CN102007573B - 在铜表面上选择性钴沉积 - Google Patents

在铜表面上选择性钴沉积 Download PDF

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CN102007573B
CN102007573B CN2009801135107A CN200980113510A CN102007573B CN 102007573 B CN102007573 B CN 102007573B CN 2009801135107 A CN2009801135107 A CN 2009801135107A CN 200980113510 A CN200980113510 A CN 200980113510A CN 102007573 B CN102007573 B CN 102007573B
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cobalt
substrate
during
deposition
copper surface
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CN102007573A (zh
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勇森河
凯文·莫拉斯
塞歇德里·盖恩济利
华·钟
仕-恩·潘
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Applied Materials Inc
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Abstract

本发明之实施例提出选择性形成钴层至露出电介质表面上之铜表面的工艺。在一实施例中，提出覆盖基板上之铜表面的方法，其包括在处理腔室内暴露基板的污染铜表面至还原剂，同时形成金属铜表面、在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成钴覆盖层至金属铜表面上，同时留下基板上露出的电介质表面、以及沉积介电阻障层至钴覆盖层和电介质表面上。在另一实施例中，沉积-处理循环包括进行气相沉积工艺和随后的后处理工艺，沉积-处理循环可反复进行而沉积多个钴覆盖层。

Description

在铜表面上选择性钴沉积
技术领域
本发明的实施例大体上是关于用以制造半导体装置的金属化工艺，更特别地，实施例是有关通过沉积钴材料至基板，以防铜去湿润(dewetting)的方法。
背景技术
铜为目前用于多层金属化工艺的金属，是半导体装置制造的关键。驱入制造工艺的多层互联需平坦化高深宽比的穿孔，包括触点、过孔、接线和其它特征结构。当特征结构具更大的深宽比时，填充特征结构、又不产生空隙或造成特征结构几何形状变形变得越来越困难。制造业者努力提高电路密度和质量的同时，也更难可靠地形成互联。
由于低成本和其处理性质，铜已广泛应用于市场，故半导体制造业者均持续寻求方法以减少铜扩散和去湿润，以改善铜与介电材料的边界区。随着特征结构尺寸缩小，已发展出数种处理方法来制造铜互联。各处理方法均会增加错误的可能性，例如铜扩散越过边界区、铜结晶结构变形和去湿润。物理气相沉积(PVD)、化学气相沉积(CVD)、原子层沉积(ALD)、化学机械研磨(CMP)、电化学电镀(ECP)、电化学机械研磨(EMCP)、和其它沉积及移除铜层的方法实行机械、电子或化学方法来操作铜构成互联。阻障层和覆盖层可沉积含有铜。
过去，钽层、氮化钽、或含锡、铝或镁的铜合金做为阻障层、或铜与其它材料间的黏着促进剂。选用这些材料很昂贵且也许只有部分有效。若沿着边界区的铜原子经历温度、压力、大气条件或多步骤半导体处理期间的其它通用处理变量改变，则铜将沿着边界区迁移而变成附聚铜。铜也会较不均匀地沿着边界区分散而变成去湿润铜。边界区变化包括应力迁移和铜原子电迁移。应力迁移和铜原子电迁移越过介电层或其它结构会提高所得结构的电阻率及降低所得装置的可靠度。
含钴阻障层已以PVD、CVD和ALD工艺沉积而获得。沉积钴的PVD工艺通常难以精确控制沉积厚度。CVD工艺通常受共形性不佳和沉积钴层中的污染物的不良影响。在典型的ALD工艺中，钴前驱物和还原剂依序接触基板而形成预定钴层。ALD工艺相较于其它气相沉积工艺有数个优点，例如能形成相当共形的膜及沉积高深宽比的过孔。然ALD工艺的沉积速度常常太慢，以致ALD工艺不宜做为商业应用。
因此，需要加强含铜层的稳定性和黏着性求，尤其是对铜种晶层而言。此外，需要改善含铜层的电迁移(EM)可靠度、同时防止铜扩散至相邻材料(如介电材料)，尤其是形成铜线时。还需要改良气相沉积工艺来沉积钴材料。
发明内容
本发明的实施例提出选择性形成钴层至露出电介质表面上的铜表面的工艺。在一实施例中，提出覆盖基板上的铜表面的方法，其包括将基板放到处理腔室内，其中基板含有遭污染的铜表面和电介质表面、在预处理工艺期间，使遭污染的铜表面接触还原剂，同时形成金属铜表面、在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成钴覆盖层至金属铜表面上，同时留下露出的电介质表面、以及沉积介电阻障层至钴覆盖层和电介质表面上。
在一些实施例中，方法还包括化学还原遭污染的铜表面上的氧化铜，以于预处理工艺期间形成金属铜表面。使遭污染的铜表面接触还原剂，并于预处理工艺期间点燃等离子体，还原剂含有试剂，例如氮气(N2)、氨气(NH3)、氢气(H2)、氨气/氮气混合物、或其组合物。在一些实施例中，遭污染的铜表面接触等离子体的时间为约5秒至约15秒。在另一实施例中，还原剂含有氢气，预处理工艺为热处理，且基板于热处理期间加热达约200℃至约400℃的温度。
在其它实施例中，方法还包括在沉积介电阻障层前，使钴覆盖层于后处理工艺期间接触试剂和等离子体。试剂可含氮气、氨气、氢气、氨气/氮气混合物、或其组合物。
在另一实施例中，沉积-处理循环包括进行气相沉积工艺和随后的后处理工艺，沉积-处理循环进行2、3或更多次以沉积多个钴覆盖层。各沉积-处理循环期间，每一钴覆盖层的沉积厚度为约3埃
Figure GSB00000928199800031
至约整体钴覆盖材料或钴覆盖层的厚度为约
Figure GSB00000928199800033
至约
Figure GSB00000928199800034
优选地，为约5埃
Figure GSB00000928199800035
至约
Figure GSB00000928199800036
在一些实施例中，钴覆盖层的厚度小于约例如约2埃
Figure GSB00000928199800038
至约
Figure GSB00000928199800039
气相沉积工艺期间，基板接触含有钴前驱物气体和氢气的沉积气体，气相沉积工艺为热化学气相沉积工艺或原子层沉积工艺，其中钴前驱物气体含有化学通式为(CO)xCoyLz的钴前驱物，其中x为1、2、3、4、5、6、7、8、9、10、11或12；y为1、2、3、4或5；z为1、2、3、4、5、6、7或8；L为分别选自环戊二烯基、烷基环戊二烯基、甲基环戊二烯基、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、烯丙基、乙烯、丙烯、烯烃、二烯烃、炔烃、亚硝酰基、氨基、其衍生物、或其组合物的配基(ligand)。钴前驱物气体可含钴前驱物，其选自由三羰基烯丙钴、二羰基环戊二烯钴、二羰基甲基环戊二烯钴、二羰基乙基环戊二烯钴、二羰基五甲基环戊二烯钴、八羰基二钴、三羰基亚硝酰钴、二环戊二烯钴、环己二烯基环戊二烯钴、1，3-己二烯基环戊二烯钴、环戊二烯基环丁二烯钴、二甲基环戊二烯钴、5-甲基环戊二烯基环戊二烯钴、五甲基环戊二烯基二乙烯钴、其衍生物、其络合物、其等离子体、或其组合物。在一实施例中，钴前驱物含有二羰基环戊二烯钴。
在另一实施例中，提出覆盖基板上的铜表面的方法，其包括将基板放到处理腔室内，其中基板含有氧化铜表面和电介质表面、在预处理工艺期间，使氧化铜表面接触氨等离子体或氢等离子体，同时形成金属铜表面、在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成钴覆盖层至金属铜表面上，同时留下露出的电介质表面、在后处理工艺期间，使钴覆盖层接触等离子体、以及沉积介电阻障层至钴覆盖层和电介质表面上。
在一些实施例中，沉积-处理循环为进行气相沉积工艺和随后的后处理工艺。沉积-处理循环进行2、3或更多次以沉积多个钴覆盖层。各沉积-处理循环期间，每一钴覆盖层的沉积厚度为约
Figure GSB00000928199800041
至约
Figure GSB00000928199800042
在另一实施例中，氧化铜表面于预处理工艺期间接触氨等离子体或氢等离子体的时间为约5秒至约15秒。后处理工艺含有氮气、氨气、氨气/氮气混合物、或氢气时，可让等离子体接触钴覆盖层。
在又一实施例中，提出覆盖基板上的铜表面的方法，其包括将基板放到处理腔室内，其中基板含有氧化铜表面和电介质表面、在预处理工艺期间，使氧化铜表面接触氨等离子体或氢等离子体，同时形成金属铜表面、在气相沉积工艺期间，使基板接触钴前驱物气体和氢气而选择性形成钴覆盖层至金属铜表面上，同时留下露出的电介质表面、以及在后处理工艺期间，使钴覆盖层接触等离子体和试剂，试剂选自由氮气、氨气、氢气、氨气/氮气混合物、和其组合物组成的群组。
再一实施例中，提出覆盖基板上的铜表面的方法，其包括将基板放到处理腔室内，其中基板含有遭污染的铜表面和电介质表面、在预处理工艺期间，使遭污染的铜表面接触还原剂，同时形成金属铜表面、以及在沉积-处理循环期间，沉积钴覆盖材料至金属铜表面上，同时留下露出的电介质表面。在一实施例中，沉积-处理循环包括在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第一钴层至金属铜表面上，同时留下露出的电介质表面、在处理工艺期间，使第一钴层接触含有氮气、氨气、氨气/氮气混合物或氢气的等离子体、在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第二钴层至第一钴层上，同时留下露出的电介质表面、以及在处理工艺期间，使第二钴层接触等离子体。方法更提出沉积介电阻障层至钴覆盖材料和电介质表面上。
在一些实施例中，方法提出在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第三钴层至第二钴层上，同时留下露出的电介质表面、以及在处理工艺期间，使第三钴层接触等离子体。
附图说明
为让本发明的上述特征更明显易懂，可配合参考实施例说明，其部分如附图所示。须注意的是，虽然附图揭露了本发明特定实施例，但其并非用以限定本发明的精神与范围，本领域的普通技术人员能够作出各种更动从而得到等效实施例。
图1示出了根据所述实施例的处理和沉积工艺的流程图；
图2A-2E示出了根据所述实施例，不同处理步骤时的基板示意图；以及
图3示出了根据另一所述实施例的沉积工艺的流程图。
具体实施方式
本发明的实施例提出一方法，其利用钴覆盖层或材料来防止铜于互联边界区扩散和去湿润(dewetting)。过渡金属(如钴)可改善铜边界区性质，因而增进黏着性、减少扩散及附聚，并于处理期间促使基板表面均匀粗糙化及润湿。根据实施例，钴覆盖层选择性沉积至基板上的铜触点或表面，同时留下基板上的露出电介质表面。
图1示出了根据本发明一实施例的工艺100的流程图。工艺100用于在研磨工艺后，清洁及覆盖基板上的铜接触表面。在一实施例中，如图2A-2E所示，工艺100的步骤110-140作用于基板200。工艺100包括施行预处理工艺于基板(步骤110)、沉积钴覆盖层至基板的露出铜表面(步骤120)、施行后处理工艺于基板(步骤130)、以及沉积介电阻障层至基板(步骤140)。
图2A示出了经研磨工艺处理后的基板200，其含有介电层204置于下层202上。铜触点208设在介电层204内，并由阻障层206隔开介电层204。介电层204含有介电材料，例如低介电常数(k)介电材料。在一实施例中，介电层204含有低k介电材料，例如碳氧化硅材料或碳掺杂的氧化硅材料(如取自美国加州圣克拉拉市的应用材料公司的BLACK
Figure GSB00000928199800061
低k介电材料)。
阻障层206共形沉积于介电层204的穿孔中。阻障层206可以PVD工艺、ALD或CVD工艺形成或沉积，且厚度介于约5埃
Figure GSB00000928199800062
至约之间，优选约
Figure GSB00000928199800064
至约阻障层206含有钛、氮化钛、钽、氮化钽、钨、氮化钨、其硅化物、其衍生物、或其组合物。在一些实施例中，阻障层206含有钽/氮化钽双层或钛/氮化钛双层。在一实施例中，阻障层206含有以PVD工艺沉积的氮化钽和金属钽层。
在研磨工艺(如化学机械研磨(CMP))期间，铜触点208的上表面暴露于基板场域210各处，污染物212则形成在铜触点208上。污染物212通常含有研磨时或之后产生的氧化铜。铜触点208的露出表面被过氧化物、水或研磨液中的其它试剂、或周围空气中的氧气氧化。污染物212还包括湿气、包括界面活性剂和其它添加剂的研磨液残余物、或研磨掉的材料微粒。
在工艺100的步骤110中，施行预处理工艺于基板200，以移除基板场域210的污染物212。如图2B所示，一旦处理或移除铜触点208的污染物212，即露出铜表面214。通过使基板200接触还原剂可化学还原氧化铜。预处理工艺让基板200于热处理或等离子体处理期间接触还原剂。还原剂可为液态、气态、等离子体态或其组合物。可用于预处理工艺的还原剂包括氢(如H2或H原子)、氨气(NH3)、氢气与氨气混合物(H2/NH3)、N原子、联氨(N2H4)、醇类(如甲醇、乙醇或丙醇)、其衍生物、其等离子体、或其组合物。预处理工艺期间，基板200可接触原位或远程形成的等离子体。
在一实施例中，施行热预处理工艺于基板200以移除铜触点208的污染物212，同时形成铜表面214。基板200放在处理腔室内、接触还原剂且加热达约200℃至约800℃，优选约250℃至约600℃，更优选约300℃至约500℃。加热基板200的时间为约2分钟至约20分钟，优选约5分钟至约15分钟。例如，在含氢气环境的处理腔室中，加热基板200达约500℃、达约12分钟。
在另一实施例中，施行等离子体预处理工艺于基板200以移除铜触点208的污染物212，同时形成铜表面214。基板200放在处理腔室内、接触还原剂且加热达约100℃至约400℃，优选约125℃至约350℃，更优选约150℃至约300℃，例如约200℃或约250℃。处理腔室可产生原位等离子体或装配远程等离子体源(RPS)。在一实施例中，基板200接触等离子体(原位或远程)的时间为约2秒至约60秒，优选约3秒至约30秒，更优选约5秒至约15秒，例如约10秒。产生等离子体的功率为约200瓦至约1000瓦，优选约400瓦至约800瓦。在一实施例中，基板200接触氢气，并在约5托耳下、以400瓦产生等离子体、达约10秒。在另一实施例中，基板200接触氨气，并在约5托耳下、以800瓦产生等离子体、达约20秒。在又一实施例中，基板200接触氢气与氨气混合物，并在约5托耳下、以400瓦产生等离子体、达约15秒。
在工艺100的步骤120中，如图2C所示，选择性沉积或形成钴覆盖层216至铜表面214，同时留下基板场域210各处裸露的介电层204露出表面。故沿着基板场域210，钴覆盖层216选择性沉积在铜表面214上，同时留下介电层204不含或至少实质不含钴覆盖层216的表面。最初，钴覆盖层216可为连续层或不连续层横越铜表面214，但经多次沉积循环后为连续层。
如图2C所示，污染物218聚集遍及基板场域210(如钴覆盖层216上和介电层204表面)。污染物218包括沉积工艺的副产物，例如碳、有机残余物、前驱物残余物和其它聚集在基板场域210上的不当材料。
在工艺100的步骤130中，基板200于后处理工艺期间接触原位或远程形成的等离子体。后处理工艺移除或减少基板200上的污染物量，并进一步密实钴覆盖层216。后处理工艺让基板200和钴覆盖层216于等离子体处理期间接触还原剂。可用于后处理工艺的还原剂包括氢(如H2或H原子)、氨气(NH3)、氢气与氨气混合物(H2/NH3)、氮(如N2或N原子)、联氨(N2H4)、其衍生物、其等离子体、或其组合物。后处理工艺期间，钴覆盖层216接触等离子体的时间为约2秒至约60秒，优选约3秒至约30秒，更优选约5秒至约15秒。
在一实施例中，钴覆盖层接触氢等离子体，其通过原位或远程点燃处理腔室的氢气而形成。在另一实施例中，钴覆盖层接触氨等离子体，其通过原位或远程点燃处理腔室的氨气而形成。在又一实施例中，钴覆盖层接触氢/氨等离子体，其通过原位或远程点燃处理腔室的氢气与氨气混合物而形成。
等离子体可于处理腔室外产生，例如利用远程等离子体源(RPS)系统，或优选地，等离子体可于具等离子体产生能力的沉积腔室内原位产生，例如等离子体处理时(如步骤130或330)于等离子体增强化学气相沉积(PECVD)腔室产生。等离子体可由微波(MW)频率产生器或射频(RF)产生器产生。在优选实施例中，原位等离子体由R F产生器产生。等离子体处理工艺期间可加压处理腔室使压力达约0.1托耳至约80托耳，优选约0.5托耳至约10托耳，更优选约1托耳至约5托耳。此外，腔室或基板可加热至约500℃以下，优选约100℃至约450℃，更优选约150℃至约400℃，例如约300℃。
处理工艺期间，等离子体可在原位等离子体处理用的处理腔室内点燃；或者，等离子体可由如RPS系统的外部源形成。RF产生器的频率可设为约100千赫(kHz)至约60兆赫(MHz)。在一实施例中，频率设为13.56MHz的RF产生器可输出约100瓦至约1000瓦的功率，优选约250瓦至约600瓦，更优选约300瓦至约500瓦。在一实施例中，频率设为350kHz的RF产生器可输出约200瓦至约2000瓦的功率，优选约500瓦至约1500瓦，更优选约800瓦至约1200瓦，例如约1000瓦。基板表面每表面积接触的等离子体功率为约0.01瓦/平方公分(W/cm2)至约10.0W/cm2，优选约0.05W/cm2至约6.0W/cm2。
在另一实施例中，反复进行步骤120至少一次、两次或更多次。步骤120可进行一次来形成单层钴覆盖层216、或进行多次而形成多层钴覆盖层216，例如2、3、4、5或更多层钴覆盖层216。在又一实施例中，依序反复进行步骤120和130至少一次、2次、3次、4次或更多次。钴覆盖层216的沉积厚度为约
Figure GSB00000928199800091
至约
Figure GSB00000928199800092
优选约
Figure GSB00000928199800093
至约
Figure GSB00000928199800094
更优选约
Figure GSB00000928199800095
至约
Figure GSB00000928199800096
更加优选约
Figure GSB00000928199800097
至约
Figure GSB00000928199800098
特别更加优选约
Figure GSB00000928199800099
至约
Figure GSB000009281998000910
例如约或约在一实施例中，进行两次步骤120和130的循环，以形成厚度约
Figure GSB000009281998000913
的钴覆盖层216。在另一实施例中，进行三次步骤120和130的循环，以形成厚度约
Figure GSB000009281998000914
的钴覆盖层216。
在步骤120中，通过热分解钝气承载的含钴前驱物，可沉积钴覆盖层216。还原气体可伴随钴前驱物一起流入或脉冲输入处理腔室。基板可加热达约50℃至约600℃，优选约100℃至约500℃，更优选约200℃至约400℃。或者，可利用ALD或CVD工艺使基板接触含钴前驱物气体而沉积钴覆盖层216。
图3示出了工艺300的流程图，用以形成含钴材料，例如钴覆盖层216。在一实施例中，工艺300包括使基板接触沉积气体而形成钴覆盖材料(步骤310)、选择性净化沉积腔室(步骤320)、施行等离子体处理工艺于基板(步骤330)、净化沉积腔室(步骤340)、以及判断基板上的钴覆盖材料是否达预定厚度(步骤350)。在一实施例中，若钴覆盖材料未达预定厚度，则反复进行步骤310-350的循环。在另一实施例中，若钴覆盖材料未达预定厚度，则反复进行步骤310和330的循环。或者，当钴覆盖材料达预定厚度时，终止工艺300。
在一实施例中，提出覆盖基板上的铜表面的方法，其包括在气相沉积工艺期间，使基板接触钴前驱物气体和氢气而选择性形成钴覆盖层至金属铜表面上，同时留下露出的电介质表面、以及在后处理工艺期间，使钴覆盖层接触等离子体和试剂，试剂例如为氮气、氨气、氢气、氨气/氮气混合物、或其组合物。
在另一实施例中，提出覆盖基板上的铜表面的方法，其包括在沉积-处理循环期间，沉积钴覆盖材料至金属铜表面上，同时留下露出的电介质表面。在一实施例中，沉积-处理循环包括在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第一钴层至金属铜表面上，同时留下露出的电介质表面、在处理工艺期间，使第一钴层接触含有氮气、氨气、氨气/氮气混合物或氢气的等离子体。方法还提出在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第二钴层至第一钴层上，同时留下露出的电介质表面、以及在处理工艺期间，使第二钴层接触等离子体。
在一些实施例中，方法提出在气相沉积工艺期间，使基板接触钴前驱物气体而选择性形成第三钴层至第二钴层上，同时留下露出的电介质表面、以及在处理工艺期间，使第三钴层接触等离子体。
适用于CVD或ALD工艺以形成所述含钴材料(如金属钴或钴合金)的钴前驱物包括羰基钴络合物、脒基钴(cobaltamidinate)化合物、二茂钴(cobaltocene)化合物、二烯基钴络合物、亚硝酰基钴络合物、其衍生物、其络合物、其等离子体、或其组合物。在一些实施例中，可以CVD和ALD工艺沉积的钴材料另详述于共同转让的美国专利号7,264,846、和美国专利申请序号10/443,648、于2003年5月22日申请且公开号为US2005-0220998的申请案，通过引用将其全部内容包含在本说明书中。
在一些实施例中，钴前驱物采用羰基钴化合物或络合物。羰基钴化合物或络合物的化学通式为(CO)xCoyLz，其中x为1、2、3、4、5、6、7、8、9、10、11或12，y为1、2、3、4或5，z为1、2、3、4、5、6、7或8。L为缺少的、相同或不同的单一配基或多个配基，且包括环戊二烯基、烷基环戊二烯基(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、烯丙基(或丙烯)、烯烃、二烯烃、炔烃、乙炔、丁基乙炔、亚硝酰基、氨基、其衍生物、其络合物、其等离子体、或其组合物。一些羰基钴络合物的例子包括二羰基环戊二烯钴(CpCo(CO)2)、三羰基烯丙钴((CO)3Co(CH2CH＝CH2))、六羰基丁基乙炔二钴(CCTBA，(CO)6Co2(HC≡CtBu))、六羰基甲基丁基乙炔二钴((CO)6Co2(MeC≡CtBu))、六羰基苯基乙炔二钴((CO)6Co2(HC≡CPh))、六羰基甲基苯基乙炔二钴((CO)6Co2(MeC≡CPh))、六羰基甲基乙炔二钴((CO)6Co2(HC≡CMe))、六羰基二甲基乙炔二钴((CO)6Co2(MeC≡CMe))、其衍生物、其络合物、其等离子体、或其组合物。
在另一实施例中，钴前驱物采用脒基钴或氨基钴络合物。氨基钴络合物的化学通式为(RR’N)xCo，其中x为1、2或3，R和R’各自为氢基、甲基、乙基、丙基、丁基、烷基、硅烷基、烷基硅烷基、其衍生物、或其组合物。一些氨基钴络合物的例子包括二(二(丁基二甲硅烷基)氨基)钴(((BuMe2Si)2N)2Co)、二(二(乙基二甲硅烷基)氨基)钴(((EtMe2Si)2N)2Co)、二(二(丙基二甲硅烷基)氨基)钴(((PrMe2Si)2N)2Co)、二(二(三甲硅烷基)氨基)钴(((Me3Si)2N)2Co)、三(二(三甲硅烷基)氨基)钴(((Me3Si)2N)3Co)、其衍生物、其络合物、其等离子体、或其组合物。
一些钴前驱物的例子包括二羰基甲基环戊二烯钴(MeCpCo(CO)2)、二羰基乙基环戊二烯钴(EtCpCo(CO)2)、二羰基五甲基环戊二烯钴(Me5CpCo(CO)2)、八羰基二钴(Co2(CO)8)、三羰基亚硝酰钴((ON)Co(CO)3)、二环戊二烯钴、环己二烯基环戊二烯钴、1，3-己二烯基环戊二烯钴、环戊二烯基环丁二烯钴、二甲基环戊二烯钴、5-甲基环戊二烯基环戊二烯钴、五甲基环戊二烯基二乙烯钴、四羰基碘化钴、四羰基三氯硅烷钴、三(三甲基磷化氢)羰基氯化钴、三羰基氢三丁基磷化氢钴、六羰基乙炔二钴、五羰基三乙基磷化氢乙炔二钴、其衍生物、其络合物、其等离子体、或其组合物。
适用于所述工艺以形成含钴材料(如金属钴、钴覆盖层或钴合金)的试剂(包含还原剂)包括氢(H2或H原子)、N原子、氨气(NH3)、联氨(N2H4)、氢气与氨气混合物(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)、磷化氢(PH3)、其衍生物、其等离子体、或其组合物。
在工艺100的步骤140中，如图2E所示，沉积介电阻障层220至钴覆盖层216和基板200上。具低介电常数的介电阻障层220沉积在基板200、遍及基板场域210和钴覆盖层216上。介电阻障层220含有低k介电材料，例如碳化硅、氮化硅、氧化硅、氮氧化硅、碳氧化硅或碳掺杂的氧化硅材料、其衍生物、或其组合物。在一实施例中，采用取自美国加州圣克拉拉市的应用材料公司的BLACK
Figure GSB00000928199800131
低k介电材料做为介电阻障层220的低k介电材料。适用于介电阻障层220的材料例子为以CVD或等离子体增强CVD(PECVD)工艺形成的碳化硅基膜，例如共同转让的美国专利号6,537,733、6,790,788和6,890,850描述的工艺，通过引用将其全部内容包含在本说明书中。
所述实施例使用的ALD处理腔室可取自美国加州圣克拉拉市的应用材料公司。ALD处理腔室的详细说明可参见共同转让的美国专利号6,916,398与6,878,206、共同转让的美国专利申请序号10/281,079、于2002年10月25日申请且公开号为US2003-0121608的申请案、和共同转让的美国专利申请序号11/556,745、11/556,752、11/556,756、11/556,758、11/556,763、其各自于2006年11月6日申请且公开号分别为US 2007-0119379、2007-0119371、2007-0128862、2007-0128863、2007-0128864的申请案，通过引用将其全部内容包含在本说明书中。在另一实施例中，以ALD模式与传统CVD模式操作的腔室可用来沉积含钴材料，其描述于共同转让的美国专利号7,024,886，通过引用将其全部内容包含在本说明书中。用于形成含钴材料的ALD工艺另详述于共同转让的美国专利申请序号10/443,648、于2003年5月22日申请且公开号为US2005-0220998的申请案、和共同转让的美国专利号7,264,846，通过引用将其全部内容包含在本说明书中。在其它实施例中，以ALD模式与传统CVD模式操作来沉积含钴材料的腔室可为取自美国加州圣克拉拉市的应用材料公司的喷淋头和CVD腔室。
在此描述的「基板表面」或「基板」是指制造工艺中在基板上进行膜处理的任何基板表面或材料表面。例如，进行处理的基板表面包括如单晶硅、多晶硅或无定形硅、应变硅、绝缘层覆硅(SOI)、掺杂硅、硅锗、锗、砷化镓、玻璃、蓝宝石、氧化硅、氮化硅、氮氧化硅、及/或碳掺杂的氧化硅(例如SiOxCy，如取自美国加州圣克拉拉市的应用材料公司的BLACK低k介电材料)的材料。基板可为各种尺寸，例如200毫米(mm)或300mm的晶圆、且具有矩形或方形窗格。除非特别说明，否则所述实施例优选是施行于直径200mm或300mm的基板，更佳为300mm。所述工艺实施例沉积硅化钴材料、金属钴材料、和其它含钴材料至许多基板与表面上，特别是含硅介电材料上。可用于本发明实施例的基板包括半导体晶圆，例如结晶硅(如Si<100>或Si<111>)、氧化硅、应变硅、硅锗、掺杂或未掺杂的多晶硅、掺杂或未掺杂的硅晶圆、和图案化或未图案化的晶圆，但不以此为限。基板可以预处理工艺处理，用以研磨、蚀刻、还原、氧化、氢氧化、退火、及/或烘烤基板表面。
虽然已经描述了本发明的优选实施例，但其并非用以限定本发明，任何本领域的技术人员在不脱离本发明的精神和范围的前提下，都可作出各种更改与变动，因此本发明的保护范围应由所附申请要求所界定的内容为准。

Claims (15)

1.一种覆盖基板上的铜表面的方法，该方法包含：
将基板放到处理腔室内，其中该基板包含遭污染的铜表面和电介质表面；
在预处理工艺期间，使该遭污染的铜表面接触还原剂，同时形成金属铜表面；
在气相沉积工艺期间，使该基板接触钴前驱物气体而选择性在该金属铜表面上形成钴覆盖层，同时留下露出的该电介质表面；以及
在该钴覆盖层和该电介质表面上沉积介电阻障层。
2.如权利要求1所述的方法，还包括化学还原该遭污染的铜表面上的氧化铜，以于该预处理工艺期间形成该金属铜表面。
3.如权利要求1所述的方法，其中该遭污染的铜表面接触该还原剂，并于该预处理工艺期间点燃等离子体，该还原剂包含试剂，该试剂选自由氮气(N2)、氨气(NH3)、氢气(H2)、氨气/氮气混合物、和其组合物组成的群组。
4.如权利要求3所述的方法，其中该遭污染的铜表面接触该等离子体的时间为约5秒至约15秒范围之间。
5.如权利要求1所述的方法，其中该还原剂包含氢气，该预处理工艺为热处理，且该基板于该热处理期间加热到约200℃至约400℃范围之间的温度。
6.如权利要求1所述的方法，还包括在沉积该介电阻障层之前，使该钴覆盖层于后处理工艺期间接触试剂和等离子体，该试剂选自由氮气(N2)、氨气(NH3)、氢气(H2)、氨气/氮气混合物、和其组合物组成的群组。
7.如权利要求6所述的方法，其中沉积-处理循环包含进行该气相沉积工艺和随后的后处理工艺，该沉积-处理循环进行2、3或更多次以相互层叠沉积多个钴覆盖层，同时留下露出的该电介质表面。
8.如权利要求7所述的方法，其中各个该沉积-处理循环期间，每个钴覆盖层的沉积厚度为约3埃至约
Figure FSB00000928199700022
范围之间。
9.如权利要求1所述的方法，其中该钴覆盖层的厚度为约4埃
Figure FSB00000928199700023
至约
Figure FSB00000928199700024
范围之间。
10.如权利要求9所述的方法，其中在该气相沉积工艺期间，该基板接触含有该钴前驱物气体和氢气的沉积气体，该气相沉积工艺为热化学气相沉积工艺或原子层沉积工艺。
11.如权利要求1所述的方法，其中该钴前驱物气体包含化学通式为(CO)xCoyLz的钴前驱物，其中：
x为1、2、3、4、5、6、7、8、9、10、11或12；
y为1、2、3、4或5；
z为1、2、3、4、5、6、7或8；以及
L为配基，分别选自环戊二烯基、烷基环戊二烯基、甲基环戊二烯基、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、烯丙基、乙烯、丙烯、烯烃、二烯烃、炔烃、亚硝酰基、氨基、其衍生物、和其组合物组成的群组。
12.如权利要求1所述的方法，其中该钴前驱物气体包含钴前驱物，选自由三羰基烯丙钴、二羰基环戊二烯钴、二羰基甲基环戊二烯钴、二羰基乙基环戊二烯钴、二羰基五甲基环戊二烯钴、八羰基二钴、三羰基亚硝酰钴、二环戊二烯钴、环己二烯基环戊二烯钴、1，3-己二烯基环戊二烯钴、环戊二烯基环丁二烯钴、二甲基环戊二烯钴、5-甲基环戊二烯基环戊二烯钴、五甲基环戊二烯基二乙烯钴、其衍生物、其络合物、其等离子体、和其组合物组成的群组。
13.如权利要求12所述的方法，其中该钴前驱物包含二羰基环戊二烯钴。
14.一种覆盖基板上的铜表面的方法，该方法包含：
将基板放到处理腔室内，其中该基板包含遭污染的铜表面和电介质表面；
在预处理工艺期间，使该遭污染的铜表面接触还原剂，同时形成金属铜表面；
在沉积-处理循环期间，沉积钴覆盖材料至该金属铜表面上，同时留下露出的该电介质表面，该沉积-处理循环包含：
在气相沉积工艺期间，使该基板接触钴前驱物气体而选择性形成第一钴层至该金属铜表面上，同时留下露出的该电介质表面；
在处理工艺期间，使该第一钴层接触含有氮气(N2)、氨气、氨气/氮气混合物或氢气的等离子体；
在该气相沉积工艺期间，使该基板接触该钴前驱物气体而在该第一钴层上选择性形成第二钴层，同时留下露出的该电介质表面；以及
在该处理工艺期间，使该第二钴层接触该等离子体；以及
在该钴覆盖材料和该电介质表面上沉积介电阻障层。
15.如权利要求14所述的方法，还包括：
在该气相沉积工艺期间，使该基板接触该钴前驱物气体而在该第二钴层上选择性形成第三钴层，同时留下露出的该电介质表面；以及
在该处理工艺期间，使该第三钴层接触该等离子体。
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