半导体的化学刻蚀

半导体的化学刻蚀，俗称湿法刻蚀，它是半导体器件制作中的一个重要工艺，按照化学作用的原理，它可分为化学反应刻蚀、电化学刻蚀和光电化学刻蚀，半导体的化学刻蚀是在众多刻蚀方法中最基本和最终不能全部被取代的一种方法，它在高新技术中有着各种挂用途，如选择准刻蚀、各向异性刻蚀和计算机控制无掩模刻蚀等。     

银辅助化学刻蚀半导体材料

微电子器件的发展趋势是小型化和多功能化,这就对半导体材料的加工技术提出了更高的要求。与传统的加工技术相比,近年发展起来的贵金属粒子辅助化学刻蚀半导体材料制备微结构技术因操作简单、不需要精密设备、反应迅速和可批量生产等优点引起了国内外学者的广泛关注。本文以Si为主,详细介绍了Ag辅助化学刻蚀半导体材料的机理、反应现象及影响因素,总结了各种微结构的制备技术及其应用。此外,对Ge,Si1-xGex和GaAs等其他半导体材料的贵金属粒子辅助化学刻蚀技术也进行了综述。同时分析了贵金属粒子辅助化学刻蚀半导体目前存在的问题,并对未来的研究方向进行了展望。     

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H3PO4液层侧面红外热像研究YBCO高温超导薄膜的激光辅助刻蚀特性

利用红外热像实时监测系统,获取钇钡铜氧激光辅助化学刻蚀中H₃PO₄液层的侧面红外热像,研究了其溶液温度分布与热对流特性,并对红外监测数据与钇钡铜氧薄膜激光化学刻蚀特性的关系进行了分析.主要实验结论包括:红外灰度图可真实反映溶液的温度分布和热对流情况,为激光化学刻蚀的热环境分析提供有价值的红外监测数据;通过任意时刻钇钡铜氧表面生成热流所到达高度的分布情况和该时刻的红外灰度图,分析出钇钡铜氧薄膜表面各区域的腐蚀启动先后和刻蚀程度差异等重要信息,为钇钡铜氧及其它材料的激光化学刻蚀特性的实时监测提供了一种新的技术手段.     

铝合金表面用化学刻蚀和阳极氧化法制备的超疏水膜层的耐蚀性能

通过化学刻蚀和阳极氧化在AA2024铝合金表面制备超疏水表面。当化学刻蚀时间超过3 min时,表面在很宽pH值范围内显示出水静态接触角大于150°。SEM和AFM照片表明化学刻蚀时间决定了试样表面形貌和粗糙度。FTIR用来研究氟硅烷(G502)与AA2024表面的结合。结果说明FAS(氟硅烷)分子与铝合金表面的三氧化二铝发生反应,并在阳极氧化膜层表面展示出优异的结合性能。超疏水表面的耐腐蚀性能通过在质量分数为3.5%的NaCl溶液中进行动电位极化和交流阻抗(EIS)测试。电化学测试结果和等效电路模型显示出超疏水表面显著改善抗腐蚀性能。     

金属辅助化学刻蚀法制备硅纳米线及应用

金属辅助化学刻蚀是近些年发展起来的一种各向异性湿法刻蚀,利用该方法可以制备出高长径比的半导体一维纳米结构。 本文综述了金属辅助化学刻蚀法可控制备硅纳米线的最新进展,简要概述了刻蚀的基本过程与机制,重点阐述了基于不同模板的金属辅助化学刻蚀可控制备高度有序、高长径比的硅纳米线阵列的具体流程与工艺,并介绍了其在锂离子电池、太阳能电池、气体传感检测和仿生超疏水等方面的潜在应用,探讨了目前存在的问题及其今后的研究发展方向。     

银辅助刻蚀单晶硅

结合高中化学原电池、氧化还原反应以及银镜反应等知识,介绍两种沉积银粒子辅助刻蚀单晶硅技术的基本原理,供一线高中化学教师用于扩展高中生的化学知识,帮助学生了解化学前沿。     

n型砷化镓微区光电化学腐蚀过程

在n-GaAs电解液界面,用聚焦He-Ne激光照射, 使n-GaAs表面发生微区光电化学腐蚀, 用计算机控制步进马达, 使试样在X-Y二维方向扫描移动, 能在晶片上得到刻蚀点直径2 μm的刻蚀图案. 研究了激光相对光强, KOH、H_2SO_4、KCl等刻蚀剡的浓度, 光腐蚀的时间, 电极电位等因素对腐蚀点的直径和深度的影响, 通过实验数据找出腐蚀过程的规律, 并用光电化学原理进行解释.     

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     

光诱导约束刻蚀体系中的TiO_2纳米管阵列光电极上Cu的沉积及抑制

光诱导约束刻蚀可作为一种无应力的化学平坦化方法用于Cu的抛光。我们发现在光诱导约束刻蚀工件Cu的过程中,工具表面的TiO_2纳米管上可能出现Cu沉积。通过扫描电子显微镜及其能谱,X射线光电子能谱等方法分析其沉积形貌和成分组成,探究在工具-工件之间的微纳尺度液层中Cu光催化还原沉积的机制,并在模拟液中研究Cu沉积对刻蚀体系的影响。探究引入搅拌、加入络合剂对TiO_2纳米管表面Cu的沉积的抑制,并考察抑制措施对于工件Cu刻蚀的影响。结果表明Cu沉积会增强TiO_2纳米管光电极的光催化性能,但随着沉积量的增加,增强机制会发生变化;在尝试抑制Cu沉积时也发现改善传质以抑制Cu沉积的同时也会带来工件Cu的刻蚀增强;采用添加络合剂结合改善传质的方法有望在抑制Cu沉积的同时提高平坦化效果。所以抑制方法和条件的选择需兼顾对工具-工件之间微纳液层中的多个化学和传质过程的影响。这些研究对于进一步优化光诱导约束刻蚀体系及其在化学平坦化中的应用有重要的指导意义。     

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.     

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.     

A preliminary study on chemical micro-machining of complex three-dimensional patterns on silicon substrates

Chemical micro-machining of complex 3-dimensional (3-D) patterns of silicon substrates was preliminarily explored by the confined etchant layer technique (CELT). Through systematic investigation, we demonstrated that cysteine as a scavenger and Br₂ as an etchant can be used to etch silicon substrates. The CELT has the potential to develop into a new means of micro-machining complex 3-D patterns on silicon substrates. However, due to the highly corrosive property of the chemicals used for the silicon etched system, great effort must be made to overcome these problems including the mold electrode with high chemical stability.Dedicated to Professor Gygy Horyi on the occasion of his 70th birthday     

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.     

Fabrication of superhydrophobic surfaces by dislocation-selective chemical etching on aluminum, copper, and zinc substrates

A surface roughening method by simple chemical etching was developed for the fabrication of superhydrophobic surfaces on three polycrystalline metals, namely aluminum, copper, and zinc. The key to the etching technique was the use of a dislocation etchant that preferentially dissolves the dislocation sites in the grains. The etched metallic surfaces, when hydrophobized with fluoroalkylsilane, exhibited superhydrophobic properties with water contact angles of larger than 150 degrees, as well as roll-off angles of less than 10 degrees for 8-microL drops. Also, the dislocation etching concept introduced here may be helpful in the fabrication of superhydrophobic surfaces on other polycrystalline substrates.     

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.     

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.     

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.