国防科学技术大学硕士学位论文硅的各向异性湿法腐蚀工艺及其在微纳结构中的应用研究姓名:陈骄申请学位级别:硕士专业:机械工程指导教师:吴学忠2010-11国防科学技术大学研究生院硕士学位论文第i页摘要硅的各向异性湿法腐蚀是硅片微机械加工的重要技术之一,它被广泛地应用于在硅衬底上加工各种各样的微结构,如膜结构、凹槽结构、悬臂梁等,近年来也被用于很多纳米结构的制造。本文以{110}、{111}和{100}三种类型硅的各向异性湿法腐蚀为研究对象,对腐蚀结构及其变化规律、腐蚀速率、腐蚀形貌和粗糙度等特性进行了研究,并制作了相应的微结构和纳米孔腔结构阵列。具体内容如下:1.详细介绍了单晶硅的晶体结构和硅的各向异性湿法腐蚀工艺,根据各种腐蚀剂的特性,选择TMAH溶液作为本文的各向异性湿法腐蚀剂。介绍了几种典型的湿法腐蚀模型,探讨了各向异性湿法腐蚀机理,并以此为基础设计了实验流程和方案。2.通过不同形状掩膜窗口的湿法腐蚀实验对比,经实验结果和理论分析,分别得出三种晶向硅的腐蚀结构变化规律,这为不同形貌的纳米硅腔阵列的制作打下了基础。通过在TMAH溶液中加入添加剂(过硫酸铵或IPA等)的对比实验,研究了硅的腐蚀速率、腐蚀形貌特征和粗糙度等特性,表明了过硫酸铵和IPA都能显著改善硅腐蚀表面的质量,且都会不同程度地降低腐蚀速率。探讨了硅的预腐蚀技术,它可以用来制作更多形貌的硅腔结构。3.根据{110}硅湿法腐蚀可得到70.5°角的倾斜结构和垂直侧壁的特性,初步研究了一种基于{110}硅的音叉式微机械陀螺的湿法腐蚀,分析结构误差并提出修正方案;根据{111}和{100}硅湿法腐蚀可分别得到八面体型腐蚀腔和倒金字塔型腐蚀腔的特性,分别制作了基于{111}硅的八面体型纳米孔腔结构阵列和基于{100}硅的倒金字塔型纳米孔腔结构阵列,这为金属纳米结构阵列的制造提供了有效的模版。主题词:各向异性湿法腐蚀硅微机械加工TMAH腐蚀特性{111}硅{110}硅{100}硅纳米孔腔结构阵列国防科学技术大学研究生院硕士学位论文第ii页ABSTRACTAnisotropicwetetchingofsiliconisoneofthemostimportanttechniquesinsiliconmicromachining,whichhasbeenextensivelyemployedtofabricateawidevarietyofmicro-structuresincludingmembranes,grooves,suspendedbeams,etc,andalsoutilizedasoneoftheeffectiveapproachsinthefabricationofnano-structuresinrecentyears.Inthisdissertation,anisotropicwetetchingof{110},{111}and{100}siliconarestudiedsystematically,includingtheetchedstructuresandtheirchanginglaws,etchingrates,etchingmorphologyandsurfaceroughness.Thecorrespondingmicro-structureandnanoporecavityarrayshavebeenmade.Theresearchresultsareshownasfollows:1.Thecrystalstructureandanisotropicwetetchingtechnologyofthemonocrystallinesiliconareintroduced.Accordingtothepropertiesofdifferentetchants,TMAHisselectedasthemainetchantinthiswork.Bythreetypicaletchingmodels,themechanismofanisotropicwetetchingofsiliconisanalyzed.Onthebasisofthemechanismandthecrystallographicproperties,theexperimentalprocessandprogramaredesigned.2.BycomparativeexperimentsunderetchingmaskwindowsofdifferentshapesinTMAHsolutions,thechanginglawsofetchedstructuresareobtainedrespectivelybyexperimentalresultsandtheoreticalanalysis,whichlayafoundationforthefabricationofnanoporecavityarrays.TheetchingcharacteristicsinTMAHsolutionwithdifferentsurfactants(ammoniumpersulfate,IPA,etc.)arealsodiscussedindetail,anditisfoundthatammoniumpersulfateandIPAcanimprovethequalityoftheetchedsurfaceremarkablywhileetchingratesdecreasetoacertianextent.Thenthepre-etchingtechniquesarebrieflydiscussed,whichprovideawaytomakemorespecialetchedcavities.3.Basedonavailabletiltedstructureswiththeincliningangleof70.5°andverticalwallsbyanisotropicwetetchingof{110}silicon,anovelmicromachinedtuningforkgyroscopeispreliminarilystudied,andafteranalyzingthestructuralerror,acorrectionschemeisproposed.Andbasedontheavailableoctahedralcavitybyetchingof{111}siliconandtheinvertedpyramidalcavityby{100}silicon,twocorrespondingnanoporecavityarraysarefabricatedseparately,whichprovideeffectivetemplatesforthefabricationofmetallicnanostructurearrays.KeyWords:AnisotropicwetetchingSiliconmicromachiningTMAHEtchingcharacteristics{111}silicon{110}silicon{100}siliconNanoporecavityarray国防科学技术大学研究生院硕士学位论文第IV页图目录图1.1腐蚀速率与KOH腐蚀剂浓度的关系............................................................1图1.2KenjiTokoro等人的腐蚀实验装置................................................................2图1.3O.Tabata等人的硅湿法腐蚀实验结果...........................................................2图1.4WerasakSonphao等人的腐蚀实验结果.........................................................3图1.5YiWeiXu、AronMichel等人的腐蚀实验结果............................................3图1.6A.Merlos和M.C.Acero等人的腐蚀实验结果............................................4图1.7贾翠萍和董玮等人的腐蚀实验研究...............................................................4图1.8司俊杰等人的腐蚀实验结果...........................................................................5图1.9电容式微机械麦克风的结构图.......................................................................6图1.10高深宽比的梳状微致动器...............................................................................6图1.11V型槽硅微通道冷却器主要部件示意图.......................................................6图1.12扫描探针显微镜的探针阵列...........................................................................7图1.13Chih-HungSun和NicholasC.Linn等人制作的纳米结构阵列...................8图1.14湿法腐蚀可制备的几种结构特征的金属纳米结构阵列...............................9图2.1硅的面心立方晶系中的一些重要的晶面及密勒指数.................................11图2.2单晶硅的常见晶面.........................................................................................12图2.3硅片的主、次定位面.....................................................................................13图2.4(a)硅晶体的单元结构(b)硅的晶体结构......................................................13图2.5硅晶体沿典型方向的晶格截面.....................................................................14图2.6硅晶体三个主要晶面的原子排列示意图.....................................................14图2.7硅晶体三个主要晶面的硅原子化学键示意图.............................................14图2.8硅的各向同性与各向异性湿法腐蚀截面示意图.........................................15图2.9硅/电解液界面的能带模型[5](上图为p型硅,下图为n型硅).............19图2.10{100}、{111}面上的化学键.........................................................................20图2.11硅湿法腐蚀的详细工艺流程.