CN112996933B - 无电镍镀敷溶液 - Google Patents

无电镍镀敷溶液 Download PDF

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Publication number
CN112996933B
CN112996933B CN201980071845.0A CN201980071845A CN112996933B CN 112996933 B CN112996933 B CN 112996933B CN 201980071845 A CN201980071845 A CN 201980071845A CN 112996933 B CN112996933 B CN 112996933B
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Prior art keywords
layer
nickel
ions
acid
plating solution
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CN201980071845.0A
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CN112996933A (zh
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H·贝拉
C·施瓦茨
A·舒尔策
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/1601—Process or apparatus
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Abstract

本发明涉及一种无电镍镀敷溶液，其包含：‑镍离子源、‑钼离子源、‑钨离子源、‑次磷酸根离子源、‑至少一种络合剂、‑浓度为0.38‑38.00μmol/L的至少一种有机含硫化合物和‑浓度为0.67‑40.13mmol/L的至少一种氨基酸；一种用于在衬底上无电镀敷镍合金层的方法，一种镍合金层以及一种包含镍合金层的物件。

Description

无电镍镀敷溶液
技术领域
本发明涉及一种无电镍镀敷溶液，一种用于在衬底上无电镀敷镍合金层的方法，一种可自所述镀敷溶液获得的镍合金层和一种包含这类层的物件。
背景技术
例如半导体晶片或半导体芯片的电子物件通常包含所谓的铜重布层(Cu-RDL)。重布层(RDL)为使得集成电路的输入衬垫或输出衬垫可用于其它部位的额外金属层。此使得芯片或晶片电路电连接至外部电路成为可能。电连接件的典型布局为可结合(可焊)连接件，例如被称为球状栅格数组和不同几何形状的衬垫。为了在Cu-RDL上产生可结合(可焊)表面，将镍层镀至其上。此层是出于防护原因(避免铜氧化和达成机械加强)和为了在Cu-RDL与沉积于其上的可结合(可焊)金属层之间产生扩散阻挡而形成的。将例如钯和任选的金层的其它金属层镀至镍层上以便获得可结合(可焊)表面，因此产生层的堆叠，也称为可结合堆叠。通过钯或金层与其它装置进行焊接连接。产生电子物件与例如印刷电路板或其它电路载体的衬底的焊接连接涉及在将堆叠加热至较高温度时施加至堆叠的热负荷。
进行镍层的退火以便测试所述层是否可承受在焊接制程期间施用的热应力。在退火之后，沉积于Cu RDL或可结合堆叠上的镍层和底层金属层通常展示分层，且层内另外出现断裂。这是造成较高电阻或降低的导电性或甚至不导电的原因。
具有不同组成的镍层自现有技术已知，还在其它应用中已知。用于线接合和覆晶焊接的无电镀镍钯金方法在现有技术中已知且于例如欧洲专利申请EP 0 701 281 A2中描述。类似方法于美国专利第6,445,069号和欧洲专利申请EP 1 126 519 A2中描述。
在现有技术EP 2 177 646 A1中，首先在晶片表面上涂布Cu或Al层，随后镀Ni-P和Pd(和任选的Au)。这可以在晶片表面的个别隔室(“衬垫”)上进行。
WO 2009092706 A2涉及一种将阻挡层沉积于金属表面上的溶液，其包含元素镍和钼的化合物、至少一种选自二级和三级环状氨基硼烷的第一还原剂、和至少一种络合剂，其中所述溶液的pH为8.5至12。
WO 2006102180 A2公开一种镍合金层。例如，镍基合金可为二元合金或三元合金，例如硼化镍(NiB)、磷化镍(NiP)、磷化镍钨(NiWP)、硼化镍钨(NiWB)、磷化镍钼(NiMoP)、硼化镍钼(NiMoB)、磷化镍铼(NiReP)、硼化镍铼(NiReB)。
本发明的目标
本发明的目标是产生一种具有降低的应力、尤其降低的拉伸应力和在退火之后增加的断裂韧性以防止底层金属层(尤其铜层或铝层)的分层和镍层的裂痕形成的镍沉积物。
发明内容
本发明提供一种无电镍镀敷溶液，一种无电镀方法，一种镍合金层，一种物件和一种根据独立技术方案的镀敷溶液的用途。其它实施例公开于附属权利要求书和本说明书中。
本发明的无电镍镀敷溶液包含
-镍离子源，
-钼离子源，
-钨离子源，
-次磷酸根离子源，
-络合剂，
-浓度为0.38-38.00μmol/L的至少一种有机含硫化合物，
-至少一种氨基酸，优选浓度为0.67-40.13mmol/L。
用于在衬底、尤其晶片上无电镀敷镍合金层的本发明方法包含使衬底与本发明的无电镍镀敷溶液接触。衬底尤其为半导体芯片或半导体晶片。
本发明的镍合金层包含：
-67.5至98.4wt％(重量百分比)、优选81.5至98.4wt％、更优选88至92wt％镍，
-1至10wt％、优选4至8.5wt％钼，
-0.1至4wt％、优选0.5至2wt％钨，
-0.5至4.5wt％、优选1.5至3wt％磷且优选不含其它合金化组分。
在一优选实施例中，镍合金层由以下各者组成：
-81.5至98.4wt％、优选88至92wt％镍，
-1至10wt％、优选4至8.5wt％钼，
-0.1至4wt％，优选0.5至2wt％钨，
-0.5至4.5wt％，优选1.5至3wt％磷和
-不含其它合金化组分。
在此背景下“不含”意味着可能自镍镀敷溶液共沉积的其它成分(例如硫与铅(Pb))的量总计为0至1wt％、优选为0至0.5wt％、更优选为0。在本发明的意义上，这些其它成分将不改变本发明层的特征。
以上镍层中所有成分的数量总计达100重量％(wt.％)，或换句话说，所有成分的总和不超过总共100重量％，在包含其它成分的情况下也是如此。如果包含其它成分，例如少量的其它合金化成分，那么镍、钼、钨和磷的wt％范围彼此的比率将不变化和彼此同等地减小。
当溶液用于镀这类层时或通过本发明的方法，本发明的镍合金层可自或自本发明的无电镍镀敷溶液获得。本发明的镍合金层优选为结晶镍合金层。
本发明的物件尤其为电子物件，具体来说半导体芯片或半导体晶片。所述物件包含本发明的镍合金层。所述物件通过或可通过本发明的方法获得。所述物件可包含层的堆叠，其具有如下次序：铜层或铝层，随后为镍合金层和钯和/或金层，其中钯层优选为外层。
半导体芯片为具有多个电子电路的小片半导体(通常为硅)晶体。半导体晶片包含多个半导体芯片。其被成形为来自半导体晶体锭的截块，其包含其携带的芯片的电路。
本发明的无电镍镀敷溶液允许沉积四元镍沉积物(NiMoWP)。四元镍沉积物显示降低的应力，尤其为降低的拉伸应力和提高的断裂韧性，尤其在例如在350-400℃下退火之后。
本发明尤其可用于制造具有Cu RDL(重布层)的电子物件，其中将镍沉积物镀至Cu-RDL上。
更具体来说，本发明可用于制造具有可结合金属涂层堆叠的电子物件，其中将堆叠涂布于铜或铝层上。典型堆叠可具有在铜或铝层上的如下金属层Ni/Pd(通过所谓的ENEP方法制得)、Ni/Pd/Au(通过所谓的ENEPIG方法制得)或Ni/Au(通过所谓的ENIG方法制得)，其中根据NiMoWP层，将Ni视为Ni合金层。通常，堆叠形成于Cu-RDL上，如在本申请的引言部分中所描述的，所述Cu-RDL为电子物件的部分。
本发明的镍镀敷溶液可尤其用于在两个金属层之间，具体来说在铜层或铝层与钯或金层之间产生阻挡层。
具体实施方式
本发明的无电镍镀敷溶液还称为无电镍浴液或无电镍镀浴液。术语溶液不排除一或多种组分可部分地以未溶解状态存在。
镍合金层还称作四元镍层或四元镍沉积物，所述四元层包含镍、钼、钨和磷。
如果在本说明书中层以金属命名，如“Pd层”或“Au层”，那么如果没有另外提及，那么这一术语还涵盖包含各别金属作为主要组分的合金。主要组分意味着组分构成至少50wt％。
当在本说明书和权利要求书中使用术语“包含”时，其不排除其它要素。出于本发明的目的，将术语“由…组成”视为术语“包含”的优选实施例。如果在下文中将群组定义为包含至少一特定数目的实施例或特征，那么也将这理解为公开优选仅由这些实施例或特征组成的群组。
在当提及单数名词时使用不定冠词或定冠词(例如“一(a)”、“一(an)”或“所述(the)”)的情况下，除非具体陈述其它某物，否则这包括多个所述名词。在本发明的上下文中，术语“约”或“大约”表示所属领域技术人员将理解仍确保所讨论的特征的技术效果的精确度间隔。所述术语通常指示自指定数值偏离±10％，且优选偏离±5％。
术语“至少一个”涵盖“正好一个”或“一个”的特殊情况。
本说明书中所给出的浓度范围是指所有提及的化合物总计的总量。换句话说，如果例如使用两种有机含硫化合物，那么所有单一有机含硫化合物一起的总浓度将不超出给定浓度范围。
在如下详细描述中，展示本发明的方面和特定实施例。
镀敷溶液
本发明的镀敷溶液可用于将本发明的镍合金层沉积至衬底上，尤其沉积至半导体晶片上或芯片上。本发明的特定物件描述于下文中。本发明的镀敷溶液可用于制造这些物件中的任一者。本发明的溶液可尤其用于在两个金属层之间，例如在铜层或铝层与另一金属层之间产生阻挡层(扩散阻挡)，以便防止铜迁移至另一金属中。另一金属为例如钯或金。
镍离子源
在一实施例中，镍离子的浓度为0.067-0.133mol/L、优选地为0.084-0.116mol/L。
在另一个实施例中，镍离子的浓度为4.0-8.0g/L、优选地为5.0-7.0g/L。
镍离子源可为一或多种化合物，其包含镍且其传递镍离子以使得可将镍并入至待形成的NiMoWP层中。在一特定实施例中，镍离子源为NiSO4×6H2O。
当镍离子源为NiSO4×6H2O时，NiSO4×6H2O的浓度可为17.53-35.05g/L、优选地为21.91-30.69g/L。
钼离子源
在一实施例中，钼离子的浓度为1.05-4.18mmol/L、优选地为1.58-3.66mmol/L。
在另一个实施例中，钼离子的浓度为0.1-0.4g/L、优选地为0.15-0.35g/L。
钼离子源可为一或多种化合物，其包含钼且其传递含有钼的离子以使得可将钼并入至待形成的NiMoWP层中。优选地，钼离子源为二水合钼酸钠。
当钼离子源为二水合钼酸钠时，二水合钼酸钠的浓度可为0.25-1.00g/L、优选地为0.38-0.88g/L。
钨离子源
在一实施例中，钨离子的浓度为12.1-109.2mmol/L、优选地为24.2-97.1mmol/L。
在另一个实施例中，钨离子的浓度为2.23-20.07g/L，优选地为4.46-17.84g/L。
钨离子源可为一或多种化合物，其包含钨且其传递含有钨的离子以使得可将钨并入至待形成的NiMoWP层中。例如，钨离子源为二水合钨酸钠。
当钨离子源为二水合钨酸钠时，二水合钨酸钠的浓度可为4.0-36.0g/L、优选地为8.0-32.0g/L。
次磷酸根离子源
次磷酸根用作还原剂，用于还原镍、钼和钨。
本发明的溶液优选不包含或含有除次磷酸根外的任何其它还原剂。本发明的溶液优选不包含任何包含硼的还原剂，尤其不包含二甲胺硼烷(DMAB)。
在一实施例中，次磷酸根离子的浓度为0.09-0.27mol/L，优选地为0.11-0.23mol/L。
在另一个实施例中，次磷酸根离子的浓度为5.85-17.55g/L，优选地为7.15-14.95g/L。
次磷酸根离子源可为一或多种化合物，其包含次磷酸盐且其传递磷以将磷并入至待形成的NiMoWP层中。次磷酸根离子源可为次磷酸或其浴可溶性盐(bath soluble salt)，例如次磷酸钠、次磷酸钾和次磷酸铵。例如，次磷酸根离子源为次磷酸钠。
当次磷酸根离子源为次磷酸钠时，次磷酸钠的浓度可为10.0-30.0g/L，优选地为12.7-26.3g/L。
络合剂
如果使用一种以上络合剂，那么如下浓度涉及所有络合剂的总量。
在一实施例中，络合剂的浓度为0.095-0.178mol/L，优选地为0.109-0.164mol/L。
络合剂可为羧酸。适用的羧酸包括单羧酸、二羧酸、三羧酸和四羧酸。羧酸可经例如羟基或氨基的各种取代基部分取代，且酸可以其钠盐、钾盐或铵盐形式引入至镀敷溶液中。
可用作本发明溶液中的络合剂的羧酸的实例包括：单羧酸，例如乙酸、羟基乙酸(乙醇酸)、氨基乙酸(甘氨酸)、2-氨基丙酸(丙氨酸)、2-羟基丙酸(乳酸)；二羧酸，例如丁二酸、氨基丁二酸(天冬氨酸)、羟基丁二酸(苹果酸)、丙烷二酸(丙二酸)、酒石酸；三羧酸，例如2-羟基-1,2,3-丙烷三甲酸(柠檬酸)；和四羧酸，例如乙二胺四乙酸(EDTA)。在一个实施例中，将上述络合剂/螯合剂中的两者或更多者的混合物用于本发明的溶液中。
络合剂可特别选自由以下组成的群组：柠檬酸、异柠檬酸、EDTA、EDTMP、HDEP和焦磷酸盐。
络合剂可为适合于碱性pH的络合剂。
在一特定实施例中，络合剂为柠檬酸。
当络合剂为柠檬酸时，柠檬酸的浓度可为18.4-34.4g/L(或在单水合柠檬酸的情况下为20.1-37.6g/L)、优选地为21.1-31.5g/L(或在单水合柠檬酸的情况下为23.1-34.6g/L)。
有机含硫化合物
使用有机含硫化合物、优选含有二价硫的化合物作为用于镀敷溶液的稳定剂。稳定剂实现在不需要镀敷的衬底区域中没有发生或只发生较少镀敷，例如在未提供开放区域的半导体衬底的钝化时。另外，其可增加浴液稳定性以防止浴液自我组合。
如果使用超过一种含硫化合物，那么如下浓度涉及所有含硫化合物的总量。
在一实施例中，有机含硫化合物选自由以下组成的群组：N,N-二甲基-二硫代氨甲酰基丙基磺酸、3-巯基丙烷磺酸、3,3-二硫代双1-丙烷磺酸、3-(2-苯并噻唑基巯基)丙烷磺酸、3-[(乙氧基-硫酮基甲基)硫代]-1-丙烷磺酸、3-S-异锍脲丙烷磺酸盐、二乙基-二硫代氨甲酸钠、硫代二乙酸、二硫代二乙酸、硫代二乙醇酸、二硫代二乙醇酸、硫代硫酸盐、硫脲、硫代氰酸盐、半胱氨酸(如果镀敷溶液中的氨基酸不为半胱氨酸)或胱氨酸。
有机含硫化合物的浓度为0.38-38.00μmol/L、优选地为1.9-19.0μmol/L。实验已显示，本发明范围内的既定范围为最佳工作范围。更高和显著更高浓度的有机含硫化合物不起作用且导致不合需要的结果。
在另一个实施例中，有机含硫化合物包含至少一个具有一或多个(例如在硫化物基团中的)自由电子对的硫原子。在一更特定实施例中，具有一或多个自由电子对的硫原子的浓度为0.38-38.00μmol/L、优选地为1.9-19.0μmol/L。
在另一个更特定实施例中，有机含硫化合物为N,N-二甲基-二硫代氨甲酰基丙基磺酸且浓度为0.1至10.0mg/L、优选地为0.5至5.0mg/L。
氨基酸
如果使用超过一种氨基酸，那么如下浓度涉及所有氨基酸的总量。
氨基酸用作应力降低添加剂。这意味着镀层中的拉伸应力降低。
在一实施例中，氨基酸为不含硫的氨基酸。优选地，氨基酸选自由甘氨酸和具有未经取代的碳水化合物侧链的氨基酸组成的群组。在一特定实施例中，氨基酸选自由甘氨酸、丙氨酸、缬氨酸、亮氨酸或异亮氨酸组成的群组。
在一实施例中，氨基酸的浓度为0.67-40.13mmol/L，优选地为5.36-26.75mmol/L。
在一更特定实施例中，氨基酸为甘氨酸且浓度为0.05-3.00g/L，优选地为0.4-2.0g/L。
氨基酸与有机含硫化合物的比率
如果使用其中超过一者，那么如下比率涉及所有含硫化合物的总和和所有氨基酸的总和。
在一实施例中，氨基酸与有机含硫化合物的摩尔比，优选地，氨基酸与具有一或多个自由电子对的硫原子的比率为282:1-14,079:1，更优选地在此优选比率内，至少一种有机含硫化合物的浓度为1.9-19.00μmol/L，和至少一种氨基酸的浓度为5.36-26.75mmol/L。
在一特定实施例中，氨基酸为甘氨酸且有机含硫化合物为N,N-二甲基-二硫代氨甲酰基丙基磺酸，且甘氨酸与N,N-二甲基-二硫代氨甲酰基丙基磺酸的摩尔比为2,000:1-5,000:1。
溶液的任选的成分
溶液可包含例如硫酸的酸作为其它成分。
溶液可包含例如氢氧化钠的碱作为其它成分。
溶液可包含一或多种稳定剂，例如Pb离子源、Sn离子源、Sb离子源、Zn离子源、Cd离子源和/或Bi离子源。这类稳定剂防止自催化无电镍镀敷溶液的自发性自我分解。
Pb离子源、Sn离子源、Sb离子源、Zn离子源、Cd离子源和/或Bi离子源可为一或多种化合物，其包含这些离子中的一或多者且其传递Pb离子、Sn离子、Sb离子、Zn离子、Cd离子和/或Bi离子。这些离子可适宜地以可溶和相容盐(例如乙酸盐等)的形式引入。
在一个实施例中，Pb离子、Sn离子、Sb离子和/或Bi离子的浓度为0.49-49.0μmol/L、优选地为2.45-24.50μmol/L。这一浓度涉及所有Pb离子、Sn离子、Sb离子和/或Bi离子的总和。
在另一个实施例中，Pb离子、Sn离子、Sb离子和/或Bi离子的浓度为0.1至10.0mg/L、优选地为0.5至5.0mg/L。这一浓度涉及所有Pb离子、Sn离子、Sb离子和/或Bi离子的总和。
在一特定实施例中，铅离子源为硝酸铅，且硝酸铅浓度为0.16-16.00mg/L、优选地为0.8-8.00mg/L。
其它材料可包括于镍镀敷溶液中，例如缓冲剂、湿润剂、加速剂、抑制剂、光亮剂等。所述等材料为所属领域中已知。
溶液的其它特性
溶液的pH可在7-11、优选地在8-10的范围内。
本发明的方法
在本发明的方法中，可使用本文所描述的本发明的任何溶液。
衬底尤其为半导体芯片或半导体晶片。通过在衬底上镀镍合金层将衬底转化成本发明的物件。因此，衬底和物件由本发明的镍合金层区分。晶片或芯片可为方法中的衬底且特可为本发明的物件，其中这两者由镍合金层区分。换句话说，即使添加本发明的镍合金层或任何其它金属层，晶片或芯片仍称为晶片或芯片。
本发明的方法可用于在另一金属上，优选地在铜或铝上沉积镍层。在一特定实施例中，衬底包含铜层或铝层，其中镍合金层镀于铜层上或铝层上。铜层或铝层可在衬底的整个表面或表面的一部分上方延伸。
在一特定实施例中，衬底为半导体晶片或芯片，所述晶片或芯片包含铜层或铝层。
在一个实施例中，所述方法进一步包含：在镍合金层上镀敷钯层。可镀敷钯层以便获得可结合(可焊)表面。
在另一个实施例中，所述方法进一步包含：在钯上或在镍层上镀敷金层。
所述方法可涉及所谓的“凸块下金属化”(UBM)。UBM已鉴于晶片级微型化、电信号完整性和金属堆叠可靠性的最新需求被开发出来。
UBM方法可一般分成四个不同部分：
第一部分涉及预处理且包括对提及的铜或铝层的表面，例如Al/Al-合金和Cu衬垫的表面进行表面准备。为了预处理Al，可采用不同的浸锌处理，例如XenolyteTM清洁器ACATM、Xenolyte Etch MATM、Xenolyte CFATM或Xenolyte CFTM(全部均可购自AtotechDeutschland GmbH)，其满足无氰化物化学方法的工业标准。
UBM方法中的第二部分涉及无电镍镀。
可优选在T＝40℃-90℃、更优选75℃-87℃的温度下执行镍合金层的无电镀。此温度为本发明溶液的温度。
本发明的溶液与经镀敷的衬底的接触持续时间为取决于镍合金的所需厚度的函数。通常，接触时间可在1至30分钟范围内。
在本发明的方法中，为了在衬底上镀镍合金层，衬底优选浸没于本发明的溶液中。
在镍合金的沉积期间，可采用轻度搅动，且这一搅动可为轻度空气搅动、机械搅动、通过泵抽的浴液循环、滚筒电镀的旋转等。本发明溶液还可经历周期性或连续过滤处理以降低其中污染物的含量。在一些实施例中，还可定期或连续地补充浴液成分以保持成分的浓度，尤其镍离子和次磷酸根离子的浓度以及在所需极限内的pH水平。
UBM方法的第三步包含自无电钯镀浴液进行镀敷。
无电钯浴液于例如US5882736A中描述。对于在较低温度下的Pd镀敷来说，活化镍合金层的步骤可任选地在无电Pd镀敷步骤之前进行。
用于无电Pd镀敷的适用浴液参数如下：
pH：优选地为5至6.5、更优选地为5.6至6.0
浴液温度：优选地为70℃至90℃，更优选地为82℃至87℃
浸没时间：优选地为3至20分钟、更优选地为5至10分钟
额外稳定剂：优选地为10至500mg/L，更优选地为100至300mg/L。
如果在无电Pd镀敷步骤之前进行活化步骤，那么Pd镀敷浴液温度可低至约40℃(和至多约95℃)。这类活化可例如通过所谓的离子生成性Pd活化剂达成，所述等活化剂通常为酸性，含有例如PdCl2或PdSO4的Pd2+源，且沉积元素Pd的晶种层于Ni合金层上。这类活化剂已为所属领域技术人员众所周知的且可作为溶液在商标Xenolyte Activator ACU1TM(Atotech Deutschland GmbH的产品)下市售。其中Pd簇由Sn包围的所谓的胶态酸性活化剂同样为众所周知的且也可使用。
可使用如EP 0 698 130中所描述的在目前先进技术的无电钯浴液中的额外稳定剂以便在本发明的镍合金层上沉积钯而无任何额外活化。此外，这类稳定剂允许在70℃与90℃之间的温度下无电沉积钯，其导致所沉积的钯层的内部应力降低。已知的无电钯浴液在这类高浴液温度下展示短寿命，其在工业应用中是不可忍受的。其它稳定剂选自包含以下的群组：磺酰亚胺、聚苯硫醚、嘧啶、多元醇和无机络合剂，如硫氰化物。优选的磺酰亚胺为糖精，优选的嘧啶为烟碱酰胺、嘧啶-3-磺酸、烟碱酸、2-羟基吡啶和烟碱。优选的多元醇为聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物和其衍生物。
最后，任选的金层可镀敷于Ni合金/Pd堆叠上。出于此目的，可使用自现有技术已知的无电镀金电解质。钯层顶部上的任选的金层的厚度为0.01至0.5μm，优选地为0.05至0.3μm。任选的金层最优选通过浸没方法沉积。用于无电镀金的适合浴液可在商标AurotechSFplusTM(T＝80至90℃；pH＝4.5至6.0；浸没时间＝7至15分钟；0.5至2g/l Au)(作为K[Au(CN)2])下市售。
如果经Al涂布的晶片在本发明中用作起始衬底，那么方法优选包含如下步骤：清洁，蚀刻，浸锌处理(作为预处理步骤)，随后镀镍合金，任选的活化镍合金层，镀钯和任选的镀金。
如果经Cu涂布的晶片用作起始衬底，那么任选的预处理优选包含如下步骤：清洁，任选的蚀刻和Pd活化，任选的随后再次进行如下步骤：镀镍，任选的活化镍合金层，镀钯和任选的镀金。
本发明的镍合金层和其它产物
当溶液用于镀敷这类层时或通过如上文所述的方法，本发明的镍合金层可自或是自上文所述的无电镍镀敷溶液获得。
镍合金层可用作在两个金属层之间，例如铜层与另一金属层之间的阻挡层，以便防止铜迁移至另一金属中。另一金属为例如钯或金。
在一个实施例中，镍合金层展示在-40至+120N/mm2范围内、优选地在-20至+40N/mm2范围内的正应力。具有正值的正应力还被称为拉伸应力。具有负值的正应力还被称为压缩应力。正应力是通过弯带法(Bent Strip Method)测量：于Cu应力带(铜-铁合金PN:1194)上沉积，随后使用沉积物应力分析仪(Deposit Stress Analyzer)(A STM标准B975)测定应力。
在一实施例中，本发明的镍合金层具有在0.1-5μm、优选地0.5-3μm范围内的厚度。
本发明的物件是通过或可通过本发明的方法获得。
在一个实施例中，本发明的物件包含铜层或铝层，且镍合金层安置于铜层上或铝层上。
因此，本发明的物件可包含如下层：
铜层或铝层/(本发明的)镍合金层，
其中本发明的镍合金层优选为外层，也就是说包含自由的可接近的表面。
符号“/”意味着与这一符号邻近的层彼此接触，也就是为相邻层。
本发明的物件可进一步包含钯层，其中将钯层安置于镍合金层上。因此，物件可以如下次序包含如下层堆叠：
铜层或铝层/(本发明的)镍合金层/钯层
其中钯层优选为外层，也就是包含自由的可接近的表面。可通过钯层产生与其它装置(例如电路载体或印刷电路板)的焊接连接。
镍合金层可用作铜层与钯层之间的阻挡层，以便防止铜迁移至钯中。
本发明的物件可进一步包含金层，其中金层直接安置于镍层上或钯层上。因此，本发明的物件可包含如下层堆叠：
铜层或铝层/(本发明的)镍合金层/金层
或铜层或铝层/(本发明的)镍合金层/钯层/金层
其中金层优选为外层，也就是包含自由的可接近的表面。可通过金层产生与其它装置(例如电路载体或印刷电路板)的焊接连接。
所提及的层可在整个表面或表面的一部分上方延伸。例如，铜层可在衬底或物件的表面的一部分或整个表面上方延伸。镍合金层可在铜层的表面的一部分或整个表面上方延伸。钯层可在镍合金层的表面的一部分或整个表面上方延伸。金层可在钯层的表面的一部分或整个表面上方延伸。
本发明的物件可进一步包含焊球的栅格数组，也称为球状栅格数组。焊球优选地位于上述钯层的表面上或上述金层的表面上。
附图说明
图1展示本发明的对象物件。
实例
方法
应力测量
正应力通过弯带法测量：于Cu应力带(铜铁合金PN:1194)上沉积，随后使用沉积物应力分析仪(ASTM标准B975)测定应力。
破裂韧性
使用Vickers经Fischerscope H100C进行压痕测试。在10分钟的时期(排除加热和冷却)内将待测试的镍层退火至400℃的温度。随后，将Vickers压痕器(用于测定Vickers硬度的试样)以1N的最大负载、4秒的保持时间和dF/dt＝+/-0.5N/s的装载/移除速率按压至层中。随后通过光学显微法检查压痕。
实例1：本发明的镀敷溶液的组分
在水中混合如下成分
实例2：层组成
实例2通过使用实例1的溶液展示来自六个不同沉积的层的组成。各沉积的镀敷时间为10分钟。
实例3：基于硼的还原剂的添加
实例3涉及使用本发明溶液的所有化合物的比较实例，但其中将还原剂次磷酸盐与增加量的DMAB(二甲氨硼烷)混合在一起。
如下镀敷溶液用于实例3中：2L来自实例1的浴液，在250rpm、88℃下搅拌。镀敷时间连续减少以获得相当的Ni厚度。
实例2a为根据本发明的实例。添加增加量的DMAB至上文所指示的镀敷溶液中以作为其它还原剂(2c-e)。
实验表明，与本发明相比，即使在本发明溶液中的N,N-二甲基-二硫代氨甲酰基丙基磺酸和甘氨酸的组合和浓度与DMAB组合使用，也不会导致应力降低。
添加基于硼的还原剂大幅度降低层的应力特性。
实例4：氨基酸的变化
实例4涉及使用具有不同量的氨基酸丙氨酸的本发明溶液的实例。
使用如下镀敷溶液：来自实例1的浴液，在250rpm、88℃下搅拌，但具有如下添加剂组合：
在所有实验中，镀敷时间为8分钟。实验展示增加量的丙氨酸改良(降低)应力，且使得有可能到达可为有益的压缩应力区(负值)，这是因为当层经加热时，应力增加且可能产生约零或零周围的区域中的值。
实例5：含硫化合物的量和量和氨基酸甘氨酸的变化
来自实例1的浴液，在250rpm、88℃、pH＝9.5、10分钟镀敷时间下搅拌，但具有如下添加剂组合：
5.1 N,N-二甲基-二硫代氨甲酰基丙基磺酸与甘氨酸的组合
前两个实验为比较实例，此处的镀浴仅包含N,N-二甲基-二硫代氨甲酰基丙基磺酸或甘氨酸中的一者。
展示两者的组合以协同方式改良层的应力特性。
5.2胱氨酸与甘氨酸的组合
无甘氨酸的两个实验为比较实例。
展示在不同量的胱氨酸下，增加量的甘氨酸以协同方式改良层的应力特性。
实例6：破裂韧性
所有样本已在400℃下退火10分钟。
如以上方法中所描述进行破裂韧性测试。本发明的层变得明显更坚韧且展示在压刻之后无裂痕。
在比较实例1和2中，缺少Mo和W，其中实例1表示具有约8.2wt.％的中等P含量的常见标准二元NiP层。这一层在压刻之后产生裂痕。实例2也是二元NiP层且甚至展示与本发明的层相同的P含量，但相比之下，其在压刻之后展示裂痕。
比较实例3为比较实例，因为P含量高于本发明中的P含量。
实例5为具有相对较高量的磷但在本发明的范围内的实例。
实例6为在相对较低量的钨存在下就本发明来说具有较少磷的实例。
实例7为也在少量钨和钼两者存在下就本发明来说具有中等P含量的实例。
图1展示(不按照比例)包含镍合金层5的本发明的电子物件1。通过使包含晶片3和铜层4的衬底2与本发明的镀敷溶液接触来制造镍合金层5。
当用本发明的镀敷溶液接触衬底2的铜层4时，将镍合金层5镀于铜层4上。在另一个方法步骤中，任选地将钯层6镀于镍合金层5上。
在所表示层堆叠中，镍合金层5充当铜层4与钯层6之间的阻挡层。
任选地将金层7镀于钯层6上，和将焊球8置放于作为球状栅格数组的部分的金层7上。此处仅展示晶片3的一部分。晶片3包含在不同位置处的若干层堆叠4、5、6、7，各层堆叠均包含焊球8。晶片可包含晶片表面的个别隔室(“衬垫”)且各隔室可包含层堆叠4、5、6、7，如此处在一个实例中所展示。

Claims (20)

1.一种无电镍镀敷溶液，其包含
-镍离子源，
-钼离子源，
-钨离子源，
-次磷酸根离子源，
-至少一种络合剂，
-浓度为0.38-38.00μmol/L的至少一种有机含硫化合物，和
-浓度为0.67-40.13mmol/L的至少一种氨基酸，
其中所述溶液不包含任何包含硼的还原剂，并且
其中所述氨基酸为不含硫的氨基酸。
2.根据权利要求1所述的镀敷溶液，其中氨基酸与有机含硫化合物的摩尔比为282:1至14,079:1。
3.根据权利要求1或2所述的镀敷溶液，其中次磷酸根离子的浓度为0.09-0.27mol/L。
4.根据权利要求1或2所述的镀敷溶液，其中镍离子的浓度为0.067-0.133mol/L。
5.根据权利要求1或2所述的镀敷溶液，其中钼离子的浓度为1.05-4.18mmol/L。
6.根据权利要求1或2所述的镀敷溶液，其中钨离子的浓度为12.1-109.2mmol/L。
7.根据权利要求1或2所述的镀敷溶液，其中所述氨基酸选自由甘氨酸、丙氨酸、缬氨酸、亮氨酸和异亮氨酸组成的群组。
8.根据权利要求1或2所述的镀敷溶液，其中所述有机含硫化合物选自由以下组成的群组：N,N-二甲基-二硫代氨甲酰基丙基磺酸、3-巯基丙烷磺酸、3,3-二硫代双-1-丙烷磺酸、3-(2-苯并噻唑基巯基)丙烷磺酸、3-[(乙氧基-硫酮基甲基)硫代]-1-丙烷磺酸、3-S-异锍脲丙烷磺酸盐、二乙基二硫代氨甲酸钠、硫代二乙酸、二硫代二乙酸、硫代二乙醇酸、二硫代二乙醇酸、硫代硫酸盐、硫脲、硫代氰酸盐、半胱氨酸和胱氨酸。
9.根据权利要求1或2所述的镀敷溶液，其中所述络合剂选自由以下组成的群组：柠檬酸、异柠檬酸、EDTA、EDTMP、HDEP和焦磷酸盐。
10.一种在衬底(2)上无电镀敷镍合金层(5)的方法，所述方法包含使所述衬底与根据权利要求1至9中一或多个权利要求所述的无电镍镀敷溶液接触。
11.根据权利要求10所述的方法，其中所述衬底是晶片。
12.根据权利要求10所述的方法，其中所述衬底包含铜层(4)或铝层，其中将所述镍合金层(5)镀敷于所述铜层(4)或所述铝层上。
13.一种由根据权利要求1至9中一或多个权利要求所述的无电镍镀敷溶液得到的四元镍合金层，其包含
-81.5至98.4wt％镍
-1至10wt％钼
-0.1至4wt％钨
-0.5至4.5wt％磷，
其中所述镍合金层具有在-40至+120N/mm2范围内的正应力，其通过以下弯带法测量：于Cu应力带上沉积，随后使用沉积物应力分析仪A STM标准B975测定应力。
14.根据权利要求13所述的四元镍合金层，其中所述Cu应力带是铜铁合金PN:1194。
15.一种物件(1)，其包含镍合金层(5)，其中所述镍合金层为根据权利要求13所述的镍合金层或根据权利要求10或12所述的方法获得的镍合金层。
16.根据权利要求15所述的物件，其中所述物件是半导体芯片或晶片。
17.根据权利要求15所述的物件，其中所述物件包含如下次序的层堆叠：
铜层或铝层，随后为所述镍合金层和钯和/或金层。
18.根据权利要求17所述的物件，其中所述钯层为外层。
19.一种根据权利要求1至9中一或多个权利要求所述的无电镍镀敷溶液的用途，其用于制造在两个金属层之间的根据权利要求13的阻挡层。
20.根据权利要求19所述的用途，其中所述阻挡层在铜层或铝层与钯或金层之间。
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