Structural optimization and performance testing of gold microarray electrode fabricated by DMD lithography and electrodeposition
doi:10.37188/CO.2021-0109
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摘要:为提高微阵列电极 (Microarray electrodes, MAE) 的检测效率，降低生产成本，提出了一种将数字微镜器件 (DMD) 无掩模投影光刻与电化学沉积相结合的技术。首先，利用光刻系统压电平台 (PZS) 的高分辨率运动和DMD生成图案的灵活性等优点，制备了用户可自定义的微结构阵列，接着，通过电化学沉积获得Au导电层，实现了均匀的Au微阵列电极 (Au/MAE) 的制备。然后通过循环伏安法，比较了不同结构的Au/MAE的电化学性能，获得了优化的结构参数。最后，研究了优化后的Au/MAE对于不同浓度和pH值的葡萄糖的电流响应，并通过计时电流法对Au/MAE检测葡萄糖的抗干扰能力进行了测试。电化学分析表明，这种简单的Au/MAE对葡萄糖的电化学检测具有显著的安培响应和较强的抗干扰能力，其灵敏度为101 μA·cm −2·mM −1。这种微阵列电极的制备方法，具有分辨率高、一致性高、工艺简单、成本低的优点，为生物传感阵列的制造提供了切实可行的操作方案。Abstract:In order to improve the detection efficiency of Micro Array Electrodes (MAE) and reduce the production cost, a technology combining Digital Micromirror Device (DMD) maskless projection lithography with electrochemical deposition was proposed. Firstly, a user-defined micro array was fabricated by using the advantages of lithography system such as high-resolution PZS motion and imaging flexibility of DMD. And a uniform Au microarray electrode (Au/MAE) was fabricated after obtaining an Au conducting layer by electrodeposition. Then, the electrochemical properties of Au/MAE with different structures were compared by cyclic voltammetry, and the optimized structural parameters were obtained. Finally, the current response of optimized Au/MAE to the glucose with different concentrations and pH values was studied, and the anti-interference of Au/MAE in glucose detection was tested by chronoamperometry. The electrochemical analysis shows that the simple Au/MAE has a significant amperometric response, a strong anti-interference ability and a sensitivity of 101 μA·cm −2·mM −1in the electrochemical detection of glucose. This method has the advantages of high resolution, high consistency, simple process and low cost, which provides a feasible operation scheme for the fabrication of biosensor array.
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图 1(a) 基于DMD的无掩模投影光刻系统示意图；(b) 电化学沉积的实验装置图
Figure 1.(a) Schematic diagram of maskless projection lithography system based on DMD and (b) experimental setup of electrochemical deposition
图 2Au/MAE的制备流程图。 (a) 基片预处理；(b) 旋涂光刻胶和前烘；(c) 曝光并显影；(d) 电化学沉积Au纳米层；(e) 去除光刻胶
Figure 2.Flow chart of Au/MAE preparation process. (a) Substrate pretreatment; (b) photoresist spin-coating and pre drying; (c) exposure and development; (d) electrochemical deposition of Au nano layer; (e) photoresist removal
图 3周期性结构测试结果。圆形 ( (a) 和 (d) ) ；六边形 ( (b) 和 (e) ) 以及三角形 ( (c) 和 (f) ) 的MAE和Au/MAE在光学显微镜下的实际曝光和电沉积结果
Figure 3.Results of periodic structures. The actual exposure and electrodeposition results of MAE and Au/MAE structures of circular ((a) and (d)); hexagonal ((b) and (e))and triangular ((c) and (f)) under optical microscope
图 4非周期性结构结果。椭圆形((a)和(d))；六边形((b)和(e))以及五角星((c)和(f))的MAE和Au/MAE在光学显微镜下的实际曝光和电沉积结果
Figure 4.Aperiodic structures results. The actual exposure and electrodeposition results of MAE and Au/MAE of elliptical ((a) and (d))；hexagonal ((b) and (e)) and five-pointed ((c) and (f)) under optical microscope
图 5总表面积不变，单元表面积对氧化还原峰电流的影响，周期性排列的(a)圆形；(b)六边形；(c)三角形以及非周期性排列的(d)椭圆；(e)六边形；(f)五角星结构的Au/MAE的CV图
Figure 5.Effect of cell surface area on REDOX peak current under the same total surface area. CV diagrams of (a) circular; (b) hexagonal and (c) triangular Au/MAE structures with periodic arrangement and of (d) elliptical; (e) hexagonal and (f) five-pointed Au/MAE structures with aperiodic arrangement
图 6(a) 总表面积一定时，氧化峰电流值与电极单元表面积的关系；(b) 氧化峰电流值与电极的总表面
Figure 6.(a) Relationship between oxidation peak current and electrode cell surface area when total surface area is constant; (b) relationship between oxidation peak current and total electrode surface area
图 7(a) 密集排列的MAE的显微镜图像；(b) 电沉积后的Au/MAE的光学显微镜图；(c)全部曝光后的显微镜图像；(d)电沉积后的单个Au电极光学显微镜图
Figure 7.(a) Microscope image of the MAE with the most densely arranged cells; (b) microscope image of Au/MAE after electrodeposition; (c) microscope image obtained after full exposure; (d) microscope image of single Au electrode after electrodeposition
图 8Au电极（a）与Au/MAE电极（b）电化学性能比较
Figure 8.Comparison of electrochemical performance between Au electrode (a) and Au/MAE (b)
图 9Au/MAE在含有1 mM葡萄糖的0.1 mM PBS(pH 7.0)缓冲溶液中, (a)不同扫描速度下 (10−1000 mV/s) 的CV图以及(b)不同扫描速率下的阳极和阴极峰值电流拟合图
Figure 9.For Au/MAE (glucose concentration: 1 mM) in 0.1 mM PBS (pH 7.0) buffer solution, (a) CV diagram at different scanning rates (10−1000 mV/s); (b) fitting diagram of anodic and cathodic peak currents at different scanning rates
图 100.1 mM PBS (pH 7.0) 条件下，(a) 葡萄糖浓度不同时Au/MAE的循环伏安图（扫描速率100 mV/s）及(b) 相应的校准曲线；(c) Au/MAE在0.5 V电压下，0.1 mM PBS中连续加入葡萄糖时的安培响应； (d) 对应的拟合曲线
Figure 10.(a) Cyclic voltammograms of Au/MAE electrode at different glucose concentrations in 0.1 mM PBS (pH 7.0) (scanning rate: 100 mV/s) and (b) the corresponding calibration curve; (c) amperometric response of Au/MAE electrode to the continuous addition of glucose to 0.1 mM PBS at the voltage of 0.5 V and (d) the corresponding fitting curve
图 11(a) 0.5 V电压下，在PBS（浓度0.1 mM，pH 7.0）缓冲溶液中连续添加1.5 mM葡萄糖、1 mM Urea、1 mM AA、1 mM乳糖、1 mM NaCl和6 mM葡萄糖时，电极的安培响应；(b) 与目标分析物相比，相应的干扰信号的百分比
Figure 11.(a) Amperometric response of the electrode to the continuous addition of 1.5 mM glucose, 1 mM urea, 1 mM AA, 1 mM lactose, 1 mM NaCl and 6 mM glucose to PBS (0.1 mM, pH 7.0) buffer solution at 0.5 V voltage; (b) the percentage of interfering signals compared with the target analyte
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