其他(光学波导光模光谱(OWLS)传感器) 2012

Optical waveguide lightmode spectroscopy (OWLS) as a sensor for thin film and quantum dot corrosion.

Sensors (Basel, Switzerland) Yu H, Eggleston CM, Chen J, Wang W, Dai Q, Tang J
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组成图示

Optical waveguide lightmode spectrosc... 传感器构成示意图

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传感器类型

其他(光学波导光模光谱(OWLS)传感器)

检测对象

氧化锌锡薄膜(zinc stannate, ZTO, Zn2SnO4)质量损失、硒化镉量子点涂层(cadmium selenide quantum dots, CdSe QDs)溶解;样品基质:pH 7 MOPS缓冲液、pH 10硼酸盐缓冲液、pH 2 HCl水溶液。

检测原理

OWLS将633 nm平面偏振激光经表面光栅耦合进入约200 nm厚的(Si,Ti)O2波导,在波导内形成全内反射光模。ZTO或CdSe量子点涂层具有较高折射率,会改变波导有效折射率N;当涂层在液体中发生腐蚀、溶解或剥离时,表面质量密度(ng·cm−2)下降,N及衍射峰角度随之变化。光电二极管检测峰位置,结合dn/dc将峰位移换算为质量变化。由于涂层预先存在且退火改变波导性质,实验前稳定基线常不可得,因此采用实验后稳定基线或指数/双指数外推估计初始质量。AFM用于验证质量损失对应的表面形貌变化。

检测灵敏度

原文未报告LOD、线性范围、灵敏度斜率或相关系数。

效应效果

ZTO涂层在pH 7 MOPS中迅速失重,一次实验总质量损失8,413 ng·cm−2,另一实验约4,910 ng·cm−2;MPA注入仅引起小质量下降,QD溶液注入加速失重,说明信号主要来自ZTO剥离而非MPA吸附。AFM确认涂层大部分去除,估算孔隙率约35%和62%。PLD CdSe量子点在pH 2 HCl中约1天溶解,双指数外推初始质量密度620 ng·cm−2,溶解约630±10 ng·cm−2,相当于完整单层的约18%;pH 10硼酸盐中稳定无溶解。OWLS与AFM互补,可原位监测液体环境中薄膜完整性,克服外原位干燥/真空技术可能改变结构的问题。

传感器的构成

  • 基底/换能器:(Si,Ti)O2波导(Si_xTi(1-x)O2,x=0.25±0.05,约200 nm),表面带417 nm衍射光栅,耦合633 nm激光并产生全内反射光模。
  • 高折射率修饰层:氧化锌锡薄膜(Zn2SnO4, ZTO),溶胶-凝胶法制备,前驱体含锡2-乙基己酸酯、乙酸锌和三乙醇胺,旋涂后500 °C退火4 h,厚度约20 nm级,作为腐蚀监测对象。
  • 量子点修饰层:硒化镉量子点(CdSe QDs),脉冲激光沉积(PLD)从CdSe靶材沉积到波导表面,用于酸性溶解稳定性监测。
  • 界面功能化层:3-巯基丙酸(MPA)0.006%溶液,通过羧基与氧化物表面内球配位,促进CdSe量子点吸附并作为对照吸附层。
  • 信号源层:ZTO薄膜或CdSe量子点涂层本身,其质量密度(ng·cm−2)随腐蚀、溶解或剥离变化,提供折射率信号。
  • 液体介质:pH 7 MOPS缓冲液、pH 10硼酸盐缓冲液或pH 2 HCl,提供腐蚀/溶解环境并影响质量变化速率。
  • 读出系统:OWLS 120仪器,633 nm平面偏振激光、光栅耦合和光电二极管检测,输出有效折射率N与衍射峰角度。

中文摘要

光学波导光模光谱(OWLS)通常作为生物传感器系统用于监测蛋白质在波导表面的吸附与解吸。本文表明,OWLS也可用于监测氧化薄膜材料和脉冲激光沉积(PLD)制备的硒化镉量子点(CdSe QDs)涂层的质量,面向太阳能应用。除数据处理和实验程序调整外,还需合成氧化层或量子点涂层波导传感器。作者合成了氧化锌锡(Zn2SnO4, ZTO)涂层的(Si,Ti)O2波导传感器,并用OWLS监测薄膜相对质量随时间的变化。薄膜随时间失重,速率因流体流动及其物理去除作用不同而异。PLD法将CdSe量子点沉积到波导上;暴露于pH 2溶液的传感器随时间近似指数失重,而pH 10条件下稳定。原子力显微镜(AFM)结果证实了上述变化。该方法受退火温度和可研究薄膜厚度限制,但仍克服了液体环境中原位监测薄膜质量的若干困难。

英文摘要

Optical waveguide lightmode spectroscopy (OWLS) is usually applied as a biosensor system to the sorption-desorption of proteins to waveguide surfaces. Here, we show that OWLS can be used to monitor the quality of oxide thin film materials and of coatings of pulsed laser deposition synthesized CdSe quantum dots (QDs) intended for solar energy applications. In addition to changes in data treatment and experimental procedure, oxide- or QD-coated waveguide sensors must be synthesized. We synthesized zinc stannate (Zn(2)SnO(4)) coated (Si,Ti)O(2) waveguide sensors, and used OWLS to monitor the relative mass of the film over time. Films lost mass over time, though at different rates due to variation in fluid flow and its physical effect on removal of film material. The Pulsed Laser Deposition (PLD) technique was used to deposit CdSe QD coatings on waveguides. Sensors exposed to pH 2 solution lost mass over time in an expected, roughly exponential manner. Sensors at pH 10, in contrast, were stable over time. Results were confirmed with atomic force microscopy imaging. Limiting factors in the use of OWLS in this manner include limitations on the annealing temperature that maybe used to synthesize the oxide film, and limitations on the thickness of the film to be studied. Nevertheless, the technique overcomes a number of difficulties in monitoring the quality of thin films in-situ in liquid environments.