CN105296971B - 利用至少两种硼烷还原剂进行无电镀敷 - Google Patents
利用至少两种硼烷还原剂进行无电镀敷 Download PDFInfo
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 111
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 238000007772 electroless plating Methods 0.000 title abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 69
- 230000008021 deposition Effects 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims description 63
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 36
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 morpholine boron Alkane Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012691 Cu precursor Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- MCQRPQCQMGVWIQ-UHFFFAOYSA-N boron;methylsulfanylmethane Chemical compound [B].CSC MCQRPQCQMGVWIQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000000454 electroless metal deposition Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012696 Pd precursors Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 35
- 238000007747 plating Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LFGFZXXKZPSRMB-UHFFFAOYSA-N [B].[Mo].[Co] Chemical compound [B].[Mo].[Co] LFGFZXXKZPSRMB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Abstract
本发明涉及利用至少两种硼烷还原剂进行无电镀敷，具体提供了一种用于提供在衬底上的无电沉积的金属层的溶液。提供一种溶剂。金属前体被提供到溶剂中。第一含硼烷还原剂被提供到溶剂中。第二含硼烷还原剂被提供给溶剂，其中第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少五倍，并且其中所述溶液不含非硼烷还原剂。
Description
技术领域
本发明涉及在半导体晶片上形成半导体器件的方法。更具体而言，本发明涉及沉积含金属层以形成半导体器件。
在形成半导体器件时，可沉积含金属层。这种沉积可以通过电镀来提供。
发明内容
为了实现上述意图并根据本发明的目的，提供了一种用于提供在衬底上的无电沉积的金属层的溶液。提供一种溶剂。金属前体被提供到该溶剂中。第一含硼烷还原剂被提供到该溶剂中。第二含硼烷还原剂被提供给该溶剂，其中第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少2倍，并且其中所述溶液不含非硼烷还原剂。
在本发明的另一种表现形式中，提供了一种用于提供在衬底上的无电沉积的金属层的溶液。提供一种溶剂。金属前体被提供到该溶剂中。二甲胺硼烷被提供到该溶剂中。吗啉硼烷被提供到该溶剂中。
在本发明的另一种表现形式中，提供了用于提供在衬底上的无电沉积的金属层的方法。将衬底暴露于无电金属沉积物，其包含金属前体、第一含硼烷还原剂和第二含硼烷还原剂，其中第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少5倍。
在一个方面，所述金属前体可以包含钴前体、镍前体、铜前体、铁前体、或钯前体中的至少一种。
本发明的这些和其它特征将在本发明的详细描述中并结合附图更详细地描述。
附图说明
在附图的图中通过实施例举例说明本发明，而不是进行限制，并且其中相似的附图标记表示类似的元件，其中：
图1是单位为埃/秒的沉积速率与DMAB百分率的关系曲线图。
图2是本发明的一个实施方案的流程图。
图3A-B是使用本发明方法形成的结构的示意图。
具体实施方式
现在参考附图中所举的几个优选实施方式详细地描述本发明。在下文的描述中阐述了许多具体细节以便提供对本发明的充分理解。然而，对于本领域技术人员而言，显而易见的是，在不需要这些具体细节中一些或全部的情况下也可实施本发明。在其他情况下，众所周知的工艺步骤和/或结构没有详细描述，以免不必要地使本发明难以理解。
必要时，无电金属/金属合金镀敷溶液通常由一种或多种金属盐、还原剂、一种或多种络合剂、一种或多种pH调节剂、缓冲剂、表面活性剂和添加剂(如果需要)制成。在大多数情况下，镀液中有一种类型的还原剂就足够了。如果第一还原剂对于待镀金属无催化活性，那么沉积无法进行。为了克服这个困难，衬底表面通常被另一种催化能力较强的金属激活或者除了第一还原剂之外向溶液中加入另一种还原剂。该第二还原剂启动衬底表面上的沉积反应。在此步骤之后，第一还原剂可以接管沉积反应。另一可能的目的是使用两种不同的还原剂以将其他的合金元素添加到待镀合金中。例如，如果硼烷还原剂加入到沉积溶液中时，则在膜中，包含作为第一还原剂的次磷酸盐的CoWP沉积溶液将通常含小于1％的硼。
在通常使用的还原剂中，硼烷是特殊种类，因为它们的反应能力受到与它们形成复合物的化合物的强烈影响。使用以不同复合物存在于溶液中的两种或更多种硼烷通常不能提供任何上述益处。然而，已经出乎意料地发现，这样的组合会有助于在不改变其它非硼烷溶液组分浓度的情况下调节镀液稳定性、起始时间以及溶液的沉积速率。此外，使用硼烷组合的合金成分与利用单一硼烷源得到的沉积物的成分非常匹配。
当溶液中只存在硼烷类型的还原剂时，沉积速率的影响是最强的。例如，在大量的次磷酸盐存在下，沉积速率的效果显著降低。还发现，可以通过不同硼烷的比例和浓度方便地调节沉积速率。图1通过提供单位为埃/秒的沉积速率与硼烷混合物(吗啉硼烷和DMAB)百分率的关系曲线图举例说明DMAB对沉积速率的影响。
对于CoMoB合金的沉积，发现溶液中使用两种硼烷还原剂的沉积速率调整的这种例子。当二甲胺硼烷复合物用作还原剂时，获得25埃/秒的沉积速率。将还原剂换为硼烷吗啉复合物时，沉积速率降低至1.5埃/秒。虽然25埃/秒太高而不能控制沉积薄膜(约100埃)，但1.5埃/秒的速率太慢。此外，二甲胺硼烷用作唯一的还原剂使溶液变得不稳定。已出乎意料地发现，二甲胺硼烷和吗啉硼烷的混合物提供了稳定的溶液，其中吗啉硼烷不完全掩盖(mask)由二甲胺硼烷提供的沉积速率。为了实现这些值之间的沉积速率，可使用二甲胺和吗啉复合物的混合物。
吗啉硼烷的沉积速率降低效果也与其它硼烷还原剂一起作用。这样的硼烷还原剂可以是硼烷二乙胺、叔丁基胺硼烷、氨硼烷和二甲基硫醚硼烷。
在另一个实施方式中，溶液可以使用两种不同的硼烷还原剂以同时调节多个膜的性质。一种还原剂可缩短起始时间，但可能会导致粗糙度高。另一种还原剂将降低粗糙度，但具有较长的起始时间。两者结合提供低粗糙度沉积(见图)并能满足起始时间短的要求。在一个替代实施方式中，一种还原剂可提供快速启动，但可能会导致形成结瘤。另一种还原剂可能引发慢，但可能会阻止或降低结瘤形成。
图2是本发明的一个实施方案的高阶流程图。在该实施方式中，提供无电沉积溶液，其包含溶剂、金属前体、二甲胺硼烷(DMAB)和吗啉硼烷(步骤204)。衬底暴露于溶液(步骤208)。
在本发明的一个优选实施方式中，提供包含溶剂、金属前体、二甲胺硼烷(DMAB)和吗啉硼烷的无电沉积溶液(步骤204)。本实施方式使用水溶液。
衬底暴露于无电沉积溶液。在该实施例中，衬底是具有图案化金属表面的介电衬底。图3A是具有多个金属图案表面304和介电表面308的衬底300的局部视图。在该实施方案中，金属图案表面304是铜的。在该实施方式中，衬底被置于无电沉积的镀液中。
在该实施方式中，溶液为金属图案表面304镀敷钴钼硼(CoMoB)层。在镀液中，二甲胺硼烷复合物起到还原剂的作用，在铜上提供CoMoB沉积，由于二甲胺硼烷复合物提供较快的沉积速率，即25埃/秒，这是加快铜表面304上初始沉积所必需的。在CoMoB层已开始沉积在铜表面304上之后，硼烷吗啉复合物沉积增加。图3B是CoMoB层312已沉积之后衬底300的局部视图。
该实施方式通过使用较快的硼烷络合物提供了快速的沉积，同时通过提供较慢的硼烷络合物提供沉积控制。如果单独使用较快的硼烷复合物，所得到的溶液将太不稳定。其它还原剂可掩盖较快的硼烷复合物，减慢整个过程。已出乎意料地发现，将较慢的硼烷复合物添加到较快的硼烷络合物中，整个过程不减慢，但所得到的溶液较稳定。该实施方式还使得能对所得沉积物中合金添加剂进行额外控制。
在其他实施方式中，金属前体是钴前体、镍前体、铜前体或钼前体中至少一种。在其他实施方式中，溶剂是水、二甲基亚砜(DMSO)、乙二醇或离子液体。优选地，溶液不含次磷酸盐。优选地，溶液还包含络合剂、表面活性剂或pH调节剂中的至少一种。在其他实施方式中，可调节pH和络合剂以使硼不沉积到所得到的沉积的金属层上。
在其他实施方式中，在使用含有一种以上含硼烷还原剂启动沉积之后，单一还原剂可用于进一步的沉积。在其他实施方式中，可以使用三种或四种含硼烷还原剂。
当二甲胺硼烷复合物用作还原剂时，获得25埃/秒的沉积速率。当硼烷吗啉复合物用作还原剂时，沉积速率降低至1.5埃/秒。因此，在该实施方式中，第一含硼烷还原剂(二甲胺硼烷复合物)的沉积速率为25埃/秒的沉积速率，其比第二含硼还原剂烷(硼烷吗啉复合物)的沉积速率(即1.5埃/秒的沉积速率)快16倍以上。优选地，第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少5倍。更优选地，第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少10倍。最优选地，第一含硼烷还原剂的沉积速率为第二含硼烷还原剂的沉积速率的至少15倍。这样的溶液不含含非硼烷的还原剂。
在另一个实施方式中，两种溶液依次使用，其中每种溶液含有不同的硼烷还原剂。例如，活性更强的硼烷还原剂可以施加到第一溶液中以快速开始沉积，无选择性的损失。这样的溶液可以用于不能重复循环的过程，不能重复循环的过程可使用该溶液并接着丢弃该溶液。接下来，含有活性较小的硼烷还原剂的溶液可用于提供较稳定的工艺。这样的溶液可以再循环。预计反应能力较强的硼烷将提供较快的起始时间(开始在衬底上发生沉积反应所需的时间)和较低的镀液稳定性(对于均相镀敷反应的较高的倾向性)。然而，利用不同硼烷进行的试验的一个出乎意料的结果显示，虽然叔丁基胺硼烷的沉积速率比吗啉硼烷快，但是后者启动较快从而提供较好的选择性。提供比吗啉硼烷较快的沉积速率的DMAB可给出较高的镀液稳定性。
虽然已通过几个优选实施方式对本发明进行了描述，但是存在落入本发明的范围之内的改变、置换和各种替代等同方案。还应当指出的是，存在实现本发明的方法和装置的许多替代方式。因此，意指下文所附权利要求书被解释为包括落入本发明的真实精神和范围内的所有这些改变、置换和各种替代等同方案。
Claims (16)
1.一种用于提供在衬底上的无电沉积的金属层的溶液，其包含：
溶剂；
金属前体；
第一含硼烷还原剂；
第二含硼烷还原剂；其中所述第一含硼烷还原剂的沉积速率为所述第二含硼烷还原剂的沉积速率的至少2倍，并且其中所述溶液不含非硼烷还原剂。
2.根据权利要求1所述的溶液，其中所述金属前体包含钴前体、镍前体、铜前体、铁前体、或钯前体中的至少一种。
3.根据权利要求2所述的溶液，其中所述金属前体包含钴前体和钼前体的混合物。
4.根据权利要求3所述的溶液，其中所述溶剂是二甲基亚砜(DMSO)、乙二醇、离子液体或水中的至少一种。
5.根据权利要求4所述的溶液，其中所述溶液还包含络合剂、表面活性剂或pH调节剂中的至少一种。
6.根据权利要求5所述的溶液，其中所述第一含硼烷还原剂是叔丁基胺硼烷、氨硼烷和二甲基硫醚硼烷或二甲胺硼烷(DMAB)中的至少一种，并且所述第二含硼烷还原剂是吗啉硼烷。
7.根据权利要求5所述的溶液，其中所述第一含硼烷还原剂包含二甲胺硼烷并且所述第二含硼烷还原剂包含吗啉硼烷。
8.根据权利要求2所述的溶液，其中所述第一含硼烷还原剂包含二甲胺硼烷并且所述第二含硼烷还原剂包含吗啉硼烷。
9.根据权利要求1所述的溶液，其中所述第一含硼烷还原剂包含二甲胺硼烷并且所述第二含硼烷还原剂包含吗啉硼烷。
10.根据权利要求1所述的溶液，其中所述第一含硼烷还原剂是叔丁基胺硼烷和二甲基硫醚硼烷中的至少一种，并且所述第二含硼烷还原剂是吗啉硼烷。
11.一种用于提供在衬底上的无电沉积的金属层的方法，包括：
将所述衬底暴露于无电金属沉积溶液，其包含金属前体、第一含硼烷还原剂和第二含硼烷还原剂，其中所述第一含硼烷还原剂的沉积速率为所述第二含硼烷还原剂的沉积速率的至少5倍，其中所述溶液不含非硼烷还原剂。
12.根据权利要求11所述的方法，其中所述金属前体包含钴前体、镍前体、铜前体、铁前体或钯前体中的至少一种。
13.根据权利要求12所述的方法，其中所述第一含硼烷还原剂是叔丁基胺硼烷、氨硼烷和二甲基硫醚硼烷或二甲胺硼烷(DMAB)中的至少一种，并且所述第二含硼烷还原剂是吗啉硼烷。
14.根据权利要求11所述的方法，其中所述第一含硼烷还原剂包含二甲胺硼烷并且所述第二含硼烷还原剂包含吗啉硼烷。
15.根据权利要求11所述的方法，其中所述第一含硼烷还原剂是叔丁基胺硼烷、氨硼烷和二甲基硫醚硼烷或二甲胺硼烷(DMAB)中的至少一种，并且所述第二含硼烷还原剂是吗啉硼烷。
16.一种用于提供在衬底上的无电沉积的金属层的方法，包括：
将所述衬底暴露于第一无电金属沉积溶液，其包含金属前体和第一含硼烷还原剂，其中所述溶液不含非硼烷还原剂；并且
随后将所述衬底暴露于第二无电金属沉积溶液，其包含所述金属前体和第二含硼烷还原剂，其中所述溶液不含非硼烷还原剂，
其中所述第一含硼烷还原剂的沉积速率为所述第二含硼烷还原剂的沉积速率的至少5倍。
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