CN1116363A - 在高温金属层上形成介质层的方法 - Google Patents

在高温金属层上形成介质层的方法 Download PDF

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CN1116363A
CN1116363A CN95101413A CN95101413A CN1116363A CN 1116363 A CN1116363 A CN 1116363A CN 95101413 A CN95101413 A CN 95101413A CN 95101413 A CN95101413 A CN 95101413A CN 1116363 A CN1116363 A CN 1116363A
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詹姆斯·A·塞勒斯
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Abstract

提供一种在高温金属层14上形成介质层的方法。通过用非氧化光致抗蚀剂去除剂处理高温金属层14而没有光致抗蚀剂硬化步骤，在高温金属层14与接下来形成在高温金属层14上的介质层16间的粘附被大大地改善。在高温环境介质层16将粘附到高温金属层14上。这个方法适于半导体集成电路的多层金属化及埋层结构。

Description

在高温金属层上形成介质层的方法
本发明总的涉及在导体层上形成钝化层的方法，特别地涉及在高温金属层上形成介质层的方法。
集成电路及内连接通常的构成中包括重掺杂多晶硅。然而由于重掺杂多晶硅薄层的表面电阻在20欧姆/方块(ohms/square)的数量级上，这些薄层造成长的阻容(RC)时间常数，因而引起了不希望的时间延迟。这个不希望的时间延迟极大地影响了制造致密和高性能半导体器件的能力。所以，已使用几种方法来改进半导体内连接的表面电阻。
一种方法是聚化物(polycide)方法，是在被掺杂的多晶硅层上形成金属硅化物。这种方法的一个缺点是，需要沉积和布图二个薄层。而且当在多晶硅上形成金属硅化物层时，硅化物的形成倾向于消耗多晶硅层中的掺杂物从而增加多晶硅层的表面电阻。
使用高温金属层，如钛Ti，钒V，铬Cr，钽Ta或它们的氮化物作为埋层或作为内连接是人们所希望的，因为只须沉积及构图的只有一个薄层。此外，高温金属层将提供一个低表面电阻并且没有在聚化物过程所产生的掺杂物消耗问题。然而当使用已成图案的高温金属层，例如作为掩埋的内连接时，在这个高温金属层上形成有介质层，在金属层与介质层间会发生脱层，这种情况尤其在这些薄层又被暴露于高温时特别真实。这种脱层可导致电子元件可靠性问题。
因而，就需要有一种方法在高温金属层上形成介质层，使介质层与高温金属层间有良好附着力。
简单地讲，本发明的目的是提供一种在高温金属层上形成介质层的方法。在基片的第一表面上形成已成图案的高温金属层。用非氧化湿性光致抗蚀剂去除剂(wet photoresist stripper)去除用来使高温金属层布图的光致抗蚀剂。然后在高温金属层上形成一介质层。
图1示出了本发明一实施例的放大的剖面图；
图2-7示出了本发明图1实施例在制备的各个阶段的放大剖面图。
图8示出了根据本发明的图1实施例在另一制备阶段的放大剖面图；
图9示出了本发明的第二实施例的放大剖面图。
总的来说，本发明提供在高温金属层上形成介质层的方法。本发明通过参照图1至9可更完全地来描述。作为本发明的实施例，图1示出了带掺杂区12的基片11以及在基片11一个表面上形成的介质层13的放大剖面图。典型地，基片11由半导体材料构成。掺杂区12与基片11比较可以是相同或相反导电率型的。
当与其它掺杂区一起形成时，掺杂区12例如形成场效晶体管的源极或漏极、或双极型晶体管的集电极、基极、或发射极。高温金属层14在介质层13上形成并与掺杂区12相接触。高温金属层14也可以，例如在没有介质层13的情况下与基片11完全接触来形成埋入层。最好，高温金属层14包括：钛Ti、氮化钛、钒V、氮化钒、铬Cr、氮化铬、钽Ta或氮化钽。这些高温金属之所以较好是因为它的表面电阻值在少于10欧姆/方块的数量级上。此外，它们拥有有利于形成氧化物的自由能因而与介质如硅氧化物形成良好接合。然而要在高温金属层14与介质间形成良好接合，必须适当处理高温金属层14。本发明提供这样的加工。在最佳实施例中，高温金属层14由氮化钛构成。介质层16在高温金属层14上形成，来为例如多层金属化法(a multi-level metallization sckeme)提供钝化。
实验表明，为了在高温金属层14与介质层16间提供好的粘合，高温金属层14在介质层16之前必须在非氧化环境中进行处理。除其它因素外还发现高温金属层14在介质层16沉积之前，其表面氧化大大地降低了两层之间的粘合，特别是当高温金属层14与介质层16被暴露于800℃以上的温度时。
作为介质层16在沉积之前在非氧化环境中处理高温金属的方法的一个例子，图2示出了在制备的早期阶段中的基片11。在介质层13上形成一开口19来提供与掺杂区12的接触。下一步如图3所示，在介质层13及基片11上形成高温金属层14来与掺杂区12相接触。在使用如溅射，活性蒸镀(reactive evaporation)及化学气相沉积技术的领域中形成高温金属层14的方法是熟知的。
在最佳实施例中，高温金属层14包括氮化钛且最好用活性离子溅射沉积来形成，在这种方法中钝钛金属靶在氮气存在的情况溅射。最好是氮化钛因为氮化钛薄膜具有表面电阻值在5欧姆/方块数量级，它们在高温下稳定，它们提供良好的扩散障碍，它们具有低应力，且对与凹蚀(undercutting)及腐蚀有关的蚀刻有很高的抵抗。
图4示出了在制造中另一阶段的基片11。光致抗蚀剂层17沉积在高温金属层14上。光致抗蚀剂层17由负性抗蚀剂或正性抗蚀剂之一构成。光致抗蚀剂层17最好用正性抗蚀剂如JRS 1X500EL 30 CD抗蚀剂，从日本Japan Synthetic Rubber Co.公司可获得。在光致抗蚀剂层17沉积后，以一低温来软烘焙光致抗蚀剂17以便脱水并去除多余溶剂。下一步，用光掩模有选择地将光致抗蚀剂层17暴露于光中。
如图5所示，在暴光之后，光致抗蚀剂层17被显影来有选择的去除光致抗蚀剂从而形成所期望图案。为了使正性光致抗蚀剂显影，使用pH值碱性的含非金属离子的显影剂如四甲基铵氢氧化物(tetrra-methyl ammonium hydroxide)。这样的显影剂是MFCD-26，从Shipley公开可获得。在显影之后，光致抗蚀剂层17最好不经受硬化处理，如深紫外线辐射或低能惰性气体等离子体以防止光致抗蚀剂过度硬化。实验表明光致抗蚀剂硬化处理会导致在去除剩余光致抗蚀剂层17之后残留光致抗蚀剂保留在高温金属层14，特别围绕在基片11的周边。当使用湿性光致抗蚀剂涂层去除剂而非干性去除剂时尤为明显。已发现在高温金属层14表面上的残留光致抗蚀剂会促成高温金属层14与介质层16间的不良粘着问题。
下一步，如图6所示，刻蚀高温金属层14形成由剩余光致抗蚀剂17提供的图案。例如用活性离子刻蚀系统与以氯为基本组分的化学剂(Chlorine based chemistry)来刻蚀高温金属层14。在某些应用中，最好不用BCl3为基本组分的化学剂来刻蚀高温金属层14因为残留的BCl3可以保留在不受光致抗蚀剂层17保护的刻蚀表面上。残留的BCl3在接下来的高温处理过程中为硼扩散进基片11提供3潜在的掺杂源，因而形成不希望的P型区。
如图7所示，在高温金属层14刻蚀后，用非氧化湿性光致抗蚀剂去除剂去除剩余光致抗蚀剂层17。当光致抗蚀剂层17由正性抗蚀剂构成时，使用由N—甲基吡咯烷酮(n-methyl pyrrolidone(NMP))构成pH值碱性的非氧化湿性光致抗蚀剂去除剂。这样的去除剂的例子是PosistripTM，从EKC Technologies of Hayward，Califomia公司可获得。当光致抗蚀剂17由负性抗蚀剂构成时，使用由重芳族有剂溶剂与磺酸衍生物(sulfonic acid derirative)构成的非氧化湿性光致抗蚀剂去除剂。这种光致抗蚀剂去除剂的例子是NS-12从Advanced Chemical Techpologies Inc.ofAllentowam Pennsylvania公开可获得。
为了防止高温金属层14的表面氧化及其带来的粘附问题，不用干性氧化基光致抗蚀剂去除方法如氧气等离子体来去除剩余光致抗蚀剂层17。实验表明如果使用任何干性氧化基光致抗蚀剂去除方法，来去除形成在高温金属层14上光致抗蚀剂层，会导致高温金属层14与其后在高温金属层14上形成的介质层间的粘附问题。已发现由于干性氧化基光致抗蚀剂去除方法造成的高温金属层14的表面氧化是粘附问题的很大成因。而且如果对高温金属层14需要光致抗蚀剂或刻蚀再加工，则必须使用湿性光致抗蚀剂去除剂来防止其后的粘附问题。
在最佳实施例中，为去除光致抗蚀剂层17，顺次使用包含NMP的二个槽。第一个槽最好再循环及过滤并保持在约75到85℃。带有光致抗蚀剂层17的基片11在第一槽中暴露于NMP约15分钟。第二槽最好保持在约45到55℃并用来去除任何残留的光致抗蚀剂层17。基片11暴露在第二槽中的NMP里约5分钟。在第二NMP槽之后，用去离子水清洗基片11并用普通的冲洗器/干燥器技术干燥基片11。
再参看图1，在去除光致抗蚀剂层17后，在高温金属层14上形成介质层16。介质层可以是氧化硅，氮化硅，氮氧化硅，PSG或BPSG。在最佳实施例中，介质层16是使用增强型等离子体(PE)化学气相沉积从四乙基原硅酸酯TEOS(tetraethylorthosilicate)中沉积出氧化硅，通常称作增强型等离子体四乙基原硅酸酯(PETEOS)。比较可取是，以约125至145埃/秒(Angstroms/Second)的生长速度在约400℃的温度下沉积。
介质层16可以被形成图案也可不形成图案。如图8所示，可以使介质层16形成图案来形成通道21提供高温金属层14与金属化触点22的接触。可用上述过程来形成多层金属及介质。在沉积之后，可选地介质层16被退火来减少介质层16内的应力，特别是位于形成图案的高温金属层14的边缘。较好地，在介质层16由PETEOS构成时，在一隋性气体如氮气中并加少于3000ppm浓度氧气在约1000℃时将介质层退火约60分钟。隋性气体的使用较好地防止由于氧气通过介质层6扩散引起的高温金属层14的氧化。此外，退火使PETEOS致密稳定化，利于进一步的高温处理。
图9示出了第二个实施例，这里在介质层16上形成第二个介质层18来提供附加的屏障防止高温金属层14氧化。当基片11在高温金属层14及介质层16形成后被暴露于侵蚀性氧化环境如高温湿性氧化过程时，第二介质层18就是一种有效抵抗各种氧化物质的障碍。这种第二介质层的一个例子是氮化硅。
到现在为止，应当理解本发明提供了一种用于在高温金属层上形成介质层的方法。通过没有光致抗蚀剂硬化步骤来处理用于为高温金属层形成图案的光致抗蚀剂层以及用非氧化光致抗蚀剂去除剂去除用于为高温金属层形成图案的光致抗蚀剂层，大大改善了在高温金属层及接着形成在高温金属层上的介质层之间的粘附问题。甚至在接下来的高温环境中介质层将粘附到高温金属层上。

Claims (10)

1.用于在高温金属层上形成介质层的方法，其特征在于包括步骤：
提供带有第一及第二表面的基片；
在基片的第一表面形成高温金属层，其中高温金属层具有利于氧化物形成的自由能；
在高温金属层上沉积光致抗蚀剂层；
有选择地将光致抗蚀剂层暴露于光；
使光致抗蚀剂层显影以便有选择地去除光致抗蚀剂来在光致抗蚀剂层形成图案；
与光致抗蚀剂层的图案相一致刻蚀高温金属层；
用非氧化光致抗蚀剂去除剂去除剩余的光致抗蚀剂；
在高温金属层上形成介质层。
2.如权利要求1所述的方法，其中在基片的第一表面上形成高温金属层的步骤包括，形成一金属层，金属层是从由钛、氮化钛、钒、氮化钒、铬、氮化铬、钽、及氮化钽组成的组中选择的；其中形成介质层的步骤包括，使用增强型等离子体化学气相沉积从TEOS中沉积出氧化硅层。
3.如权利要求1所述的方法，其中使光致抗蚀剂层显影的步骤包括，在刻蚀高温金属步骤之前且没有光致抗蚀剂硬化步骤，使光致抗蚀剂层显影。
4.如权利要求1所述的方法，其中沉积光致抗蚀剂层的步骤包括，沉积正性光致抗蚀剂，且用非氧化光致抗蚀剂去除剂去除光致抗蚀剂层的步骤包括，用包含pH值碱性的N—甲基吡咯烷酮构成的去除剂去除光致抗蚀剂层。
5.如权利要求4所述的方法，其中去除光致抗蚀剂的步骤包括有：在保持在约75到85℃温度的N—甲基吡咯烷酮第一槽中去除光致抗蚀剂层并在保持在约45到55℃温度的N—甲基吡咯烷酮第二槽中去除残留光致抗蚀剂。
6.如权利要求1所述的方法，进一步的特征在于包括在隋性气体中介质层退火的步骤。
7.如权利要求6所述的方法，其中退火步骤包括将介质层在氮气中加热到约1000℃。
8.在氮化钛层上形成介质层的方法，其中介质层在高温条件下粘附在氮化钛上，其特征在于包括步骤：
提供具有第一表面或第二表面的半导体基片；
在第一面上形成氮化钛层；
在氮化钛层上沉积光致抗蚀剂层；
将光致抗蚀剂层有选择地暴光；
将光致抗蚀剂层显影来有选择地去除光致抗蚀剂以便在光致抗蚀剂层内形成图案，其中光致抗蚀剂层被显影而没有接下来的光致抗蚀剂的硬化步骤；
刻蚀氮化钛，使氮化钛层与光致抗蚀剂层的图案相一致；
用非氧化光致抗蚀剂去除剂去除剩余光致抗蚀剂；
在氮化钛层上沉积介质层；且
在带有少于3000ppm氧气的惰性环境中使介质层退火。
9.如权利要求8所述的方法，其中沉积光致抗蚀剂层的步骤包括，沉积正性光致抗蚀剂，且用非氧化光致抗蚀剂去除剂去除光致抗蚀剂层的步骤包括有：用包含pH值碱性的N—甲基吡咯烷酮组成的去除剂去除光致抗蚀剂层，其中在温度保持在约75到85℃的N—甲基吡咯烷酮第一槽中去除光致抗蚀剂，并且在温度保持在45—55℃的N—甲基吡咯烷酮第二槽中去除残留光致抗蚀剂。
10.如权利要求8所述的方法，其中沉积介质层的步骤包括：
用包含TEOS的加增型等离子体源沉积氧化硅。
CN95101413A 1994-02-02 1995-01-20 在高温金属层上形成介质层的方法 Pending CN1116363A (zh)

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