CN101307475A - 铟组合物 - Google Patents

铟组合物 Download PDF

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Publication number
CN101307475A
CN101307475A CNA2007101441976A CN200710144197A CN101307475A CN 101307475 A CN101307475 A CN 101307475A CN A2007101441976 A CNA2007101441976 A CN A2007101441976A CN 200710144197 A CN200710144197 A CN 200710144197A CN 101307475 A CN101307475 A CN 101307475A
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China
Prior art keywords
indium
metal
composition
alloy
acid
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CNA2007101441976A
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CN101307475B (zh
Inventor
E·佐克斯
F·J·施瓦格
T·加伊斯克
N·E·布雷斯
M·P·托本
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C08L71/03—Polyepihalohydrins
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Abstract

公开了含有一种或多种铟离子源和一种或多种表卤代醇共聚物的铟组合物和在基体上由所述组合物电化学沉积金属铟的方法。还公开了由铟组合物制备的制品。

Description

铟组合物
技术领域
本发明涉及用于电化学沉积金属铟和铟合金的铟组合物。更具体地，本发明涉及用于电化学沉积金属铟和铟合金的包括一种或多种氢抑制化合物的铟组合物。
背景技术
由于金属铟沉积与水电解析出氢同时发生，电化学沉积金属铟具有挑战性。氢的析出危害阴极电流效率，导致低的金属铟沉积率以及不合需要的粗糙粉状铟金属沉积物或无铟沉积物。
然而，由于其独特的物理性质，铟是许多行业中需求很高的金属。例如，其足够软使得易于变形并填充于两个配件间的微结构中，其具有低熔融温度(156℃)和高热导率(～82W/m°K)。这些性质使得铟在电子及相关行业中具有多种用途。
例如，铟及其合金可用作热界面材料(TIMs)。TIMs对于防止例如集成电路(IC)和如微处理器的有源半导体装置的电子装置超过其操作温度极限至关重要。他们可粘结发热装置(例如硅半导体)与散热器或传热器(例如铜或铝部件)而不产生过量的热障。TIM也可用于构成全部热阻抗路径的其它散热器或传热器叠层部件的组合。
形成有效的热路径是TIMs的重要性质。热路径可描述为通过TIM的有效热导率。TIM的有效热导率主要归因于TIMs和传热器之间的界面热导率的整体性以及TIM的(固有)整体热导率。取决于特定的应用，许多其它的性质对于TIM也很重要，例如：当连接两种材料时减轻热膨胀应力的能力(也称为“顺从性”)，形成热循环期间稳定的合理机械连接的能力，对湿度和温度变化不敏感，制造可行性及成本。
使用多种类型的材料作为TIMs，例如热油脂、热凝胶、粘合剂、弹性体、热衬垫和相变材料。尽管前述TIMs对于许多半导体装置已经足够，但是增强的半导体装置性能使得这种TIMs并不能满足要求。许多当前TIMs的热导率不超过5W/m°K并且许多小于1W/m°K。然而目前需要有效热导率超过15W/m°K的形成热界面的TIMs。
前述TIMs的一种替代物为具有低熔融温度和高热导率的金属、焊料及其合金。例如铟的金属TIMs在软熔时还显示出可产生促进低界面阻力的良好焊接或润湿特性。在软熔过程中，加热焊料和基体并利用表面张力和局部表面合金化熔融并润湿焊料。界面由金属互化物或互扩散金属构成，其热性能通常不如那些整体TIM金属但是强于聚合物基TIMs。在许多情况下，软熔处理金属TIMs以形成可靠的热界面。然而由于TIM和半导体和散热器组件间热膨胀系数(CTEs)的相对大的差异和缺少顺从性，金属TIMs并不适用于某些应用。金属铟至少具有低熔点和适于作为TIM的高热导率。
Sreeram等人的US6,653,741公开了用于TIM的铟的实施例。铟用作焊料的粘结材料。Sreeram所描述的焊料材料由于固有的氧气吸收成分与水性电镀通常不相容因而不适用于电镀。此外，焊膏通常含有可降低焊料基TIMs热性能的高量污染物。
另一个使用铟的实施例是在电气装置中作为表层和底层以防止形成锡和锡合金晶须。这在Shimauchi等人的US4,959,278中被公开。晶须可导致电气装置中的缺陷，从而导致设备故障。晶须形成典型的在例如但不局限于焊接框架的金属组件的应力和应变点处发生。当改变金属组件的形状以机械或电接触电气装置的另一个组件时，应力或应变点会形成锡、锡合金或其它金属的金属晶体或晶须。因此，铟是电子装置中非常合乎需要的金属，需要有一种用于电化学沉积金属铟和其合金的改进的铟组合物。
发明内容
一方面，组合物包括一种或多种铟离子源和一种或多种表卤代醇共聚物。
另一方面，方法包括提供包括一种或多种铟离子源和一种或多种表卤代醇共聚物的组合物；以及在基体上电化学沉积铟。
在另一方面，产品包括一模具，第一面与基体连接，与第一面相对的模具的第二面包括由铟或其合金构成的热界面材料。
铟组合物是稳定的并提供致密、即无孔、光滑、厚度分布均匀并且几乎无边缘缺陷的金属铟和铟合金沉积物，也就是说在电镀基体面形成厚的沉积物。表卤代醇共聚物在金属铟和铟合金沉积过程中抑制氢气的形成从而能够形成所需的金属铟和铟合金沉积物。由于金属铟具有低熔点和高热导率，金属铟在许多电气装置中非常适合用作热界面材料。此外，金属铟分散在界面处由两个配套材料的CTE失配引起的应变，这也使其适合用作TIM。另外，由铟组合物电化学沉积的金属铟和铟合金可用作底层以防止或阻止晶须形成。由铟组合物电化学沉积的金属铟和铟合金也可用作焊料块以提供电连接。
附图说明
图1为从铟电解质中低效率电镀于基体上的铟的照片。
图2为从本发明的铟电解质组合物中电镀于基体上的铟的照片。
具体实施方式
如整个说明书中所使用的，下述缩写具有下述含义，除非文中明显另有所指：℃＝摄氏度；°K＝开氏温度；GPa＝千兆帕斯卡；g＝克；mg＝毫克；L＝升；m＝米；A＝安培；dm＝分米；μm＝微米；ppm＝百万分之；ppb＝十亿分之；mm＝毫米；M＝摩尔；MEMS＝微机电系统；TIM＝热界面材料；CTE＝热膨胀系数；IC＝集成电路以及EO＝环氧乙烷。
术语“沉积”和“电镀”在整篇说明书中可替代使用。整篇说明书中所使用的术语“底层”指置于基体和锡或锡合金层或其它适合金属或金属合金层之间的金属层或涂层。术语“共聚物”是由两种或多种不同基体构成的化合物。除非另有所指，所有的量为重量百分比，所有的比率以重量计。所有的数值范围包含端点并可以以任意顺序结合，其中这些数值范围之和合乎逻辑地限定为100％。
组合物包括一种或多种可溶于水性环境的铟离子源。这些铟离子源包括但不局限于铟的烷基磺酸和芳族磺酸盐，例如铟的甲磺酸盐、乙磺酸盐、丁烷磺酸盐、苯磺酸盐、甲苯磺酸盐；氨基磺酸盐；硫酸盐；铟的氯盐和溴盐；硝酸盐；氢氧化物；氧化铟；氟硼酸盐；铟的羧酸盐，例如铟的柠檬酸盐、乙酰乙酸盐、乙醛酸盐、丙酮酸盐、乙醇酸盐、丙二酸盐、异羟肟酸盐、亚氨基二乙酸盐、水杨酸盐、甘油酸盐、琥珀酸盐、苹果酸盐、酒石酸盐、羟基丁酸盐；铟的氨基酸盐，例如铟的精氨酸盐、天冬氨酸盐、天冬酰胺盐、谷氨酸盐、甘氨酸盐、谷酰胺盐、亮氨酸盐、赖氨酸盐、苏氨酸盐、异亮氨酸盐和缬氨酸盐。典型地，铟离子源为一种或多种铟的硫酸盐、氨基磺酸盐、烷基磺酸盐、芳族磺酸盐和羧酸盐。更典型地，铟离子源为一种或多种铟的硫酸盐和氨基磺酸盐。
组合物中包含足量的水溶性铟盐以提供所需厚度的铟沉淀物。典型地，组合物中包含水溶性铟盐以在组合物中提供5g/L-70g/L，或者例如10g/L-60g/L，或者例如15g/L-30g/L的铟(3+)离子。
铟组合物中包含的缓冲液或导电盐可为一种或多种酸，以提供0-5，典型地0.5-3，更典型地1-1.5的pH值。这些酸包括但不局限于烷基磺酸盐、芳基磺酸盐，例如甲磺酸、乙磺酸、苯磺酸、甲苯磺酸；氨基磺酸；硫酸；盐酸；氢溴酸；氟硼酸；硼酸；羧酸，例如柠檬酸、乙酰乙酸、乙醛酸、丙酮酸、乙醇酸、丙二酸、异羟肟酸、亚氨基二乙酸、水杨酸、甘油酸、琥珀酸、苹果酸、酒石酸、羟基丁酸；氨基酸，例如精氨酸、天冬氨酸、天冬酰胺、谷氨酸、甘氨酸、谷酰胺、亮氨酸、赖氨酸、苏氨酸、异亮氨酸和缬氨酸。还可使用一种或多种酸的相应盐。典型地，一种或多种烷基磺酸、芳基磺酸和羧酸用作缓冲液或导电盐。更典型地，使用一种或多种烷基磺酸、芳基磺酸或其相应的盐。
使用足量的缓冲液或导电盐以提供组合物所需的pH值。典型地，缓冲液或传导盐的用量为组合物的5g/L-50g/L，或例如10g/L-40g/L，或例如15g/L-30g/L。
铟组合物中包含一种或多种氢抑制剂以在金属铟沉积过程中抑制氢气的形成。氢气抑制剂为可驱动作为氢气来源的水分解的电位到更高的阴极电位以使金属铟沉积而不同时析出氢气的化合物。这在阴极提高铟沉积的电流效率并能够形成外观光滑均匀的铟层，而且与许多常规的铟电化学浴相比还可以形成更厚的铟层。可使用现有技术和文献中熟知的循环伏安法(CV)研究来显示该方法。典型地，不包含一种或多种氢抑制剂的铟电化学水浴形成外观粗糙不均匀的铟沉淀物。这些沉淀物不适用于电子装置。通常这些浴中不形成铟沉淀物。
氢气抑制剂为表卤代醇共聚物。表卤代醇包括表氯醇和表溴醇。典型地，使用表氯醇的共聚物。这些共聚物为表氯醇或表溴醇和一种或多种包括氮、硫、氧原子或其组合的有机化合物的水溶性聚合产物。
可与表卤代醇共聚的含氮有机化合物包括但不局限于：
1)脂肪链胺；
2)具有至少两个活性氮位点的未取代杂环氮化合物；和
3)具有至少两个活性氮位点和1-2个选自烷基、芳基、硝基、卤素和氨基的取代基的取代杂环氮化合物。
脂肪链胺包括但不局限于二甲胺、乙胺、甲胺、二乙胺、三乙胺、乙二胺、二亚乙基三胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、2-乙基己胺、异辛胺、壬胺、异壬胺、癸胺、十一胺、十二胺、十三胺和链烷醇胺。
具有至少两个活性氮位点的未取代杂环氮化合物包括但不局限于咪唑、咪唑啉、吡唑、1，2，3-三唑、四唑、哒嗪、1，2，4-三唑、1，2，3-噁二唑、1，2，4-噻二唑(thiadiazole)和1，3，4-噻二唑。
具有至少两个活性氮位点和1-2个取代基的取代杂环氮化合物包括但不局限于苯并咪唑、1-甲基咪唑、2-甲基咪唑、1，3-二甲基咪唑、4-羟基-2-氨基咪唑、5-乙基-4-羟基咪唑、2-苯基咪唑啉和2-甲苯基咪唑啉。
典型地，使用一种或多种包括1或2个选自甲基、乙基、苯基和氨基的取代基的选自咪唑、吡唑、咪唑啉、1，2，3-三唑、四唑、哒嗪、1，2，4-三唑、1，2，3-噁二唑、1，2，4-噻二唑、1，3，4-噻二唑及其衍生物的化合物形成表卤代醇共聚物。
一些表卤代醇共聚物可商购于例如来斯琪股份有限公司(Raschig GmbH)，德国路威沙芬公司(Ludwigshafen Germany)和巴斯福公司(BASF，美国密歇根州，怀恩多特市)，或者可以利用文献中公开的方法制备。一个商购咪唑/表卤代醇共聚物的例子是可从巴斯福公司获得的LugalvanTMIZE。
可通过在任何适合的反应条件下使表卤代醇与上述含氮、硫或氧的化合物反应形成表卤代醇共聚物。例如在一种方法中，两种材料都以适当的浓度溶解于互溶剂体中并在其中反应例如45-240分钟。通过蒸馏溶剂分离出反应的水溶液化学产物，然后加入到作为电镀液的溶解了铟盐的水体中。在另一个方法中，这两种材料置于水中并在持续强烈搅拌下加热至60℃直到其溶解于水中并反应。
可使用宽范围的反应化合物与表卤代醇的比率，例如0.5∶1-2∶1。典型地，比率为0.6∶1-2∶1，更典型地，比率为0.7-1∶1，最典型地，比率为1∶1。
另外，在通过加入铟盐形成电镀组合物之前，反应产物可进一步与一种或多种试剂反应。因此，所述产物可进一步与至少为氨、脂肪胺、聚胺和聚酰亚胺中的一种的试剂反应。虽然可使用满足本文定义的其它种类，但是典型地试剂至少为分子量至少150的氨、乙二胺、四亚乙基五胺和聚乙烯亚胺中的一种。反应可通过搅拌在水中进行。
例如，表氯醇和如上所述的含氮有机化合物的反应产物和选自氨、脂肪胺和芳基胺或聚酰亚胺中的一种或多种的试剂之间的反应可以在例如30℃-60℃的温度下进行例如45-240分钟。含氮化合物-表氯醇反应的反应产物与试剂之间的摩尔比典型地为1∶0.3-1。
组合物中含有的表卤代醇共聚物的量为5g/L-100g/L。典型地，所含有表卤代醇共聚物的量为10g/L-80g/L，更典型地，其含有的量为20g/L-70g/L，最典型地，含量为30g/L-60g/L。
组合物中还可含有可选的添加剂以使组合物适于电镀条件和基板。这种可选的添加剂包括但不局限于一种或多种表面活性剂、螯合剂、匀平剂、抑制剂(载体)，一种或多种合金金属和其它在铟电化学制剂中使用的常规添加剂。
可使用与组合物中其它成分相适应的任意表面活性剂。典型地，表面活性剂为消泡或不起泡表面活性剂。这些表面活性剂包括但不局限于例如含有12摩尔EO的乙氧基化聚苯乙烯酚、含有5摩尔EO的乙氧基化丁醇、含有16摩尔EO的乙氧基化丁醇、含有8摩尔EO的乙氧基化丁醇、含有12摩尔EO的乙氧基化辛醇、含有12摩尔EO的乙氧基化辛基酚、乙氧基化/丙氧基化丁醇、含有13摩尔EO的乙氧基化β萘酚、含有10摩尔EO的乙氧基化β萘酚、含有10摩尔EO的乙氧基化双酚A、含有13摩尔EO的乙氧基化双酚A、含有30摩尔EO的硫酸化乙氧基化双酚A和含有8摩尔EO的乙氧基化双酚A的非离子表面活性剂。这些表面活性剂以常规量加入。典型地，其在组合物中加入的量为0.1g/L-20g/L，或例如0.5g/L-10g/L。其可商购并可用文献中公开的方法制备。
其它的表面活性剂包括但不局限于两性表面活性剂，例如烷基二亚乙基三胺醋酸和季铵化合物和胺。这些表面活性剂为现有技术中所熟知的并且许多可以商购。其可以常规量使用。典型地其在组合物中的含量为0.1g/L-20g/L，或例如0.5g/L-10g/L。典型地，所使用的表面活性剂为季铵化合物。
螯合剂包括但不局限于例如羧酸，丙二酸和酒石酸；羟基羧酸，例如柠檬酸和苹果酸；及其盐。也可使用例如乙二胺四乙酸(EDTA)的较强螯合剂。螯合剂可单独使用或组合使用。例如，变化量的相对强螯合剂(例如EDTA)可与变化量的一种或多种较弱螯合剂(例如丙二酸、柠檬酸、苹果酸和酒石酸)结合使用以控制用于电镀的铟的量。螯合剂可以常规量使用。典型地，螯合剂的用量为0.001M-3M。
匀平剂包括但不局限于聚烷撑二醇醚。这些醚包括但不局限于二甲基聚乙二醇醚、二叔丁基聚乙二醇醚、聚乙烯/聚丙烯二甲醚(混合或嵌段共聚物)和辛基一甲基聚烷撑醚(混合或嵌段共聚物)。这些匀平剂以常规量加入。典型地这些匀平剂的加入量为100ppb-500ppb。
抑制剂包括但不局限于菲咯啉及其衍生物，例如1，10-菲咯啉；三乙醇胺及其衍生物，例如三乙醇胺硫酸月桂酯，十二烷基硫酸钠，乙氧基化十二烷基硫酸铵；聚乙烯亚胺及其衍生物，例如羟丙基聚乙烯亚胺(HPPEI-200)；以及烷氧基化聚合物。铟组合物中包含的这些抑制剂为常规量。典型地，抑制剂的含量为200ppm-2000ppm。
一种或多种合金金属包括但不局限于铝、铋、铈、铜、金、镁、银、锡、钛、锆和锌。典型地，合金金属为银、铋和锡。合金金属可以水溶性金属盐加入到铟组合物中。这些水溶性金属盐是广为人知的。许多可以商购或者根据文献的描述制备。铟组合物中加入足量水溶性金属盐以形成含有1wt％-5wt％或者例如2wt％-4wt％合金金属的铟合金。典型地，加入到铟组合物中的水溶性金属盐的量使铟合金中含有1wt％-3wt％的合金金属。
铟中加入一种或多种合金金属可改变铟的性质。3wt％或更少的合金金属的量可改善TIM耐高温腐蚀性、润湿性以及与基体(例如硅片)的粘结性。另外，例如银、铋和锡的合金金属可与铟形成低熔点低共熔混合物。铟组合物中合金金属的含量为0.01g/L-15g/L，或例如0.1g/L-10g/L，或例如1g/L-5g/L。
铟组合物可用于在基体上沉积金属铟或铟合金层。沉积金属铟的纯度以重量计可达99％或更高，除非包含合金金属。层的厚度取决于金属铟或铟合金层的功能而变化。通常，厚度范围为0.1μm或更厚，或例如1μm-400μm，或例如10μm-300μm，或例如20μm-250μm，或例如50μm-200μm。典型地，金属铟和铟合金层厚度范围为150μm-200μm。
用于将金属铟和铟合金沉积到基体上的设备为常规的。可使用常规的电极。典型地，使用可溶性电极。更典型地，使用可溶性铟电极作为阳极。用金属铟电镀的基体为阴极或工作电极。如果需要，可使用任意适合的参考电极。典型地，参考电极为氯化银/银电极。电流密度范围可为0.5A/dm2-30A/dm2，或例如1A/dm2-25A/dm2，或例如10A/dm2-20A/dm2。
金属铟电镀过程中铟组合物的温度范围为30℃-80℃。典型地，温度范围为40℃-80℃。
铟组合物可用于在包括电子装置、磁场装置和超导MRIs组件的不同基体上沉积金属铟和铟合金。也可利用常规照片成像方法使用铟组合物在例如硅或GaAs晶片的各种基体上电化学沉积金属铟或铟合金焊块。
例如，铟组合物可用于在电气装置组件上电化学沉积金属铟或铟合金作为例如但不局限于集成电路、半导体装置的微处理器、MEMS和光电装置组件的TIM。这些电子组件可包含于印刷电路板和气密性密封的芯片级和晶片级管壳(package)中。典型地这些管壳包括在基础基体和盖板之间形成的气密性密封的封闭箱体，其中电子装置置于该密封箱体之中。管壳为密封装置提供密封和保护以防止管壳外大气中污染物和水蒸汽的影响。管壳中污染物和水蒸汽的存在会产生例如金属部件腐蚀以及光电装置和其它光学部件的光损耗的问题。金属铟的低熔点(156℃)和高热导率(～82W/m°K)是使金属铟非常适合作为TIM的性质。
铟TIMs从加工模具(即树脂密封硅基片)中移除热量并将热量传递到盖板/散热器。铟TIMs也可吸收由电子装置中连接在一起的不同材料间CTE的不匹配引起的应力。铟的热膨胀系数为29ppm/℃，而硅和铜分别为3和17。铟的模数为10GPa，而较硬的硅和铜的模数分别为50和130。
在一个实施方案中，金属铟或铟合金层电化学沉积到加工模具基体表面作为TIM，散热器通过金属铟或合金层连接到加工模具上。散热器为常规材料，例如涂覆镍的铜、碳化硅或铝。加工模具可通过在与金属铟或合金层相对的加工模具的一侧上的焊料块连接到印刷电路板基体或陶瓷基体上。焊料块可由常规材料组成，例如锡或锡合金或用于电子工业的其它常规材料。焊料块也可以为由如上所述的组合物电化学沉积得到的金属铟或铟合金。
在另一个实施方案中，金属铟或合金层电化学沉积到加工模具基体表面作为TIM和覆盖加工模具并置于模具和金属铟或合金层之上的凹盖(即具有与顶部垂直的连续面的顶部)。该盖体可具有常规的设计(即矩形或椭圆形的)，且可以用常规的材料例如铜或铜合金制成。铟或合金层连接盖体与模具。加工模具通过焊接块连接到印刷电路板基体或陶瓷基体上。在凹盖侧面的底表面上的焊接块连接盖体与印刷电路板基体或陶瓷基体。
在另一个实施方案中，金属铟或铟合金层电化学沉积到传热器表面作为TIM。传热器与盖体为常规材料，例如铜、铜合金、碳化硅或金属与陶瓷复合材料，例如铝浸渍碳化硅的。金属铟或铟合金层连接盖体与模具。
在进一步的实施方案中，金属铟层电化学沉积到加工模具基体表面作为TIM和覆盖加工模具并置于模具和金属铟或合金层之上的凹盖(即具有与顶部垂直的连续侧面的顶部)。盖体可为常规设计(即矩形或椭圆)并可为常规材料。铟层连接盖体与模具。加工模具通过焊料块连接到印刷电路板基体或陶瓷基体上。在凹盖侧面的底表面上的焊料块连接盖体与印刷电路板基体或陶瓷基体。第二金属铟层电化学沉积于盖体顶部作为第二TIM，并且散热器通过第二金属铟层连接到盖体顶部。
除了在加工模具基体和传热器上沉积铟和铟合金，铟和铟合金可沉积于盖体上。
作为TIMs的金属铟或合金层的厚度可以变化。典型地，层厚为230μm或更少。更典型地，层厚范围为50μm-230μm或例如100μm-220μm或例如140μm-210μm。
除了TIMs，铟组合物可用于在基体上电化学沉积底层以防止在电子装置中形成晶须。基体包括但不局限于电气或电子组件或部件，例如安放半导体晶片的载体膜、印刷电路板、引线框；接触元件，例如触点或接头；以及要求良好外观和高操作可靠性的电镀构件。
金属铟可用作锡或锡合金顶层的底层以防止或阻止形成晶须。晶须通常在锡或锡合金层沉积在例如构成电气或电子组件的铜或铜合金的金属材料上时形成。已知晶须可引起导致电气装置故障的电子短路。此外，界面处铟和其它金属间CTE的不匹配引起的应变的分散改善了金属层间的粘附。典型地，铟底层的厚度为0.1μm-10μm或例如0.5μm-5μm。锡或锡合金层为常规厚度。
下述实施例进一步描述了本发明，但是并不意欲限制发明的范围。
实施例I(比较例)
制备下述含水铟电化学组合物：
表1
  组分 量
  铟(3+)离子(来自硫酸铟)   30g/L
  氢氧化铵   170g/L
  硼酸   80g/L
  酒石酸   300g/L
  常规铟电镀浴添加剂   0.5g/L
  水   所需量
  pH   3
用于电化学沉积金属铟的设备为常规的商购电解池。
保持铟电化学组合物的pH为3并且温度为60℃。在金属铟电镀期间持续搅拌组合物。阴极电流密度保持在10A/dm2，铟沉积率为20秒1μm(23mg/A)。
图1显示了阴极效率小于60％的金属铟涂覆工作电极的照片。照片利用常规35mm镜头相机拍摄。如照片所示，沉积物外观为海绵状，具有不均匀金属铟沉积物。这些沉积物不适合用于电子装置的组件，例如TIMs和底层。海绵状和不均匀表面可引起电气装置中的低效率热传送和电流，从而导致装置故障。海绵状和不均匀表面被认为是由金属铟沉积期间氢气析出和铟组合物中有机添加物分解引起的。
实施例II
制备下述含水铟电化学组合物：
表2
  组分 量
  铟(3+)离子(来自硫酸铟)   60g/L
  甲磺酸   30g/L
  咪唑-表氯醇共聚物1   100g/L
  水   所需量
  pH   1-1.2
1.LugalvanTM IZE，获自巴斯福(IZE含48-50％共聚物)
用于电镀金属铟的设备为常规的商购电解池。
在金属铟沉积期间，保持铟电镀组合物的pH为1-1.2。在电镀期间组合物的温度保持为60℃。在金属铟沉积期间持续搅拌电镀组合物。在整个电镀期间，阴极电流密度保持在10A/dm2，20秒内在工作电极上沉积1μm的金属铟(23mg/A)。铟组合物保持稳定，也就是说在电镀期间无肉眼可见的混浊。持续沉积金属铟，直到在工作电极上形成200μm金属铟层。
图2显示了金属铟涂覆的工作电极的照片。如照片所示，金属铟沉积物外观光滑并且沉淀物是均匀的。因此，与对比铟组合物不同，含有咪唑-表氯醇共聚物的铟电化学组合物产生改善的金属铟沉积物。
这些光滑并且均匀的沉积物是电子装置的组件(例如TIMs和底层)非常需要的。当铟用作TIM时，光滑并且均匀的表面可在加工模具和散热器间产生有效的热传递。
实施例III
重复上述实施例II中的方法，除了表卤代醇共聚物为由现有技术中已知的常规方法制备的咪唑啉-表氯醇共聚物。预期包含咪唑啉-表氯醇共聚物的铟组合物在铟电镀期间抑制氢气的形成并如图2所示在工作电极上沉积光滑均匀的金属铟层。也预期由该组合物沉积的铟底层在40℃或更高的温度以及至少95％的相对湿度下保存至少一个月后还可防止或者至少抑制晶须的形成。
实施例IV
重复上述实施例II中的方法，除了表卤代醇共聚物为由现有技术中已知的常规方法制备的1，2，3-三唑-表氯醇共聚物。预期包含1，2，3-三唑-表氯醇共聚物的铟组合物在铟电镀期间抑制氢气的形成并如图2所示在工作电极上沉积光滑均匀的金属铟层。也预期由该组合物沉积的铟底层在40℃或更高的温度以及至少95％的相对湿度下保存至少一个月后还可防止或者至少抑制晶须的形成。
实施例V
重复上述实施例II中的方法，除了表卤代醇共聚物为由现有技术中已知的常规方法制备的哒嗪-表溴醇共聚物。预期包含哒嗪-表溴醇共聚物的铟组合物在铟电镀期间抑制氢气的形成并如图2所示在工作电极上沉积光滑均匀的金属铟层。也预期由该组合物沉积的铟底层在40℃或更高的温度以及至少95％的相对湿度下保存至少一个月后还可防止或者至少抑制晶须的形成。
实施例VI
重复上述实施例II中的方法，除了表卤代醇共聚物为由现有技术中已知的常规方法制备的2-甲基咪唑-表溴醇共聚物。预期包含2-甲基咪唑-表溴醇共聚物的铟组合物在铟电镀期间抑制氢气的形成并如图2所示在工作电极上沉积光滑均匀的金属铟层。也预期由该组合物沉积的铟底层在40℃或更高的温度以及至少95％的相对湿度下保存至少一个月后还可防止或者至少抑制晶须的形成。
实施例VII
重复上述实施例II中的方法，除了铟电化学组合物还包括2wt％硫酸锡。电流密度保持为10A/dm2 30秒并在铟电极上沉积铟/锡金属合金。预期此电化学组合物在电镀期间保持稳定并且预期在沉淀期间利用循环伏安分析法没有检测出氢析出。预期铟/锡合金层外观光滑均匀。
实施例VIII
重复实施例II中的方法，除了铟电化学组合物还包括2wt％硫酸锌。电流密度保持为10A/dm2 20分钟并在铟电极上沉积铟/锌金属合金。预期该电化学组合物为稳定的并且预期在合金沉积期间利用循环伏安分析法没有检测出氢析出。预期铟/锌合金层外观光滑均匀。
实施例IX
重复实施例II中的方法，除了铟电化学组合物还包括1wt％五水合硫酸铜。电流密度保持为5A/dm2 40分钟并在铟电极上沉积铟/铜金属合金。预期该电化学组合物为稳定的并且预期在合金沉积期间利用循环伏安分析法没有检测出氢析出。预期铟/锌合金层外观光滑均匀。

Claims (10)

1.一种组合物，其中该组合物含有一种或多种铟离子源和一种或多种表卤代醇共聚物。
2.如权利要求1所述的组合物，其中所述表卤代醇共聚物含有表卤代醇和一种或多种含氮有机化合物。
3.如权利要求2所述的组合物，其中所述含氮化合物选自咪唑、咪唑衍生物、咪唑啉和咪唑啉衍生物。
4.如权利要求1所述的组合物，其中，该组合物还含有一种或多种合金金属。
5.一种方法，包括：
a)提供含有一种或多种铟离子源和一种或多种表卤代醇共聚物的组合物；和
b)在基体上电镀铟金属层。
6.如权利要求5所述的方法，其中所述组合物还包括一种或多种合金金属。
7.如权利要求5所述的方法，其中所述铟金属层厚度为0.1μm或更厚。
8.如权利要求5所述的方法，其中所述基体选自加工模具、盖体和传热器。
9.如权利要求5所述的方法，其中所述基体选自金属、金属合金、陶瓷和金属与陶瓷复合材料。
10.一种制品，包括第一面与基底相连的模具，与第一面相对的模具的第二面包括由金属铟或铟合金组成的热界面材料。
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CN102574250A (zh) * 2009-09-08 2012-07-11 阿斯特恩先进材料有限公司 使用电沉积的铟和/或镓的焊接方法、以及包含具有铟和/或镓的中间层的制品
CN102877042A (zh) * 2011-07-12 2013-01-16 财团法人工业技术研究院 硫化铟薄膜的制备方法
CN108603300A (zh) * 2016-01-29 2018-09-28 埃托特克德国有限公司 含水的铟或铟合金镀浴以及用于沉积铟或铟合金的方法
CN108603300B (zh) * 2016-01-29 2021-01-05 埃托特克德国有限公司 含水的铟或铟合金镀浴以及用于沉积铟或铟合金的方法
CN107630236A (zh) * 2016-07-18 2018-01-26 罗门哈斯电子材料有限责任公司 含有2‑咪唑烷硫酮化合物的铟电镀组合物和电镀铟的方法
CN107630239A (zh) * 2016-07-18 2018-01-26 罗门哈斯电子材料有限责任公司 含有1,10‑啡啉化合物的铟电镀组合物和电镀铟的方法
CN107630238A (zh) * 2016-07-18 2018-01-26 罗门哈斯电子材料有限责任公司 铟电镀组合物和用于电镀铟的方法
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CN107630239B (zh) * 2016-07-18 2020-11-06 罗门哈斯电子材料有限责任公司 含有1,10-啡啉化合物的铟电镀组合物和电镀铟的方法

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US9206519B2 (en) 2015-12-08
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US8460533B2 (en) 2013-06-11
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CN101307475B (zh) 2011-10-12

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