CN100442498C - 利用无电镀化学的深通孔晶种修复 - Google Patents

利用无电镀化学的深通孔晶种修复 Download PDF

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CN100442498C
CN100442498C CNB2004100806921A CN200410080692A CN100442498C CN 100442498 C CN100442498 C CN 100442498C CN B2004100806921 A CNB2004100806921 A CN B2004100806921A CN 200410080692 A CN200410080692 A CN 200410080692A CN 100442498 C CN100442498 C CN 100442498C
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托马斯·S·多里
肯尼思·N·黄
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Abstract

本发明描述了在纵横比较大的通孔内形成连续晶种层的方法及其相关结构。这些方法包括：在衬底中形成凹槽，在该凹槽内形成非连续的金属层，激活该凹槽内非连续的金属层和多个未沉积区域，在该凹槽内经激活的非连续金属层和多个未沉积区域上无电地沉积晶种层，以及在晶种层上电镀金属填充层，从而形成基本无空隙的经填充的凹槽。

Description

利用无电镀化学的深通孔晶种修复
技术领域
本发明涉及微电子处理领域，更具体地涉及在深通孔内形成连续金属膜的方法及其形成的结构。
背景技术
在微电子器件制造中，现在正在实践的技术是制备凹槽或通孔来连接衬底内多级导电(通常是金属)层。随着器件尺寸缩减到1微米以下，要采用多个金属化层来适应更高的密度。被广泛用作通孔金属化材料的一种金属膜是铜。通常，铜晶种层12(见图2)被溅射进通孔开口14内，接着通过电镀用铜填充层(未示出)填充通孔开口14。然而，将铜晶种层12溅射进通孔开口14内存在一个严重的缺点，即铜晶种层12在通孔开口14的顶部拐角16附近的沉积速率大于在通孔开口14的侧壁18和底部20附近的沉积速率。这样导致在通孔开口14的顶部形成突出物22，其遮蔽(即减损)了铜在通孔开口14的侧壁18和底部20上的沉积。由于通孔开口14顶部的突出物22往往会阻碍向通孔开口14内的进一步溅射沉积，额外的溅射沉积也无法足以到达通孔开口14的底部20和侧壁18，所以这种遮蔽效应可能导致通孔开口14内形成空隙(void)24或者金属不连续区域。
对于微电子器件内纵横比(aspect ratio)较高(即，大于3∶1)的通孔，在溅射沉积工艺过程中，由于这种遮蔽效应，在通孔的侧壁和底部上溅射沉积出连续的晶种层非常困难或者根本不可能。换句话说，溅射出的晶种层在通孔内将不会连续。这意味着当随后电镀铜膜来填充通孔时，通孔在通孔填充金属化过程中将出现空隙，这种空隙可能给器件的可靠性和性能带来负面影响。因此，希望能形成连续的晶种层，再在其上镀金属填充层，从而防止了纵横比较高的通孔内空隙的形成。本发明即提供了这种方法及其相关结构。
发明内容
一方面，本发明提供了一种形成晶种层的方法，包括：在衬底中的凹槽内形成非连续的金属层；激活所述凹槽内的所述非连续的金属层和至少一个未沉积区域；以及在所述凹槽内的所述非连续的金属层上和所述至少一个未沉积区域上无电地沉积晶种层。
另一方面，本发明提供了一种形成微电子结构的方法，包括：在衬底中形成凹槽；在所述凹槽内形成非连续的金属层；激活所述凹槽内的所述非连续金属层和至少一个未沉积区域；在所述凹槽内的所述非连续金属层上和所述至少一个未沉积区域上无电地沉积晶种层；以及在所述晶种层上方形成金属填充层。
另一方面，本发明提供了一种微电子结构，包括：衬底中的凹槽；设置在所述凹槽内的非连续金属层；设置在所述凹槽内的所述非连续金属层上和至少一个未沉积区域上的晶种层；和设置在所述晶种层上的金属填充层。
附图说明
虽然本说明书、权利要求书已经具体指出并明确要求了本发明的权利要求，但结合附图，阅读下面对本发明的描述可更容易地理解本发明的优点，其中附图包括：
图1A-1I表示当实施本发明方法实施例时，可以形成的结构的横截面。
图2表示现有技术中结构的横截面。
具体实施方式
在下面详细的描述中，参照了附图；为了说明起见，这些附图示出了其中可以实施本发明的具体实施例。这些实施例被足够详细地描述出，以使本领域的技术人员能够实施本发明。应该理解到，本发明的各种实施例虽然不同，但并不一定是相互排斥的。例如，这里结合一个实施例所描述的特定特征、结构或特性可以在其他的实施例中实现，而没有偏离本发明的精神和范围。此外，应该理解到，每个公开实施例中单个元件的位置或布置可以被修改，而不偏离本发明的精神和范围。因此，下面详细的描述不应认为是限制性的，而本发明的范围仅由被恰当解释的所附权利要求以及该权利要求能够要求的全部等同范围来限定。在图中，相同标号表示这几幅视图中相同或类似的功能元件。
下面将要描述到在纵横比较大的凹槽内形成铜膜的方法及其相关结构。这些方法包括：形成凹槽，在该凹槽内形成非连续的金属层，激活该凹槽内非连续的金属层和多个未沉积区域，在该凹槽内无电地镀出晶种层，以及在晶种层上电镀金属填充层，从而形成基本无空隙的、金属填充的凹槽。溅射出非连续金属层、接着在该非连续金属层上无电地镀出晶种层，这种组合的方法使得能够在凹槽的底部和侧壁上形成基本无空隙的、几乎是100％的金属覆盖层。
图1A-1F示出了制备微电子结构的方法。在本发明的一个方法实施例中，图1A示出了衬底102，其包括但不限于硅、二氧化硅、氮化硅、氧氮化硅等。当然，应该理解到，衬底102可以出现在微电子器件内的任意位置处。如本领域所公知的，该衬底还可以包括对着主要器件面的一面，即硅晶片的“背面”。衬底102包括第一表面106。
如图1B所示，接着，衬底102被本领域公知的方法图案化并蚀刻，从而形成从衬底102的第一表面106向衬底102内延伸的凹槽104(例如沟槽或通孔)。凹槽104包括内壁108和底部110。凹槽104可以是纵横比较大的凹槽，其中凹槽104的高度122与凹槽104的宽度120的比可以大于3∶1，即凹槽104的纵横比优选大于3∶1。
因为凹槽104是高纵横比的凹槽，所以由前面讨论的遮蔽效应会导致凹槽104内可能形成非连续金属层112。如本领域公知的，这种非连续金属层112可以由溅射沉积工艺、或例如原子层沉积(ALD)的其他物理溅射沉积工艺、或例如等离子增强化学沉积(PECVD)的化学沉积工艺形成。沉积温度可以是约100-200℃。压力可以是约1-10mTorr，功率可以为5至约10KW。用来形成非连续金属层112的材料可以包括但并不限于钽、氮化钽、氮化钽硅、钨、钛、钛钨、氮化钛、氮化钛硅以及这些材料的组合。非连续金属层112为随后形成的铜层或铜合金层提供了扩散屏障(barrier)。非连续金属层112的厚度可以为约300至约500埃，优选为不到500埃。
因为凹槽104优选是高纵横比的凹槽，所以非连续金属层112不可能充分形成在凹槽104的内壁108和底部110上，或完全覆盖这两部分。由于溅射遮蔽效应的现象(前面所述的，见图2)，凹槽104内可能形成未沉积区域；其中，高纵横比的凹槽(例如凹槽104)的顶部附近溅射层比该凹槽底部附近更厚，并且凹槽顶部附近的更厚层往往阻碍了高纵横比凹槽内完全的金属覆盖。因此，凹槽104内可能存在多个没有被非连续金属层112覆盖的未沉积区域，如图1C中所示的未沉积内壁区域109和未沉积底部区域111。这些凹槽104内的未沉积区域上没有非连续金属层112。
如图1D所示，凹槽104内的非连续金属层112、未沉积内壁区域109和未沉积底部区域111可以通过在非连续金属层112、未沉积内壁区域109和未沉积底部区域111上形成活化层114而被激活。活化层114可以包括但不限于钯或铂，并且可以被包含在例如包括氯化钯(PdCl2)或氯化铂(PtCl2)的溶液中。
活化层114可以通过接触置换法形成在非连续金属层112上，在这种接触置换法中，非连续金属层112被置入溶液浴中，所述溶液可以包括Pd或Pt离子、还原剂(例如但不限于次磷酸盐、二甲基胺硼烷或肼)、络合剂(例如乙酸或柠檬酸)以及酸(例如但不限于氢氟酸、盐酸或硝酸)或碱(例如但不限于氢氧化四甲基铵或氢氧化钾)。活化层114可以不到300埃，并且通常为100埃。活化层114激活非连续金属层112、未沉积内壁区域109和未沉积底部区域111以进行自催化反应，例如无电沉积反应。
如图1E所示，晶种层116可以通过无电沉积形成在活化层114上。晶种层116可以含有金属材料，包括但不限于铜。晶种层116在活化层114上形成几乎是100％连续的金属膜覆盖层(因此在凹槽104的内壁108和底部110上提供了几乎100％的台阶覆盖)。无电镀出的晶种层116包括多个其直径118一般约为1微米或更大的晶粒117(见图1F)。如本领域所公知的，活化层114可以在晶种层116的无电沉积过程中几乎被包容(subsumed)(见图1G)，或者可以如图1E所绘的保持原样不动。
各种已知的无电沉积方案的其中一种可用来无电地沉积出晶种层116。优选实施例的无电溶液可包括提供Cu2+阳离子的硫酸铜、作为Cu2+阳离子络合剂的乙二胺四乙酸(EDTA)、提供氢氧根阴离子的氢氧化季铵、作为还原剂的甲醛(HCHO)或乙醛酸、作为表面活性剂和润湿剂的RHODAFAC RE 610TM或聚乙二醇、和作为稳定剂和延展促进剂的氰化铵或2，2-联吡啶。在晶种层116的无电沉积之后，衬底102可以在去离子水中清洗以去除无电沉积溶液。应该认识到，晶种层116的形成需要控制时间，以使它不会充分地填充凹槽104。
如图1H所示，金属填充层120可以形成在晶种层116上。金属填充层120可以包括金属材料，其包括但不限于铜。如本领域所公知的，金属填充层120可以利用电镀工艺形成在晶种层116上。金属填充层120形成在凹槽104内的晶种层116上，这样使得凹槽被金属填充层充分填充120，而不存在空隙(如现有技术中在非连续金属层112上没有沉积无电晶种层116而存在的空隙)。
无电沉积的晶种层116防止了金属填充层120中空隙的形成，这是因为金属填充层120可以镀在或形成在连续的电镀晶种层膜上，例如晶种层116。利用直接沉积在非连续的金属层112上的溅射晶种层(如现有技术中采用的)，无法形成这种连续的晶种层，这是因为由于前述的遮蔽效应，使用溅射出来的晶种层不能在凹槽内形成连续膜。随后，利用例如本领域公知的化学机械抛光技术，可以抛光金属填充层120(见图1I)。
如上所述，本发明提供了在高纵横比的凹槽内形成连续晶种层的方法和相关结构，这样能够形成基本无空隙的金属填充层，从而大大增强了根据本发明各种实施例所制得的微电子器件的可靠性和性能。
虽然前面的描述已经指明了本发明方法中可以使用的某些步骤和材料，但本领域的技术人员将认识到可以进行许多修改和替换。所有这样的修改、变化、替换和添加都被视为落在所附权利要求所限定的本发明的精神和范围内。此外，应该认识到，在例如硅衬底的衬底上制备多个金属层以制造微电子器件是本领域公知的。因此，应认识到，这里所提供的图仅仪示出了示例性的、与实施本发明有关的微电子器件的部分。因此，本发明并不限于这里所述的结构。

Claims (21)

1.一种形成晶种层的方法，包括：
在衬底中的凹槽内形成非连续的金属层；
在所述凹槽内的所述非连续的金属层上和至少一个未沉积区域上形成活化层，其中所述活化层的厚度小于300埃；以及
在所述活化层上无电地沉积晶种层。
2.如权利要求1所述的方法，其中形成所述凹槽的步骤包括形成高纵横比的凹槽，其纵横比大于约3∶1。
3.如权利要求1所述的方法，其中形成所述非连续金属层的步骤包括形成至少一种下列材料的非连续层，所述材料包括钽、氮化钽、氮化钽硅、钨、钛、钛钨、氮化钛、氮化钛硅及它们的组合。
4.如权利要求1所述的方法，其中形成活化层的步骤包括激活所述凹槽内的所述非连续金属层和所述至少一个未沉积区域。
5.如权利要求4所述的方法，其中激活所述凹槽内的所述非连续金属层和所述至少一个未沉积区域的步骤包括在所述凹槽内的所述非连续金属层上和在所述至少一个未沉积区域上形成至少一个钯层或铂层。
6.如权利要求1所述的方法，还包括在所述晶种层上形成金属填充层。
7.如权利要求6所述的方法，还包括利用化学机械抛光工艺来抛光所述金属填充层。
8.如权利要求6所述的方法，其中形成所述金属填充层的步骤包括形成基本无空隙的金属填充层。
9.一种形成微电子结构的方法，包括：
在衬底中形成凹槽；
在所述凹槽内形成非连续的金属层；
在所述凹槽内的所述非连续的金属层上和至少一个未沉积区域上形成活化层，其中所述活化层的厚度小于300埃；
在所述活化层上无电地沉积晶种层；以及
在所述晶种层上方形成金属填充层。
10.如权利要求9所述的方法，其中形成所述凹槽的步骤包括形成高纵横比的凹槽，其纵横比大于约3∶1。
11.如权利要求9所述的方法，其中形成所述非连续金属层的步骤包括形成至少一种下列材料的非连续层，所述材料包括钽、氮化钽、氮化钽硅、钨、钛、钛钨、氮化钛、氮化钛硅及它们的组合。
12.如权利要求9所述的方法，其中无电地沉积所述晶种层的步骤包括无电地沉积含有直径约为1微米或更大的晶粒的铜层。
13.如权利要求9所述的方法，其中形成所述金属填充层的步骤包括电镀出所述金属填充层。
14.如权利要求9所述的方法，其中形成所述金属填充层的步骤包括形成基本无空隙的金属填充层。
15.如权利要求9所述的方法，其中形成所述金属填充层的步骤包括电镀出铜层。
16.一种微电子结构，包括：
衬底中的凹槽；
设置在所述凹槽内的非连续金属层；
设置在所述凹槽内的所述非连续金属层上和至少一个未沉积区域上的活化层，其中所述活化层的厚度小于300埃；
设置在所述活化层上的晶种层；和
设置在所述晶种层上的金属填充层。
17.如权利要求16所述的结构，其中所述晶种层包括直径约为1微米或更大的晶粒。
18.如权利要求16所述的结构，其中所述非连续金属层包括钽、氮化钽、氮化钽硅、钨、钛、钛钨、氮化钛、氮化钛硅及它们的组合的至少其中之一。
19.如权利要求16所述的结构，其中所述晶种层包括铜。
20.如权利要求16所述的结构，其中所述凹槽包括高纵横比的凹槽，其中所述高纵横比包括大于约3∶1的纵横比。
21.如权利要求16所述的结构，其中所述金属填充层包括基本无空隙的金属填充层。
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