硅基MEMS三维微电极阵列的超电容特性

三维微电极是一种具有空间结构优势、电化学性能比二维微电极更加优越的微型储能结构.本文提出一种基于光刻、感应耦合等离子体刻蚀和溅射等MEMS工艺加工三维结构硅基微电极阵列的新方法.采用电化学阴极沉积工艺在微电极表面制备了纳米氧化钌功能薄膜.借助扫描电子显微镜、循环伏安测试和电化学交流阻抗谱测试等手段对三维微电极的表面形貌和电化学性能进行了表征,系统研究了阴极沉积电流密度、电沉积时间以及硅基微结构表面"微草效应"对三维微电极超电容特性的影响.所制备三维微电极的比电容达到1.57 F/cm2,与平面电极比电容0.42 F/cm2相比明显提高,而电化学阻抗比二维平面微电极显著降低.相关实验数据表明基于MEMS技术加工的三维结构微电极具有优于平面电极的电化学电容储能特性.     

钨丝微电极阵列的简易制备方法

本文提出了一种简易、低成本的钨丝微电极阵列制作工艺和方法.该方法采用MEMS工艺制作的玻璃模具实现钨丝阵列的精密有序排列,同时,在钨丝电极表面涂覆一层光敏性的聚酰亚胺作为绝缘层,结合"双面光刻"技术和电化学腐蚀技术实现电极位点大小和电极丝几何尺寸的精确控制.最后,通过注模、光刻制作SU-8固定座体完成钨丝微电极阵列的组装固定.整个制作工艺简单快速,且玻璃模具可重复使用,大大降低了制作成本.此外,本文还测试和评价了所制作微电极的表面形貌、电学性能以及生物相容性.     

视网膜前假体中柔性凸起微电极的研制

采用聚对二甲苯（Parylene C）作为结构材料,借助微细加工技术设计并制作了按6×6矩阵排布的柔性凸起微电极阵列．微电极直径为80μm,引线线宽40μm,电极间距为280μm,引线间距为80μm．电极位点高度约为10μm,呈明显的圆滑凸起结构特征．电极和引线表面均平整光滑,轮廓清晰,结构完好．阻抗测试结果表明：随着频率的增加,凸起微电极的阻抗呈下降趋势,显示出明显的高通特性;1kHz时凸起微电极的阻抗约为10kΩ,较具有相同基底面积的平面电极约低30％,有助于提高电极的信噪比,可望用于视网膜前假体中．柔性凸起微电极制作工艺简单,利于高效率批量制作并提高微电极的集成度．     

一种集成纳米金柱结构的神经薄膜微电极阵列

在神经假体系统中,神经微电极是实现信号检测以及激励任务的重要组成部分.然而,神经微电极由于尺寸微小,往往具有很高的电极/组织界面阻抗.本文提出了一种在电极位点表面处集成纳米结构来增大电极有效表面积的方法.这种方法结合了光刻、局部氧化铝以及电子束蒸发等技术,在薄膜微电极的表面集成了纳米金柱结构.最后,本文测试和评价了此微电极的表面形貌以及电学性能.实验结果表明,这种集成有纳米金柱结构的微电极其界面阻抗降低了约25倍,促进了这种微电极在神经工程领域的广泛应用.     

MEMS用新型微型超级电容器的制造及性能分析

采用微加工工艺为MEMS制作了一种基于电化学赝电容原理储能的微型能量存储器件——新型微型超级电容器.通过光刻、感应耦合等离子体刻蚀和溅射等MEMS微加工工艺制作了硅基3D微电极阵列,并在其表面用阴极电沉积法制备了氧化钌功能薄膜.采用循环伏安法和交流阻抗法研究了3D微电极的性能,系统比较了3D微电极与平面微电极的电化学性能,测试结果表明3D微电极的比电容达1.57F· cm-2.基于三维微电极阵列阳极和钌钛金属氧化物阴极组装了微型超级电容器,恒流充放电测试结果表明该电容器的比容量达0.73F·cm-2,比功率达0.50mW·cm-2,比能量达0.36J·cm-2.     

基于Parylene的柔性生物微电极阵列的制作

在神经工程中,微电极阵列是神经系统与外界电子电路的接口,其性能决定了整个神经系统的信号采集和刺激的效果.提出了一种基于Parylene的半球形柔性生物微电极阵列.在微电极的制备过程中,使用了光刻胶热熔技术和MEMS技术.半球形形貌的微电极有利于形成和神经组织的良好接触,并且相比同底面积的平板电极,表面积增加为2倍,这有利于降低界面阻抗,降低系统功耗.使用化学气相沉积法沉积Parylene C薄膜作为微电极的封装材料,它具有良好的生物相容性和柔性,可以降低对神经组织的损害.实验结果表明,与此半球形微电极底面积大1.3倍的平板电极相比,半球形微电极的界面阻抗下降了55%,并且界面阻抗随着微电极顶部开口直径的变化而变化.使用Comsol有限元软件进行了电极/组织液液面流出电流密度仿真,仿真结果也表明,微电极的流出电流密度也随着微电极顶部开口直径的变化而变化,因此可以通过调整微电极顶部开口直径来调节电流密度,从而满足不同部位需要不同电流密度刺激的要求.     

铅/二氧化铅二元电极

铅和铅合金在氯化物溶液里以高电流密度进行阳极极化时,其表面上,生成厚的、肿胀而又多孔的氯化铅沉积物。当微铂电极嵌入铅表面后,在氯化物介质里,以同样高的电流密度下进行阳极极化,其铅表面能生成过氧化铅。为了代替昂贵的铂,将过氧化铅微电极(在过氧化铅电沉积时脱落下来的过氧化铅薄片加工成小圆柱体)嵌入铅或铅合金电极里,并在氯化物溶液里进行阳极极化。在这种情况下,铅和铅合金电极表面上,也能生成过氧化铅。在室温下,铅/二氧化铅二元电极在3％的NaCl溶液里以3安/分米~2电流密度下进行阳极极化时,发现在电极表面上能很好地生成PbO_2膜。二氧化铅微电极的取出与插入,以及二氧化铅微电极与铅电极的面积之比对过氧化铅生成的影响,也进行了研究。嵌有二氧化铅微电极的铅和铅合金阳极,在氯化物溶液及人造海水里进行了阳极极化,从重量的变化及表面生成致密、无龟裂的PbO_2膜来考虑,1％Ag(Pb)/PbO_2二元电极是很好的阳极。     

基于碳纤维的新型自支撑电极制备方法

借鉴自支撑电极的制备原理,利用电化学沉积结合(NH₄)₂S₂O₈和NaOH沉积液进行表面处理等手段制备了基于碳纤维表面Cu(OH)₂纳米结构的自支撑电极,分析测试了碳纤维表面的微观形貌、表面元素组成及其分布和表面物质的晶型以及利用水热反应在其表面附着电化学物质MnO₂后的电化学性能。结果发现,当(NH₄)₂S₂O₈的浓度为0.43 g/L、NaOH浓度为30.48 g/L、处理时间为12 min时,由SEM观察发现碳纤维表面的Cu(OH)₂纳米纤维的直径、长度、数量都较适宜;XPS、XRD和EDS的测试结果,沉积液处理后碳纤维表面部分单质铜转化为Cu(OH)₂,此结构非常有利于电化学物质的负载而由此构成开放、具有核壳结构的高性能电极材料;恒电流充放电(GCD)测试结果表明此电极材料具有极快的充放电速度。因此本文首次成功地在碳纤维表面的铜层表面原位生长出Cu(OH)₂纳米纤维,为未来以超级电容器为代表的能源设备的性能提升和商业化应用开拓了一种新的电极制备方法。      

微型超级电容器PPy/GO-RuO2复合膜电极的制备与电化学性能

为了解决氧化钌(RuO₂)沉积电位过高, 难以在三维微结构金属集流体上直接沉积的问题, 提出采用分步电沉积方法在微三维结构镍(Ni)集流体上制备RuO₂复合膜电极, 即先在三维微结构Ni集流体上沉积聚吡咯/氧化石墨烯(PPy/GO)薄膜作为基底, 经热处理后, 在基底上二次沉积出RuO₂颗粒, 最后再对RuO₂复合薄膜进行二次热处理。扫描电子显微镜(SEM)观察显示, 随着热处理温度的升高, 薄膜表面多孔结构增多, 达到了提高膜电极结构孔隙分布的目的。能量分散谱(EDS)和X射线光电子能谱分析(XPS)表明, 薄膜中无定形RuO₂·xH₂O的存在保证了膜电极的大比容量。电化学性能测试结果表明, 经105℃处理后的膜电极电化学性能最佳, 比电容为28.5 mF/cm², 能量密度为0.04 Wh/m², 功率密度为14.25 W/m²。采用分步电沉积方法制备出的RuO₂复合薄膜是一种良好的MEMS超级电容器电极材料。     

金刚石膜紫外光电导探测器及性能

用化学气相沉积法生长金刚石膜,在此膜上制作紫外光电探测器,并作了性能测试。该器件是叉指式电极结构,可以减小电极间隙,减少光激发载流子的损失,提高器件的响应灵敏度。表面处理可除去金刚石膜的低电阻表面层,提高器件对紫外光的探测性能。测试表明,用金刚石制作的器件对波长小于２２５ｎｍ的紫外光的响应比可见光高４个量级。     

Fabrication of integrated microelectrodes for electrochemical detection on electrophoresis microchip by electroless deposition and micromolding in capillary technique

A new method for the fabrication of an integrated microelectrode for electrochemical detection (ECD) on an electrophoresis microchip is described. The pattern of the microelectrode was directly made on the surface of a microscope slide through an electroless deposition procedure. The surface of the slide was first selectively coated with a thin layer of sodium silicate through a micromolding in capillary technique provided by a poly(dimethylsiloxane) (PDMS) microchannel; this left a rough patterned area for the anchoring of catalytic particles. A metal layer was deposited on the pattern guided by these catalytic particles and was used as the working electrode. Factors influencing the fabrication procedure were discussed. The whole chip was built by reversibly sealing the slide to another PDMS layer with electrophoresis microchannels at room temperature. This approach eliminates the need of clean room facilities and expensive apparatus such as for vacuum deposition or sputtering and makes it possible to produce patterned electrodes suitable for ECD on microchip under ordinary chemistry laboratory conditions. Also once the micropattern is ready, it allows the researchers to rebuild the electrode in a short period of time when an electrode failure occurs. Copper and gold microelectrodes were fabricated by this technique. Glucose, dopamine, and catechol as model analytes were tested.     

A nano-structured Ni(II)–chelidamic acid modified gold nanoparticle self-assembled electrode for electrocatalytic oxidation and determination of methanol

A nano-structured Ni(II)–chelidamic acid (2,6-dicarboxy-4-hydroxypyridine) film was electrodeposited on a gold nanoparticle–cysteine–gold electrode. The morphology of Ni(II)–chelidamic acid gold nanoparticle self‐assembled electrode was investigated by scanning electron microscopy (SEM). Electrocatalytic oxidation of methanol on the surface of modified electrode was studied by cyclic voltammetry and chronoamperometry methods. The hydrodynamic amperometry at a rotating modified electrode at constant potential versus reference electrode was used for detection of methanol. Under optimized conditions the calibration plots are linear in the concentration range 0–50 mM with a detection limit of 15 μM. The formed matrix in our work possessed a 3D porous network structure with a large effective surface area, high catalytic activity and behaved like microelectrode ensembles. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for analytical purposes.     

Immobilized diaphorase surfaces observed by scanning electrochemical microscope with shear force based tip-substrate positioning

Imaging of a coimmobilized diaphorase and albumin surface was investigated by scanning electrochemical microscopy (SECM) with shear force based tip-substrate distance control. A microelectrode tip was attached to a commercially available tuning fork to detect the shear force between the microelectrode tip and the surface. We used the standing approach mode, which repeats an approach and retraction at each data point of the surface to obtain simultaneous current and topographic images. To check the performance of our SECM system, we imaged a platinum-patterned array electrode and a diaphorase/albumin coimmobilized glass surface. Since the system acquires current when the tip is retracted to a desired distance, this mode is useful for a relatively large microelectrode (approximately 10 microm) and for scanning a large area (few hundreds of micrometers). Furthermore, by retracting the tip when the tip moves laterally to the next data point to avoid contact between the tip and sample surface, we successfully imaged the surface without destroying its morphology.     

用于电刺激的植入式铂黑微电极

传统的植入式电刺激微电极表面积小,电极／组织界面阻抗高,并且电荷存储容量（CSC）小,这些都会增加植入式系统的功耗并影响电刺激效果．提出了一种在电极点电镀铂黑的方法来增加微电极的有效面积（ESA）．通过在超声波浴下使用脉冲电流电镀的方法,可以极大地增加微电极的ESA,降低界面阻抗并增加CSC和电荷注入容量．铂黑微电极的几何特性和电学特性分别由扫描电子显微镜（SEM）和电化学分析仪测定,并与未镀铂黑的电极特性进行了对比,对铂黑镀层的机械稳定性也做了相应的测试．实验结果表明,铂黑镀层的纳米结构使铂黑电极相比普通铂电极界面阻抗降低了1／16,CSC扩大13倍．在5min的室温超声波衰减实验中,阴极电荷存储容量（CSCc）仅减小20％．     

Hydrophilic modification of neural microelectrode arrays based on multi-walled carbon nanotubes

To decrease the impedance of microelectrode arrays, for neuroscience applications we have fabricated and tested MEA based on multi-walled carbon nanotubes. With decreasing physical size of a microelectrode, its impedance increases and charge-transfer capability decreases. To decrease the impedance, the effective surface area of the electrode must generally be increased. We explored the effect of plasma treatment on the surface wettability of MWCNT. With a steam-plasma treatment the surface of MWCNT becomes converted from superhydrophobic to superhydrophilic; this hydrophilic property is attributed to?-OH bonding on the surface of MWCNT. We reported the synthesis at 400?°C of MWCNT on nickel-titanium multilayered metal catalysts by thermal chemical vapor deposition. Applying plasma with a power less than 25?W for 10?s improved the electrochemical and biological properties, and circumvented the limitation of the surface reverting to a hydrophobic condition; a hydrophilic state is maintained for at least one month. The MEA was used to record neural signals of a lateral giant cell from an American crayfish. The response amplitude of the action potential was about 275?μV with 1?ms period; the recorded data had a ratio of signal to noise up to 40.12?dB. The improved performance of the electrode makes feasible the separation of neural signals and the recognition of their distinct shapes. With further development the rapid treatment will be useful for long-term recording applications.     

Sb掺杂钛基SnO2电极的制备、表征及其电催化性能研究

采用电沉积 热氧化法制备了含有中间层的Sb掺杂钛基SnO2 电催化电极(Ti/SnO2),采用SEM、EDX以及 XRD 等检测方法对所制备电极的表面形貌、元素组成及结构进行分析,并以苯酚为目标有机物,研究所制备电极对有机污染物的电催化降解能力。研究结果表明所制备 Ti/SnO2 电极可在较短时间内将苯酚彻底降解,其较大的真实表面积以及电极中间层的存在是所制备电极性能提高的重要原因。阳极极化曲线扫描(LSV)的分析结果表明所制备的 Ti/SnO2电极具有较高的阳极析氧电位,有利于有机物的阳极氧化降解。     

Highly sensitive detection of exocytotic dopamine release using a gold-nanoparticle-network microelectrode

Here we report a new type of microelectrode sensor for single-cell exocytotic dopamine release. The new microsensor is built by forming a gold-nanoparticle (AuNP) network on a carbon fiber microelectrode. First a gold surface is obtained on a carbon fiber microdisk electrode by partially etching away the carbon followed by electrochemical deposition of gold into the pore. The gold surface is chemically functionalized with a sol-gel silicate network derived from (3-mercaptopropyl)trimethoxysilane (MPTS). A AuNP network is formed by immobilizing Au nanoparticles onto the thiol groups in the sol-gel silicate network. The AuNP-network microelectrode has been characterized by scanning electron microscopy (SEM) and steady-state voltammetry. The AuNP-network microelectrode has been used for amperometric detection of exocytotic dopamine secretion from individual pheochromocytoma (PC12) cells. The results show significant differences in the kinetic peak parameters including shorter rise time, decay time, and half-width as compared to a bare carbon fiber electrode equivalent. These results indicate AuNP-network microelectrodes possess an excellent sensing activity for single-cell exocytotic catecholamine release, specifically dopamine. Moreover, key advantageous properties inherent to bare carbon fiber microelectrodes (i.e., rigidity, flexibility, and small size) are maintained in addition to an observed prolonged shelf life stability and resistance to cellular debris fouling and dopamine polymerization.     

双电层电容器用中孔活性炭电极的电化学性能

选用中孔活性炭作为双电层电容器的电极材料，实验发现，中孔活性炭电化学性能优异，比表面积利用率高达93．5％，用水蒸气活化可以增加活性炭的比表面积，随着活化时间的延长，活性炭收率降低，活化2h收率仅为26．5％,同时比表面积从原来的760m^2/g增加到1480m^2/g，且主要在2nm附近孔结构分布强度增强，比电容随活化时间的延长而增加，但增速低于比表面积的增加幅度。