CN1168125C - 铜沉淀方法 - Google Patents

铜沉淀方法 Download PDF

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CN1168125C
CN1168125C CNB008134510A CN00813451A CN1168125C CN 1168125 C CN1168125 C CN 1168125C CN B008134510 A CNB008134510 A CN B008134510A CN 00813451 A CN00813451 A CN 00813451A CN 1168125 C CN1168125 C CN 1168125C
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exposed surface
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copper
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加利·W·弗雷尔
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Abstract

用于把铜可控地沉淀在工件暴露表面,例如半导体表面上的方法和系统。铜的晶种厚度可选择地沉淀在所述暴露表面上,最好使用无氧液体氨来加强该沉淀。然后在适当的压力和温度下,把所述工件暴露表面浸入到包括铜和液体氨的电镀溶液中,并以可控速率把铜电镀在所述暴露表面上。当沉淀在所述暴露表面上的铜达到选定的总厚度时,停止电镀,除去电镀溶液,并回收气态氨与液体氨以循环再利用。

Description

铜沉淀方法
技术领域:
本发明涉及在选择表面,例如半导体基片表面上产生和沉淀金属铜。
背景技术:
出于某些原因,用铜表面和触点替换半导体电路中的铝表面和触点是有吸引力的。铜几乎具有与银一样高的相对导电系数(100对106)和具有比金(65)、铝(59)及其它任何金属的相应系数高得多的导电系数。铜的导热系数也比铝的相应导热系数高得多。铜具有比铝高的熔化温度(660℃对1083℃)。当铜暴露在氧气中时,其形成氧化表面而不形成在类似的条件下铝形成的讨厌的表面杂质。使用较高电导率的金属将允许使用较小驱动电压,该电压和1.8V一样低且可能更低,又不会产生从芯片或其它半导体设备中扩散的过多的热量。使用高电导率和高导热率金属也将允许选择较宽范围的与这些设备一起使用的导线结构材料。
然而,在半导体表面或电触点上产生和可控地沉淀选定小厚度的金属铜是成问题的,这部分是因为这种铜工艺技术还没有与相应的铝工艺技术一样充分地发展。在T=25℃时,Cu(铜)具有适度的电极或减少的电位(E0=0.32-0.34V),与此相比,Ag(银)、Au(金)和Pt(铂)的E0大约为1V,Al(铝)的E0约为-1.7V。铜如同Al(铝)一样具有几种氧化状态。
于是需要一种方法,其使用从正常大气压到几百个psig(磅/每平方英寸)范围内的压力,和使用从约-78℃到约100℃范围内的温度,在工件的暴露表面例如半导体材料上,产生和可控地沉淀选定厚度的金属铜。该方法最好可通过控制参数例如环境温度、沉淀时间间隔和所用的电解沉淀电压来控制铜的沉淀速率和所沉淀的铜的总厚度。
发明内容:
本发明可满足这些需要。本发明提供一种用于在暴露表面上产生和受控地沉淀选定厚度的金属铜的方法和系统。
根据本发明的第一方面,提供一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:在包含液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;使用无电沉积在选定工件的工件暴露表面上沉淀选定金属的晶种表面,该晶种表面具有不大于0.1μm的第一选定厚度,其中所述选定金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;使包括选定金属和液体氨的电镀溶液与所述工件暴露表面相接触;使电镀溶液中的选定金属以选定速率在所述工件暴露表面上沉淀;和当沉淀在所述工件暴露表面上的选定金属已经达到第二选定厚度时,除去剩余的电镀溶液并在液体氨中清洗所述工件暴露表面。
根据本发明的第二方面,提供一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:在包括液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;使用无电沉积在选定工件的暴露表面上沉淀具有0.1-2μm的第一选定厚度的选定金属的晶种表面,其中所述金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;和在液体氨中清洗所述工件暴露表面。
根据本发明的第三方面,提供一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:在包括液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;使包含选定金属和液体氨的电镀溶液与所述工件暴露表面相接触,其中所述金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;使电镀溶液中的选定金属以选定速率沉淀在所述工件暴露表面上;和当沉淀在所述工件暴露表面上的选定金属已经达到的选定厚度时,去除剩余电镀溶液并在液体氨中清洗该工件暴露表面。
根据上述方法的实施例,使用一种包括液体氨(NH3)和卤化铜(CuCla、CuBrb、CuIc其中a、b和c≈1-2)或铜胺(copper amine)(NCuR1R2)的液体,其保持在足够的压力下以把氨维持在液态状态下。例如,在T=-33℃和T=20℃时,把氨维持在液态下所需的最小压力分别是0psig(磅/每平方英寸)和115psig(磅/每平方英寸)。铜的晶种厚度(seedthickness)首先沉淀在一个或更多暴露晶片或工件表面上。然后从铜盐/液体氨溶液中进行铜的无电沉积(electroless deposition)和/或电镀以把想要的铜的总厚度沉淀在已沉积有铜晶种的工件表面上。回收所述氨流体(液态和或气态)并可有选择地循环再使用。
附图说明:
图1、2和3是阐明本发明实践的流程图;
图4是把氨维持在液态下作为环境温度函数的所需近似压力的曲线图;
图5是适合于实践本发明的装置的示意图。
具体实施方式:
在第一可选择方法中,如图1的流程图所示,在步骤11中,该方法从定位工件例如晶片开始,在处理室中铜表面将沉淀在该工件上。在步骤13中,排空该处理室(最好达到至少10-4乇(Torr)的真空)并在适当压力和温度下以液体NH3充入该处理室。在步骤15中,排出液体氨并用N2或另一种最好不含游离氧的惰性气体清洗该处理室。在步骤17中,用所选非电镀电解质部分地或全部地充入所述处理室,所述电解质包含Cu(例如CuCla、CuBrb或CuIc其中a、b和c约为1-2或铜胺NCuR1R2),在步骤19中加入所选还原剂以产生自由电子,该自由电子与Cu离子结合形成铜金属颗粒。在步骤21中,使Cu金属颗粒从溶液中析出并沉淀或电镀在工件的暴露表面上,并且在步骤23中最好粘合到该工件的暴露表面。最好在-78℃≤T1≤90℃范围内的选定温度T1下执行步骤21和/或23。如果想要,在所述处理室中可使所述工件表面绕横切于该工件暴露表面的轴选择性地旋转以提高电镀铜厚度的均匀度。可使金属Cu进行无电沉积(electroless deposition)以在工件暴露表面上产生厚度Δh=0.1-2μm(如果想要,或者更厚)的金属Cu表面。
在步骤25中,所述电解质和还原剂从所述处理室中排空,并用液体氨清洗所述工件和处理室,以便清除掉可能出现的大部分或全部剩余的含铜电解质和/或有机物质和/或蒸汽。在步骤27中,从所述处理室中排空液体氨,并用一种选定的惰性气体清洗该室。在步骤29中(可选择),最好使用一种无氧气体把该室吹净(blow down)变干。在这一替代方法中,使用无电沉积以基本上把所有金属Cu沉淀在工件上。
在第二可选方法中,如图2所示,如同图1所示执行步骤11、13、15、17、19和21。在步骤23中,在得到工件表面上作为铜晶种或基层(substrate)的选定厚度Δh=0.01-0.1μm的铜后,停止铜无电沉积。最好是可能提供金属Cu晶种表面,这至少因为两个原因:(1)铜晶种表面的体电导率增加到可进行电镀的某一点,如果希望的话,还可以进一步增加该晶种表面的铜厚度;和(2)Cu晶种表面提供更合适的表面,以使Cu颗粒可以随后粘附在该表面上。如同第一可选择方法中那样执行步骤25、27和29。
在第二可选择方法的步骤31中,所述处理室中的工件浸没在溶解在液体氨中的电镀铜溶液中或与其接触,该电镀铜溶液维持在-78℃≤T2≤90℃范围内的选择温度T2。在步骤33中,使用连接到工件(阴极)和一浸入到电镀溶液中的导电板(阳极)上的电触点将电镀溶液中的铜电镀到沉淀有铜晶种的工件的一个或更多表面上。用于该电镀步骤的电镀电压对于铜来说最好是约为0.32V,或为更高的值更佳。电镀到工件表面上的铜总厚度可以通过阳极-阴极电压的变化和该电镀步骤所持续的时间间隔的变化来控制。电镀到工件表面上适当的铜厚度Δh=0.1-2μm,但是如果想要可以更高或更低。铜沉淀发生的速率将随电镀电压V和电镀温度T3而变化。电镀电压V(板极)合适的范围是0.3伏≤V(板极)≤1伏,但是如果想要更高的沉淀速率,则该电压可以更高。所述电镀时间间隔长度Δt可以在15秒≤Δt≤300秒范围内。
在步骤35中,剩余的电镀溶液从所述处理室中排空,在步骤37中,用液体氨清洗所述工件和处理室。在步骤39中,液体氨和任何剩余的蒸汽从第二处理室排空或去除,并回收所述液体氨和气体。这个方法把金属铜电镀到由无电沉积所沉淀的铜的“晶种”表面上。
如图3中所示,在第三可选择方法中,如同第一或第二可选择方法中那样执行步骤11、13、15、31、33、35、37和39。在该第三可选择方法中,使用电镀方法来把所有金属铜基本上沉淀在工件表面上。为了得到适度的铜厚度,该第三可选择方法常常需要比第一或第二可选择方法更多时间来完成。如果所述工件表面是塑料的或类似聚合物,在只有电镀的方法中,开始时在暴露表面上沉淀石墨可能加强铜的电镀。
图4是把氨维持在液态下需要的近似最小压力p(min)的曲线图。把氨维持在液态下需要的处理室压力p将依赖温度T变化并随其增加。在温度T1的范围内,压力p将从约0psig(磅/每平方英寸)变化到约350psig。通过利用不高于约66℃的溶液温度T,所述工艺步骤31、33和35可能在正常大气压或更低压力下执行。
该方法在所述处理室中的完全封闭的系统中完成,并且在该方法中使用的液体氨实质上完全地回收并再利用。如所希望的那样,从所述处理室中去除的铜盐和有机物可以循环或进一步处理。在整个工艺过程中所述晶片或其它工件保持在所述处理室中,所以在此不需要移动和输送所述工件,直到铜沉淀工艺过程完成。此外,该方法只使用液体氨而不是水,所以极少的或没有氧气与金属铜结合以形成较弱的铜氧化形态,其具有较小的电导率和不同的材料特性。
图5示意性地示出了适合于实践本发明的装置51。该装置包括一封闭处理室61、一含铜电解质液体源53(可选择)、一用于清洗处理室的惰性气体源59、一液体氨源63、一选定铜电镀溶液源65(可选择)(其可能与源53相同或可能不相同)、一个或多个位于处理室61中的阳极67(最好是铜、铂、或其它不会溶解于电镀溶液的金属)。所述装置51也包括一氨流体循环和回收系统69,其从所述处理室61中接收氨流体、金属盐和有机物并回收氨(以及,可选择地,也可回收金属电解质和有机物)。
该沉淀方法可以应用到处于周期表中类似的位置的其它金属的沉淀,包括Cu(铜)(在25℃时,E0=0.32V)、Ag(银)(E0=0.8V)、Au(金)、Ni(镍)、Pd(钯)、Pt(铂)、Fe(铁)(E0=-0.44V)、Co(钴)、Zn(锌)(E0=-0.76V)和Cd(镉)(E0≈0.9V),当存在(液态)氨时,所有这些金属都具有类似的反应。电镀溶液的选择以及阳极的选择将随着选择沉淀在工件暴露表面上的金属的变化而变化。

Claims (17)

1.一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:
在包含液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;
使用无电沉积在选定工件的工件暴露表面上沉淀选定金属的晶种表面,该晶种表面具有不大于0.1μm的第一选定厚度,其中所述选定金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;
使包括选定金属和液体氨的电镀溶液与所述工件暴露表面相接触;
使电镀溶液中的选定金属以选定速率在所述工件暴露表面上沉淀;和
当沉淀在所述工件暴露表面上的选定金属已经达到第二选定厚度时,除去剩余的电镀溶液并在液体氨中清洗所述工件暴露表面。
2.根据权利要求1所述的方法,还包括选择Cu作为选定金属。
3.根据权利要求1所述的方法,还包括步骤:
在选定范围0psig≤p≤350psig内的压力p,以及在-78℃≤T≤90℃范围内的选定温度T下,执行所述无电沉积过程和所述电镀沉积过程中的至少一个;
在所述电镀溶液中提供一导电板;和
在选定长度Δt的时间间隔内,在所述工件暴露表面和导电板之间提供至少0.3V的电压差ΔV,其中Δt在15秒≤Δt≤300秒范围内。
4.根据权利要求1所述的方法,其中把所述金属无电沉积在所述工件暴露表面上的所述过程包括步骤:
使所述工件暴露表面与包含至少一种选定铜盐或铜胺的流体相接触;
使铜盐或铜胺中的一部分铜沉淀在所述工件暴露表面上;
在液体氨中使所述工件暴露表面与沉淀在其上的铜接触,并允许所述液体氨与所存在的铜盐和选定的有机物质中的至少一个反应;和
去除液体氨以及与该液体氨发生反应的铜盐和选定的有机物质中的至少一个。
5.根据权利要求1所述的方法,还包括:在所述无电沉积过程和所述电镀过程中至少一个的至少一部分期间,绕横切于所述工件表面的轴旋转所述工件。
6.根据权利要求1所述的方法,还包括:选择所述工件使其包括半导体材料。
7.一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:
在包括液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;
使用无电沉积在选定工件的暴露表面上沉淀具有0.1-2μm的第一选定厚度的选定金属的晶种表面,其中所述金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;和
在液体氨中清洗所述工件暴露表面。
8.根据权利要求7所述的方法,还包括选择Cu作为选定金属。
9.根据权利要求7所述的方法,还包括:
在选定范围0psig≤p≤350psig内的压力p,以及在-78℃≤T≤90℃范围内的选定温度T下,执行所述方法。
10.根据权利要求7所述的方法,其中把所述金属无电沉积在所述工件暴露表面上的所述过程包括步骤:
使包含至少一种选定铜盐或铜胺的流体与所述工件暴露表面相接触;
使铜盐或铜胺中的一部分铜沉淀在所述工件暴露表面上;
在液体氨中使所述工件暴露表面与沉淀在其上的铜接触,并允许所述液体氨与所存在的铜盐和选定的有机物质中的至少一个反应;和
去除液体氨以及已经与该液体氨发生反应的铜盐和选定的有机物质中的至少一个。
11.根据权利要求7所述的方法,还包括:在所述无电沉积过程的至少一部分期间,绕横切于所述工件表面的轴旋转所述工件。
12.根据权利要求7所述的方法,还包括:选择所述工件以使其包括半导体材料。
13.一种用于把金属可控地沉淀在目标表面上的方法,所述方法包括步骤:
在包括液体氨的无氧溶液中清洗选定工件的暴露表面并排空该溶液;
使包含选定金属和液体氨的电镀溶液与所述工件暴露表面相接触,其中所述金属从包括Cu、Ag、Au、Ni、Pd、Pt、Fe、Co、Zn和Cd的一组金属中选择;
使电镀溶液中的选定金属以选定速率沉淀在所述工件暴露表面上;和
当沉淀在所述工件暴露表面上的选定金属已经达到的选定厚度时,去除剩余电镀溶液并在液体氨中清洗该工件暴露表面。
14.根据权利要求13所述的方法,还包括选择Cu作为选定金属。
15.根据权利要求13所述的方法,其中使所述选定金属沉淀在所述工件暴露表面上的所述过程包括步骤:
在选定范围0psig≤p≤350psig内的压力p,以及在-78℃≤T≤90℃范围内的选定温度T下,执行所述电镀沉积过程;
在所述电镀溶液中提供导电板;和
在选定长度Δt的时间间隔内,在所述工件暴露表面和导电板之间提供至少0.3V的电压差ΔV,其中Δt在15秒≤Δt≤300秒范围内。
16.根据权利要求13所述的方法,还包括在所述电镀过程的至少一部分期间,绕横切所述工件表面的轴旋转所述工件。
17.根据权利要求13所述的方法,还包括选择所述工件以使其包括半导体材料。
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