JP7437057B2 - Ｓｎ層又はＳｎ合金層を含む構造体 - Google Patents

Ｓｎ層又はＳｎ合金層を含む構造体 Download PDF

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JP7437057B2
JP7437057B2 JP2021575155A JP2021575155A JP7437057B2 JP 7437057 B2 JP7437057 B2 JP 7437057B2 JP 2021575155 A JP2021575155 A JP 2021575155A JP 2021575155 A JP2021575155 A JP 2021575155A JP 7437057 B2 JP7437057 B2 JP 7437057B2
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layer
alloy
acid
alloy layer
ubm
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JPWO2021156970A1 (ja
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貴大 田中
浩智 山田
大樹 高瀬
賢 幡部
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Ishihara Chemical Co Ltd
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Ishihara Chemical Co Ltd
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    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
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    • B23K35/262—Sn as the principal constituent
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Description

本発明は、Ｓｎ層又はＳｎ合金層を含む構造体に関し、特に電子部品等の電極や配線等の導電部品や接合部品として設けられるＳｎ層又はＳｎ合金層を含む構造体に関する。
従来、Ｓｎ及びＳｎ合金は融点が低く、延展性に優れていることから接合材料として電子部品等に利用されてきた。この場合、Ｓｎ及びＳｎ合金は主にボールマウント工法、ペースト工法、めっき工法、インクジェット工法等により基材に付与される。基材としては、Ｃｕ又はＣｕ合金系基材や、Ｎｉ合金系基材等が用いられ、又は他の非金属系基材を用いる場合はめっきやスパッタリング等により基材上にＣｕ層やＮｉ層が施されていることが一般的である。例えばフリップチップバンプ等では、基材のＣｕスパッタ層の上に、数μｍ程度のＮｉめっき層が設けられ、さらにその上にＳｎ又はＳｎ系合金のめっき層が設けられた構造体がよく用いられている。基材上に設けられたＮｉめっき層は、通常、アンダーバリアメタル（以下、ＵＢＭともいう）と呼ばれ、ＣｕとＳｎ又はＳｎ系合金との間で金属拡散に起因する金属間化合物が生成することを抑制するのが、ＵＢＭの生成の目的の１つである。
しかしながら、Ｎｉめっき層のＵＢＭを設けたとしても、近年の電子回路の微細化により、Ｃｕ基材又は基材上のＣｕスパッタ層とＳｎ層又はＳｎ系合金層との接合部における金属間化合物の比率が大きくなり、電気的特性や接続信頼性を悪化させる問題が見られるようになってきた。このような問題を解決するために、ＵＢＭとしてＣｏめっき層やＮｉ－Ｆｅ合金めっき層をＳｎ層又はＳｎ合金層の下層に設け、金属間化合物の生成量を低減することが研究されている（例えば、特許文献１及び非特許文献１等を参照）。
米国特許第９０８２７６２号明細書
Ｊａ－Ｋｙｕｎｇ Ｋｏｏ及びＪａｅ－Ｈｏ Ｌｅｅ著，Ｍａｔｅｒｉａｌｓ Ｔｒａｎｓａｃｔｉｏｎｓ，Ｖｏｌ．５８（２０１７），Ｎｏ．２，ｐ．１４８－１５１．
前記特許文献１や非特許文献１に開示されたＵＢＭを採用することにより、一定の効果は認められるが、より過酷な条件においてはＣｏめっき層やＮｉ－Ｆｅ合金めっき層では金属間化合物の生成を充分に抑制することが困難であり、より新しい組成のＵＢＭが求められている。
本発明は、前記の問題に鑑みてなされたものであり、その目的は、金属を含む基材とＳｎ層又はＳｎ合金層との間において金属間化合物の生成をより抑制できるＵＢＭを得ることにある。
前記の目的を達成するために、本発明者らは、鋭意研究の結果、Ｓｎ層又はＳｎ合金層を含む構造体において、ＵＢＭとして、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層を用いることにより、金属間化合物の生成を顕著に抑制できることを見出して、本発明を完成した。
具体的に、本発明に係るＳｎ層又はＳｎ合金層を含む構造体は、基材と、前記基材の上に形成されたＳｎ層又はＳｎ合金層と、前記基材と前記Ｓｎ層又はＳｎ合金層との間に形成されたアンダーバリアメタルとを備えており、前記アンダーバリアメタルは、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層であることを特徴とする。
本発明に係るＳｎ層又はＳｎ合金層を含む構造体によると、基材とＳｎ層又はＳｎ合金層との間に、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層であるアンダーバリアメタルが形成されている。このため、当該アンダーバリアメタルによって基材中の金属の金属拡散による当該金属とＳｎ層又はＳｎ合金層中のＳｎとが反応して金属間化合物が生成することを抑制できる。従って、当該構造体は電気的特性や接続信頼性が良好であり、電子部品等に用いるのに適している。
前記のとおり、アンダーバリアメタルは、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層であるが、この場合、Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層であることが好ましい。
さらに、前記のとおり、アンダーバリアメタルがＮｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層である場合、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉを５０％以下の質量比率で含むＮｉ合金層であることが好ましい。
これらのようにすると、アンダーバリアメタルによる金属間化合物の生成の抑制能をより向上させることができる。
本発明に係るＳｎ層又はＳｎ合金層を含む構造体によると、基材中の金属の金属拡散による当該金属とＳｎ層又はＳｎ合金層中のＳｎとが反応して金属間化合物が生成することを充分に抑制できる。このため、当該構造体は、電気的特性や接続信頼性が良好であり、電子部品等に用いるのに適している。
本発明の一実施形態に係るＳｎ層又はＳｎ合金層を含む構造体を示す図である。
以下、本発明を実施するための形態を図面に基づいて説明する。以下の好ましい実施形態の説明は、本質的に例示に過ぎず、本発明、その適用方法或いはその用途を制限することを意図するものではない。
本発明の一実施形態に係るＳｎ層又はＳｎ合金層を含む構造体について、図１を参照しながら説明する。
図１に示すように、本実施形態に係る構造体において、基材１０の上にアンダーバリアメタル（ＵＢＭ）１１が形成されており、ＵＢＭ１１の上にＳｎ層１２が形成されている。基材１０は特に限定されないが、例えばＣｕやＮｉ等からなる金属基板、ガラス基板、シリコン基板又はサファイア基板、有機材料基板等を用いることが可能である。但し、金属基板以外では、めっきやスパッタリングによって、その上面にＣｕやＮｉ又はそれらを含む合金等からなる金属薄膜が形成され、さらにその上にＣｕやＮｉ又はそれらを含む合金等からなる突起状の構造物を形成する場合がある。なお、ここでは、そのような基材上面に形成された金属薄膜及び構造物を含めて基材１０と呼ぶ。また、基材１０は、平板状の基板に限らず、例えば棒状や線状の条材であっても構わない。Ｓｎ層１２は、単一金属としてのＳｎ、又はＳｎを含むＳｎ合金からなる。特に、Ｓｎ合金としては、以下のものに限られないが、例えばＳｎ－Ａｇ、Ｓｎ－Ａｇ－Ｃｕ、Ｓｎ－Ｃｕ、Ｓｎ－Ｂｉ、又はＳｎ－Ｉｎ等が挙げられる。Ｓｎ層１２は、以下のものに限られないが、例えばボールマウント法、ペースト法、めっき法、又はインクジェット法等により形成される。
Ｓｎ層１２を電解めっき法により形成する場合、用いられるＳｎめっき液は、基本的に、可溶性第一スズ塩と、液ベースとしての酸又はその塩と、必要に応じて、酸化防止剤、安定剤、錯化剤、界面活性剤、光沢剤、平滑剤、ｐＨ調整剤、導電性塩、防腐剤等の各種添加剤を含有する。また、前記可溶性第一スズ塩としては、例えば、メタンスルホン酸、エタンスルホン酸、２－プロパノールスルホン酸、スルホコハク酸、ｐ－フェノールスルホン酸等の有機スルホン酸の第一スズ塩をはじめ、ホウフッ化第一スズ、硫酸第一スズ、酸化第一スズ、塩化第一スズ、スズ酸ナトリウム、スズ酸カリウム等を用いることができる。また、Ｓｎ層１２をＳｎ合金で構成する場合、例えばＳｎ塩とＡｇやＣｕ等の他の金属塩とを含むめっき液を用いてＳｎ合金膜を形成してもよいし、Ｓｎめっき膜とＡｇやＣｕ等の他の金属膜とを積層した後に熱処理して溶融することによってＳｎ合金膜を形成してもよい。
前記酸化防止剤は、浴中のＳｎ２＋の酸化を防止するものであり、例えば、次亜リン酸又はその塩、アスコルビン酸又はその塩、ハイドロキノン、カテコール、レゾルシン、フロログルシン、クレゾールスルホン酸又はその塩、フェノールスルホン酸又はその塩、カテコールスルホン酸又はその塩、ハイドロキノンスルホン酸又はその塩、ヒドラジン等を用いることができる。
前記安定剤は、めっき浴の安定又は分解を防止するためのものであり、例えば、シアン化合物、チオ尿素類、チオ硫酸塩、亜硫酸塩、アセチルシステインなどの含イオウ化合物、クエン酸等のオキシカルボン酸類等の公知の安定剤を用いることができる。
前記錯化剤は、中性領域でＳｎ２＋を安定化させて、白色沈殿が生じたり、浴が分解したりすることを防止するために含有され、例えば、オキシカルボン酸、ポリカルボン酸、モノカルボン酸等を用いることができ、具体的には、グルコン酸、クエン酸、グルコヘプトン酸、グルコノラクトン、グルコヘプトラクトン、ギ酸、酢酸、プロピオン酸、酪酸、アスコルビン酸、シュウ酸、マロン酸、コハク酸、グリコール酸、リンゴ酸、酒石酸、ジグリコール酸、或いはこれらの塩等を用いることができる。特に、グルコン酸、クエン酸、グルコヘプトン酸、グルコノラクトン、グルコヘプトラクトン、或いはこれらの塩が好ましい。さらに、エチレンジアミン、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ニトリロ三酢酸（ＮＴＡ）、イミノジ酢酸（ＩＤＡ）、イミノジプロピオン酸（ＩＤＰ）、ヒドロキシエチルエチレンジアミン三酢酸（ＨＥＤＴＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、エチレンジオキシビス（エチルアミン）－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラ酢酸、グリシン類、ニトリロトリメチルホスホン酸、１－ヒドロキシエタン－１，１－ジホスホン酸、或いはこれらの塩等も用いることができる。
前記界面活性剤は、めっき膜の外観、緻密性、平滑性、密着性等の改善に寄与し、通常のノニオン系、アニオン系、両性、或いはカチオン系等の各種界面活性剤を用いることができる。前記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩等を用いることができる。カチオン系界面活性剤としては、モノ～トリアルキルアミン塩、ジメチルジアルキルアンモニウム塩、トリメチルアルキルアンモニウム塩などが挙げられる。ノニオン系界面活性剤としては、Ｃ１～Ｃ２０アルカノール、フェノール、ナフトール、ビスフェノール類、Ｃ１～Ｃ２５アルキルフェノール、アリールアルキルフェノール、Ｃ１～Ｃ２５アルキルナフトール、Ｃ１～Ｃ２５アルコキシルリン酸（塩）、ソルビタンエステル、ポリアルキレングリコール、Ｃ１～Ｃ２２脂肪族アミドなどにエチレンオキシド（ＥＯ）及び／又はプロピレンオキシド（ＰＯ）を２～３００モル付加縮合させたもの等を用いることができる。両性界面活性剤としては、カルボキシベタイン、スルホベタイン、イミダゾリンベタイン、アミノカルボン酸等を用いることができる。
前記光沢剤又は半光沢剤としては、例えば、ベンズアルデヒド、ｏ－クロロベンズアルデヒド、２，４，６－トリクロロベンズアルデヒド、ｍ－クロロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、フルフラール、１－ナフトアルデヒド、２－ナフトアルデヒド、２－ヒドロキシ－１－ナフトアルデヒド、３－アセナフトアルデヒド、ベンジリデンアセトン、ピリジデンアセトン、フルフリリデンアセトン、シンナムアルデヒド、アニスアルデヒド、サリチルアルデヒド、クロトンアルデヒド、アクロレイン、グルタルアルデヒド、パラアルデヒド、バニリンなどの各種アルデヒド、トリアジン、イミダゾール、インドール、キノリン、２－ビニルピリジン、アニリン、フェナントロリン、ネオクプロイン、ピコリン酸、チオ尿素類、Ｎ－（３－ヒドロキシブチリデン）－ｐ－スルファニル酸、Ｎ－ブチリデンスルファニル酸、Ｎ－シンナモイリデンスルファニル酸、２，４－ジアミノ－６－（２’－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－エチル－４－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－ウンデシルイミダゾリル（１’））エチル－１，３，５－トリアジン、サリチル酸フェニル、或いは、ベンゾチアゾール、２－メチルベンゾチアゾール、２－メルカプトベンゾチアゾール、２－アミノベンゾチアゾール、２－アミノ－６－メトキシベンゾチアゾール、２－メチル－５－クロロベンゾチアゾール、２－ヒドロキシベンゾチアゾール、２－アミノ－６－メチルベンゾチアゾール、２－クロロベンゾチアゾール、２，５－ジメチルベンゾチアゾール、５－ヒドロキシ－２－メチルベンゾチアゾール等のベンゾチアゾール類等を用いることができる。
前記平滑剤としては、前記光沢剤等と重複するが、β－ナフトール、β－ナフトール－６－スルホン酸、β－ナフタレンスルホン酸、ｍ－クロロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、（ｏ－、ｐ－）メトキシベンズアルデヒド、バニリン、（２，４－、２，６－）ジクロロベンズアルデヒド、（ｏ－、ｐ－）クロロベンズアルデヒド、１－ナフトアルデヒド、２－ナフトアルデヒド、２（４）－ヒドロキシ－１－ナフトアルデヒド、２（４）－クロロ－１－ナフトアルデヒド、２（３）－チオフェンカルボキシアルデヒド、２（３）－フルアルデヒド、３－インドールカルボキシアルデヒド、サリチルアルデヒド、ｏ－フタルアルデヒド、ホルムアルデヒド、アセトアルデヒド、パラアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、プロピオンアルデヒド、ｎ－バレルアルデヒド、アクロレイン、クロトンアルデヒド、グリオキサール、アルドール、スクシンジアルデヒド、カプロンアルデヒド、イソバレルアルデヒド、アリルアルデヒド、グルタルアルデヒド、１－ベンジリデン－７－ヘプタナール、２，４－ヘキサジエナール、シンナムアルデヒド、ベンジルクロトンアルデヒド、アミン－アルデヒド縮合物、酸化メシチル、イソホロン、ジアセチル、ヘキサンジオン－３，４、アセチルアセトン、３－クロロベンジリデンアセトン、ｓｕｂ．ピリジリデンアセトン、ｓｕｂ．フルフリジンアセトン、ｓｕｂ．テニリデンアセトン、４－（１－ナフチル）－３－ブテン－２－オン、４－（２－フリル）－３－ブテン－２－オン、４－（２－チオフェニル）－３－ブテン－２－オン、クルクミン、ベンジリデンアセチルアセトン、ベンザルアセトン、アセトフェノン、（２，４－、３，４－）ジクロロアセトフェノン、ベンジリデンアセトフェノン、２－シンナミルチオフェン、２－（ω－ベンゾイル）ビニルフラン、ビニルフェニルケトン、アクリル酸、メタクリル酸、エタクリル酸、アクリル酸エチル、メタクリル酸メチル、メタクリル酸ブチル、クロトン酸、プロピレン－１，３－ジカルボン酸、ケイ皮酸、（ｏ－、ｍ－、ｐ－）トルイジン、（ｏ－、ｐ－）アミノアニリン、アニリン、（ｏ－、ｐ－）クロロアニリン、（２，５－、３，４－）クロロメチルアニリン、Ｎ－モノメチルアニリン、４，４’－ジアミノジフェニルメタン、Ｎ－フェニル－（α－、β－）ナフチルアミン、メチルベンズトリアゾール、１，２，３－トリアジン、１，２，４－トリアジン、１，３，５－トリアジン、１，２，３－ベンズトリアジン、イミダゾール、２－ビニルピリジン、インドール、キノリン、モノエタノールアミンとｏ－バニリンの反応物、ポリビニルアルコール、カテコール、ハイドロキノン、レゾルシン、ポリエチレンイミン、エチレンジアミンテトラ酢酸二ナトリウム、ポリビニルピロリドン等を用いることができる。また、ゼラチン、ポリペプトン、Ｎ－（３－ヒドロキシブチリデン）－ｐ－スルファニル酸、Ｎ－ブチリデンスルファニル酸、Ｎ－シンナモイリデンスルファニル酸、２，４－ジアミノ－６－（２’－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－エチル－４－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－ウンデシルイミダゾリル（１’））エチル－１，３，５－トリアジン、サリチル酸フェニル、或いは、ベンゾチアゾール類も平滑剤として有効である。前記ベンゾチアゾール類としては、ベンゾチアゾール、２－メチルベンゾチアゾール、２－メルカプトベンゾチアゾール、２－（メチルメルカプト）ベンゾチアゾール、２－アミノベンゾチアゾール、２－アミノ－６－メトキシベンゾチアゾール、２－メチル－５－クロロベンゾチアゾール、２－ヒドロキシベンゾチアゾール、２－アミノ－６－メチルベンゾチアゾール、２－クロロベンゾチアゾール、２，５－ジメチルベンゾチアゾール、６－ニトロ－２－メルカプトベンゾチアゾール、５－ヒドロキシ－２－メチルベンゾチアゾール、２－ベンゾチアゾールチオ酢酸等を用いることができる。
前記ｐＨ調整剤としては、塩酸、硫酸等の各種の酸、アンモニア水、水酸化カリウム、水酸化ナトリウム等の各種の塩基等を用いることができ、さらに、ギ酸、酢酸、プロピオン酸などのモノカルボン酸類、ホウ酸類、リン酸類、シュウ酸、コハク酸などのジカルボン酸類、乳酸、酒石酸などのオキシカルボン酸類等も用いることができる。
前記導電性塩としては、硫酸、塩酸、リン酸、スルファミン酸、スルホン酸等のナトリウム塩、カリウム塩、マグネシウム塩、アンモニウム塩、アミン塩等を用いることができる。なお、導電性塩は、前記ｐＨ調整剤で共用できる場合もある。
前記防腐剤としては、ホウ酸、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、塩化ベンザルコニウム、フェノール、フェノールポリエトキシレート、チモール、レゾルシン、イソプロピルアミン、グアヤコール等を用いることができる。
ＵＢＭ１１は、基材１０に含まれる金属の金属拡散により当該金属とＳｎ層１２のＳｎとの反応により金属間化合物１３が生成されることを抑制するために設けられている。
ＵＢＭ１１は、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層である。本実施形態において、当該Ｎｉ合金層としては、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉとからなるＮｉ合金層、すなわち、Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層や、例えばＮｉ－Ａｕ－Ｂｉ合金、Ｎｉ－Ａｕ－Ｐｔ合金、Ｎｉ－Ａｕ－Ｉｒ合金、Ｎｉ－Ａｕ－Ｗ合金、Ｎｉ－Ｐｔ－Ｉｒ合金、Ｎｉ－Ｐｔ－Ｗ合金、Ｎｉ－Ｐｔ－Ｂｉ合金、Ｎｉ－Ｉｒ－Ｗ合金、Ｎｉ－Ｉｒ－Ｂｉ合金、Ｎｉ－Ｗ－Ｂｉ合金等の、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも２種とからなるＮｉ合金層が挙げられる。これらの中では、金属間化合物１３の生成を抑制する効果が大きいという点から、Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層がより好ましい。
ＵＢＭ１１が、前記Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層である場合、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉを、５０％以下、さらには３５％以下、特に２５％以下の質量比率で含むＮｉ合金層であることが好ましい。ＵＢＭ１１をこのようなＮｉ合金層とすることにより、金属間化合物１３の生成を抑制する効果をさらに向上させることができる。なお、当該Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層において、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉの質量比率は、１％以上、さらには３％以上であることが好ましい。Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉの質量比率が前記下限値未満であると、金属間化合物１３の生成を抑制する効果が充分に発揮されない恐れがある。
さらに、ＵＢＭ１１が、前記Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも２種とからなるＮｉ合金層である場合も、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも２種を、５０％以下、さらには３５％以下、特に２５％以下の質量比率で、また１％以上、さらには３％以上の質量比率で含むＮｉ合金層であることが好ましい。
ＵＢＭ１１は、例えばめっき、スパッタリング、蒸着、ボールマウント、ペースト印刷等の方法で形成することができる。例えばＵＢＭ１１を電解めっきにより形成する場合、水溶性のＮｉ塩と、水溶性のＷ塩、Ｉｒ塩、Ｐｔ塩、Ａｕ塩、及びＢｉ塩の少なくとも１種とが溶解された溶液に、適宜液ベースとしての酸又はその塩と、必要に応じて、前記のごとき酸化防止剤、安定剤、錯化剤、界面活性剤、光沢剤、平滑剤、ｐＨ調整剤、導電性塩、防腐剤等の各種添加剤とを含有させためっき液を用いることができる。
前記のような組成のＵＢＭ１１を採用した本実施形態に係る構造体では、図１に示すように金属間化合物１３は生成するものの、その厚みを、従来の構造体よりも極めて小さくすることができる。
本実施形態に係る構造体は、以下のものに限られないが、例えばプリント配線板、半導体集積回路、抵抗器、コンデンサ、フィルタ、サーミスタ、水晶振動子、スイッチ、リード線又は太陽電池等の電子部品に適用可能である。
以下に、本発明に係るＳｎ層又はＳｎ合金層を含む構造体を詳細に説明するための実施例を示す。
本実施例では、本発明に係る前記ＵＢＭを備えたＳｎ層又はＳｎ合金層を含む構造体（実施例１～１２）と、前記ＵＢＭとは異なる従来のＵＢＭを備えたＳｎ層又はＳｎ合金層を含む構造体（比較例１～５）とにおいて、生成される金属間化合物の厚みを測定して比較した。
具体的に、実施例１～１２及び比較例１～５では、半導体ウェハ上面に銅めっき層を施して基材とし、この基材上にＵＢＭ、及びＳｎ層又はＳｎ合金層を順次電解めっきにより形成した。電解めっきは通常の周知方法を用い、形成するめっき膜の種類に従って、実施例１～１２では、水溶性のＮｉ塩と、水溶性のＷ塩、Ｉｒ塩、Ｐｔ塩、Ａｕ塩、及びＢｉ塩の少なくとも１種とが溶解された溶液に、比較例１～５では、水溶性のＮｉ塩、又は水溶性のＮｉ塩及びＦｅ塩、又は水溶性のＡｕ塩、又は水溶性のＢｉ塩が溶解された溶液に、各種添加剤を含有させためっき液を用いた。また、めっき条件は５０℃、２Ａ／ｄｍ２とし、各めっき膜の膜厚は３μｍとした。
各実施例及び比較例において形成したＵＢＭ、及びＳｎ層又はＳｎ合金層の組成を、表１に示す。なお、表１のＵＢＭの欄の数字は質量比を示し、例えば「Ｎｉ９０Ａｕ１０」は、Ｎｉを９０質量％、Ａｕを１０質量％含む合金を示す。
実施例１～１２及び比較例１～５における構造体に対して、１８０℃で１５０時間の熱処理を行って、その後にＳｎ層又はＳｎ合金層の下に生成された金属間化合物の厚みを測定した。その結果を表１に示す。なお、実施例１～１２及び比較例２～５における金属間化合物の厚みは、比較例１の結果を基準（１００％）とした割合で示している。
Figure 0007437057000001
表１に示すように、従来のＵＢＭと同様にＮｉ層をＵＢＭとして用い、Ｓｎ－Ａｇ合金層をその上に形成した場合（比較例１）と比較して、Ｎｉ－Ｆｅ合金層をＵＢＭとして用いた場合、その上にＳｎ－Ａｇ層（比較例２）を形成しても、Ｓｎ層（比較例３）を形成しても、生成された金属間化合物の厚みは比較例１よりも大きくなった。
また、Ｎｉを含まないＡｕ層をＵＢＭとして用いてＳｎ層を形成しても（比較例４）、Ｎｉを含まないＢｉ層をＵＢＭとして用いてＳｎ－Ａｇ層を形成しても（比較例５）、やはり、生成された金属間化合物の厚みは比較例１よりも大きくなった。
一方、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とのＮｉ合金層をＵＢＭとして用いた場合（実施例１～１２）は、Ｓｎ層を形成しても、Ｓｎ合金層を形成しても、いずれも、生成された金属間化合物の厚みは比較例１よりも小さくなった。すなわち、このような、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層をＵＢＭとして用いることによって、従来のＵＢＭよりも、金属間化合物の生成を充分に抑制することが可能となることが明らかである。
本発明に係るＳｎ層又はＳｎ合金層を含む構造体によると、基材中の金属の金属拡散による当該金属とＳｎ層又はＳｎ合金層中のＳｎとが反応して金属間化合物が生成することを充分に抑制できる。このため、本発明に係る当該構造体は、電気的特性や接続信頼性が良好であり、電子部品等に用いるのに適している。
１０ 基材
１１ アンダーバリアメタル（ＵＢＭ）
１２ Ｓｎ層（又はＳｎ合金層）
１３ 金属間化合物

Claims (3)

  1. 基材と、
    前記基材の上に形成されたＳｎ層又はＳｎ合金層と、
    前記基材と前記Ｓｎ層又はＳｎ合金層との間に形成されたアンダーバリアメタルと
    を備えており、
    前記アンダーバリアメタルは、Ｎｉと、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種とからなるＮｉ合金層であり、
    前記Ｎｉ合金層は、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、及びＢｉの少なくとも１種を５％以上の質量比率で含むことを特徴とする、Ｓｎ層又はＳｎ合金層を含む構造体。
  2. 前記アンダーバリアメタルは、Ｎｉ－Ｗ合金、Ｎｉ－Ｉｒ合金、Ｎｉ－Ｐｔ合金、Ｎｉ－Ａｕ合金、又はＮｉ－Ｂｉ合金からなるＮｉ合金層であることを特徴とする、請求項１に記載のＳｎ層又はＳｎ合金層を含む構造体。
  3. 前記Ｎｉ合金層は、Ｗ、Ｉｒ、Ｐｔ、Ａｕ、又はＢｉを５０％以下の質量比率で含むことを特徴とする、請求項２に記載のＳｎ層又はＳｎ合金層を含む構造体。
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