CN1309784A - 具有脱模剂的表面 - Google Patents

具有脱模剂的表面 Download PDF

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CN1309784A
CN1309784A CN99808687A CN99808687A CN1309784A CN 1309784 A CN1309784 A CN 1309784A CN 99808687 A CN99808687 A CN 99808687A CN 99808687 A CN99808687 A CN 99808687A CN 1309784 A CN1309784 A CN 1309784A
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斯蒂芬·Y·舒
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University of Minnesota
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Abstract

持续的脱模材料的薄涂层(小于或接近于十亿分之一分子涂层)包括下列公式的化合物:RELEASE－M(X)n－1－,RELEASE－M(X)n－m－1Qm或RELEASE－M(OR)n－1－,其中,RELEASE是在长度上4到20个原子的分子链,M是金属原子、半导体原子或半金属原子,X是卤素或氰基,特别是CI、F、Br,Q是氢、烃基基团,R是氢、烃基、苯基,较好是1到4个碳原子的氢或烃基;n－m－1至少是1特别用于平板印刷方法和装置,以在基片上涂敷的薄膜中产生超微细(亚－25nm)图形,在该图形中,至少由一个突出的功能部件的铸模被压入基片上支撑的薄膜内。

Description

具有脱模剂的表面
发明领域
本发明涉及脱膜表面，特别涉及到可以被复制的具有细微特征的脱膜表面，以及可以用来产生集成电路和微器件的平板印刷术。更具体地说，本发明涉及到使用改善的铸模或微复制表面的方法，该方法可以在基片的表面上支撑的薄膜中产生具有非常细微特征的图形。
现有技术
在许多不同的技术领域和商业应用中，高度要求的是所提供的表面具有非粘着功能。这种技术类型的应用范围非常广泛，从织物和表面的防污处理(例如，工作台面、炉子表面)到器具(例如，煮饭或实验室器具和表面)，用于成像技术的脱离表面(例如，图形转移表面、临时载体)、铸模脱膜表面。抗粘着功能具有明确的润滑含义，即，以实质或保持的方式在基片上提供抗粘着功能。
在半导体集成电路、集成光路、集成磁路、机械电路和微器件的制作中，关键处理方法之一是平板印刷术，特别是照相平板印刷术。可以使用平板印刷术，连同在印刷平板形成和光刻胶图像形成中的传统的光刻胶成像在基片上的薄膜中产生图形，在随后的处理步骤中，图形可以在基片上或在附加到基片上的其它材料上被复制。在平板印刷处理期间，接受图形或图像的薄膜常常被称为光刻胶。光刻胶可以是正的光刻胶或负的光刻胶，取决于它的形成操作。例如，正的光刻胶在他被照射的地方较容易溶解，而负的光刻胶在它被照射的地方不容易溶解。用于集成电路制作的一种典型的平板印刷方法包括用辐射波束或粒子曝光或照射薄膜的光刻胶成分或具有射线束或粒子的薄膜，包括光、高能粒子、(可以是电子)光子或离子，是把大波束通过掩膜或扫描聚焦的波束。离子束的辐射改变了膜的曝光区域的化学结构，所以，当冲洗或浸渍在显影液或用显影液冲洗时，光刻胶的曝光区域或未曝光区域将被除去，以在掩膜或扫描的正面重新产生图形。平板印刷术的分辨率由粒子的波长和波束的分辨率、在光刻胶和基片中的粒子散射、光刻胶的特性所限制。
目前，在平板印刷术中存在一个日益增长的生产较小图形尺寸的需要，同时保持处理中的低成本。巨大的需要是对大量生产亚-50nm结构发展低成本的技术，因为这种技术在工程和科学的许多领域有巨大的影响。不仅半导体集成电路的将来将受到影响，而且，远比当前器件高级的许多创新的电子、光学、磁学和机械微器件的商业化也依赖于这种技术的可能性。此外，按照平板印刷技术，包括反射涂层和反射片(可用于安全的目的或标记)的光学材料可以使用微复制技术。
已经发展了许多技术服务于这些需要，但它们都有致命的缺点，没有一种技术可以以低成本大量生产亚-50nm平板印刷。电子束平板印刷术已经显示了10nm平板印刷分辨率，A.N.Broers,J.M.Harper,和W.W.Molzen应用物理通讯，33,192(1978)和P.B.Fischer和S.Y.Chou,应用物理通讯，62,2989(1993)。但是，由于串行处理工具中的固有低输出，在大量生产亚-50nm结构中使用这些技术看起来在经济上是不可行的。具有高产量的X-射线平板印刷术已经显示了50nm平板印刷分辨率。K.Early,M.L.Schattenburg,和H.I.Smith,微电子工程11,317(1990)。但是，X-射线平板印刷工具是相当昂贵的，并且没有在商业上显示大量生产亚-50nm结构的能力。基于扫描探针的平板印刷术已经在很薄的材料层中生产了亚-10nm结构。但是，在这一点上很难判断这种平板印刷术能作为制造工具。
使用热塑聚合物的压缩铸模刻印技术是低成本的大量生产技术，并已经使用了几十年。尺寸大于1微米的功能部件已经常规地刻印在塑料中。基于聚碳酸酯刻印的CD盘是商业使用这种技术的一个例子。另一个刻印的例子是制造微机械部件用10微米量级的功能部件尺寸的聚甲基丙烯酸甲酯结构。M.Harmening,W.Bacher,P.Bley,A.Ej-Kholi,H.Kalb,B.Kowanz,W.Menz,A.Michel,和J.Mohr, IEEE会刊，微电子机械系统，202(1992)。具有几十微米功能部件尺寸的铸模聚酯微机械部件也已经被使用。H.Li和S.D.Senturia,1992,13届IEEE/CHMT国际电子制造技术会议，145(1992)。但是，没有人承认使用刻印技术提供具有高纵横比的25nm结构。此外，组合刻印技术和其它技术代替在半导体集成电路制造中使用常规的平板印刷术的平板印刷方法还没有出现。
发明简述
本发明涉及通过键合于表面的分子的涂层改变表面的特性的方法，以形成非连续的分子键合的涂层。本发明的特殊优点是形成具有分子键合涂层的铸模或微复制表面，以及使用这些涂层和表面的铸模和微复制的方法。当涂层材料不必须很紧密地与被涂覆的表面平行时，涂层可以被视为非连续的涂层，但分子仍然一个接一个地键合到表面上，例如，像从基板的表面突出的草，一片接一片。
本发明涉及提供具有处理表面的方法，该处理可以在铸模或微复制处理中有效地补偿表面。向其它材料具有脱膜特性的(例如，氟化碳氢化合物链或聚硅氧烷)和对于可模压聚合物的低化学反应的分子嵌段被键合到铸模或微复制表面。具有脱膜特性的分子嵌段的脱膜特性提高了铸模的器件的分辨率，因为铸模的材料从分子级上的铸模的最小功能部件被脱膜。较普通的聚合物涂层脱膜表面可以填注开口或部分填注铸模的开口。仅仅平滑的脱膜表面暴露了磨损的铸模的表面，并与铸模材料反应。下面描述非-连续涂层。连续涂层一般是在表面上从薄膜一端到另一端没有直线路线的形成薄膜。像没有真正的薄膜涂层形成在本发明中一样，而是单个的分子趋于叠置在表面上，即使在表面上存在均匀特性，也不存在连续的涂层。在分子级上，表面将呈现出在分子键合到表面的相对线性的一端具有一个嵌段的表面。相对的线性分子从表面延伸开去，用分子的“尾部”提供的脱膜特性从表面延伸开去。在表面上尾部的相对浓度控制了表面的亲水的/疏水的/极性的/非极性的特性，所以，它将能够准备脱膜铸模或微复制处理提供的材料。粘附分子的脱膜部分最好在尾部上有几个反应点，特别是在相对线性链中的最后一个、两个、三个或四个骨架原子中(例如，碳氢化合物基链、在链中的alpha、beta、gamma、delt原子)。避免这样的嵌段将特别包括自由氢容纳基团(例如，酸基、羧基酸基或盐、磺酸基或盐、胺基、乙烯不饱和化合物基团等)。
本发明也涉及生产集成电路和微器件的进行微细线平板印刷的方法和装置。薄膜层被淀积在基片上。具有铸模表面的铸模用本发明的脱膜材料处理，至少一个突出的功能部件和一个凹槽被压入薄膜，因此，在突出的功能部件下的薄膜的厚度薄于在凹槽下的薄膜的厚度，并且，浮雕被形成在薄膜内。浮雕通常与铸模上的功能部件的形状一样。从薄膜除去铸模之后处理薄膜，以至除去浮雕中膜的较薄部分暴露下面的基片。因此，铸模中的图形被复制在薄膜中，完成了平板印刷。在随后的处理中，薄膜中的图形将被重现在基片或加到基片上的其它材料中。在铸模表面上使用脱膜处理提高了图像的分辨率，并保护了铸模，以便它可以经常使用而没有在铸模中的微小功能部件上显示磨损。
在此描述的本发明基本上是基于与常规平板印刷术的不同原理。本发明可以排除加在常规平板印刷术上的许多分辨率限制，例如，波长限制、在光刻胶和基片中粒子的背散射、光学干涉。已经表明，本发明包括产生亚-25nm功能部件的高产量大批量生产平板印刷的方法。此外，本发明具有以低成本大量生产亚-10nm功能部件的能力。本发明的这些能力是现有技术难以达到的。使用粘着的脱膜特性涂层改善了耐用性，甚至方法的分辨率。但是，本方法已经暗示并用于在铸模表面可用肉眼观察细节，并包括超-50nm、超-100nm、超-200nm范围的功能部件，以及在功能部件的视觉范围内观察尺寸(例如，0.1mm和更大)。
附图简述
图1A是本发明铸模和基片的剖面图。
图1B试图1A所示的铸模被压入基片上的薄膜内的铸模和基片的剖面图。
图1C是图1B铸模压入薄膜内压缩后的基片的剖面图。
图1D是图1C除去薄膜的压缩部分后暴露下面的基片的剖面图。
图2是由压缩铸入图1C所示的PMMA膜形成的具有120nm周期的25nm直径孔的顶视图的扫描电子显微照片。
图3是由压缩铸入图1C所示的PMMA膜形成的具有100nm宽槽的顶视图的扫描电子显微照片。
图4是由压缩铸入图1C所示的PMMA膜形成的条带的透视图的扫描电子显微照片。条带是70nm宽，200nm高，并具有高的纵横比，表面粗糙度小于3nm，几乎是完美的90度角。
图5A是图1D淀积材料之后的基片的剖面图。
图5B是图5A脱模处理选择除去材料之后的基片的剖面图。
图6是图2淀积材料和脱模处理之后的基片的扫描电子显微照片。金属点有25nm直径，与图2所示的在PMMA中产生的孔的直径相同。
图7是图3淀积材料和脱模处理之后的基片的扫描电子显微照片。金属线宽是100nm，与图3所示的在PMMA槽的宽度相同。
图8是图1D随后处理之后的基片的剖面图。
图9是本发明实施例的装置的简化的方框图。
发明的详细描述
本发明涉及通过键合分子的非连续涂层改变表面的特性的方法，具有分子键合的非连续的涂层的表面，具有分子键合的非连续涂层的铸模或微复制表面，以及使用这些涂层和表面的铸模和微复制的方法。
本发明也涉及到高分辨率、高产量、低成本平板印刷的方法和装置。不像目前的微平板印刷术，本发明的优选实施例放弃使用高能光或粒子波束。通过使用键合到铸模表面上起反应的脱膜层，照相平板印刷术可以得益于本发明。在不需要使用照相平板印刷术的本发明的实施例中，本发明是基于把铸模压入基片上的薄膜产生浮雕，之后，除去薄膜的压缩区域，曝光下面的基片，并在复制了铸模的突出图形的正面的基片上形成光刻胶图形。
本发明也显示了图形的产生，例如，在基片上的薄膜内的孔、柱、槽，其最小尺寸是25nm，深度超过100nm，侧壁平滑度好于3nm，接近完美的90度角。目前，人们发现刻印的功能部件的尺寸受到使用的铸模的尺寸的限制；使用适当的铸模，本发明可以产生高纵横比的亚-10nm结构。此外，使用包括材料淀积和脱模处理方法的本发明的一个实施例，已经生产出200nm周期的100nm宽的金属线，125nm周期的25nm直径的金属点。使用本发明产生的光刻胶图形已经被用作为掩膜把十亿分之一结构(尺寸小于1000nm，做好小于500nm的功能部件)蚀刻入基片。
本发明与现有技术相比具有许多优点。首先，因为本发明基于不同于现有技术的范例，它放弃使用能量粒子束，例如，光子、电子、和离子，本发明消除了许多限制常规平板印刷术分辨率的因素，例如，由于有限的波长，波的衍射限制，在光刻胶和基片中的粒子的散射限制，以及干扰。因此，本发明提供了非常好的平板印刷分辨率，与现有技术相比，在整个基片上提供了非常均匀的平板印刷。结果显示可以得到亚-25nm分辨率。其次，本发明可以在大面积上平行产生亚-25nm功能部件，并导致了高产量。现有技术是不可能得到该结果的。第三，因为没有包含复杂的能量粒子束产生器，本发明与现有技术相比可以低成本在大面积上获得亚-25nm平板印刷。这些优点使得本发明优于现有技术，并对将来的集成电路制造和需要十亿分之一平板印刷术的科学和工程的其它领域是至关重要的。
分子的非连续涂层由特殊类型反应化合物形成。这些化合物由下列结构表征：
RELEASE-M(X)n或RELEASE-M(OR)n，其中
RELEASE是在长度上4到20个原子的分子链，长度上最好是6到16个原子，其中，分子具有极性或非极性，取决于对铸模剂要求的疏水性；
M是无机原子，特别是金属原子、半导体原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基，最好是氢、甲基、乙基；
(n)是M的-1价，通常是1、2、3，取决于M的性质。
在与铸模表面反应期间，键和到表面的实际嵌段具有键合到除去的金属或半金属原子上的基团之一，并具有下面的结构式：
RELEASE-M(X)n-1 -或RELEASE-M(OR)n-1 -，其中
RELEASE是在长度上4到20个原子的分子链，长度上最好是6到16个原子，其中，分子具有极性或非极性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
(n)是M的-1价。如上所述，RELEASE的特性部分地由表面所用的铸模材料的性质或表面上所要求的特性的性质确定。这就是表面被使用在具有极性聚合材料的微复制的地方，脱模特性必须是非极性。例如，非极性RELEASE组最好从特别包括硅氧烷和高氟化或碳氟化合物单元的非极性分子选择。这些非极性分子单元最好是在线性链中从4到20个骨架原子的线性单元。较短的链不能形成所要求的脱模特性的连续，而较长的链可以在被复制的表面上掩膜功能部件。高氟化意思是至少在碳上的所有取代的2/3是氟化单元，而剩余的单元包括CI或H。末端碳较好是全氟化，末端碳原子最好是全氟化，没有氢原子呈现在三个末端碳原子上，链最好是全氟化。
M最好是金属原子、半导体原子或半金属原子，例如，Si、Ti、Zr、Cr、Ge等。M最好是Si。在这些例子中，n最好是3。
使用在本发明中的化合物的例子包括全氟己基三氯硅烷、全氟辛基三氯硅烷、全氟癸基三氯硅烷、全氟十二烷基三氯硅烷、全氟己基丙基三氯硅烷、全氟癸基三氯化钛、全氟癸基二氯溴硅烷、聚二甲基硅氧烷-三氯硅烷(对聚二甲基硅氧烷，n最好是4到20)、全氟癸基二氯溴化锗、全氟癸基二氯溴化铬。
用于铸模的表面可以是提供分子可能键合的脱膜的任何表面。通过选择适当的提供分子的脱膜，可以使用任何脱膜表面。在铸模和微复制中已知的脱膜表面可以是金属的、半金属的、金属氧化物的、金属和半金属碳化物和氮化物的、半金属化氧化物、聚合物、半导体、光导体、陶瓷、玻璃、复合物等。特别有用的基片包括(但没有局限于)硅、硅氮化物、硅碳化物、掺杂半导体的硅氯化物、光导体(有机和无机)。模制方法包括上述的模压法、喷射模铸法、粉末模铸法、吹塑法、浇铸法或浇铸模制法、汽相淀积模铸法、分解模铸法(使材料分解形成淀积在表面的新材料)。可以生产均匀形状的图形和任意形状的图形，如前所述，通过冷却热软化材料、可聚合的材料、化学反应材料、汽相淀积材料等使模制化合成物变硬。优选的材料包括半导体、电介质、光响应、热响应、电响应基片或表面，例如(但不局限于)无机氧化物(或硫化物、卤化物、碳化物、氮化物)、稀土氧化物(或硫化物、卤化物、碳化物、氮化物)、无机或有机硅化物(例如，硅氧化物、硫化物、卤化物、碳化物、氮化物)和它们的钛、锗、镉、锌，以及相同的对应物(例如，四价钛的、锌氧化物(粒子或层)锗氧化物、镉硫化物)作为连续的或非连续的涂层，并作为混合物、分散物或掺杂物的层结构。
本发明的脱膜涂层形成材料可以适用在形成小于脱膜材料的连续单分子层的涂层。即，通过与指定的分子的无机端反应，脱膜材料形成了保护表面的脱膜部分尾部的涂层(例如，硅、钛、锗)。当脱膜分子趋于防止其它分子沿表面均匀排列时(至少在图形中均匀)，基片的整个表面不需要涂敷。如图1A所示，在表面的单个涂敷分子之间总是存在某些空间，涂层没有形成平行于涂敷表面的连续层，而是只在一端形成键合到表面的扩展的分子，剩下向外扩展的RELEASE组，提供了脱膜(非-粘着)特性。但是，化合物的脱膜嵌段尾部证实为一平滑的区域，所以，均匀的涂敷不是必须的。考虑到它们的效果，使用的脱膜涂敷材料的涂敷量是不可思议的小。例如，小于每平方米0.001mg的表面积的涂敷重量已经提供了重要的脱膜涂敷效果。每平方米0.001到100mg的表面积、每平方米0.005到5mg的表面积、最好每平方米0.01到1-5mg的表面积的涂敷重量通常是有用的。
图1A-1D显示了一个实施例的步骤。图1A显示了具有基体12和模铸层14的模铸层10。尽管不是按比例，脱膜涂敷材料Si-RELEASE连接到到所述的膜铸层10。Si-RELEASE化合物被视为键合在Si端部的单个分子，RELEASE尾部从那扩展，向铸模14提供了脱膜特性。脱膜化合物残留-Si-RELEASE的尺寸是相对于图1A所示的铸模表面14的单分子的分子。连接到Si的残余基团(例如，未反应的H、氰基或卤素)没有示出，仅仅是为了制图方便。从这个较少的文字表达可以看出，RELEASE嵌段从模铸层14扩展。这些RELEASE“尾部”提供了脱模特性并趋于合理地持续和稳固。所示的膜铸层14包括具有要求形状的多个功能部件16。显示的脱膜层17键合到模铸层14上的功能部件16的表面。基片18支撑薄膜层20。薄膜层20通过任何适当的技术淀积，例如，旋转浇铸法、狭缝涂布法、滑动涂敷法、幕帘涂敷法、溶解涂敷法、凹版印刷涂敷法、屏幕涂敷法、汽相淀积法、溅射法等。
图1B显示了压缩模铸步骤，其中，铸模10在箭头22所示的方向被压入薄膜层20，形成了压缩的区域24。在该实施例中，如图1A-1D所示，功能部件16不是都压入薄膜20，并且，不接触基片18。在某些实施例中，薄膜20的顶部24a接触铸模10的压缩的表面16a。这使得顶部表面24a基本上与表面16a的形状一致，例如，平板型。当接触发生时，这也可以停止铸模进一步移入薄膜20，当压缩力是常数时，由于接触面积的突然增加，减小了压缩的压力。本发明的脱膜层17从铸模10的功能部件16改善了薄膜层20的脱膜。
图1C是除去铸模10后的薄膜层20的剖面图。
图1D是图1C除去薄膜的压缩部分后暴露下面的基片的剖面图。层20包括多个形成在压缩区域24的凹槽，压缩区域通常与涂敷脱膜层17的功能部件16的形状一致。层20进行后面的图1D所示的处理步骤，在这个步骤中，薄膜20的压缩部分24被除去，因此暴露了基片18。可以通过适当的方法进行除去处理，例如，反应离子蚀刻法、湿化学蚀刻法。这就在基片18的表面上形成了具有凹槽28的挡板26。凹槽28形成了与功能部件16和铸模10的形状一致的浮雕功能部件。
使用电子束平板印刷术、反应离子蚀刻(RIE)和其它适当方法，包括具有最小侧壁功能部件尺寸25nm的柱、孔和槽的功能部件在铸模10上形成图形。功能部件典型的深度是5nm到200nm(包括脱膜层17的尺寸或排除这些分子的尺寸)，取决于要求的侧壁尺寸。一般来说，选择的铸模比柔软的薄膜硬，铸模可由金属、电介质、聚合物、半导体、陶瓷或它们的组合物制成。在一个实施例中，铸模10由硅基片12上的硅二氧化物的层14和功能部件16构成。
薄膜层20包括热塑聚合物或其它热塑料、可硬化的或可固化的材料，这些材料根据条件可从液态变为固态(例如，温度、聚合反应、固化、辐射)。在图1B所示的压缩模铸步骤期间，以一定的温度加热薄膜20，使薄膜足够软化。例如，在玻璃转变温度之上，聚合物有低粘性并可以流动，因此，与功能部件16一致，由于脱膜层17的存在而不含对表面形成强粘性。薄膜层包括任何材料，从材料的连续薄膜到轻烧结材料，以及直到铸模或微复制的压缩和粘着步骤处理之后，由重力保持在适当位置的松粉。例如，材料可以是聚合物薄膜、胶乳薄膜、粘性聚合物涂层、复合物涂层、可溶性的粉末涂层、粘着剂和粉末的混合物、轻微烧结粉末等。聚合物包括任何可模压的聚合物，包括(但不局限于)(甲基)丙烯酸脂(包括丙烯酸酯和(甲基)丙烯酸酯)、聚碳酸酯、乙烯聚合物树脂、聚酰胺、聚酰亚胺、聚氨酯、聚硅氧烷、聚酯(例如，聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯)、聚醚等。如二氧化硅、氧化铝、氧化锆、三价铬、四价钛和其它金属氧化物(卤化物)或半金属氧化物(卤化物)的材料不管是以干的形式还是以溶胶的形式(含水的、无机溶液或有机溶液)可以被用作为可模压的材料。混合聚合物和非聚合物材料的复合材料包括微纤维和微粒也可以被用作为铸模材料。
在一个实施例中，薄膜20是在硅晶片18上的PMMA细丝。PMMA的厚度是50nm到250nm。有几种原因选择PMMA。首先，即使由于PMMA的亲水表面，它没有与SiO2铸模粘着很好，也可以适用本发明的脱膜层进一步减小粘性。好的铸模脱模特性是制造十亿分之一功能部件的基本条件。其次，PMMA的收缩在大的温度和压力变化下小于0.5％。见I.Rubin，注射模压，(Wiley,New York)1992。在模铸处理中，铸模10和PMMA20首先被加热到高于PMMA的玻璃转变温度105℃的温度200C。见M.Harmening,W.Bacher,P.Bley,A.EI-Kholi,H.Kalb,B.Kowanz,W. Menz,A.Michel,and J.Mohr,IEEE微电子机械系统，202(1992)。然后，相对薄膜20压缩铸模10和功能部件16，并保持在那，直到温度降到PMMA的玻璃转变温度以下。已经试验了多种压力。已经发现一个优选的压力是400-1900psi，特别是500-1000psi。在这个压力上，特别是当脱膜由脱膜层17的存在加速时，功能部件16的图形可以全部转入PMMA。在除去铸模10之后，使用氧等离子体除去压缩区域中的PMMA，暴露下面的硅基片，在PMMA的整个厚度上复制铸模的图形。当然，铸模压力取决于所用的特殊的聚合物，因此，根据不同的材料而变化。
图2是由压缩铸入图1C所示的PMMA膜形成的具有120nm周期的25nm直径孔的顶视图的扫描电子显微照片。在相同铸膜上的数十微米大的功能部件与十亿分之一的铸模功能部件一样已经被刻印。
图3显示图lC所示的在PMMA形成的具有200nm周期、100nm宽槽的顶视图的扫描电子显微照片。
图4是使用本发明在PMMA膜中形成的槽的透视图的扫描电子显微照片，薄膜20的顶部24a接触铸模10的压缩的表面16a。条带是70nm宽，200nm高，并具有高的纵横比。这些PMMA功能部件的表面非常平滑，表面粗糙度小于3nm。条带的角几乎是完美的90度角。这种平滑度、尖锐的直角和在70nm功能部件尺寸上的这么高的纵横比在现有技术中是不能获得的。
此外，PMMA图形和铸模的扫描电子缩微照片显示使用本发明制造的侧面的功能部件尺寸和PMMA图形的侧壁的平滑度与铸模一致。根据我们的观察，很明显目前由本发明获得的功能部件的尺寸由我们的铸模尺寸所限制。从刻印的PMMA的结构看，本发明可以制造10nm的功能部件。
在步骤1A-1D之后，薄膜20中的图形可以被复制在加到基片18上的材料内，或可以直接复制在基片18内。图5A和5B显示了图1A-1D后的步骤的一个例子。在图1D所示的形成凹槽28之后，材料30的层被淀积在图5A所示的基片18上。材料30通过任何要求的技术淀积在隔墙26上，并进入隔墙26之间的凹槽28。例如，材料30包括用于制造集成电路的电导体、半导体或电介质，还包括制造磁性器件的铁磁插件。下一步，进行脱模处理，在该处理中，选择化学蚀刻除去隔墙26，使得淀积在隔墙26的顶部上的材料30被除去。
图5B显示了脱模处理之后的结构。由材料30形成的多个单元32在基片18的表面被脱模。单元32是用于形成小型化器件如集成电路的类型。重复类似于步骤1A-1D的后面的处理步骤在基片18上形成附加的层。
图6是图2淀积5nm钛和15nm金和脱模处理后基片的扫描电子显微照片。在脱模处理中，晶片被浸泡在丙酮中溶解PMMA，因此，脱去了PMMA上的金属。金属点有25nm直径，其与使用本发明在PMMA中产生的孔相同。
图7是图3淀积5nm钛和15nm金和脱模处理之后的基片的扫描电子显微照片。金属线宽是100nm，与图3所示的在PMMA槽的宽度相同。图6和图7已经显示在本发明的氧RIE处理期间，压缩的PMMA区域完全被除去，PMMA功能部件的侧面尺寸没有改变。
图8是另一处理步骤例子之后的图1D基片的剖面图，该步骤把薄膜20中的图形直接复制在基片18内。在图8中，基片18已经暴露到蚀刻处理，例如，反应离子蚀刻、化学蚀刻等，以至凹槽40形成在基片18内。这些凹槽40可以被用于随后的处理步骤。例如，凹槽40可以用制造器件的材料填充。这正好是连同本发明所用的随后处理步骤的例子。
模制处理基本上使用两块平板在其之间形成可伸展的材料。在本发明中，基片18和基体12(铸模10)作用就像用于本发明的刻印处理的平板。基片18和基体12应当足够硬，以在形成刻印时减少弯曲。这样的弯曲在薄膜20中形成图形时容易变形。
图9是本发明进行十亿分之一平板印刷术的装置50的简化的方框图。装置50包括支撑基片18的固定刻板52，支撑铸模10的可移动的铸模刻板54。刻板52和54支撑图1A-1D所示的基片18和铸模10。控制器56连接到x-y定位器58和z定位器60。对齐标记64是在铸模10上，标记68在基片18上。刻板54携带的传感器62连接到对齐标记64和68，并向控制器56提供对齐信号。控制器56也提供输入输出电路。
在操作中，控制器56是用来控制铸模10刻印入基片18上的膜20，通过在相对刻板52的z方向驱动z定位器60移动刻板54。在刻印处理期间，铸模10和薄膜20的精确对齐是至关重要的。这可以使用光或电对齐技术得到。例如，传感器62和对齐标记64和68可以是光学检测器和产生波纹对齐图形的光对齐标记，以至采用波纹对齐技术定位相对薄膜20的铸模10。这种技术由Nomura等论述在‘用于混合和匹配平板印刷系统的波纹对齐技术“J.Vac.Sci.Technol.B6(1),Jan/Feb 1988,pg.394和Hara等论述的“使用偏转波纹信号的对齐技术”J.Vac.Sci,Technol.B7(6),Nov/Dec 1989,pg.1977。控制器56处理这个对齐信息，并使用x-y定位器58在相对薄膜20的x-y平面调整刻板54的位置。在另一个实施例中，对齐标记64和68包括电容器板，以便传感器62检测标记64和68之间的电容量。使用这种技术，通过在x-y平面移动刻板54使对齐标记64和68之间的电容量最小而获得对齐。在刻印期间，控制器56也监视和控制薄膜20的温度。
应当理解，本发明没有局限于在此论述的特殊技术，可以以任何适当的平板印刷处理实施。一般说来，在铸模处理期间，铸模应当比薄膜硬。例如，这可以通过加热薄膜获得。此外，应当理解，本发明没有局限于在此论述的特殊薄膜。例如，可以使用其他类型的薄膜。在另一个实施例中，可以显影薄膜，该薄膜具有在压力下改变的化学成分。因此，在刻印处理之后，应当对薄膜进行化学蚀刻，选择性地蚀刻掉在压力下改变成分的这些部分。在另一个实施例中，薄膜的模制在薄膜中产生厚度差异之后，在薄膜上淀积一种材料，然后，厚度差异转入基片。
尽管本发明已经参考优选实施例进行了描述，本领域的技术人员将理解，在没有远离本发明的精神和范围内，可以在形式和细节上进行变化。
实施例
按照本发明的平板印刷处理的实施例，形成在基片上的薄膜中的图形将通过在基片上淀积薄膜的步骤，以提供具有突出的功能部件和凹槽的铸模，功能部件和凹槽具有形成铸模的形状。至少表面的一部分(在这个例子中，最好是二氧化硅或硅一氮化物)，如突出的功能部件，如果不是薄膜被淀积的全部表面(在突出之间的突出和凹谷)，被涂敷有脱膜材料，脱膜材料具有下述公式：
RELEASE-M(X)n-1 -’         公式Ⅰ
RELEASE-M(X)n-m-1Qm’公式Ⅱ
或
RELEASE-M(OR)n-1 -’       公式Ⅲ
RELEASE是在长度上4到20个原子的分子链，长度上最好是6到16个原子，其中，分子具有极性或非极性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
Q是氢或烃基；
M是Q基团的数量；
R是氢、烃基、苯基，最好是1到4个碳原子的氢或烃基；
公式Ⅱ中的n-m-1至少是1(m是2或小于2)，较好是2(m是1或小于1)，最好是3(m是0)。
(n)是M的-1价。
C1到C4烃基(对R)的硅化合物(纯或在溶液中)是优选的，其中X是F，RELEASE是全氟烃基。特别地，已经发现1H、1H、2H、2H-全氟十二烷基甲基三氯硅烷(市场上可以得到97％的固溶体)在本发明中特别有用。(三乙氧基硅烷的相似物趋于要求较活跃的激励确保扩展健合到表面。1H、1H、2H、2H-全氟十二烷基甲基三氯硅烷在效果上与1H、1H、2H、2H-全氟十二烷基三氯硅烷相近，具有稍微减少的在硅烷上代替氯基之一的附加甲基的活跃性。类似地，商业上可得到的1H、1H、2H、2H-全氟十二烷基二甲基氯硅烷将有稍微少的反应)。这个1H、1H、2H、2H-全氟十二烷基三氯硅烷成分被涂敷在大约表面积的0.01mg/m2(室温、气密的、通风环境)，并加热(摄氏40到50度)到反应材料到表面，并且冷却。这在表面上形成涂层，在涂层中，分子的反应部分(SiF健合)与二氧化硅或硅氮表面反应，形成的涂层包括键合到从表面延伸的全氟烃基的尾部的表面的硅原子，剩下减少的摩擦表面。然后，铸模被推入薄膜，因此，在突出的功能部件下的薄膜被减少，薄区形成在薄膜内。从薄膜除去铸模，对浮雕进行处理。除去薄区，暴露了在薄区下面的基片表面的部分。基片表面的暴露部分基本上复制了铸模图形。至少所述突出的功能部件部分和本发明键合的脱模材料的脱模部分的改善改进了脱模和铸模操作的分辨率。重要的是，本发明的脱膜涂层已经证明是持续的和可重新使用的，特别是，使用适度的压力(例如，小于1000psi)，以及，薄膜不包括化学上腐蚀脱膜涂层的成分。全氟化R基的脱膜涂层的选择帮助提供耐化学腐蚀的涂层。重要的是应当注意，本发明的处理和脱膜涂层材料可由简单的涂敷和脱膜涂层的反应制成，形成本发明的材料，并且，这些材料可以在等效的大范围内广泛使用。材料可以作为纯材料涂敷，并允许在周围环境下反应(材料特别对表面活跃)，它们可以在溶液中稀释涂层(小心选择溶剂，溶剂本身对形成脱膜涂层的化合物是不活跃的，最好对表面也是不活跃的)，它们的反应可由热、催化剂、引发剂(例如，热气或光引发剂，如氟化磺酸、锍、具有复杂卤化物阳离子的碘翁光引发剂，例如，三芳基锍-六氟锑酸盐、二芳基碘-四氟硼酸盐)加速剂等加速。
本发明的脱膜形成涂层可以通过简单的施加化学成分到与它反映的表面作为脱膜涂层(基本上具有自由氢原子的任何表面，该表面与卤素、有机酸、硅或无机酸、羟基、含氢的胺基、硫醇基)。表面可以是聚合物表面、金属化表面、合金表面、陶瓷表面、复合物表面、有机表面、无机表面、平滑表面、粗糙表面、结构表面、图形表面等。温度和溶剂的使用仅由它们对基片和涂层的影响所限制。即，在降解表面或降解涂层材料，或快速挥发没有粘着的涂层材料期间，不使用温度。如上所述，可以使用催化剂和引发剂，但是，本发明的形成化合物的脱膜涂层可以在室温反应，而不需要使用激励。
已经将1H、1H、2H、2H-全氟十二烷基三氯硅烷作为脱模表面涂布到Si表面上、Sin表面上等，只是在室温对该表面使用商业上可得到的1H、1H、2H、2H-全氟十二烷基三氯硅烷(没有改变)。公式Ⅰ的化合物是最优选的(主要因为它们的活跃性)，公式Ⅱ是较少优选，公式Ⅲ是最少优选，因为它们对表面减少的活跃性。

Claims (29)

1．一种在基片上支撑的薄膜内形成图形的平板印刷方法，包括步骤：
在基片上淀积薄膜，提供具有突出的功能部件和形成在附近的凹槽，功能部件和凹槽具有形成的铸模图形的形状；
把铸模压入薄膜，在突出的功能部件下的薄膜的厚度被减小，在薄膜中形成薄区；
从薄膜中除去铸模；
处理浮雕，因此，除去薄区，暴露了薄区下的基片的表面部分；
基片表面的暴露部分基本上复制了铸模图形，
改进包括至少所述突出的功能部件的一部分和所述脱模的一部分已经健合了脱模材料，所述脱模材料包括键合到具有脱模特性的分子链的无机连接基。
2．按权利要求1所述的方法，其特征在于脱模材料包括具有下述公式的材料：
RELEASE-M(X)n-1 -
或
RELEASE-M(OR)n-1 -，其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
(n)是M的-1价。
3．按权利要求2所述的方法，其特征在于RELEASE包括高氟化的有机基团。
4．按权利要求3所述的方法，其特征在于高氟化基团包括全氟化烃基基团。
5．按权利要求2所述的方法，其特征在于X是卤素。
6．按权利要求2所述的方法，其特征在于X是氯或溴。
7．按权利要求1或2或3或4或5或6所述的方法，其特征在于M是Si。
8．一种改进表面的脱模特性的方法，包括
(a)提供一个表面；
(b)用脱膜形成材料接触该表面，其中，所述脱膜形成材料包括具有下述公式的材料：
RELEASE-M(X)n-1 -
或
RELEASE-M(OR)n-1 -，其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
(n)是M的-1价。
9．按权利要求8所述的方法，其特征在于所述脱模形成材料包括具有下述公式的材料：
RELEASE-M(X)n-1 -
其中
RELEASE是在长度上4到20个原子的分子链，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
(n)是M的-1价。
10．按权利要求9所述的方法，其特征在于RELEASE包括高氟化有机基团。
11．按权利要求10所述的方法，其特征在于高氟化基团包括全氟化有机基团。
12．按权利要求11所述的方法，其特征在于高氟化基团包括4到16个碳原子的全氟化烃基基团。
13．按权利要求8或9或10或11或12所述的方法，其特征在于M是Si。
14．一种具有良好的抗粘着特性的表面，包括表面已经健合，有材如下公式的材料的残余物：
RELEASE-M(X)n-1 -
或
RELEASE-M(OR)n-1 -，其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
(n)是M的-1价。
所述的材料只通过直接键合到M被键合到所述表面，其中，基团X或OR已经被除去，以能够键合到表面，而基团RELEASE仍然敷着到M。
15．按权利要求14所述的表面，其特征在于所述材料包括下述公式的材料：
RELEASE-M(OR)n-1 -，
其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
(n)是M的-1价。
16．按权利要求15所述的表面，其特征在于RELEASE包括高氟基团。
17．按权利要求16所述的表面，其特征在于所述高氟基团包括全氟基团。
18．按权利要求17所述的表面，其特征在于高氟化基团包括4到16个碳原子的全氟基团。
19．按权利要求14或15或16或17或18所述的表面，其特征在于M是Si。
20．一种具有良好的抗粘着特性的表面，包括表面已经健合，有下述公式的材料：
RELEASE-M(X)p-2
或
RELEASE-M(OR)p-2’其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
p是M的原子价。
所述的材料只通过直接键合到M被键合到所述表面。
21．按权利要求20所述的表面，其特征在于表面包括形成图形的铸模表面。
22．按权利要求1所述的方法，其特征在于从基团选择的材料在铸模上形成的功能部件包括：半导体、电介质、金属、陶瓷、聚合物和它们的组合物。
23．按权利要求14所述的表面，其特征在于表面包括从以下组类选择的材料：半导体、电介质、金属、陶瓷、聚合物和它们的组合物。
24．按权利要求1所述的方法，其特征在于处理步骤包括反应性的离子蚀刻。
25．按权利要求1所述的方法，其特征在于包括重复获得铸模、压入、除去和处理的步骤，以形成多层器件。
26．一种在基片上支撑的薄膜内形成图形的平板印刷方法，包括步骤：
获得由化合物反应形成的具有脱膜涂层的基片，按下述公式
RELEASE-M(X)n-1 -
或
RELEASE-M(OR)n-1 -，其中
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
R是氢、烃基、苯基，较好是1到4个碳原子的氢或烃基；
(n)是M的-1价；
在基片上淀积薄膜；
获得具有突出的功能部件和形成在附近的凹槽的铸模，功能部件和凹槽具有形成的铸模图形的形状；
把铸模压入薄膜，在薄膜中产生厚度反差图形；
从薄膜中除去铸模；
转移薄膜中的厚度反差图形到基片上。
27．一种改进表面的脱模特性的方法，包括：
     (a)提供一个表面；
     (b)用脱模形成材料接触该表面，其中，所述脱模形成材料包括具有下述公式的材料：
RELEASE-M(X)n-m-1Qm，
RELEASE是在长度上4到20个原子的分子链，长度最好是6到16个原子，其中，分子具有极性特性或非极性特性；
M是金属原子或半金属原子；
X是卤素或氰基，特别是CI、F、Br；
Q是氢、烃基基团；
n-m-1至少是1；
n是M的-1价。
28．按权利要求27所述的方法，其特征在于所述的脱模材料包括具有下述公式的材料：
RELEASE-M(X)n-1 -
29．按权利要求28所述的方法，其特征在于M是Si；
X是卤素CI或Br；
RELEASE是6到20个碳原子的全氟烃基；以及
N是3。
CNB998086878A 1998-06-30 1999-06-30 具有脱模剂的表面 Expired - Lifetime CN1230713C (zh)

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