CN103053228B - 用于在衬底上形成焊料沉积和非熔融凸块结构的方法 - Google Patents
用于在衬底上形成焊料沉积和非熔融凸块结构的方法 Download PDFInfo
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- CN103053228B CN103053228B CN201180038004.3A CN201180038004A CN103053228B CN 103053228 B CN103053228 B CN 103053228B CN 201180038004 A CN201180038004 A CN 201180038004A CN 103053228 B CN103053228 B CN 103053228B
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
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- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
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- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4007—Surface contacts, e.g. bumps
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3473—Plating of solder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/4853—Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
- H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/11—Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
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Abstract
描述一种将金属或者金属合金层形成到衬底上的方法,该方法包括以下步骤:i)提供衬底(102),该衬底(102)包括在至少一个接触区域(101)顶部上的持久树脂层(103)和在持久树脂层顶部上的临时树脂层(104),ii)使包括至少一个接触区域的整个衬底区域与适合于在衬底表面上提供传导层(106)的溶液接触,并且iii)将金属或者金属合金层(107)电镀到传导层上。
Description
技术领域
本发明涉及通过电镀形成焊料沉积,特别地涉及倒装芯片封装(flip chippackage),更特别地涉及通过电镀的金属或者金属合金形成的倒装芯片接头(flip chipjoint)和板到板焊点(solder joint)。
背景技术
自从IBM于20世纪60年代早期引入倒装芯片技术,倒装芯片器件已经安装于昂贵陶瓷衬底上,其中在硅芯片与陶瓷衬底之间的热膨胀失配的不太关键。与引线键合技术比较,倒装芯片技术能够更好地通过更高封装密度(更低器件轮廓)和更高电性能(更短可能的引线和更低电感)。在这一基础上,过去40年已经在陶瓷衬底上使用高温焊料(可控塌陷芯片连接C4)在工业上实现了倒装芯片技术。然而近年来,受用于现代电子产品小型化趋势的高密度、高速度和低成本半导体器件的需求驱动,为了减轻在硅芯片与有机板结构之间的热膨胀失配所引起的热应力而用环氧树脂底部填充剂(epoxy underfill)在低成本有机电路板(例如印刷电路板或者衬底)上安装的倒装芯片器件已经经历明显的爆炸式增长。低温倒装芯片接头和基于有机物的电路板的这一显著问世已经使当前产业能够获得用于制作倒装芯片器件的廉价解决方案。
在当前低成本倒装芯片技术中,半导体集成电路(IC)芯片的顶表面具有电接触焊盘(pad)阵列。有机电路板也具有对应接触网格。在芯片与电路板之间放置并且恰当对准低温焊料凸块(solder bump)或者其他传导粘合材料。颠倒翻转并且在电路板上安装芯片,其中焊料凸块或者传导粘合材料提供在芯片与电路板之间的电输入/输出(I/O)和机械互连。对于焊料凸块接头,有机底部填充剂密封剂可以进一步分配到在芯片与电路板之间的间隙中以约束热失配并且降低对焊点的应力。
一般而言,为了通过焊点实现倒装芯片装配,普遍在芯片的焊盘电极表面上预成形金属凸块,诸如焊料凸块、金凸块或者铜凸块,其中凸块可以是任何形状、诸如立柱凸块、球凸块、柱状凸块或者其他形状。通常使用低温焊料也在电路板的接触区域上形成对应焊料凸块(或者称为预焊料(presolder)凸块)。在回流(reflow)温度,借助焊点将芯片键合到电路板。在分配底部填充剂密封剂之后,因此构造了倒装芯片器件。这样的方法在本领域中众所周知,并且例如在US 7,098,126中描述了使用焊点的倒装芯片器件的典型示例。
目前,用于在电路板上形成预焊料凸块的最普遍方法是模板印刷(stencilprintin)方法。关于模板印刷方法的一些在先提议可以参照US 5,203,075、US 5,492,266和US 5,828,128。用于倒装芯片组件的焊料凸块化技术需要关于凸块间距(pitch)和尺寸小型化的设计考虑。根据实践经验,一旦凸块间距减少至0.15毫米以下,模板印刷将变得不可行。对照而言,通过电镀沉积的焊料凸块通过了用于将凸块间距进一步减少下至0.15毫米以下的能力。可以在US 5,391,514和US 5,480,835中发现关于用于倒装芯片键合的电路板上的电镀凸块的在先提议。虽然电路板上的电镀焊料凸块化提供相对于模板印刷更细微的凸块间距,但是它带来针对初始实施的若干挑战。
在US 7,098,126中描述用于在有机衬底上形成焊料的多步过程。在该方法中,有初始提供的有机电路板,该有机电路板包含承载电路的表面,该表面包括至少一个接触区域。在板表面上放置并且图案化焊料掩模层以暴露焊盘。随后通过物理气相沉积、化学气相沉积、使用催化铜(catalytic copper)的化学镀(electroless plating)或者使用催化铜的电镀在板表面之上沉积金属种子层。在金属种子层之上形成并且然后图案化抗蚀层。然后通过电镀在开口中形成焊料材料。最后,去除抗蚀剂和在抗蚀剂之下的金属种子层。为了应用这一方法,需要各种图案化步骤,这从过程效率的总体观点来看是不希望的。每个图案化步骤是失配的图案的潜在起因。另外,如果在相邻接触区域之间的距离(间距)由于电子器件的小型化而很小,则该方法具有它的限制。
在US 2006/0219567 A1中公开一种电路板的传导凸块结构的制作方法。将焊料材料电镀到部分地由图案化的焊料掩模保护的衬底上。接着将抗蚀剂沉积到焊料材料层上。然后以在后继蚀刻步骤期间保护焊料材料涂覆的连接焊盘的方式图案化抗蚀剂。然后蚀刻掉焊料贮存(solder depot)不需要的焊料材料,从而仅在连接焊盘上方留下抗蚀剂保护的焊料贮存。接着去除抗蚀剂。
欧洲专利申请EP 2 180 770 A1公开一种用于形成焊料沉积层的方法,其中将焊料树脂层沉积到具有接触区域的衬底上。图案化所述焊料树脂层以便暴露所述接触区域。接着将附加树脂层沉积到图案化的焊料树脂层上并且再次图案化附加树脂层。这一方法可能在小的接触面积大小和窄的间距距离的情况下导致个别图案化的焊料树脂层和附加树脂层的未对准。
发明内容
因此本发明的目的是采用一种用于在衬底上产生焊料沉积的均匀层的锡和锡合金的电镀方法以及因此适合的镀锡镀液(bath)组成。这样的镀制方法应当适合于填充拥有高纵横比的凹进结构而未留下空隙或者凹陷。
本发明的另一目的是提供非熔融凸块结构。
本发明的另一目的是提供一种用于焊料沉积和非熔融凸块结构的形成的方法,该方法具有减少的镀制步骤的数量并且即使在焊料抗蚀剂开口具有不同尺度时仍然通行地适用。
本发明的另一目的是提供一种避免图案未对准的用于焊料沉积和非熔融凸块结构形成的方法。
概括而言,公开一种用于在衬底上制作电镀焊料沉积和非熔融凸块结构用于形成倒装芯片接头和板到板焊点的方法。根据本发明,提供包括至少一个接触区域的非传导衬底,比如电路板。
用临时树脂层涂覆具有由持久树脂层覆盖的至少一个接触区域的衬底。通过诸如激光钻孔、等离子体蚀刻、电火花腐蚀和机械钻孔的方法在衬底中生成接触区域开口以便暴露至少一个接触区域。
接着,然后在衬底的传导区域上镀制包含金属或者金属合金的层以形成焊料沉积或者非熔融凸块结构。
附图说明
图1示出了根据在本领域中已知的过程的具有未对准的接触区域开口的两步形成。
图2示出了根据本发明的用于在衬底上获得金属或者金属合金层的方法。
图3示出了用于获得具有可焊接覆层(cap layer)的非熔融凸块结构的方法。
图4示出了用于获得具有可焊接覆层的非熔融凸块结构的另一方法。
图5示出了用于获得具有可焊接覆层的非熔融凸块结构的又一方法。
图6示出了用于获得非熔融凸块结构的方法,这些非熔融凸块结构具有由阻挡层分离的可焊接覆层。
图7示出了回流的焊料沉积和非熔融凸块结构。
(101) 接触区域
(102) 非传导衬底
(103) 持久树脂层
(104) 临时树脂层
(105) 接触区域开口
(106) 第一传导种子层
(107) 金属或者金属合金层
(108) 回流的焊料沉积层
(109) 焊料树脂层
(110) 焊料树脂开口
(111) 临时树脂开口
(112) 非熔融凸块结构
(113) 可焊接覆层
(114) 抗蚀剂层
(115) 阻挡层
(116) 第二传导种子层
(117) 保护层。
具体实施方式
本发明提供一种通过电镀金属或者金属合金层在衬底上形成金属层的方法。该过程特别适合于在具有良好镀制均匀性的电路板上制作焊料凸块和非熔融凸块结构。下文更详细地描述该方法。这里所示图仅举例说明该过程。图未按比例绘制,即它们未反映芯片封装结构中的各种层的实际尺寸或者特征。同样标号贯穿说明书指代同样单元。
现在参照图2,根据本发明的一个优选实施例,提供一种非传导衬底(102),该非传导衬底(102)具有嵌入式接触焊盘作为接触区域(101)实施例(图2a)。至少一个接触区域(101)可以是接触焊盘、通路或者沟槽。非传导衬底(102)可以是电路板,该电路板可以由有机材料或者纤维增强的有机材料或者颗粒增强的有机材料、例如环氧树脂、聚酰亚胺、双马来酰亚胺三嗪(bismeleimide triazine)、氰酸酯、聚苯并环丁烯(polybenzocyclobutene)或者其玻璃纤维化合物等制成。非传导衬底(102)也可以是晶片或者重新分布的晶片的部分。在这样的情况下,例如电介质材料的非传导表面附着到至少一个接触区域上,从而导致如图2a中所示结构。
至少一个接触区域(101)通常由金属材料形成,金属材料诸如铜。可选地,第一阻挡层形成于至少一个接触区域(101)上并且可以例如是镍、镍合金的粘合层或者金的保护层。所述第一阻挡层也可以由镍、铬、钛、银、金、钯、其合金及其多层制成,其可以通过电镀、化学镀、物理气相沉积或者化学气相沉积制成。
至少一个接触区域(101)由至少一个持久树脂层(103)覆盖,该至少一个持久树脂层(103)优选地由有机材料或者纤维增强的有机材料或者颗粒增强的有机材料等制成,这些材料例如环氧树脂、聚酰亚胺、双马来酰亚胺三嗪、氰酸酯、聚苯并环丁烯或者其玻璃纤维化合物等。
在本发明的一个实施例中,持久树脂层(103)是焊料树脂层。
接着将至少一个临时树脂层(104)沉积到至少一个持久树脂层(103)上(图2b)。从诸如干膜抗蚀剂、液体抗蚀剂和可印刷树脂(printable resin)之类的材料选择至少一个临时树脂层(104)。
可以从聚合物材料选择临时树脂层(104),该聚合物材料选自丙烯酸酯、乙烯/乙醛共聚物(EEAC)、乙烯/甲基丙烯酸酯共聚物(EMA)、乙烯/丙烯酸共聚物(EAA)、乙烯/丁基丙烯酸盐共聚物(EBA)、聚甲基戊烯酸酯(PMP)和聚甲基丙烯酸甲酯(PMMA)中的一种或者多种材料中的一个或多个。
从由丙烯酸酯和聚甲基戊烯酸酯构成的组选择用于临时树脂层(104)的更优选的聚合物材料。
用于临时树脂层(104)的最优选聚合物材料是具有20000-200000、更优选为25000-150000并且最优选为30000-100000的分子量MW的丙烯酸脂。聚合物的Tg应当在如根据ISO11357-1测量的20-130℃、更优选为30-120℃并且最优选为40-110℃的范围中。
分子量太高将造成所选溶剂中的溶解度减少。分子量太低,对生产溶液(processsolution)(碱性、氧化、酸性)的灵敏度往往不足。Tg也必须不太低,因为在这一情况下,对聚合物膜的灵敏度在处理化学剂的升高温度不充分。
可选地,填充物可以并入于临时树脂层(104)的聚合材料中。从由硼酸铝、氧化铝、三羟基铝、无烟煤、锑酸钠、五氧化锑、三氧化锑、磷灰石、绿坡缕石、偏硼酸钡、硫酸钡、硫酸锶、钛酸钡、斑脱土、氧化铍、氮化硼、碳酸钙、氢氧化钙、硫酸钙、炭黑、粘土、方石英、硅藻土、白云石、铁酸盐、长石、玻璃丸、石墨、水合硅酸钙、氧化铁、高岭土、钡白、氧化镁、云母、二硫化钼、珍珠岩、聚合填充物,诸如 PTFE、PE、聚酰亚胺、浮石、叶蜡石、橡胶微粒、烟化二氧化硅、熔铸二氧化硅、沉淀二氧化硅、海泡石、石英、沙、板岩粉、滑石、二氧化钛、蛭石、木粉、钙二氧化硅、沸石、硼酸锌、氧化锌、锡酸锌、硫酸锌、芳香尼龙纤维、碳纤维、纤维素纤维和玻璃纤维及其混合物构成的组选择适当填充物。
从由熔铸二氧化硅、烟化二氧化硅、沉淀二氧化硅、白云石、高岭土、滑石、碳酸钙、云母、长石、蛭石和浮石构成的组选择用于临时树脂层(104)的优选可选填充物材料。
从由高岭土、滑石、云母和长石构成的组选择用于临时树脂层(104)的最优选可选填充物材料。
在去除溶剂之后的在总配方中的填充物的量是在按重量为1-70%、按重量更优选为2-65%、按重量最优选为3-60%的范围中。
可以通过诸如浸渍涂覆、旋涂、条式涂覆(bar coating)、喷镀、网印和辊涂之类的方法以液体形式将临时树脂层(104)沉积到持久树脂层(103)上。在另一实施例中,在载体箔上的干膜首先由液体树脂制成,并且然后在持久树脂层(103)上层叠这一干膜。需要这样的载体箔,因为稍后用作临时树脂层(104)的聚合物材料不能制造为箔。用于将临时树脂层(104)沉积到持久树脂层(103)上的优选方法是液体树脂的辊涂、液体树脂的网印、衬底的浸渍或者将(由干膜和载体箔构成的)相应干膜层叠到衬底上。最优选的液体树脂的网印、液体树脂的辊涂和将(由干膜和载体箔构成的)相应干膜层叠到衬底上。
根据用于配制漆的溶剂,必须调整炉温度和干燥时间。重要的是干燥的涂层的所得硬度。根据Koenig的硬度测量应当在20秒到200秒、更优选为40秒到180秒、最优选为60秒到160秒的范围中。
可以通过使临时树脂层(104)与溶剂接触从持久树脂层(103)去除(剥离)临时树脂层(104)而不损坏持久树脂层(103),该溶剂从包括以下内容的组中选择:丙酮、戊醇、n-乙酸戊酯、苯甲醇、1,4-丁二醇、甲氧基乙酸丁酯、n-丁基、乙酸仲丁酯、n-丁醇、2-丁醇、丁基二甘醇、二乙二醇单丁醚醋酸酯、二乙二醇二丁醚、丁基乙二醇、丁基乙二醇醋酸酯、n-三乙二醇单丁醚、氯仿、环己烷、环己醇、环己酮、环己氨、n-癸烷、萘烷、二丙酮醇、1,2-二氯乙烷、1,2-二氯苯、1,2-二氯丙酮、二乙醇胺、二甘醇、二乙二醇二丁醚、二乙二醇二乙醚、二甘醇二甲醚、二乙二醇单丁醚、二乙二醇单丁醚醋酸酯、二乙二醇单乙醚、二乙二醇单甲醚、二乙二醇单甲醚乙酸酯、二乙醚、二乙基酮、二甘醇二甲基乙醚、二异丁酮、二异丙胺、二异丙醇胺、异丙醚、二甲基乙酰胺、二甲基甲酰胺、二甲亚砜、1,4-二氧杂环乙烷、二戊烯、二丙二醇、二丙二醇丁醚、二丙二醇单甲醚、正十二烷、丙二醇二乙酸酯、丙二醇甲醚、丙二醇甲醚醋酸酯、丙二醇甲醚、丙二醇甲醚醋酸酯、三丙二醇单甲醚、三丙二醇单丁醚、3-乙氧基丙酸乙酯、乙醇胺、丙二醇乙醚、乙氧基醋酸、乙酸乙酯、乙基戊基甲酮(ethaylamylketone)、乙苯、2-乙基丁醇、乙基丁基酮、乙基二乙二醇、二乙二醇单乙基醚醋酸酯、1,2-二氯乙烷、乙二醇、乙二醇乙醚、乙二醇二甲基乙醚、乙二醇单丁醚、乙二醇单丁醚醋酸酯、乙二醇单乙醚、乙二醇单乙醚醋酸酯、乙二醇异丙基醚、乙二醇单甲醚、乙二醇单甲醚乙酸酯、乙二醇丙基醚、甲酸乙酯、乙二醇、乙基乙二醇醋酸酯、乙二醇二乙醚(ethyleneglycoldietehylether)、2-乙氧基乙醇、2-乙氧基乙醇醋酸酯、乳酸乙酯、乙基甲基酮(ethylmethylketone)、甲酸、甲基乙基酮肟(ethylmethylketoxime)、三甘醇一乙醚、糠醛、糠醇、呋喃醛(furfurylaldehyde)、甘油、三醋精、庚烷、正十六烷、正已烷、己烯乙二醇、乙酸异戊酯、异戊醇、乙酸丁酯、异丁醇、异庚烷、异辛烷、异戊烷、异佛乐酮、异丙醇胺、醋酸异丙酯、异丙醇、氯异丙烷、异丙醚、异丙基乙二醇(isopropylglycol)、甲氧基乙酸丙酯(methoxypropyl)、乙酸甲酯、甲醇、甲基戊基酮、甲丁酮、甲基环己烷、甲基环己醇、甲基环己酮、甲基环戊烷、甲基二乙二醇、甲基二乙二醇醋酸酯、二氯甲烷、乙酸、丁酮、甲基乙基酮肟、甲基乙二醇、醋酸丙二醇、甲基异戊醇(methylisoamylalcohol)、甲基异戊基酮、甲基异丁基甲醇(methylisobutylcarbinol)、甲基异丁酮、甲基异丙酮、甲基丙基酮、N-甲基吡咯烷酮、甲基叔丁基醚、一氯苯、羟基乙胺、单异丙醇胺、硝基乙烷、硝基甲烷、1-硝基丙烷、2-硝基丙烷(2-ntropropane)、正壬烷、正辛烷、正辛醇(n-octylalcohol)、十五烷、丙酸正戊酯、全氯乙烯、乙酸丙酯、正丙醇、二氯丙烷、丙二醇、丙二醇二乙酸酯、丙二醇丁醚、丙二醇单丁醚醋酸酯(monobutyletheracetate)、丙二醇单乙醚、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙基乙二醇、氮(杂)苯、乙酸仲丁酯、正十四烷、四甘醇、四乙二醇二甲醚、四氢呋喃、四氢糠醇、四氢化萘、甲苯、三氯乙烷、三氯乙烯、十三烷、三乙醇胺、三甘醇、三乙二醇单乙醚(triethethyleneglycol monoethylether)、三乙二醇二甲醚、三丙二醇(tripropyleneglycol)、过氧化氢、三亚丙酯乙二醇单丁醚(tripropylengylcolmonobutylether)、三亚丙酯乙二醇单甲醚、正十一烷、二甲苯、三甲基苯、乙酰苯、乙醛、丁内酯、碳酸次乙酯、碳酸丙烯、乙腈(acetonitrle)、丁腈、N-乙基吡咯烷酮(N-ethylpyrrolidone)及其混合物。前述溶剂的混合物还可以包括水。
更优选地,从由苯甲醇、蚁酸、乙酰二甲胺、二甲基甲酰胺、环己酮、乙醇胺、三乙醇胺、二乙二醇丁醚醋酸酯、二乙二醇单乙醚及其混合物构成的组选择溶剂。
最优选地,从由蚁酸、苯甲醇、二乙二醇丁醚醋酸酯、二乙二醇单乙醚及其混合物构成的组选择溶剂。
通过浸没、喷洒或者浸渍使临时树脂层(104)接触溶剂。出于剥离的目的,将溶剂保持在5到100℃、更优选为10到90℃并且最优选为15到80℃的范围中的温度。在剥离期间的接触时间范围从1到600秒、更优选为从10到540秒并且最优选为从20到480秒。在剥离期间,未损坏持久树脂层(104)。
在下一步骤中形成至少一个接触区域开口(105)(图2c)。接触区域开口(105)通过临时树脂层(104)和持久树脂层(103)延伸并且暴露接触焊盘(101)。适合于形成所述接触区域开口(105)的方法例如是激光钻孔、等离子体蚀刻、电火花腐蚀和机械钻孔。在单个步骤中去除来自持久树脂层(103)和临时树脂层(104)的材料以便形成接触区域开口(105)。
所述“多层钻孔”方法的主要优点在于可以不出现持久树脂层(103)和临时树脂层(104)中的开口的未对准。这样的开口未对准在应用本领域已知的方法时尤其对于≤150μm的开口直径而言是严重问题。在已知方法中,在两个单独步骤中形成接触焊盘开口(图1)。通过诸如光构造(photo structuring)、钻孔或者网印之类的方法(图1b)在可以是焊料抗蚀剂层(109)的持久树脂层(103)中形成第一焊料抗蚀剂开口(110)。接着附着临时树脂层(104)(图1c),并且在第二种光构造方法中通过钻孔或者网印来形成临时树脂开口(111)(图1d)。接触区域开口(105)然后由未对准的焊料树脂开口(110)和临时树脂层开口(111)构成。
为了在非传导表面(102)上通过电镀来制作金属或者金属合金层(107),需要形成于非传导表面上的传导种子层以启动电镀。在图2d中描绘了这样的第一传导种子层(106)。种子层例如在非传导表面的常规制造中通过无电沉积来形成并且在本领域中众所周知。
根据本发明,在包括至少一个接触区域(101)、持久树脂层(103)和临时树脂层(104)的非传导衬底(102)的整个表面之上沉积第一传导种子层(106)(图2d)。
通过例如在McGraw Hill的Printed Circuits Handbook, C. F. Coombs Jr.(Ed.)第6版第28.5到28.9页和第30.1到30.11页中描述的各种方法活化非传导衬底。这些过程涉及到形成包括碳粒子、Pd胶体或者传导聚合物的传导层。
在专利文献中描述这些过程中的一些过程并且下文给出示例:
欧洲专利EP 0 616 053描述一种用于将金属涂层涂覆到非传导衬底(没有无电涂覆)的过程,该过程包括:
a.使所述衬底与包括贵金属/IVA族金属溶胶(sol)的活化剂(activator)接触以获得处理的衬底;
b.使所述处理的衬底与具有在11到pH 13以上的pH的自加速和补充浸没金属化合物接触,该化合物包括以下溶液:
(i)Cu(II)、Ag、Au或者Ni可溶金属盐或者其混合物,
(ii)IA族金属氢氧化物,
(iii)包括有机材料的络合剂,该有机材料具有用于所述金属盐的金属的离子的、从0.73到21.95的累积形成常数对数K。
这一过程产生可以用于后续电镀的薄传导层。这一过程在本领域中称为“连接”过程。
US 5,503,877描述非传导衬底的金属化,该金属化涉及到将络合化合物用于在非金属衬底上生成金属种子。这些金属种子提供用于后续电镀的充分传导性。这一过程在本领域中称为所谓的“沉淀铜(Neoganth)”过程。
US 5,693,209涉及一种用于金属化非传导衬底的过程,该过程涉及到使用传导吡咯聚合物。该过程在本领域中称为“紧凑CP”过程。
EP 1 390 568 B1也涉及非传导衬底的直接电解金属化。它涉及到使用传导聚合物以获得用于后续电涂覆的传导层。传导聚合物具有噻吩单位。该过程在本领域中称为“Seleo CP”过程。
最后,也可以用胶体或者包含离化钯离子的溶液活化非传导衬底,例如在McGrawHill的Printed Circuits Handbook, C. F. Coombs Jr. (Ed.)第6版第28.9页和第30.2至30.3页中描述的方法。
可以可选地实现薄中间金属涂层的后续化学镀以便增强第一传导种子层(106)。借助种子层,然后可以实现根据本发明的金属或者金属合金层(107)的电镀。
根据本发明,所述第一传导种子层(106)可以由单个金属层、单个金属合金层制成或者由至少两个不同单层的多层制成。从由铜、锡、钴、镍、银、锡-铅合金、锡-银合金、铜-镍合金、铜-铬合金、铜-钌合金、铜-铑合金、铜-银合金、铜-铱合金、铜-钯合金、铜-铂合金、铜-金合金和铜-稀土合金、铜-镍-银合金、铜-镍-稀土金属合金构成的组选择适合作为传导种子层的金属和金属合金。铜和从由铜-镍合金、铜-钌合金以及铜-铑合金构成的组选择的铜合金最优选作为第一传导种子层(106)。
根据本发明的一个优选实施例,也可以通过化学镀方法形成所述第一传导种子层(106),其中催化金属未使用贵金属,但是使用铜作为催化金属。可以在 US 3,993,491和US3,993,848中发现用于在非传导表面上形成这样的催化铜的典型示例。
所述第一传导种子层(106)的厚度优选地小于0.1毫米并且更优选地在0.0001毫米与0.005毫米之间。根据所述第一传导种子层(106)在金属或者金属合金层(107)中的溶解度,所述第一种子层(106)可以完全溶解到金属或者金属合金层(107)中或者在回流过程之后仍然至少部分地存在。
可选地,将银或者银合金层镀制到金属或者金属合金层(107)上作为保护层(117)。
在金属或者金属合金层(107)是锡或者锡合金层的情况下,可以根据第一传导种子层(106)的厚度和第一传导种子层(106)在回流时溶解到金属或者金属合金层(107)中的量从层(107)获得回流的焊料沉积(108)或者非熔融凸块结构(112)。
在回流时从由具有小于250℃的熔点的锡或者锡合金构成的金属或者金属合金层(107)获得回流的焊料沉积(108)。
在回流时从由具有多于250℃的熔点的锡合金层构成的金属或者金属合金层(107)或者从沉积为金属或者金属合金层(107)的铜或者铜合金的获得非熔融凸块结构(112)。
优选更薄的第一传导种子层(106),因为可以在蚀刻溶液中更快去除更薄种子层,所以可以缩短在蚀刻溶液中浸没所述非传导衬底(102)所需要的时间。在这样的情况下,所述蚀刻溶液对所述临时树脂层(104)的损坏将降低至可接受的低水平。
现在参照图2e:然后通过电镀在第一传导种子层(106)上形成包含从由锡、铜、锡合金和铜合金构成的组选择的金属或者金属合金的金属或者金属合金层(107)。
根据本发明的一个优选实施例,从由锡、铜、锡合金和铜合金构成的组选择所述金属或者金属合金层(107),该锡合金由锡与从由铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、镓和稀土元素构成的组选择的元素的混合物制成,该铜合金具有从由钒、铬、锰、铁、钴、镍、锌(zink)、锗、硒、铑、钯、银、镉、铟、锡、锑、钨、铼、铱、铂、金、铅、铋、铊和稀土元素构成的组选择的至少一种合金元素。
锡和锡合金镀制镀液在本领域中已知。在下文中描述用于镀制的常用锡或者锡合金镀制镀液组成和过程参数。
在锡或者锡合金镀液的其他成分之中可以添加Sn2+离子源、抗氧化剂和表面活性剂。
Sn2+离子源可以是可溶含锡阳极或者在使用不可溶阳极时是可溶Sn2+离子源。锡甲磺酸Sn(MSA)2由于它的高溶解度而是优选Sn2+离子源。通常,Sn2+离子源的浓度足以向镀液中提供在约10 g/l与约100 g/l之间的Sn2+离子、优选地在约15 g/l与约95 g/l之间、更优选地为在约40 g/l与约60 g/l之间。例如可以添加Sn(MSA)2以向镀制镀液添加在约30g/l与约60 g/l之间的Sn2+离子。
优选锡合金是锡银合金。在这样的情况下,镀制镀液还包含可溶银盐,常用的是硝酸盐、醋酸盐并且优选地是甲基磺酸(methane sulfonate)。通常,Ag+离子源的浓度足以向镀液中提供在约0.1 g/l与约1.5 g/l之间的Ag+离子、优选地在约0.3 g/l与约0.7 g/l之间、更优选地为在约0.4 g/l与约0.6 g/l之间。例如可以添加Ag(MSA)以向镀制镀液提供在约0.2 g/l与约1.0 g/l之间的Ag+离子。
可以向本发明的镀液添加抗氧化剂以针对溶液中的Sn2+离子的氧化来稳定镀液。可以按照在约0.1 g/l与约10 g/l之间、优选地在约0.5 g/l与约3 g/l之间的浓度添加优选抗氧化剂、诸如对苯二酚、儿茶酚和在羟基、二羟基或者三羟基苯甲酸中的任何酸。例如,可以约2 g/l的浓度向镀液添加对苯二酚。
可以添加表面活性剂以促进衬底的润湿。表面活性剂看来充当温和沉积抑制剂,该抑制剂可以在某一程度上抑制三维生长,由此改进膜的形态和形貌(topography)。它也可以帮助精化颗粒大小,这产生更均匀凸块。示例性阴离子表面活性剂包括烷基膦酸盐、烷基醚磷酸盐、烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基醚磺酸盐、羧酸醚、羧酸酯、烷基芳基磺酸盐、芳基烷基醚磺酸盐、芳基磺酸盐和磺基琥珀酸酯。
本发明的电解锡或者锡合金镀制镀液优选地具有酸性pH以 抑制阳极钝化、实现更好阴极效率并且实现更有延性(ductile)的沉积。因而镀液pH优选地在约0与约3之间。在优选实施例中,镀液的pH是0。因而可以使用硝酸、乙酸和甲基磺酸来实现优选酸性pH。在一个优选实施例中,酸是甲基磺酸。酸的浓度优选地在约50 g/l与约200 g/l之间、更优选地在约70 g/l与约120 g/l之间。例如在约50 g/l与约160 g/l之间的甲基磺酸可以添加到电镀镀液以实现pH 0的镀液并且充当传导电解质。
例如在Jordan: The Electrodeposition of Tin and its Alloys, 1995, p.71-84中公开典型锡或者锡合金镀液组成。
可以通过直流(DC)或者脉冲镀制来执行用于焊料贮存镀制的锡和锡合金的镀制。脉冲镀制的优点是更好的表面分布均匀性和改进的晶体结构、具有拥有更细微的颗粒大小的锡沉积,并且因此更好的可焊接性质。通过与DC镀制相比的脉冲镀制也可以获得更高的适用电流密度并且因此获得更高吞吐量。
一般而言,可以施加按照1-20 A/dm2的有效电流密度的电流脉冲。替代地,可以执行用按照1-3 A/dm2的电流密度的DC操作镀液。
例如施加具有3 A/dm2的电流密度的锡脉冲镀制在30分钟镀制时间内产生40μm的锡沉积平均厚度。表面上的厚度变化仅为+/-15%。施加DC镀制,可以获得仅1 A/dm2的最大电流密度。用于获得40μm的锡沉积厚度的镀制时间是86分钟。表面上的变化为+/-33%、因此比针对脉冲镀制的变化高得多。
优选脉冲参数如下:
至少一个前向电流脉冲的持续时间与至少一个反向电流脉冲的持续时间之比调整至至少为1:0-1:7、优选地至少为1:0.5-1:4并且更优选地至少为1:1-1:2.5。
至少一个前向电流脉冲的持续时间可以调整成优选地至少为5ms到1000ms。
至少一个反向电流脉冲的持续时间优选地调整成至多为0.2-5ms并且最优选地为0.5-1.5ms。
至少一个前向电流脉冲在工件的峰电流密度优选地调整成至多为1-30 A/dm2的值。特别优选的是在水平过程中至少一个前向电流脉冲在工件的约2-8 A/dm2的峰电流密度。在竖直过程中,至少一个前向电流脉冲在工件的最优选峰电流密度至多为1-5 A/dm2。
至少一个反向电流脉冲在工件的峰电流密度将优选地调整成0-60 A/dm2的值。特别地,优选的是在水平过程中至少一个反向电流脉冲在工件的约0-20 A/dm2的峰电流密度。在竖直过程中,至少一个前向电流脉冲在工件的最优选峰电流密度至多为0-12 A/dm2。
铜和铜合金镀制镀液在本领域中已知。可以应用用于镀制的常用铜或者铜合金镀制镀液组成和过程参数。
在本发明的一个优选实施例中,所述第一传导种子层(106)由铜制成,并且金属或者金属合金层(107)由锡或者锡合金构成。在回流操作期间,所述第一传导种子层(106)完全溶解到锡层(107)中,从而形成由均匀锡-铜合金构成的回流的焊料沉积层(108)(图7a)。可以根据锡层(107)的体积调整第一传导种子层(106)的目标厚度以便在回流之后获得与典型的无铅焊料材料类似的锡-铜合金,例如具有0.7 wt.-%的铜的锡-铜合金。
在由铜制成的第一传导种子层(106)的更高厚度的情况下,所述传导种子层溶解到锡层(107)中产生具有在250℃以上的熔点的锡-铜合金。这样的锡-铜合金是非熔融凸块结构(112)(图7b)。作为金属或者金属合金层(107)的铜或者铜合金也类似于非熔融凸块结构(112)。
在本发明的另一优选实施例中,所述第一传导种子层(106)由铜或者铜合金构成,并且金属或者金属合金层(107)由铜构成。这一组合也产生非熔融凸块结构(112)(熔点在250℃以上)。
根据图2的结构中的开口表示为接触区域开口(105)并且优选地具有约5-1.000μm的直径、更优选地约为10-500μm并且最优选为20-150μm。
接触区域开口(105)的高度在5-250μm、优选地约10-60μm之间变化。相邻接触区域的中心点的距离表示为间距并且范围对于IC衬底从20-150μm并且对于印刷电路从150-1.000μm。
由于临时树脂层(104)也由第一传导种子层(106)覆盖,所以金属或金属合金层(107)的镀制也在这一层上。这样的金属或者金属合金层(107)的厚度应当在临时树脂层(104)上面优选地不超过10μm并且更优选不超过6μm。
尽管已经针对根据图2的衬底详细描述这一过程序列,但是它不限于此并且可以应用于所有种类的衬底。
一种用于将可焊接覆层(113)或者阻挡层沉积到金属或者金属合金层(107)顶部的方法包括在去除临时树脂层(104)之后直接沉积可焊接覆层(113)或者阻挡层(图3)。通过化学镀锡或者锡合金来沉积可焊接覆层(113)或者阻挡层,该化学镀包括浸没型镀制和自动催化镀制。所得可焊接覆层(113)或者阻挡层可以不仅沉积于金属或者金属合金层(107)顶部上而且沉积于金属或者金属合金层(107)的侧壁上,侧壁在去除临时树脂层(104)之后暴露(图3d)。
在图4中示出了另一种用于在非熔融凸块结构(112)的顶表面上沉积可焊接覆层(113)或者阻挡层的方法:
提供通过图1中示出的方法获得的衬底(图4a)。
向衬底的表面上沉积并且图案化抗蚀剂层(114)。然后暴露金属或者金属合金层(107)的顶表面(图4b)。
接着,将从由锡、镍、铬、钛、银、金、钯、其合金及其多层构成的组选择的金属或者金属合金层沉积到由图案化的抗蚀剂层(114)形成的开口中(图4c)。如果所述层由锡或者锡合金构成,则它具有可焊接覆层(113)的功能。在该层由镍、铬、钛、银、金、钯、其合金及其多层构成的情况下,该层具有阻挡层的功能。
通过本领域已知的方法剥离图案化的抗蚀剂层(114)。从第一传导种子层(106)去除临时树脂层(104)顶部的传导种子层(106)和金属或者金属合金层(107)(图4d)。在去除金属或者金属合金层(107)和第一传导种子层(106)之前未向至少一个接触区域(101)上方的金属或者金属合金层(107)上涂覆附加抗蚀剂。
术语“抗蚀剂”这里定义为任一种图案化的阻挡物,例如光可成像或者网印的有机抗蚀剂和金属蚀刻抗蚀剂,这些抗蚀剂防止在蚀刻期间对在所述抗蚀剂之下的材料的非所需去除。
优选地通过化学蚀刻某一量的金属或者金属合金层(107)来执行去除,该量足以从第一传导种子层(106)去除金属或者金属合金层(107),从而在开口(105)中留下至少一个接触区域(101)上的金属或者金属合金层(107)。
在金属或者金属合金层(107)由锡和锡合金构成的情况下,可以电解或者化学地执行蚀刻。也可以单独或者与电解或者化学剥离组合地施加机械抛光以去除金属或者金属合金层(107)。
例如在Jordan: The Electrodeposition of Tin and its Alloys, 1995, p.373-377中公开用于由锡或者锡合金构成的金属或者金属合金层(107)的典型蚀刻或者剥离组成。
在电解剥离方法期间,锡或者它的合金在70-90℃阳极地溶解于10 wt.-%的NaOH溶液中。
一般在70-90℃的升高温度处在包含比如NaOH(约为10wt.-%)的强碱的溶液中执行化学剥离。可以向溶液添加有机添加剂,特别是硝基芳烃化合物(nitroaromticcompounds)、比如p-硝基笨酚,
替代地,可以在以下溶液中执行化学剥离:
- 经常具有添加的氟化物的过氧化氢,
- 基于硝酸和硝酸盐的系统,5-40 wt.-%的硝酸盐,
- 基于HCL/氯化铜的系统,这些系统包含5-20wt.-%的HCL而氯化铜的初始浓度为为2.5 mg/l。
在金属或者金属合金层(107)由铜和铜合金构成的情况下,可以电解或者化学地执行蚀刻。也可以单独或者与电解或者化学剥离组合施加机械抛光以去除金属或者金属合金层(107)。
例如在C. F. Coombs, Jr, “Printed Circuits Handbook”, 5th Ed. 2001,McGraw-Hill, Chapter 33.4中公开用于由铜或者铜合金构成的金属或者金属合金层(107)和由铜或者铜合金构成的第一传导种子层(106)的典型蚀刻或者剥离组成。
在例行实验中选择适当蚀刻溶液和蚀刻条件。
可选地,将银或者银合金层镀制到可焊接覆层(113)上作为保护层(117)。
在图5中示出了又一种用于将可焊接覆层(113)或者阻挡层(115)沉积到非熔融凸块结构(112)的顶表面上的方法:
提供通过图1中示出的方法获得的衬底(图5a)。
通过蚀刻从第一传导种子层(106)去除金属或者金属合金层(107)而不使用抗蚀剂(图5b)。金属或者金属合金层(107)的仅镀制到开口(105)中的那些部分保留。
向衬底的表面上沉积并且图案化抗蚀剂层(114)。暴露金属或者金属合金层(107)的顶表面(图5c)。
接着,将从由锡、镍、铬、钛、银、金、钯、其合金及其多层构成的组选择的金属或者金属合金层沉积到由图案化的抗蚀剂层(114)形成的开口中(图5d)。如果所述层由锡或者锡合金构成,则它具有可焊接覆层(113)的功能。在该层由镍、铬、钛、银、金、钯、其合金及其多层构成的情况下,该层具有阻挡层的功能。
通过在本领域中已知的方法剥离图案化的抗蚀剂层(114)。如上文描述的那样去除临时树脂层(104)顶部上的传导种子层(106)、之后剥离临时树脂层(104)(图5e)。
非熔融凸块结构(112)在顶表面上具有可焊接覆层(113)或者阻挡层。图5f示出了在回流之后的非熔融凸块结构(112)和可焊接覆层(113)。可选地,在回流之前将银或者银合金层镀制到可焊接覆层(113)上作为保护层(117)。
在图6中示出了又一种用于将可焊接覆层(113)沉积到非熔融凸块结构(112)的顶表面上的方法:
提供通过图1中示出的方法获得的根据图6的衬底。
通过蚀刻来去除第一传导种子层(106)(图6b)。例如在C. F. Coombs, Jr,“Printed Circuits Handbook”, 5th Ed. 2001, McGraw-Hill, Chapter 33.4中公开用于由铜或者铜合金构成的第一传导种子层(106)的典型蚀刻或者剥离组成。
接着,将阻挡层(115)沉积到金属或者金属合金层(107)的顶部上(图6c)。阻挡层(115)可以是镍、镍合金的粘合层和/或金的保护层。所述阻挡层(115)也可以由通过镍、铬、钛、银、金、钯、其合金以及可以通过化学镀、物理气相沉积或者化学气相沉积制成的及其多层制成。
将第二传导种子层(116)沉积到临时树脂层(104)和阻挡层(115)的外表面上(图6d)。与上文针对第一传导种子层(106)讨论的材料和沉积方法相同种类的材料和沉积方法应用于第二传导种子层(116)。
接着,将稍后作为可焊接覆层(113)来工作的锡或者锡合金层沉积到第二传导种子层(116)上(图6e)。
随后,从第二传导种子层(116)的在临时树脂层(104)顶部上的那些部分去除可焊接覆层(113)。在从第二传导种子层(116)的外表面去除可焊接覆层(113)之前,未将附加抗蚀剂涂覆到在至少一个接触区域(101)上方的可焊接覆层(113)上。也去除第二传导种子层(116)和临时树脂层(104)从而留下包括非熔融凸块、阻挡层(115)和可焊接覆层(113)的凸块结构(图6f)。
可选地,将银或者银合金层镀制到可焊接覆层(113)上作为保护层(117)。以下示例进一步举例说明本发明。
在回流温度,回流的焊料沉积(108)(图7a)或者非熔融凸块结构(112)(图7b)可以由金属或者金属层(107)形成。产生回流的焊料沉积(108)的金属或者金属合金层(107)具有小于250℃的熔点,而在回流温度产生非熔融凸块结构(112)的金属或者金属合金层(107)具有多于250℃的熔点。
根据本发明的一个优选实施例,可以通过从临时树脂层(104)进一步去除第一传导种子层(106)并且剥离临时树脂层(104)来形成回流的焊料沉积(108)。这样的回流的焊料沉积(图7a)可以应用于形成倒装芯片接头和板到板焊点。
回流的焊料沉积(108)可以是任何形状,诸如立柱凸块、球凸块、柱状凸块或者其他形状。
用与应用于制造回流的焊料沉积(108)的相同的方法制造非熔融凸块结构(112)。在回流期间,传导种子层可以部分或者完全溶解于非熔融凸块结构(112)中(图7b)。这依赖于种子层厚度及其组成以及施加的温度的持续时间。在部分溶解的种子层的情况下,凸块的中心将作为通过扩散形成的更高熔融温度的桶而具有更低熔点。这样的非熔融凸块结构能够耐受最少一个回流周期以支持用于后续清洁和下填充过程的充分支座(standoff)高度。
非熔融凸块结构(112)可以用于在有或没有沉积可焊接覆层(113)的情况下形成倒装芯片接头和板到板焊点。在可焊接覆层的情况下,这将优选地通过在所述非熔融凸块结构(112)的顶表面上电镀可焊接覆层(113)来完成。
在非熔融凸块结构(112)顶部上的阻挡层防止焊料材料在焊接期间扩散到非熔融凸块结构(112)中并且由此维持非熔融凸块结构(112)的热和机械性质。
示例
示例1
使用IC衬底,该IC衬底具有根据图2a的接触焊盘结构。
非传导衬底(102)由GX-13材料(制造商:Ajinomoto Fine-Techno Co., Inc)构成,持久树脂层(103)由GX-92材料(制造商:Ajinomoto Fine-Techno Co., Inc.,层的高度:25μm)构成,并且接触焊盘由铜构成。
将临时树脂层(104)(DuPont PM 200,高度:50μm)层叠到持久树脂层(103)上。
接着,在一个步骤中用UV激光经过临时树脂层(104)和持久树脂层(103)形成接触区域开口(105)。接触区域开口(105)的直径为100μm。
镀制序列根据图2d至e。首先,在整个衬底表面上形成铜的第一传导种子层(106)。为此,使表面首先与包含离化钯的酸性溶液并且然后与用于无电铜沉积的溶液接触。
随后,从镀液在传导层上镀制锡层(107),该镀液包含:
45 g/L Sn2+作为Sn(MSA)2、60 mL/L MSA(70%溶液)、2 g/L对苯二酚和100 mg/L苯亚甲基丙酮。
镀液的pH为0,温度为25℃。镀制持续15分钟。施加具有1 A/dm2的电流密度的标准DC镀制。
根据图2d的接触区域开口(105)完全由锡焊料沉积填充而无任何空隙形成。此外,锡已经沉积到临时树脂层(104)区域上,该区域的厚度为3μm(图2e)。
随后通过在40℃的温度在包含30 vol.-%的硝酸的溶液中处理1分钟来直接去除临时树脂层(104)区域上的锡层(107)以及第一传导种子层(106)。
在蚀刻过程之后,锡层(107)仅保留于开口中,而已经完全去除临时树脂层(104)区域上的锡层(107)以及铜的第一传导种子层(106)。接着,通过在2 wt.-%的碳酸钾的水合溶液中浸没衬底来去除临时树脂层(104)。锡层、即焊料沉积表现很均匀的表面分布并且无须状物(whisker)。它适合于焊接到芯片或者电路。
例2
制造由锡-铜合金构成的非熔融凸块结构(112),该非熔融凸块结构(112)具有由锡制成的可焊接覆层(113)。使用IC衬底,该IC衬底具有根据图2a的至少一个接触区域结构。
非传导衬底(102)由GX-13材料(制造商:Ajinomoto Fine-Techno Co., Inc)构成,持久树脂层(103)由GX-92材料(制造商:Ajinomoto Fine-Techno Co., Inc.,层的高度:25μm)构成,并且接触焊盘(101)由铜构成。
将临时树脂层(104)(DuPont PM 200,高度:50μm)层叠到持久树脂层(103)上。
接着,在一个步骤中用UV激光经过临时树脂层(104)和持久树脂层(103)形成接触区域开口(105)。接触区域开口(105)的直径为100μm。
镀制序列根据图2d至e。在整个衬底表面上形成铜的第一传导种子层(106)。为此,使表面首先与包含离化钯的酸性溶液并且然后与用于无电铜沉积的溶液接触。开口(105)中的第一传导种子层(106)的厚度足以在回流操作期间用锡层(107)形成锡-铜合金。所得的锡-铜合金具有在250℃以上的熔点并且因此充当非熔融凸块(112)。
随后,从镀液在第一传导种子层(106)上镀制锡层(107),该镀液包含:
45 g/l Sn2+作为Sn(MSA)2、60 ml/l MSA(70 wt.-%溶液)、2 g/l对苯二酚、基于共聚物的表面活性和100 mg/l 苯亚甲基丙酮。
镀液的pH为0,温度为25℃。镀制持续15分钟。施加具有1 A/dm2的电流密度的标准DC镀制。
根据图2d的接触区域开口(105)完全由锡焊料沉积填充而无任何空隙形成。此外,锡已经沉积到临时树脂层(104)区域上,该区域的厚度为3μm(图2e)。
随后通过在40℃的温度在包含体积比为30 vol.-%硝酸的溶液中处理1分钟来去除第一传导种子层(106)上的锡层(107)。未涂覆抗蚀剂。在蚀刻过程之后,锡层(107)仅保留于开口(105)中。
在剥离溶液中去除抗蚀剂层(114),之后蚀刻掉第一传导种子层(106)。
接着,通过在剥离溶液中浸没衬底来去除临时树脂层(104)。锡焊料沉积表现很均匀的表面分布并且无须状物。它适合于焊接到芯片或者电路。
例3
制造由铜构成的非熔融凸块结构(112),该非熔融凸块结构(112)具有由锡制成的可焊接覆层(113)。
提供IC衬底,该IC衬底包括如在例1中使用的非传导衬底(102)、接触区域(101)、持久树脂层(103)和临时树脂层(104)。
在一个步骤中用UV激光经过临时树脂层(104)和持久树脂层(103)形成接触区域开口(105)。接触区域开口(105)的直径为100μm。镀制序列根据图2d至e。在整个衬底表面上形成铜的第一传导种子层(106)。为此,使表面首先与包含离化钯的酸性溶液并且然后与用于无电铜沉积的溶液接触。
随后,从镀液向第一传导种子层(106)上电镀铜层(107),该镀液包含:45 g/l Cu2+作为CuSO4、50 ml/l H2SO4、1 ml/l增白剂和20 ml/l调平添加剂(leveler additive)。镀液的pH为0,温度为25℃。镀制持续45分钟。施加具有4 A/dm2的平均电流密度的标准脉冲参数。
根据图2c的接触区域开口(105)完全由铜沉积填充而无任何空隙形成。此外,铜已经沉积到临时树脂层(104)区域上,该区域的厚度为<15μm(图2e)。
随后向铜层(107)上层叠并且图案化抗蚀剂层(114)(DuPont PM 200)。
接着,从镀制镀液组成电镀锡以形成可焊接低熔融覆层(113),该镀制镀液组成包括45 g/l Sn2+作为Sn(MSA)2、60 ml/l MSA(70 wt.-%溶液)、2 g/l对苯二酚、基于共聚物的表面活性剂和100 mg/L 苯亚甲基丙酮。
在标准干膜抗蚀剂剥离溶液中剥离掉抗蚀剂层(114)。
随后通过在40℃的温度在包含30 vol.-%的硝酸的溶液中处理1分钟从临时树脂层(104)的表面去除沉积到临时树脂层(104)的表面上的第一传导种子层(106)和铜层(107)。
接着,再次通过在剥离溶液中浸没衬底来去除临时树脂层(104)。
非熔融凸块和焊料覆层沉积表现很均匀的表面分布并且无须状物。它适合以充足的立架高度焊接到芯片或者电路。
制备适合作为临时树脂层(104)的树脂材料
量为32g的丙烯酸树脂溶解于45g的溶剂中,该丙烯酸树脂具有如根据ISO11357-1测量的53℃ Tg和根据ISO1628-1测量的粘度数33,该溶剂适合于网印配制并且在搅拌(500-700rpm)和80℃加热之下具有180-200℃的沸点。当溶液已经达到80℃时,添加15g的分层填充物和包含添加剂的硅,它们是为了使液体配制触变(thixotropic)并且因此适合于网印应用而需要的。将混合物搅拌10分钟并且在三重辗磨之上碾磨混合物。在持久树脂层(103)上网印并且在对流炉中干燥这样获得的配制(在干燥之后的Koenig硬度:100s)。可以将这样获得的涂层浸渍到酸性溶液(在50℃的2.5%盐酸,pH<1)中持续5分钟而无损坏。以相同方式,它可以浸渍到碱性溶液(在50℃的3%氢氧化钠,pH<13)中而无损坏。在酸性或者碱性中两者处理之后,可以通过用二甲基乙酰胺的处理(50℃,4分钟)从衬底完全去除该涂层。在那些条件之下未冲击下面的持久树脂层(103)。
Claims (11)
1.一种在衬底上形成焊料沉积的方法,包括以下步骤:
i)提供衬底(102),所述衬底(102)包括至少一个接触区域(101)和叠加所述至少一个接触区域(101)的至少一个持久树脂层(103)以及叠加所述持久树脂层(103)的至少一个临时树脂层(104),
ii)形成通过所述临时树脂层(104)和所述持久树脂层(103)延伸的至少一个接触区域开口(105),
iii)使包括所述持久树脂层(103)、所述临时树脂层(104)和所述至少一个接触区域(101)的整个衬底(102)与适合于在衬底表面上提供第一传导种子层(106)的溶液接触,
iv)将金属或者金属合金层(107)电镀到所述第一传导种子层(106)上,其中从由锡、铜、锡合金和铜合金构成的组选择所述金属或者金属合金层(107),
v)将抗蚀剂层(114)沉积到金属或者金属合金层(107)上并且图案化所述抗蚀剂层(114)以形成开口,所述开口暴露镀制到所述至少一个接触区域开口(105)中的所述金属或者金属合金层(107),
vi)将可焊接覆层(113)或者阻挡层(115)沉积到由所述抗蚀剂层(114)形成的所述开口中,
vii)剥离图案化的抗蚀剂层(114),以及
viii)直接在步骤vii)之后蚀刻掉某一量的所述金属或者金属合金层(107),所述量足以从所述第一传导种子层(106)区域去除所述金属或者金属合金层(107)从而留下所述至少一个接触区域开口(105)中的金属或者金属合金层(107)。
2.根据权利要求1所述的方法,其中在步骤(iv)与(v)之间应用步骤(viii)。
3.根据前述权利要求中任一项所述的方法,其中从由铜和铜合金构成的组选择所述金属或者金属合金层(107)。
4.根据权利要求1至2中任一项所述的方法,其中从由锡和锡合金构成的组选择所述可焊接覆层(113)。
5.根据权利要求1至2中任一项所述的方法,其中在所述至少一个接触区域(101)上镀制第一阻挡层。
6.根据权利要求1至2中任一项所述的方法,其中所述阻挡层由从由镍、锡、铬、钛、银、金、钯、其合金及其多层构成的组选择的金属或者合金构成。
7.根据权利要求1至2中任一项所述的方法,其中所述临时树脂层(104)包括丙烯酸脂、乙烯/丙烯酸乙酯共聚物、乙烯/甲基丙烯酸甲酯共聚物、乙烯/丙烯酸共聚物、乙烯/丙烯酸丁酯共聚物、聚甲基戊烯和聚甲基丙烯酸甲酯中的一种或者多种。
8.根据权利要求7所述的方法,其中所述临时树脂层(104)还包括从由硼酸铝、氧化铝、氢氧化铝、无烟煤、偏锑酸钠、五氧化二锑、三氧化二锑、磷灰石、绿坡缕石、偏硼酸钡、硫酸钡、硫酸锶、钛酸钡、斑脱土、氧化铍、一氮化硼、碳酸钙、氢氧化钙、硫酸钙、炭黑、粘土、方石英、硅藻土、白云石、亚铁盐、长石、玻璃丸、石墨、水合硅酸钙、氧化铁、锌钡白、氧化镁、云母、二硫化钼、珍珠岩、聚合填充物及其混合物构成的组选择的填充物。
9.根据权利要求8所述的方法,所述聚合填充物包括PTFE、PE、聚酰亚胺、浮石、叶蜡石、橡胶粒子、煅制氧化硅、熔融硅石、沉淀二氧化硅、海泡石、石英、沙、板岩粉、滑石、二氧化钛、蛭石、木粉、硅灰石、沸石(zeolithes)、硼酸锌、氧化锌、锡酸锌、硫化锌、芳族聚酰胺纤维、碳纤维、纤维素纤维和玻璃纤维。
10.根据权利要求1至2中任一项所述的方法,其中所述至少一个接触区域(101)包括通路或者沟槽。
11.根据权利要求1至2中任一项所述的方法,其中通过无电沉积从由铜、铜-镍合金、铜-钌合金和铜-铑合金构成的组选择的金属或者金属合金来形成所述第一传导种子层(106)。
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- 2011-07-29 EP EP11737966.9A patent/EP2601822B1/en active Active
- 2011-07-29 WO PCT/EP2011/063141 patent/WO2012016932A1/en active Application Filing
- 2011-08-02 TW TW100127458A patent/TW201212138A/zh unknown
Patent Citations (3)
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US6127731A (en) * | 1999-03-11 | 2000-10-03 | International Business Machines Corporation | Capped solder bumps which form an interconnection with a tailored reflow melting point |
CN100463587C (zh) * | 2002-08-22 | 2009-02-18 | 捷时雅株式会社 | 使用双层叠合膜在电极垫上形成突起的方法 |
EP2180770A1 (en) * | 2008-10-21 | 2010-04-28 | Atotech Deutschland Gmbh | Method to form solder deposits on substrates |
Also Published As
Publication number | Publication date |
---|---|
EP2601822A1 (en) | 2013-06-12 |
US20130105329A1 (en) | 2013-05-02 |
KR102055459B1 (ko) | 2019-12-12 |
EP2601822B1 (en) | 2019-07-10 |
PT2601822T (pt) | 2019-10-28 |
TW201212138A (en) | 2012-03-16 |
JP2013534367A (ja) | 2013-09-02 |
KR20190014128A (ko) | 2019-02-11 |
WO2012016932A1 (en) | 2012-02-09 |
KR20140000663A (ko) | 2014-01-03 |
CN103053228A (zh) | 2013-04-17 |
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