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。     

(Au-Probe)@SiO_2单层纳米粒子膜制备及表面增强拉曼光谱研究

表面增强拉曼光谱(SERS)因其高达单分子检测的表面灵敏度而广受青睐,其增强机理主要包括电磁场增强效应(EM)和电荷转移增强(CT)。通常,前者占主导作用,且局域电磁场可极大地增强表面吸附分子的拉曼信号。而介质通常对局域电磁场和EM增强有一定影响,从而影响SERS检测,通过壳层隔绝纳米粒子(SHINs)可避免介质与SERS增强源间的直接接触。但迄今为止,几乎未见有关介质对其增强拉曼光谱(SHINERS)影响的研究,主要因SERS基底均匀性较差所致。制备了两种探针分子内嵌且Au核尺寸不同的核壳纳米粒子,即(55 nm Au-PNTP)@SiO_2和(110 nm Au-pMBA)@SiO_2,壳层厚度分别为3.5和4.0 nm,壳层结构连续且无针孔效应。采用液-液两相成膜法制备其单层膜,转移至固相基底上可作为SERS基底,(55 nm Au-PNTP)@SiO_2单层膜上SERS谱峰强度的相对标准偏差约为5.38%,(110 nm Au-pMBA)@SiO_2单层膜上相对标准偏差约为5.97%,其重现性及均匀性优良,符合作为SERS基底的要求。研究它们分别在空气和水两种介质中的SERS效应,结果表明Au核被致密无针孔效应的SiO_2壳层包裹,且探针分子内嵌其中,由此完全隔绝了电磁场增强源内核Au纳米粒子与介质的直接接触,当改变基底所处的环境时,其实际介质仍为SiO_2,因此在两种介质中SERS信号几乎不发生改变。内嵌探针分子的PNTP或pMBA被包裹在SiO_2壳层内,溶剂及氧气等均无法参与反应,因此探针分子未发生SPR催化反应,保持稳定的光谱特征。由此可见内嵌探针分子的SERS信号强度及光谱特征不受介质的影响,可望作为多介质环境使用的高灵敏度SERS检测以及稳定内标或标记的重要基底。     

胶带快速转移水油液液界面自组装纳米金制备透明柔性SERS基底

表面增强拉曼(SERS)是一种快速灵敏的表面分析检测技术。提出了一种简便快捷的制备高活性的透明柔性SERS基底,使用乙醇诱导Au NPs从水溶液中组装到水/油界面的形成致密的Au MLF后再用透明胶带转移即制备完成了SERS基底。UV-Vis和SEM测试结果显示纳米金被紧密的吸附在透明胶带上。通过调控Au溶胶的浓度以及加入乙醇与Au溶胶的体积比来控制Au纳米粒子在胶带的密度,发现加入的氯金酸体积0.4mL,乙醇与Au溶胶体积比10∶4时,制备完成的Au/Tape基底具有最佳的活性,以孔雀石绿分子为拉曼探针计算了Au/Tape基底的增强因子EF为1.8×107。此基底在非平整表面现场超灵敏快速检测具有潜力。     

Cu2O-Au复合结构的制备及其在SERS中的应用

表面等离激元催化反应为表面过程的拓展提供了一条新的途径,但在单一贵金属表面的反应效率往往较低,因此发展符合纳米结构已经成为该领域的研究热点。通过合成八面体的氧化亚铜(Cu₂O),并引入高均匀性和高SERS活性的金纳米粒子单层膜(Au MLF),将两者完全结合,构建了Cu₂O-Au复合异质结SERS基底。以对硝基苯硫酚(PNTP)为探针,通过表面增强拉曼光谱(SERS)研究了Cu₂O-Au表面等离激元驱动的偶联反应。结果表明,Cu₂O与Au MLF的复合,其SERS性能及催化活性都得到了较大的提升,为发展高性能的新型复合纳米结构提供了实验基础。     

挥发性有机物的非接触SERS检测

挥发性有机物在自然环境中普遍存在,对人体健康造成显著影响,为此亟待发展高灵敏度的快速识别和检测技术。本文通过制备和优化表面增强拉曼散射(surface-enhanced Raman scattering,SERS)基底,实现了强吸附和弱吸附型挥发性有机物的检测。首先利用化学方法合成了粒径约为30nm的均匀准球形金纳米粒子,该粒子具有SERS效应以及良好的化学稳定性,以该纳米粒子为单元,通过气液两相界面自组装技术制备增强性能好、SERS信号均匀的金纳米粒子单层膜(Au MLF),并以此为SERS基底对挥发性有机物苯硫酚进行了检测。为了实现弱吸附挥发物质的检测,对Au MLF表面进行了修饰,构建了聚二甲基硅氧烷(PDMS)-Au MLF复合基底,实现了苯及二甲苯等弱吸附型挥发性有机物的检测。     

新型冠状病毒S蛋白在金纳米粒子中的表面增强拉曼效应

表面增强拉曼光谱技术因其高灵敏度、操作简单、快速检测等优点,被广泛用于病毒检测方面。国内外的病毒拉曼检测研究主要集中在检测病毒核酸以及组成核酸的各种碱基的表面增强拉曼光谱(SERS),但少见对病毒蛋白的SERS检测。以新型冠状病毒（SARS-CoV-2）的S蛋白为检测对象,采用无标记SERS检测方法,对比SARS-CoV-2固态、饱和液态S蛋白的普通拉曼光谱和选用40 nm金纳米粒子为基底的SARS-CoV-2低浓度S蛋白SERS光谱。结果表明,以40 nm金纳米粒子为基底,采用SERS技术检测SARS-CoV-2的S蛋白是完全可行的。SARS-CoV-2的S蛋白分子中的羧基与金纳米粒子发生了分子增强,氨基与金纳米粒子发生了电磁增强,从而使得SARS-CoV-2的S蛋白拉曼效应得到了增强,并使得峰位发生一定移动。实验获得了较好的SARS-CoV-2低浓度S蛋白SERS光谱,为建立敏感、特异、快速的SARS-CoV-2检测新技术提供了一种方法。     

基于自组装技术的柔性SERS基底拉曼增强研究

利用自组装技术将单层银纳米粒子修饰到Whatman No. 1滤纸表面,成功制备了柔性表面增强拉曼散射(SERS)基底。实验结果表明：当银粒子尺寸为20 nm时,拉曼增强性能达到最佳。采用此参数制备的SERS基底对罗丹明6G(R6G)分子的检测极限为10^-10 mol/L,最大增强因子为5.66×10⁸,相对标准偏差(RSD)为10.9%。同时,该柔性基底能够准确地识别和区分多种目标分子,并具有良好的柔软性和可恢复性。此外,还结合基底的扫描电子显微镜(SEM)表征情况,利用时域有限差分(FDTD)仿真软件对样品的电磁场增强特性进行了数值分析,并对其与实验结果进行了对比。     

金银/氮化钛表面增强拉曼基底制备及对烟酸的定量检测

表面增强拉曼光谱技术对分子具有特异性识别以及快速无损检测的能力,使其在药物检测方面具有重大的潜力。通过贵金属和氮化钛之间协同作用,使复合基底具有较高的SERS性能,提供了一种基于SERS技术的药物检测方法。采用电化学沉积及自组装法,制备出贵金属/氮化钛复合薄膜。研究表明,在复合薄膜中存在面心立方晶型TiN、金属单质Au和Ag三种物相;电子显微镜显示平均粒径分别为90和50 nm的金属Au和Ag颗粒均匀分布在TiN薄膜表面;基底的紫外-可见吸收图谱中出现了贵金属金与银纳米颗粒及TiN薄膜三者的特征等离子体共振吸收峰。以该复合薄膜为SERS基底,对烟酸溶液进行拉曼检测。结果显示,贵金属/氮化钛复合薄膜对烟酸具有显著的SERS效应,最低检测浓度为10-5 mol·L-1,对1 033 cm-1处烟酸拉曼信号强度及浓度取对数,发现两者间呈一定线性关系,其R2为0.969,得益于TiN,Au和Ag之间可发生表面等离子体共振引起电磁场增强,以及电荷转移效应。研究还发现,烟酸通过COO-基团垂直吸附在贵金属/氮化钛基底表面;在酸性环境下,烟酸N原子质子化主要以阳离子N＋H（Ⅰ）形式存在;在碱性环境时,主要以阴离子COO-（Ⅲ）形式存在。绞股蓝总甙溶液中模拟烟酸非法添加,该复合基底对其最低的拉曼检测浓度是10-5 mol·L-1,为现场快速检测非法添加药物提供了新途径。     

CdTe QDs/Au NRs的SERS及光诱导电荷转移研究

控制和利用半导体基底的荧光背景是解决半导体纳米材料应用在表面增强拉曼(SERS)领域的关键问题。该研究通过将具有高荧光背景的碲化镉量子点(CdTe QDs)与贵金属金纳米棒(Au NRs)纳米材料复合,依赖于光激发下CdTe QDs与Au NRs之间的电荷转移,获得了兼具多功能特性(例如表面增强拉曼散射和光催化)的纳米复合材料。在该研究中,将染料分子亚甲基蓝(MB)作为探针分子,CdTe QDs/Au NRs纳米复合材料的之间的电荷转移降低了CdTe QDs的荧光背景,展现出良好的SERS增强性能。     

一种简单的方法制备SERS基底用于染料分子的富集、降解与检测

用一种简单的方法制备银纳米粒子, 研究了此纳米粒子作为SERS基底、吸附剂和光催化剂的多功能性。在光照条件下研究其对染料分子的光催化性能, 用紫外光谱和表面增强拉曼光谱对整个光催化过程进行动态跟踪检测, 实验结果表明染料分子光照条件下确实被催化降解了。本实验不仅合成了多功能的基底材料, 还赋予了表面增强拉曼光谱新的应用价值, 为光催化实验提供了新的动态跟踪检测方法。     

Guided-Wave Two-Dimensional Acousto-Optic Scanner Using Proton-Exchanged Lithium Niobate Waveguide

Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.     

Effect ofγ-radiation on the spectral luminescence characteristics of impure cadmium tungstate crystals

Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·10⁴ Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.     

Measurement of nonlinear coefficient of optical fiber based on small chirped soliton transmission

We measure the waveform and phase curves of short optical pulses before and after transmission over different lengths of fibers by use of the pulse analyzer with the frequency-resolved optical gating (FROG),and numerically simulate pulse evolution under the experimental conditions.The nonlinear coefficient of the fiber is given by comparing the experimental results with the numerical ones.Difference between the experiment and numerical simulation is analyzed.     

Resonance scattering of canonical elastic shells in absorbing fluid medium

Resonance scattering of elastic spherical shell and cylindrical shell while the surrounding fluid medium has absorption is studied. The normal mode solution derived using exact elastic theory and the separation of variables is still applicable. However, the scattering form function has to be modified for the absorbing medium, otherwise the unreasonable result would be obtained. The backscattering form function in the absorbing medium is redefined, and the form function of elastic spherical and cylindrical shell with vacuum or solid matter filled is calculated in various absorption conditions. The results show that the absorption of surrounding fluid leads to notable attenuation of the coincidence resonances in the mid-frequency, but it has a little influence on the low-frequency resonance scattering induced by the filler inside the shell.     

Single-beam self-referenced phase-sensitive surface plasmon resonance sensor with high detection resolution

A versatile and low-cost single-beam self-referenced phase-sensitive surface plasmon resonance(SPR)sensing system with ultra-high resolution performance is presented.The system exhibits a root-mean-square phase fluctuation of ±0.0028.over a period of 45 min.i.e.a resolution of±5.2×10-9 refractive index units.The enhanced performance has been achieved through the incorporation of three design elements:a true single-beam configuration enabling complete self-referencing so that only the phase change associated with SPR gets detected,a differential measurement scheme to eliminate spurious signals not related to the sensor response,and the elimination of retardation drifts by incorporating temperature stabilization in the liquid crystal phase modulato .Our design should bring the detection sensitivity of non-labeling SPR biosensing closer to that achievable by conventional fluorescence-based techniques.     

Influences of SiO2 protective layers and annealing on the laser-induced damage threshold of Ta2O5 films

Ta2O5 films are prepared on BK7 substrates with conventional electron beam evaporation deposition.The effects of SiO2 protective layers and annealing on the laser-induced damage threshold (LIDT) of the films are investigated.The results show that SiO2 protective layers exert little influence on the electric field intensity(EFI)distribution,microstructure and microdefect density but increase the absorption slightly.Annealing iS effective on decreasing the microdefect density and the absorption of the films.Both SiO2 protective layers and annealing are beneficial to the damage resistance of the films and the latter is more effective to improve the LIDT.Moreover,the maximal LIDT of Ta2O5 films is achieved by the combination of SiO2 protective layers and annealing.     

A stereo matching algorithm using multi-peak candidate matches and geometric constraints

Gray cross correlation matching technique is adopted to extract candidate matches with gray cross correla- tion coefficients less than some certain range of maximal correlation coefficient called multi-peak candidate matches. Multi-peak candidates are extracted corresponding to three closest feature points at first. The corresponding multi-peak candidate matches are used to construct the model polygon. Correspondence is determined based on the local geometric relations between the three feature points and the multi-peak candidates. The disparity test and the global consistency checkout are applied to eliminate the remaining ambiguous matches that are not removed by the local geometric relational test. Experimental results show that the proposed algorithm is feasible and accurate.     

Fiber Modal Index Measurements Based on Fiber Gratings

A novel method based on fiber gratings for measuring the effective indices of fiber modes is proposed. The effective index difference between the core mode and a cladding mode was obtained by analyzing the interference fringe of a pair of cascaded long-period fiber gratings. In order to extract the core mode index from the measured index difference, an index matching oil immersion method is proposed. By analyzing the interaction between the cladding mode and the oil applied on the cladding surface, the mode order and the effective index of the involved cladding mode might be calculated. Experimental results about the interference fringe shifts induced by the oil index and the oil-applied length are also presented.     

Optical Pulse Compression Schemes That Use Nonlinear Bragg Gratings

Nonlinear optical pulse compression of picosecond pulses typically requires long lengths of optical fiber and multiple components. Periodic structures, such as fiber Bragg gratings, are highly dispersive at wavelengths outside of the photonic bandgap. This implies that such gratings can be used as very short all-fiber compressors. In this paper a number of such compression schemes are reviewed involving uniform and nonuniform fiber Bragg gratings, relying on both soliton and nonsoliton compression principles. Experimental results supporting the corresponding underlying theory are also presented. Finally, an extension of one of the compression schemes is shown, which allows the generation of adjustable high-repetition rate soliton trains.