场效应晶体管(FET)生物传感器 2011

Characteristics of polysilicon wire glucose sensors with a surface modified by silica nanoparticles/γ-APTES nanocomposite.

Sensors (Basel, Switzerland) Lin JJ, Hsu PY, Wu YL, Jhuang JJ
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组成图示

Characteristics of polysilicon wire g... 传感器构成示意图

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传感器类型

场效应晶体管(FET)生物传感器

检测对象

葡萄糖(glucose,β-D-glucose);样品基质:磷酸盐缓冲液葡萄糖溶液,面向体外血糖/临床诊断样品

检测原理

葡萄糖进入磷酸盐缓冲液后,被GOx催化氧化为葡萄糖酸并生成H2O2。PSW在源漏电压VDS=5 V下形成通道电场,H2O2在电场中电解产生H+。H+与γ-APTES修饰层中的NH2结合,改变PSW表面电荷态和界面能带,从而调制多晶硅通道导电性,表现为通道电流密度变化ΔJ。葡萄糖浓度越高,生成的H2O2和H+越多,ΔJ越大。C-AFM针尖涂覆的超薄γ-APTES+NPs膜使表面/体积比增大,窄线宽PSW具有更强通道电场,因此灵敏度更高;宽线宽PSW通道电场和边缘电场较弱,干扰物乙酰氨基酚难以被电解,抗干扰性更好。UV照射可增强NH2与SiO2相互作用并增加表面粗糙度,提高响应。

检测灵敏度

旋涂γ-APTES+NPs+90 s UV:LOD: 0.75 mM(100 nm)、0.82 mM(200 nm)、0.52 mM(300 nm)、1.32 mM(500 nm);线性范围: 1 mM–6 mM(所有线宽) C-AFM针尖涂覆γ-APTES+NPs+90 s UV:LOD: 32 pM(100 nm)、0.2 nM(200 nm)、1 nM(300 nm)、5 nM(500 nm);线性范围: 0.1 nM–1 mM(100 nm)、1 nM–1 mM(200 nm)、5 nM–1 mM(300 nm)、10 nM–1 mM(500 nm)

效应效果

重现性方面,100次旋涂膜厚RSD为12.76%,C-AFM针尖涂覆膜厚RSD为5.33%;单根PSW不同位置10次厚度RSD为5.483%。抗干扰方面,在AP/葡萄糖摩尔比0.003:1至600:1范围内,γ-APTES+NPs+UV膜均优于γ-APTES膜;500 nm宽PSW在600:1时ΔJ百分比变化低于3.5%,300 nm为4.8%,200 nm为6.1%,100 nm为9.7%。作者未报告实际样品加标回收率或与ELISA/HPLC/qPCR的对比。结果表明FIB加工C-AFM针尖可重复涂覆超薄均匀γ-APTES+NPs膜,使PSW葡萄糖传感器兼具高灵敏度、良好线性与高抗干扰性,适用于体外血糖检测。

传感器的构成

  • 基底/换能器:p型(100)硅片上12 nm SiO2绝缘层与80 nm磷掺杂多晶硅线(PSW),线宽100–500 nm、通道长3 µm、方阻40–50 Ω/□,作为导电通道与电流换能器
  • 纳米材料修饰层:γ-APTES(3-氨基丙基三乙氧基硅烷)与PDMS处理疏水气相二氧化硅纳米颗粒(NPs,R202,平均一次粒径14 nm)按质量比100:1混合,形成γ-APTES+NPs纳米复合膜,部分经365 nm UV照射
  • 识别/催化元件:葡萄糖氧化酶(GOx,EC 1.1.3.4,Sigma),30 mg溶于磷酸盐缓冲液,与β-D-葡萄糖反应生成H2O2和葡萄糖酸
  • 信号转换层:H2O2在PSW通道电场下电解生成H+,H+与γ-APTES的NH2结合,改变表面电荷态
  • 样品介质:磷酸盐缓冲液(phosphate buffer solution)含β-D-葡萄糖,用于溶解GOx和测试
  • 读出系统:半导体参数分析仪Agilent 4156C,在VDS=5 V下测量PSW通道电流变化ΔI/ΔJ

中文摘要

本文研究多晶硅线(PSW)葡萄糖生物传感器的传感特性,重点考察膜厚、线宽对检测限、线性范围和抗干扰能力的影响,并比较微吸管/旋涂与聚焦离子束(FIB)加工毛细原子力显微镜(C-AFM)针尖扫描/涂覆两种成膜方法。PSW表面修饰由3-氨基丙基三乙氧基硅烷(γ-APTES)和经聚二甲基硅氧烷(PDMS)处理的疏水气相二氧化硅纳米颗粒(NPs)组成的纳米复合膜。结果显示,C-AFM针尖重复扫描/涂覆可将γ-APTES+NPs膜厚稳定控制在约22 nm,相对标准偏差较小。通过针尖涂覆时,PSW线宽越小,检测限越低、线性范围越宽;线宽越大,抗干扰能力越强。对于500 nm宽PSW,在乙酰氨基酚(AP)与葡萄糖浓度比高达600:1时,通道电流密度变化(ΔJ)的百分比变化可保持在3.5%以下。数值模拟表明,抗干扰性的线宽依赖性与PSW通道电场强度密切相关。

英文摘要

This report investigates the sensing characteristics of polysilicon wire (PSW) glucose biosensors, including thickness characteristics and line-width effects on detection limits, linear range and interference immunity with membranes coated by micropipette/spin-coating and focus-ion-beam (FIB) processed capillary atomic-force-microscopy (C-AFM) tip scan/coating methods. The PSW surface was modified with a mixture of 3-aminopropyl-triethoxysilane (γ-APTES) and polydimethylsiloxane (PDMS)-treated hydrophobic fumed silica nanoparticles (NPs). We found that the thickness of the γ-APTES+NPs nonocomposite could be controlled well at about 22 nm with small relative standard deviation (RSD) with repeated C-AFM tip scan/coatings. The detection limit increased and linear range decreased with the line width of the PSW through the tip-coating process. Interestingly, the interference immunity ability improves as the line width increases. For a 500 nm-wide PSW, the percentage changes of the channel current density changes (ΔJ) caused by acetaminophen (AP) can be kept below 3.5% at an ultra-high AP-to-glucose concentration ratio of 600:1. Simulation results showed that the line width dependence of interference immunity was strongly correlated with the channel electrical field of the PSW biosensor.