400 nm;模板去除后,获得了完全自支撑的Au40Ag60空心微球结构的圆柱状泡沫材料。制备的金银合金泡沫由直径约10 m的空心球壳组成,圆柱体直径约5 mm,密度约1.2 g/cm3。     

Origin of localized surface plasmon resonances in thin silver film over nanosphere patterns

Film over nanosphere (FON) patterns are formed by depositing a silver film on top of a close-packed polystyrene (PS) sphere template. Multiple localized surface plasmon resonance (LSPR) peaks are experimentally measured in the three-dimensional FON pattern for thin silver films. Increasing the sphere size in the close-packed template or the deposited silver film thickness red shifts the LSPR peaks to varying degrees. A finite difference time domain analysis reveals that the main LSPR peaks originate from a quadrupole and a dipole coupling mode near the triangle gap surrounded by three adjacent PS spheres. The physical location and the electromagnetic enhancement of the two resonant modes are determined for different thicknesses of deposited silver films.     

银覆盖冠状硅柱阵列基底的制备、SERS特性分析及肿瘤标志物miRNA-106a的检测

以聚苯乙烯(PS)小球为模板,采用金属辅助刻蚀和湿法化学刻蚀技术,制备大面积冠状硅柱阵列,再原位生长银纳米粒子后得到银覆盖冠状硅柱阵列(Ag/Si CPA)基底。实验表明,制备的基底具有优良的表面增强拉曼散射(SERS)特性,电磁增强因子达到1.81×10~6。同时,将制备的罗丹明分子(R6G)标记的DNA发卡探针与基底链接,在与miRNA-106a互补杂交后进行SERS信号检测,获得相应的剂量-响应曲线。结果表明,基于(Ag/Si CPA)基底的SERS特性,开展miRNA-106a的检测,具有特异性好和灵敏度高的优势,检测范围为1 fmol·L~(-1)～100 pmol·L~(-1),检测极限为0.917 fmol·L~(-1)。此外,与实时荧光定量多聚核苷酸链式反应(RT-qPCR)方法相比,不仅检测结果一致,而且基于SERS光谱技术的检测方法具有更高的灵敏度。     

Fabrication and magnetic behaviour of 2D ordered Fe/SiO2 nanodots array

We have demonstrated a simple and universal morphology-controlled growth of 2D ordered Fe/SiO₂ magnetic nanodots array, which was based on 2D colloidal monolayer template composed of polystyrene (PS) spheres and one-step sol-gel spin-coating technique. The Fe/SiO₂ nanodots have a well-ordered structure arranged in a hexagonal pattern. The dots have the shape of quasi-pyramidal tetrahedron, which reside in the interstitial region between three PS spheres and the substrate. Magnetic measurements reveal that the nanodots array exhibits the in-plane easy magnetization direction. Compared with the unpatterned Fe/SiO₂ thin film, the dots array has lower saturated field, higher remanence and coercivity. The present method is applicable to 2D ordered nanodots array of other magnetic materials.     

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     

Surface enhanced Raman scattering of molecules related to highly ordered gold cavities

We presented a controlled particles‐in‐cavity (PIC) pattern for surface‐enhanced Raman scattering (SERS) detection. The periodic gold cavity array was fabricated by electrodeposition using highly ordered polystyrene spheres as a template. The as‐prepared gold cavities can be used as a SERS active substrate with significant spectral enhancement and reproducibility, which was evaluated by SERS signals using 4‐mercaptobenzoic acid (4‐MBA) as probe molecules. The surface of these gold cavities was further functionalized with cetyltrimethylammonium bromide molecules, which may immobilize the 4‐MBA‐modified silver nanoparticles in the gold cavity to form a PIC structure via the electrostatic interaction. We have demonstrated that there exists a pH window for the immobilization of the nanoparticles inside cavities. Therefore, the silver nanoparticles can be selectively immobilized into the functionalized gold cavities under the optimized pH value of the media. Further enhancement of the Raman scattering of the labeled molecules can be achieved due to the interconnection between the silver nanoparticles and gold cavity. Copyright © 2013 John Wiley & Sons, Ltd.     

Heterogeneous nucleation and growth of silver nanoparticles on unmodified polystyrene spheres by in situ reduction

The in situ reduction growth of Ag nanoparticles (NPs) on unmodified polystyrene (PS) spheres is investigated via controlling Ag nucleation and growth rates by continuous dripping addition of reductant solution in the absence of surfactants. The sub-micro PS spheres were coated by a uniform coverage of Ag NPs with several shapes like elongated islands, spherical particles, and particle aggregates. The reaction temperature and reductant concentration are demonstrated to influence the crystal structure, distribution, and stability of the Ag NPs on the PS substrates. The heterogeneous nucleation and growth of Ag NPs on PS spheres are found to depend on the inhibition of in-solution reduction and homogeneous nucleation.     

Synthesis of hollow silver spheres using poly-(styrene-methyl acrylic acid) as templates in the presence of sodium polyacrylate

Hollow silver spheres were successfully prepared by reducing AgNO₃ with ascorbic acid and using negatively charged poly-(styrene-methyl acrylic acid) (PSA) spheres as templates in the presence of sodium polyacrylate as a stabilizer. Firstly, silver cations adsorbed on the surface of PSA spheres via electrostatic attraction between the carboxyl groups and silver cations were reduced in situ by ascorbic acid. The silver nanoparticles deposited on the surface of PSA spheres served as seeds for the further growth of silver shells. After that, extra amount of AgNO₃ and ascorbic acid solutions were added to form PSA/Ag composites with thick silver shells. In order to obtain compact silver shells, the as-prepared PSA/Ag composites were heated at 150 °C for 3 h. Then hollow silver spheres were prepared by dissolving PSA templates with tetrahydrofuran.     

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.