大孔柚子型微结构光纤探针的表面增强拉曼散射性能研究  

Surface-Enhanced Raman Scattering Performance of Macroporous Grapefruit-Type Microstructured Fiber Optic Probes

作　　者：李佳轩 付子珍 曹茜清 胡志国 付兴虎[1] 付广伟[1] 金娃 毕卫红[1] LI Jia-xuan;FU Zi-zhen;CAO Xi-qing;HU Zhi-guo;FU Xing-hu;FU Guang-wei;JIN Wa;BI Wei-hong(School of Information Science and Engineering,The Key Laboratory for Special Fiber and Fiber Sensor of Hebei Province,Yanshan University,Qinhuangdao 066004,China)

机构地区：[1]燕山大学信息科学与工程学院,河北省特种光纤与光纤传感重点实验室,河北秦皇岛066004

出　　处：《光谱学与光谱分析》2024年第2期527-533,共7页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(61675176);河北省高等学校科学技术研究项目重点项目(ZD2022108);河北省中央引导地方科技发展资金项目(216Z1702G);河北省研究生创新资助项目(CXZZSS2022118)资助。

摘　　要：随着光纤制备工艺以及纳米材料制备技术的发展,光纤探针已成为一种新型的表面增强拉曼散射(SERS)基底,通过在普通单模光纤或多模光纤上制备不同的结构并修饰相应的纳米材料,可以得到多种类型的光纤表面增强拉曼散射探针,并实现较好的检测效果。但受限于光纤本身的结构,普通光纤仅能利用端面或侧表面提供拉曼检测的“热点”区域,限制了其SERS性能的进一步提高。因此制备了大孔柚子型微结构光纤(MSF)表面增强拉曼散射(SERS)探针,其中大孔柚子型MSF SERS探针结构通过一段阶跃多模光纤与柚子型微结构光纤熔接制得。实验分别对自制的纳米银溶胶基底以及大孔柚子型MSF SERS探针的SERS性能进行检测。采用溶胶自组装法制备负载银纳米颗粒的MSF SERS探针,通过控制自组装时间制备不同光纤SERS探针(Ag/MSF-x,其中x为自组装时间,分别为15、30、45、60 min)。采用溶液检测方法,利用Ag/MSF-x探针对10^(-3) mol·L^(-1)的亚甲基蓝(MB)探针分子进行检测,通过比较相同条件下的增强效果筛选得到Ag/MSF-45探针。为进一步检测Ag/MSF-45探针的SERS性能,制备不同浓度的MB溶液,分别利用纳米银溶胶基底和Ag/MSF-45探针对其进行检测。实验结果表明,纳米银溶胶基底对MB的检测限(LOD)为10^(-6) mol·L^(-1),Ag/MSF-45探针对MB的检测限(LOD)为10^(-7) mol·L^(-1);拉曼信号的再现性结果表明纳米银溶胶基底以及Ag/MSF-45探针在各个特征峰处的RSD值均在合理范围内;在1619 cm^(-1)拉曼位移处对纳米银溶胶基底以及Ag/MSF-45探针检测MB的拉曼强度和浓度进行对数转换拟合,纳米银溶胶基底的拟合优度R2达0.91628,Ag/MSF-45探针的拟合优度R2达0.98848;纳米银溶胶基底和Ag/MSF-45探针的再现性结果表明,其在各个特征峰处的RSD值均处于合理范围,但Ag/MSF-45探针的各特征峰RSD值均小于纳米银溶胶基底,最大为13.89%;利用10^(-6) mol·LWith the development of optical fiber preparation technology and nanomaterial preparation technology,fiber probes have become a new type of surface-enhanced Raman scattering(SERS)substrate;by preparing different structures on common single mode fiber or multimode fiber and modifying the corresponding nanomaterials can obtain a variety of types of optical fiber surface-enhanced Raman scattering probes,and achieve better detection results.But the structure of the fiber itself has limited it,common fiber can only use the end face or measurement surface to provide Raman detection“hot spot”area,limiting its SERS performance to further improve.In this paper,a surface-enhanced Raman scattering(SERS)probe for a macroporous grapefruit-type microstructured fibre(MSF)is prepared,in which the macroporous grapefruit-type MSF SERS probe structure is fabricated by fusing a section of stepped multimode fiber to a grapefruit-type microstructured fibre.The SERS performance of the home-made silver nanosol substrates and the macroporous grapefruit-type MSF SERS probes are examined separately.MSF SERS probes loaded with silver nanoparticles are prepared by the sol-gel self-assembly method,and different fibre-optic SERS probes are prepared by controlling the self-assembly time(Ag/MSF-x,where x is the self-assembly time,15,30,45,60 min,respectively).The solution detection method was used to detect 10^(-3) mol·L^(-1) methylene blue(MB)probe molecule with Ag/MSF-x probe,and the Ag/MSF-45 probe was screened by comparing the enhancement effect under the same conditions.In order to further detect the SERS performance of the Ag/MSF-45 probe,MB solutions with different concentrations are prepared,and the nano silver soluble substrates and Ag/MSF-45 probe are used to detect them.The experimental results showed that MB's limit of detection(LOD)was 10^(-6) mol·L^(-1) for the nano-soluble substrate and 10^(-7) mol·L^(-1) for the Ag/MSF-45 probe.The reproducibility of the Raman signal shows that the RSD values for the nanosilver soluble sub

关 键 词：表面增强拉曼散射 柚子型微结构光纤 光纤探针 纳米银溶胶 亚甲基蓝 

分 类 号：TN247[电子电信—物理电子学]