CN103390565B - 包括在优选方向生长的Cu6Sn5晶粒的电性连接结构及其制备方法 - Google Patents
包括在优选方向生长的Cu6Sn5晶粒的电性连接结构及其制备方法 Download PDFInfo
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- CN103390565B CN103390565B CN201210154178.2A CN201210154178A CN103390565B CN 103390565 B CN103390565 B CN 103390565B CN 201210154178 A CN201210154178 A CN 201210154178A CN 103390565 B CN103390565 B CN 103390565B
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- crystal grain
- copper
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- electric connection
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- 239000013078 crystal Substances 0.000 title claims abstract description 247
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 246
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 229910000679 solder Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- 229910000765 intermetallic Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910018471 Cu6Sn5 Inorganic materials 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 4
- 229910000635 Spelter Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 pyrovinic acid) Chemical class 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
本发明公开了一种包括在优选方向生长的Cu6Sn5晶粒的电性连接结构及其制备方法。本发明的电性连接结构的制备方法包括步骤:A、提供一第一基板;B、在第一基板的部分表面形成一第一纳米双晶铜层;C、使用一焊料将第一基板与一第二基板连接,第二基板具有一第二电性垫,第二电性垫包括第二纳米双晶铜层,且焊料配置于第一及第二纳米双晶铜层之间;以及D、以200℃至300℃的温度进行回焊(reflow)使焊料部分转换为一介金属化合物(intermetallic?compound,IMC)层,且介金属化合物层包括在优选方向(preferred?orientation)生长的Cu6Sn5晶粒;其中,第一及第二纳米双晶铜层的50%以上的体积分别包括双晶铜晶粒。
Description
技术领域
本发明涉及一种电性连接结构及其制备方法,尤其是一种包括方向性生长的Cu6Sn5晶粒的电性连接结构及其制备方法。
背景技术
铜金属因具备高导电性与散热性,同时又与焊锡的湿润性良好,因此广泛地使用于金属连接装置中(例如,金属互连接线(metalinterconnect)、凸块下金属(underbumpmetal,UBM)、铜柱凸块(Cupillar)、或直通硅晶穿孔(throughsiliconvia,TSV))。
例如,应用于封装结构的凸块下金属中,铜金属经常借助焊锡与其他电子元件电性连接。其电性连接加工过程中需要进行高温回焊处理,因而铜金属与焊锡反应产生介金属化合物(intermetalliccompounds,IMCs)。
如图1所示,例如目前三维集成电路(3D-IC)结构技术中,包括二个芯片11,12,芯片11,12分别具有电性垫13,14(其组成为一般铜金属),电性垫13,14以焊锡17连接。经回焊后,电性垫13,14中的铜原子会扩散至焊锡17中并与焊锡17中的锡反应,使部分焊锡17转换成为介金属化合物层171,172(分别形成在焊锡17与电性垫13,14之间)。而此介金属化合物层171,172会造成可靠性降低的问题。
而在目前的公知技术中,对于焊锡接点质量的改善,多以减少介金属化合物层的厚度为手段。例如,增加扩散阻挡层以防止介金属化合物层的生长(如美国专利公告第US6,867,503B2号所示)。而这会增加了生产成本,且使得电子元件存在可靠性的风险。
因此,本领域亟需一种新的电性连接结构,以改善焊锡接点质量,并降低生产成本,达到更符合经济的效益。
发明内容
为此,本发明提出了一种包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,包括步骤:A、提供一第一基板;B、在该第一基板的部分表面形成一第一纳米双晶铜层;C、使用一焊料将该第一基板与一第二基板连接,该第二基板具有一第二电性垫,该第二电性垫包括一第二纳米双晶铜层,且该焊料配置于该第一纳米双晶铜层与该第二纳米双晶铜层之间;以及D、以200℃至300℃的温度进行回焊(reflow)使该焊料至少部分转换为一介金属化合物(intermetalliccompound,IMC)层,且该介金属化合物层包括在优选方向(preferredorientation)生长的多个Cu6Sn5晶粒;其中,该第一及第二纳米双晶铜层的50%以上的体积分别包括多个双晶铜晶粒。
本发明中,回焊温度需足够使焊料可在液态下进行反应生长Cu6Sn5晶粒。若温度低于此范围,则会生长出较厚的Cu3Sn层,且Cu3Sn层的厚度会多于Cu6Sn5晶粒高度的一半。甚至存放时间越久,Cu3Sn层的厚度会渐渐增加,而Cu6Sn5晶粒会渐渐消失不见。
但相反的,在本发明的回焊温度范围(200℃至300℃)内进行回焊,在正常使用时(例如温度100℃的正常使用状况下),时间越久,会使Cu3Sn层的厚度增加相对缓慢,且Cu6Sn5晶粒尺寸渐渐变大。因此,回焊温度的控制变得相当重要。
本发明的电性连接结构的制造方法,可控制Cu6Sn5晶粒的生长方向,使这些微凸块(Cu6Sn5晶粒)的性质互相接近(最好是性质一致),达到各接点电性一致化的效果,使整体电性表现提升。
本发明的电性连接结构的制造方法,通过控制Cu6Sn5晶粒的生长方向,解决了在一般焊锡接点中,受到锡晶粒不同晶向的影响,而遭受的早期破坏。应用于三维集成电路封装(3D-ICpackaging)与硅芯片穿孔(TSV)连接的电性接点时,可以确实控制焊锡接点的质量。并且,本发明的电性连接结构的制造方法不仅可控制接点的机械性质、电性、可靠度、以及使用寿命等,更降低了生产成本(这是由于本发明不需使用额外的阻挡材料、或是高温热处理等步骤),因此具有相当高的经济价值。
本发明的电性连接结构的制备方法中,优选地,该多个Cu6Sn5晶粒的生长方向大致上垂直该第一纳米双晶铜层的一表面。
本发明的电性连接结构的制备方法中,优选地,50%以上(更优选为70%以上;最好为90%以上)相邻的该多个Cu6Sn5晶粒方向的夹角为0至40度(亦即,50%以上任二个相邻的晶粒其晶粒方向的夹角为0至40度)。
此外,本发明的电性连接结构的制备方法中,优选为50%以上(更优选为70%以上;最好为90%以上)的该多个Cu6Sn5晶粒的[0001]方向与纳米双晶铜层的[111]方向的夹角为0至40度。
本发明的电性连接结构的制备方法中,该步骤D中,回焊的时间优选为30秒至10分钟。在此,回焊的时间越久,Cu6Sn5晶粒则生长越大/越高。
本发明的电性连接结构的制备方法中,该步骤D中,回焊的温度优选为240℃至280℃,最好为260℃。
本发明的电性连接结构的制备方法中,该多个Cu6Sn5晶粒与该第一纳米双晶铜层之间优选为还包括一Cu3Sn层,且该Cu3Sn层的厚度与该多个Cu6Sn5晶粒中高度最高的晶粒高度比[Cu3Sn层的厚度]/[多个Cu6Sn5晶粒中高度最高的晶粒高度]优选为0至0.5(更优选为1×10-4至0.3)。随着置放时间越长,Cu3Sn层的厚度会缓慢增加,因此[Cu3Sn层的厚度]/[多个Cu6Sn5晶粒中高度最高的晶粒高度]优选地大约为0至0.5之间(更优选为1×10-4至0.3)。
此外,该多个Cu6Sn5晶粒所构成的层的厚度优选为500nm至10μm;且该Cu3Sn层的厚度优选为1nm至1000nm。
本发明的电性连接结构的制备方法中,该多个双晶铜晶粒优选为柱状双晶体(columnartwinnedgrain)。此外,本发明的电性连接结构的制备方法中,该多个双晶铜晶粒优选为彼此间互相连接,该每一双晶铜晶粒由多个纳米双晶铜沿着[111]晶轴方向堆叠而成,且相邻的该双晶铜晶粒间的堆叠方向(即,排列方向)的夹角为0至20度。
本发明的电性连接结构的制备方法中,该步骤B的该第一纳米双晶铜层的形成方法优选为选自直流电镀、脉冲电镀、物理气相沉积、化学气相沉积、以及蚀刻铜箔所组成的集合。
本发明的电性连接结构的制备方法中,当该步骤B使用电镀形成该第一纳米双晶铜层时,电镀所使用的一电镀液优选为包括有:一铜的盐化物、一酸、以及一氯离子源。此外,本发明的电性连接结构的制备方法中,该电镀液优选为还可包括一物质,其选自明胶(gelatin)、界面活性剂、晶格修整剂、及其混合所组成的集合。并且,该电镀液中的酸优选为硫酸、甲基磺酸、或其混合。
本发明的电性连接结构的制备方法中,该第一基板优选为包括有一第一电性垫,该第一电性垫优选为包括该第一纳米双晶铜层,或是该第一纳米双晶铜层即为该第一电性垫。
本发明的电性连接结构的制备方法中,该第二基板的第二电性垫优选为包括有一第二纳米双晶铜层,或是该第二纳米双晶铜层即为该第二电性垫。
本发明的电性连接结构的制备方法中,焊料的材质优选为选自共晶型锡/铅(eutecticSn/Pb)焊料、锡/银/铜焊料、锡/银焊料、以及无铅焊料所组成的集合。
本发明的电性连接结构的制备方法中,该第一及/或第二纳米双晶铜层的厚度优选为0.1μm~500μm,更优选为0.1μm~100μm,最好为0.1μm~20μm。
本发明另提供一种包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,包括:一第一基板,其具有一第一电性垫,该第一电性垫包括一第一纳米双晶铜层;一第二基板,其具有一第二电性垫,该第二电性垫包括一第二纳米双晶铜层;以及至少一介金属化合物(intermetalliccompound,IMC)层,其位于该第一与第二纳米双晶铜层的表面,该介金属化合物层配置于该第一基板与该第二基板之间,并电性连接该第一电性垫以及该第二电性垫,且该介金属化合物层包括多个在优选方向排列的Cu6Sn5晶粒;其中,该第一及第二纳米双晶铜层的50%以上的体积分别包括多个双晶铜晶粒。
本发明的电性连接结构通过控制Cu6Sn5晶粒的生长方向(使Cu6Sn5晶粒在优选方向排列),解决了一般焊锡接点中,受到锡晶粒不同晶向的影响而遭受的早期破坏。应用于三维集成电路封装(3D-ICpackaging)与硅芯片穿孔(TSV)连接的电性接点时,可以确实控制焊锡接点的质量。详细地说,本发明的电性连接结构中可控制Cu6Sn5晶粒的生长方向,使这些微凸块(Cu6Sn5晶粒)的性质互相接近(最好是性质一致),降低电性连接结构的电性与机械性质歧异度,使整体电性及可靠度表现提升。
并且,本发明的电性连接结构的制造方法不仅可控制接点的机械性质、电性、可靠度、以及使用寿命等,更降低了生产成本(这是由于本发明不需使用额外的阻挡材料、或是高温热处理等步骤),因此具有相当高的经济价值。
本发明的电性连接结构中,优选地,50%以上(更优选为70%以上;最好为90%以上)相邻的该多个Cu6Sn5晶粒方向的夹角为0至40度(亦即,50%以上任二个相邻的晶粒其晶粒方向的夹角为0至40度)。
此外,本发明的电性连接结构中,优选为50%以上(更优选为70%以上;最好为90%以上)的该多个Cu6Sn5晶粒的[0001]方向与纳米双晶铜层的[111]方向的夹角为0至40度。本发明的电性连接结构中,该多个Cu6Sn5晶粒与该第一纳米双晶铜层之间还包括一Cu3Sn层,且该Cu3Sn层的厚度与该多个Cu6Sn5晶粒中高度最高的晶粒高度比[Cu3Sn层的厚度]/[多个Cu6Sn5晶粒中高度最高的晶粒高度]为0至0.5(更优选为1×10-4至0.3)。
此外,该多个Cu6Sn5晶粒所构成的层的厚度优选为500nm至10μm;且该Cu3Sn层的厚度优选为1nm至1000nm。
本发明的电性连接结构中,该多个双晶铜晶粒优选为彼此间互相连接,该每一双晶铜晶粒由多个纳米双晶铜沿着[111]晶轴方向堆叠而成,且相邻的该双晶铜晶粒间的堆叠方向的夹角为0至20度。
本发明的电性连接结构中,该第一基板优选为包括有一第一电性垫,该第一电性垫包括该第一纳米双晶铜层。
本发明的电性连接结构中,该第二基板的第二电性垫优选为包括有一第二纳米双晶铜层。
本发明的电性连接结构中,该第一纳米双晶铜层及该第二纳米双晶铜层的厚度优选分别为0.1μm~500μm。
本发明的电性连接结构中,该第一基板及/或该第二基板优选为各自独立地选自一半导体芯片、一电路板、及一导电基板所组成的集合。
本发明的电性连接结构,优选为还包括一焊料层,其配置于该第一基板与第二基板之间(更详细地,配置于该第一纳米双晶铜层与该第二电性垫之间)。焊料层是由于回焊时,部分焊料未转换为介金属化合物层而残留下来。该焊料层的材质优选为选自共晶型锡/铅(eutecticSn/Pb)焊料、锡/银/铜焊料、锡/银焊料、锡/铜焊料以及其他无铅焊料所组成的集合。
本发明的电性连接结构优选为还包括一晶种层(seedlayer),其配置于该第一纳米双晶铜层与该半导体芯片的一黏着层(adhesionlayer)之间。
本发明的电性连接结构优选为还包括一黏着层(adhesionlayer),其配置于该晶种层(seedlayer)与该半导体芯片(如硅芯片)之间。黏着层的材质,其选自钛、钨钛(TiW)、氮化钛(TiN)、氮化钽(TaN)、钽(Ta)、及其合金所组成的集合。
本发明的电性连接结构中,双晶铜晶粒的直径优选为0.1μm~50μm,且该晶粒的厚度优选为0.01μm~1000μm,更优选为0.01μm~100μm,最好为0.01μm~200μm。
附图说明
图1是公知的三维集成电路(3D-IC)结构;
图2A至图2D是本发明实施例1的电性连接结构的制备流程图;
图3A是本发明实施例1的Cu6Sn5层的俯视面电子背向散射绕射(ElectronBack-ScatteredDiffraction,简称EBSD)示意图;
图3B是图3A的图案参考依据示意图;
图4是本发明实施例1的电性连接结构的聚焦离子束(FIB)剖面图;
图5是本发明实施例2的电性连接结构的示意图;
图6A是本发明优选实施例的纳米双晶铜层的聚焦离子束(FIB)剖面图;
及6B是本发明优选实施例的纳米双晶铜层的立体示意图。
【主要元件的附图标记说明】
11,12芯片
13,14电性垫
15,18Cu3Sn层
16,19Cu6Sn5层
17焊锡
171,172介金属化合物层
2电镀装置
22阳极
24电镀液
26直流电供应源
31基板
32线路层
33第一纳米双晶铜层
41半导体芯片
42电性垫
43纳米双晶铜层
51焊料
52,54Cu3Sn层
53,55Cu6Sn5层
531,551Cu6Sn5晶粒
57介金属化合物层
66晶粒
661纳米双晶平面
662晶界
69堆叠方向
D直径
L高度
T厚度
(111)(111)晶面
[111][111]晶轴
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明作进一步的详细说明。本领域的技术人员可由本说明书所描述的内容轻易地了解本发明的其他优点与功效。本发明也可借助其他不同的具体实施例来实施或应用,本说明书中的各项细节亦可基于不同观点与应用,在不悖离本发明之要义下进行各种修饰与变更。
[实施例1]
图2A至图2D是本实施例的电性连接体的制备流程图。如图2A所示,首先提供一基板31,在此,基板31是一具有线路层32(亦可作为电性垫)的印刷电路板。接着,如图2B所示,将该基板31置入于一电镀装置2中作为阴极。该电镀装置1包括有阳极22,其浸泡于电镀液24中并连接至一直流电供应源26(在此使用Keithley2400)。阳极22使用的材料为金属铜、磷铜或惰性阳极(如钛镀白金)。电镀液24包括有硫酸铜(铜离子浓度为20~60g/L)、氯离子(浓度为10~100ppm)、以及甲基磺酸(浓度为80~120g/L),并可添加其他界面活性剂或晶格修整剂(如BASFLugalvan1~100ml/L)。可选地,本实施例的电镀液24还可包括有机酸(例如,甲基磺酸)、明胶(gelatin)、或以上的混合物,用以调整晶粒结构与尺寸。
接着,以2~10ASD的电流密度的直流电进行电镀,由基板31开始朝着箭头所指的方向(如图2B所示)在线路层32表面生长纳米双晶铜。在生长过程中,双晶的(111)晶面以及纳米双晶铜金属层的平面大致垂直于电场的方向,并以约1.76μm/min的速率生长双晶铜。生长完成的第一纳米双晶铜层33(作为电性垫)包括有多个双晶铜晶粒,该双晶铜晶粒由多个双晶铜所组成,此纳米双晶铜晶粒延伸到表面,因此第一纳米双晶铜层33表面所显露的同样是(111)晶面。电镀完成后得到的第一纳米双晶铜层33厚度约20μm。[111]晶轴为垂直(111)面的轴。
接着,如图2C所示,取一半导体芯片41,该半导体芯片41具有一同样为纳米双晶铜层所构成的电性垫42(亦即第二纳米双晶铜层,其制作方法可参考第一纳米双晶铜层33的形成方法)。接着,以一焊料51黏接该半导体芯片41的电性垫42以及该基板31上的第一纳米双晶铜层33。
其后,进行回焊(reflow),回焊所使用温度为260℃,时间可为30秒以上(例如,1分钟、3分钟或5分钟,依照所使用的焊料的多少而不同,在此为5分钟)。如图2D所示,回焊完成后,焊料51的部分会转换为介金属化合物层57,介金属化合物层57包括有Cu3Sn层54以及Cu6Sn5层55,Cu6Sn5层55包括有多个方向性的Cu6Sn5晶粒551由Cu3Sn层54表面生长出来。由于回焊温度需足够使焊锡可在液态下进行反应而生长Cu6Sn5晶粒,因此回焊温度优选为可使焊料熔融的温度,例如大约230℃以上。但须注意,若回焊温度过高,仍有可能伤害到电子元件构造,因此回焊温度需适当的控制。
如图3A及3B所示,其图3A是本实施例的Cu6Sn5层55(多个Cu6Sn5晶粒551)的横截面电子背向散射绕射(ElectronBack-ScatteredDiffraction,简称EBSD)示意图,而图3B则为图3A的图案参考依据示意图。由图3B中显示的图案可知,当图3A中的图案显示为点状时,则表示Cu6Sn5晶粒551生长方向接近[0001]方向;当图案显示为十字状时,则表示Cu6Sn5晶粒551生长方向接近晶轴方向;当图案显示为圆圈状时,则表示Cu6Sn5晶粒551生长方向接近方向。如图3A所示,本实施例的Cu6Sn5晶粒551的生长方向大部分偏向[0001]方向,亦即呈现点状图案的Cu6Sn5晶粒占大部分,因此可证实本实施例成功地控制了Cu6Sn5晶粒的生长方向。
本发明通过控制Cu6Sn5晶粒的生长方向,解决了一般焊锡接点中,受到锡晶粒不同晶向的影响,而遭受的早期破坏。应用于三维集成电路封装(3D-ICpackaging)与硅芯片穿孔(TSV)连接的电性接点时,可以确实锡接点的质量。并且,本发明不仅可控制接点的机械性质、电性、可靠度、以及使用寿命等,更降低了生产成本(这是由于本发明不需使用额外的阻挡材料、或是高温热处理等步骤),因此具有相当高的经济价值。
图4所示为本实施例的电性连接结构的聚焦离子束(FIB)剖面图。请同时参考图2D以及图4,本实施例的方向性排列的Cu6Sn5晶粒的电性连接结构包括有:基板31,其具有线路层32,线路层32表面具有第一纳米双晶铜层33(以作为电性垫);半导体芯片41,其具有纳米双晶铜层所构成的电性垫42;以及至少一介金属化合物(intermetalliccompound,IMC)层57,其位于第一纳米双晶铜层33的表面,该介金属化合物层57配置于基板31与该半导体芯片41之间,且介金属化合物层57包括Cu3Sn层54,52以及Cu6Sn5层53,55,Cu6Sn5层53,55包括多个具方向性排列的Cu6Sn5晶粒551,531;其中,该第一纳米双晶铜层33的50%以上的体积包括多个双晶铜晶粒。在本实施例中,Cu6Sn5层55的厚度约为1μm至5μm,Cu3Sn层54的厚度约为10nm至50nm。
此外,第一纳米双晶铜层33的构造将在后续更详细介绍。
[实施例2]
如图5所示,其是本实施例的电性连接结构的示意图。本实施例的电性连接结构大致与实施例1相似,差别在于,本实施例的回焊时间较长(约5至6分钟),会使Cu6Sn5晶粒551,531的尺寸增加(使厚度达到约10μm至30μm)。因此,本实施例经由焊料51厚度、以及回焊时间的调整,使得基板31以及半导体芯片41表面的Cu6Sn5晶粒551,531上下互相黏合。且经过本发明的发明人实验证实,即使Cu6Sn5晶粒551,531上下互相黏合,Cu6Sn5晶粒仍具有方向性。因此,证实了本发明的技术可控制Cu6Sn5晶粒的生长方向性。
而当Cu6Sn5晶粒551,531上下互相黏合,代表原所使用的焊料51可能全部转换成为介金属化合物层,或是仅留存少部分的焊料51存在于Cu6Sn5晶粒551,531之间。如此,Cu6Sn5晶粒551,531上下互相黏合的结构,可控制接点的机械性质、电性、可靠度、以及使用寿命等,因此可大幅降低焊接点变异所造成的可靠度问题,确实提升电子装置的使用寿命。
图6A所示为上述各个实施例的纳米双晶铜层的聚焦离子束(FIB)剖面图,图6B是纳米双晶铜层的立体示意图。如图6A及6B所示,本发明的纳米双晶铜层43的50%以上的体积包括有多个柱状晶粒66,而每一晶粒中有多个层状纳米双晶铜(例如,相邻的一组黑线与白线构成一个双晶铜,其以堆叠方向69堆叠而构成晶粒66),因此本发明中,纳米双晶铜层整体则包括非常多的纳米双晶铜。这些柱状晶粒66的直径D的范围是约为0.5μm至8μm且高度L约为1μm至500μm(或1μm至100μm,更优选为1μm至20μm),纳米双晶平面661(水平条纹)与(111)晶面平行,双晶晶粒间是晶界662,铜的(111)晶面垂直于厚度T方向,且双晶铜层的厚度T在此约为20μm(可在0.1μm~500μm之间任意调整)。相邻的该晶粒间的堆叠方向(几乎等同于[111]晶轴)的夹角约为0至20度。
综上所述,本发明的电性连接结构及/或其制造方法,通过控制Cu6Sn5晶粒的生长方向,解决了焊锡接点中介金属化合物层造成可靠度降低的问题,确实控制焊锡接点的质量。并且,本发明的电性连接结构及/或其制造方法不仅可控制接点的机械性质、电性、可靠度、以及使用寿命等,更降低了生产成本(这是由于本发明不需使用额外的阻挡材料、或是高温热处理等步骤),因此具有相当高的经济价值。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (25)
1.一种包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,包括步骤:
A、提供一第一基板;
B、在该第一基板的部分表面形成一第一纳米双晶铜层;
C、使用一焊料将该第一基板与一第二基板连接,该第二基板具有一第二电性垫,该第二电性垫包括一第二纳米双晶铜层,且该焊料配置于该第一纳米双晶铜层与该第二纳米双晶铜层之间;以及
D、以200℃至300℃的温度进行回焊(reflow)使该焊料至少部分转换为一介金属化合物(intermetalliccompound,IMC)层,且该介金属化合物层包括在优选方向(orientational)生长的多个Cu6Sn5晶粒;
其中,该第一纳米双晶铜层及该第二纳米双晶铜层的50%以上的体积分别包括多个双晶铜晶粒。
2.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,50%以上相邻的该多个Cu6Sn5晶粒方向的夹角为0至40度。
3.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,50%以上的该多个Cu6Sn5晶粒的[0001]方向与该第一纳米双晶铜层的[0001]方向的夹角为0至40度,且50%以上的该多个Cu6Sn5晶粒的[0001]方向与该第二纳米双晶铜层的[0001]方向的夹角为0至40度。
4.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该步骤D中,回焊的时间为30秒至10分钟。
5.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该步骤D中,回焊的温度为240℃至280℃。
6.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该多个Cu6Sn5晶粒与该第一纳米双晶铜层之间还包括一Cu3Sn层,且该Cu3Sn层的厚度与该多个Cu6Sn5晶粒中高度最高的晶粒高度比[Cu3Sn层的厚度]/[多个Cu6Sn5晶粒中高度最高的晶粒高度]为0至0.3。
7.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该多个Cu6Sn5晶粒所构成的层的厚度为500nm至10μm。
8.如权利要求6所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该Cu3Sn层的厚度为1nm至1000nm。
9.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该多个双晶铜晶粒彼此间互相连接,该每一双晶铜晶粒由多个纳米双晶铜沿着[111]晶轴方向堆叠而成,且相邻的该双晶铜晶粒间的堆叠方向的夹角为0至20度。
10.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该步骤B的该第一纳米双晶铜层的形成方法选自直流电镀、脉冲电镀、物理气相沉积、化学气相沉积、以及蚀刻铜箔所组成的集合。
11.如权利要求10所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,当该步骤B使用电镀形成该第一纳米双晶铜层时,电镀所使用的一电镀液包括有:一铜的盐化物、一酸、以及一氯离子源。
12.如权利要求11所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该电镀液还包括一物质选自明胶(gelatin)、界面活性剂、晶格修整剂、及其混合所组成的集合。
13.如权利要求11所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该电镀液中的酸为硫酸、甲基磺酸、或其混合。
14.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该第一基板包括有一第一电性垫,该第一电性垫包括该第一纳米双晶铜层。
15.如权利要求1所述的包括在优选方向生长的Cu6Sn5晶粒的电性连接结构的制备方法,其中,该第一纳米双晶铜层的厚度为0.1μm~500μm。
16.一种包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,包括:
一第一基板,其具有一第一电性垫,该第一电性垫包括一第一纳米双晶铜层;
一第二基板,其具有一第二电性垫,该第二电性垫包括一第二纳米双晶铜层;以及
至少一介金属化合物(intermetalliccompound,IMC)层,其位于该第一纳米双晶铜层及该第二纳米双晶铜层的表面,该介金属化合物层配置于该第一基板与该第二基板之间,并电性连接该第一电性垫以及该第二电性垫,且该介金属化合物层包括多个在优选方向性排列的Cu6Sn5晶粒;
其中,该第一纳米双晶铜层及该第二纳米双晶铜层的50%以上的体积分别包括多个双晶铜晶粒。
17.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,50%以上相邻的该多个Cu6Sn5晶粒方向的夹角为0至40度。
18.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,50%以上的该多个Cu6Sn5晶粒的[0001]方向与纳米双晶铜层的[0001]方向的夹角为0至40度,且50%以上的该多个Cu6Sn5晶粒的[0001]方向与该第二纳米双晶铜层的[0001]方向的夹角为0至40度。
19.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该多个Cu6Sn5晶粒与该第一纳米双晶铜层之间还包括一Cu3Sn层,且该Cu3Sn层的厚度与该多个Cu6Sn5晶粒中高度最高的晶粒高度比[Cu3Sn层的厚度]/[多个Cu6Sn5晶粒中高度最高的晶粒高度]为0至0.3。
20.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该多个Cu6Sn5晶粒所构成的层的厚度为500nm至10μm。
21.如权利要求19所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该Cu3Sn层的厚度为1nm至1000nm。
22.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该多个双晶铜晶粒彼此间互相连接,该每一双晶铜晶粒由多个纳米双晶铜沿着[111]晶轴方向堆叠而成,且相邻的该双晶铜晶粒间的堆叠方向的夹角为0至20度。
23.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该第一纳米双晶铜层及该第二纳米双晶铜层的厚度分别为0.1μm~500μm。
24.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该第一基板选自一半导体芯片、一电路板、及一导电基板所组成的集合。
25.如权利要求16所述的包括在优选方向排列的Cu6Sn5晶粒的电性连接结构,其中,该第二基板选自一半导体芯片、一电路板、及一导电基板所组成的集合。
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