CN1714168A - 用于下一代镶嵌阻挡应用的具有良好抗氧化性的双层膜 - Google Patents

用于下一代镶嵌阻挡应用的具有良好抗氧化性的双层膜 Download PDF

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CN1714168A
CN1714168A CNA2003801004692A CN200380100469A CN1714168A CN 1714168 A CN1714168 A CN 1714168A CN A2003801004692 A CNA2003801004692 A CN A2003801004692A CN 200380100469 A CN200380100469 A CN 200380100469A CN 1714168 A CN1714168 A CN 1714168A
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gaseous mixture
layer
silicon carbide
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silicoorganic compound
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郑毅
斯里尼瓦斯·D·内马尼
夏立群
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Abstract

本发明提供了用于处理衬底的方法，包括：向处理室提供包括含有苯基的有机硅化合物的处理气，并使处理气进行反应以沉积低k值碳化硅阻挡层，该阻挡层可用作具有低k值介电材料的镶嵌或双镶嵌应用中的阻挡层。本发明还提供了用于由包括无氧有机硅化合物的处理气在低k值碳化硅阻挡层上沉积基本没有与硅原子连接的苯基的碳化硅帽层的方法。

Description

用于下一代镶嵌阻挡应用的具有良好抗氧化性的双层膜
技术领域
本发明涉及集成电路的制备，更具体地涉及在衬底上沉积介电层的方法，以及由该介电层所形成的结构。本发明还涉及在衬底上沉积阻挡层的方法，以及由该阻挡层所形成的结构。
背景技术
自从几十年前半导体器件首次引入市场，这种器件的几何尺寸已经大幅减小了。自那时起，集成电路一般已经遵循“两年/一半大小”的规律(经常被称为Moore法则)，这意味着固定在芯片上的器件数量每两年加倍。当今的制造厂家通常生产0.35μm、甚至0.18μm特征大小的器件，很快将来的制造厂家将能生产几何尺寸更小的器件。
为了进一步减小集成电路上的器件大小，有必要使用低电阻率的导电材料和使用低介电常数(介电常数小于4.0)的绝缘体，以减小相邻金属线之间的电容耦合。这种低k值材料包括由化学气相沉积工艺所沉积的碳氧化硅和碳化硅，二者都可用作制备波纹镶嵌(damascene)特征的介电材料。
一种低电阻率的导电材料是铜及其合金，由于铜比铝具有更低的电阻率(铜为1.7μΩ-cm，铝为3.1μΩ-cm)、更高的电流和更高的承载能力，所以它们已经成为亚四分之一微米互连技术中的首选材料。这些性质对于支持更高的电流密度而言较重要，这种高电流密度在高度集成以及器件速度增加的情况下会遇到。而且，铜具有良好的导热率，并且能以高纯态使用。
在半导体器件中使用铜的一大困难是：铜较难蚀刻并难于获得精确的图案。利用形成互连的传统沉积/蚀刻工艺蚀刻铜不能令人满意。因此，生产具有含铜材料和低k值介电材料的互连的新方法正在发展中。
一种形成垂直和水平互连的方法是通过镶嵌(damascene)或双镶嵌(dual damascene)方法。在镶嵌方法中，例如低k值介电材料的一种或多种介电材料被沉积，并被蚀刻图案以形成例如通孔的垂直互连和例如线的水平互连。导电材料(例如含铜材料)和其他材料(例如用来防止含铜材料扩散进周围低k值介电材料内的阻挡层材料)接着被充填到蚀刻出的图案内。接着，去除任何在蚀刻图案外(例如在衬底区域上)的多余的含铜材料和多余的阻挡层材料。
但是，低k值介电材料经常是多孔的，容易造成例如铜的导电材料发生层间扩散，这样可能导致形成短路和器件故障。而且，低k值介电材料经常容易氧化。介电阻挡层材料经常被设置在铜材料和周围的低k值材料之间来防止层间扩散。但是，例如氮化硅的传统介电阻挡层材料的介电常数经常高达7或更大。这种高k值介电材料和周围低k值介电材料的组合导致介电叠层的介电常数高于所期望的值。
因此，一直需要一种改进的方法来沉积用于镶嵌应用的且其介电常数较低并且能较好地抗氧化的介电阻挡层材料。
发明内容
本发明一般地提供了用于沉积低介电常数的阻挡层和邻近该阻挡层的帽层的方法。一方面，本发明提供了一种处理衬底的方法，包括：通过将包括有机硅化合物的处理气体导入处理室中，并将该处理气体进行反应以沉积阻挡层，从而在衬底上沉积出碳化硅阻挡层，其中有机硅化合物具有结构式SiHa(CH3)b(C6H5)c，a为0-3，b为0-3，c为1-4，阻挡层的介电常数小于4，并包含与硅原子连接的苯基基团；以及通过将包括无氧有机硅化合物的第二处理气体混合物导入所述处理室中，并将第二处理气体混合物进行反应以沉积碳化硅帽层，从而在阻挡层上沉积出碳化硅帽层，其中碳化硅帽层基本没有与硅原子连接的苯基基团。
另一方面，本发明提供了一种处理衬底的方法，包括：通过将包括第一有机硅化合物的第一处理气体混合物导入处理室中，并将该处理气体进行反应以沉积阻挡层，从而在衬底上沉积出碳化硅阻挡层，其中所述第一有机硅化合物具有结构式SiHa(CH3)b(C6H5)c，a为0-3，b为0-3，c为1-4，阻挡层的介电常数小于4；以及通过将包括第二有机硅化合物的第二处理气体混合物导入处理室中，并将第二处理气体混合物进行反应以沉积碳化硅帽层，从而在阻挡层上沉积出碳化硅帽层，其中第二有机硅化合物具有结构式SiHx(CH3)y(C6H5)z，x为1-3，y为0-3，z为0-3。
附图说明
为使实现本发明上述方面的方式能够被详细理解，通过参照附图中所说明的其实施例，给出了本发明的更具体描述。
但是，应该注意到附图仅图示了本发明的典型实施例，因此不应认为是限制其范围，本发明承认其他等同有效的实施例。
图1是表示包括这里所述的低k值阻挡层和低k值介电层的双镶嵌结构的横截面视图；和
图2A-2H是表示本发明的双镶嵌沉积顺序的横截面视图。
为进一步理解本发明的方面，应该参照随后的详细描述。
具体实施方式
这里所述的本发明的一方面涉及用于沉积低介电常数的碳化硅阻挡层的方法和前驱体(precursor)。碳化硅阻挡层也可含有氢，并且可掺杂氧、氮、硼、磷及其组合，从而改善膜的性能。经掺杂的碳化硅一般包括少于约15原子百分比(atomic％)或更少的掺杂剂，例如氧、氮、硼、磷及其组合。
碳化硅阻挡层是这样沉积的：通过将包括结构式为SiHa(CH3)b(C6H5)c有机硅化合物的处理气在等离子体中进行反应，以形成包括碳-硅键并且介电常数小于4、优选小于约3.5的介电层，其中结构式中a为0-3，b为0-3，c为1-4。该沉积工艺过程中也可以存在含掺杂剂材料，例如用于掺杂氧的氧气(O2)或硅氧烷化合物，或用于掺杂硼的硼烷(BH3)。
意外并令人惊讶地发现：在这里所述的处理参数下，用结构式为SiHa(CH3)b(C6H5)c(其中a为0-3，b为0-3，c为1-4)有机硅化合物沉积碳化硅材料，生成介电常数小于4且阻挡层性能得以改善的碳化硅膜，例如其层间扩散阻力要比通过商用烷基硅烷前驱体(例如三甲基硅烷(TMS))生成的碳化硅膜约大100％。这一点是未预料到的，因为已观察到苯基增加了所沉积的介电材料的孔隙率，从而减小了所沉积的介电材料的层间扩散阻力。在阻挡层邻近介电层沉积的实施例中，阻挡层优选地邻近这样的介电层而沉积，该介电层包括硅、氧、碳和氢，其介电常数小于约4，例如小于约3。
用于阻挡层材料的有机硅化合物一般包括如下结构：
Figure A20038010046900081
其中R是苯基，R1、R2和R3是含H、C和/或Si的基团。该有机硅化合物包括结构式SiHa(CH3)b(C6H5)c，其中a为0-3，b为0-3，c为1-4，并且a+b+c等于4。由这种结构式所衍生的合适前驱体实例包括二苯基硅烷、二甲基苯基硅烷、二苯基甲基硅烷、苯基甲基硅烷及其组合。优选地，b为1-3，且c为1-3。用于作为阻挡层材料沉积的最优选有机硅化合物包括结构式SiHa(CH3)b(C6H5)c的有机硅化合物，其中a为1或2，b为1或2，c为1或2。优选的前驱体实例包括二甲基苯基硅烷和二苯基甲基硅烷。处理气也可以包括惰性气体，例如氩气(Ar)、氦气(He)、氖气(Ne)、氙气(Xe)、氮气(N2)及其组合。
处理气还可以包括具有Si-O-Si键基团的化合物(例如有机硅氧烷化合物)，具有Si-N-Si键基团的化合物(例如硅氮烷化合物)，以及它们的组合，从而分别用氧和氮来掺杂所沉积的碳化硅材料。例如三甲基硅烷(TMS)的烷基硅烷前驱体也可以与这里所述的有机硅前驱体一块使用，以改进或改变所期望的膜性能。
具有硅氧烷键的前驱体为碳化硅膜提供了键合的氧，这样可以减小膜的介电常数，并减小膜的漏电流。合适的硅氧烷前驱体实例包括例如1，3，5，7-四甲基环四硅氧烷(TMCTS)或八甲基环四硅氧烷(OMCTS)的环状化合物和例如1，1，3，3-四甲基二硅氧烷(TMDSO)的脂肪族化合物。
具有成键的氮的化合物可以提高膜的硬度，并减小膜的漏电流，例如在硅氮烷化合物中。合适的硅氮烷前驱体实例包括例如六甲基二硅氮烷和二乙烯基四甲基二硅氮烷的脂肪族化合物以及例如六甲基环三硅氮烷的环状化合物。
阻挡层还可以掺杂氧、硼或磷来减小所沉积材料的介电常数。处理气中掺杂剂与有机硅化合物的原子比约为1∶5或更大，例如在约1∶5与约1∶100之间。将磷和/或硼掺杂到低k值碳化硅层可以这样进行：即在沉积工艺过程中，将膦(PH3)或硼烷(BH3)，或例如二硼烷(B2H6)的其硼烷衍生物引入室内。
氧掺杂可以通过任选地包括含氧气体来进行，例如氧气(O2)、臭氧(O3)、一氧化二氮(N2O)、一氧化碳(CO)、二氧化碳(CO2)或它们的组合。硅氧烷化合物也可以与处理气一起使用以对所沉积材料进行氧掺杂。氮掺杂可以通过任选地包括含氮气体来进行，例如氨气(NH3)、氮气(N2)、硅氮烷化合物或它们的组合。
在一个实施例中，碳化硅阻挡层可以是这样沉积的：即以约10mg/min(mgm)-约1500mgm之间的流速向等离子处理室中提供例如二苯基硅烷的有机硅化合物，任选地以约10sccm-约2000sccm之间的流速提供掺杂剂，以约1sccm-约10000sccm之间的流速提供惰性气体，保持衬底温度在约0℃-约500℃之间，保持室压力在约500Torr以下，RF(射频)功率在约0.03W/cm2-约1500W/cm2之间。
RF功率可以以例如在13MHz-14MHz之间的高频和/或例如在100KHz-1000KHz之间的低频提供。RF功率可以被连续提供或者以短的持续周期提供，其中对于小于约200Hz的周期，所提供的功率都处在规定水平(stated level)，并且提供功率的周期总和占总的工作周期的约10％-约30％。处理气可以通过气体分配器而被引入室内，该气体分配器可以放置在距离衬底表面约200mil-约1200mil处。在沉积工艺过程中，该气体分配器可以放置在约300mil-约800mil处。
用于进行这里所述工艺的合适反应器是来自Applied Materials，Inc.，Santa Clara，California的商用DxZTM化学气相沉积室。可应用这里所述工艺的CVD反应器实例在授权给Wang等并被转让给Applied Materials，Inc.的、题为“A Thermal CVD/PECVD Reator and Use for Thermal ChemicalVapor Deposition of Silicon Dioxide and In-situ Multi-step PlanarizedProcess”的美国专利No.5,000,113中描述了。
当在Applied Materials，Inc.，Santa Clara，California的沉积室中200mm(毫米)衬底上实现时，以上工艺参数提供了在约50/min-约20,000/min范围内的碳化硅层沉积速率，例如在约100/min-约3,000/min范围内。
优选的碳化硅阻挡层沉积工艺实例包括：以约500mg/min的流速将二甲基苯基硅烷引入处理室内，以约1000sccm的流速将氦气引入处理室内，通过施加200W的RF功率在处理室中生成等离子体，保持衬底温度约为350℃，保持室压力约为6Torr，从而沉积碳化硅阻挡层。气体分配器与衬底表面之间的间距为450mil。通过这种工艺，可以以约1500/min的速率沉积碳化硅阻挡层。所沉积的碳化硅阻挡层的介电常数约为3.4。
优选的碳化硅阻挡层沉积工艺的其他实例包括：以约100mg/min的流速将二甲基苯基硅烷引入处理室内，以约2000sccm的流速将氦气引入处理室内，通过施加100W、200W或300W的RF功率在处理室中生成等离子体，保持衬底温度约为350℃，保持室压力约为6Torr，从而沉积碳化硅阻挡层。气体分配器与衬底表面之间的间距为650mil。所沉积的碳化硅阻挡层的介电常数约为3.42-约3.96。
沉积之后，所沉积的介电材料，即所沉积的碳化硅阻挡层可以在约100℃-约450℃之间的温度下被退火约1分钟-约60分钟，优选退火约30分钟，以减少水分含量并增加介电材料的坚固性和硬度(如果希望的话)。退火优选在沉积下一层之前进行，这是防止介电层发生收缩和变形的。例如氩气和氦气的惰性气体可以被加入退火环境中。
所沉积的碳化硅阻挡层可以经等离子处理以去除污染物，或者在后续的在其上沉积材料步骤之前，清洗碳化硅层的暴露表面。等离子处理可以在用来沉积含硅和碳材料的相同室中进行。等离子处理被认为通过形成比未经处理的碳化硅材料更高密度的材料保护层而提高了膜的稳定性。等离子处理还被认为提高了膜对相邻层的粘附。这种更高密度的碳化硅材料被认为比未经处理的碳化硅材料更能防止化学反应(例如当在氧气中暴露时，形成氧化物)的发生。
等离子处理一般包括将惰性气体和/或还原气体引入处理室中，其中惰性气体包括氦气、氩气、氖气、氙气、氪气及其组合，其中氦气是优选的，还原气体包括氢气、氨气及其组合。惰性气体或还原气体被以约500sccm-约3000sccm的流速引入处理室中，并在处理室中生成等离子体。
利用在约0.03W/cm2-约3.2W/cm2之间的功率密度，可以生成该等离子体，这个功率密度是对于200mm衬底，在约10W-约1000W之间的RF功率水平。优选地，对于200mm衬底上的碳化硅材料，功率水平约为100W。RF功率可以以例如在13MHz-14MHz之间的高频和/或例如在100KHz-1000KHz之间的低频提供。RF功率可以被连续提供或者以短的持续周期提供，其中对于小于约200Hz的周期，所提供的功率都处在规定水平，并且提供功率的周期总和占总的工作周期的约10％-约30％。
优选地，处理室保持在约1Torr-约12Torr的室压力下，例如约3Torr。优选地，在等离子处理过程中，衬底保持在约200℃-450℃的温度下。在等离子处理过程中，可以使用与碳化硅沉积过程大致相同的衬底温度，例如约290℃。等离子处理可以进行约2秒-约100秒，并且等离子处理优选进行约15秒-约60秒。处理气可以通过气体分配器而被引入室内，该气体分配器可以放置在距离衬底表面约200mil-约1200mil处。在等离子处理过程中，该气体分配器可以放置在约300mil-约800mil处。
但是，应该注意到，各个参数都可以变化，以在各种室中、对不同大小的衬底进行等离子处理，例如300mm的衬底。用于含硅和碳的膜的等离子处理实例在1999年6月18日提交的、题为“Plasma treatment toEnhance adhesion and to Minimize Oxidation of Carbon-Containing Layers”的美国专利申请No.09/336,525中进一步公开了，以与这里所述的公开内容和所要求的方面相一致的程度，通过引用将其内容结合于此。
优选地，阻挡层邻近帽层(cap layer)而沉积，并任选地，邻近其介电常数小于约4(例如小于约3)的、包括硅、氧和碳的介电层而沉积。与这里所述的阻挡层材料一起使用的邻近或附近的介电层含有约1原子百分比(不包括氢原子)的碳，优选含有在约5-约30原子百分比(不包括氢原子)之间的碳。如这里所用的，“附近”介电层指通过介于其间的帽层而与阻挡层隔开的介电层。这种邻近或附近的介电层可以通过在等离子增强化学气相沉积技术中氧化有机硅烷化合物而被沉积。例如，合适的邻近或附近的介电层可以是这样沉积的：在等离子增强化学气相沉积技术中，利用在包括约0.16W/cm2-约0.48W/cm2的高频RF功率密度的条件下形成的等离子体，使三甲基硅烷和氧气进行反应。
在2000年5月25日授权的美国专利No.6,054,379、2001年9月11日授权的美国专利No.6,287,990和2001年10月16日授权的美国专利No.6,303,523中都更进一步地描述了这种其介电常数约小于3的、包括硅、氧和碳的邻近或附近介电层的方法和应用实例，并以与这里所述的公开内容和权利要求相一致的程度，通过引用将其内容结合于此。
通过使包括无氧有机硅化合物的处理气在等离子体中进行反应以形成碳化硅帽层，从而邻接这里所述的阻挡层而沉积出邻近帽层。在一个实施例中，该无氧有机硅化合物的结构式为SiHx(CH3)y(C6H5)z，其中x为1-3，v为0-3，z为0-3，并且x+y+z等于4。这种无氧有机硅化合物可以是烷基硅烷，例如甲基硅烷、二甲基硅烷、三甲基硅烷或四甲基硅烷。优选地，这种无氧有机硅化合物是三甲基硅烷。这种碳化硅帽层也可以包括氮。
在另一个实施例中，该无氧有机硅化合物可以是含苯基的有机硅化合物。这种含苯基的有机硅化合物可以是用于沉积碳化硅阻挡层(该帽层沉积在其上)的有机硅化合物。但是，阻挡层是利用这样的处理条件沉积的，即在所沉积的阻挡层中允许苯基保持连接到硅原子上。碳化硅帽层是利用这样的处理条件沉积的，即在所沉积的帽层中基本没有苯基连接到硅原子上。
在一个实施例中，碳化硅帽层可以是这样沉积的：即以约50sccm-约800sccm之间的流速向等离子处理室中提供例如三甲基硅烷的无氧有机硅化合物，以约50sccm-约2000sccm之间的流速提供无氧载气，例如氦气、氩气、氮气或氨气，保持衬底温度在约250℃-约450℃之间，保持室压力在约3Torr-约15Torr之间，RF功率在约0.02W/cm2-约5W/cm2之间，或者在约200W-约800W之间。
RF功率可以以例如在13MHz-14MHz之间的高频和/或例如在100KHz-1000KHz之间的低频提供。RF功率可以被连续提供或者以短的持续周期提供，其中对于小于约200Hz的周期，所提供的功率都处在规定水平，并且提供功率的周期总和占总工作周期的约10％-约30％。处理气可以通过气体分配器而被引入室内，该气体分配器可以放置在距离衬底表面约200mil-约1200mil处。在沉积工艺过程中，该气体分配器可以放置在约300mil-约800mil处。
该帽层可以在沉积阻挡层的相同室中被沉积。在一个实施例中，该帽层在Applied Materials，Inc.，Santa Clara，California的Producer室中被沉积。Producer室的实例在美国专利No.5,855,681中描述了，这里通过引用将其内容结合于此。
当在沉积室中200mm衬底上实现时，以上工艺参数提供了在约100/min-约1000/min范围内的帽层沉积速率。
优选的碳化硅帽层沉积工艺实例包括：以约320sccm的流速将三甲基硅烷引入处理室中，以约800sccm的流速将氦气引入处理室中，通过施加约400W的RF功率而在处理室中生成等离子体，保持衬底温度约为350℃，保持室压力约为12Torr，从而沉积碳化硅帽层。气体分配器与衬底表面之间的间距约为400mil。通过这种工艺，可以以约370/min的速率沉积碳化硅帽层，并且所沉积的碳化硅帽层的介电常数约为4.2。
如对所沉积的碳化硅阻挡层所述的，所沉积的碳化硅帽层可以被等离子处理。
这里所述的邻近低k值介电层而沉积碳化硅层的实施例被提供来说明本发明，所示的具体实施例不应被用来限制本发明的范围。
双镶嵌结构的阻挡层的沉积
图1示出了利用这里所述的碳化硅材料作为阻挡层而形成的镶嵌结构50的实例。碳化硅阻挡层10一般是根据这里所述的工艺、利用前驱体而沉积在衬底表面上的，从而去除衬底与随后沉积的材料之间的层间扩散。衬底表面可以包括形成在介电层5中的金属特征7。
利用这里所述的用于沉积碳化硅帽层的前驱体，一般在碳化硅阻挡层10上沉积第一碳化硅帽层11。如这里所述的包括硅、氧和碳的第一介电层12沉积在碳化硅帽层11上。接着，碳化硅材料的蚀刻终止层(或第二阻挡层)14或被氧化的有机硅烷层被沉积在第一介电层12上。蚀刻终止层14可以包括由这里所述的有机硅前驱体沉积的碳化硅材料或被氧化的有机硅烷层。或者，蚀刻终止层14可以是含氮的碳化硅材料。接着，蚀刻终止层14被图案化蚀刻，以限定出互连或接头/通孔16的开口。
接着，第二介电层18被沉积在经图案化的蚀刻终止层上。接着，通过本领域已知的常规方法来沉积光刻胶，并将其图案化，以定义接头/通孔16。接着，进行单独的蚀刻工艺来将接头/通孔16向下定义到蚀刻终止层，并蚀刻被经图案化的蚀刻终止层所暴露的未被保护的电介质来定义接头/通孔16。接着，例如铜的一种或多种导电材料被沉积填充所形成的接头/通孔16。
根据本发明所制得的优选双镶嵌结构包括通过这里所述的工艺而沉积的碳化硅阻挡层和碳化硅帽层，该结构在图2A-2H中被依次示意性地描绘，这些图是其上进行本发明步骤的衬底的横截面视图。
如图2A所示，碳化硅阻挡层110由这里所述的、用于沉积碳化硅阻挡层的有机硅前驱体而被沉积在衬底表面上。碳化硅阻挡层110可以掺杂氧、硼、磷及其组合。碳化硅阻挡层110可以是这样沉积的：即以约500mg/min的流速将二苯基硅烷引入处理室中，以约500sccm的流速将氦气引入处理室中，通过施加100W的RF能量而在处理室中生成等离子体，保持衬底温度在约290℃，保持室压力在约3Torr，从而沉积出碳化硅阻挡层。通过这种工艺，可以以约1500/min的速率沉积碳化硅材料。所沉积的碳化硅层的介电常数约为3.4。
碳化硅帽层111被沉积在阻挡层110上。利用在沉积工艺过程中被最小化或被消除的氮气源、通过氮掺杂碳化硅工艺，可以原位沉积该碳化硅帽层。优选地，通过这里所描述的由包括无氧有机硅化合物、并被反应形成等离子体的气体混合物沉积碳化硅帽层的工艺来沉积帽层111。
用包括氦气(He)、氩气(Ar)、氖气(Ne)及其组合的惰性气体和/或包括氢气、氨气及其组合的还原气体，可以等离子处理碳化硅阻挡层110和帽层111。该等离子处理可以与阻挡层和帽层的沉积原位地进行。这种等离子处理被认为清除了碳化硅材料暴露表面的污染物，并可用来稳定这些层，这样使得它们在大气条件下变得不易与水分和/或氧气进行反应，以及形成在其上的层的粘附。
等离子体工艺包括在对200mm衬底施加约5秒-约60秒的约200W-约800W之间的功率水平条件下的氦气处理气或例如氢气的还原气。在反应清洗工艺过程中，处理室保持在约8.7Torr或更低的压力下，在大约是该层沉积温度的衬底温度下，例如对二甲基苯基硅烷而言约是350℃。
通过氧化有机硅烷或有机硅氧烷，例如三甲基硅烷，而在帽层111上沉积层间介电材料的第一介电层112，其厚度为约5,000-约15,000，这取决于要制备的结构大小。可用作层间介电材料的低介电常数材料实例有Applied Materials，Inc.，Santa Clara，California的商用Black DiamondTM膜。或者，第一介电层也可以包括其他低k值介电材料，例如包括聚对二甲苯基的低k值聚合物材料或例如未掺杂硅玻璃(USG)和掺氟硅玻璃(FSG)的低k值旋涂(spin-on)玻璃。
接着，第一介电层112可以被等离子体工艺处理，该工艺包括在对200mm衬底施加约5秒-约60秒的约200W-约800W之间的功率水平下的氦气或还原气(例如氢气)。在反应清洗工艺过程中；处理室保持在大约是第一介电层112的沉积压力和沉积温度的压力和衬底温度下。
如图2B所示，可以是碳化硅材料的低k值蚀刻终止层114接着被沉积到第一介电层上，沉积厚度约为200-1000。低k值蚀刻终止层114可以由与碳化硅阻挡层110相同的前驱体和相同的工艺来沉积。如这里对碳化硅阻挡层110所述的，可以对低k值蚀刻终止层114进行等离子处理。接着，低k值蚀刻终止层114被图案化蚀刻，以定义出接头/通孔116，并在要形成接头/通孔的区域中暴露第一介电层112，如图2C所示。优选地，利用常规光刻法和使用氟离子、碳离子和氧离子的蚀刻工艺，图案化蚀刻低k值蚀刻终止层114。在沉积其他材料之前，可以在蚀刻终止层114上沉积厚度约在100-500之间的无氮碳化硅或氧化硅帽层115，例如厚约30-100。通过由这里所述的由包括无氧有机硅化合物的气体混合物沉积帽层的工艺，可以沉积无氮碳化硅帽层115。
在低k值蚀刻终止层114和帽层115(如果存在)已经被蚀刻以图案化接头/通孔，并且光刻胶已经被去除之后，沉积厚约为5,000-15,000的碳氧化硅第二介电层118，如图2D所示。在对200mm衬底施加约15秒-约60秒的约600W-约800W之间的功率水平下，用氦气或例如氢气的还原气等离子处理第二介电层118。在反应清洗工艺过程中，处理室保持在约20Torr或更低的压力和约450℃或更低的衬底温度下。该等离子处理被认为降低了层118的表面与随后沉积材料之间的反应性。
在另一实施例中，在沉积其他材料之前，例如光刻胶材料，可以在第二介电层118上沉积厚在约100-500之间的无氮碳化硅或氧化硅帽层(未示出)。在又一可替换的实施例中，在沉积其他材料之前，例如光刻胶材料，可以由与沉积碳化硅阻挡层110相同的前驱体和相同的工艺在第二介电层118上沉积无氮碳化硅或氧化硅帽层。
接着，在第二介电层118(或帽层)上沉积光刻胶材料122，并优选利用常规光刻工艺将其图案化以定义互连线120，如图2E所示。光刻胶材料122包括本领域常规已知的材料，优选是高活化能的光刻胶，例如来自Shipley Company Inc.of Marlborough，Massachusetts的商用UV-5。接着，利用反应性离子蚀刻或其他各向异性蚀刻技术来蚀刻互连和接头/通孔，以定义金属化结构(即，互连和接头/通孔)，如图2F所示。利用氧气抽提或其他合适工艺，去除用于图案化蚀刻终止层114、帽层115或第二介电层118的任意光刻胶或其他材料。
接着，用例如铝、铜、钨或其组合的导电材料形成金属化结构。目前，由于铜的电阻率较低(铜为1.7μΩ-cm，铝为3.1μΩ-cm)，往往趋向于使用铜形成更小的特征结构。优选地，如图2G所示的，例如氮化钽的合适阻挡层124首先被共形地沉积在金属化图案中，以防止铜向周围的硅和/或介电材料内迁移。随后，利用化学气相沉积、物理气相沉积、电镀或其组合沉积铜126，以形成导电结构。一旦该结构已经被填充了铜或其他金属，即利用化学机械抛光将表面平坦化，如图2H所示。
实例
这里所述的有机硅化合物被作为阻挡层沉积在衬底表面上，并被分析。在一个实例中，由二苯基硅烷化合物沉积碳化硅阻挡膜，并将其与由常规碳化硅前驱体三甲基硅烷沉积的碳化硅阻挡膜进行比较。
二苯基硅烷和三甲基硅烷前驱体都是这样被沉积的：通过以约500mg/min的流速将二苯基硅烷或三甲基硅烷引入处理室中，以约500sccm的流速将氦气引入处理室中，通过施加100W的RF能量而在处理室中生成等离子体，保持衬底温度在约290℃，保持室压力在约3Torr，从而沉积出碳化硅阻挡层。加热器与衬底表面的间距约为450mil。
所沉积的膜被检查并分析其介电常数和阻挡层扩散。所测得的二苯基硅烷碳化硅膜的介电常数约为3.4，三甲基硅烷碳化硅膜的介电常数约为4.3。
通过偏压温度测试法来测试阻挡层的性能，这种测试法是这样进行的：利用上述碳化硅膜形成镶嵌器件，并在使所沉积的膜经历约275℃的衬底温度的同时，测量器件漏电流。漏电流随阻挡层性能的降低而增加。当漏电流达到约10-3A/cm2时，阻挡层被认为已经失效。当在这些处理条件下，50％器件出现故障时，测量该时间来表示所沉积膜的阻挡效率。对膜的比较表明：二苯基硅烷碳化硅的漏电流在1MV/cm下约为1e-09A/cm2，在2MV/cm下约为1e-8A/cm2，在约7.9h后达50％的故障率，而三甲基硅烷碳化硅的漏电流在1MV/cm下约为1e-09A/cm2，在2MV/cm下约为1e-6A/cm2，在约4.4h后达50％的故障率。
在另一实施例中，二苯基甲基硅烷被用来沉积碳化硅阻挡层：通过以约500mg/min的流速将二苯基甲基硅烷引入处理室中，以约500sccm的流速将氦气引入处理室中，通过施加100W的RF能量而在处理室中生成等离子体，保持衬底温度在约290℃(对二苯基硅烷沉积膜的)，保持室压力在约3Torr，从而沉积出碳化硅层。加热器与衬底表面的间距约为450mil。
所沉积的膜被检查并分析其介电常数和阻挡层扩散。相比较三甲基硅烷所沉积的碳化硅膜约为4.3的介电常数，所测得的二苯基甲基硅烷碳化硅膜的介电常数约为3.6。对膜的比较表明：二苯基甲基硅烷碳化硅的漏电流在1MV/cm下约为3e-9A/cm2，在2MV/cm下约为4e-8A/cm2，在约10h后达50％的故障率，而三甲基硅烷碳化硅的漏电流在1MV/cm下约为1e-09A/cm2，在2MV/cm下约为1e-6A/cm2，在约4.4h后达50％的故障率。
在另一实施例中，二甲基苯基硅烷被用来沉积碳化硅阻挡层：通过以约500mg/min的流速将二甲基苯基硅烷引入处理室中，以约1000sccm的流速将氦气引入处理室中，通过施加200W的RF能量而在处理室中生成等离子体，保持衬底温度在约350℃下(对二苯基硅烷沉积膜的)，保持室压力在约6Torr，从而沉积出碳化硅层。加热器与衬底表面的间距约为450mil。
所沉积的膜被检查并分析其介电常数和阻挡层扩散。相比较三甲基硅烷所沉积的碳化硅膜约为4.3的介电常数，所测得的二甲基苯基硅烷碳化硅膜的介电常数约为3.5。对膜的比较表明：二甲基苯基硅烷碳化硅的漏电流在1MV/cm下约为1e-9A/cm2，在2MV/cm下约为2e-8A/cm2，在约11h后达50％的故障率，而三甲基硅烷碳化硅的漏电流在1MV/cm下约为1e-09A/cm2，在2MV/cm下约为1e-6A/cm2，在约4.4h后达50％的故障率。
这些数据表明了与现有的阻挡层工艺相比较，二苯基硅烷或烷基取代的二苯基硅烷化合物的阻挡层性能和介电常数都得到了显著的且出人意料的改善。
数据还被采集来将这里所述阻挡层的性能与这里所述阻挡层和帽层结合的性能进行比较。在Producer室中，利用等离子体，由在约100mg/min和约300mg/min之间的二甲基苯基硅烷流，在约500sccm到约2000sccm之间的氦气流，在约350mil和约600mil之间的间距，以及在约200W和约500W之间的RF能量来沉积阻挡层。该阻挡层的介电常数k为3.4，在1MV/cm下漏电流为2e-9A/cm2。利用Producer室，利用等离子体，由约320sccm的三甲基硅烷流，800sccm的氦气流，400mil的间距，12Torr的压力以及400W的RF能量来沉积碳化硅帽层。该碳化硅帽层的介电常数k为4.2，在1MV/cm下漏电流为3.5e-9A/cm2。阻挡层和帽层的叠层组合的介电常数k为3.43，在1MV/cm下漏电流为2e-9A/cm2。这样，阻挡层和帽层的叠层并不具有明显高于单个阻挡层的k值。
用氧气(O2)等离子体来处理这里所述的阻挡层、帽层以及阻挡层和帽层的组合叠层以测量这些层的氧化。结果在表1中示出了。
表1
  层   厚层()   O2处理前介电常数   O2处理后氧化层厚度()   O2处理后非氧化层厚度()   O2处理后介电常数
  ～1000帽层   11341001   4.184.24   108117   936810   4.1324.285
  ～3000帽层   35582930   102116   33902714
  阻挡层+～50帽层   11041028   3.4333.417   101122   936873   3.4523.536
  阻挡层+～100帽层   11811096   3.4283.486   99108   1045961   3.5543.583
  ～1000阻挡层   10351120   3.4293.438   340392   558614
由于采集了Producer室两个处理区域的其中每个中所沉积层的数据，所以对于每种类型的沉积层都示出了两组值。在氧气等离子体处理之后，无帽层的阻挡层的氧化层厚度远远大于带帽层的阻挡层的氧化层厚度，如表1中所示的。这样，我们相信这里所述的帽层减少了这里所述阻挡层的氧化量，即氧化深度。
虽然前面涉及本发明的优选实施例，但在不偏离本发明的基本范围以及由下面权利要求所确定范围的情况下，可以设计本发明的其他实施例。

Claims (32)

1.一种处理衬底的方法，包括：
通过将包括有机硅化合物的第一处理气体混合物导入处理室中，并将所述第一处理气体混合物进行反应以沉积阻挡层，从而沉积出碳化硅阻挡层，其中所述有机硅化合物具有结构式SiHa(CH3)b(C6H5)c，其中a为0-3，b为0-3，c为1-4，所述阻挡层的介电常数小于4，并包含与硅原子连接的苯基基团；以及
在沉积所述阻挡层之前或之后，通过将包括无氧有机硅化合物的第二处理气体混合物导入所述处理室中，并将所述第二处理气体混合物进行反应以沉积碳化硅帽层，从而沉积出邻近所述阻挡层的碳化硅帽层，其中所述碳化硅帽层基本没有与硅原子连接的苯基基团。
2.如权利要求1所述的方法，其中所述第二处理气体混合物的无氧有机硅化合物是三甲基硅烷，并且所述第二处理气体混合物还包括氦气。
3.如权利要求1所述的方法，其中所述碳化硅帽层是在包括约0.02W/cm2-约5W/cm2的高频射频功率密度的等离子条件下被沉积的。
4.如权利要求1所述的方法，其中所述第二处理气体混合物的无氧有机硅化合物以在约50sccm与约800sccm之间的流速流进所述室内。
5.如权利要求1所述的方法，其中所述第二处理气体混合物还包括选自氩气、氦气、氮气或氨气的无氧气体。
6.如权利要求5所述的方法，其中所述第二处理气体混合物的无氧气体以在约50sccm与约2000sccm之间的流速流进所述室内。
7.如权利要求1所述的方法，其中所述第一处理气体混合物的有机硅化合物包括二苯基甲基硅烷、二甲基苯基硅烷、二苯基硅烷或它们的组合。
8.如权利要求1所述的方法，其中所述第一处理气体混合物还包括选自含氧化合物、含氮化合物、含硼化合物、含磷化合物或它们的组合的掺杂剂组分。
9.如权利要求8所述的方法，其中所述含氧化合物选自氧气、臭氧、硅氧烷或它们的组合。
10.如权利要求8所述的方法，其中所述含氮化合物选自氮气、氨气、硅氮烷或它们的组合。
11.如权利要求1所述的方法，其中所述第一处理气体混合物还包括选自氩气、氦气、氖气、氙气、氪气或它们的组合的惰性气体。
12.如权利要求1所述的方法，其中所述阻挡层包括小于约15原子百分比的氧。
13.如权利要求1所述的方法，其中a为1或2，b为1或2，并且c为1或2。
14.一种处理衬底的方法，包括：
通过将包括第一有机硅化合物的第一处理气体混合物导入处理室中，并将所述处理气体进行反应以沉积阻挡层，从而在衬底上沉积出碳化硅阻挡层，其中所述第一有机硅化合物具有结构式SiHa(CH3)b(C6H5)c，其中a为0-3，b为0-3，c为1-4，所述阻挡层的介电常数小于4；以及
通过将包括第二有机硅化合物的第二处理气体混合物导入所述处理室中，并将所述第二处理气体混合物进行反应以沉积碳化硅帽层，从而在所述阻挡层上沉积出碳化硅帽层，其中所述第二有机硅化合物具有结构式SiHx(CH3)y(C6H5)z，其中x为1-3，y为0-3，z为0-3。
15.如权利要求14所述的方法，其中所述第二处理气体混合物的第二有机硅化合物是三甲基硅烷，并且所述第二处理气体混合物还包括氦气。
16.如权利要求14所述的方法，其中所述碳化硅帽层是在包括约0.02W/cm2-约5W/cm2的高频射频功率密度的等离子条件下被沉积的。
17.如权利要求14所述的方法，其中所述第二处理气体混合物的第二有机硅化合物以在约50sccm与约800sccm之间的流速流进所述室内。
18.如权利要求14所述的方法，其中所述第二处理气体混合物还包括选自氩气、氦气、氮气或氨气的无氧气体。
19.如权利要求18所述的方法，其中所述第二处理气体混合物的无氧气体以在约50sccm与约2000sccm之间的流速流进所述室内。
20.如权利要求14所述的方法，其中所述第一处理气体混合物的第一有机硅化合物包括二苯基甲基硅烷、二甲基苯基硅烷、二苯基硅烷或它们的组合。
21.如权利要求14所述的方法，其中将所述第一处理气体混合物进行反应包括将所述第一处理气体混合物的第一有机硅化合物与选自氧气、臭氧、硅氧烷或它们的组合的含氧化合物进行反应。
22.如权利要求21所述的方法，其中所述含氧化合物选自氧气、臭氧、硅氧烷或它们的组合。
23.如权利要求14所述的方法，其中所述第一处理气体混合物还包括选自含氮化合物、含硼化合物、含磷化合物或它们的组合的掺杂剂组分。
24.如权利要求23所述的方法，其中所述含氮化合物选自氮气、氨气、硅氮烷或它们的组合。
25.如权利要求14所述的方法，其中所述第一处理气体混合物还包括选自氩气、氦气、氖气、氙气、氪气或它们的组合的惰性气体。
26.如权利要求14所述的方法，其中所述阻挡层包括小于约15原子百分比的氧。
27.如权利要求14所述的方法，其中a为1或2，b为1或2，并且c为1或2。
28.如权利要求14所述的方法，还包括在所述帽层上沉积介电层，其中所述介电层的介电常数小于约4。
29.如权利要求28所述的方法，其中所述介电层的碳含量在约5和约30原子百分比之间，该原子百分比的计算不包括氢原子。
30.如权利要求29所述的方法，其中所述介电层是通过在等离子增强化学气相沉积技术中氧化有机硅烷或有机硅氧烷化合物而被沉积的。
31.如权利要求30所述的方法，其中所述介电层是通过在等离子增强化学气相沉积技术中将三甲基硅烷与氧气进行反应而被沉积的。
32.如权利要求31所述的方法，其中所述介电层是在包括约0.16W/cm2-约0.48W/cm2的高频射频功率密度的等离子条件下被沉积的。
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US20040067308A1 (en) 2004-04-08
US7749563B2 (en) 2010-07-06
CN100510168C (zh) 2009-07-08
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WO2004033752A2 (en) 2004-04-22

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