CN102132383A - 于阻障表面上的钴沉积 - Google Patents

于阻障表面上的钴沉积 Download PDF

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CN102132383A
CN102132383A CN2009801341725A CN200980134172A CN102132383A CN 102132383 A CN102132383 A CN 102132383A CN 2009801341725 A CN2009801341725 A CN 2009801341725A CN 200980134172 A CN200980134172 A CN 200980134172A CN 102132383 A CN102132383 A CN 102132383A
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cobalt
layer
base material
plasma
hydrogen
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J·陆
H-C·哈
P·马
S·甘古利
J·F·奥布充
S·H·于
M·纳拉辛汉
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Applied Materials Inc
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Abstract

本发明的实施例提供一种在一阻障层上沉积一钴层并接着沉积一导电材料，如铜或一铜合金于其上的工艺。在一实施例中，提供一沉积材料于一基材表面的方法，其包括以下步骤：在一基材上形成一阻障层，于气相沉积工艺期间曝露此基材至二钴六羰基丁基乙炔(CCTBA)及氢(H2)以在该阻障层上形成一钴层，及沉积一导电材料于此钴层之上。在某些范例中，此阻障层及/或此钴层于如热工艺、原位等离子体工艺或远距等离子体工艺的处理工艺期间可曝露至一气体或一试剂。

Description

于阻障表面上的钴沉积
技术领域
本发明的实施例大致有关用于制造电子及半导体组件的金属化工艺，更详言之，本发明的实施例为有关在沉积一导电层或接触材料于阻障层前沉积一钴层于阻障层的方法。
背景技术
铜为目前选用于多层金属化工艺的金属，其对组件的制造为重要的。多层互连迫使制造工艺要求高深宽比的孔的平坦化，该孔包括触点、通孔、线及其它特征。当特征具有较高深宽比时，填充此特征而不产生空隙或形变此特征的几何为更困难的。因制造者力求电路密度及质量，可靠地形成互连亦较困难。
因为铜相对低成本及工艺性质，铜的使用已扩展至市场，故半导体制造商持续关注经由减少铜扩散与抗湿润性以改良在铜与介电材料间的边界区的方法。因特征尺寸已减小，已开发数种工艺方法以制造铜互连。每一工艺方法可增加误差的可能性，如铜扩散越过边界区、铜结晶结构变形及抗湿润。物理气相沉积(PVD)、化学气相沉积(CVD)、原子层沉积(ALD)、电化学电镀(ECP)、无电沉积、化学机械研磨(CMP)、电化学机械研磨(ECMP)及其它沉积与移除铜层的方法利用机械、电或化学方法以操作形成互连的铜。可沉积阻障及覆盖层以含有铜。
过去，使用一具有锡、铝或镁的钽、氮化钽或铜合金层提供在铜与其它材料间的阻障层或一黏合促进剂。此些选择通常成本高且仅部份有效。因沿此边界区的铜原子在多重步骤半导体处理期间遭受一般在温度、压力、大气条件或其它工艺变量的改变，铜可能沿此边界区移动并成为黏聚的铜。铜亦可能沿此边界区较不均匀分散并成为湿润的铜。在边界区的此些改变包括铜原子的应力迁移及电迁移。铜穿越介电层或其它结构的应力迁移及电迁移的增加此生成结构的电阻且减少此生成组件的可靠度。
因此，存在一提升在阻障层上一导电层或接触材料的安定性与黏合性的需求。亦然，存在改良含铜层的电迁移可靠度的需求，尤其是对于铜线的形成，同时防止铜扩散入邻近的材料，如介电材料。
发明内容
本发明的实施例为提供在沉积一导电层于阻障层前沉积一钴层于阻障层的工艺。在一实施例中，提供一沉积材料于基材表面的方法，其包括在基材上形成一阻障层，曝露此基材至二钴六羰基丁基乙炔(CCTBA)及氢(H2)以于气相沉积工艺期间在该阻障层上形成一钴层，及沉积一导电材料于此钴层上。
在一范例中，基材可于热CVD工艺期间曝露于一含有CCTBA及氢的沉积气体。在另一范例中，基材可接着于ALD工艺期间曝露于CCTBA与氢。此基材在CVD或ALD工艺期间亦可加热至一自约100℃至约250℃范围间的温度。此钴层沉积少于约
Figure BPA00001327617700021
的厚度。
在某些范例中，阻障层及/或钴层在处理工艺期间可曝露至一气体或一试剂。此处理可为一热工艺、一原位等离子体工艺或一远程等离子体工艺。此气体或试剂可含有或为氮(N2)、氨(NH3)、氢(H2)、氨/氢混合物、硅烷、二硅烷、氦、氩、其之等离子体、其之衍生物或其等之组合。此阻障层或此钴层可曝露于此气体、试剂或等离子体约1秒至约30秒范围内的一段时间。此基材在处理工艺期间可加热至约50℃至约400℃的温度范围。
在某些范例中，此导电材料可含有铜或铜合金。此导电材料可含有一种晶层及块体层(bulk layer)。或者，此导电材料可直接沉积于此钴层上，如经由电化学电镀(ECP)工艺。在一范例中，一含有铜的种晶层可经由PVD工艺或CVD工艺沉积。在另一范例中，此块体层含有铜且可经由一ECP工艺沉积。此阻障层可含有钽、氮化钽、钛、氮化钛、钨、氮化钨、其之合金、其之衍生物或其等的组合。在一范例中，此阻障层可为一配置在钽层上的氮化钽层。
在另一实施例中，提供一种用于在一基材表面上沉积材料的方法，其包括以下步骤：在一基材上形成一阻障层，在预处理工艺期间曝露该阻障层至第一等离子体，曝露该基材至CCTBA及氢以于气相沉积工艺期间在该阻障层上形成一钴层，于后处理工艺期间曝露该钴层至一第二等离子体，及经由一气相沉积工艺沉积一铜层于该钴层上，如经由一PVD工艺或CVD工艺。
在另一实施例中，提供一种用于在一基材表面上沉积材料的方法，其包括以下步骤：在一基材上形成一阻障层，在预处理工艺期间曝露此阻障层至一等离子体，曝露该基材至CCTBA及一还原气体以于气相沉积工艺期间在该阻障层上形成一钴层，于后处理工艺期间曝露该钴层至一氢等离子体，及沉积一铜材料于该钴层之上。在一范例中，此用于沉积该钴层的气相沉积工艺及该后-处理工艺为依序重复以形成一钴材料。此钴材料含有多钴层，其中每一者在另一钴层沉积前已曝露至一氢等离子体。
附图说明
在前文概述的本发明的更详细描述可参考实施例，其之部份为说明于附图中，以此方式，本发明于前文述及的特征可更详尽的了解。然而，需了解附图仅为用以说明本发明的典型实施例，故因此不能被视为限制本发明的范畴，因为本发明容许其它等效的实施方面。
图1图示根据本文描述的一实施例说明一工艺的流程图；及
图2A-2F图示根据本文描述的一实施例在不同工艺步骤中基材的示意图。
具体实施方式
本发明的实施例为提供在沉积一导电层于阻障层前沉积一钴层于阻障层或层的方法。此钴层及阻障层可各自可选择地曝露至一处理工艺，如等离子体工艺或一热工艺。此导电层可含有铜或一铜合金且经由物理气相沉积(PVD)工艺、原子层沉积(ALD)工艺、电化学电(ECP)工艺或一无电沉积工艺沉积。此钴层改良铜边界区性质以促进黏合性、改良沟槽填充及电移动性能、减少扩散及黏聚并助长在工艺期间基材表面的均匀的粗糙度与湿润性。
图1图示一说明本发明实施例的工艺100的流程图。工艺100可用于在一基材上形成一互连或其它组件。在一实施例中，工艺100的步骤110-150可在基材200上进行，如在图2A-2F中图示。工艺100包括在一基材上沉积或形成一阻障层(步骤110)，可选择地曝露此阻障层至一预处理工艺(步骤120)，沉积一钴层于此阻障层上(步骤130)，可选择地曝露此钴层至一后处理工艺(步骤140)，及沉积至少一个导电层于此钴层上(步骤150)。
图2A图标含有配置于下层202之上的介电层204的基材200。孔206形成于介电层204内且可为一通孔、镶嵌、穿孔或其它形成于其内的通道。下层202可为一基材、基材表面、接触层或视组件结构而定的另一层。介电层204可含有一介电材料，如一低k介电材料。在一范例中，介电层204含有一低k介电材料，如一碳氧化硅材料，或一碳掺杂的氧化硅材料，例如BLACK
Figure BPA00001327617700041
II低k介电材料，其可得自位于美国加州圣克拉拉市的Applied Materials公司。用于介电层204的合宜材料的另一范例为碳化硅基膜，其使用如述于共同让渡的美国专利第6,537,733、6,790,788及6,890,850号的化学气相沉积(CVD)或等离子体辅助CVD(PE-CVD)工艺形成，该些专利并入本案做为参考。
在一实施例中，在工艺100的步骤110期间至少一个阻障层或材料可沉积或形成于一基材上。在一范例中，图2B图标阻障层210配置于基材200上、在介电层204之上，并共形地位于孔206内。阻障层210可为一层或多层。阻障层210可含有钛、氮化钛、钽、氮化钽、钨、氮化钨、其等之硅化物、其等之衍生物或其等之组合。在某些实施例中，阻障层210可含有钽/氮化钽，钛/氮化钛或钨/氮化钨的双层。阻障层210可具有一在自约
Figure BPA00001327617700042
至约
Figure BPA00001327617700043
范围间的厚度，较佳为自约
Figure BPA00001327617700044
至约
Figure BPA00001327617700045
且可经由PVD、ALD、等离子体辅助ALD(PE-ALD)、CVD、PE-CVD、脉冲-CVD或其等的组合形成或沉积。
在一范例中，阻障层210含有经由PVD工艺沉积的金属钽的一下层及一经由另一PVD工艺沉积一配置在此氮化钽下层的上的上层。在另一范例中，阻障层210含有经由ALD工艺沉积的金属钽的一下层及一经由CVD工艺沉积一配置于此氮化钽下层之上的上层。在另一范例中，阻障层210含有经由PVD工艺沉积的金属钽的一下层及一经由CVD工艺沉积一配置此氮化钽下层的上的上层。
例如，阻障层210可含有使用CVD工艺或一ALD工艺沉积的氮化钽，其中含钽化合物或钽先驱物(例如，PDMAT)与氮先驱物(例如氨)反应。在一实施例中，钽及/或氮化钽经由述于共同让渡之于2002年10月25日申请的美国专利申请案第10/281,079号，且以US 2003-0121608公开的专利申请案中的ALD工艺沉积为一阻障层210，该专利并入本案做为参考。在一范例中，Ta/TaN双层可沉积为一阻障层210，如各自以ALD、CVD及/或PVD工艺以任何顺序沉积一层于另一层上的一金属钽层及一氮化钽层。
在另一范例中，一Ti/TiN双层可沉积为一阻障层210，如各自以ALD、CVD及/或PVD工艺以任何顺序沉积一层于另一层上的一金属钛层及一氮化钛层。在另一范例中，一W/WN双层可沉积为一阻障层210，如各自以ALD、CVD及/或PVD工艺以任何顺序沉积一层于另一层上的一金属钨层及一氮化钨层。
在步骤120，阻障层210可选择地曝露至一预处理工艺，如一等离子体工艺或一热工艺。在等离子体或热预处理工艺期间可曝露至基材200的工艺气体及/或试剂包括氢(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、氢与氨混合物(H2/NH3)、联胺(N2H4)、硅烷(SiH4)、二硅烷(Si2H6)、氦、氩、其之衍生物、其的等离子体或其等之组合。工艺气体可以在自约500sccm至约10slm范围间的流速流入至此工艺腔室或曝露至此基材，较佳为自约1slm至约6slm，例如约3slm。
在一实施例中，在步骤120于此预处理工艺期间，基材200及阻障层210可曝露至一等离子体以除去阻障层210的污染物。基材200可置于一工艺腔室内且曝于一工艺气体，该气体可点燃以形成等离子体。工艺气体可含有一种气体化合物或多种气体化合物。基材200可在室温(例如23℃)，但通常预热至后续沉积工艺的需求温度。基材200可加热至自约100℃至约400℃范围间的温度，较佳为自约125℃至约350℃，且更佳为约150℃至约300℃，如约200℃或约250℃。
此工艺腔室可产生一原位等离子体或装设有一远距等离子体源(RPS)。在一实施例中，基材200可曝露至此等离子体(例如，原位或远距)自约0.5秒至约90秒的范围间的一段时间，较佳为自约10秒至约60秒，且更佳为自约20秒至约40秒。此等离子体在功率为自约100瓦特至约1,000瓦特范围间产生，较佳为约200瓦特至约600瓦特，且更佳为约300瓦特至约500瓦特。此工艺腔室通常具有一为约100托耳或更少的内部压力，如在自约0.1托耳至约100托耳范围间，较佳为自约0.5托耳至约50托耳，且更佳为自约1托耳至约10托耳。
在一范例中，基材200及阻障层210可曝露至由氢、氨、氮或其等的混合物产生的等离子体。在另一范例中，基材200及阻障层210可曝露至由氢及氨产生的等离子体。在另一范例中，基材200及阻障层210可曝露至由氢、氮、硅烷、二硅烷或其等之混合物产生的等离子体。在另一范例中，基材200及阻障层210可曝露至由氢、氮、氩、氦或其等的混合物产生的等离子体。
在另一实施例中，在步骤120，基材200及阻障层210于热预处理工艺期间可曝露至一工艺气体以除去阻障层210的污染物。此热预处理工艺可为一快速热工艺(RTP)或一快速热退火(RTA)工艺。基材200可置于一工艺腔室内且曝于至少一工艺气体及/或试剂。此工艺腔室可为一用于后续沉积工艺的沉积腔室，如一PVD腔室、一CVD腔室或一ALD腔室。或者，此工艺腔室可为一热退火腔室，如
Figure BPA00001327617700061
RTA腔室，其可购自位于美国加州圣克拉拉市的Applied Materials公司。基材200可加热至自约25℃至约800℃范围间的温度，较佳为自约50℃至约400℃，且更佳为自约100℃至约300℃。基材200可加热自约2分钟至约20分钟范围间的一段时间，较佳为自约5分钟至约15分钟。例如，基材200在此工艺腔室中可加热至约400℃约12分钟。
在一范例中，基材200及阻障层210当在此工艺腔室中加热时可曝于氢、氨、氮或其等之混合物。在另一范例中，基材200及阻障层210当在此工艺腔室中加热时可曝于氨/氢混合物。在另一范例中，基材200及阻障层210当在此工艺腔室中加热时可曝于氢、氮、硅烷、二硅烷或其等之混合物。在另一范例中，基材200及阻障层210当在此工艺腔室中加热时可曝于氢、氮、氩、氦或其等之混合物。
在另一实施例中，在工艺100的步骤130期间，至少钴材料或层可沉积或形成于此基材上。在一范例中，图2C说明钴层220配置于基材200上，在阻障层210之上，且在孔206内共形。钴层220通常为单一层，但可含有多层。钴层220在遍及阻障层210上可为一连续或一不连续层。钴层220可具有一约
Figure BPA00001327617700062
或更少的厚度，如在自约
Figure BPA00001327617700063
至约
Figure BPA00001327617700064
的范围间，较佳为约至约
Figure BPA00001327617700066
钴层220可经由一气相沉积工艺，如CVD、PE-CVD、脉冲CVD、ALD、PE-ALD或PVD形成或沉积。此等离子体辅助气相沉积工艺，亦即PE-CVD及PE-ALD，在此工艺腔室内可为一原位等离子体工艺，或可为一远距等离子体工艺以致等离子体可经由一RPS点燃并直接进入此工艺腔室。在许多范例中，钴层220含有金属钴。或者，在其它范例中，钴层220可含有一种或更多种钴材料，如金属钴、硅化钴、硼化钴、磷化钴、其之合金、其之衍生物或其等之组合。
在某些实施例中，钴层220可在热CVD工艺、脉冲-CVD工艺、PE-CVD工艺或脉冲PE-CVD工艺期间经由同时导入一钴先驱物与一试剂至工艺腔室而形成或沉积。在其它实施例中，此钴先驱物可在热CVD工艺、脉冲CVD工艺、PE-CVD工艺或脉冲PE-CVD工艺期间于无一试剂下导入至此工艺腔室。或者，在其它实施例中，钴层220可在热ALD工艺或PE-ALD工艺期间经由依序导入一钴先驱物与一试剂至工艺腔室而形成或沉积。
在某些范例中，钴层220可含有金属钴，但在其它范例中，可含有其它钴材料。可经由本文描述的CVD或ALD工艺形成钴材料(例如，金属钴或钴合金)的合宜钴驱物包括钴羰基错合物、钴脒化合物、双环戊二烯钴化合物、钴二烯基错合物、钴亚硝基错合物、其之衍生物、其之错合物、其之等离子体或其等之组合。在某些实施例中，钴材料可经由更进一步描述于共同让渡的美国专利第7,264,846及7,404,985号中的CVD与ALD工艺沉积，该些专利并入本案做为参考。
在某些实施例中，可使用钴羰基化合物或错合物做为钴先驱物。钴羰基化合物或错合物具有化学通式(CO)xCoyLz，其中X可为1、2、3、4、5、6、7、8、9、10、11、或12，Y可为1、2、3、4或5，及Z可为1、2、3、4、5、6、7或8。此基团L为不存在、一配位体或多个配位体，其可为相同配位体或不同配位体，且包括环戊二烯基、烷基环戊二烯基(例如甲基环戊二烯基或五甲基环戊二烯基)、戊二烯基、烷基戊二烯基、环丁二烯基、丁二烯基、乙烯基、烯丙基(或丙烯基)、烯、二烯、炔、乙炔、丁基乙炔、亚硝基、氨、其之衍生物、其之错合物、其之等离子体或其等之组合。
在一实施例中，在沉积工艺期间可使用二钴六羰基乙酰基化合物以形成钴材料(例如，钴层220)。二钴六羰基乙酰基化合物可具有化学通式(CO)6Co2(RC≡CR′)，其中R及R′为独立选自氢、甲基、乙基、丙基、异丙基、丁基、第三丁基、戊基、苯甲基、芳香族羟基、其之异构物、其之衍生物或其等之组合。在一范例中，二钴六羰基丁基乙炔(CCTBA，(CO)6Co2(HC≡CtBu))为此钴先驱物。二钴六羰基乙酰基化合物的其它范例包括二钴六羰基甲基丁基乙炔((CO)6Co2(MeC≡CtBu))、二钴六羰基苯基乙炔((CO)6Co2(HC≡CPh))、二钴六羰基甲基苯基乙炔((CO)6Co2(MeC≡CPh))、二钴六羰基甲基乙炔((CO)6Co2(HC ≡CMe))、二钴羰基二甲基乙炔((CO)6Co2(MeC≡CMe))、其之衍生物、其之错合物、其之等离子体或其等之组合。其它范例的钴羰基错合物包括环戊二烯基钴双(羰基)(CpCo(CO)2)、三羰基烯丙基钴((CO)3Co(CH2CH＝CH2))、其之衍生物、其之错合物、其之等离子体或其等之组合。
在另一实施例中，可使用钴脒酸盐或钴酰胺错合物做为钴先驱物。钴酰胺错合物具有化学通式(RR’N)xCo，其中X可为1、2或3，且R与R’独立为氢、甲基、乙基、丙基、丁基、烷基、硅烷基、烷基硅烷基、其之衍生物或其等之组合。一些范例的钴酰胺错合物包括双(二(丁基二甲基硅烷基)酰胺)钴(((BuMe2Si)2N)2Co)、双(二(乙基二甲基硅烷基)酰胺)钴(((EtMe2Si)2N)2Co)、双(二(丙基三甲基硅烷基)酰胺)钴(((PrMe2Si)2N)2Co)、双(二(三甲基硅烷基)酰胺)钴(((Me3Si)2N)2Co)，三(二(三甲基硅烷基)酰胺)钴(((Me3Si)2N)3Co)、其之衍生物、其之错合物、其之等离子体或其等之组合。
一些范例的钴先驱物包括甲基环戊二烯基钴双(羰基)(MeCpCo(CO)2)、乙基环戊二烯基钴双(羰基)(EtCpCo(CO)2)、五甲基环戊二烯基钴双(羰基)(Me5CpCo(CO)2)、二钴八(羰基)(Co2(CO)8)、亚硝基钴三(羰基)((ON)Co(CO)3)、双(环戊二烯基)钴、(环戊二烯基)钴(环己二烯基)、环戊二烯基钴(1，3-己二烯基)、(环丁二烯基)钴(环戊二烯基)、双(甲基环戊二烯基)钴、(环戊二烯基)钴(5-甲基环戊二烯基)，双(乙烯)钴(五甲基环戊二烯基)、四羰基碘化钴、钴四羰基三氯硅烷、羰基氯三(三甲基膦)钴、钴三羰基-氢三丁基膦、乙炔二钴六羰基、乙炔二钴五羰基三乙基膦、其之衍生物、其之错合物、其之等离子体或其等之组合。
在某些范例中，当经由本文描述的工艺形成钴材料(例如，金属钴或钴合金)时，可使用交替试剂与钴先驱物反应，该试剂包括还原剂，其包括氢(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、联胺(N2H4)、一氢与氨的混合物(H2/NH3)、硼烷(BH3)、二硼烷(B2H6)、三乙基硼烷(Et3B)、硅烷(SiH4)、二硅烷(Si2H6)、三硅烷(Si3H8)、四硅烷(Si4H10)、甲基硅烷(SiCH6)、二甲基硅烷(SiC2H8)、膦(PH3)、其的衍生物、其的等离子体或其等之组合。
在一实施例中，含金属钴的钴层220在热CVD工艺期间经由同时将基材200曝露至一钴先驱物气体与一还原剂而沉积。在一可替代的实施例中，含金属钴的钴层220在等离子体辅助CVD工艺期间经由同时将基材200曝露至一钴先驱物气体与一还原剂而沉积。此等离子体源可为在CVD腔室内的原位等离子体源或装设在CVD腔室外的RPS。此钴先驱物气体可经由将一载体气体(例如，氮或氩)通过一钴先驱物(例如，CCTBA)安瓿而形成。此还原剂气体可为单一化合物(例如，H2)，且因此不具有载体气体。或者，此还原剂气体可经由将载体气体通过一还原剂安瓿而形成。
此安瓿的加热可依工艺期间使用的钴先驱物或还原剂而定。在一范例中，一含有钴先驱物的安瓿，如二钴六羰基乙酰基化合物或其它钴羰基化合物(例如，(CO)xCoyLz)可加热至一自约30℃至约500℃范围间的温度。此钴先驱物气体通常具有一自约100sccm(每分钟标准立方公分(standard cubic centimeters per minute))至约2,000sccm范围间的流速，较佳为自约200sccm至约1,000sccm，且更佳为自约300sccm至约700sccm，例如约500sccm。此还原剂气体通常具有一自约0.5slm(每分钟标准升(standard liters per minute))至约10slm范围间的流速，较佳为自约1slm至约8slm，且更佳为自约2slm至约6slm。在一范例中，还原剂气体为氢且具有一自约2slm至约6slm范围间的流速，如约4slm。
此钴先驱物气体及此还原剂气体于沉积工艺期间可在进入工艺腔室前、当时或之后组合以形成一沉积气体以沉积钴层220。基材200可置于一工艺腔室内且可加热至自约25℃至约800℃范围间的温度，较佳为自约50℃至约400℃，且更佳为自约100℃至约250℃，如约150℃。一旦在预定温度，基材200可曝露至含有钴先驱物气体与还原剂气体的沉积气体自约0,1秒至约120秒范围间的一段时间，较佳为自约1秒至约60秒，且更佳为自约5秒至约30秒。例如，基材200当于CVD工艺期间形成钴层220时，其在此工艺腔室中可加热至约150℃约10分钟。
在步骤140，钴层220可选择地曝于一后处理工艺，如一等离子体工艺或一热工艺。在等离子体或热后处理工艺期间可曝于基材200及钴层220的工艺气体及/或试剂包括氢(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、一氢与氨的混合物(H2/NH3)、联胺(N2H4)、硅烷(SiH4)、二硅烷(Si2H6)、氦、氩、其之衍生物、其之等离子体或其等之组合。此工艺气体可以自约500sccm至约10slm范围间的流速流入此工艺腔室或曝至基材，较佳为自约1slm至约6slm，例如约3slm。
在一实施例中，在步骤140于此后处理工艺期间，基材200及钴层220可曝露至一等离子体以除去钴层220的污染物。基材200可置于一工艺腔室内且曝于一工艺气体，该气体可点燃以形成等离子体。此工艺气体可含有一气体化合物或多个气体化合物。基材200可在室温(例如23℃)，但通常预热至后续沉积工艺的需求温度。基材200可加热至自约100℃至约400℃范围间的温度，较佳为自约125℃至约350℃，且更佳为自约150℃至约300℃，如约200℃或约250℃。
此工艺腔室可产生一原位等离子体或装设有一RPS。在一实施例中，基材200可曝露至此等离子体(例如，原位或远距)自约0.5秒至约90秒的范围间的一段时间，较佳为自约10秒至约60秒，且更佳为自约20秒至约40秒。此等离子体在功率为自约100瓦特至约1,000瓦特范围间产生，较佳为自约200瓦特至约600瓦特，且更佳为自约300瓦特至约500瓦特。此工艺腔室通常具有一内部压力为约100托耳或更少，如在自约0.1托耳至约100托耳范围间，较佳为自约0.5托耳至约50托耳，且更佳为自约1托耳至约10托耳。
在一范例中，基材200及钴层220可曝露至由氢、氨、氮或其等的混合物产生的等离子体。在另一范例中，基材200及钴层220可曝露至由氢及氨产生的等离子体。在另一范例中，基材200及钴层220可曝露至由氢、氮、硅烷、二硅烷或其等之混合物产生的等离子体。在另一范例中，基材200及钴层220可曝露至由氢、氮、氩、氦或其等之混合物产生的等离子体。
在某些范例中，基材200及钴层220可曝至由RPS点燃的氢气产生的氢等离子体。钴层220可曝至具自约2slm至约4slm范围间的流速的氢气体。此工艺腔室可具有一内部压力自约1托耳至约10托耳范围间，且此等离子体经由具自约300瓦特至约500瓦特范围间的功率的RPS点燃。在一实施例中，此等离子体对于每一具有自约
Figure BPA00001327617700101
至约
Figure BPA00001327617700102
范围间厚度的钴材料沉积层曝至钴层220自约20秒至约40秒范围间的一段时间。当形成钴层220时，可在沉积钴材料的多层后进行多重处理。
在另一实施例中，在步骤140于此后处理工艺期间，基材200及钴层220可曝露至一工艺气体以除去钴层220的污染物。此热后处理工艺可为一RTP或RTA工艺。基材200可置于一工艺腔室内且曝于至少一种工艺气体及/或试剂。此工艺腔室可为一在先前沉积工艺使用或将在后续沉积工艺使用的沉积腔室，如一PVD腔室、一CVD腔室或一ALD腔室。或者，此工艺腔室可为一热退火腔室，如RTA腔室，其可购自位于美国加州圣克拉拉市的Applied Materials公司。基材200可加热至自约25℃至约800℃范围间的温度，较佳为自约50℃至约400℃，且更佳为自约100℃至约300℃。基材200可加热自约2分钟至约20分钟范围间的一段时间，较佳为自约5分钟至约15钟。例如，基材200在此工艺腔室中可加热至约400℃约12分钟。
在一范例中，基材200及钴层220当在此工艺腔室中加热时可曝于氢、氨、氮或其等之混合物。在另一范例中，基材200及钴层220当在此工艺腔室中加热时可曝于氨/氢混合物。在另一范例中，基材200及钴层220当在此工艺腔室中加热时可曝于氢、氮、硅烷、二硅烷或其等之混合物。在另一范例中，基材200及钴层220当在此工艺腔室中加热时可曝于氢、氮、氩、氦或其等之混合物。
图2C图示在基材200上于介电层204内形成孔206。孔206含有共形配置于其内的阻障层210及钴层220。在另一实施例中，在工艺100的步骤150期间，一导电层可沉积或形成于钴层220上。在一实施例中，此导电层为块体层240，其可直接沉积于钴层220上，如在图2D中所图示。或者，在另一实施例中，此导电层为种晶层230及块体层240。种晶层230可沉积遍及钴层220且接着块体层240可沉积遍及种晶层230，如在第2E-2F图中说明。
种晶层230及块体层240可在单一沉积工艺或多重沉积工艺期间沉积或形成。种晶层230可含有铜、钨、铝、钌、钴、银、铂、钯、其之合金、其之衍生物或其等之组合。块体层240可含有铜、钨、铝、其之合金、其之衍生物或其等之组合。通常，种晶层230及块体层240可独立含有铜、钨、铝、其之合金、其之衍生物或其等之组合。种晶层230及块体层240可独立地经由使用一或一以上的沉积工艺沉积，如一CVD工艺、ALD工艺、PVD工艺、无电沉积工艺、ECP工艺、其之衍生物或其等之组合。
在一范例中，种晶层230及块体层240的每一者含有铜或一铜合金。例如，含有铜的种晶层230可经由PVD工艺形成于钴层220上，且接着含有铜的块体层240可经由ECP工艺或无电沉积工艺沉积以填充孔206。在另一范例中，含有铜的种晶层230可经由ALD工艺形成于钴层220上，且接着含有铜的块体层240可经由ECP工艺或无电沉积工艺沉积以填充孔206。在另一范例中，含有铜的种晶层230可经由CVD工艺形成于钴层220上，且接着含有铜的块体层240可经由ECP工艺或无电沉积工艺沉积以填充孔206。在另一范例中，含有铜的种晶层230可经由无电工艺形成于钴层220上，且接着含有铜的块体层可经由ECP工艺或无电沉积工艺沉积以填充孔206。在另一范例中，钴层220做为一种晶层，则含有铜的块体层240可经由ECP工艺或无电沉积工艺直接沉积于其上以填充孔206。
在一范例中，种晶层230及块体层240的每一者含有钨或一钨合金。例如，含有钨的种晶层230可经由PVD工艺形成于钴层220上，且接着含有钨的块体层240可经由CVD工艺或脉冲CVD工艺沉积以填充孔206。在另一范例中，含有钨的种晶层230可经由ALD工艺形成于钴层220上，且接着含有钨的块体层240可经由CVD工艺或脉冲CVD工艺沉积以填充孔206。在另一范例中，含有钨的种晶层230可经由脉冲CVD工艺形成于钴层220上，且接着含有钨的块体层240可经由CVD工艺或脉冲CVD工艺沉积以填充孔206。在另一范例中，含有钨的种晶层230可经由无电工艺形成于钴层220上，且接着含有钨的块体层240可经由CVD工艺或脉冲CVD工艺沉积以填充孔206。在另一范例中，钴层220做为一种晶层，则含有钨的块体层240可经由CVD工艺或脉冲CVD工艺直接沉积于其上以填充孔206。
在本文实施例中使用的ALD工艺腔室可得自位于美国加州圣克拉拉市的Applied Materials公司。ALD工艺腔室的详细说明可见于共同让渡的美国专利第6,916,398及6,878,206号，共同让渡之于2002年10月25日申请的美国专利申请案第10/281,079号，且以US 2003-0121608早期公开的专利申请案，及共同让渡之各别于2006年11月6日申请的美国专利申请号第11/556,745、11/556,752、11/556,756、11/556,758、11/556,763号且以美国专利公开号第2007-0119379、2007-0119371、2007-0128862、2007-0128863及2007-0128864号早期公开的申请案，该些专利并入本案做为参考。在另一实施例中，建构可用于ALD模式以及传统CVD模式操作以沉积含钴材料的腔室描述于共同让渡的美国专利第7,204,886号，该专利并入本案做为参考。一用于形成含钴材料的ALD工艺的详细描述更进一步揭露于共同让渡美国专利第7,264,846及7,404,985号，该些专利并入本案做为参考。在其它实施例中，建构可用于ALD模式以及传统CVD模式操作以沉积含钴材料的腔室
Figure BPA00001327617700131
喷洒头及CVD腔室，其可得自位于美国加州圣克拉拉市的AppliedMaterials公司。合宜的气相沉积腔室的范例包括WXZTM CVD腔室，其可购自位于美国加州圣克拉拉市的Applied Materials公司。此气相沉积腔室可适于经由传统CVD、脉冲CVD或PE-CVD技术以及经由ALD与PE-ALD技术沉积材料。亦然，此气相沉积腔室可用于处理工艺，如一原位等离子体工艺、一远距等离子体工艺或热退火工艺。
本文使用的“基材表面”或“基材”指任何在一基材上形成的基材或材料表面，在其上可于一制造工艺期间进行膜处理。例如，一可进行工艺的基材表面包括材料如单晶、多晶或非晶硅、应变硅、在绝缘体上硅(SOI)、掺杂硅、硅化锗、锗、砷化镓、玻璃、蓝宝石、氧化硅、氮化硅、氮氧化硅及/或碳掺杂氧化硅，如SiOxCy，例如BLACK
Figure BPA00001327617700132
低k介电材料，其可得自位于美国加州圣克拉拉市的Applied Materials公司。基材可具有不同尺寸，如100mm、200mm、300mm或450mm直径晶圆，以及矩形或方形片。除非特别指明，本发明描述的实施例及范例通常在具有200mm直径或300mm直径的基材上进行，更佳为300mm直径。本发明描述的工艺可用于在许多基材及表面上沉积钴材料(例如，金属钴)，尤其是阻障层及层。在本发明的实施例可使用的基材包括但未限制为半导体晶圆，如结晶硅(例如，Si<100>或Si<111>)、氧化硅、应变硅、硅化锗、掺杂或未掺杂的多晶硅、掺杂或未掺杂的硅晶圆、及图案化或未图案化的晶圆。基材可曝露至预处理工艺以研磨、蚀刻、还原、氧化、羟化、加热、及/或退火此基材或基材表面。
虽然前述为有关本发明的实施例，但本发明的其它及进一步的实施例可未偏离本发明的技术的基本视野下完成，且本发明的范畴由权利要求书界定。

Claims (15)

1.一种用于沉积材料在一基材表面的方法，其包含以下步骤：
在一基材上形成一阻障层；
曝露该基材至二钴六羰基丁基乙炔(CCTBA)及氢(H2)以于一气相沉积工艺期间在该阻障层上形成一钴层；及
沉积一导电材料于该钴层之上。
2.如权利要求1所述的方法，其更包含以下步骤：于一处理工艺期间曝露该阻障层或该钴层至一等离子体，其中该等离子体包含一选自由氮(N2)、氨(NH3)、氢(H2)、一氨/氢混合物、其之衍生物及其等之组合所组成的群组的一试剂。
3.如权利要求2所述的方法，其中该阻障层或该钴层曝露至一氢等离子体自约20秒至约40秒范围间的一段时间且该氢等离子体经由一远距等离子体源形成。
4.如权利要求1所述的方法，其更包含以下步骤：于一热处理工艺期间曝露该阻障层或该钴层至一气体，其中该气体选自由氮(N2)、氨(NH3)、氢(H2)、一氨/氢混合物、其之衍生物及其等之组合所组成的群组，且该基材在该热处理工艺期间加热至约50℃至约400℃范围的一温度。
5.如权利要求1所述的方法，其中该基材于一热化学气相沉积工艺期间曝露至一包含该CCTBA与该氢的沉积气体，且该基材在于该热化学气相沉积工艺期间加热至约100℃至约250℃范围的一温度。
6.如权利要求1所述的方法，其中该气相沉积工艺包含：于一原子层沉积工艺期间依序将该基材曝露至该CCTBA与该氢。
7.如权利要求1所述的方法，其中该阻障层包含：钽、氮化钽、钛、氮化钛、钨、氮化钨、其之合金、其之衍生物及其等之组合。
8.如权利要求1所述的方法，其中该导电材料包含铜或一铜合金，且该导电材料包含一种晶层及一块体层。
9.如权利要求8所述的方法，其中该种晶层包含铜且经由一物理气相沉积工艺或一化学气相沉积工艺沉积，且该块体层包含铜且经由一电化学电镀工艺沉积。
10.一种用于在一基材表面上沉积材料的方法，其包含以下步骤：
在一基材上形成一阻障层；
在一预处理工艺期间曝露该阻障层至一第一等离子体；
曝露该基材至二钴六羰基丁基乙炔(CCTBA)及氢以于一气相沉积工艺期间在该阻障层上形成一钴层；
于一后处理工艺期间曝露该钴层至一第二等离子体；及
经由一气相沉积工艺沉积一铜层于该钴层上。
11.如权利要求10所述的方法，其中该第一等离子体或该第二等离子体独自包含：一选自由氮(N2)、氨(NH3)、氢(H2)、氩、氦、一氨/氢混合物、其之衍生物及其等之组合所组成的群组中的气体。
12.如权利要求11所述的方法，该阻障层曝露至该第一等离子体或该钴层曝露至该第二等离子体自约20秒至约40秒范围间的一段时间，且该第一及第二等离子体由一远距等离子体源形成。
13.如权利要求10所述的方法，其中该沉积工艺包含于一热化学气相沉积工艺期间将该基材曝露至包含该CCTBA与该氢的一沉积气体，且该基材在该热化学气相沉积工艺期间可加热至约100℃至约250℃范围的一温度。
14.如权利要求10所述的方法，其中该气相沉积工艺包含在原子层沉积工艺期间依序将该基材曝露至该CCTBA与该氢中。
15.一种用于在一基材表面上沉积材料的方法，其包含以下步骤：
在一基材上形成一阻障层；
在一预处理工艺期间曝露该阻障层至一等离子体；
于一气相沉积工艺期间曝露该基材至二钴六羰基丁基乙炔(CCTBA)及一还原气体以在该阻障层上形成一钴层；
于一后处理工艺期间曝露该钴层至一氢等离子体；及
沉积一铜材料于该钴层之上。
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