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．     

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     

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.     

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.     

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。     

用规整膜板对砷化镓的三维微结构图形加工刻蚀

以微齿轮图形结构作为规整模板 ,用约束刻蚀剂层技术对GaAs样品表面进行了加工刻蚀 .在有捕捉剂H3AsO3存在的情况下 ,规则微齿轮图形能够很好地在样品表面复制 .刻蚀结果与没有捕捉剂存在时的刻蚀结果做了比较 .另外还测试了不同方法制得膜板的性能 ,初步探讨了电化学模板的制作工艺 .     

电化学微/纳米加工技术

介绍电化学微／纳米加工技术，特别是厦门大学电化学微／纳米加工课题组建立起来的约束刻蚀剂层技术，旨在让广大师生了解这一特种加工技术，共同促进我国电化学微／纳米加工技术的研究及产业化进程。     

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.     

微圆盘电极技术测定表面化学微加工时的约束刻蚀剂浓度分布

利用微圆盘电极技术, 测定了KBr、L-胱氨酸和硫酸组成的刻蚀溶液体系中Pt电极表面电化学氧化产生的刻蚀剂Br2浓度分布, 为约束刻蚀剂层技术(CELT)中刻蚀体系的选择和优化提供更直观的依据. GaAs表面CELT微加工实验证明了用微圆盘电极测得的表面刻蚀剂的浓度分布趋势与微加工实验所得到的结果一致     

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.     

电化学微/纳加工分辨率的影响因素及对策

The etching resolution of electrochemical fabrication technique is influenced significantly by the diffusion layer of the etchant. It has been shown that a fast etching rate can achieve higher etching resolution due to so-called heterogeneous scavenging effect, while a lower etching rate will result in rather lower etching resolution. For the latter case, the confined etchant layer technique(CELT) has been employed to improve the etching resolution. i. e., a certain redox couple which can consume the etchant homogeneously and rapidly was added to the solution. The homogeneous scavenging effect confined the etchant within a narrow layer around the electrode surface and much improved etching resolution was achieved. Using the CELT and a needle-shaped microelectrode, an etching spot of several micro-meters was obtained at silicon wafer surface.     

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     

The coupling effect of slow-rate mechanical motion on the confined etching process in electrochemical mechanical micromachining

By introducing the mechanical motion into the confined etchant layer technique (CELT), we have developed a promising ultra-precision machining method, termed as electrochemical mechanical micromachining (ECMM), for producing both regular and irregular three dimensional (3D) microstructures. It was found that there was a dramatic coupling effect between the confined etching process and the slow-rate mechanical motion because of the concentration distribution of electrogenerated etchant caused by the latter. In this article, the coupling effect was investigated systemically by comparing the etchant diffusion, etching depths and profiles in the non-confined and confined machining modes. A two-dimensional (2D) numerical simulation model was proposed to analyze the diffusion variations during the ECMM process, which is well verified by the machining experiments. The results showed that, in the confined machining mode, both the machining resolution and the perpendicularity tolerance of side faces were improved effectively. Furthermore, the theoretical modeling and numerical simulations were proved valuable to optimize the technical parameters of the ECMM process.     

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.     

Effects of acid etching on the structure of PtNi catalyst and total exposed active sites

The integration technology of hydrogen preparation–hydrogen storage not only can utilize hydrogen energy efficiently but also can improve the selectivity of the electrode maximally. In the present work, the structure and composition of the PtNi catalyst was characterized by X-ray diffraction (XRD); and its electrochemical properties, morphology, and surface binding energy were analyzed by cyclic voltammetry (CV) and linear scanning voltammetry (LSV), scanning electron microscopy equipped with energy-dispersive spectrometry (SEM-EDS), and X-ray photoelectron spectroscopy (XPS), respectively. The effects of different acid etching treatments (e.g., etching time, etchant concentration, and etching temperature) on the structure and surface active sites were investigated by the orthogonal experiment. The experimental results reveal that after etching with 0.5 mol/L of perchloric acid for 0.5 h at 60°C, the electrode weight loss of the PtNi catalyst is mainly attributed to the large loss of Ni atoms in film layer. This results in the reduced alloy phase in film layer and the appearance of Pt characteristic diffraction peak. The relative content of Pt on the surface of the film electrode increases significantly, and the total number of active sites also increases correspondingly. The binding energy of Pt4f_7/2 decreases by 0.19 eV, and the number of active sites involved in hydrogen release decreases, indicative of the reduced promotion effect of the PtNi catalyst on hydrogen release.     

铝阳极氧化膜阻挡层的去除方法

多孔型铝阳极氧化膜常被用作制备纳米阵列材料的模板,然而阻挡层的存在却在很多方面制约了其应用.为此,已经提出了各种不同的方法来去除阻挡层.本文将这些方法分为2类,即剥离氧化膜去阻挡层和不剥离氧化膜去阻挡层.前者包括化学腐蚀法、干蚀法、电解剥离法;后者包括阶梯降压法、高电流击穿法、电化学法和有多孔铝支撑的化学溶解法.其中,化学腐蚀法和干蚀法的工艺条件已相当成熟,得到了广泛应用,而其它几种方法还多处于实验室研究阶段.由于氧化膜脆性很大,因此,不剥离氧化膜原位去除阻挡层的方法具有更大的实用价值.