CN101978469B - 具有受限于以均等优先湿润两嵌段的上界面的嵌段共聚物膜的热退火 - Google Patents

具有受限于以均等优先湿润两嵌段的上界面的嵌段共聚物膜的热退火 Download PDF

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CN101978469B
CN101978469B CN2009801103820A CN200980110382A CN101978469B CN 101978469 B CN101978469 B CN 101978469B CN 2009801103820 A CN2009801103820 A CN 2009801103820A CN 200980110382 A CN200980110382 A CN 200980110382A CN 101978469 B CN101978469 B CN 101978469B
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block copolymer
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substrate
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CN101978469A (zh
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丹·B·米尔沃德
蒂莫西·奎克
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Micron Technology Inc
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Abstract

本发明提供使用自我组装嵌段共聚物以制造亚光刻纳米级微结构的方法、和自所述方法形成的膜及装置。

Description

具有受限于以均等优先湿润两嵌段的上界面的嵌段共聚物膜的热退火
技术领域
本发明实施例涉及制造自我组装嵌段共聚物薄膜的方法和自所述方法产生的装置。
背景技术
随着纳米级机械、电学、化学和生物装置及系统的加速发展，人们需要制造纳米级装置和组件的新颖方法和材料。随着半导体特征的尺寸缩小至通过常规光刻不易获得的大小，与导线进行电接触已变成一个重大挑战。光学光刻加工方法难以制造低于60纳米级别的结构和特征。自我组装二嵌段共聚物的使用为在纳米级尺寸上进行图案化提供另一途径。二嵌段共聚物膜可通过聚合物构成嵌段在退火后(例如，通过在高于所述聚合物的玻璃转变温度时实施热退火或通过溶剂退火)进行微相分离而自发地组装成周期性结构，从而在纳米级尺寸上形成有序结构域。
可通过二嵌段共聚物中AB嵌段的分子量和体积分率来控制膜形态(包含微相分离结构域的大小和形状)以主要产生薄片状、圆柱体或球形形态。例如，在二嵌段聚合物中两种嵌段(AB)的体积分率的比例大于约80∶20时，嵌段共聚物膜可微相分离并自我组装成周期性球形结构域，其中聚合物A的基质包围聚合物B的球体。对于两嵌段的比例介于约60∶40与80∶20间的情形来说，所述二嵌段共聚物在聚合物A基质内组装成周期性六方形密堆积或蜂窝状阵列的聚合物B圆柱体。对于介于约50∶50与60∶40间的比例来说，可形成所述嵌段的薄片状结构域或交替条带。结构域的大小通常介于5-50nm之间。
自我组装嵌段共聚物(BCP)在光刻中的许多应用需要自我组装结构域垂直于衬底进行定向，其中两种结构域均在空气界面处进行湿润和暴露。利用选择性去除一种聚合物嵌段以形成蚀刻掩膜，然后可将垂直定向的空隙结构用于蚀刻下伏衬底。
大多数BCP(例如，PS-b-PVP等)在空气或真空中的常规热退火通常会使得一种嵌段优先湿润空气蒸气界面。称作区域退火的热退火变化形式可提供快速自我组装(例如，约数分钟)，但仅对少数具有均等湿润空气蒸气界面的聚合物结构域的BCP(例如，PS-b-PMMA、PS-b-PLA)有效。BCP的溶剂退火已用于产生与衬底垂直定向的自我组装结构域，但所述方法通常极慢(通常约数天)、且可需要大量溶剂。典型溶剂退火是通过在25℃下将BCP膜暴露于饱和溶剂气氛达至少12小时(通常更长)来实施。
有利地提供可解决所述问题的有序纳米结构阵列的膜的制造方法。
发明内容
参照附图，下列说明提供本发明实施例的装置和方法的说明性实例。此说明仅出于阐明本发明目的而非出于对本发明加以限制的目的。
在本申请案的上下文中，术语“半导体衬底”或“半导电性衬底”或“半导电性晶片片段”或“晶片片段”或“晶片”应理解为意指包括半导体材料的任一构造，包含但不限于体型半导电性材料(例如，半导体晶片(仅含半导电性材料或为上面包括其它材料的组合件))和半导电性材料层(仅含半导电性材料或包括其它材料的组合件)。术语“衬底”是指任一支撑结构，包含但不限于上述半导电性衬底、晶片片段或晶片。
本文所用“Lo”为结构的固有周期性或间距值(区段周期或重复单元)，所述结构在退火后会由自我组装(SA)嵌段共聚物自我组装。本文所用“LB”为嵌段共聚物与其一或多种构成均聚物的掺合物的周期性或间距值。“L”在本文中用以指示所述嵌段共聚物或掺合物中各圆柱体的中心至中心的圆柱体间距或间隔，且对于纯净嵌段共聚物来说等于“Lo”，且对于共聚物掺合物来说等于“LB”。
在本发明实施例中，通过引导嵌段共聚物自我组装来制备聚合物材料(例如，膜、层)，其中两种聚合物结构域均位于空气界面处。嵌段共聚物材料在退火后通过聚合物构成嵌段的微相分离自发地组装成周期性结构，从而在沟槽内以纳米级尺寸形成垂直定向圆柱体的有序结构域。
参照图1-8来说明根据本发明实施例制造可界定一维(1-D)纳米级、垂直定向圆柱体阵列的自我组装嵌段共聚物材料的方法。
所述实施例涉及在溶剂气氛下圆柱状嵌段共聚物的热退火。退火是与使用以光刻界定的沟槽作为引导的制图外延技术组合实施，所述沟槽具有由对两种聚合物嵌段呈中性湿润的材料组成的底面、和对一种聚合物嵌段呈优先湿润的侧壁和端部，且所述侧壁和端部可用作限制来诱导嵌段共聚物在聚合物基质中自我组装成与沟槽底面垂直定向且与沟槽侧壁对齐的有序1-D单行圆柱体阵列。在一些实施例中，可在每一沟槽中形成两行或两行以上垂直定向的圆柱体。
附图说明
在下文中参照下列附图阐述本发明实施例，所述附图仅用于说明目的。在下列所有视图中，在图式中使用多个参考标号，并且在所述多个视图和说明书中通篇使用的相同参考标号指示相同或类似部件。
图1绘示衬底的一部分在本揭示内容实施例的初级处理阶段的图示性俯视平面图，其展示上面具有中性湿润材料的衬底。图1A-1B分别为沿线条1A-1A和1B-1B所取的图1中所描绘衬底的横截面正视图。
图2绘示图1的衬底在后续阶段的图示性俯视平面图，其展示在中性湿润材料上所形成材料层中的沟槽的形成。图2A-2B分别绘示沿线条2A-2A和2B-2B所取的图2中所描绘衬底部分的横截面正视图。
图3绘示衬底的一部分在本揭示内容另一实施例的初级处理阶段的侧视图，其展示在衬底上所形成材料层中具有沟槽的衬底。图4绘示图3的衬底在后续阶段的侧视图，其展示在沟槽内中性湿润材料的形成。
图5为图2的衬底在后续阶段的图示性俯视平面图，其展示沟槽内的嵌段共聚物材料。图5A-5B分别绘示沿线条5A-5A和5B-5B所取的图5中所描绘衬底部分的横截面正视图。
图6-8为图5的衬底在后续阶段的图示性俯视平面图，其展示通过区域退火技术对本发明实施例的一部分膜的退火。图6A-8A分别绘示沿线条6A-6A、7A-7A和8A-8A所取的图6-8中所描绘衬底的横截面正视图，其展示对膜实施区域退火的加热装置的实施例。图6B为沿线条6B-6B所取的图6中所描绘衬底的横截面正视图。
图9为图5的衬底在本发明方法的另一实施例的后续阶段的俯视平面图，其显示在退火期间将非优先湿润材料置于嵌段共聚物材料上。图9A-9B分别为沿线条9A-9A和9B-9B所取的图9中所描绘衬底的横截面正视图。图10A-10B分别为图9A-9B中所示衬底在后续阶段的横截面图，其展示退火后经退火自我组装嵌段共聚物材料和非优先湿润材料的去除。
图11-13为图8的衬底在后续阶段的俯视平面图，其描绘在去除一种聚合物嵌段后使用自我组装嵌段共聚物膜作为掩膜来蚀刻衬底并填充所蚀刻开孔的实施例。图11A-13A分别绘示沿线条11A-11A至13A-13A所取的图11-13中所描绘衬底部分的横截面正视图。图11B-13B分别为沿线条11B-11B至13B-13B所取的图11-13中所描绘衬底的横截面图。
具体实施方式
如图1-1B中所描绘，提供衬底10，其尤其可为硅、氧化硅、氮化硅、氧氮化硅、氧碳化硅。其中进一步描绘，导线12(或其它有源区，例如，半导电区域)位于衬底10内。
在任一所述实施例中，可在衬底中形成单一沟槽或多个沟槽，且其可跨越导线(或其它有源区)阵列的整个宽度。在本发明实施例中，提供具有间距为L的导线12(或其它有源区)阵列的衬底10。在有源区12(例如，导线)上方形成沟槽以便当对嵌段共聚物材料实施退火时每一圆柱体均位于单一有源区12(例如，导线)上方。在一些实施例中，形成多个沟槽，其中每一个相邻沟槽18的端部(24)彼此对准或彼此稍微偏移小于5％L，以使相邻沟槽中的各圆柱体对准并位于相同线路12上方。
在所示实施例中，在衬底10上方形成中性湿润材料14(例如，无规共聚物)。然后，可在中性湿润材料上方形成材料层16(或一或多个材料层)且对其进行蚀刻以形成与导线12阵列垂直定向的沟槽18，如图2-2B中所示。部分材料层16在沟槽外和沟槽之间形成间隔区20。沟槽18具有下述结构：相对侧壁22、相对端部24、底面26、宽度(wt)、长度(lt)和深度(Dt)。
在另一实施例中，可在衬底10′上形成材料层16′，对其进行蚀刻以形成沟槽18′，如图3中所描绘；且然后可在沟槽底面26′上形成中性湿润材料14′，如图4中所示。例如，可将无规共聚物材料沉积至沟槽18′中且使其发生交联以形成中性湿润材料层。随后可去除沟槽外部表面上(例如，间隔区20′上)的材料(例如，未经交联的无规共聚物)。
可使用具有能够以L级别(例如，约10-100nm)进行图案化的暴露系统的光刻工具来形成单个或多个沟槽18(如图所示)。所述暴露系统包含(例如)如此项技术中已知和使用的极紫外光(EUV)光刻、近接X射线和电子束(e-beam)光刻。常规光学光刻可获得(最小)约58nm的特征。
还可使用称作“间距重复”或“间距倍增”的方法来扩展光学光刻技术超越其最小间距的能力，如在(例如)美国专利第5,328,810号(劳瑞(Lowrey)等人)、美国专利第7,115,525号(阿巴切夫(Abatchev)等人)、US 2006/0281266(韦尔斯(Wells))和US 2007/0023805(韦尔斯(Wells))中所述。简单来说，导线图案是以光学光刻方式形成于衬底的上覆消耗性材料层的上覆光阻剂材料中，所述消耗性材料层经蚀刻以形成预留位置或心轴，剥离所述光阻剂，于心轴侧面上形成间隔区，继而去除心轴，从而留下间隔区作为对衬底实施图案化的掩膜。因此，如果初始光学光刻形成界定一个特征和一个间隔的图案，则现在相同宽度可界定两个特征和两个间隔，其中所述间隔由间隔区来界定。因此，通过光学光刻技术可能形成的最小特征大小会有效地降至约30nm或更小。
在沟槽内形成垂直定向纳米圆柱体的单(1-D)阵列或层的因素包含沟槽宽度(wt)和深度(Dt)、拟达成期望间距(L)的嵌段共聚物或掺合物的配方、和沟槽内嵌段共聚物材料的厚度(t)。
随着(例如)通过添加两种构成均聚物来形成三元掺合物而使沟槽宽度(wt)减小和/或嵌段共聚物的周期性(L值)增加，在沟槽中心内两行垂直圆柱体转变为一行垂直圆柱体。沟槽侧壁22在x轴和y轴上的边界条件产生每一沟槽含有“n”个特征(例如圆柱体)的结构。例如，沉积至具有中性湿润底面的75-nm宽沟槽中且具有35-nm间距或L值的嵌段共聚物或掺合物在退火后会产生17.5-nm直径(约0.5*L)垂直圆柱体的Z字形图案，所述垂直圆柱体相对沟槽的长度(lt)方向大约偏移间距距离的半(约0.5*L)，而非产生沿所述沟槽中心与侧壁对准的垂直圆柱体的单直线行。
在所示实施例中，可将沟槽18构造为具有嵌段共聚物的约1.5-2*L(或1.5-2X间距值)的宽度(wt)，从而使约L的浇注嵌段共聚物材料(或掺合物)在退火后可自我组装成单行垂直圆柱体(直径为约0.5*L)，其中，相邻圆柱体的中心至中心间距距离(p)为或约为L。例如，在使用具有约50nm间距值或L的圆柱状嵌段共聚物时，沟槽18的宽度(wt)可为约1.5-2*50nm或约75-100nm。沟槽的长度(lt)为或约为n*L或L的整数倍，通常在约n*10至约n*100nm的范围内(其中，n为特征或结构(例如圆柱体)的数量)。沟槽18的深度(Dt)大于或等于L(Dt＞L)。在相邻沟槽间的间隔区20的宽度可有所变化且通常为约L至约n*L。在一些实施例中，沟槽尺寸为约20-100nm宽(wt)且长度(lt)为约100-25,000nm，深度(Dt)为约10-100nm。
通常以膜形式将固有间距为或约为Lo的自我组装圆柱状嵌段共聚物材料28(或掺和后间距为或约为LB的嵌段共聚物与均聚物的三元掺合物)沉积至沟槽18中(如图5-5B)。
嵌段共聚物(或掺合物)经构造以使所有聚合物嵌段对沟槽底面上的中性湿润材料均具有均等优先。可对嵌段共聚物材料实施构造以提供期望性质，例如，缺陷容限和易显影性和/或一种嵌段的易去除性。在本发明一些实施例中，对嵌段共聚物或掺合物实施构造以便可选择性去除次要结构域。
二嵌段共聚物的实例尤其包含(例如)：聚(苯乙烯)-b-聚(乙烯吡啶)(PS-b-PVP)、聚(苯乙烯)-b-聚(甲基丙烯酸甲酯)(PS-b-PMMA)或其它PS-b-聚(丙烯酸酯)或PS-b-聚(丙烯酸甲酯)、聚(苯乙烯)-b-聚(丙交酯)(PS-b-PLA)、聚(苯乙烯)-b-聚(丙烯酸叔丁酯)(PS-b-PtBA)、和聚(苯乙烯)-b-聚(乙烯-共-丁烯)(PS-b-(PS-共-PB))、聚(苯乙烯)-b-聚(环氧乙烷)(PS-b-PEO)、聚(异戊二烯)-b-聚(环氧乙烷)(PI-b-PEO)、聚(异戊二烯)-b-聚(甲基丙烯酸甲酯)(PI-b-PMMA)、聚(丁二烯)-b-聚(环氧乙烷)(PBD-b-PEO)、在PS与PEO嵌段之间具有诸如三苯基甲基(三苯甲基)醚键等可断裂连接的PS-b-PEO嵌段共聚物(任选地与诸如KCl、KI、LiCl、LiI、CsCl或CsI等稀浓度(例如，约1重量％)盐络合)(张(Zhang)等人，高等材料(Adv.Mater.)2007，19，1571-1576)、掺杂有尺寸小于自我组装圆柱体直径的涂布有PEO的金纳米颗粒的PS-b-PMMA嵌段共聚物(帕克(Park)等人，高分子(Macromolecules)，2007，40(11)，8119-8124)、和具有诸如二巯基等可断裂连接的聚(苯乙烯)-b-聚(2-乙烯吡啶)(PS-b-P2VP)嵌段共聚物，其中在所示实施例中使用PS-b-PVP。可使用其它类型的嵌段共聚物(亦即，三嵌段或多嵌段共聚物)。三嵌段共聚物的实例尤其包含诸如聚(苯乙烯-b-甲基丙烯酸甲酯-b-环氧乙烷)(PS-b-PMMA-b-PEO)等ABC聚合物、和诸如PS-PMMA-PS、PMMA-PS-PMMA和PS-b-PI-b-PS等ABA共聚物。
膜形态(包含微相分离结构域的结构域大小和周期(Lo))可通过嵌段共聚物的链长度(分子量，MW)和二嵌段共聚物的AB嵌段的体积分率加以控制以(主要)产生圆柱形形态。例如，在两种嵌段的体积分率比通常介于约60∶40与80∶20(A∶B)之间时，二嵌段共聚物会微相分离并于聚合物A基质内自我组装成聚合物B的周期性圆柱形结构域。于PS基质中形成约14nm直径圆柱形PVP结构域的圆柱体形成PS-b-PVP共聚物材料(Lo约为28nm)的实例是由约70重量％PS和30重量％PVP组成，总分子量(Mn)为44.5kg/mol。于PS基质中形成约20nm直径圆柱形PMMA结构域的圆柱体形成PS-b-PMMA共聚物材料(Lo＝35nm)的实例是由约70重量％PS和30重量％PMMA组成，总分子量(Mn)为67kg/mol。作为另一实例，总分子量(Mn)为约60.5kg/mol的PS-b-PLA共聚物材料(L＝49nm)可由约71重量％PS和29重量％PLA组成以在PS基质中形成约27nm直径的圆柱形PLA结构域。
可通过(例如)调节嵌段共聚物的分子量来改变所述嵌段共聚物的L值。还可将嵌段共聚物材料调配为包括嵌段共聚物和与所述嵌段共聚物中聚合物嵌段同类型的聚合物的一或多种均聚物(HP)的二元或三元掺合物，从而产生可增大聚合物结构域的大小并增加L值的掺合物。所述掺合物中均聚物的浓度可介于0至约60重量％之间。
三元二嵌段共聚物掺合物的实例为PS-b-P2VP/PS/P2VP掺合物，例如，60重量％的32.5K/12K PS-b-P2VP、20重量％的10K PS、和20重量％的10K P2VP。三元二嵌段共聚物掺合物的另一实例为PS-b-PMMA/PS/PMMA掺合物，例如，60重量％的46K/21K PS-b-PMMA、20重量％的20K聚苯乙烯和20重量％的20K聚(甲基丙烯酸甲酯)。又一实例为60∶20∶20(重量％)PS-b-PEO/PS/PEO的掺合物、或约85-90重量％PS-b-PEO和至多10-15重量％PEO的掺合物；据信，所添加PEO均聚物至少在一定程度上可起到将PEO结构域的表面能降至PS的表面能的作用。
在本发明实施例中，将沟槽底面26结构化为呈中性湿润(对共聚物的两种嵌段具有均等亲和力)以诱导形成垂直沟槽底面定向的圆柱形聚合物结构域，且将沟槽侧壁22和端部24结构化为受嵌段共聚物的一种嵌段优先湿润以在聚合物嵌段自我组装时引导圆柱体与侧壁对齐。因应沟槽表面的湿润性质，在退火后，圆柱状嵌段共聚物的优选或次要嵌段将发生自我组装以沿沟槽长度方向于聚合物基质中心形成单行圆柱形结构域，且分离至沟槽的侧壁和边缘处以形成薄界面刷状层或湿润层(例如，如图6-6B中所示)。熵力驱动两种嵌段湿润中性湿润表面，而焓力驱动优选嵌段(例如，次要嵌段)湿润优先湿润表面。
例如，为提供优先湿润表而，在使用PS-b-PVP(或PS-b-PMMA等)嵌段共聚物时，材料层16尤其可由对PVP(或PMMA等)嵌段表现优先湿润的以下材料组成：硅(和自生氧化物)、氧化物(例如，氧化硅SiOx)、氮化硅、氧碳化硅、氧化铟锡(ITO)、氧氮化硅、和抗蚀剂材料(例如基于丙烯酸甲酯的抗蚀剂和聚二甲基戊二酰亚胺抗蚀剂)。例如，在使用PS-b-PVP圆柱状嵌段共聚物材料时，嵌段共聚物材料将发生自我组装而在PS基质内形成PVP的薄界面层和圆柱体。
在其它实施例中，例如，可通过旋涂将优先湿润材料(例如经含有-OH的部分(例如，甲基丙烯酸羟乙基酯)修饰的聚甲基丙烯酸甲酯(PMMA))施加至沟槽表面上，随后加热(例如，至约170℃)以便末端OH基团末端接枝至沟槽的氧化物侧壁22和端部24上。未接枝的材料可通过用适当溶剂(例如，甲苯)冲洗来去除。例如，参见曼斯基(Mansky)等人，科学(Science)，1997，275，1458-1460和殷(In)等人，朗缪尔(Langmuir)，2006，22，7855-7860。
中性湿润沟槽底面26容许共聚物材料的两种嵌段湿润沟槽底面。中性湿润材料14可通过下述步骤提供：将中性湿润聚合物(例如，中性湿润无规共聚物)施加至衬底10上，形成材料层16且随后蚀刻沟槽以暴露下伏中性湿润材料，如图2-2B中所示。
在图3-4中所绘示的另一实施例中，中性湿润无规共聚物材料可在形成沟槽18′后通过浇注或旋涂以(例如)毯覆涂层形式施加至所述沟槽中，如图4中所描绘。随后可对无规共聚物材料实施热处理以使所述材料通过毛细管作用流入沟槽底部，此会产生由经交联中性湿润无规共聚物组成的层(垫)14′。在另一实施例中，可将沟槽内的无规共聚物材料曝光(例如，通过掩膜或光掩膜)以使所述无规共聚物在沟槽内交联从而形成中性湿润材料14′。随后可去除沟槽外(例如，在间隔区20′上)的未经交联的无规共聚物材料。
具体来说，可通过以下方式来制备中性湿润表面：施加由与嵌段共聚物中的单体相同的单体组成的无规共聚物，且对其进行调整以使每一单体的摩尔分率适合形成中性湿润表面。例如，在使用PS-b-PVP嵌段共聚物时，中性湿润材料14可自对PS和PVP表现非优先或中性湿润的光可交联的无规PS-r-PVP的薄膜形成，可将所述中性湿润材料浇注至衬底10上(例如，通过旋涂来浇注)。所述无规共聚物材料可通过化学接枝(于氧化物衬底上)或通过热或光解交联(任一表面)而固定在适当位置，从而形成对PS和PVP呈中性湿润且在浇注嵌段共聚物材料时因交联而不溶解的垫。在另一实例中，在使用PS-b-PMMA时，可使用光可交联的PS-r-PMMA无规共聚物(例如，含有约0.6摩尔分率苯乙烯者)。
在衬底10为硅(和自生氧化物)的实施例中，可通过氢端接硅来提供PS-b-PMMA的另一中性湿润表面。可(例如)通过氢等离子来蚀刻沟槽18的底面26以去除氧化物材料并形成氢端接硅，所述氢端接硅对嵌段共聚物材料的两种嵌段具有均等亲和力且呈中性湿润。可通过常规制程来制备H-端接硅，例如，通过使硅衬底暴露于氟化氢(HF)和缓冲HF或氟化铵(NH4F)的水溶液中对所述硅衬底(存在自生氧化物，约
Figure BPA00001229874200071
Figure BPA00001229874200072
)实施氟离子蚀刻，通过HF蒸气处理，或通过氢等离子处理(例如，原子氢)。
可通过将无规共聚物(例如，PS-r-PVP、PS-r-PMMA等)选择性地接枝至衬底上来进一步处理H-端接硅衬底，从而产生对应嵌段共聚物(例如，PS-b-PVP、PS-b-PMMA等)的中性湿润表面。例如，通过苯乙烯与甲基丙烯酸甲酯的原位自由基聚合使用可将聚合物连接至表面上的二烯连接体(例如，二乙烯基苯)来提供PS-r-PMMA无规共聚物的中性湿润层，从而产生约10-15nm厚膜。
再次参照图3-4，在另一实施例中，可在形成材料层16′和沟槽18′后施加中性湿润无规共聚物材料14′，其选择性地与沟槽底面26′(由衬底10′材料组成)而非沟槽侧壁22′或端部24′(由材料层16′组成)发生反应。例如，含有环氧化物基团的无规共聚物(或均聚物与嵌段共聚物表面活性剂的适宜掺合物)可相对于氧化硅或硅选择性地与氮化硅和氧氮化硅表面上的末端胺官能团(例如，-NH-和-NH2)发生反应。在沟槽底面26′为硅或多晶硅且侧壁22′为诸如氧化物(例如，SiOx)等材料的另一实例中，可对所述底面实施处理以形成H-端接硅，且可仅在所述底面表面原位形成无规共聚物材料14′(例如，PS-r-PVP、PS-r-PMMA等)。
在另一实施例中，可通过接枝基于三氯硅烷的自我组装单层(SAM)(例如，接枝至氧化物(例如，SiO2)的3-(对-甲氧基苯基)丙基三氯硅烷)的SAM来提供中性湿润表面(例如，PS-b-PMMA和PS-b-PEO)，例如，如由D.H.帕克在纳米技术(Nanotechnology)18(2007)，第355304页中所述。
在另一实施例中，可通过在约160℃下加热约48小时使聚苯乙烯(PS)、具有羟基的聚甲基丙烯酸酯(PMMA)(例如，甲基丙烯酸2-羟基乙基酯)的中性湿润无规共聚物(例如，P(S-r-MMA-r-HEMA))(例如，约58重量％PS)作为厚约5-10nm的中性湿润层14选择性地接枝至衬底10(例如，氧化物)上。参见，例如，殷等人，朗缪尔，2006，22，7855-7860。
在又一实施例中，可将羟基末端均聚物与相应低分子量嵌段共聚物的掺合物接枝(共价键结)至衬底上以尤其形成PS-b-PMMA和PS-b-P2VP的中性湿润界面层(例如，约4-5nm)。嵌段共聚物在接枝前可起到乳化均聚物掺合物的作用。例如，可将约20-50重量％(或约30-40重量％)OH-端接均聚物(例如，Mn＝6K)与约80-50重量％(或约70-60重量％)低分子量嵌段共聚物(例如，5K-5K)的掺合物的约1重量％溶液(例如，存于甲苯中)旋涂于衬底10(例如，SiO2)上，加热(烘烤)(例如，在160℃下)，并通过(例如)用溶剂(例如，甲苯)冲洗去除未接枝(未键结)的聚合物材料。例如，可自约30重量％PS-OH(Mn＝6K)和PMMA-OH(Mn＝6K)(重量比率为4∶6)与约70重量％PS-b-PMMA(5K-5K)的掺合物或自PS-OH(6K)、P2VP-OH(6K)与PS-b-2PVP(8K-8K)的三元掺合物等制备中性湿润材料。
对PS-b-PMMA呈中性湿润的表面还可通过旋涂诸如苯乙烯和甲基丙烯酸甲酯的苯并环丁烯-或叠氮基甲基苯乙烯-官能化无规共聚物(例如，聚(苯乙烯-r-苯并环丁烯-r-甲基丙烯酸甲酯)(PS-r-PMMA-r-BCB))等光-或热可交联无规共聚物的毯覆层来制备。例如，此一无规共聚物可包括约42重量％的PMMA、约(58-x)重量％的PS和x重量％(例如，约2-3重量％)的聚苯并环丁烯或聚(对-叠氮基甲基苯乙烯)。可对叠氮基甲基苯乙烯-官能化无规共聚物实施UV光交联(例如，1-5MW/cm^2曝光约15秒至约30分钟)或热交联(例如，在约170℃下保持约4小时)以形成交联聚合物垫作为中性湿润层14。可对苯并环丁烯-官能化无规共聚物实施热交联(例如，在约200℃下保持约4小时或在约250℃下保持约10分钟)。
如图5-5B中所示，可将固有间距为或约为Lo的自我组装圆柱状嵌段共聚物材料28(或经掺和间距为或约为LB的嵌段共聚物与均聚物的三元掺合物)浇注或沉积至沟槽18中直至厚度(t1)为或约为嵌段共聚物材料的L值(例如，约L+20％)以便在退火后(例如，图6A)，厚度(t2)为或约为L值且嵌段共聚物材料可自我组装以在每一沟槽18中的聚合物基质内以单行形式形成直径为约0.5*L(例如，5-50nm，或约20nm)的圆柱体单层。例如，可通过椭圆测量技术来测量嵌段共聚物材料28的厚度。
例如，可通过自共聚物存于诸如二氯乙烷(CH2Cl2)或甲苯等有机溶剂中的稀溶液(例如，约0.25-2重量％溶液)旋转浇注(旋涂)来沉积嵌段共聚物材料。毛细管力将过量的嵌段共聚物材料28(例如，多于单层者)拉至沟槽18中。如图所示，可将嵌段共聚物材料的薄层或膜28a沉积至沟槽外的材料层16上(例如，间隔区20上)。退火后，薄膜28a将流入沟槽中，从而使得自俯视角度观察在材料层16上留下无结构刷状层。
然后在含有部分饱和浓度有机溶剂的蒸气相下将嵌段共聚物(BCP)材料28加热至高于其玻璃转变温度的温度以根据沟槽表面的优先和中性湿润使聚合物嵌段进行相分离和自我组装，从而形成自我组装聚合物材料30，如图6-6B中所示。在特定温度下达成中性湿润蒸气界面的溶剂蒸气的适宜分压至少部分地取决于所用嵌段共聚物且可根据经验来确定。
在高于嵌段共聚物材料的玻璃转变温度(Tg)但低于其分解或降解温度(Td)的热退火温度下加热所述嵌段共聚物。例如，可在约150-275℃温度下于溶剂蒸气气氛中对PS-b-PVP嵌段共聚物材料实施退火约1-24小时以达成自我组装形态。可在约150-275℃温度下于溶剂蒸气气氛中对PS-b-PMMA嵌段共聚物材料实施退火约1-24小时以达成自我组装形态。
在真空热退火的大多数应用中，空气界面对种聚合物结构域呈优先湿润且BCP材料并不定向成垂直结构。在本发明实施例中，在加热期间，将BCP材料28暴露于两种嵌段的“良好”溶剂(亦即，可充分地溶剂化两种构成嵌段的中性有机溶剂)的溶剂蒸气中。
溶剂退火通常由两个阶段组成。在第一阶段中，将BCP材料暴露于可用于塑化膜并增加链移动性的溶剂蒸气中，从而造成结构域混杂并丧失自浇注所述聚合物材料获得的固有有序性。所用有机溶剂至少在一定程度上是基于其在嵌段共聚物材料中的溶解度以便使足够溶剂分子进入所述嵌段共聚物材料中，从而促进聚合物结构域的有序-无序转变并使得可达成所需的分子重排。溶剂实例尤其包含芳香族溶剂，例如，苯、甲苯、二甲苯、二甲氧基乙烷、乙酸乙酯、环己酮等；和氯化溶剂，例如，氯仿、二氯甲烷、氯仿/辛烷混合物等。在第二阶段中，自溶剂蒸气移出衬底并使溶剂和溶剂蒸气自聚合物材料中扩散并蒸发。嵌段共聚物材料随着溶剂自所述材料蒸发而开始“变干”。溶剂蒸发具有高定向性且自BCP材料“顶部”(表面)至沟槽底面处的BCP材料“底部”形成可诱导结构定向和自我组装的溶剂梯度，所述定向和自我组装始于空气-表面界面(因界面处溶剂的分压而呈中性湿润)且向下进行至沟槽底面，同时由沟槽侧壁引导形成垂直定向的圆柱形结构域(34)且其自空气界而(46)完全延伸至衬底表面(沟槽底面)。
在本发明实施例中，在高于溶剂沸点的温度下加热衬底10和BCP材料28以阻止溶剂对BCP材料的溶胀。
在嵌段共聚物材料上方使用部分饱和的溶剂蒸气相可提供中性湿润界面，此与溶剂退火的第二阶段相似。在邻近BCP材料的蒸气界面处使空气中的溶剂浓度维持于饱和状态或不饱和状态以维持中性湿润界面以便两种(或所有)聚合物嵌段可均等地湿润蒸气界面。因空气和沟槽底面二者均为中性湿润，故在整个膜层内结构域均可垂直定向，且优先湿润的侧壁可诱导侧序。
尤其可使用(例如)原子力显微镜(AFM)、穿透式电子显微镜(TEM)、扫描式电子显微镜(SEM)来检查经退火共聚物材料30的所得形态(例如，圆柱体的垂直定向)。
在本发明实施例中，通过在溶剂气氛中全面加热沟槽内的嵌段共聚物来实施退火。
在其它实施例中，通过局部施加热能(例如热量)实施区域退火以对衬底10上沟槽内嵌段共聚物材料28的部分或区段实施退火。区域退火可使嵌段共聚物材料快速自我组装(例如，约数分钟)。
例如，如图6-8中依次所描绘，衬底10(处于蒸气气氛中)和热或热源32(或加热及冷却组合源)可彼此相对移动(例如，箭头←)以便将热量施加于衬底10上方(或下方)。开始时，仅将一部分BCP材料加热至高于玻璃转变温度，且然后横跨衬底“拉动”经加热区域(或反之亦然)。例如，可使用诸如电机平移台等机构(未图示)以平移设定速度(例如，约0.05-10μm/秒)横跨衬底10移动热源32。横跨衬底“拉动”所述经加热区域(或反之亦然)相对于全而热退火可更快速地处理并产生更有序结构。
在一些实施例中，可在衬底上方(或下方)提供热-至-冷温度梯度以便以可控速率将衬底的某一部分加热然后冷却。在其它实施例中，可将衬底暴露于冷-至-热温度梯度中以将BCP材料退火，然后实施冷却。
在其它实施例中，例如，可将BCP材料加热至高于有序-无序转变温度且然后冷却至低于所述温度(但高于玻璃转变温度)以去除(熔化去除)缺陷且促使材料再结晶，前提为所述嵌段共聚物材料的有序-无序转变温度(To-d)低于分解温度(Td)。有序-无序转变温度是由嵌段共聚物的温度相依性、Chi值、每个链中的单体总数量、和单体组成来界定。
嵌段共聚物材料中仅所述加热至高于聚合物构成嵌段的玻璃转变温度(Tg)的部分会自我组装，且未经充分加热的材料区保持无序且未自我组装。例如，如图6-6B中所示，开始时，可对沟槽18a内的嵌段共聚物材料实施加热和退火以形成自我组装材料30，同时沟槽18b、18c内的未退火嵌段共聚物材料28保持无序。嵌段共聚物材料28中仅所述加热至高于玻璃转变温度(Tg)的部分可发生自我组装。如图7-7A中所示，然后可选择性加热衬底的相邻部分，从而使得沟槽18b内的嵌段共聚物材料发生自我组装。然后可对衬底的剩余区域实施加热，例如，如图8-8A中所描绘。
退火后，圆柱状嵌段共聚物材料28将因应嵌段共聚物组合物(例如，固有间距为或约为L的PS-b-PVP)的特征和边界条件自我组装成聚合物材料30(例如，膜)，所述边界条件包含沟槽18宽度(wt)所提供的限制和沟槽表面(包含对两种聚合物嵌段(例如，无规接枝共聚物)显示中性或非优先湿润的沟槽底面26、由嵌段共聚物的次要(优选)嵌段(例如，PVP嵌段)优先湿润的侧壁22)的湿润性质、和与沟槽中嵌段共聚物材料表面26接触的中性或非优先溶剂(或在一些实施例中，呈中性或非优先湿润的膜或材料)的存在。退火可在主要聚合物嵌段(例如，PS)的基质36内产生一行(或数行)次要聚合物(优选)嵌段(例如，PVP)的垂直定向圆柱体34，其中所述圆柱体与沟槽的侧壁22对齐且平行。圆柱体34的直径通常为或约为0.5*L(例如，大约圆柱体间的中心至中心距离的一半)。此外，次要(优选)嵌段(例如，PVP)将发生分离且湿润沟槽18的优先湿润侧壁22和端部24以形成厚度通常为相邻圆柱体34间中心至中心距离的大约1/4的薄界面或湿润刷状层34a。例如，PVP嵌段层可湿润氧化物界面，其中所连接的PS结构域自氧化物材料向外伸出。
在一些实施例中，自我组装嵌段共聚物材料30是由单层圆柱形结构域(圆柱体)34阵列来界定，每一圆柱体的直径为或约为0.5*L(例如，大约圆柱体间中心至中心距离的一半)，行中圆柱体的数量(n)与沟槽长度(lt)相对应，且每一圆柱体间的中心至中心距离(间距距离，p)为或约为L。
任选地，在嵌段共聚物材料退火且有序化后，可处理共聚物材料以交联聚合物区段(例如，PS区段)从而固定自我组装聚合物嵌段且增强其强度。可将聚合物结构化为内在交联(例如，通过暴露于紫外线(UV)辐射，包含深紫外线(DUV)辐射)，或可将共聚物材料的一种聚合物嵌段调配为含有交联剂。
通常，沟槽外(例如，间隔区20上)的膜28a不会厚至可进行自我组装。任选地，例如，如图8-8A中所示，可通过蚀刻技术或平坦化方法来去除未结构化薄膜28a以提供大致均匀的平面。例如，可通过光掩膜(未图示)使沟槽区选择性地曝光以使沟槽18内仅经退火且自我组装的聚合物材料30发生交联，且随后可用适宜溶剂(例如，甲苯)实施洗涤以去除嵌段共聚物材料28a的未经交联部分(例如，间隔区20上者)，从而在所述沟槽内留下对齐的自我组装聚合物材料并暴露所述沟槽上方/外部的材料层16的表面。在另一实施例中，对经退火聚合物材料30实施全面交联，可施加光阻剂材料以图案化并暴露在沟槽区外的聚合物材料28a区，且可(例如)通过氧(O2)等离子处理来去除聚合物材料28a的暴露部分。
参照图9，在本发明方法的另一实施例中，实施热退火，同时将非优先湿润材料37′施加至沟槽中嵌段共聚物(BCP)材料28′的表面上。在一些实施例中，非优先湿润材料37′是由可以物理方式置于BCP材料28′上的固体材料组成，例如，可提供中性湿润外表面的柔软、挠性或橡胶样固体材料，例如交联的聚(二甲基硅氧烷)(PDMS)弹性体(例如，道康宁(Dow-Corning)的Sylgard-184)或其它弹性聚合物材料(例如，硅橡胶、聚氨基甲酸酯等)。可衍生固体材料(例如，通过接枝无规共聚物)以使其表现中性湿润表面。
对于与嵌段共聚物材料28′的表面接触的非优先湿润材料37′，实施热退火过程(箭头↓，图9A-9B)以使聚合物嵌段因应沟槽表面的优先和中性湿润和上覆材料37′的非优先(中性)湿润而发生相分离，且形成自我组装聚合物材料30′，如图10A-10B中所示。
退火后，可去除与经退火聚合物材料30′接触的非优先湿润材料37′(箭头↑)，如图10A中所描绘。可(例如)通过自经退火聚合物材料表面举离或剥离材料来去除PDMS或其它弹性材料层37′。此外，可施加(例如，通过浸泡)相容于且不溶解嵌段共聚物材料30′的溶剂(例如，水、醇、和诸如此类)以渗透且溶胀弹性材料(例如，PDMS)从而促进物理去除。还可施加稀氟化物溶液(例如，NH4F、HF、NaF等)来蚀刻和溶解PDMS材料以自经退火聚合物材料中将其去除。
在自我组装后，随后可根据需要进一步处理在衬底上形成的垂直定向圆柱体图案以(例如)形成蚀刻掩膜，以供通过选择性去除自我组装嵌段共聚物的一种嵌段在下伏衬底10中图案化形成纳米级特征。由于此方法中所涉及的结构域大小和周期(L)是由嵌段共聚物的链长度(MW)确定，因此分辨率可超过其它技术(例如，常规光学光刻)。使用所述技术的处理成本显著低于极紫外线(EUV)光学光刻，但其具有相当的分辨率。
例如，如图11-11B中所示，在一实施例中，可通过选择性去除自我组装聚合物材料30的圆柱形聚合物结构域34以在聚合物基质36(例如，PS)内产生开孔40来形成蚀刻掩膜38，从而暴露沟槽底面26处的下伏衬底10。例如，可通过选择性湿蚀刻(例如，通过UV暴露/乙酸显影来去除PMMA和PLA，通过含有氢氧化钠的水-甲醇混合物来去除PLA，通过氢碘酸水溶液或水来去除PEO，等等)或通过选择性反应性离子蚀刻(RIE)方法来去除圆柱形结构域34。在嵌段共聚物包含可断裂连接基团的实施例中，可将膜暴露于含有裂解剂且对次要结构域具有选择性的溶剂(例如，对于PVP为醇，对于PEO或PLA为水，且对于PMMA为乙酸)中以去除(例如，洗涤掉)所述次要结构域。如图12-12B中所描绘，然后可使用剩余多孔聚合物(例如，PS)基质36作为光刻模板或掩膜来蚀刻(箭头↓↓)一系列直抵下伏衬底10(或下层)中导线12或其它有源区(例如，半导电区域等)的纳米级(例如，约10-100nm)圆柱形开孔或接触孔42。例如，可使用选择性反应性离子蚀刻(RIE)方法来形成开孔42。
随后，可根据需要实施进一步处理。例如，如图13-13B中所描绘，可去除残余聚合物基质36(例如，通过诸如等离子O2蚀刻等氧化方法来去除PS)，且可使用诸如金属或金属合金(例如，尤其为Cu、Al、W、Si、和Ti3N4)等材料44来填充衬底开孔42以形成与导线12接触的圆柱形阵列。还可使用金属-绝缘体-金属堆叠填充衬底中的圆柱形开孔42以形成具有诸如SiO2、Al2O3、HfO2、ZrO2、SrTiO3、和诸如此类等绝缘材料的电容器。
本发明实施例使用热退火方法与溶剂退火的组合，与单独使用溶剂退火相比，此可提供更快处理且将可处理的嵌段共聚物(BCP)类型扩展至基本所有BCP。在使用区域退火与有机溶剂气氛的组合的实施例中，可快速处理多种嵌段共聚物以形成垂直定向的纳米结构(例如，圆柱体)。
此外，本发明方法提供于聚合物基质中产生由垂直定向圆柱体组成的自我组装二嵌段共聚物膜的手段。与电子束光刻、EUV光学光刻或常规光学光刻相比，所述方法可以更低成本制备有序且对齐的纳米级元件。本发明可产生并获得常规光学光刻不易制备的特征大小。所述方法和系统可容易地应用于并纳入现有半导体制造方法流程中，且提供用于制造小结构的低成本、高通量技术。
虽然本文已说明且阐述了具体实施例，但所属领域技术人员将了解，在所示具体实施例中旨在达成相同目的的任何布置均可加以替换。本申请案意欲涵盖可根据所阐述本发明原则进行的任何改动或改变。因此，本发明意欲仅受限于权利要求书和其等效内容。本申请案中所引用的专利、参考文献和出版物的揭示内容均以引用方式并入本文中。

Claims (32)

1.一种在衬底上形成纳米结构聚合物材料的方法，其包括：
在所述衬底上的一材料层中的沟槽内沉积圆柱状嵌段共聚物材料，所述沟槽具有中性湿润底面、对所述嵌段共聚物的第一嵌段呈优先湿润的相对侧壁和端部；和
在对任一嵌段呈非优先的溶剂蒸气中和高于所述嵌段共聚物材料的玻璃转变温度(Tg)的温度下，对所述嵌段共聚物材料实施热退火；
其中，所述嵌段共聚物材料在所述嵌段共聚物的第二嵌段基质内自我组装成所述嵌段共聚物的第一嵌段的圆柱形结构域，所述自我组装嵌段共聚物材料具有一厚度，且所述圆柱形聚合物结构域垂直定向于所述沟槽底面并沿所述沟槽长度穿过所述自我组装嵌段共聚物材料的所述厚度呈单一阵列延伸。
2.如权利要求1所述的方法，其中所述溶剂蒸气包括部分饱和浓度的有机溶剂。
3.如权利要求1所述的方法，其中所述嵌段共聚物材料的所述退火包括将所述嵌段共聚物材料加热至所述溶剂的沸点，其中不发生所述溶剂对所述嵌段共聚物材料的溶胀。
4.如权利要求1所述的方法，其中对所述嵌段共聚物材料实施全面加热。
5.如权利要求1所述的方法，其中对所述嵌段共聚物材料实施区域退火。
6.如权利要求1所述的方法，其中所述退火包括加热所述嵌段共聚物材料的一部分，从而仅在所述嵌段共聚物材料的所述经加热部分内形成所述自我组装的圆柱形结构域。
7.如权利要求6所述的方法，其进一一步包括施加热至所述嵌段共聚物材料的第二部分上，从而在所述嵌段共聚物材料的所述第二部分内形成自我组装的圆柱形结构域。
8.如权利要求1所述的方法，其中所述退火包括选择性加热所述嵌段共聚物材料的第一部分。
9.如权利要求1所述的方法，其中所述退火包括在所述衬底上方移动热源。
10.如权利要求1所述的方法，其中所述退火包括：
加热所述嵌段共聚物材料的第一部分；和
加热所述嵌段共聚物材料的第二部分；
其中在高于所述玻璃转变温度下加热所述嵌段共聚物材料以使聚合物嵌段发生相分离。
11.如权利要求1所述的方法，其中所述退火包括加热随后冷却所述嵌段共聚物材料的第一部分。
12.如权利要求1所述的方法，其中所述退火包括将所述嵌段共聚物材料暴露于冷-至-热温度梯度中。
13.如权利要求1所述的方法，其中所述嵌段共聚物材料的所述退火包括：
将所述嵌段共聚物材料加热至高于有序-无序转变温度且高于所述玻璃转变温度；和
使所述嵌段共聚物材料冷却至低于所述有序-无序转变温度但高于所述玻璃转变温度。
14.一种在衬底上形成纳米结构聚合物材料的方法，其包括：
将圆柱状嵌段共聚物材料暴露于对任一嵌段呈非优先的溶剂蒸气中，同时在高于所述嵌段共聚物材料的玻璃转变温度(Tg)的温度下实施加热，所述嵌段共聚物材料位于所述衬底上的材料层中的沟槽内，所述沟槽具有宽度、长度、中性湿润底面、和对所述嵌段共聚物的第一嵌段呈优先湿润的相对侧壁和端部；
其中所述嵌段共聚物材料发生微相分离，以在所述沟槽内的第二聚合物嵌段基质中形成由第一聚合物嵌段组成的圆柱形结构域，所述圆柱形聚合物结构域垂直定向于所述沟槽底面且在沿所述沟槽长度方向延伸的单一阵列中与所述侧壁对齐。
15.如权利要求14所述的方法，其中所述中性湿润底面包括无规共聚物材料。
16.如权利要求14所述的方法，其中所述中性湿润底面包括接枝均聚物的掺合物。
17.如权利要求14所述的方法，其中所述中性湿润底面包括氢端接硅。
18.如权利要求14所述的方法，其中所述沟槽的侧壁和端部包括选自由以下物质组成的群组的材料：氧化物、氮化硅、氧碳化硅、氧氮化硅、氧化铟锡(ITO)、甲基丙烯酸酯抗蚀剂、和聚二甲基戊二酰亚胺抗蚀剂。
19.如权利要求14所述的方法，其中在所述沟槽中的嵌段共聚物材料具有约为所述嵌段共聚物的L值或更大的厚度，“L”是所述嵌段共聚物中各圆柱体的中心至中心的圆柱体间距或间隔。
20.如权利要求14所述的方法，其进一步包括使所述第二聚合物嵌段的基质选择性交联。
21.如权利要求14所述的方法，其进一步包括选择性去除所述第一聚合物嵌段以形成穿过所述第二聚合物嵌段的基质延伸的圆柱形开孔。
22.如权利要求21所述的方法，其进一步包括通过所述开孔蚀刻所述衬底的未遮盖部分。
23.一种在衬底上形成纳米结构聚合物材料的方法，其包括：
将对任一嵌段呈非优先的材料施加至所述衬底上的一材料层中沟槽内的圆柱状嵌段共聚物材料的上方且与其接触，所述沟槽具有中性湿润底面、对所述嵌段共聚物的第一嵌段呈优先湿润的相对侧壁和端部；和
在高于所述嵌段共聚物材料的玻璃转变温度(Tg)的温度下对与所述非优先材料接触的嵌段共聚物材料实施退火；
其中所述嵌段共聚物材料于所述嵌段共聚物的第二嵌段基质内自我组装成所述嵌段共聚物的第一嵌段的圆柱形结构域，所述自我组装嵌段共聚物材料具有一厚度，且所述圆柱形结构域垂直定向于所述沟槽底面并沿所述沟槽长度穿过所述自我组装嵌段共聚物材料的所述厚度呈单一阵列延伸。
24.如权利要求23所述的方法，其中施加所述非优先材料包括使所述嵌段共聚物材料与具有非优先表面的固体弹性材料相接触。
25.一种蚀刻衬底的方法，其包括：
在对任一嵌段呈非优先的溶剂蒸气中对嵌段共聚物材料实施退火，同时在高于所述嵌段共聚物材料的玻璃转变温度(Tg)的温度下加热，所述嵌段共聚物材料位于所述衬底上的材料层中的沟槽内，所述沟槽具有宽度、长度、中性湿润底面、和对所述嵌段共聚物的次要嵌段呈优先湿润的相对侧壁和端部；其中所述嵌段共聚物材料在主要聚合物嵌段基质内形成所述次要聚合物嵌段的单一阵列垂直定向的圆柱体，所述经退火嵌段共聚物材料具有一厚度，且所述圆柱体穿过所述经退火嵌段共聚物的所述厚度延伸至所述沟槽底面；
选择性去除所述次要聚合物嵌段以在所述主要聚合物嵌段基质内形成开孔并暴露所述衬底；和
通过所述开孔蚀刻所述衬底。
26.如权利要求25所述的方法，其进一步包括在去除所述次要聚合物嵌段之前，使所述主要聚合物嵌段选择性地交联。
27.如权利要求25所述的方法，其进一步包括用填充材料填充所述衬底中的开孔。
28.如权利要求27所述的方法，其中所述填充材料包括金属、金属合金、和金属/绝缘体/金属堆叠。
29.一种蚀刻衬底的方法，其包括：
通过在高于嵌段共聚物材料的玻璃转变温度(Tg)的温度下加热以对所述嵌段共聚物实施退火，在所述嵌段共聚物材料上方具有对任一嵌段呈非优先且与其接触的材料，所述嵌段共聚物材料位于所述衬底上的材料层中的沟槽内，所述沟槽具有宽度、长度、中性湿润底面、和对所述嵌段共聚物的次要嵌段呈优先湿润的相对侧壁和端部；其中所述嵌段共聚物材料在主要聚合物嵌段基质内形成所述次要聚合物嵌段的单一阵列垂直定向的圆柱体，所述经退火嵌段共聚物材料具有一厚度，且所述圆柱体穿过所述经退火嵌段共聚物的所述厚度延伸至所述沟槽底面；
选择性去除所述次要聚合物嵌段以在所述主要聚合物嵌段基质内形成开孔并暴露所述衬底；和
通过所述开孔蚀刻所述衬底。
30.如权利要求29所述的方法，其中所述非优先材料包括选自由聚(二甲基硅氧烷)和聚(氨基甲酸酯)组成的群组的固体弹性材料。
31.如权利要求29所述的方法，其进一步包括去除所述非优先材料以暴露所述沟槽内的所述经退火嵌段共聚物材料。
32.如权利要求31所述的方法，其进一步包括将溶剂施加至所述非优先材料中以促进去除。
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