CN100350079C - 用于电镀操作的阳极以及在半导体基体上形成材料的方法 - Google Patents
用于电镀操作的阳极以及在半导体基体上形成材料的方法 Download PDFInfo
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- CN100350079C CN100350079C CNB01823934XA CN01823934A CN100350079C CN 100350079 C CN100350079 C CN 100350079C CN B01823934X A CNB01823934X A CN B01823934XA CN 01823934 A CN01823934 A CN 01823934A CN 100350079 C CN100350079 C CN 100350079C
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Abstract
本发明包括用于电镀液的阳极。该阳极具有至少99.99%的纯度,并且包括银、金、镍、铬、铜或各种焊料组合物中的一种或多种。例如,该阳极包括以重量计至少99.995%的铜/磷合金,或者至少99.995%的镍和硫。本发明也包括在半导体基体上电镀材料的方法。
Description
发明领域
本发明涉及在半导体基体上电镀材料的方法。尤其是,本发明涉及用于电镀操作的阳极。另一方面,本发明涉及纯度至少为99.995%并且适用于装载电解槽的电解液的金属。
发明背景
许多希望在基体上形成含金属层的应用中使用了电镀方法。参考图1来描述示意性的现有技术电镀装置10。装置10包括盛有液体14(具体地说是电解液)的容器12。容器12可由任何合适的材料制成,该材料包括比如具有非腐蚀性内衬(未示出)的金属,该内衬沿容器内表面延伸,从而使金属不与液体14反应。也可选择的是,容器12可由塑料或玻璃组成。在一些应用中,使容器12具有可以控制液体14的温度的结构,从而在电镀过程中,使液体14能够保持在理想的操作温度下。
阳极16和基体18被设置在容器12中。阳极16所包括的金属最终将会被镀覆于基体18的导电表面上。在所示出的应用中,基体18具有导电表面20。电源22与阳极16和基体18电连接,并且在阳极和基体之间产生了电势差。该电势差使得导电材料从阳极16迁移通过电解液14而到达导电表面20。导电材料沿基体18的表面20形成了导电材料的镀覆层24。
导电材料从阳极16向基体18的迁移实质上是一系列的质量传递过程。具体地说,在第一质量传递过程中,导电材料从阳极16被迁移至电解液14中,并且在随后的第二质量传递过程中,从电解液14迁移到基体18。在电解液14中,如果阳极16的导电材料的起始浓度低,则大量的材料可被从阳极16迁移至电解液14中,从而使阳极材料向基体18进行有效的传递之前,在电解液14和阳极16之间建立了平衡。这可严重地导致阳极16的有效部分的浪费,原因是该部分被用于建立平衡而不是被传输至基体18。避免该浪费的一种方法是,预先装载含有将被传输至阳极16的类型的导电材料的电解液14。这种预先装载使得电解液14一开始就具有接近于电镀操作过程中将建立的平衡浓度的导电材料浓度。通过将阳极16的导电材料颗粒加入到合适的溶剂(比如合适的酸)中以使颗粒溶解、并且形成含有阳极16的导电材料的溶液来实施该预先装载。随后可将该溶液加入到液体14中,以形成预先装载的电解液14。
电解液14可包括任何合适的导电溶液。在特定的应用中,基体18可包括半导体晶片,比如单晶硅片。在该应用中,希望在电解液14中避免使用钠或钾,因为它们会影响半导体材料的导电性。在该应用中,电解液14中可包括的合适的盐例如是:用于铜电解液的硫酸铜、用于镍电解液的氨基磺酸镍和用于铅/锡电解液的氟硼酸盐。
现有技术的另一种应用涉及半导体处理应用。利用附图2来描述半导体晶片结构50的一部分。该结构50包括半导体基体52。为了有助于解释后续的权利要求,术语“半导体基体”是指包括半导体材料的任何结构,该结构包括但不限于块状的半导体材料,比如半导体晶片(或者是单一的晶片,或者是其上包括其它材料的组件)、以及半导体材料层(或者是单一的半导体材料层,或者是其上包括其它材料的组件)。术语“基体”指任何支持结构,这包括但不限于上述半导体基体。
例如,基体52可包括其上形成有各种绝缘和导电材料的单晶硅片。另外,基体52可包括许多电路元件(未示出),它们被一起引入集成电路中。
导电材料54在基体52上形成,并且可构成与基体52有关的电路(未示出)进行电连接的接线层。导电材料54例如可包括铝和/或铜。
绝缘材料56在导电材料54上形成。将绝缘材料56形成图案,从而具有在其中延伸的开口58。导电材料60和62在开口内形成。导电材料60可包括例如铬、钴、镍、铜、银和金中的一种或多种;并且层62也可包括例如铬、镍、铜、银和金中的一种或多种。在特定的应用中,层60包括镍并且层62包括金。
在层62上形成焊料凸起64。焊料凸起64可包括例如锡-基焊料或铅-基焊料,术语“-基”应理解为代表焊料的主要成分。焊料凸起64最终可被用于与基体52外部的电路形成电连接,并且因此可与层54、60和62结合使用,以在与基体52有关的电路和基体52外部的其它电路(未示出)之间形成互连。
可通过各种方法来形成材料54、60、62和64,这些方法包括例如电镀。但是,在使用电镀方法时,很难形成具有理想纯度和物理性质的材料54、60、62和64。因此,希望开发一种在半导体基体上电镀材料的新方法。
发明概述
本发明包括用于电镀液的阳极。尤其是,这些阳极具有至少99.99%的纯度,并且包括银、金、镍、铬、钴、铜或各种焊料成分中的一种或多种。例如,这些阳极可包括至少99.995重量%的铜/磷合金;或至少99.995重量%的镍和硫。作为另一个实例,这些阳极可包括至少99.9995重量%的铜;或至少99.999重量%的焊料成分。
本发明也包括在半导体基体上电镀材料的方法。
附图说明
以下将参考如下的附图来描述本发明的优选实施方式。
图1为现有技术电镀装置的截面示意图。
图2为现有技术半导体晶片的部分截面示意图。
图3是本发明用于形成阳极的方法中,在初始处理步骤时坯体的等尺寸示意图。
图4是由图3的坯体形成的毛坯的示意图。
图5是可用于本发明形成阳极的方法中的其它毛坯的等尺寸示意图。
优选实施方式详述
现有技术的阳极(比如图1所示的阳极16)存在的问题是,在形成阳极的过程中未严格控制阳极材料的组成和物理性质。本发明所包括的阳极材料相对于现有阳极材料而言具有改进的组成和物理性质。
通过本发明方法可控制的组成参数是纯度和均匀性。具体地说,本发明的方法可使由银、金、镍、铬、钴和铜形成的阳极具有至少99.99重量%的纯度(即4N的纯度,术语“4N”应理解为是四个九);并且特别是至少99.995%(4N5)、99.999%(5N)、99.9999%(6N)或至少99.99999%(7N)的纯度。
优选地,该阳极包括极少的或不包括产生α颗粒的材料,因为α颗粒可严重地损坏半导体结构。因此,优选的组成将具有小于3ppb的铀和小于3ppb的钍;并且优选的铀和钍的总量小于3ppb;更优选的铀和钍的总量小于1ppb;并且进一步优选的铀和钍的总量小于0.5ppb。
再一方面,本发明的阳极材料可包括至少99.995重量%(4N5)的铜/磷合金;优选磷的含量以重量计是约200ppm-约1000ppm;例如以重量计是约200ppm-约600ppm。铜/磷合金可以具有5N、6N并且甚至至少7N的纯度。铜/磷合金也可被任选地称为掺磷的铜。磷的掺入有助于在阳极表面产生黑氧化物膜。该膜具有两个重要的功能。首先,它可以通过在膜中捕获杂质而作为过滤物。其次,该膜可以调节铜的溶解速率,并且由此使铜在溶液中的含量保持在一定并且理想水平。而且,通过掺入磷和/或其它合金元素可促进晶粒细化。
另一方面,本发明的阳极材料可包括至少99.995重量%(4N5)的镍和硫;并且尤其可包括5N、6N或至少7N纯度的镍/硫组合。硫的含量以重量计是约0.01%-约5%;并且优选硫的含量以重量计是约0.01%-约0.04%。掺入硫的有利之处在于硫可促进晶粒细化。另外,与不掺有硫的情况相比,硫可促进阳极更均匀地溶解。再者,掺入硫可以降低电阻,由此可降低电镀操作的电消耗。而且,如果图2中结构50的层54包括铜、并且层60包括镍时,在材料60的电解沉积过程中,材料60内掺入硫有利于改进含镍材料60与含铜层54的结合。
本发明的其它方面中,阳极的组合物可以是高纯焊料的组合物,比如是纯度至少99.99重量%(4N)的焊料组合物,该组合物包括选自由锡、锑、铅、银、铜和铋组成的组中的一种或多种元素。再一方面,焊料组合物可具有至少5N、5N5、6N、6N5或7N的纯度。焊料组合物的实例包括纯度至少5N的锡、锡/锑、锡/铅、锡/银、锡/银/铜、银/铋和锡/铜。
焊料合金中可以包括磷。如果包括磷,则优选其含量小于1000ppm,例如其含量是大于0ppm到约500ppm。
可优选焊料中不含有铅,以减少该组合物中产生α颗粒的材料的量。具体地说,自然会产生铅的同位素,而同位素的放射系衰变链导致产生了α颗粒。再者,利用常规的提纯方式不能将这些铅的同位素从铅中去除。合适的无铅组合物是锡/银、锡/铋、锡/银/铜、铋/银/和锡/铜。该组合物中铀的含量优选小于3ppb,并且优选该组合物中钍的含量也小于3ppb。在特定的方面,本发明的焊料组合物阳极中,铀和钍的总量小于3ppb。另外,对于包括本发明焊料组合物的优选阳极而言,优选该阳极具有小于或等于0.001个/(cm2·hr)、更优选小于0.02个/(cm2·hr)并且甚至更优选小于0.002个/(cm2·hr)的α数量。消除焊料中α颗粒产生物的优点在于:α颗粒可不利地影响主要是本领域称之为暂时性错误(soft errors)的性能。随着线宽的降低,α颗粒可能会永久地损坏电路。其它的优点在于:消除或减少铅可导致电解沉积工艺产生了更清洁的废物流。
形成含有至少5N纯度的铜、银和金的阳极组合物代表性的方法例如是真空铸造。
形成含有至少4N纯度的镍和铬中的一种或多种的阳极组合物的代表性方法例如包括热压和真空铸造。
形成含有铜/磷的组合物的代表性方法例如利用真空铸造和中间合金方法,所述铜/磷合金具有至少5N的纯度,并且磷的含量是约200ppm-约1000ppm。可通过电解精炼来提纯铜。
形成镍组合物的代表性方法例如利用真空铸造和中间合金方法,其中所述镍成分包括至少4N5的镍和硫、并且硫的含量以重量计是约0.01%-约5%。其它的方法例如是:将镍粉和硫粉混合,并且接着将组合物热压成基本与所需的最终形状一致的近净形。
包括纯度至少5N的锡、锑、铅、银、铜和铋的一种或多种并且适用于电解沉积焊料凸起的阳极组合物的形成方法例如包括铸造所需材料的合金。
本发明各种阳极材料成分方面的其它特点是该材料的均匀性。术语“均匀性”是针对材料的说明整个阳极中的阳极材料优选具有均匀的组成,并且夹杂物和沉积物被均匀地分散。优选地夹杂物和沉积物的平均尺寸不超过10微米。在特定的应用中,沿各个夹杂物和沉积物的最大尺寸方向上的所有夹杂物和沉积物的平均长度小于或等于10微米,更优选小于1微米,并且进一步优选所有夹杂物和沉积物的平均长度小于或等于十分之一微米。
利用本发明方法可控制的阳极成分的物理特性是晶体组织和晶粒尺寸。具体地说,本发明整个阳极的平均晶粒尺寸优选小于100微米,更优选小于50微米,甚至更优选小于10微米,并且在特定实施方式中小于1微米。可通过本领域的标准方法来确定平均晶粒尺寸。在本发明的特定方面,阳极晶粒的最大平均尺寸小于100微米,更优选小于50微米,甚至更优选小于10微米,并且在特定实施方式中小于1微米。为了解释本发明以及随后的权利要求,被称为具有所述平均颗粒的阳极应被理解为阳极的所有晶粒均具有该平均晶粒尺寸,除非具体说明了仅仅是该阳极的一部分具有所述的平均颗粒尺寸。
上述优选晶粒尺寸与本发明所包括的任何阳极成分都有关,例如该组合物基本上由铜、镍、银、金、铬、钴、锡、锑、铅和铋中的一种或多种组成,或者是由所述元素组成。
术语“晶体组织”是指晶体取向的分布,具有相对无规取向分布的材料被称为具有弱的晶体组织,而具有相对非无规取向分布的材料被称为具有强的晶体组织。可以对本发明阳极的微观结构进行组织化处理,以使金属的不同晶粒的消耗速度一致。已熟知在大部分电解槽中不同的结晶面消耗速率不同,并且有利的是,可腐蚀金相学样品,以使得在目视的显微检测过程中,不同的晶粒是可见的。在阳极微观结构被组织化处理、以使得所有晶粒都暴露相同的结晶面(或非常接近的结晶面)的实施方式中,可以减少、最小化或甚至消除阳极的不同消耗速率。由此可导致相对均匀的阳极消耗。与其它的情况相比,均匀的消耗可产生更均匀的镀覆膜、延长的阳极寿命以及镀液中较小的颗粒。因此,利用本发明阳极中合适的晶体组织可改进阳极向镀液的均匀溶解,这最终会既延长阳极的使用寿命又改进由阳极形成的电镀膜的均匀性。均匀并且基本上无规的晶体组织是各种阳极所需要的,这些阳极包括例如基本上由铜、铜/磷、镍、镍合金或镍/硫组成的阳极;基本上由铬或铬合金组成的阳极;基本上由银或银合金组成的阳极或焊料组合物组成的阳极,所述焊料组合物包括选自由锡、锑、铅、银、铜和铋组成的组中的一种或多种。
一方面,控制阳极中晶体组织的优点可通过如下方式来描述:将金属物质内的每个颗粒都视为晶体,该晶体相对于基准面而言具有以特定方式取向的晶格。基准面例如可以是阳极的消耗面。由于每个晶粒与其它晶粒无关,因此,每个晶格相对于该基准面具有自己的取向。当晶格取向相对于基准面而言是非无规,但晶面趋向于以某一方式对准时,该材料被称为具有非无规的“晶体组织”。利用表示相对于晶面方向的标准参数来表示这些晶体组织。例如,由具有立方晶体结构的金属、比如铜制成的阳极可具有<100>、<110>或其它晶体组织。与此相似的是,由具有六角晶体结构的金属、比如钴制成的阳极可具有<0002>的晶体组织。所产生的精确晶体组织取决于金属类型和阳极的加工与热处理过程。由“( )”内的数字参数代表的Miller参数也被用于描述对称晶体结构中的平面或取向类型。可通过改变大多数金属的热机械处理来产生不同的晶体组织。
在American Vacuum Society出版的J.Vac.Sci.Technol.A5(4),July/August 1987中、名称为Crystallographic Target Effectsin Magnetron Sputtering的C.E.Wickersham,Jr.,的文章,描述了溅射耙材的结晶取向对溅射沉积速度和膜均匀性的影响。在该文章中,作者指出,可通过控制制造耙材的处理工艺来改进硅片上的膜的均匀性。出版的几个专利也教导了在许多应用中如何控制溅射耙材的晶体组织来达到最佳的性能(例如参见专利US6302977、6238494、5993621、5809393、5780755、5087297)。但是,所述专利没有教导控制晶体组织会在与形成用于电镀液的阳极有关的方面有的任何应用。
通过蚀刻用于金相学评估的材料表明,晶体结构可影响材料的腐蚀或溶解行为。不同的取向晶粒会被“蚀刻”或被消耗至不同的程度。因此,对于均匀地溶解以及由此得到的均匀膜沉积而言,控制阳极的晶体组织或晶体取向均匀性是有利的。可以以两种典型的形式控制晶体组织一控制主要的晶体组织取向以及控制晶体组织密度。
晶体组织密度或具有共同取向的晶粒的相对份数对于均匀溶解很重要。如果存在无规的晶体组织(任何特定的晶体组织和晶粒的无规取向的密度都很低),则取向有利的那些晶粒将消耗的较快,由此产生了不均匀的表面。也可存在弱的晶体组织(此时一个取向比其它的取向占优或更普遍),但是大部分晶粒显示出与此不同的取向。在强的晶体组织中,高百分比的晶粒具有相同的取向,因此可导致更均匀地消耗。
对于特定阳极来说,具体需要的晶体组织可取决于阳极的材料和几何特征。例如,对于平坦的表面而言,紧密堆积的晶面与阳极表面对准的晶体组织是有利的。例如对于钴这样的HCP金属而言,该组织是(001)面或(001)晶体组织。对于FCC金属比如铜而言,该组织是(111)晶体组织,而对于BCC金属比如铬而言,该组织是(110)晶体组织。在特定的方面,本发明所包括的阳极中,占晶粒总数的至少25%的晶粒、至少50%的品粒、至少75%的晶粒或至少90%的晶粒具有特定的理想晶体学组织。对于HCP金属而言,具体的理想组织通常是(001),而对于FCC金属而言,具体的理想组织通常是(111),并且对于BCC金属而言,具体的理想组织通常是(110)。
在本发明的阳极组合物中形成理想的晶粒尺寸和组织的方法实例将参考图3-5来描述。
图3中,示出了阳极组合物的坯体100。可通过使上述阳极组合物中的一个熔化、将该组合物倒入模具中并且将该组合物冷却成圆柱形来形成坯体100。换言之,可将阳极材料铸造成圆柱形。该圆柱形可直接被作为坯体100使用。也可选择的是,在将该铸造材料用作坯体100之前,可将铸造的圆柱形的一端或两端切割,以除去与端部有关的凹坑或其它缺陷。坯体100具有宽度105和长度110。
可以以铸造体的形式使用该坯体材料。也可选择的是,可将坯体100的材料热机械加工成所需形状的坯体,与此同时赋予该材料理想的晶体尺寸和晶体组织。而且,在铸造过程中可使用梯度冷却。梯度冷却可在坯体100的材料内形成柱状微晶。形成坯体100的另一种方法是:对坯体100的材料进行长时间的热力学处理(比如长时间的热处理),以形成单晶形式的坯体100。
图4表示出了毛坯(blank)101。可通过对坯体100(图3)进行各种热机械加工比如热锻造、轧制和/或横轧来形成毛坯101。热机械加工使坯体的宽度增加至新的宽度115,并且使长度减小至新的长度120。长度120与长度110的变化值除以长度110而得到的比率等于毛坯101相对于坯体100的减小率。优选该减小率是约50%-最高90%。热机械加工可减小阳极材料的平均晶粒尺寸、减小颗粒尺寸、减小夹杂物的尺寸并且使夹杂物分散于整个阳极材料中。另外,热机械加工可得到理想的晶体组织。除了锻造、轧制和横轧的机械加工技术之外,还可通过对图4的毛坯进行热处理来进一步影响晶体组织、晶粒尺寸、颗粒尺寸和夹杂物的尺寸。
如果对毛坯101进行了充分的热机械加工处理,则毛坯内的平均粒径可降到小于100微米。另外,毛坯内的组织可转变为无规组织;或在特殊用途中转变为在所需方向取向的较强组织。专利US.6,238,494、6,113,761、5,993,621和5,780,755描述了适宜的热机械加工处理,本文参考引用所述专利。
图5表示可用于本发明方法的另一毛坯。具体地说,图5所示为基本上是方形的毛坯150。例如,可通过切除图4的毛坯获得毛坯150。对毛坯150进行等通道角度挤压(ECAE),以使得毛坯内的组织无规化,并且使平均粒径降到小于100微米、小于50微米、小于10微米并且在特殊用途时小于1微米。例如,US.专利5,600,989和5,780,755描述了ECAE方法,在此一并参考引用。通过使用具有足够数量(优选至少4个,并且经常是至少6个)的通道的ECAE装置、并且同时使毛坯150在通道之间旋转以使得从一个通道到达另一个通道的毛坯具有不同的取向,可由此实现粒径的减小和晶体组织的无规化。
利用参考图3-5所述的方法制造的材料可被用作电解装置、例如图1所描述的现有装置中的阳极。另外,可将该材料切割、压制或轧制,以制造粉末、颗粒、轧制的条或其它易于溶解于合适酸中的形式,以形成预先装载的电解液。颗粒和粉末是指材料的颗粒形式。粉末、颗粒或轧制的条是指金属材料。任何合适的酸可被用于溶解颗粒和/或金属材料。用于溶解相当于含焊料组合物的阳极的金属材料的代表性酸例如是甲基磺酸,并且用于溶解含铜组合物的阳极的代表性酸例如是硫酸。
本发明的阳极材料可被用于电解沉积工艺中,以形成图2的半导体结构50所示的一个或多个导电层。具体地说,本发明包括的方法中,提供了半导体基体,并且在该基体上形成接线层(比如图2的接线层54)。可通过溅射沉积铜晶种层、并且随后在该晶种层上电解沉积铜来形成该接线层。可从根据本发明形成的阳极来沉积铜,因此具有至少4N5的纯度,并且具有减少的夹杂物和颗粒数量。希望避免阳极中有夹杂物和颗粒,因为在电解沉积过程中,夹杂物和颗粒与周围的阳极材料的行为不同,并且由此可导致电化学沉积材料的不均匀。在特定的实施方式中,可利用基本上由铜或铜和磷组成的阳极来电解沉积接线层54的至少一部分。
在形成接线层54之后,形成掩膜56,并且随后在接线层54上电解沉积欠凸起(under-bump)材料60。材料60可含有银、镍、铬、钴和铜中的至少一种,并且可通过利用银纯度至少99.995%的阳极、镍纯度至少99.995%的阳极、或镍、铬、钴、铜和银中的一种或多种的纯度至少99.995%的阳极进行电化学沉积得到该材料。
利用本发明的方法可将多种金属用于欠凸起材料冶金中。例如,铬通常被用作欠凸起冶金材料的一部分,该部分位于硅模上的电路衬垫和焊料之间,焊料会损坏叼焊晶片凸起。铬与电路衬垫金属(通常是Al)的结合强,并且在剩余的欠凸起材料冶金和电路之间形成扩散阻挡层。使用的铬通常是Cr/Cu系列层,并且通常通过在现有方法中进行蒸发来产生该层。但是,可根据本发明的方法来镀覆Cr和Cu层,以形成Cr/Cu层。
在形成欠凸起层60之后,可在层60上形成第二欠凸起层62。在特定的实施方式中,层60基本上由镍组成,或基本上由镍和硫组成,并且层62基本上由银组成。因此,可由银纯度至少4N5的阳极来沉积层62。也可选择的是,层62可含有银,或该层基本上由银组成,或者该层由银和其它金属组成。例如,可由银、铬和铜中的一种或多种纯度至少为4N5的阳极来沉积层62。
随后在层62上形成焊料层64。可由纯度至少为4N的选自锡、锑、铅、银、铜和铋中的一种或多种元素的阳极来形成层64。
根据本发明方法形成的结构50可被用于例如叨焊晶片技术或晶片规模包装中。
上述方法是示范性的方法,应理解为本发明包括除具体描述的实施方式之外的其它实施方式。例如,本发明包括这样的一个实施方式,其中阳极材料被用于主互连电路的电解沉积。具体地说,本发明包括的方法中,提供的半导体基体具有蚀刻于其中的沟槽和/或通孔。接着利用PVD或CVD工艺来沉积连续的阻挡层。接着利用PVD、CVD或无电解沉积来沉积导电金属晶种层、优选铜或铜合金层。接着通过铜的电化学沉积来形成大部分半导体形貌。可利用根据本发明形成的阳极来沉积铜,因此,沉积的铜具有至少4N5的纯度,并且具有减少的夹杂物和颗粒数量。
相对于现有技术材料而言,利用本发明的高纯阳极和预装载材料的优点在于:本发明的材料可改进电解液的使用期限;可改进阳极寿命;可改进沉积膜的成分、质量和均匀性;并且由此可降低与电解沉积方法有关的成本。
已参考几个示范性的方法描述了本发明。但是,应理解为本发明包括对上述示范性方法作出许多修正和变化的实施方式。以下将描述几种示范性的修正和变化。
在一种变化形式中,可将表面层施加至阳极的一部分,以使这些部分在镀覆过程中不会被消耗掉。一种施加该表面层的方法是,在阳极没有被保护的部分通过火焰喷射法施加该层。火焰喷射法可将脆性材料和/或比阳极组合物的熔点高的材料施加在阳极上。则施加的材料可起到保护性的阻挡层的作用。例如,可通过火焰喷射法将相对不活泼的金属(比如Ti)或陶瓷(例如氧化铝)施加在含Cu的阳极上。在其它示范性的应用中,可通过火焰喷射法将其它材料施加在多种阳极上,以产生非消耗的表面层。也可选择的其它施加保护层的方法是利用聚乙烯涂料进行粉末涂覆。
在其它变化形式中,可在阳极中设置有补偿部分,以补偿消耗的轮廓。当阳极溶解在阳极有效寿命内进行时,阳极表面产生了消耗的轮廓。消耗的轮廓取决于阳极的许多具体特性以及镀覆设备的设置和操作。这些因素包括但不限于阳极材料、槽的几何形状、阳极与阴极的比率、镀覆的化学机理、电流密度、屏蔽和槽内的流体动力学。两个因素将决定阳极的有效寿命。当消耗的轮廓变得更明显时,会影响沉积在晶片表面的薄膜的均匀性。特定用户对于非均匀性可容忍的程度决定了阳极的使用寿命。第二个因素是阳极的烧穿,此时阳极的消耗实际上使得阳极的底部出现了孔。阳极表面没有材料会强烈地影响薄膜均匀性。一旦针对特定的工艺确定了消耗轮廓,则可研究补偿设计,此时可直接依据这些区域的消耗速率向阳极表面添加材料。这对于延长阳极寿命和得到可接受的沉积特性具有有利的影响,而不是仅仅增加了整体厚度,也就是说,不是仅仅在使用寿命周期结束时填补了消耗轮廓。
在另一种变化形式中,为了运输和处理阳极,可设计出“特定”的阳极包装。在将阳极放置于镀覆反应器的过程中,该特定的包装可减少或消除对阳极的处理,由此可减少将杂质引入镀液中。该特定的包装也可减少运输过程中将阳极暴露于氧,从而消除或减少了在运输过程中高纯阳极材料的氧化。例如,在运输过程中,阳极的真空包装可有利于减少暴露于阳极的氧量,由此可减少阳极的氧化。
在另一种变化形式中,可赋予阳极一个或多个表面粗糙化的纹理。这样做可以增加给定部分的表面积,从而可提高阳极材料的溶解率。在希望镀液迅速达到平衡的阳极使用初期或老化阶段,这是特别有利的。可通过多种方法使物体具有粗糙的表面。可通过机械加工来产生一些纹理比如突起。可通过对表面进行颗粒喷砂处理或使磨蚀介质碰撞表面来产生其它的粗糙表面。化学蚀刻是另一种使表面粗糙化的方法。
颗粒喷砂通常是非常经济的工艺,但是,不利的是,一些颗粒介质部分会嵌入阳极表面。这对于软材料比如焊料阳极特别成问题。颗粒喷砂的一种改进方法是使用干冰作为颗粒介质。干冰会升华,因此,在阳极上没有残留物。在利用干冰进行颗粒喷砂之后,该阳极通常适合使用,并且可避免与利用常规颗粒介质进行的颗粒喷砂或机加工(在这种情况下,通常需要清洁机加工部件表面的油)有关的清洁。
在另一种变化形式中,可铸造阳极,以使得组成该阳极的一个或少量的晶粒具有优选的晶体组织。这种铸造可消除在电解液中优先消耗的高能晶界。可通过将阳极组合物的金属倒入已加热至该金属熔点以上温度的模具中,并且接着从模具的一侧或一端缓慢冷却金属来铸造阳极。该缓慢冷却可导致少量晶粒成核并且接着生长。通常从模具的底侧进行冷却,这样会使产生的微结构所包括的少量晶粒具有基本上平行的侧面(该晶粒微结构通常被称为柱状微结构)。柱状微结构实质上可消除形成颗粒的诱因。具体地说,柱状微结构实质上可消除这样的问题:由于小晶粒周围的晶界消耗而形成了颗粒,接着小晶粒脱落并且在电解液中形成了颗粒。
在另一种变化形式中,可利用铸造和热机械加工之外的不同方法来制造阳极。一种方法例如是将阳极材料的形状挤压成所需要阳极的近净形,并且接着将该材料切成所需要的厚度。该工艺可被用于管状部件以及实心部件。
在另一种变化形式中,可在阳极的一部分上施加保护层,以保护将电极引入阳极的引线点。该保护层可用于阻止阳极与电极连接处的阳极消耗。当电解液消耗阳极时,该位置处的消耗是个严重的问题。如果不施加保护层,电接触会随着阳极消耗而降低。
Claims (6)
1.一种用于电镀液的阳极,其中,该阳极中包含晶粒,并且其中晶粒总数的至少25%彼此具有共同的晶体学组织,并且其中共同的晶体学组织是(001)。
2.权利要求1的阳极,其中晶粒总数的至少50%彼此具有共同的晶体学组织。
3.权利要求1的阳极,其中晶粒总数的至少75%彼此具有共同的晶体学组织。
4.权利要求1的阳极,其中晶粒总数的至少90%彼此具有共同的晶体学组织。
5.权利要求1的阳极,它含有HCP金属。
6.权利要求1的阳极,它含有钴。
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US20030188975A1 (en) * | 2002-04-05 | 2003-10-09 | Nielsen Thomas D. | Copper anode for semiconductor interconnects |
DE10355953B4 (de) * | 2003-11-29 | 2005-10-20 | Infineon Technologies Ag | Verfahren zum Galvanisieren und Kontaktvorsprungsanordnung |
US8192596B2 (en) * | 2004-01-29 | 2012-06-05 | Jx Nippon Mining & Metals Corporation | Ultrahigh-purity copper and process for producing the same |
US7411303B2 (en) * | 2004-11-09 | 2008-08-12 | Texas Instruments Incorporated | Semiconductor assembly having substrate with electroplated contact pads |
JP2008184637A (ja) * | 2007-01-29 | 2008-08-14 | Nec Electronics Corp | 電解Niめっき装置および半導体装置の製造方法 |
US20080187194A1 (en) * | 2007-02-05 | 2008-08-07 | Zhang Daoxian H | Cad image normalization |
JP5066577B2 (ja) * | 2007-11-01 | 2012-11-07 | Jx日鉱日石金属株式会社 | 銅アノード又は含燐銅アノード、半導体ウエハへの電気銅めっき方法及びパーティクル付着の少ない半導体ウエハ |
CN103160868A (zh) * | 2011-12-17 | 2013-06-19 | 鞍钢重型机械有限责任公司 | 一种用于生产含硫活性镍的电解液及其使用方法 |
CN103073513B (zh) * | 2012-12-14 | 2015-12-02 | 雅本化学股份有限公司 | 1-取代-5-氯-2h-1,2,3-三氮唑-4-羧酸衍生物及其制备方法 |
WO2017154740A1 (ja) * | 2016-03-09 | 2017-09-14 | Jx金属株式会社 | 高純度錫及びその製造方法 |
JP6960363B2 (ja) * | 2018-03-28 | 2021-11-05 | Jx金属株式会社 | Coアノード、Coアノードを用いた電気Coめっき方法及びCoアノードの評価方法 |
TWI749818B (zh) * | 2020-10-22 | 2021-12-11 | 元智大學 | 金屬導線結構改質方法 |
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US20050000821A1 (en) | 2005-01-06 |
WO2003044246A1 (en) | 2003-05-30 |
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