CN102482779A - 可粘合晶片表面的低应力镍磷/钯叠层 - Google Patents
可粘合晶片表面的低应力镍磷/钯叠层 Download PDFInfo
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- CN102482779A CN102482779A CN2009801331776A CN200980133177A CN102482779A CN 102482779 A CN102482779 A CN 102482779A CN 2009801331776 A CN2009801331776 A CN 2009801331776A CN 200980133177 A CN200980133177 A CN 200980133177A CN 102482779 A CN102482779 A CN 102482779A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12889—Au-base component
Abstract
本发明涉及一种具有可粘合金属涂层的基底,在铝表面或铜表面上,该涂层按顺序包括:(a)镍磷层,(b)钯层,同时还可以选择(c)金层,其中,镍磷层(a)的厚度为0.2-10μm,钯层(b)的厚度为0.05-1.0μm,而可选择的金层(c)的厚度为0.01-0.5μm,同时,镍磷层(a)的磷含量为10.5-14wt.-%。由此产生的镍磷/钯叠层的沉积内应力通常不高于34.48MPa(5000Psi)。此外,本发明还描述了准备该基底的方法过程。
Description
技术领域
本发明涉及一种具有可粘合金属涂层的基底,在铝表面或铜表面上,其包括具有特定厚度和约化应力的镍磷层和钯层。另外,本发明还涉及准备该基底的方法过程。
背景技术
在现有技术中已知打线接合和倒装焊合的化学镀镍钯金工艺,例如在欧洲专利申请EP 0701281A2中对此有所描述。而美国专利No.6,445,069以及欧洲专利申请EP 1126519A2中也描述了类似工艺。突块底部金属喷涂是以晶圆级微型化、电子信号完整化和金属叠层可靠性等技术方面的需求为动力。晶片变得更薄,因而,任何所采用的金属叠层都可能使晶片不希望出现的翘曲。
根据现有技术,首先在晶片表面镀一层铜或铝,然后在晶片表面(“衬垫”)的每个格上镀镍磷层和钯层(还可以选择添加镀金层)。现有技术的镀层叠层具有沉积内应力,会导致晶片的翘曲。
发明内容
最大限度地减小或避免晶片的翘曲。
为了实现该目的,本发明利用具有可粘合金属涂层的基底,在铝表面或铜表面上,该涂层按顺序包括:(a)镍磷层,(b)钯层,同时还可以选择(c)金层,其中,镍磷层(a)的厚度为0.2-10μm,钯层(b)的厚度为0.05-1.0μm,而可选择的金层(c)的厚度为0.01-0.5μm,同时,镍磷层(a)的磷含量为10.5-14wt.-%。由此产生的镍磷/钯叠层(层(a)与层(b))的(拉张)沉积内应力通常不高于34.48MPa(5000Psi)。
附图说明
无
具体实施方式
本发明的基本根据是,在上述范围内选择叠层各层的厚度并选择镍磷层的上述磷含量,产生的镍磷/钯叠层的沉积内应力为不高于34.48MPa(5000Psi)的张应力或甚至是压应力,因此镀有该叠层的晶片可以最大限度地减小或者完全避免翘曲。
根据本发明的叠层中,镍磷层的厚度范围是0.2-10μm,更优选为0.5-3.0μm。
钯层的厚度范围是0.05-1.0μm,更优选为0.1-0.5μm。
作为选择的金层的厚度范围是0.01-0.5μm,更优选为0.01-0.3μm。
镍磷层的磷含量的范围是10.5-14wt.-%。以下将该层称为“高磷镍磷层”。
高磷镍磷层的沉积内应力通常为压应力(0-34.48MPa(0-5000Psi))。磷含量在4wt.-%与大约10.5wt.-%之间的(“中磷”)镍磷层的应力为张应力,而当磷含量超过10.5wt.-%(“高磷”)时则为压应力(参见整理出版公司于1991年出版的沃尔特·里德尔所著的《化学镀镍》,第111页)。
钯层的拉张沉积内应力优选为不高于137.9MPa(20000Psi),更优选为不高于103.4MPa(15000Psi),而最好为不高于68.96MPa(10000Psi)。在这一点上需要指出,现有的镍磷/钯叠层的钯层中的薄膜应力是高达206.9-344.8MPa(30000-50000Psi)的张应力(参见专利号为4424241的美国专利)。
在沉积产生叠层的同等条件下,将各层分别沉积在一个铜基底(测试条)上,然后利用一种商用测量装置测试各层的应力,由此可以这样确定各层的堆积内应力值。
接下来会详细描述根据本发明的具有可粘合晶片表面的低应力镍磷/钯叠层的基底的准备方法:
在此过程中会涉及到根据最近对晶圆级微型化、电子信号完整化和金属叠层可靠性的需求而研发的所谓“突块底部金属喷涂”(UBM)。
UBM工艺可大致分为四个不同部分。
第一部分为预处理以及铝/铝合金和铜衬垫的表面处理。对铝或铝合金的预处理可以采用不同的浸锌工艺,例如XenolyteTM的ACATM清洁剂、Xenolyte Etch MATM、Xenolyte CFATM或者Xenolyte CFTM(全部出自安美特德国公司(Atotech Deutschland GmbH)),它们符合行业内的无氰化学标准。
UBM工艺的第二部分为化学镀镍。
在该化学镀镍的步骤中,化学镀镍水溶液的成分有镍盐,还有次亚磷酸或选自次亚磷酸钠、次亚磷酸钾和次亚磷酸铵的可溶性盐溶液。该溶液无需添加次亚磷酸镍,同时也不含可生成不可溶正亚磷酸盐的碱或碱土金属离子。
在化学镀镍溶液中,镍离子的作业浓度通常约为1至18克/升(g/l),优选为约3至9克/升。也就是说,镍阳离子的浓度范围是0.02至约0.3摩尔/升,或者可以优选为约0.05至约0.15摩尔/升。
镀镍溶液还具有作为还原剂的次亚磷酸盐离子,其来源于亚磷酸或如次亚磷酸钠、次亚磷酸钾和次亚磷酸铵的可溶性盐溶液。
镀液中还原剂的数量至少足够用来按化学反应计量式将化学镀镍反应中的镍离子还原成自由镍金属,该浓度通常保持在约0.05至约1.0摩尔/升的范围内。也就是说,通过引入次亚磷酸盐还原离子,次亚磷酸盐离子的浓度为约2至60克/升,或是12至50克/升,甚至是20至45克/升。传统的做法是,反应进行中补充还原剂。
本发明的镀溶液包含镍和磷还原剂(如次亚磷酸盐或钠、钾或铵盐),镀溶液使涂在基底的镍磷合金连续沉积。高含量磷(“高磷”)的标准通常为约10.5wt.-%,而高达约14wt.-%的重量则要求镀作业的酸碱度为约3至6之间,为了使合金镀层具有很高的磷含量,酸碱度可优选为约4至5.6之间。
镀镍溶液还可以包括其他材料,如缓冲剂、螯合或络合剂、润湿剂、加速剂、缓蚀剂、光亮剂,等等。这些都是现有技术中已知的材料。
因此,在一个实施例中,镀镍溶液可能包括络合剂或络合剂的混合物。本领域中的络合剂也被称为螯合剂。包含在镀镍溶液中的络合剂的数量应该足够络合溶液中存在的镍离子,并且进一步溶解电镀过程中生成的次亚磷酸盐降解产物。一般来说,络合剂的数量低于约200克/升,常规数量为约15至75克/升。在另一个实施例中,络合剂的数量为约20至60克/升。
在一个实施例中,镍络合剂或螯合剂可以选为羧酸、聚胺或璜酸或它们的混合物。可用的羧酸包括单羧酸、二羧酸、三羧酸以及四羧酸。羧酸可以用多种取代基部分来代替,例如羧基或氨基,同时由于其中存在钠盐、钾盐或铵盐,可以将酸引入镀溶液中。一些络合物(例如乙酸)还可以作为缓冲剂,而由于这些添加成分的双重功效,可以优化任何镀溶液的适当浓度。
本发明的溶液中作为镍络合剂或螯合剂的可用羧酸的实例包括:一元羧酸(如乙酸)、氨基乙酸(乙醇酸)、氨基醋酸(甘氨酸)、二元-氨基丙酸、(丙氨酸);二元-羧基丙酸(乳酸);二羧酸(如丁二酸)、氨基丁二酸(天冬氨酸)、羟基丁二酸(苹果酸)、丙二酸钠(丙二酸)、酒石酸;三羧酸(如二-羟基-一/二/三丙烷三羧酸(柠檬酸));以及四羧酸(如乙二胺四乙酸(EDTA))。在一个实施例中,在镀镍溶液中使用两种或两种以上上述络合剂或螯合剂的混合物。
本发明的化学镀镍水镀液可以在上述酸碱度范围内作业。由于在作业过程中生成的氢离子使镀溶液的酸性变强,则需要添加可溶并互溶的碱性物质溶液,如钠、钾或氢氧化铵、碳酸盐和碳酸氢盐,从而可以周期性地或持续地调节酸碱度。为了提高电镀液的作业酸碱度的稳定性,可以增添乙酸、丙酸、硼酸等类似的各种缓冲化合物,添加量不多于约30克/升,常规添加量为约2至10克/升。如上所述,某些缓冲化合物(如乙酸和丙酸)同时具有络合剂的功效。
该化学镀镍溶液还可以包含现有技术中迄今已知的有机和/或无机稳定剂类型,其中包括铅离子、镉离子、锡离子、铋离子、锑离子和锌离子,可在在生成可溶并互溶的盐(如醋酸盐等)溶液时将其适时引入。用于化学电镀液的有机稳定剂包括含硫化合物,例如硫脲、硫醇、璜酸盐、硫氰酸酯,等等。所采用的稳定剂的剂量很少,比如是溶液的百万分之零点零五到大约百万分之五(0.05-ca.5ppm),常规剂量比例为百万分之零点一到百万分之二或三(0.1-2/3ppm)。
该镀镍溶液可选择使用一种或多种迄今已知的各种湿润剂,该湿润剂具有可溶性并于其它溶液成分互相兼溶。在一个实施例中,使用这样的湿润剂可以预防或防止镍合金镀层上有凹点,湿润剂的使用剂量为不多于大约1克/升。
将待镀基底与镀溶液在从至少大约40℃到溶液沸点的温度范围内互相接触。在一个实施例中使用酸性类型的化学镀镍镀液,其温度范围是从大约70℃到大约95℃,更常规的温度范围是从大约80℃到大约90℃。碱性类化学镀镍镀液的作业温度更广,但通常比酸性化学镀镍溶液的温度更低。
化学镀镍溶液与被镀基底的接触时间为一个函数,它依赖于需要的镍磷合金的厚度。典型地,接触时间的范围是从1到30分钟。
在沉积镍合金的过程中,通常需要轻微的搅拌,该搅拌可以使用轻微的充气搅拌、机械搅拌、泵动镀液循环、电镀滚筒,等等。还会对电镀液进行周期性或连续的过滤处理,从而降低其中污染物的水平。在一些实施例中,为了保持成分的浓度,特别是,为了保持镍离子和次磷酸盐离子的浓度,以及所需限制内的酸碱度水平,还可以周期性或连续地补充镀液的成分。
UBM工艺的第三部分为在化学镀钯镀液中镀钯。
化学镀钯镀液在专利EP 0 698 130 B1中有所描述,在本发明中的改进之处是额外添加稳定剂。有趣的是,无需预活化就可以使用该镀液在高磷镍-磷层上再镀一层钯。然而,特别是在低温下镀钯,在化学镀钯的步骤之前,可以选择进行对高磷镍-磷层的活化。
化学镀钯的优选镀液参数如下:
酸碱度:优选为5-6.5,更优选为5.6-6.0
镀液温度:优选为70-90℃,更优选为82-87℃
浸泡时间:优选为3-20分钟,更优选为5-10分钟
添加的稳定剂:优选为10-500毫克/升,更优选为100-300毫克/升
如果在化学镀钯步骤之前进行一个活化步骤,则钯镀液的温度可以低至大约40℃(不高于大约95℃)。例如,可以使用所谓的离化钯活化剂来获得活化,该活化剂通常是酸性的,包含钯2+源(如PdCI2或PdSO4)并且在镍-磷层上沉积一个钯元素的种子层。这种活化剂对技术人员来说是众所周知的,并已经开发出商标为Xenolyte Activator ACU 1TM(由安美特德国公司生产)的商业上的可用溶液。同样众所周知的可用的所谓的胶质酸性活化剂中,钯簇周围被锡包裹。
在专利EP 0 698 130中描述的化学镀钯镀液技术中额外添加稳定剂可以不用活化即在高磷镍-磷层上沉积钯。此外,这种稳定剂允许的化学镍沉积的温度范围在70℃与90℃之间,这可以减少沉积的钯层的内应力。已知的化学钯镀液在如此高的镀液温度下寿命很短,因此在工业应用中不能承受如此高温。该额外添加的稳定剂可以选择为:硫酰亚胺、聚苯基硫、嘧啶、多元醇以及无机络合剂如硫氰化物。硫酰亚胺优选为糖精,嘧啶优选为烟碱酰胺、嘧啶三硫酸基酸、烟酸、二羟基吡啶和尼古丁。聚醇优选为聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物和衍生物。
最后,在镍磷/钯叠层上可选择镀金层。为此,可以利用现有技术中已知的化学镀金电解液。钯层上面所镀的可选金层的厚度为0.01至0.5μm,优选为0.05至0.3μm。最好是通过浸泡沉积可选金层。例如,在勒兹出版公司于2002年出版的哈索·凯瑟所著的《贵金属镀层:分离、属性及应用》中第43页就描述了这种浸泡方法。Aurotech SFplusTM已经推出商用的适合化学镀金的镀液(温度为80至90℃;酸碱度为4.5至6.0;沉浸时间为7至15分钟;金(例如:K[Au(CN)2])的含量为0.5至2克/升)。
因此,如果在本发明中采用涂铝晶片作为初始基底,则该方法包括以下步骤:清洗、蚀刻、浸锌(作为预处理步骤)、然后是镀镍、可选择地活化高磷镍磷层、镀钯以及可选择地镀金。
如果在本发明中采用涂铜晶片作为初始基底,则预处理包括以下步骤:清洗、可选择地蚀刻以及活化钯,再接下来的步骤是镀镍、可选择地活化高磷镍磷层、镀钯以及可选择地镀金。
下面的实例和对比例进一步说明了本发明。
各钯或镍磷层以及镍磷/钯叠层的内应力值是由“沉积应力分析”(模型683;专业测试及发展有限公司)确定的。该公司设计的专用测试条涂有镍磷层、钯层或镍磷/钯层,并根据设备提供者描述的程序进行测试。
例1(对比试验)
在5.5的酸碱度和55℃的温度下,在中磷镍磷层(XenolyteTM Ni MTM,安美特德国公司)上镀纯钯层的镀液(由EP0698130公开)的成分包括:1克/升钯2+离子、27.6克/升甲酸和3克/升乙二胺。
已经镀上镍-磷(1.3μm厚)的铜基底在钯镀液中的沉浸时间为5分钟。在拉伸方向产生的堆积应力为103.4MPa(15000Psi)(应力的计算考虑到镍磷和钯层的总厚度;钯层的厚度是0.27μm)。
例2(对比试验)
在低应力钯镀液(在美国专利4,424,241中公开)中,在铜基底的中磷镍磷层(XenolyteTM Ni MTM,安美特德国公司)上镀一层纯钯。该铜基底在该XenolyteTM Ni MTM镀液中沉浸5分钟,用去离子水漂洗后,在钯镀液中沉浸5分钟。
钯镀液的成分是:
钯2+离子为1克/升
乙二胺为3克/升
甲酸钠40.8克/升
糖精氯化钠水化物(无水基础)为0.2克/升
酸碱度为5.8,镀液温度为85℃。
在所得到的镍磷/钯叠层中,镍磷层的厚度为0.9μm,钯层的厚度为0.21μm。观测到的整体堆积张应力为53.79MPa(7800Psi)。
例3
确定了在例2中使用的低应力钯镀液中镀钯层并且在高磷镍磷镀液中镀镍磷层所得到的镀在铜上面的镍磷/钯叠层的薄膜应力。
高磷镍磷镀液的成分是:
镍2+离子为6克/升
次亚磷酸钠-水为30克/升
苹果酸为10克/升
琥珀酸为18克/升
乳酸为30克/升
铅离子为0.2毫克/升
酸碱度为4.8,镀液温度为85℃。
所得到的镍磷层的厚度为0.92μm,钯层的厚度为0.19μm。所得到的叠层的张应力值为21.38MPa(3100Psi)。
例4
通过使用Xenolyte Activator ACU1(由安美特德国公司生产)增加镍磷层的活化后,在例1中的钯镀液中,在高磷镍磷层(其利用例3中的高磷镍磷镀液)上沉积钯层。
由此所得的叠层的镍磷层的厚度是0.84μm,钯层的厚度是0.25μm,整体张应力值是27.58MPa(4000Psi)。镀钯前的镍磷层在压缩方向的应力为34.48MPa(5000Psi)。
例5
在高磷镍磷镀液(镀液成分参见例3)中的铜上镀高磷镍层,产生很小的压应力,该压应力由厚度为1μm时的27.58MPa(4000Psi)下降到厚度为至少3μm时的25.52MPa(3700Psi)。在如例2所述的镀液中镀一层0.3μm厚的钯层,1μm的镍磷层镀钯后的整体叠层张应力为20.69MPa(3000Psi),3μm的镍磷层镀钯后的整体叠层张应力为21.38MPa(3100Psi)。
例6(对比试验)
在5.5的酸碱度和55℃的温度下,在例1中所述的镀液中直接在铜上沉积钯层,其间利用Xenolyte Activator ACU1(由安美特德国公司生产)进行活化,产生的平均张应力值为241.4MPa(35000Psi)。
例7
在5.8的酸碱度和85℃的温度下,在例2中的低应力镀液中直接在铜上沉积钯层,并且利用Xenolyte Activator ACU1(由安美特德国公司生产)进行活化,产生的平均张应力值为89.65MPa(13000Psi)。此外,钯镀液在该温度下的48小时内保持稳定,而如例1的镀液在85℃的3个小时后就会析出。
Claims (7)
1.一种具有可粘合金属涂层的基底,在铝表面或铜表面上,该涂层按顺序包括:
(a)镍磷层,
(b)钯层,同时,可选择
(c)金层,
其中,镍磷层(a)的厚度为0.2-10μm,钯层(b)的厚度为0.05-1.0μm,而可选择的金层(c)的厚度为0.01-0.5μm,
其中,镍磷层(a)的磷含量为10.5-14wt.-%,而且
其中,包含镍磷层(a)与钯层(b)的叠层的沉积内应力不高于34.48MPa(5000Psi)。
2.根据权利要求1所述的基底,其中镍磷层(a)的厚度为0.5-3.0μm,钯层(b)的厚度为0.1-0.5μm,而可选择的金层(c)的厚度为0.01-0.3μm。
3.根据权利要求1所述的基底,其中钯层(b)具有不大于137.9MPa(20000Psi)的沉积张内应力。
4.一种准备权利要求1所述的基底的方法,其包括以下步骤:
(1)将具有铝或铜表面的基底沉浸在一种镍磷镀液中,该镍磷镀液的成分有镍盐,还有次亚磷酸或选自次亚磷酸钠、次亚磷酸钾和次亚磷酸铵的可溶性盐溶液。该溶液无需添加次亚磷酸镍,同时也不含可生成不可溶正亚磷酸盐的碱或碱土金属离子,
获得基底上的镍磷层需要的温度为大约70℃至大约95℃,酸碱度为大约3至大约6,沉浸时间为1至30分钟,然后
(2)将由步骤(1)得到的具有镍磷涂层的基底沉浸在一种钯镀液中,该钯镀液的成分有至少一种钯离子源、至少一种还原剂、至少一种络合剂以及至少一种硫酰亚胺稳定添加剂,该稳定添加剂的数量为10至500毫克/升,
获得基底上的钯层需要的酸碱度为5至6.5,沉浸时间为3至20分钟,
其中,在沉积所述钯层前无需任何对所述镍磷层的活化就可以将所述钯层沉积在由步骤(1)得到的所述镍磷层上,进行步骤(2)所需的温度是大约70至大约90℃,或者
其中,在活化所属镍磷层后将所述钯层沉积在由步骤(1)得到的所述镍磷层上,进行步骤(2)所需的温度是大约40至大约95℃。
5.根据权利要求4所述的方法,其中基底为一个铝晶片,在镀镍(1)前对铝晶片的表面进行清洁和蚀刻或者还有浸锌。
6.根据权利要求4所述的方法,其中基底为一个铜晶片,在镀镍(1)前对铝晶片的表面进行清洁、可选择地蚀刻以及还有活化钯。
7.根据权利要求4-6中任意一个权利要求所述的方法,其还包括:
(3)一个将涂有镍磷层和钯层的基底沉浸在一种金镀液中的步骤。
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