CN101227984B - 低氢压力下的远程等离子预清洁 - Google Patents

低氢压力下的远程等离子预清洁 Download PDF

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CN101227984B
CN101227984B CN2006800270470A CN200680027047A CN101227984B CN 101227984 B CN101227984 B CN 101227984B CN 2006800270470 A CN2006800270470 A CN 2006800270470A CN 200680027047 A CN200680027047 A CN 200680027047A CN 101227984 B CN101227984 B CN 101227984B
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X·福
J·福斯特
J·于
A·巴特纳格尔
P·高普拉佳
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Abstract

本发明揭示一种等离子清洁方法，其对于在溅镀沉积之前从一具有高碳含量的多孔性低k介电质移除光阻与氧化物残余物是特别有用。一远程等离子源(52)产生一主要为氢自由基H＊的等离子。氢压力可以被维持非常低，例如30milliTorr。选择性地，氦可以被添加至处理气体，而使氢分压被保持在低于150milliTorr。在400milliTorr的氢与氦中，70％氦可以获得良好结果。较佳地，一离子过滤件(例如磁性过滤件(62，64)从远程等离子源的输出移除氢与其他离子，并且一来自远程等离子源的供应管(54)是包括一可移除的介电质衬里(66)，供应管(54)与介电质喷洒头(40)及岐管衬里(58)形成组合。

Description

低氢压力下的远程等离子预清洁
技术领域
本发明大体上是有关于在制造集成电路的制程中的等离子清洁。特别地，本发明是有关于被执行于图案化蚀刻介电层与沉积之间的等离子清洁。
背景技术
先进集成电路(例如为了45nm节点被构想出的先进集成电路)必须使用超低k介电(电绝缘)材料，以用于连接两阶层的配线之间的阶层间(interlevel)介电层。具有介电常数低于3.9(二氧化硅的介电常数值)的低k材料已经进入商业量产。然而，未来将会需要更低的介电常数，例如低于2.5。此材料的一范例为Black DiamondTM II(BDII)介电质，其可由美国加州圣大克劳拉市Applied Materials公司所购得。Li在美国专利申请案号2003/0194495中描述到，此介电材料的特征是其为碳掺杂的氧化硅(也被称为碳氧化硅)，其具有高于10at％的碳百分比。改良物是包括有BDIIx介电质(其是被UV硬化且具有30％的孔隙度)，以及DBIIebeam介电质(其是以电子来硬化)。其他含碳的低k介电质是已知，包括有
Figure G2006800270470D00011
与
Figure G2006800270470D00012
(苯环丁烯)介电材料，其可由Dow Chemical公司获得。许多这些材料的特征在于其是为有机或聚合介电质。
用来形成阶层间内连线(interlevel interconnect)的一原型结构是被绘示在图1的截面图中。一下介电层10包括一形成于其表面的导电特征12。用于先进阶层间连线的导电特征12是典型地由铜组成，但是类似的几何结构应用于接触硅基材的主动半导体区域。一超低k介电材料的上介电层14被沉积在下介电层10与导电特征12上方。一孔洞16是被光微影定义，且被蚀刻穿过上介电层14至导电特征12。对于用在铜金属化的典型的双镶嵌内连线，孔洞16是由一窄的下方介层洞(其形成了至导电特征12的垂直内连线)与一宽的上方沟渠(其形成了集成电路不同部分之间的水平内连线)所构成。对于双镶嵌结构，导电特征12可以为形成在下介电层10中的被填满铜的沟渠。在孔洞已经被蚀刻之后，一薄的共形阻障层(例如Ta/TaN)是被镀覆(典型地是藉由磁控溅镀)至孔洞16的侧壁上，以及至上介电层14的整个场区域表面上。接着，一薄的共形铜晶种层被沉积在阻障层上，也是典型地藉由磁控溅镀。之后，铜被电镀至孔洞16内与场区域上方。最后，化学机械研磨(CMP)被利用来移除孔洞16外面的铜。
光微影蚀刻步骤，甚至在光阻灰化之后，常常残余碳或氟碳聚合层18于孔洞16的侧壁上，其是有利地能够达到高非等向性蚀刻，但是在蚀刻停止后会残留。也会残余一蚀刻残余物20于沟渠底部，其是为蚀刻化学的碳、硅与氟副产物的组合。再者，导电特征12中暴露的铜可能已经氧化成氧化铜。又，灰化残余物22倾向于形成在孔洞16的唇部。若孔洞16底部的蚀刻残余物20与氧化铜没有在金属化沉积之前阻障层沉积以先被移除，蚀刻残余物20与氧化铜会增加接触电阻。聚合覆层18与灰化残余物22会干扰阻障层至介电层14的键结，因此阻障层与铜介层洞结构在制造或操作期间会分层(delaminate)，造成了可靠度问题。是以，在阻障层沉积以先移除残余物18、20、22与氧化铜是有需要的。
就传统的氧化硅介电质而言，藉由在蚀刻与沉积步骤之间溅镀蚀刻经图案化晶片以移除残余物来干式清洁晶片是普遍的。这样的溅镀蚀刻典型地包括有高能量离子，高能量离子不会显著地影响相当硬的氧化硅介电质。然而，低k介电层倾向于相当软。所以，溅镀蚀刻倾向于有害地蚀刻且劣化低k介电层。一较软的的化学蚀刻可以利用一被产生在清洁腔室内且邻近于晶片的氧等离子(即原位等离子)而被执行。对于早期型式的具有约3.7介电常数k且非多孔性的低k介电质，此清洁制程已经被证明令人满意。然而，对于大部分近期的具有约2.5介电常数k与大于10％孔隙度的超低k膜，原位氧等离子已经被证明无法令人满意。所被相信的是，氧等离子包括高比例的氧原子，该些氧原子被吸引至负自我偏压，其中该负自我偏压形成在一暴露于等离子的漂浮体上。接着，氧离子撞击超低k膜，且具有足够能量来破坏超低k膜。是以，此技术已经被发展出以一从远程等离子源(remote plasma source，RPS)产生的氧等离子来清洁经图案化晶片，如同Wood等人于美国专利公开案号2004/0219789中所揭示者。远程产生的等离子是强调电中性自由基；而原位等离子是强调带电荷离子。远程产生的氧等离子会发射许多中性且低能量氧自由基至晶片，其会氧化且与不同的残余物发生化学反应以将其移除。
然而，对于超低k介电材料，激化的氧已经被证明无法令人满意。介电常数的降低常常是藉由介电材料中高孔隙度来获得。BDII介电层可以具有超过10％(甚至高于30％)的孔隙度。因此，该些介电层不仅非常柔软，该些介电层对于一氧化干式清洁也是极易反应的。此外，被并入介电质中的氧倾向于产生比硅与碳键更极性的键，而增加了介电常数。是故，基于还氧化学的干式清洁已经被发展出，其是使用例如远程产生的NH3(参阅授予Kropewnicki等人的美国专利US6,440,864)或相当高H2压力的等离子。氢方式已经普及，但是结果依然无法完全令人满意。甚至氢等离子中非常少量的水蒸气会显著地降低多孔性低k膜的厌水性质，且因而倾向于增加了介电常数。甚至一纯氢等离子会倾向于增加介电常数。再者，合理的蚀刻速率已经藉由增加腔室压力被达到，但是电源能力必须依循所增加的压力。又，在更高的氢压力，来自远程等离子源而被离子化且泄漏入清洁腔室的氢的比例会增加。氢离子倾向于被吸引至晶片，且我们相信该些氢离子会破坏多孔性低k材料。
发明内容
本发明的一态样是包括利用被远程等离子源产生的一氢自由基等离子来等离子干式清洁一基材，特别是一包含大量碳的低k介电质且具有高孔隙度。不需要包括有氧或水蒸气。较佳地，氢压力被维持在适度地低，例如介于10与150milliTorr之间，30milliTorr为特别较佳的压力。
替代性地，等离子可以包含氢与一惰性气体(较佳为氦)的组合物，氢分压小于200milliTorr且大于40milliTorr，总压力介于200与600milliTorr之间。
远程等离子源与腔室之间的供应管是有利地包括一陶瓷材料(例如氧化铝)的介电质衬里。也有利地，一离子过滤件被设置在远程等离子源与处理腔室之间，以从等离子移除氢与其他离子。离子过滤件可以是一磁性过滤件，其产生一磁场横越供应管的轴。
附图说明
图1为一阶层间内连线结构或介层洞的截面图。
图2为可用于本发明的一远程等离子清洁腔室的截面图。
图3为一图表，其绘示预清洁一低k介电质时的蚀刻速率与其均匀性，其为来自远程等离子源的氢压力的函数。
图4为一磁性过滤件的轴向截面图，其被用在图2的远程等离子清洁腔室内。
图5为离子偏斜的图表，其中该离子偏斜是在磁性过滤件中获得。
图6为使用与不使用离子过滤件的离子耗尽的图表，其中该离子耗尽为深度的函数。
图7为一长条图，其显示等离子预清洁时水接触角对于氢压力的依赖性。
图8为根据本发明的两实施例的一图表，其绘示蚀刻速率与其非均匀性对于氦浓度的依赖性
图9为根据习知技术与本发明的数个实施例的等离子清洁一低k介电质时介电常数增加的长条图。
主要元件符号说明
10下介电层              12导电特征
14上介电层              16孔洞
18碳或氟碳聚合层        20蚀刻残余物
22灰化残余物            30远程等离子清洁腔室
32真空腔室              34真空唧筒系统
36基座                  38晶片
40气体喷洒头            42穿孔
44氢气源                46质流控制器
48氦气源                50质流控制器
52远程等离子源        54供应管
56气体岐管            58岐管衬里
62磁铁                64磁铁
66介电质衬里
具体实施方式
已经被观察到的是，来自远程等离子源(其基本上不存在有氧与水)的非常低的压力或甚至氢分压是在干式清洁期间提供了可接受的且甚至良好的蚀刻速率，并且显著地减少了介电常数增加。
图2绘示的一远程等离子清洁腔室30是包括一真空腔室32，真空腔室32是由一真空唧筒系统34来唧筒抽吸。一位在真空腔室32内的基座36是支撑一欲被清洁的晶片38，晶片38相对于一气体喷洒头40，气体喷洒头40供应一制程气体通过许多穿孔42。基座36包括一加热器46，以升高晶片38温度至所希望的蚀刻温度。根据本发明的一态样，制程气体为纯氢气(H2)，或氢与氦(He)的组合物，其中该纯氢气是从一氢气源44经由一质流控制器46被供应，该组合物是从一氦气源48经由另一质流控制器50被供应。一远程等离子源52是接收气体，且将其激化成等离子。远程等离子源52可以是一对电极，其被设置在一用于制程气体的输送管的相对侧上，且被RF电源或输送管周围的RF诱导线圈或其他型式天线(antenna)所驱动，虽然其他型式的等离子产生器是可行的。被激化的气体是被输送经由一供应管54至位在喷洒头42后方的一气体岐管56。被激化的气体因此可以经由喷洒头40被均匀地输送至正被清洁的晶片38。
对于被形成在基材上的BDII介电质上方且于约300℃在各种腔室压力下被暴露至纯氢激化气体(其被激化于一远程等离子源中且被磁性地过滤以形成一中性激化气体)的光阻，光阻的蚀刻速率与蚀刻非均匀性被测量。结果被绘制在图3。250与400milliTorr之间的结果是显示为何400milliTorr先前是被建议为最佳的实施条件，这是因为光阻蚀刻速率是与在该范围内氢压力成比例地改善了(如同所被预期者)，并且非均匀性相当恒定。甚至更高的压力可能提供更佳的结果，但是需要极大的电源供应。再者，更高的压力有可能会增加氢离子泄漏与其他带电荷微粒进入制程区域。令人惊讶地，蚀刻速率依赖氢压力时，测试是显示出一双尖峰结构。在250milliTorr以下，蚀刻速率开始随着减低的压力而增加，且在其下降之前抵达一在非常低压力(very low-pressure，VLP)范围中的约40milliTorr的尖峰。此外，在低于约250milliTorr，非均匀性持续地减小。根据制程与腔室条件的细节而定，有利的氢压力是被相信位在10至150milliTorr的范围内，较佳为介于20至120milliTorr之间。然而，本发明不被限制在这些范围。
所被相信的是，较低的尖峰形成自自由基H＊产生与H＊再结合成中性H2之间的竞争。在较低的尖峰以下，对应至用于再结合的平均自由径，再结合是可忽略的，并且H＊产生细随着增加的压力而增加。在高于较低尖峰以上的增加的压力，H＊再结合成H2的增加是超过任何在H＊产生的增加。
先进介电膜(例如Black Diamond)的低介电常数是至少部分地藉由增加的碳比例来产生。在习知技术中等离子清洁产生的有害的增加介电常数，是被相信由碳耗尽所造成(尤其是在介电质的表面)。
在过去，氢离子H+对于粗糙氧化硅介电质是令人满意的等离子清洁试剂。然而，甚至发展在一漂浮基座16上的自我偏压是足以加速氢离子至足够能量，以破坏低k介电质。在本发明的一态样中，一磁性离子过滤件(其额外地被绘示在图4的截面图中)是被设置在远程等离子源52与喷洒头40之间。离子过滤件包括两个水平相对的永久磁铁62、64，该两磁铁62、64被置放在供应管54的相对侧上，以产生一水平磁场B，磁场B在该两此铁之间延伸而垂直于供应管54的轴。较佳地，磁铁62、64(或是构成一有效组合磁铁的多个磁铁)具有足够的横向宽度，使得其磁场在越过垂直于场方向的供应管54尺寸时是基本上恒定。磁场是在沿着供应管54而流经供应管54的氢离子上建立一洛伦兹力(Lorentz force)，藉此将该些氢离子偏斜至供应管54的壁，其为氢离子被吸收或至少被中性化之处。在一些情况下，离子被捕获在磁场线上，且在此处中性化或飘移至壁。图5是说明了转向力，其对于5与10eV动能的氢与氧被测量为回旋半径R，其中回旋半径R为所施加磁场B的函数。一3×2磁铁阵列被估计在供应管54的边缘可以建立一500高斯的磁场，且在供应管54的中心可以建立一650高斯的磁场。磁性过滤件已经被发现到对于移除约99％的从远程等离子源52所泄漏的带电荷微粒是有效的。另一方面，中性氢自由基H＊不受磁场影响，且持续随着气体飘移至岐管56且接着排出喷洒头40的穿孔42。氢自由基形成了一激化的但是中性的气体，且不会技术上地构成一包含离子与电子的等离子。可以使用其他离子过滤件，例如静电偏斜器(electrostaticdeflector)。
然而，自由基倾向于短寿命，这是因为自由基具有大的截面且倾向于再结合。自由基寿命可以藉由在供应管54内设置一管状介电质衬里66而被显著地增加，如图2所示，其中该供应管54是由远程等离子源52延伸至岐管56。自由站立的介电质衬里66可以由例如石英(SiO2)或氧化铝(Al2O3)来构成。有利地，当腔室盖子被开启以进行维护时，介电质衬里66可以从底部被移除，而不肖拆解远程等离子源52或离子过滤件或盖子的剩下部件。
同样的理由，喷洒头40与岐管衬里58可以由介电质来构成，例如氧化铝或更佳者为石英。
X射线光谱学是被用来测量碳含量，其为在200nm厚度BlackDiamond II(BDII)介电膜的深度的函数。在第一测试中，BDII介电膜是在沉积后且在等离子清洁前被探测。图6绘示的线70是显示出，未被处理的膜具有在其主体上约20at％的碳含量，而上升至在其表面处约30at％。在第二测试中，一远程等离子源被用来清洁BDII膜，但是不使用磁性过滤件。线72是显示出主体几乎没有耗尽，但是碳在表面处是显著地被耗尽。在第三测试中，磁性过滤件被启动。线74是显示出，磁性过滤件基本上减少了碳的表面耗尽。减少的碳耗尽是有助于解释碳为主低k介电质中减少的介电常数增加，当其根据本发明的一态样被预清洁时。
相关的测试涉及了以富立叶转换红外线(Fourier-transform infrared，FTIR)光谱学来探测BDII介电膜。碳含量是由对应至Si-C键共振的1276cm-1波数处的讯号来监测。不使用磁性过滤件时，光谱在1276cm-1于讯号中显示一下跌，指出了碳耗尽。使用磁性过滤件时，下跌基本上被减少，其与减少的碳耗尽一致。
另外一连串的测试是测量BDIIx膜形成之后、以高压氢(400milliTorr)等离子清洁之后、以及以低压氢(30milliTorr)等离子清洁之后无任何处理的其水接触角。低的水接触角是显示出材料是较亲水性的，即吸引水。亲水的膜被预期会呈现对于水分破坏的劣等阻抗性，其被相信是导因自水分子的高极性。图7的长条图结果证明了，低压氢的等离子清洁具有小的接触角降低，但是高压氢的等离子清洁具有大的接触角降低。换句话说，结果意味着，在低氢压力时可以减小水分破坏。
似乎氢分压为低压氢等离子预清洁的有效性的一测试方式。在BDIIx介电膜上蚀刻速率与其非均匀性是在30与40milliTorr腔室压力而具有纯氢与三种氢及氦混合物(更详细地说为50％、70％与95％的氦)下被测量。图8的结果显示了，70％He(即120milliTorr氢分压)的蚀刻速率在400milliTorr时是基本上大于95％He，且在30milliTorr时是基本上大于0％He，且在400milliTorr时是基本上大于50％He。这些结果可以被外插到在200至600milliTorr的氦/氢总压力中所希望30至200milliTorr的氢分压的范围(或者50至92％氦)。一较窄的范围为300至500milliTorr的氦/氢总压力中80至150milliTorr的氢分压。然而，本发明不必被限制在这些范围。所被推测的是，额外的氦吸收在腔室壁上且避免自由基被吸附在该处，或者氦减少了自由基之间的碰撞与其再结合或与氢交互作用的氦介稳定状态。所被了解的是，氢与氦的混合物是从一结合源被供应，尤其是因为纯氢是被认为特别有害的。
其他惰性气体(例如氖或氩)提供了氦的一些益处，但是氦被相信是相关于等离子清洁低k介电质为最有效的气体。
具有介电常数2.5且被各种方法预清洁的BDIIx膜的介电常数变化是被测量。这些结果显示在图9的长条图中。原位(in situ)结果为一比较性测试，其使用95％He与5％H2的原位等离子且显示大于10％的劣化。对于来自远程等离子源的400milliTorr氢等离子，结果显示大于1％的劣化。对于来自远程等离子源的30milliTorr纯H2与400milliTorr30％H2及70％He，结果显示介电常数基本上没有变化。是以，不仅远程产生的氢等离子对于预清洁低k介电膜比原位等离子更佳，减少的氢压力或分压也基本上减少，若不忽略介电常数增加。
虽然本发明已经藉由参照图2的预清洁腔室而被叙述，本发明可以被实施在其他型式的腔室中，例如不需要包含喷洒头的腔室。再者，预清洁腔室不需要是一专用的腔室，其可以结合于其他腔室(例如用在蚀刻如阶层间介电质蚀刻、化学气相沉积或溅镀的腔室)，因而多个操作可以被执行在同一腔室内。又，本发明不需要被限制在预清洁多孔性低k介电质上的光阻残余物，本发明可以被用在其他型式的软还原蚀刻。
因此，本发明藉由增加蚀刻速率与减少介电质劣化且小幅改变硬体而改善了易碎低k介电质的等离子清洁。

Claims (17)

1.一种等离子处理包含一介电层的基材的方法，其至少包含下列步骤：
设置该基材于一真空腔室中，该真空腔室接附至一远程等离子源；
将一还原处理气体流动通过该远程等离子源，因而通过一磁性离子过滤件以从该处理气体中移除离子，且因而进入该腔室内，气体混合物包含氢且基本上不包含氧或水；以及
维持该腔室内一压力，使得该腔室内的氢分压小于120milliTorr且大于20milliTorr。
2.如权利要求1所述的方法，其中该处理气体基本上由氢所构成。
3.如权利要求1所述的方法，其中该处理气体基本上由氢与氦所构成。
4.如权利要求1所述的方法，其中该介电层包含至少20at％碳，且具有至少10％的孔隙度。
5.如权利要求1所述的方法，其中该介电层具有不大于2.5的介电常数。
6.一种等离子处理一基材的方法，其至少包含下列步骤：
设置该基材于一真空腔室中，该真空腔室接附至一远程等离子源；以及
将一还原处理气体流动通过该远程等离子源，因而通过一磁性离子过滤件以从该处理气体中移除离子，且因而进入该真空腔室内，该处理气体包含氢与一惰性气体且基本上不包含氧或水。
7.如权利要求6所述的方法，其中该惰性气体为氦。
8.如权利要求7所述的方法，其中该处理气体基本上由氢与氦所构成。
9.如权利要求6至8项中任一所述的方法，更包含维持该真空腔室中总压力介于200与600milliTorr之间。
10.如权利要求9所述的方法，更包含维持该真空腔室中氢分压介于40与200milliTorr之间。
11.如权利要求9所述的方法，其中总压力被维持在介于300与500milliTorr之间。
12.如权利要求11所述的方法，其中氢分压被维持在介于80与150milliTorr之间。
13.一种等离子清洁腔室，其至少包含：
真空腔室，其包括一基座以支撑欲被清洁的基材；
介电质喷洒头，其位在该基座的对面；
远程等离子源；
输送管，其连接该远程等离子源的输出至该喷洒头，且包括一可移除的介电质衬里；
磁性离子过滤件，其设置在该输送管上以从穿过该输送管的气体中移除离子；以及
氢气源，其用于该远程等离子源。
14.如权利要求13所述的腔室，其中该磁性离子过滤件包含一磁铁组件，该磁铁组件产生一磁场横越该输送管的一轴，该磁场足以将氢离子偏斜朝向该输送管的一壁。
15.如权利要求13所述的腔室，更包含一氦气源，其用于该远程等离子源。
16.如权利要求13所述的腔室，其中该介电质衬里包含氧化铝，且该喷洒头包含石英。
17.如权利要求13所述的腔室，更包含一第二介电质衬里，其内衬在该喷洒头的一岐管。
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