CN101416280B - 由液相形成原子层薄膜的方法和微电子结构 - Google Patents
由液相形成原子层薄膜的方法和微电子结构 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 12
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- -1 aminoethylamino Chemical group 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical class CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 4
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- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010949 copper Substances 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010410 layer Substances 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 4
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- 239000003599 detergent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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Abstract
描述一种处理衬底的方法。将偶联剂和金属离子溶液施用于衬底。施用活化溶液来活化金属离子溶液的金属离子,从而由离子形成金属薄膜。
Description
技术领域
一般来说,本发明的实施例涉及一种处理衬底的方法,更具体地说,涉及一种由液相形成均匀原子层薄膜的方法。
背景技术
电镀已经被用来在半导体衬底上形成互连及其他结构。对于许多集成电路应用,电镀不再是一种可行的选择,这是因为晶圆上到处会出现大的电压降。电镀也无法在整个晶圆上产生最佳均匀度,而且它的沉积率也常常难以控制。
其他一些金属沉积技术也已经发展成为电镀的替代技术。一种称为无电镀膜法的技术涉及采用化学手段而不是电气手段将金属沉积在衬底上。为了保证这种技术能够进行,衬底必须首先被涂上活化层。然后,进行化学处理,使得能利用该活化层随后形成金属。跟电镀一样,电镀也无法在整个晶圆上产生最佳均匀度,而且其沉积率也难以控制,特别是在为了形成非常薄的层时。
发明内容
根据本发明的一个方面,提供一种由液相形成原子层薄膜的方法,包括:
将偶联剂和金属离子溶液施用于衬底;以及
施用活化溶液以活化所述金属离子溶液的金属离子,从而由所述离子形成原子层厚度的金属薄膜。
根据本发明的另一个方面,提供一种由液相形成原子层薄膜的方法,包括:
(1)交替地:
(1.1)将偶联剂和金属离子溶液施用于衬底;以及
(1.2)施用活化溶液以活化所述金属离子,从而由所述离子形成原子层厚度的金属薄膜;以及
(2)对所述金属薄膜退火以去除所述偶联剂。
根据本发明的又一个方面,提供一种微电子结构,包括:
衬底,具有在其中形成的沟槽;
在所述沟槽的侧壁和底部形成的阻挡层;
在所述阻挡层上形成的原子层厚度的种子层;以及
在所述种子层上镀的金属结构。
附图说明
参照附图举例说明本发明的实施例,附图如下:
图1是说明根据本发明的一个实施例处理衬底的方法的流程图;
图2示出在处理衬底的过程中的横截面侧视图;
图3说明图2的处理中使用的偶联剂分子;
图4是横截面侧视图,说明在图2的处理中形成的薄膜如何可在镀微电子电路的金属结构时用作种子层;以及
图5是可能用到图4的结构的计算机系统的框图。
具体实施方式
图1和图2说明根据本发明的一个实施例的一种处理衬底的方法。该方法利用液相材料来沉积保形的原子层均匀薄膜。该薄膜是在50℃至70℃之间的低温下沉积,并在大约300℃的相对低温下进行退火。
在块101,清洗衬底。衬底的清洗使其表面官能化,带有羟基基团。清洁剂溶液一般含有在碱性介质中的表面活性剂、磷酸盐或者碳酸盐。这类清洁剂溶液通过使羟基基团官能化而使衬底更加亲水。
在块102,用水对衬底进行冲洗。水冲洗掉残留的清洁剂溶液,从而露出官能化的羟基基团。
在块104,将偶联剂和金属离子溶液施用于衬底。在图2中以参考标号10来表示衬底,以参考标号12来表示偶联剂和金属离子溶液。偶联剂优选为氨基硅烷。对于铂族金属(铂族金属包括钯、钌和铂)来说,诸如咪唑硅烷或者氨丙基三甲氧基硅烷之类的氨基硅烷是好的偶联剂。推荐用诸如氨基乙基氨基聚三甲氧基硅烷衍生物之类的氨基硅烷来使钴、镍或者铜固定化。偶联剂与离子之间形成一种分子。图3中说明这种分子的一个例子,其中的离子是Pd+。
在块106,施用活化溶液。活化溶液使离子官能化而将单层原子14作为薄膜留在残留的偶联剂12上。活化溶液包含诸如次磷酸或者二甲胺硼烷之类的还原剂。
在块108,冲洗掉多余的材料。不是所有偶联剂的离子在正常情况下一遍就能够被活化,因此,由金属原子14形成的薄膜上通常会留下针孔16。块104、块106以及块108中的处理通常会重复一次或者多次,以留下没有针孔的连续薄膜18。
参照块104、块106以及块108描述的处理是低温处理。偶联剂和活化溶液都在50℃至70℃之间的温度下以液相施用。
在块110,对包括薄膜18和偶联剂12的整个结构进行退火。退火是在320℃以下的温度进行,一般是在大约300℃的温度进行。偶联剂12是由有机材料在大约300℃的相对低温下烧制而成。退火因此去除了偶联剂12,并把薄膜18直接留在衬底10上。退火也提高了薄膜18与衬底10之间的结合。
如图4所示,形成薄膜18的处理过程可以用来形成在镀层操作中的金属种子层。在衬底10的硅层或者层间介电层中形成沟槽20。然后在衬底10上,包括在沟槽20的底部和侧壁上形成阻挡层22。阻挡层22一般由金属、如钽或者由合金、如硝酸钽制成。薄膜18构成覆盖阻挡层22的种子层。薄膜18则可作为为了在薄膜18上镀金属层24的种子层。薄膜18和金属层一般是由同一种金属、如铜制成的。
接下来用化学-机械抛光操作将金属层24整平,化学-机械抛光操作也去除了薄膜18和阻挡层22的上面部分。沟槽20内留下金属结构。金属结构可以是沟槽20内的插头、通路或者金属线。
衬底10和在沟槽20内形成的金属结构构成微电子结构,微电子结构构成微电子电路中一部分。这样的微电子电路可以是例如处理器或者计算机的存储器。
图5给出了以计算机系统500为示例形式的机器的图示,计算机系统500可包括具有图4的微电子结构的微电子电路。该机器可以是个人计算机(PC)、写字板式PC、机顶盒(STB)、个人数字助理(PDA)、蜂窝电话、万维网设备、网络路由器、交换机或者桥、或者任何能够执行一套指定机器要完成的动作的指令的机器。
示例的计算机系统500包括处理器502、主存储器504以及静态存储器506,处理器502、主存储器504以及静态存储器506通过总线508互相通信。
计算机系统500还可包括视频显示器501。计算机系统500还包括字母数字输入装置512(例如键盘)、光标控制装置514(例如鼠标)、盘驱动单元516、信号产生装置518(例如扬声器)以及网络接口装置520。
所描述的单元包括机器可读媒介522,其上存储有一套或者多套指令524(例如软件)。软件也可以全部或者至少部分驻留在主存储器504内,以及/或者在计算机系统500执行软件时,驻留在处理器502内,主存储器504和处理器502也构成机器可读媒介。
还可以通过网络528经由网络接口装置520发送或者接收软件。
尽管在这里已经参照多个图解说明的实施例描述了本发明,但是应当理解,还有其他大量的可以被本领域的技术人员想到的修改和实施例都会落入本发明原理的精神和范围内。更具体地说,在前面公开、附图以及所附权利要求的范围内的主题组合方案的零部件以及/或者方案中,在不偏离本发明精神的情况下,合理的变化和修改是可能的。除了这些零部件以及/或者方案上的变化和修改,替代性的应用对本领域的技术人员来说也可能是显而易见的。
此外,为了便于理解,可能对某些功能块按照独立的块进行描述;但是,这些独立描述的块不一定要按照它们被讨论或者表示的顺序。例如,一些块可能能够按照一种替代的顺序或者同时被执行。
Claims (20)
1.一种由液相形成原子层薄膜的方法,包括:
将偶联剂和金属离子溶液施用于衬底;以及
施用活化溶液以活化所述金属离子溶液的金属离子,从而由所述离子形成原子层厚度的金属薄膜。
2.如权利要求1所述的方法,还包括:清洗所述衬底以使所述衬底的表面官能化,带有羟基基团,所述偶联剂附着于所述羟基基团。
3.如权利要求2所述的方法,还包括:用水冲洗所述衬底。
4.如权利要求1所述的方法,其中,所述偶联剂为咪唑硅烷、氨丙基三甲氧基硅烷或者氨基乙基氨基聚三甲氧基硅烷衍生物中的一种。
5.如权利要求1所述的方法,其中,所述偶联剂为咪唑硅烷或者氨丙基三甲氧基硅烷中的一种,并且所述离子是来自铂族的离子,使得所述金属薄膜由来自铂族的金属制成。
6.如权利要求1所述的方法,其中,所述偶联剂为氨基乙基氨基聚三甲氧基硅烷衍生物,并且所述离子为钴、镍或者铜离子,使得所述金属薄膜为钴膜、镍膜或者铜膜。
7.如权利要求1所述的方法,其中,在50℃至70℃之间的温度施用所述偶联剂。
8.如权利要求1所述的方法,其中,所述活化溶液是次磷酸或者二甲胺硼烷。
9.如权利要求1所述的方法,其中,在50℃至70℃之间的温度施用所述活化溶液。
10.如权利要求1所述的方法,还包括重复以下步骤:
将偶联剂和金属离子溶液施用于所述衬底;以及
施用活化溶液以活化所述金属离子,从而由所述离子形成薄膜。
11.如权利要求1所述的方法,还包括对所述金属薄膜退火以去除所述偶联剂。
12.如权利要求11所述的方法,其中,在低于320℃的温度对所述金属薄膜退火。
13.如权利要求1所述的方法,还包括:
在所述衬底中形成沟槽;
在所述沟槽的侧壁和底部形成阻挡层,其中所述金属薄膜为形成在所述阻挡层上的金属种子层;以及
在所述种子层上镀金属结构。
14.如权利要求13所述的方法,其中,所述种子层和所述金属结构是相同金属的。
15.一种由液相形成原子层薄膜的方法,包括:
(1)交替地:
(1.1)将偶联剂和金属离子溶液施用于衬底;以及
(1.2)施用活化溶液以活化所述金属离子,从而由所述离子形成原子层厚度的金属薄膜;以及
(2)对所述金属薄膜退火以去除所述偶联剂。
16.如权利要求15所述的方法,其中,所述偶联剂为咪唑硅烷、氨丙基三甲氧基硅烷或者氨基乙基氨基聚三甲氧基硅烷衍生物中的一种。
17.如权利要求15所述的方法,其中,所述活化溶液为次磷酸或者二甲胺硼烷。
18.一种微电子结构,包括:
衬底,具有在其中形成的沟槽;
在所述沟槽的侧壁和底部形成的阻挡层;
在所述阻挡层上形成的原子层厚度的种子层;以及
在所述种子层上镀的金属结构。
19.如权利要求18所述的微电子结构,还包括处理器,所述金属结构形成所述处理器的一部分。
20.如权利要求19所述的微电子结构,其中,所述种子层和所述金属结构是相同金属的。
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US11/394,732 US20070235876A1 (en) | 2006-03-30 | 2006-03-30 | Method of forming an atomic layer thin film out of the liquid phase |
PCT/US2007/064507 WO2007117909A1 (en) | 2006-03-30 | 2007-03-21 | Method of forming an atomic layer thin film out of the liquid phase |
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US6555158B1 (en) * | 1999-01-22 | 2003-04-29 | Sony Corporation | Method and apparatus for plating, and plating structure |
CN1599949A (zh) * | 2001-12-05 | 2005-03-23 | 先进微装置公司 | 具有改良阻挡层接着力的互连结构 |
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US5882736A (en) * | 1993-05-13 | 1999-03-16 | Atotech Deutschland Gmbh | palladium layers deposition process |
US7045461B2 (en) * | 2000-01-07 | 2006-05-16 | Nikkon Materials Co., Ltd. | Metal plating method, pretreatment agent, and semiconductor wafer and semiconductor device obtained using these |
EP1279750B1 (en) * | 2000-04-25 | 2016-05-04 | JX Nippon Mining & Metals Corporation | Pretreating agent for metal plating |
DE10048844A1 (de) * | 2000-10-02 | 2002-04-11 | Basf Ag | Verfahren zur Herstellung von Platinmetall-Katalysatoren |
DE10054544A1 (de) * | 2000-11-01 | 2002-05-08 | Atotech Deutschland Gmbh | Verfahren zum chemischen Metallisieren von Oberflächen |
KR100499557B1 (ko) * | 2001-06-11 | 2005-07-07 | 주식회사 하이닉스반도체 | 반도체소자의 배선 형성방법 |
US6767828B2 (en) * | 2001-10-05 | 2004-07-27 | International Business Machines Corporation | Method for forming patterns for semiconductor devices |
JPWO2003091476A1 (ja) * | 2002-04-23 | 2005-09-02 | 株式会社日鉱マテリアルズ | 無電解めっき方法及び金属めっき層が形成された半導体ウエハー |
KR100772798B1 (ko) * | 2002-12-20 | 2007-11-01 | 삼성전자주식회사 | 유기금속 화합물을 이용한 도전성 금속 배선 패턴 형성방법 |
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US6555158B1 (en) * | 1999-01-22 | 2003-04-29 | Sony Corporation | Method and apparatus for plating, and plating structure |
US6294425B1 (en) * | 1999-10-14 | 2001-09-25 | Samsung Electronics Co., Ltd. | Methods of forming integrated circuit capacitors by electroplating electrodes from seed layers |
CN1599949A (zh) * | 2001-12-05 | 2005-03-23 | 先进微装置公司 | 具有改良阻挡层接着力的互连结构 |
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