不同类型GaAs上应用约束刻蚀剂层技术进行电化学微加工

应用约束刻蚀剂层技术(CELT)对GaAs进行电化学微加工. 研究了刻蚀溶液体系中各组成的浓度比例、GaAs类型、掺杂以及阳极腐蚀过程对GaAs刻蚀加工过程的影响. 循环伏安实验表明, Br-可以通过电化学反应生成Br2作为刻蚀剂, L-胱氨酸可作为有效的捕捉剂. CELT中刻蚀剂层被紧紧束缚于模板表面, 模板和工件之间的距离小于刻蚀剂层的厚度时, 刻蚀剂可以对GaAs进行加工. 利用表面具有微凸半球阵列的导电模板, 可以在不同类型GaAs上加工得到微孔阵列. 实验结果表明: 在相同刻蚀条件下, GaAs的加工分辨率与刻蚀体系中各组分的浓度比例有关, 刻蚀结构的尺寸随着刻蚀剂与捕捉剂浓度比的增加而增大; 在加工过程中, p-GaAs相对于n-GaAs和无掺杂GaAs受到阳极氧化过程的影响较为显著, p-GaAs表面易生成氧化物层, 影响电化学微加工过程. X射线光电子能谱(XPS)和极化曲线实验也证明了这一点.     

金属铜表面的三维齿状图形的化学微加工

金属铜表面的三维齿状图形的化学微加工;约束刻蚀剂层技术(CELT);化学刻蚀     

镍表面三维微图形的复制加工

运用约束刻蚀剂层技术(CELT)在金属镍(Ni)表面实现三维微图形加工,以规整的三维齿状微结构作模板,获得可有效CELT加工的化学刻蚀和捕捉体系,在Ni表面得到了与齿状结构互补的三维微结构并应用扫描电子显微镜(SEM)和原子力显微镜(AFM)表征刻蚀图案,证实CELT可用于金属表面Ni的三维微图形刻蚀加工．     

镁合金表面微结构阵列的电化学微加工

研究了镁合金的约束刻蚀微加工方法. 通过对电解过程中电极表面氢离子浓度变化以及刻蚀体系对镁合金的腐蚀速率的测量与分析, 对一些可能有刻蚀作用的刻蚀体系进行了研究. 选用亚硝酸钠作为产生刻蚀剂(硝酸)的前驱体、氢氧化钠作为捕捉剂、少量硅酸钠作为缓蚀剂的约束刻蚀体系, 使用具有规整三维微立方体点阵结构的模板, 在金属镁表面加工出具有与模板互补特性的点阵微结构, 复制加工的分辨率为亚微米级. 并对刻蚀过程机理进行了探讨与分析.     

基于约束刻蚀原理的电化学微纳加工研究进展

与机械加工相比,电化学加工技术具有无刀具磨损、无热效应、无机械损伤、加工效率高等优点,而且适用于柔性、脆性及超硬材料,具备传统方法难以实现的复杂结构加工能力,因而在航空航天、汽车、微电子等领域有着重要应用,日益成为一种重要的工业制造技术.随着超大规模集成电路(ULSI)、微机电系统(MEMS)、微全分析系统(μ-TAS)、现代精密光学系统等高技术产业的迅速发展,功能性结构/器件的微型化和集成化的要求越来越高.由于传统电化学只适用于金属材料,为了应对微纳制造的时代要求,拓展电化学加工的材料普适性,1992年田昭武院士提出了具有我国自主知识产权的约束刻蚀剂层技术(CELT).一般的,约束刻蚀包括3个步骤:(1)通过电化学、光化学或光电化学的方法在模板电极表面生成刻蚀剂;(2)通过后续的均相化学反应或自由基衰变反应将刻蚀剂约束在微/纳米厚度的液层内;(3)将模板电极逼近加工基底,当约束刻蚀剂层接触被加工基底时,通过刻蚀反应实现微纳加工.最近,联合课题组通过仪器、原理和方法3个方面的努力,引入外部物理场调制技术,实现一维铣削、二维抛光、三维微/纳结构加工,大幅提升了CELT的技术水平.     

微系统科技的发展及电化学的新应用

本文根据田昭武在中国化学会第一届全国纳米技术与应用会议 (2 0 0 0 .11.2 8,厦门 )特邀大会报告内容整理而成 :1　微系统技术概述 (技术的必要性和前景 )2　发展微系统技术的特殊困难3　电化学在微系统技术中的应用　 3.1　用于复杂 3D 图形微加工的约束刻蚀剂层技术 (CELT)　 3.2　聚焦电泳和微系统在 (生物 )化学中的应用 (μ TAS或芯片上实验室 )　 3.3　芯片实验室中微流体输运网络的合理选择之一 -灵巧 (Smart)电渗泵4　结论     

约束刻蚀剂层技术对金属铝的微结构加工研究

采用约束刻蚀剂层技术, 以亚硝酸钠为先驱物, 通过电化学氧化产生刻蚀剂(硝酸)刻蚀铝, 并以NaOH为捕捉剂, 在电极模板上形成约束刻蚀剂层. 在金属铝表面加工出梯型槽微结构, 加工分辨率约为500 nm. 通过测量表面氢离子浓度, 对捕捉剂的约束效果进行了分析.     

砷捕捉刻蚀剂反应速率常数研究

采用约束刻蚀剂层技术（ＣＥＬＴ）有可能实现纳米级的超微加工目的￣［１，２］。约束刻蚀层形成的方法之一是：通过电化学反应在模板表面上产生刻蚀剂，其在向外扩散过程中即与其它未有刻蚀作用的溶液组分发生快速均相化学反应，从而使刻蚀剂失去活性，刻蚀剂的扩散层厚度可约束在紧靠模板的范围内。而ＣＥＬＴ技术则取决于产生能对特定材料具有高度腐蚀性的腐蚀剂和具有合理的清除反应体系；象强氧化剂溴，邻菲绕啉铁（Ⅲ）和过氧化氢等均可作为刻蚀剂，Ｂａｒｄｅｔａｌ￣［３］等研究者借助扫描电化学显微镜（ＳＥＣＭ）通过电化学产生的溴和邻菲绕啉铁（Ⅲ）直接来刻蚀进行微加工，但未采用约束刻蚀层技术，所刻的线条较宽。本文研究溴和邻菲绕啉铁（Ⅲ）的均相捕捉反应速率常数，为利用约束刻蚀层技术进行微加工打下必要的基础。     

利用约束刻蚀剂层技术提高硅的刻蚀分辨率

高分辨率刻蚀技术对于微机械及微电子器件的加工具有十分重要的意义，而硅是其中极为重要并占统制地位的材料，近年来，扫描电化学显微镜用于表面加工的研究颇受注目，然而，ＳＥＣＭ刻蚀分辨率往往因为刻蚀剂的横向扩散而受到限制。最后，田昭武等提出一种可进行高分辨率微加工的新方法－－约束刻蚀剂层技术，可使刻蚀反应具有高度的距离敏感性，刻蚀分辨率得到极大改善。我们利用ＣＥＬＴ技术刻蚀硅表面，以６０μｍ及１００μｍ直     

电位无标型糖化血红蛋白免疫微传感器

研制了基于标准CMOS工艺和微加工技术的电位无标型免疫微传感器,可实现糖化血红蛋白浓度与血红蛋白浓度的简便检测。该微传感器包括含有信号读出电路的场效应型微传感集成芯片和一次性测试试条。微传感集成芯片由本实验室设计并经新加坡Chartered半导体公司流片制备。一次性测试试条采用微加工技术制备于柔性塑料片上,包括敏感电极阵列和三维微结构测量池。基于自组装单层膜并引入纳米金颗粒的方法,在测试试条电极表面固定抗体。采用循环伏安法和交流阻抗法对电极表面的修饰过程进行了测试和分析。该传感器对糖化血红蛋白和血红蛋白检测的线性范围分别为4～24mg/L和60～180mg/L。     

A comparative study on electrochemical micromachining of n-GaAs and p-Si by using confined etchant layer technique

The confined etchant layer technique has been applied to achieve effective three-dimensional (3D) micromachining on n-GaAs and p-Si. This technique operates via an indirect electrochemical process and is a maskless, low-cost technique for microfabrication of arbitrary 3D structures in a single step. Br(2) was electrogenerated at the mold surface and used as an efficient etchant for n-GaAs and p-Si; l-cystine was used as a scavenger, for both substrates. The resolution of the fabricated microstructure depended strongly on the composition of the electrolyte, and especially on the concentration ratio of l-cystine to Br(-). A well-defined, polished Pt microcylindrical electrode was employed to examine the deviation of the size of the etched spots from the real diameter of the microelectrode. The thickness of the confined etchant layer can be estimated, and thus the composition of the electrolyte can be optimized for better etching precision. The etched patterns were approximately negative copies of the mold, and the precision of duplication could reach the micrometer level for p-Si and the submicrometer level for n-GaAs. Although the same etchant (Br(2)) and scavenger (l-cystine) were used in the etching solutions for GaAs and Si, the etching process, or mechanism, is completely different in the two cases. Compared with the fast etching process on GaAs in an etching solution with a concentration ratio of 3:1 of l-cystine to Br(-), the concentration ratio needs to be 50:1 for etching of Si. For the micromachining of Si, the addition of a cationic surfactant (cetyltrimethylammonium chloride, CTACl) is necessary to reduce the surface tension of the substrate and hence reduce the influence of evolution of the byproduct H(2). The function of the surfactant CTACl in comparison with an anionic surfactant (sodium dodecyl sulfate) was studied in contact-angle experiments and micromachining experiments and then is discussed in detail.     

Electrochemical Behavior of Mitoxantrone and Its Determination at a Pt／C Implanted Modified Microelectrode

In a 0.02 mol/L Na2HPO4-KH2PO4(PBS) buffer solution(pH=6.82), the electrochemical behavior of mitoxantrone was studied by linear-sweep voltammetry and cyclic voltammetry at a Pt/C ion implantation modified microelectrode. A sensitive reduction peak was observed. The peak potential was -0.72 V(vs.SCE), the peak current was proportional to the concentration of mitoxantrone within the ranges of 7.0×10-8-9.0×10-7 mol/L and 1.0×10-6-2.4×10-5 mol/L, with a detection limit of 4.0×10-8 mol/L. The linear correlation coefficients were 0.9994 and 0.9992, respectively. This method has been applied to the direct determination of mitoxantrone in simulated urine. The recoveries were in the range from 96.2% to 105.9%. The reduction process was a quasi-reversible one with adsorptive characteristics at the Pt/C microelectrode. The electrode reaction rate constant ks and the electron transfer coefficient α of the system were determined to be 4.5 and 0.65 s-1, respectively. The experiments showed that Pt element had surely been implanted into the surface of the carbon fiber, and the atomic Pt improved the electrocatalytic activity. The Pt/C microelectrode had a good stability and reproducibility.     

微电流法直接检测非电活性气体二氧化碳

基于非电活性气体CO_2在‘二甲亚砜/铂微电极’体系中定量的电还原反应,提出微电流法常温直接检测二氧化碳.在常规气敏微电极和硅一体化薄膜微电极器件上获得了满意的气敏响应特性:好的线性响应关系、灵敏度和响应速度.用硅微机械加工技术批量构制的薄膜微电极器件,既保持了微电极的全部优点,又实现了微电流器件结构的一体化,电流响应异常稳定和重现.     

吸附中间物表面扩散对Pt/Nafion体系氢析出反应影响初步研究

实验表明 ,铂黑粉末 /Nafion复合微电极的析氢超电势比同样面积的平面铂复合微电极为低 .这是由于Nafion膜与平面铂电极或者铂黑粉末形成的Pt/Nation界面之外还存在可供反应中间物扩散及进行复合反应的自由铂表面 ,这些扩散和复合反应降低了Pt/Nafion界面上电化学反应中间物浓度 ,从而降低了氢超电势 ,加速了析氢反应的速度 .     

Development of a Pt modified microelectrode aimed for the monitoring of ammonium in solution

The development of selective and sensitive analytical methods for ammonium detection is important for the evaluation of the environmental effects of water pollution and the understanding of nitrogen cycling in ecosystems. In the current study, a new Pt nanoparticle microelectrode with high selectivity, sensitivity, accuracy and anti-interference capacity was successfully prepared for the quantitative measurement of ammonia concentration in artificial and real wastewater samples. The prepared Pt nanoparticle microelectrode had a selectively electrochemical catalytic oxidation activity for ammonium. Ammonium oxidation peak current presented a linear correlation with ammonium concentrations in artificial and real wastewater samples. Ammonium response was 92% of the initial value after 120 measurements, indicating that the prepared microelectrode is reliable and stable as an ammonium sensor. The lifetime of the modified microelectrode was of at least 150 days at room temperature and of at least 500 repetitive measurements. The present method is a simple way of preparing an ammonium sensor with very good reproducibility. Moreover, the proposed electrochemical method has been validated by comparing the obtained results of the analysis of ammonium in artificial and real wastewater samples with those obtained from spectrophotometry.     

Synthesis of Pd-Pt bimetallic nanocrystals with a concave structure through a bromide-induced galvanic replacement reaction

This article describes a systematic study of the galvanic replacement reaction between PtCl(6)(2-) ions and Pd nanocrystals with different shapes, including cubes, cuboctahedrons, and octahedrons. It was found that Br(-) ions played an important role in initiating, facilitating, and directing the replacement reaction. The presence of Br(-) ions led to the selective initiation of galvanic replacement from the {100} facets of Pd nanocrystals, likely due to the preferential adsorption of Br(-) ions on this crystallographic plane. The site-selective galvanic replacement resulted in the formation of Pd-Pt bimetallic nanocrystals with a concave structure owing to simultaneous dissolution of Pd atoms from the {100} facets and deposition of the resultant Pt atoms on the {111} facets. The Pd-Pt concave nanocubes with different weight percentages of Pt at 3.4, 10.4, 19.9, and 34.4 were also evaluated as electrocatalysts for the oxygen reduction reaction (ORR). Significantly, the sample with a 3.4 wt.% of Pt exhibited the largest specific electrochemical surface area and was found to be four times as active as the commercial Pt/C catalyst for the ORR in terms of equivalent Pt mass.     

Reactions of halogens with Pt(II) complexes of N-alkyl- and N,N-dialkyl-N'-benzoylthioureas: oxidative addition and formation of an I2 inclusion compound

The treatment of cis-[Pt(II)(L(1a/b)-S,O)2] complexes of N,N-diethyl- (HL(1a)) and N,N-di(n-butyl)-N'-benzoylthiourea (HL(1b)) with I2 or Br2 in chloroform, leads to rapid oxidative addition to yield several geometric isomers of [Pt(IV)(L-S,O)(2)X(2)](X = I, Br); the reactions can be monitored by (195)Pt NMR and UV-visible spectrophotometry. The products cis-[Pt(IV)(L(1a)-S,O)2I2] and cis-[Pt(IV)(L(1a)-S,O)2Br2], which have been isolated and structurally characterized, are the first-reported crystal structures of complexes of Pt(iv) with this class of ligand. Molecules of 6 pack such that the I-Pt-I axes are essentially aligned, with unusually close nearest-neighbour iodide contacts (3.553(1)A). These short II intermolecular interactions lead to infinite chains of weakly connected molecules in crystals of the compound. No such interactions are evident in the corresponding crystals of . Reaction of the Pt(II) complex of N-propyl-N'-benzoylthiourea (H2L(2a))cis-/trans-[Pt(II)(H2L(2a)-S)2Br2] with Br2 also results in oxidative addition, to yield trans-Pt(IV)(H2L(2a)-S)2Br4. By contrast, treatment of cis-/trans-[Pt(II)(H2L(2a)-S)2I2] with I2 does not lead to an oxidative addition product, yielding instead an interesting iodine inclusion compound of Pt(II), trans-[Pt(II)(H2L(2a)-S)2I2.I2. In 8, short intermolecular II distances of 3.453(1)A between I2 and coordinated iodide ions in trans-[Pt(II)(H(2)L(2a)-S)(2)I(2)] molecules, result in infinite chains of weakly linked trans-[Pt(II)(H2L(2a)-S)2I2]...I2 groups in the lattice. However, the empirically estimated bond order of 0.75 for the included I2 molecules does not support the possible existence of discrete tetraiodide ions (I4(2-)) in the lattice of compound 8.     

Icosahedral Pt-centered Pt13 and Pt19 carbonyl clusters decorated by [Cd5(μ-Br)5Br(5-x)(solvent)x]x+ rings reminiscent of the decoration of Au-Fe-CO and Au-thiolate nanoclusters: a unifying approach to their electron counts

The new [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) and [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) clusters have been obtained in good yields by reaction of [Pt(12)(CO)(24)](2-) with CdBr(2)·H(2)O in dmf at 90 °C and structurally characterized by X-ray diffraction. Their structures consist of a Pt-centered Pt(13)(CO)(12) icosahedron and a Pt(19)(CO)(17) interpenetrated double icosahedron, respectively, decorated by two Cd(5)(μ-Br)(5)Br(5-x)(solvent)(x) rings. Their surface decoration may be related to that of Au-Fe-CO clusters as well as to the staple motifs stabilizing gold-thiolates nanoclusters. An oversimplified and unifying approach to interpret their electron count is suggested.     

Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt...Pt interactions

Pentanuclear linear chain Pt(II,III) complexes [[Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]2[PtX'4]].nCH3COCH3 (X = X' = Cl, n = 2 (1a), X = Cl, X' = Br, n = 1 (1b), X = Br, X' = Cl, n = 2 (1c), X = X' = Br, n = 1 (1d)) composed of a monomeric Pt(II) complex sandwiched by two amidate-bridged Pt dimers were synthesized from the reaction of the acetonyl dinuclear Pt(III) complexes having equatorial halide ligands [Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]X' ' (X = Cl (2a), Br (2b), X' ' = NO3-, CH3C6H4SO3-, BF4-, PF6-, ClO4-), with K2[PtX'4] (X' = Cl, Br). The X-ray structures of 1a-1d show that the complexes have metal-metal bonded linear Pt5 structures, and the oxidation state of the metals is approximately Pt(III)-Pt(III)...Pt(II)...Pt(III)-Pt(III). The Pt...Pt interactions between the dimer units and the monomer are due to the induced Pt(II)-Pt(IV) polarization of the Pt(III) dimeric unit caused by the electron withdrawal of the equatorial halide ligands. The density functional theory calculation clearly shows that the Pt...Pt interactions between the dimers and the monomer are made by the electron transfer from the monomer to the dimers. The pentanuclear complexes have flexible Pt backbones with the Pt chain adopting either arch or sigmoid structures depending on the crystal packing.     

Determination of sulfur dioxide in vitriol plant wastewater by using a polyNiMe4TAA electrochemically modified Pt microelectrode

A Pt microelectrode modified with nickel(II) polytetramethyldibenzo[b,i]tetraaza[14]annulene was prepared by electropolymerization of nickel(II) tetramethyldibenzo[b,i]tetraaza[14]annulene monomers and applied to determine sulfur dioxide in vitriol plant wastewater. For determination of SO2 with this electrochemically modified Pt microelectrode, the linear range was from 9.6 x 10(-6) to 2.4 x 10(-4) mol L-1, the sensitivity was 1.8 x 10(-4) A L mol-1, the detection limit was calculated to be 4.8 x 10(-6) mol L-1 (S/N = 3), the response time was less than 20 s and the relative standard deviation was found to be 2.1% on analyzing 4.8 x 10(-5) mol L-1 SO2 solution repeatedly (n = 7). These results demonstrated good accuracy compared with those obtained by the conventional iodimetric method.