Electrochemical Micromachining as an Enabling Technology for Advanced Silicon Microstructuring

Based on previous theoretical and experimental results on the electrochemical etching of silicon in HF‐based aqueous electrolytes, it is shown for the first time that silicon microstructures of various shapes and silicon microsystems of high complexity can be effectively fabricated in any research lab with sub‐micrometer accuracy and high aspect ratio values (about 100). This is well beyond any up‐to‐date wet or dry microstructuring approach and is achieved using a wet etching, low‐cost technology: silicon electrochemical micromachining (ECM). Dynamic control of the etching anisotropy (from 1 to 0) as the electrochemical etching progresses allows the silicon dissolution to be switched in real‐time from the anisotropic to the isotropic regime and enables advanced silicon microstructuring to be achieved through the use of high‐aspect‐ratio functional and sacrificial structures, the former being functional to the microsystem operation and the latter being sacrificed for accurate microsystem fabrication. World‐wide dissemination of the ECM technology for silicon microstructuring is envisaged in the near future, due to its low cost and high flexibility, with high‐potential impact on, though not limited to, the broad field of microelectronics and microfabrication.     

Dopant-selective photoenhanced wet etching of GaN

A dopant-selective photoelectrochemical wet etching process for GaN is described. The process utilizes KOH solution and Hg arc lamp illumination to achieve selective etching of n-type GaN with respect to intrinsic and p-type GaN. An intrinsic GaN etch-stop layer as well as the selective undercutting of a buried n-type layer within a p-n GaN homostructure are demonstrated.     

一种控制硅深刻蚀损伤方法的研究

提出了提高硅深反应离子刻蚀的新方法。该方法在硅的侧壁PECVD淀积SiO2,硅的底部采用热氧化的方法形成SiO2。由于在刻蚀中硅与SiO2的刻蚀选择比为120∶1~125∶1,因此SiO2层可以抑制在硅-玻璃结构的刻蚀中出现的lag和footing效应,扫描电镜结果也证明,采用改进工艺后的硅结构在经过长时间的过刻蚀后仍然保持了完整性。硅陀螺测试结果也证明了改进工艺的正确性。     

体微加工技术在MEMS中的应用

微机电系统(MEMS)技术的基础是由微电子加工技术发展起来的微结构加工技术，包括表面微加工技术和体微加工技术。其中体微加工技术是微传感器、微执行器制造中最重要的加工技术。该文主要介绍以加工金属、聚合物以及陶瓷为主的LIGA技术，先进硅刻蚀技术(ASE)和石英晶体深槽湿法刻蚀技术。最后给出用LIGA技术和牺牲层技术制作微加速度传感器的例子。     

Metal‐Catalyzed Etching of Vertically Aligned Polysilicon and Amorphous Silicon Nanowire Arrays by Etching Direction Confinement

A systematic study of metal‐catalyzed etching of (100), (110), and (111) silicon substrates using gold catalysts with three varying geometrical characteristics: isolated nanoparticles, metal meshes with small hole spacings, and metal meshes with large hole spacings is carried out. It is shown that for both isolated metal catalyst nanoparticles and meshes with small hole spacings, etching proceeds in the crystallographically preferred <100> direction. However, the etching is confined to the single direction normal to the substrate surface when a catalyst meshes with large hole spacings is used. We have also demonstrated that the metal catalyzed etching method when used with metal mesh with large hole spacings can be extended to create arrays of polycrystalline and amorphous vertically aligned silicon nanowire by confining the etching to proceed in the normal direction to the substrate surface. The ability to pattern wires from polycrystalline and amorphous silicon thin films opens the possibility of making silicon nanowire array‐based devices on a much wider range of substrates.     

Fabrication of Single‐Crystalline Silicon Nanowires by Scratching a Silicon Surface with Catalytic Metal Particles

A novel strategy for preparing large‐area, oriented silicon nanowire (SiNW) arrays on silicon substrates at near room temperature by localized chemical etching is presented. The strategy is based on metal‐induced (either by Ag or Au) excessive local oxidation and dissolution of a silicon substrate in an aqueous fluoride solution. The density and size of the as‐prepared SiNWs depend on the distribution of the patterned metal particles on the silicon surface. High‐density metal particles facilitate the formation of silicon nanowires. Well‐separated, straight nanoholes are dug along the Si block when metal particles are well dispersed with a large space between them. The etching technique is weakly dependent on the orientation and doping type of the silicon wafer. Therefore, SiNWs with desired axial crystallographic orientations and doping characteristics are readily obtained. Detailed scanning electron microscopy observations reveal the formation process of the silicon nanowires, and a reasonable mechanism is proposed on the basis of the electrochemistry of silicon and the experimental results.     

单晶硅各向异性湿法刻蚀的研究进展

单晶硅各向异性湿法刻蚀是制作硅基微电子机械系统(MEMS)器件的重要步骤之一,由于具有刻蚀均匀性好、批量大、成本低的优点而深受关注。首先回顾了单晶硅各向异性湿法刻蚀的刻蚀机理,比较了三种常用各向异性刻蚀液的刻蚀性质,讨论了刻蚀形状的控制技术。然后着重介绍了表面活性剂修饰的单晶硅各向异性湿法刻蚀速率和刻蚀表面光滑度等特性,以及面向MEMS应用的基于该刻蚀技术的各种微纳新结构;分析了表面活性剂分子在刻蚀过程中的作用,强调了表面活性剂分子在单晶硅表面的吸附性对改变刻蚀表面的物理性质的重要性。最后在此基础上,归纳了单晶硅各向异性湿法刻蚀的发展情况,探讨了其未来的发展方向。     

硅各向同性深刻蚀中的多层掩模工艺

掩模制备是硅各向同性刻蚀中的一项重要工艺.要实现深刻蚀,掩模必须满足结构致密、强度大及抗腐蚀性好的要求.一般光刻胶掩模无法在刻蚀液中较长时间地保持其掩蔽性能,很难实现深刻蚀;而金属掩模也容易出现针孔及裂纹等缺陷.因此提出使用Su-8负性光刻胶结合铬金属制备多层掩模.这种掩模结构制备工艺简单,经济实用;提高了掩模在高速刻蚀时的掩蔽性能,实现了深刻蚀.实验表明,其能满足300μm以上深刻蚀的要求,可用于硅及玻璃等材料的微加工.     

准分子激光电化学刻蚀硅的刻蚀质量研究

为了解决现有硅刻蚀工艺中存在的刻蚀质量等问题,采用激光加工技术和电化学加工技术相结合的工艺对硅进行了刻蚀,研究了该复合工艺的工艺特性。实验中采用248nm-KrF准分子激光作光源聚焦照射浸在KOH溶液中的阳极n-Si上,实现激光诱导电化学刻蚀。在实验的基础上,研究了激光电化学刻蚀Si的刻蚀孔的基本形貌,并对横向刻蚀和背面冲击等质量问题进行了分析。结果表明,该工艺刻蚀的孔表面质量好、垂直度高;解决了碱液中Si各向异性刻蚀的自停止问题,具有加工大深宽比微结构的能力;也具有不需光刻显影就能进行图形加工的优越性。     

利用湿法刻蚀的方式制备黑硅

采用一种简便的方法制备出具有很好光吸收性能的黑硅材料,利用化学气象沉积和光刻的方式在硅片（100）表面形成圆形Si3N4掩膜,然后采用两种湿法刻蚀相结合方式来制备黑硅材料。首先采用碱刻蚀的方式对硅片进行各向异性刻蚀,刻蚀完成后在硅片表面形成尖锥形貌;后期利用金纳米颗粒作为催化剂,采用酸刻蚀的方式对硅片表面进行改性,在硅片表面形成多孔结构。这种黑硅材料在250～1000nm波段的光吸收率可以达到95％以上。     

多晶黑硅表面微结构对电池效率的影响

采用Ag离子辅助化学刻蚀法制备了多晶黑硅薄片,使用NaOH溶液处理多晶黑硅表面,增大其表面纳米孔直径,使SiNx薄膜能够均匀覆盖整个黑硅表面,提高黑硅的钝化效果,进而提高多晶黑硅电池光电转化效率.通过反射谱仪、扫描电子显微镜(SEM)、太阳电池测试系统等测试和表征不同扩孔时间对多晶黑硅各方面性能的影响.结果表明:未被NaOH扩孔处理的多晶黑硅的反射率最低,为5.03％,多晶黑硅太阳电池的光电转化效率为16.51％.当多晶黑硅被NaOH腐蚀40 s时,反射率为10.01％,电池的效率为18.00％,比普通多晶硅太阳电池的效率高2.19％,比未被扩孔处理的多晶黑硅太阳电池的效率高1.49％.     

单晶硅表面机械划痕和氧化层在湿法刻蚀中的掩膜行为对比研究

摩擦诱导选择性刻蚀具有加工成本低、流程简单、低加工损伤等优势,是实现单晶硅表面微纳米结构构筑的重要途径.为探究摩擦诱导机械划痕在单晶硅表面微纳加工中的掩膜行为,实验研究了选择性刻蚀中机械划痕掩膜下的线/面结构形貌与高度特征,并将其与氧化层掩膜进行对比.实验发现机械划痕掩膜性能与氧化层无明显差异,并讨论了两种不同掩膜下选择性刻蚀中纳米结构的形貌演变机理.最后,实现了采用不同掩膜的复合纳米图案加工.研究结果可为基于摩擦诱导选择性刻蚀的单晶硅表面高质量可控加工提供依据.     

低温酸刻蚀对多晶硅表面织构化的影响

采用低温酸刻蚀,通过优化HF-HNO3-H2O腐蚀溶液体系配比及相关工艺参数,在多晶硅材料的表面制备了绒面结构,并进行SEM表面形貌分析和反射谱的测试。结果表明,低温刻蚀比常温刻蚀在生产工艺中更有利于控制反应速度,从而得到效果较好的绒面结构。研究中发现,在不同HF-HNO3-H2O腐蚀溶液体系配比中,温度对反应速率的影响有较大差异,当HNO3含量相对较低时,低温刻蚀工艺有较好的效果。所得最佳绒面制备方案为:酸腐蚀溶液体系配比为VHF∶VHNO3∶VH2O=1∶4∶2,温度为3℃,反应速率控制为2.6μm/min。该方案已在25MW多晶硅太阳电池生产线上实施,不增加工艺难度和生产成本,适合于工业生产。     

异丙醇在硅碱性腐蚀液中的作用

在硅单晶的碱性腐蚀过程中,往往由于碱性腐蚀液对单晶硅的腐蚀速率过快,从而增大了硅单晶片表面的粗糙度。异丙醇有着减缓腐蚀速率的功效因而降低了硅单晶片表面的粗糙度。主要讨论了异丙醇在碱性腐蚀液中的作用原理并对腐蚀实验结果做了分析。     

一维纳米硅光子晶体的制备与优化

采用双槽电化学腐蚀法制备了纳米多孔硅,主要研究了腐蚀时间和腐蚀电流对重掺杂p型(100)硅衬底上制备的多孔硅层有效光学厚度的影响,采用U-4100光谱仪、场发射扫描电子显微镜(FESEM)技术对所制备的多孔硅光子晶体的结构和有效光学厚度进行了分析表征。研究结果表明,通过合理地选择腐蚀时间和腐蚀电流,可以比较精确地制备特定有效光学厚度的多孔硅薄膜,此方法可广泛应用于纳米多孔硅光子晶体的制备中。     

Effect of Protective Layer and Etch Process on Silicon Molded Micro Peltier Arrays

We used silicon molding and examined the protective layer on a silicon molded Peltier array. Both a large p-type array and n-type array were created with the protective layer. Because the conventional bismuth-antimony-telluride (BiSbTe) alloys react with XeF₂ etching gas rapidly, we need to place the protective layer at the interface between the silicon and the thermoelectric material using the water vapor thermal oxidization method. As the xenon difluoride selective etching ratio of silicon and SiO₂ is about 100:1, the protective layer is damaged if the removal ratio of silicon is high and the etching process time is long. Next we examined a new method involving both an anisotropic process using deep reactive ion etching (DRIE) and an isotropic process using XeF₂ etching, and we formulated an etching process that causes no damage to the protective layer.     

各向异性腐蚀表面粗糙度的"应力模型"

微电子机械系统(MEMS)关键的体加工工艺——各向异性腐蚀的样品表面会出现一定程度的不平面貌，针对这一现象提出了“应力模型”，用来解释腐蚀后表面粗糙度出现的物理机制，对表面激活能、腐蚀液激活能等物理概念进行了分析，提出了腐蚀表面粗糙度的计算公式，解释了各向异性腐蚀与表面形貌相关的实验现象。     

直拉重掺硼硅单晶的碱腐蚀特性研究

直拉重掺硅硼单晶作为重要的外延衬底材料,具有其优越的特性。由于其硬度大,杂质含量高．在抛光片的加工过程中表现出腐蚀速率慢、表面均匀性差等特点,不利于硅片腐蚀减薄和抛光清洗等。研究了直拉重掺硅硼单晶的碱性腐蚀速率随腐蚀液温度和浓度变化趋势,从直拉重掺硅硼单晶化学反应的微观角度解释了这种变化规律,在此基础上,研究了不同的添加剂对腐蚀速率和表面均匀性的影响,从理论和实验两方面证实了,在腐蚀液中加入碱性氧化剂有利于腐蚀速率的提高,并能有效改善硅片的表面均匀性。     

硅场发射微尖阵列的制备工艺研究

主要阐述了用于场发射硅锥阵列的制备工艺,实验中在101.6mm(4in)的n型(100)晶向低阻硅片上氧化出一层厚度约为650nm的氧化层,再用投影曝光的方法光刻出边长2μm,间距4μm的方形掩膜。再分别使用反应离子刻蚀(RIE)技术和湿法刻蚀制备硅锥阵列,干法刻蚀并结合氧化削尖工艺得到了曲率半径为90nm左右且具有良好一致性的尖锥,湿法刻蚀同样得到较理想的结果。     

硅各向异性腐蚀的原子级模拟

应用原子级模型中的随机CA算法，针对硅材料和具体的工艺特点，构造了相应的函数，并在此基础上编制了应用软件——SSAE．该软件可独立运行，能够模拟出硅在KOH中不同腐蚀条件下腐蚀的过程和结果，并且克服了其他采用原子级模型的模拟软件中常出现的边界模糊等缺点．该结果与其他软件和实验结果相比，较为一致，并且该软件具有占用系统资源少、运行时间快等优点，具有一定的实用价值．