JP6132716B2 - 金属粒子ペースト、これを用いた硬化物、および半導体装置 - Google Patents
金属粒子ペースト、これを用いた硬化物、および半導体装置 Download PDFInfo
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- JP6132716B2 JP6132716B2 JP2013187709A JP2013187709A JP6132716B2 JP 6132716 B2 JP6132716 B2 JP 6132716B2 JP 2013187709 A JP2013187709 A JP 2013187709A JP 2013187709 A JP2013187709 A JP 2013187709A JP 6132716 B2 JP6132716 B2 JP 6132716B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- 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
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- B23K35/264—Bi as the principal constituent
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- B23K35/3033—Ni as the principal constituent
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Description
(b)グリコールエーテル類(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールブチルエーテル等の(ポリ)アルキレングリコールモノアルキルエーテル;2−フェノキシエタノール等の(ポリ)アルキレングリコールモノアリールエーテル等)
(c)グリコールエステル類(例えば、酢酸カルビトール等の(ポリ)アルキレングリコールアセテート等)
(d)グリコールエーテルエステル類(例えば、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等の(ポリ)アルキレングリコールモノアルキルエーテルアセテート)
(e)エステル類(例えば、酢酸ベンジル、酢酸イソボルネオール、安息香酸メチル、安息香酸エチル等)
(f)アミノ化合物(モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン等)
(g)上記以外の脂肪族炭化水素類(例えば、テトラデカン、オクタデカン、ヘプタメチルノナン、テトラメチルペンタデカン等の飽和又は不飽和脂肪族炭化水素類)
(h)上記以外の芳香族炭化水素類(例えば、トルエン、キシレン等))
また、極性溶媒として水を用いることもできる。これらの極性溶媒は、分離せず均一に混合できる限り、2種以上組み合わせて使用してもよい。
極性溶媒へ可溶であって、所望の硬化物が形成可能であれば、第二の金属の含有量は特に限定されない。金属粒子ペースト中における第二の金属の量が、溶解度に対して小過剰量の場合でも、硬化物中で第一の金属の拡散を抑制する効果は確認されている。第二の金属は、量が少ないほど極性溶媒へ容易に溶解し、硬化物の強度や電気伝導性および熱伝導性へ及ぼす影響も小さい。
第一の金属としてAgを用い、第二の金属としてNiを用いて、金属粒子ペーストを調製した。第一の金属の粒子としては、粒子径20nm程度のAg粒子が含有されており、このAg粒子が極性溶媒としてのテルピネオール中に分散されている。ペースト中におけるAg粒子の量は、80質量%程度である。
表1に記載された金属粒子ペーストを用いて試験片を作製し、ダイシェア試験を行なった。まず、Cu貼りセラミック基板を用意し、アセトン中での超音波洗浄および塩酸中での酸洗いによる前処理を施した。なお、Cu膜は電極として用いられる。次いで、水洗し、乾燥してCu電極上の酸化膜を除去した。このCu電極上に0.05mm厚のメタルマスクを用い、金属粒子ペーストを4mm□のパターンに印刷した。
前述と同様の処理を施して、Cu電極表面の酸化膜が除去されたCu貼りセラミック基板を用意した。このCu貼りセラミック基板上に、前述と同様のメタルマスクを用いて金属粒子ペーストを8mm□のパターンに印刷した。それを100℃で30分乾燥させた後、印刷パターンの中央に7mm□のSiCチップを配置した。用いたSiCチップの裏面最表面には、Au電極が設けられている。ダイボンダを用いて窒素雰囲気中、300℃/5MPaで5分加熱加圧することにより接合して試験片を作製した。
断面組織中のボイド及び金属の面積は、市販の画像処理ソフトを用いて断面組織写真を二値化した後、それぞれの画素数から算出した。
このボイド面積比の値が1に近いほど、接合層6中におけるボイドが偏りなく存在していることになる。高温放置試験前(初期)においては、いずれの金属粒子ペーストを用いた試験片でもボイド面積比は1であった。
極性溶媒と、
前記極性溶媒中に分散され、第一の金属を含む粒子とを含有し、
前記極性溶媒中には、前記第一の金属とは異なる第二の金属が溶解されていることを特徴とする金属粒子ペースト。
前記第二の金属の濃度は、前記第一の金属に対して0.001原子%以上であることを特徴とする付記1に記載の金属粒子ペースト。
前記第一の金属は、Au、Pt、Pd、Ru、Rh、Ir、Ag、Cu、Ni、Zn、Bi、Fe、Mo、Al、Cr、およびVからなる群から選択されることを特徴とする付記1または2に記載の金属粒子ペースト。
前記第二の金属は、アルカリ土類金属、Ag、Cu、Cr、Ni、Nb、Mo、Sn、Bi、In、Sb、Ge、Co、Zn、Ti、Al、V、Y、Zr、Hf、Be、Mg、Mn、Fe、Zr、およびWからなる群から選択されることを特徴とする付記1〜3のいずれかに記載の金属粒子ペースト。
前記第二の金属の量は、前記極性溶媒に対する溶解度以下であることを特徴とする付記1〜4のいずれかに記載の金属粒子ペースト。
前記第二の金属は、金属単体または有機金属のイオンとして含有されていることを特徴とする付記1〜5のいずれかに記載の金属粒子ペースト。
前記第二の金属は、有機金属化合物または塩として添加されたものであることを特徴とする付記1〜5のいずれかに記載の金属粒子ペースト。
付記1〜7のいずれかに記載の金属粒子ペーストを乾燥させてなる乾燥物であって、前記第二の金属が析出した粒子を含むことを特徴とする乾燥物。
前記第一の金属を含む粒子は凝集体を形成し、個々の粒子の粒子径は500nm以下であり、前記第二の金属が析出した粒子の粒子径は100nm以下であることを特徴とする付記8に記載の乾燥物。
バインダーをさらに含有する付記8または9に記載の乾燥物。
付記1〜7のいずれかに記載の金属粒子ペースト、または付記8〜10のいずれかに記載の乾燥物を硬化させてなる硬化物であって、前記第一の金属の粒界及び粒界近傍に前記第二の金属が存在することを特徴とする硬化物。
配線を有する基板と、接合部を介して前記基板上に設けられた電子部品および/または電極とを具備する半導体装置であって、
前記配線、前記接合部、および前記電極の少なくとも1つに付記11に記載の硬化物を含むことを特徴とする半導体装置。
4…第二の金属が溶解された極性溶媒; 5…SiCチップ; 6…接合層
6a…上側層; 6b…下側層; 7…Cu貼りセラミック基板; 9…試験片
10…金属粒子ペースト; 12…金属粒子ペースト; 13…Cu電極
14…ボイド。
Claims (6)
- 極性溶媒と、
前記極性溶媒中に分散された、第一の金属を含む粒子と、
前記極性溶媒中に溶解された、前記第一の金属とは異なる第二の金属とを含み、
前記第一の金属はAgであり、前記第二の金属はNiであり、前記極性溶媒はアルコール、グリコールエーテル、エステル、アミノ化合物、脂肪族炭化水素、および芳香族炭化水素からなる群より選択され、前記第二の金属であるNiはNiカルボン酸塩として添加されていることを特徴とする金属粒子ペースト。 - 前記第二の金属の濃度は、前記第一の金属に対して0.001原子%以上であることを特徴とする請求項1に記載の金属粒子ペースト。
- 前記第二の金属の量は、前記極性溶媒に対する溶解度以下であることを特徴とする請求項1または2に記載の金属粒子ペースト。
- 請求項1〜3のいずれか1項に記載の金属粒子ペーストを乾燥させてなる乾燥物であって、前記第二の金属が析出した粒子を含むことを特徴とする乾燥物。
- 請求項1〜3のいずれか1項に記載の金属粒子ペースト、または請求項4に記載の乾燥物を硬化させてなる硬化物であって、前記第一の金属の粒界及び粒界近傍に前記第二の金属が存在することを特徴とする硬化物。
- 配線を有する基板と、接合部を介して前記基板上に設けられた電子部品および/または電極とを具備する半導体装置であって、
前記配線、前記接合部、および前記電極の少なくとも1つに請求項5に記載の硬化物を含むことを特徴とする半導体装置。
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US14/337,624 US10086478B2 (en) | 2013-09-10 | 2014-07-22 | Metallic particle paste, cured product using same, and semiconductor device |
EP14178910.7A EP2858101A3 (en) | 2013-09-10 | 2014-07-29 | Paste comprising first metal particles and a polar solvent with a second metal dissolved therein, cured product obtained therefrom, and semiconductor device comprising the cured product |
CN201410452753.6A CN104425055B (zh) | 2013-09-10 | 2014-09-05 | 金属粒子膏糊、使用了其的固化物及半导体装置 |
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CN109317859B (zh) * | 2018-11-05 | 2021-05-07 | 复旦大学 | 纳米铜焊膏、其制备方法及铜-铜键合的方法 |
KR102561654B1 (ko) * | 2019-04-09 | 2023-07-31 | 이시카와 테크놀로지 라보라토리 컴퍼니 리미티드 | 땜납 제품의 제조 방법, 땜납, 납땜 부품, 땜납 제품, 프린트 배선판, 프린트 회로판, 선재, 납땜 제품, 플렉시블 프린트 기판, 전자 부품, 주석 성형품의 제조 방법, 주석 중간제품의 제조 방법, 주석 성형품, 주석 중간제품 및 도전부재 |
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US20150069638A1 (en) | 2015-03-12 |
EP2858101A2 (en) | 2015-04-08 |
CN107262958A (zh) | 2017-10-20 |
US10086478B2 (en) | 2018-10-02 |
CN104425055A (zh) | 2015-03-18 |
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