CN101295145B - 用水蒸汽和稀释气体增强的氢灰化 - Google Patents

用水蒸汽和稀释气体增强的氢灰化 Download PDF

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CN101295145B
CN101295145B CN200810095009XA CN200810095009A CN101295145B CN 101295145 B CN101295145 B CN 101295145B CN 200810095009X A CN200810095009X A CN 200810095009XA CN 200810095009 A CN200810095009 A CN 200810095009A CN 101295145 B CN101295145 B CN 101295145B
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晨-思扬·杨
昌珲·李
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Abstract

本发明公开了一种特别适用于基于氢化的氧碳化硅的低介电常数材料的无氧的氢等离子体灰化工艺。主要的灰化步骤包括将事先被刻蚀的电介质层暴露于从氢气(50)、可选的氮气(54)、大量的水蒸气(60)、和大量的氩气(80)或氦气形成的等离子体(48)。尤其是对于多孔低介电常数电介质，主要的灰化等离子体额外地包括碳氢化合物气体(84)，例如甲烷。在主要的灰化步骤之前可以有一个短时间的表面处理步骤，这通过含有诸如氢气和可选的氮气的含氢还原气体的等离子体来实现。

Description

用水蒸汽和稀释气体增强的氢灰化
技术领域
本发明一般性地涉及集成电路制造中材料的等离子刻蚀。具体地，本发明涉及光刻胶的灰化。
背景技术
在硅集成电路制造中广泛使用等离子刻蚀技术。其中一个工艺步骤通常被称为电介质刻蚀，该步骤被用于形成穿过电介质层的孔，从而在集成电路的不同层之间提供垂直电连接。在图1的横截面图中示意性地示出了一种原型过孔(via)结构。形成在晶片表面上的下电介质层10在其表面内形成有导电构件(feature)12。上电介质层14沉积在下电介质层10和其导电构件12的上方。平面光刻胶16层被旋涂在未图案化的上电介质层14上，利用步进式光刻机按照辐射图案对其进行曝光形成穿过光刻胶层16的掩膜孔18，从而形成具有掩膜孔18的光刻掩膜，掩膜孔18位于导电构件12上方并借助过孔与其电连接。在上电介质层14和光刻胶层16之间可能还形成有其它层，例如刻蚀硬掩膜或者抗反射涂层。被光刻掩膜覆盖的晶片被放进等离子刻蚀反应器中，在其中上电介质层14被向下刻蚀到导电构件从而形成过孔20。典型地，可以使用相同的刻蚀反应器来刻蚀抗反射涂层和硬掩膜(如果有的话)，而对不同的层使用不同的刻蚀化学试剂。电介质刻蚀通常利用碳氟化合物，例如使用六氟丁二烯(C4F6)。
在电介质刻蚀之后，利用铝或铜等金属填充过孔20从而提供与导电构件12的垂直电连接。对于双镶嵌结构，通常使用铜金属化，过孔20被上电介质层14下部的更短的过孔代替，其连接至在顶部水平延伸的沟槽(trench)，两者同时用铜填充。对于接触层的金属化，下电介质层10被活性硅层代替，并且导电构件12也由硅构成，但是在过孔20的界面处可能有复合硅化物和栅极氧化物，在这种情况下过孔20被称为接触孔。
在完成电介质刻蚀后，一些光刻胶可能残留在电介质层14顶部，或者刻蚀残余物(通常是碳质材料)可能残留在过孔18内。残余物可能在过孔20的侧面上形成多聚物涂层22，这有助于产生垂直的刻蚀轮廓，或者残余物形成被隔离的刻蚀残余物24(包括在过孔20底部的一些)。类似的多聚物涂层可能覆盖光刻胶的剩余部分产生硬化外表面。金属填充过程要求过孔20包覆上一层保形的衬里(包括阻挡层)，并且在通过电化学镀覆(ECP)工艺进行铜金属化时，铜层可以作为晶种层和电镀电极。目前，阻挡层通常是TaN/Ta双层，并且阻挡层和铜晶种层可以通过先进溅射法进行沉积。重要的是在沉积过孔的衬里层之前将光刻胶和其它残余物从结构中除去，因为它们分解粘附在过孔侧壁上并且增大了过孔底部的接触电阻，两者都会影响器件的良率和可靠性。
等离子灰化(plasma ashing)早已被用于在刻蚀之后除去光刻胶和其它残余物。氧等离子体对于刻蚀除去碳基材料层非常有效。尽管以前在被设计来批处理大量晶片的筒状灰化器中进行灰化，更新的技术采用单晶片等离子灰化器，其或者是一个单独的刻蚀反应器或者是在用于电介质刻蚀的同样的等离子刻蚀反应器中进行的单独处理步骤。
当电介质层由二氧化硅形成、具有SiO2的近似化学组成和约3.9的介电常数时，传统的灰化工艺是有效的。但是用于先进集成电路所需的更低介电常数电介质时会遇到很多困难。早期的低介电常数电介质是通过用氟掺杂二氧化硅使介电常数降低到约3.5来形成的。更低的低-3介电常数可以通过氢化的氧碳化硅(silicon oxycarbide)来得到，例如加利福尼亚州Santa Clara的Applied Materials公司的Black Diamond电介质。更低的低于3的介电常数可以通过沉积这些材料并使其多孔化来得到。这些材料的氧灰化引起了很多问题。氧等离子体不仅攻击碳质光刻胶的残余物和其它残余物，它也会消耗氧碳化硅中的碳，从而增大其介电常数。多孔介电材料相对易碎，并且更容易被氧等离子体破坏，原因是部分氧穿透进入孔中以及孔的坍缩。
因此，先进灰化工艺已经从氧等离子体的氧化化学试剂转移到由氢和可能的氮的一些组合(例如，H2、H2/N2或NH3)形成的等离子体的还原化学试剂。与氧灰化相比，基于氢自由基H*的灰化具有更好的性能和更少的电介质破坏。但是，由于还原反应速率低并且在仅有还原气体的环境中产生的氢自由基密度低，氢灰化是非常慢的工艺。氧灰化工艺可能需要20秒的处理，而氢灰化可能需要10倍的时间，从经济角度考虑这明显是个缺点。因此，通常将少量的氧加到还原气体中以便提高灰化速率和灰化效率。然而，多孔低介电常数材料对即使少量的氧也是敏感的，这些氧会从氧碳化硅材料除去大量的碳并使孔结构坍缩，从而增大介电常数。
发明内容
进行无氧等离子体灰化工艺，其中主要的灰化步骤包括从氢气、可选的氮气、水蒸气、和非活性气体或稀释气体(例如氩或氦)形成的等离子体。可以用氨气代替氢和氮。形成等离子体的水蒸气多于氢气，并且非活性气体多于水蒸气。
该灰化工艺特别适用于含碳和氧化硅的低介电常数材料，例如氢化的氧碳化硅。
可选地，可以向主要的灰化步骤中的等离子体加入碳氢化合物气体，例如甲烷。碳氢化合物的引入特别适用于多孔低介电常数材料，例如介电常数小于3的材料。
初始的无氧等离子体灰化步骤或表面处理步骤包括从含氢还原气体(例如氢气或氨气)和可选的氮气(但没有水蒸气)形成的等离子体。表面处理步骤可以比主要灰化步骤用时短。
附图说明
图1是介电刻蚀后的过孔的横截面图，包括残余光刻胶、侧壁多聚物涂层、和其它需要被灰化工艺除去的刻蚀残余物。
图2是可用于本发明的等离子灰化器的横截面示意图。
具体实施方式
在基于氢的灰化等离子体中加入水蒸气和大量氩气或氦气，这大大增加了氢自由基的浓度，并增大了灰化速率而对低介电常数电介质的损坏更小。
本发明可以在等离子灰化反应器30中进行，如图2的横截面图所示。用真空泵浦***36将真空处理室32抽至低压力范围。室32内的基座38支撑着待灰化的晶片40，与气体喷头42相对，气体喷头42通过大量小孔44供应处理气体。
处理气体通过远程等离子源48被供应到喷头42后面的歧管46，远程等离子源48激发处理气体而形成等离子体。远程等离子源48可以位于远离真空室32的一定距离处，但它仍被认为附属于真空室32，因为含有在远程等离子源48产生的等离子体的气体在其等离子状态下流入真空室32。优选地，绝大多数自由基和相对很少的等离子体离子被送到处理室32。远程等离子源和歧管的一些细节公开在Fu等2006年2月10日递交的美国专利申请11/351,676中，现在该申请已公开为美国专利申请公开2007/0190266。远程等离子源48可以使用在低GHz范围(例如2.54GHz)操作的微波激发源或者在亚GHz范围(例如270-650kHz)操作的RF激发源。远程等离子源48有利地具有带电粒子过滤器，使得送到处理室的等离子体仅包含中性自由基，而没有带电离子。如果氢气(H2)被用作主要的灰化气体，则从氢气源50通过质量流量控制器52向远程等离子源48供应氢气。氮气(N2)可以从氮气源54通过另一个质量流量控制器56供应。氮往往用作氢自由基刻蚀的钝化剂。
从含有液体水池62的真空密封的水安瓿60向远程等离子体源48供应水蒸汽(H2O)。质量流量控制器64从安瓿60计量供应水蒸汽。室温下水的蒸汽压约为20Torr，这远高于通常操作远程等离子源48的真空压强水平。因此，一旦安瓿60被反向抽吸，具有约20Torr压力的水蒸汽就会出现在安瓿60中液体水池62上方的顶部空间66中。安瓿60可以直接安装在室32上以使管道长度最短，水会在管道壁上凝结。
按照***控制器70中、存储在可读介质72(例如CDROM)上的指令集来操作控制器70，从而控制泵浦***36、远程等离子源48和各个质量流量控制器，包括已经提到的质量流量控制器52、56、64以及其它质量流量控制器。
根据本发明，另外的非活性气体(如Ar)从氩气源80经质量流量控制器82计量供应。可以用氦代替氩。氩促进了H2O解离成H*和OH*，这被认为是在Penning过程中发生的，其中激发态氩自由基的能量被转移给水分子。因而，与单独的H2相比，水蒸汽产生氢自由基H*密度更高。结果，尽管氩气和氦气通常被认为是非活性的稀释气体，它们在实际灰化过程中保持非活性，但是促进了高密度的活性灰化自由基的生成。然而，在配方中有利地包括H2可以抑制氧自由基O*的产生。此外，还有利地加入N2，不仅增强H2O的解离，还在灰化过程中提供了一定的钝化效果。
氢化的氧碳化硅的灰化工艺的一个实施例在表1中示出。表1中示出的是一个两步骤工艺，其中处理气体流量的单位是标准立方厘米(sccm)。
表1
  步骤1   步骤2
  H2(sccm)   600   600
  N2(sccm)   100
  H2O(sccm)   1000
  Ar(sccm)   3000
  压力(Torr)   1   1
  RPS功率(W)   5000   5000
  时间(s)   20   60
第一个步骤是中度的软刻蚀或者表面处理，它并不会使光刻胶或多聚物侧壁涂层表面***。第一个步骤主要基于氢还原化学物质，因此较慢。然而，它只是用于刻蚀掉表面。可以用其它还原气体(如单独的H2或氨气NH3)来代替H2/N2。第二个步骤用于迅速除去光刻胶的主体部分和残余物。第二个步骤是主要的灰化步骤，并且比初始的表面处理步骤用时长。
应该理解这里概括的配方仅是本发明工艺的代表性例子。压力范围可以容易地扩展到0.5-5Torr，RPS源功率范围对于300mm的室介于2kW-8kW之间，氢流量为200-2000sccm，氩气流量为3000-10000sccm，水蒸汽流量为500-3000sccm。如前所述，可以用氦代替氩。通常，在第一步骤中，主要供给氢，但也可以供给少量的氮。在第二步骤中供给的氩比水多，供给的氢比水蒸汽少。在这两个步骤中都不供给氧气或其自由基形式的臭氧。
也可以在不进行第一步骤的初步表面处理或进行其它初步处理的情况下，实施第二步骤的主要灰化工艺。
表1的配方对于氢化的氧碳化硅非多孔低介电常数电介质是有效的。然而，对于目前更好的同样组成的多孔低介电常数电介质，额外的钝化是理想的。因此，可以从碳氢化合物气体源84通过另一个质量流量控制器86供应碳氢化合物，例如甲烷(CH4)，但也可以替换成其它由碳和氢组成的碳氢化合物，例如乙烷(C2H6)、乙烯(C2H4)和乙炔(C2H2)，以及其它高级烷烃、烯烃、炔烃等。表2中示出了一种用于多孔低介电常数电介质的优选配方。
表2
Figure S200810095009XD00061
  RPS功率(W)   5000   5000
  时间(s)   20   60
表2的配方与表1的配方基本一致，只是在第二步骤中引入了用量远少于其它组分的甲烷。这些少量的碳氢化合物被认为可以通过封闭电介质材料的孔来钝化和保护暴露的低介电常数电介质，从而防止刻蚀等离子体(尤其是氧)穿透进入孔内的深处并降解电介质材料。
本发明并不限于使用远程等离子源的等离子体灰化器，本发明也可以在二极管等离子刻蚀反应器中实现，其中在靠近晶片或其它衬底的真空室内产生等离子体，但是等离子体的离子浓度需要被最小化。此外，本发明也不限于上面描述的氢化的氧碳化硅低介电常数电介质，也可以用于其它类型的电介质材料，并可以在金属刻蚀或硅刻蚀工艺之后应用。
本发明提供了特别适用于低介电常数电介质材料的快速且具有保护性的灰化工艺。
附图标记索引
10    下电介质层
12    导电构件
14    上电介质层
16    光刻胶层
18    掩膜孔
20    过孔
22    多聚物涂层
24    被隔离的刻蚀残余物
30    等离子灰化反应器
32    真空处理室
36    真空泵浦***
38    底座
40    晶片
42    气体喷头
44    小孔
46    歧管
48    远程等离子源
50    氢气源
52    质量流量控制器
54    氮气源
56    质量流量控制器
60    水安瓿
62    池
64    质量流量控制器
66    顶部空间
70    控制器
72    可读介质
80    氩气源
82    质量流量控制器
84    氢气源
86    质量流量控制器

Claims (19)

1.一种灰化工艺，包括主要灰化步骤，其中所述主要灰化步骤包括：
将主要灰化气体供应到远程等离子体源，其中所述主要灰化气体包括：第一量的选自氢气和氨气的还原气体；大于第一量的第二量的水蒸气；大于第二量的第三量的选自氩气和氦气的稀释气体，且不含有有效量的氧气；
在所述远程等离子体源中由所述主要灰化气体生成等离子体；
在带电粒子过滤器中将离子从所述等离子体去除；以及
将从所述带电粒子过滤器输出的所述等离子体施加于衬底。
2.如权利要求1所述的工艺，其中所述还原气体包括氢气。
3.如权利要求1所述的工艺，其中所述还原气体包括氨气。
4.如权利要求2所述的工艺，其中所述主要灰化气体额外含有第四量的碳氢化合物气体。
5.如权利要求4所述的工艺，其中所述第四量小于第一量。
6.如权利要求4所述的工艺，其中所述碳氢化合物气体包括甲烷。
7.如权利要求1所述的工艺，其中所述衬底包括电介质层，所述电介质层中具有暴露于灰化工艺的孔。
8.如权利要求7所述的工艺，还包括按照一个光刻胶掩膜刻蚀所述电介质层中的孔的在先步骤。
9.如权利要求1-8中任一项所述的工艺，还包括在主要灰化步骤之前进行的初始灰化步骤，其中将初始灰化气体的等离子体施加于衬底，所述初始灰化气体包括第六量的含氢还原气体且不含有效量的水蒸气或碳氢化合物。
10.如权利要求9所述的工艺，其中所述含氢还原气体包括氢气。
11.如权利要求9所述的工艺，其中所述初始灰化气体还包括小于第六量的第五量的氮气。
12.如权利要求9所述的工艺，其中所述衬底包括电介质层，所述电介质层中具有暴露于灰化工艺的孔。
13.如权利要求12所述的工艺，还包括按照一个光刻胶掩膜刻蚀所述电介质层中的孔的在先步骤。
14.一种对衬底进行灰化的工艺，所述衬底具有事先在其中刻蚀有孔的电介质层，所述工艺包括在其中放置有所述衬底且包括附属装置的等离子体刻蚀室中进行的如下步骤：
将第一气体混合物激发成第一等离子体的第一步骤，所述第一气体混合物包括第一量的氢气，且不含有有效量的氧气和水蒸气；
随后进行的将第二气体混合物激发成第二等离子体的第二步骤，所述第二气体混合物包括：第二量的氢气、第三量的水蒸气、第四量的选自氩气和氦气的非活性气体，且不含有有效量的氧气，其中所述第三量大于第二量且小于第四量，并且所述第一步骤和第二步骤包括在带电粒子过滤器中从所述第一和第二等离子体去除离子。
15.如权利要求14所述的工艺，其中第二步骤进行的时间比第一步骤长。
16.如权利要求14所述的工艺，其中所述附属装置包括远程等离子体源，在其中第一和第二等离子体被激发并通过所述带电粒子过滤器流入所述室中。
17.如权利要求14所述的工艺，其中所述第一气体混合物还含有氮气。
18.如权利要求14-17中任一项所述的工艺，其中所述第二气体混合物还含有第五量的碳氢化合物气体，并且所述第一气体混合物不含碳氢化合物气体。
19.如权利要求18所述的工艺，其中所述碳氢化合物气体包括甲烷。
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