KR20060109830A - 응력 성능이 향상된 다이 부착 접착제 - Google Patents

응력 성능이 향상된 다이 부착 접착제 Download PDF

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KR20060109830A
KR20060109830A KR1020060033556A KR20060033556A KR20060109830A KR 20060109830 A KR20060109830 A KR 20060109830A KR 1020060033556 A KR1020060033556 A KR 1020060033556A KR 20060033556 A KR20060033556 A KR 20060033556A KR 20060109830 A KR20060109830 A KR 20060109830A
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South Korea
Prior art keywords
resin
die attach
die
group
adhesive composition
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KR1020060033556A
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English (en)
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은숙 채
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내쇼날 스타치 앤드 케미칼 인베스트멘트 홀딩 코포레이션
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Publication of KR20060109830A publication Critical patent/KR20060109830A/ko

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Abstract

베이스 화합물 또는 수지 및 비닐 작용기를 가진 에폭시 수지를 함유하고, 상기 에폭시 수지에 대한 경화제가 없는 접착제 조성물은 향상된 응력 성능을 나타낸다. 상기 조성물은 마이크로전자 응용분야에 사용될 수 있다.
다이 부착 접착제 조성물, 자유 라디칼 중합, 수소화규소 첨가, 에폭시 수지, 경화제, 전단 응력, 휨

Description

응력 성능이 향상된 다이 부착 접착제{DIE ATTACH ADHESIVES WITH IMPROVED STRESS PERFORMANCE}
본 발명은 자유 라디칼 중합에 의해 경화 가능한 수지, 자유 라디칼 경화제 및 알릴이나 비닐 불포화기를 가진 에폭시 화합물 또는 수지를 포함하고, 에폭시 화합물에 대한 경화제가 함유되어 있지 않은, 응력 성능이 향상된 다이 부착 접착제에 관한 것이다.
접착제 조성물은 반도체 패키지의 제조 및 어셈블리 분야에서 다양한 목적, 예를 들면 리드프레임 또는 다른 기판에 대한 집적회로 칩의 본딩, 적층된 다이 어셈블리 및 인쇄회로 기판에 대한 회로 패키지 또는 어셈블리의 본딩 등에 사용된다. 이러한 용도에 있어서 주된 요건은 전통적으로 에폭시 수지에서 얻어지는 빠른 경화와 높은 접착 강도이다. 그러나, 에폭시 수지는 부서지기 쉬워서 패키지에 높은 응력을 야기하므로, 가요성 및 소수성과 같은 다른 성질을 증진하기 위해 다른 수지들을 평가하고 활용하였다. 그러나, 대체용 수지가, 에폭시 수지에 의해 제공되는 강한 접착성을 항상 나타내는 것은 아니다. 따라서, 반도체 패키지의 제조에 사용되는 접착제에 대한 모든 요건에 대응하도록 물성들의 균형을 구현하는 다이 부착 접착제가 요구된다.
본 발명의 목적은 반도체 패키지의 제조 및 어셈블리 분야에 사용되는 향상된 응력 성능을 가진 다이 부착 접착제를 제공하는 것이다.
본 발명은 미국 특허 제6,750,301호에 개시된 발명을 개선한 것으로서, (a) 자유 라디칼 중합 또는 수소화규소 첨가(hydrosilation)에 의해 경화될 수 있는 수지, (b) 알릴 또는 비닐 불포화기를 함유한 에폭시 화합물, (c) 상기 수지용 경화제, 및 (d) 선택적으로, 하나 이상의 충전재(filler)를 포함하고, 상기 에폭시 화합물에 대한 경화제가 없는 것을 특징으로 하는 접착제 조성물이다. 본 명세서 및 청구의 범위에서 사용되는 자유 라디칼 중합 또는 경화 가능한 화합물 또는 수지라 함은, 탄소-탄소 불포화기를 함유하는 화합물 또는 수지를 의미하고, 수소화규소 첨가에 의해 중합 또는 경화 가능한 화합물 또는 수지라 함은 실리콘-하이드라이드기를 함유하는 화합물 수지를 의미한다. 상기 조성물은 또한 접착 촉진제 또는 커플링제를 함유할 수도 있다.
본 발명자는 에폭시 화합물에 대한 경화제를 제거할 경우, 에폭시에 대한 경화제를 함유하는 포뮬레이션(formulation)에 비해 응력 성능(휨(warpage)에 의해 측정)이 예상외로 향상되는 한편, 접착성이 유지되거나 향상된다는 사실을 발견했다. 또 다른 실시예에서, 본 발명은 본 발명에 따른 접착제로 기판에 접착된 반도체 다이를 가진 반도체 패키지를 제공한다.
발명의 상세한 설명
마이크로전자 응용분야에서 접착제로서 사용할 수 있는 자유 라디칼 경화형 수지로는, 예를 들면, Ciba Specialty Chemicals사로부터 입수 가능한 말레이미드류; BASF사로부터 입수 가능한 폴리에테르류; Uniqema사 또는 Bayer사로부터 입수 가능한 폴리에스테르류; Elf-Atochem사로부터 입수 가능한 폴리(부타디엔)류; Bayer사 또는 BASF사로부터 입수 가능한 폴리우레탄류; 및 UCB Radcure사로부터 입수 가능한 아크릴레이트 수지 등이 포함된다. 상기 폴리에테르, 폴리에스테르 및 폴리우레탄은 말단 불포화 결합을 함유하지만, 또한 폴리머 사슬 내에도 불포화 결합을 함유한다.
수소화규소 첨가에 의해 경화되는 실록산 및 폴리실록산은 선형 또는 환형 폴리머일 수 있고, 1 분자당 2개 이상의 실리콘-하이드라이드 작용성(functionality)을 갖는다. 그러한 화합물의 예는 Gelest사로부터 구입할 수 있다.
유동학적 성질, 친수성 또는 소수성, 인성(toughness), 강도, 또는 가요성과 같은 특정한 물성을 최종 포물레이션에 부여하기 위해 당업자는 특별한 수지를 선택할 것이다. 그러한 수지는 접착제 조성물 중에 10∼80 중량%의 범위로 존재할 것이다.
상기 에폭시 화합물은 알릴 또는 비닐 작용기를 가진 임의의 에폭시 화합물일 수 있다. 그 예로는 2,6-디글리시딜페닐알릴 에테르, 리모넨 디옥사이드, 글리시딜비닐벤질 에테르 또는 글리시딜비닐 에테르가 포함된다. 상기 에폭시는 접착 제 조성물 중에 0.1∼30 중량%의 범위로 존재할 것이다.
자유 라디칼 개시제의 예는 열 개시제(thermal initiator) 또는 광 개시제(photo-initator) 개시제일 수 있고, 접착제 조성물 중에 0.1∼10 중량%, 바람직하게는 0.1∼3.0 중량%의 범위로 존재할 것이다. 바람직한 열 개시제로는, 디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트, 부틸 퍼옥토에이트, 디큐밀 퍼옥사이드와 같은 퍼옥사이드류 및 2,2'-아조비스(2-메틸-프로판니트릴), 2,2'-아조비스(2-메틸-부탄니트릴)과 같은 아조 화합물이 포함된다. 바람직한 계열의 광 개시제는 Ciba Specialty Chemicals사에 의해 Irgacure라는 상표로 판매되는 것이다. 일부 포뮬레이션에 따라서는, 광경화와 열경화가 모두 바람직할 수 있고, 예컨대 광 조사(irradiation)에 의해 경화 공정이 시작될 수 있고, 그 후의 공정 단계에서 열을 가함으로써 경화가 완결될 수 있다.
일반적으로, 이들 조성물은 70℃ 내지 250℃의 온도 범위에서 경화될 것이고, 10초 내지 3시간 범위의 시간에 경화가 이루어질 것이다. 각 포뮬레이션의 경화 프로파일의 시간 및 온도는 포뮬레이션의 성분에 따라 변동될 것이지만, 경화 프로파일의 파라미터는 과도한 실험을 행하지 않고도 당업자에 의해 조절될 수 있을 것이다.
일부 조성물에 따라서는, 유기 또는 무기 충전재를 첨가하는 것이 바람직할 수 있다. 적합한 도전성 충전제는 카본블랙, 흑연, 금, 은, 구리, 백금, 팔라듐, 니켈, 알루미늄, 실리콘카바이드, 질화붕소 및 알루미나이다. 적합한 비도전성 충전제는 질석(vermiculite), 운모, 규회석(wollastonite), 탄산칼슘, 티타니아, 모 래, 유리, 용융 실리카, 흄드 실리카, 황산바륨, 및 할로겐화 에틸렌 폴리머, 예컨대 테트라플루오로에틸렌, 트리플루오로에틸렌, 비닐리덴플루오라이드, 비닐플루오라이드, 비닐리덴클로라이드 및 비닐클로라이드 등의 입자이다. 충전재가 존재할 경우, 그 양은 조성물의 20∼90 중량% 범위이다.
또한, 실란, 실리케이트 에스테르, 금속 아크릴레이트 또는 메타크릴레이트, 티타네이트 등을 포함하는 접착 촉진제 또는 커플링제, 및 포스핀, 머캅탄, 아세토아세테이트 등과 같은 킬레이팅 리간드(chelating ligand)를 함유하는 화합물을 첨가하는 것이 바람직할 수 있다. 이러한 물질이 존재할 경우, 그 양은 조성물의 0.1∼3.0 중량% 범위이다.
이하에서 실시예에 의해 본 발명을 보다 구체적으로 예시하는데, 이들 실시예에 의해 본 발명이 제한되는 것은 아니다.
실시예
이하의 실시예에 있어서, 기판에 대한 반도체 다이의 접착 강도는 다이 전단 강도(단위; Kg-힘)로서 측정했다. 테스트는 2층 BT 인쇄회로 기판에 부착된 3×3 mm 실리콘 다이의 비-캡슐화(unencapsulated) 어셈블리를 사용하여 실시했다. 상기 비-캡슐화 어셈블리를 오븐에서, 실온으로부터 175℃까지 30분 동안에 승온시킨 다음, 175℃에서 15분간 유지하여 경화시켰다. 이어서, 상기 어셈블리를 2개의 그룹으로 분리했다. 한 그룹에 대해서는 경화 직후(포스트 큐어)에 다이 전단 강도를 시험했다. 제2의 그룹은 175℃에서 4시간 동안 포스트-몰드 베이킹(post-mild baking)의 시뮬레이션 처리한 다음, 실온으로 복귀시키고 다이 전단 강도(포스트- 몰드 베이크)를 시험했다. 상기 포스트 큐어 그룹과 포스트 몰드 베이크 그룹 모두를 다시 2개의 하부 그룹으로 분할하고, 제1 하부 그룹에 대해서는 실온에서의 다이 전단 강도를 시험하고, 제2 그룹에 대해서는 260℃에서의 다이 전단 강도를 시험했다. 상기 어셈블리는 모두 기판에 다이를 접착시키는 접착이 이루어지지 않는 점착 모드(cohesive mode)를 나타냈다.
패키지에 존재하는 응력의 수준은 비-캡슐화 어셈블리에 있는 다이의 휨에 의해 나타낸다. 휨 값이 클수록 다이 부착 어셈블리에서의 응력이 높은 것을 나타낸다. 이들 실시예에 있어서, 두 가지 형태의 어셈블리를 시험했다. 제1 형태는 12.7×12.7×0.38 mm 치수의 실리콘 다이를 0.2 mm 두께의 은 도금된 구리 리드프레임에 부착한 것이다. 제2 형태는 7×8×0.076 mm 치수의 실리콘 다이를 0.2 mm 두께의 비스말레이미드 트리아진(BT) 기판에 부착한 것이다. 상기 어셈블리를 오븐에서, 실온으로부터 175℃까지 30분 동안에 승온시킨 다음, 175℃에서 15분간 유지하여 경화시켰다. 그런 다음, 어셈블리를 실온으로 되돌리고, 표면 조도 측정기를 이용하여 다이의 휨을 측정했다.
하기 실시예에서, 알릴 또는 비닐 작용기를 가진 에폭시에 대한 경화제 포함 및 불포함 포뮬레이션에 대해 실온 및 고온 건식 다이 전단 강도(kg-힘을 단위로 하여 측정)를 시험하고, 전술한 프로토콜을 이용하여 휨(단위; ㎛)을 시험했다. 접착제 조성물 및 성능 시험 데이터를 하기 표에 제시하는데, 알릴 또는 비닐 작용기를 가진 에폭시에 대한 경화제를 포함하지 않는 접착제 포뮬레이션이 동등하거나 더 높은 다이 전단 강도를 가지며 휨이 더 낮은 것으로 나타나 있다. 따라서, 상 기 데이터는 알릴 또는 비닐 불포화기를 가진 에폭시 화합물에 대한 경화제를 포함하지 않는 포뮬레이션은 접착 성능을 현저히 향상시키는 것을 나타낸다. 조성물은 중량%로 보고되어 있다.
[실시예 1]
실시예 1 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 26.57% 26.51%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.53 0.53
디-트리메틸로프로판 테트라아크릴레이트 3.99 3.97
2-페녹시에틸아크릴레이트 7.97 7.95
폴리(부타디엔) 5.31 5.30
비스페놀 F 에폭시 수지 중의 40% CTBN 3.99 3.98
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 6.64 6.63
2-에틸-4-메틸이미다졸-CN 0 0.13
실리카 1 30 30
실리카 2 15 15
합 계 100% 100%
실시예 1; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 7.7㎛ 20.7㎛
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 8.3 1.7 23.3 5.3 10.6 1.6 24.9 5.8
[실시예 2]
실시예 2 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 28.65% 28.58%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.57 0.57
디-트리메틸로프로판 테트라아크릴레이트 4.30 4.29
2-페녹시에틸아크릴레이트 8.59 8.57
폴리(부타디엔) 5.73 5.71
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 7.16 7.14
2-에틸-4-메틸이미다졸-CN 0 0.14
실리카 1 30 30
실리카 2 15 15
합 계 100% 100%
실시예 2; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 12.3㎛ 26.7㎛
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 11.7 1.8 22.4 3.8 9.1 1.6 25.6 4.0
[실시예 3]
실시예 3 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 43.30% 43.14%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.89 0.86
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 10.82 10.78
2-에틸-4-메틸이미다졸-CN 0 0.22
실리카 1 30 30
실리카 2 15 15
합 계 100% 100%
실시예 3; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 포스트 큐어, BT 1.0 3.8 3.2 8.5
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 10.0 2.5 18.6 4.1 0.3 0.2 7.5 1.7
[실시예 4]
실시예 4 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 35.03% 34.92%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.70 0.70
2-페녹시에틸아크릴레이트 10.51 10.48
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 8.76 8.73
2-에틸-4-메틸이미다졸-CN 0 0.17
실리카 1 30 30
실리카 2 15 15
합 계 100% 100%
실시예 4; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 포스트 큐어, BT 1.7 4.8 2.0 8.8
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 7.5 1.8 15.1 2.9 1.2 0.4 8.6 1.7
[실시예 5]
실시예 5 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 35.03% 34.92%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.70 0.70
디-트리메틸로프로판 테트라아크릴레이트 10.51 10.48
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 8.76 8.73
2-에틸-4-메틸이미다졸-CN 0 0.17
실리카 1 30 30
실리카 2 15 15
합 계 100% 100%
실시예 5; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 포스트 큐어, BT 3.1 15.5 6.8 15.5
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 11.3 2.5 17.7 4.0 9.0 1.4 18.0 2.8
[실시예 6]
실시예 6 조성물 에폭시 화합물에 대한 경화제 불포함 에폭시 화합물에 대한 경화제 포함
독점적인 비스말레이미드 14.13% 14.08%
디-(4-t-부틸사이클로헥실)퍼옥시디카보네이트 0.28 0.28
디-트리메틸로프로판 테트라아크릴레이트
2-페녹시에틸아크릴레이트 4.24 4.23
폴리(부타디엔) 2.82 2.82
(2,6-디글리시딜페닐알릴 에테르) 에폭시 수지 3.53 3.52
2-에틸-4-메틸이미다졸-CN 0 0.07
은 플레이크(silver flake) 75 75
합 계 100% 100%
실시예 6; 성능
다이 휨(실온에서) 포스트 큐어, SPCLF 포스트 큐어, BT 15.5 22.5 19.8 23.5
다이 전단 강도 실온에서의 포스트 큐어 260℃에서의 포스트 큐어 실온에서의 포스트 몰드 베이크 260℃에서의 포스트 몰드 베이크 9.7 2.5 13.1 4.2 8.7 3.0 17.9 3.8
본 발명에 의하면, 반도체 패키지의 제조 및 어셈블리 분야에 사용되는 향상된 응력 성능을 가진 다이 부착 접착제를 얻을 수 있다.

Claims (4)

  1. (a) 자유 라디칼 중합 또는 수소화규소 첨가(hydrosilation)에 의해 경화될 수 있는 수지 10 중량% 내지 80 중량%,
    (b) 비닐 또는 알릴 작용기를 가지는 에폭시 화합물 0.1 중량% 내지 30 중량%,
    (c) 상기 수지(a)에 대한 경화제 0.1 중량% 내지 10 중량%, 및
    (d) 선택적으로, 충전재(filler) 20 중량% 내지 90 중량%
    를 포함하고,
    상기 에폭시 화합물에 대한 경화제가 함유되어 있지 않은 것을 특징으로 하는
    다이 부착 접착제 조성물.
  2. 제1항에 있어서,
    상기 수지가, 말레이미드, 폴리에테르, 폴리에스테르, 폴리(부타디엔), 폴리우레탄, 아크릴레이트, 실록산 및 폴리실록산으로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 다이 부착 접착제 조성물.
  3. 제1항에 있어서,
    상기 에폭시 화합물이, 2,6-디글리시딜페닐알릴 에테르, 리모넨 디옥사이 드(limonene dioxide), 글리시딜비닐벤질 에테르 및 글리시딜비닐 에테르로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 다이 부착 접착제 조성물.
  4. 제1항에 있어서,
    상기 충전재가 존재하고, 상기 충전재는 카본블랙, 흑연, 금, 은, 구리, 백금, 팔라듐, 니켈, 알루미늄, 실리콘카바이드, 질화붕소, 다이아몬드, 알루미나, 질석(vermiculite), 운모, 규회석(wollastonite), 탄산칼슘, 티타니아, 모래, 유리, 용융 실리카, 흄드 실리카, 황산바륨, 테트라플루오로에틸렌, 트리플루오로에틸렌, 비닐리덴플루오라이드, 비닐플루오라이드, 비닐리덴클로라이드 및 비닐클로라이드로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 다이 부착 접착제 조성물.
KR1020060033556A 2005-04-18 2006-04-13 응력 성능이 향상된 다이 부착 접착제 KR20060109830A (ko)

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