岛状纳米多孔金制备及其SERS特性研究

表面增强拉曼散射（surface-enhanced Raman scattering,SERS）技术将纳米结构材料和拉曼光谱相结合,解决了传统拉曼散射技术灵敏度低的问题,为痕量物质检测提供了新的技术手段。高SERS活性基底材料是将拉曼光谱应用到痕量物质检测中的关键。采用磁控溅射技术结合脱合金工艺在硅片上制备出岛状纳米多孔金SERS基底,该基底的孔隙尺寸和金韧带宽度的比值远小于传统纳米多孔金,有效地增强了金韧带之间的电磁耦合效应,表现出更强的局域电磁场。该基底的检测极限可达约10-10 mol·L-1,且SERS光谱相对强度与浓度呈现出较好的线性关系,动态响应范围可达3个数量级。同时该基底结构均匀、性能稳定,制备工艺具有良好的可重复性。     

纳米多孔银的制备及其表面增强拉曼散射特性研究

表面增强拉曼散射(SERS)因其具有高达单分子检测量级的灵敏度，在医学诊断、食品安全、环境监测等领域有着较大的应用前景。制备具有高密度“热点”的SERS基底是这项技术走向实际应用的关键。双连续结构的纳米多孔金属由于近邻纳米结构之间的耦合效应，所以具有很好的SERS增强特性。采用溅射方法制备了银锌合金前驱体，采用自由脱合金工艺和电化学脱合金工艺制备了具有纳米多孔结构的银基底，通过调制脱合金参数，获得了具有高增强因子的SERS基底。所制备的纳米多孔银基底对结晶紫的检测极限达到了10^-12 mol/L，可应用于超灵敏检测。     

基于纳米修饰透射式光纤传感测试

基于金属纳米颗粒结构的光学特性,结合光纤传感技术,对金属纳米颗粒的光纤传感特性进行了研究.实验中采用种子溶液生长法合成了粒径在60～80 nm的星形纳米金颗粒,以此作为光纤传感敏感部分的修饰体,修饰到锥形光纤表面作为表面拉曼增强基底.最后选取了不同浓度的酒精溶液对其进行了透射谱和拉曼谱测试,结果表明金属纳米颗粒的激发谱对周围介质特性非常敏感,同时对基于金属纳米颗粒锥形SERS基底的拉曼谱存在非常高的增强.     

基于磁控溅射制备铜基表面增强拉曼散射基底

为了提高拉曼光谱仪的探测灵敏度,设计了铜基表面增强拉曼散射(surface enhanced Raman scattering, SERS)薄膜基底。以Cu_(40)Ti_(60)合金为靶材,通过控制磁控溅射参数获得了一系列铜钛合金薄膜,采用脱合金法进一步获得了不同结构的铜基薄膜,系统地研究了不同溅射参数对铜基薄膜的SERS特性的影响,确定了制备SERS基底的最佳溅射参数。脱合金后所得铜膜具有多孔结构,能形成高强度局域电磁场,即SERS"热点"(hotspots),从而表现出优异的SERS增强性能。该基底制备成本低,重复性好,能用于灵敏检测且SERS增强因子可达1.8×10~7,具有较好的应用前景。     

激光辐照制备银纳米基底及其用于葡萄糖检测

通过激光辐照的方法制备银纳米条纹表面增强拉曼散射基底,该基底具有制备方法简单、均匀性好、重复性强的优点。用巯基吡啶(4-MPY)作为探针分子,葡萄糖和葡萄糖氧化酶产生的过氧化氢会改变银纳米条纹的形貌,进而影响探针分子的表面增强拉曼光谱强度,从而实现葡萄糖的间接检测。得到的探针分子的表面增强拉曼光谱的强度与葡萄糖溶液的浓度具有较好的线性关系。实验结果表明,该基底在葡萄糖的检测及定量分析方面具有良好的应用前景。     

宽束离子束刻蚀快速加工金属纳米间隙结构

提出并演示了利用宽束离子束刻蚀方法一次性对多个杠铃形金属纳米结构进行“横向抽减”,形成极小纳米间隙,从而实现多个金属纳米间隙结构的快速加工。利用电子束曝光定义图形化抗蚀剂结构,通过传统的金属沉积和湿法剥离将抗蚀剂图案转移至杠铃形金属纳米结构,最后使用宽束离子束刻蚀进行修剪。实验表明,精确控制刻蚀时间可以使杠铃形结构的两个纳米天线间的间隙距离达到10 nm以下,通过结合基于HSQ负性抗蚀剂的图案化工艺,可在HSQ纳米模板上制得悬空金属纳米间隙结构。利用表面结构形貌表征获得刻蚀过程中纳米结构的形态演变规律,并通过系统的实验和模拟验证了悬空金属间隙结构用于表面增强拉曼散射的优势。该方案为多个极小金属纳米间隙结构的一次成型提供了新的思路,在大面积拉曼传感衬底的低成本高效制备方面具有可观的应用前景。     

过渡金属二硫化物拉曼散射在免疫检测中的应用

为了利用可见光激发下半导体拉曼散射信号实现生物检测,以窄带隙的MoS_2材料构建了拉曼免疫标记探针,用于实现对人IgG分子的高特异性识别。首先,运用液相剥离法分别获得了MoS_2和WS_2微米材料,以加热陈化处理分析了温度对532nm激发下样品拉曼散射信号强度的影响。之后借助3-巯基丙酸修饰向MoS_2材料表面引入羧基,进而获得了可用于免疫检测的拉曼探针。最后,以"抗体-待测物-抗体"的三层结构分析了基于MoS_2拉曼散射的免疫检测性能。实验发现适当温度下加热陈化处理可增强过渡金属二硫化物的拉曼散射强度(70℃下最优)。多组对照实验结果表明,免疫检测生物芯片的拉曼信号强度随人IgG浓度的升高而升高,最终趋于饱和,最低浓度的检测限达到1fM,实现了可见光激发下利用半导体拉曼散射信号对目标分子的高灵敏度、高特异性免疫检测。     

等离激元Fano共振纳米结构及其应用

金属纳米体系中的局域表面等离激元具有丰富的光学性质,广泛应用于化学、材料和生物等领域。等离激元Fano共振的发现,使等离激元纳米结构具有更大的场增强、更密集的谱间隔以及更高的光谱灵敏度,从而成为了表面等离激元光子学中的研究热点之一。对表面等离激元Fano共振的形成机理进行了解释。研究了目前能产生Fano共振效应的3种典型的等离激元微纳结构:对称性破缺、颗粒团簇和纳米阵列,这些结构在表面增强拉曼散射、生物探测和光电器件等方面有很多潜在的应用。     

激光刻蚀金银合金胶体的制备及其SERS应用

金属胶体是一种新兴的表面增强拉曼散射(SERS)活性衬底,利用激光液相刻蚀技术制备了金银合金胶体,并通过透射电镜、吸收光谱、表面增强拉曼散射光谱等手段对其特性进行表征。结果表明,合金粒子多数为球形颗粒,颗粒大小在5nm左右,并且有很好的分散性,等离子体共振吸收峰位于428nm。此外,该胶体表现出很好的表面增强拉曼散射活性,且性能稳定可在室温下长时间保存。     

双金属分形材料制备取得进展

中国科学技术大学教授曾杰研究组在铂铜双金属分形材料可控合成和生长机制研究方面取得新进展。研究人员通过对铂铜双金属晶体的成核及生长进行动力学调控,成功合成了不同尺寸的具有三角双锥外形的铂铜双金属分形结构。铂与铜结合得到的合金材料不仅能降低铂的用量,而且在催化反应中往往有更好的表现。除了组分之外,纳米晶体的结构同样对催化反应具有重要影响。由于其开放的结构特征,纳米框架结构同时具有较大的比表面积和表面积,这大大提高了其在催化反应中的原子利用率。同时,它良好的表面渗透性使得表面和内部的原子都能够参与到     

Varying SiO2 thickness of core–shell noble-grains on a gradient sensing plate to enhance field Raman scattering

This study demonstrates a strong surface-enhanced Raman scattering (SERS) of crystal violet (CV) dye by using SiO₂ shell/Ag core nanoparticle in gradient-size surface plate. The excitation of CV dye can be enhanced by the localized surface plasmons of Ag core/shell SiO₂ grains due to electromagnetic (EM) enhancement induced. For SERS resonance, the change of dielectric environment of grains results in red shift and magnification of spectra in varying SiO₂ thickness. Herein, the enhanced SERS conducted the core/shell grain with an SiO₂ thickness of 8.7 nm to magnify the intensity about 83 %-fold that is a direct evidence in enhanced charge transport and mutative dielectric environment.

Analysis of Deposits from Friction at Head-Tape Interfaces by Raman Spectroscopy

To demonstrate the applicability of Raman spectroscopy to the analysis of thin heterogeneous deposits on surfaces, a sample of brown stain or friction polymer produced on sendust (85% Fe, 9% Si, 6% Al) surfaces of a simulated read/write head by a magnetic oxide tape making prior contact with a copper, aluminum or nickel surface was investigated. Raman spectra identified the base film of the tape as poly(ethylene terephthalate) or PET, and the magnetically active layers as containing mostly γ-Fe₂O₃. Conversely, Raman spectra of brown slain showed it to consist mainly of Fe₃O₄ and organic compounds. More brown stain was produced after copper contact than after aluminum contact, but only organic deposits were produced after nickel contact in these tests. It is speculated on the basis of these spectral data that the inhibiting effect of nickel could be the result of catalytically produced organic materials, which change the tribology on the head surface and inhibit the formation of brown slain or friction polymer.     

二氧化硅包覆对纳米多孔金增强荧光特性的调制

为了减弱金属基底对表面增强荧光的淬灭效应,设计了增强效果更好的荧光增强基底。采用化学生长二氧化硅的方法对纳米多孔金(NPG)表面进行修饰,避免荧光分子和NPG表面直接接触引起的淬灭效应,在SiO_2@NPG表面分别组装上罗丹明6G(R6G)和辐射中心波长为700 nm的量子点(QD 700)。通过探测分析荧光光谱,可以得出:二氧化硅包覆的基底可以使表面增强荧光得到显著的增强,并且二氧化硅厚度对荧光强度有调节作用;在基底增强量子点荧光信号的同时,量子点和NPG之间还出现非辐射的能量转移现象,二氧化硅的厚度对能量转移同样有调节作用,厚度约为5 nm时能量转移现象最显著。本实验为基于荧光能量转移的检测以及设计更好的荧光增强基底提供了参考。     

Surface Damage Characteristics of Self-Assembled Monolayers of Alkanethiols on Metal Surfaces

The effect of metal oxide layer on the nano-tribological characteristics of single chain alkanethiol (CH₃(CH₂) _n SH) self-assembled monolayers (SAMs) on various metal surfaces (gold, silver, copper) was investigated. In order to correlate the surface structures with the tribological characteristics, various surface analysis techniques such as Scanning Probe Microscopy, X-ray Photoelectron Spectroscopy, Secondary Ion Mass Spectrometry and Spectroscopic Ellipsometry were used. Results of surface analyses showed that thiols on a metal surface were susceptible to forming multilayers if the metal surface was oxidized before the thiol assembly process. From the friction and wear tests conducted using an Atomic Force Microscope and a Lateral Force Microscope, it was found that thiols on copper oxide surface could be easily removed even under a few nano-Newton normal load. On the other hand, thiols on gold and copper fresh surfaces (the surface which was made by minimizing oxide formation) could endure up to micro-Newton level loads. Based on these findings, it could be concluded that the nano-tribological characteristics of alkanethiol SAMs on various metal surfaces were largely dependent on the oxide layer that already formed on the metal surface before the thiol adsorption process.     

Note: Production of sharp gold tips with high surface quality

We present a simple method to produce sharp gold tips with excellent surface quality based on electrochemical etching with potassium chloride. Radii of curvature lie in the range of 20-40 nm and the surface roughness is measured to less than 0.8?nm. The tips are well suited for field emission, field ion microscopy, and likely for tip-enhanced Raman scattering as well as tip-enhanced near-field imaging.     

Experimental study on physical properties of nanoporous anodic aluminum oxide by proton implantation

Implantation is a promising method to control the surface characteristics by changing surface energy of target materials. Previously, polymer surfaces have been investigated for the change of their morphology and the corresponding contact angle after implantation. Furthermore, oxide thin films have been studied for how their surface properties are changed by implantation. However, nanoporous oxide materials have rarely explored for the effect of implantation. Here, we investigated the effects of proton implantation on morphological, mechanical, electrical, and surface properties of anodic aluminum oxide (AAO). We prepared nanoporous amorphous AAO films with different thicknesses (5 and 10 μm). Atomic force microscopy (AFM), contact angle (CA) measurements, two-probe electrical measurements, and nanoindentation were used to analyze the physical properties. By increasing fluences from 10¹⁵ to 10¹⁶ ions/cm², CA is significantly changed up to about 40°, but the other properties hardly changed.     

An experimental study of cutting performance on monocrystalline germanium after ion implantation

Monocrystalline materials, such as silicon and germanium, are widely used in the semiconductor industry and optical engineering due to their excellent electrical and optical characteristics. However, it is difficult to achieve an ultraprecise mirrored surface with the turning process due to the hard and brittle nature of those materials. It has been proved that the machinability of silicon and silicon carbide can be enhanced in nanometric or ultra-precise diamond cutting by ion implantation. In this paper, we present diamond cutting of monocrystalline germanium implanted with copper ions and study the brittle–ductile transition phenomenon. Raman spectra and transmission electron microscopy are used to investigate details of the modified layer. The results show that a uniform amorphous layer is produced after implantation. The brittle–ductile transition depth of the modified germanium is up to 730 nm, which is an obvious increase from unmodified c-Ge.     

Effects of Chemical Additives of CMP Slurry on Surface Mechanical Characteristics and Material Removal of Copper

Investigations were performed to study the effects of H₂O₂ as oxidant, glycine as complexing agent, and benzotriazole (BTA) as inhibitor on surface mechanical characteristics and material removal of copper. Etch rates and surface roughness of Cu samples were measured in the presence of these chemicals at pH 4 or pH 10 under static conditions. Scanning electron microscopy images revealed that the surface of etched copper samples became layered and porous. Scratching experiments were carried out on the etched surface to investigate effects of these chemicals on mechanical removal of copper using atomic force microscopy. It was observed that the scratched depth of these etched Cu samples was higher than that of Cu metal. The addition of glycine enhanced chemical dissolution and mechanical removal greatly. However, the further addition of BTA made both of them decreased, suggesting BTA not only inhibitor of chemical dissolution, but also inhibitor of mechanical removal. In most cases, the measured hardness values of etched copper surface were slightly higher than that of Cu metal. These results indicated that changes of surface structure were the primary reason for increase of mechanical removal of copper, but not changes of copper surface nanohardness.     

Label‐free identification of antibiotic resistant isolates of living Escherichia coli: Pilot study

We introduce a label‐free spectroscopic method to classify subtypes of quinolone‐nonsusceptible Escherichia coli (E. coli ) isolates obtained from human blood cultures. Raman spectroscopy with a 30‐nm gold‐deposited, surface‐enhanced Raman scattering (SERS) substrate was used to evaluate three multilocus sequencing typing (MLST)‐predefined groups including E . coli ATCC25922, E . coli ST131:O75, and E . coli ST1193:O25b. Although there was a coffee‐ring effect, the ring zone was selected at the ideal position to screen E. coli isolates. Strong Raman peaks were present at 1001–1004 cm^?1 (C? C aromatic ring breathing stretching vibrational mode of phenylalanine), 1447–1448 cm^?1 (C? H₂ scissoring deformation vibrational mode), and 1667 cm^?1 (amide I α‐helix). Although the three MLST‐predefined E . coli isolates had similar Raman spectral patterns, a support vector machine (SVM) learning algorithm‐assisted principal component analysis (PCA) analysis had superior performance in detecting the presence of quinolone‐nonsusceptible E. coli isolates as well as classifying similar microbes, such as quinolone‐nonsusceptible E . coli ST131:O75 and E . coli ST1193:O25b isolates. Therefore, this label‐free and nondestructive technique is likely to be useful for clinically diagnosing quinolone‐nonsusceptible E. coli isolates with the MLST method.