KR102019761B1 - 도전성 조성물 - Google Patents
도전성 조성물 Download PDFInfo
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- KR102019761B1 KR102019761B1 KR1020177016427A KR20177016427A KR102019761B1 KR 102019761 B1 KR102019761 B1 KR 102019761B1 KR 1020177016427 A KR1020177016427 A KR 1020177016427A KR 20177016427 A KR20177016427 A KR 20177016427A KR 102019761 B1 KR102019761 B1 KR 102019761B1
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- South Korea
- Prior art keywords
- conductive composition
- group
- compound
- maleic acid
- film
- Prior art date
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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Abstract
반도체 파워 소자를 금속 리드 프레임에 접합할 때, 내열성과 실장 신뢰성이 뛰어나고, 또한 납이 첨가되지 않아 환경에 대한 부하가 작은 수단을 제공하는 것을 목적으로 한다. 즉, 적어도 R-S-R'로 표시되는 술피드 화합물과, 적어도 Cu, Sn, Ni 중 어느 하나를 포함하는 금속 입자를 필수 성분으로 포함하는 도전성 조성물. (R은 적어도 탄소를 포함하는 유기기이고, R'은 R과 동일하거나 혹은 다른 유기기이다. 또한, R과 R'은 결합하고 있어도, 즉, 이른바 환상 술피드여도 좋다.) 그리고, 상기 도전성 조성물을 이용하여 제조되는 도전성 페이스트, 도전성 접착 필름, 또한 상기 도전성 접착 필름과 점착 테이프를 맞붙여서 이루어지는, 다이싱 다이 본딩 필름.
Description
본 발명은, 도전성 조성물에 관한 것이다. 구체적으로는, 도전성 페이스트나, 도전성 접착제 조성물 및 그것으로 이루어지는 도전성 접착 필름, 및 그것과 점착 테이프를 맞붙여서 이루어지는 다이싱 다이 본딩 필름에 관한 것이다.
IGBT(절연 게이트 양극성 트랜지스터), MOS-FET(전계 효과 트랜지스터) 등의 반도체 파워 소자를 금속 리드 프레임에 접합할 때, 종래에는 무연 땜납이 널리 사용되어 왔지만, 요즘은 납의 유해성이 문제시되고 있다. 또한, 근년에는 보다 고밀도의 에너지 제어가 요구되고 있는 것을 배경으로, 200℃ 이상의 접합 온도에 견디는 SiC, GaN 등의 와이드 갭 반도체를 이용한 파워 소자의 연구가 진행되고 있지만, 땜납의 공정(共晶) 융점이 낮기 때문에 접합 부분의 내열성 부족이 장애가 되고 있다.
상기 배경으로부터, 납을 함유하지 않는 여러 가지 타입의 무연 땜납이 등장하였고, 그 중에서도 AuGe 등의 고융점 땜납이 와이드 갭 반도체 소자의 접합재로서 주목받고 있지만, 재료가 고가인 점, 실장 온도가 높아짐으로써 프로세스 비용이 높아지는 점이 장해가 되어 보급이 진행되지 않았다. 또한, 많은 무연 땜납은 땜납보다 젖음성이 나쁘기 때문에 다이 패드 부분에는 땜납이 퍼지지 않고, 다이의 모퉁이 등에서 땜납이 빠진 상태가 되기 쉬우며, 그 부분이 접합 불량의 위험을 야기하는 점이 문제가 되고 있다. 무연 땜납의 젖음성은 융점이 높아질수록 더욱 나빠지는 경향이 있기 때문에, 내열성과 실장 신뢰성이 양립하기 어렵다.
상기 과제를 해결하기 위해서, Cu/Sn계 땜납 등 확산 소결형 땜납의 연구가 진행되고 있다. 이들 확산 소결형 땜납은 실장시의 융점이 낮은데도 불구하고, 확산 소결 반응 후에는 불가역적으로 고융점화 하기 때문에, 내열성과 실장 신뢰성의 양립이 종래의 무연 땜납보다 유리하다. 그러나, 확산 소결형은 땜납에서도 젖음성이 땜납보다 약간 뒤떨어지기 때문에, 5mm사방(□) 이상의 큰 면적 소자의 접합시에는 역시 땜납 누락의 위험이 있고, 또한 소결체가 딱딱하고 깨지기 쉬우며, 응력 완화성이 낮기 때문에 내열 피로 특성이 낮고, 소자의 수명을 짧게 해버리는 결점이 있다.
상기 무연 땜납 외에, Ag 페이스트 등도 이용되고 있지만, 재료 비용이 매우 고가인 점과, Ag 이온의 마이그레이션에 의한 오염이 문제가 되고 있다.
또한, 땜납이나 무연 땜납의 대부분은 금속의 산화 피막을 제거할 목적으로, 카르본산이나 알코올로 이루어지는 플럭스를 첨가하는 것이 일반적이지만, 이들 플럭스 성분은 흡습하기 쉬운 데다가 흡출되기 쉽고, 흡습분과 플럭스 흡출분의 양방이 반도체 소자의 밀봉 패키지에 있어서의 흡습 후 내리플로우 신뢰성(MSL)에 악영향을 주는 것으로 알려져 있으며, 종래에는 땜납 부착 후의 플럭스 세정이 필요했지만, 그에 대한 수고나 세정 폐액의 처리가 문제시되고 있다. 그렇다고 해도, 흡습 및 흡출을 낮추기 위해서 카르본산이나 알코올을 첨가하지 않으면 산화막 제거능이 부족하여, 도전성, 그 밖의 성능이 발현되기 어려웠다.
또한, 특허문헌 4에서는, 반도체 장치에 이용되는 무기 필러로서 은을 바람직하게 이용하는 접착제 조성물에 있어서, 플럭스로서 티올이나 티오에테르를 이용하는 점이 기재되어 있지만, 은은 고가인데다가 이온이 마이그레이션 하기 쉽기 때문에, 전극 간에 의도하지 않은 합선을 발생시킬 위험이 크다.
본 발명은, 반도체 파워 소자를 금속 리드 프레임에 접합할 때, 내열성과 실장 신뢰성이 뛰어나고, 또한 납이 첨가되지 않아 환경에 대한 부하가 작은 수단을 제공하는 것을 목적으로 한다.
출원인은 예의검토한 결과, 상기 과제를 해결하는 도전성 조성물, 및 그것을 이용하여 이루어지는 도전성 페이스트, 도전성 접착 필름 및 다이싱 다이 본딩 필름에 관련된 발명에 이른 것이다.
즉, 본 발명은, 적어도 하기 일반식 (1)로 나타나는 술피드 화합물과, 적어도 Cu, Sn, Ni 중 어느 하나를 포함하는 금속 입자를 필수 성분으로서 포함하는 도전성 조성물에 관한 것이다.
(R은 적어도 탄소를 포함하는 유기기이고, R'은 R과 동일하거나 혹은 다른 유기기이다. 또한, R과 R'은 결합하고 있어도 좋다.)
일반식 (1)
[화학식 1]
여기서, 상기 술피드 화합물은 1분자 중에 황 원자를 2개 이상 포함하는 화합물인 것이 바람직하다.
또한, 상기 술피드 화합물은, 비닐기, 아크릴로일기, 1급 아미노기, 2급 아미노기, 페놀성 수산기, 티올기, 히드로실릴기, 히드로붕소기, 말레산 에스테르기, 말레산 아미드기, 말레산 이미드기 중 적어도 어느 하나를 가지는 화합물인 것이 바람직하다.
또한, 상기 술피드 화합물의 수평균 분자량은, 200 이상인 것이 바람직하다.
또한, 본 발명은, 적어도 상기 술피드 화합물, 금속 입자 및 열경화성 수지를 포함하는, 상기 도전성 조성물에 관한 것이다.
여기서, 상기 열경화성 수지가, 이미드기를 1분자에 2단위 이상 포함하는 말레산 이미드 화합물을 포함하는 것이 바람직하다.
또한, 상기 말레산 이미드 화합물이, C10 이상의 지방족 아민에 유래하는 골격을 포함하는 것이 바람직하다.
또한, 상기 말레산 이미드 화합물의 수평균 분자량이, 3000 이상인 것이 바람직하다.
또한, 상기 열경화성 수지가, 에폭시 수지인 것도 바람직하다.
또한, 상기 금속 입자 중 적어도 일부가, Cu, Ag, Au, Ni, Sn 중 어느 하나를 포함하는 것이 바람직하다.
또한, 상기 금속 입자가, 서로 금속간 화합물 형성이 가능한 조합을 포함하는 2종 이상 금속의 혼합물인 것이 바람직하다.
또한, 상기 2종 이상 금속 입자 중 적어도 2종이, Cu, Ag, Ni, Ti, Al, Sn, Zn, Au, In로부터 선택되는 것이 바람직하다.
또한, 본 발명은, 소결 전은 DSC(시차주사열량 측정)에 의해 관측되는 흡열 피크가 100℃~250℃에서 적어도 1개 존재하고, 또한, 소결 후에는 그것이 관측되지 않게 되는 것을 특징으로 하는, 상기 도전성 조성물에 관한 것이다.
또한, 본 발명은 상기 도전성 조성물을 이용해서 이루어지는 도전성 접착제 조성물에 관한 것이다.
또한, 본 발명은 상기 도전성 접착제 조성물을 기재에 도포 건조, 압출하거나, 그 외의 방법으로 막 형상으로 성형된 도전성 접착 필름에 관한 것이다.
이에 더하여, 본 발명은, 상기 도전성 접착 필름과 점착 테이프를 맞붙여서 이루어지는, 다이싱 다이 본딩 필름에 관한 것이다.
본 발명이 제공하는 도전성 조성물을 이용하여 이루어지는 도전성 페이스트, 도전성 접착 필름, 혹은 그것과 다이싱 테이프를 조합한 다이싱 다이 본딩 필름을 이용함에 따라, 저온에서 실장할 수 있으면서도 소결 후의 내열성이 뛰어나고, 땜납이 빠지는 불량이 없으며, 플럭스 세정 공정을 생략해도 내열 피로 및 흡습 후 내리플로우성이 뛰어나고, 파워 반도체를 리드 프레임 등에 전기적으로 접합할 수 있으며, 저렴하면서 환경에 대한 부하도 작은 수단을 제공하는 것을 가능으로 했다.
도 1은 본 발명의 실시형태와 관련되는 다이싱 다이 본딩 필름을 나타내는 단면도이다.
도 2는 본 발명의 다이싱 다이 본딩 필름을 반도체에 첩합(貼合)한 상태를 나타내는 도면이다.
도 3은 다이싱 공정을 설명하기 위한 도면이다.
도 4는 픽업 공정을 설명하기 위한 도면이다.
도 5는 다이 본딩 공정을 설명하기 위한 도면이다.
도 6은 주형이 완료된 반도체 소자의 단면을 나타내는 도면이다.
도 2는 본 발명의 다이싱 다이 본딩 필름을 반도체에 첩합(貼合)한 상태를 나타내는 도면이다.
도 3은 다이싱 공정을 설명하기 위한 도면이다.
도 4는 픽업 공정을 설명하기 위한 도면이다.
도 5는 다이 본딩 공정을 설명하기 위한 도면이다.
도 6은 주형이 완료된 반도체 소자의 단면을 나타내는 도면이다.
본 발명의 도전성 조성물은, 적어도 하기 일반식 (1)로 나타나는 술피드 화합물과, 적어도 Cu, Sn, Ni 중 어느 하나를 포함하는 금속 입자를 필수 성분으로 포함하는 것을 특징으로 한다.
(R은 적어도 탄소를 포함하는 유기기이고, R'은 R과 동일하거나 혹은 다른 유기기이다. 또한, R과 R'은 결합하고 있어도, 즉, 이른바 환상 술피드여도 좋다.)
일반식 (1)
[화학식 1]
여기서, 금속 입자는 도전성 및 열전도성을 담당하고, 일반식 (1)로 나타나는 술피드 화합물은 금속 입자 표면의 산화막을 제거함으로써 그 기능을 돕는, 소위 "플럭스" 기능을 갖는다. 금속 입자로는, 특히 Cu, Sn, Ni와 같은 산화되기 쉬운 금속에서 현저한 효과를 나타낸다. 또한, 저렴하면서 이온 마이그레이션하기 어려운 점에서도 바람직하다.
(술피드 화합물)
플럭스로서, 일반식 (1)로 나타나는 술피드 화합물을 이용하는 것은, 종래 플럭스로서 일반적인 카르본산 혹은 알코올과 비교하여, 매우 흡습하기 어려운 점에서 바람직하다.
또한, 상기 술피드 화합물은, 1분자 중에 황 원자를 2개 이상 포함하는 화합물인 것이, 금속 산화막의 환원능을 높이는 점에서 바람직하다.
또한, 상기 술피드 화합물은, 비닐기, 아크릴로일기, 1급 아미노기, 2급 아미노기, 페놀성 수산기, 티올기, 히드로실릴기, 히드로붕소기, 말레산 에스테르기, 말레산 아미드기, 말레산 이미드기 중 적어도 어느 하나의 관능기를 가지는 화합물인 것이 바람직하고, 또 경화하기 쉬운 점에서, 아크릴로일기를 가지는 화합물인 것이 보다 바람직하다.
또한, 상기 술피드 화합물의 수평균 분자량은 200 이상인 것이, 소결시 등의 흡출을 억제하는 점에서 바람직하다. 상기 분자량 및 경화에 의해, 흡출을 매우 적게 할 수 있음에 따라서, 리드 프레임의 오염에 의한 패키지 신뢰성 저하를 방지하는 동시에, 흡출로 인해 술피드 플럭스가 소용없게 되는 양이 매우 적기 때문에, 플럭스의 환원능을 거의 100% 유효하게 활용할 수 있다.
이러한 술피드 화합물의 구체적인 예로서는, 2-메틸티오페노티아진, 비스(4-메타크릴로일티오페닐)술피드, 비스(2-메타크로일티오에틸)술피드를 들 수 있다.
이러한 아크릴로일 술피드 화합물은, 말레이미드 수지와의 공중합체를 형성할 수 있는 열경화성 수지 성분으로도 작용한다. 이와 같이, 흡습하기 어렵고, 분자량이 충분히 크며, 또한 중합성이기 때문에 저흡출인 플럭스 성분을 이용하면서, 흡습하기 쉬운 알코올 혹은 카르본산을 대부분 혹은 전혀 포함하지 않음에 따라, 플럭스 세정을 거치지 않아도 흡출 위험을 저감할 수 있고, 충분한 신뢰성, 특히 흡습 후의 내리플로우성을 담보할 수 있다.
상기 술피드 화합물의 도전성 조성물 중의 중량분율은, 금속 산화막의 제거능을 충분히 가지는 관점에서 1~10wt%가 바람직하고, 더욱 바람직하게는 2~5wt%이다.
(금속 입자)
금속 입자로서는, 적어도 일부가 Cu, Ag, Au, Ni, Sn 중 어느 하나를 포함하는 것이 바람직하다.
또한, 그 중 적어도 일부가 서로 금속간 화합물 형성이 가능한 조합을 포함하는 것이, 실장 온도를 낮추면서도 소결 후 실장 온도 이상의 내열성을 가지는 점에서 바람직하다.
그러한 조합으로는, 적어도 2종이 Cu, Ag, Ni, Ti, Al, Sn, Zn, Au, In으로부터 선택되는 것이 바람직하고, 예를 들면 Cu 혹은 Ni 혹은 Ag와 Sn 혹은 Zn와의 조합, Ag와 Sn와의 조합, Ni 혹은 Sn 혹은 Al와 Ti와의 조합, Au와 In의 조합 등을 들 수 있지만, 특히 실장 온도를 낮게 하는 관점에서 저융점의 Sn를 포함하는 조합이 바람직하고, 특히 바람직하게는 Cu 혹은 Ni와 Sn를 포함하는 조합이다.
상기 금속간 화합물 형성이 가능한 금속의 조합에 더하여, 필요에 따라서 그 외의 금속 성분을 더해도 좋다. 예를 들면, Sn에 Zn나 Bi, Ag, In, Ga, Pd 등을 더해서 미리 합금화 한 것을 입자화하여 이용함으로써, 더욱 저융점화 하는 것도 가능하다.
상기 금속 입자의 도전성 조성물 중의 중량분율은 70~96wt%인 것이 바람직하다.
상기 금속 입자에는, 납 및 수은 및 안티몬 및 비소를 가능한 한 포함하지 않는, 구체적으로는 도전성 조성물 중 0.1wt% 미만인 것이 환경에 대한 부하가 적은 관점에서 바람직하다.
후술하는 다이싱 후에 실시하는 소결 전에는, DSC에 의해 흡열 피크로 관측되는 적어도 1종의 금속 성분에 귀속할 수 있는 융점이 있는 점에서, 피착체 표면에 그 성분을 바를 수 있는 것이 저온에서의 실장을 유리하게 한다. 또한, 그 성분이 소결 후에는 금속간 확산 반응에 의해 고융점화 함에 따라, 예를 들면 실장 후에 고융점 무연 땜납으로 와이어 본딩 하거나 리플로우 처리 등을 해도 견딜 수 있는 충분한 내열성을 가진다. 실장 온도는 100~250℃가 바람직하고, 더욱 바람직하게는 100~200℃이다. 내열 온도는 250℃ 이상이 바람직하고, 더욱 바람직하게는 300℃ 이상이다.
(열경화성 수지)
본원 발명에서의 도전성 조성물에는, 추가로 열경화성 수지를 함유하는 것이 바람직하다. 열경화성 수지는 소결 전의 필름성 및 소결 후의 열 사이클에 의해 발생하는 응력 등에 대한 완화성을 부여하는 효과를 가진다.
열경화성 수지는, 내열성과 금속 입자를 혼합했을 때의 필름성의 관점에서, 이미드기를 1분자에 2단위 이상 포함하는 말레산 이미드 화합물을 포함하는 말레산 이미드 수지(말레이미드 수지) 혹은 에폭시 수지가 바람직하다. 상기 말레산 이미드 수지는, 예를 들면 말레산 혹은 그 무수물과 디아민 혹은 폴리아민을 축합하는 등으로 얻을 수 있지만, C10 이상의 지방족 아민에 유래하는 골격을 포함하는 것이 응력 완화성의 관점에서 바람직하고, 특히 바람직하게는 C30 이상이며, 하기 일반식 (2)과 같은 골격을 가지는 것이 바람직하다.
일반식 (2)
[화학식 2]
상기 말레산 이미드 수지에는, 말레산 이외의 산 성분, 예를 들면 벤젠테트라카르본산 혹은 그 무수물, 하이드록시 프탈산 비스 에테르 혹은 그 무수물 등에 유래하는 골격을 포함함에 따라서 분자량이나 Tg 등을 조정해도 좋다. 말레산 이미드 수지의 경화제로는, 페놀 수지, 라디칼 발생제 등이 바람직하다.
이러한 구조의 비스말레이미드 수지로는, 예를 들면 하기 구조식에 나타내는 것과 같은 것을 들 수 있다.
[화학식 3]
또한, 상기 식 중, 「C36」이란, 하기 구조이다.
[화학식 4]
또한, 상기 말레산 이미드 화합물의 수평균 분자량은 3000 이상인 것이 바람직하다.
열경화성 수지로서 에폭시를 선택하는 경우, 응력 완화성과 필름성의 균형의 관점에서 비스페놀 A형 에폭시 수지와 비스페놀 F형 에폭시 수지 및 이들 조합이 바람직하고, 더욱 바람직하게는 그것들과 분자량이 큰 에폭시 수지인 페녹시 수지와의 혼합물이다. 에폭시 수지의 경화제로는, 산무수물, 페놀 수지, 아민, 이미다졸이나 디시안디아미드 등을 선택할 수 있다.
상기와 같은 응력 완화성을 갖춘 열경화성 수지를 포함함으로써, 본 발명의 도전성 조성물의 소결체는, 종래 금속만의 무연 땜납이 딱딱하고 깨지기 쉽기 때문에 열피로 특성이 나쁘다는 결점을 극복하는 동시에, 소결 전의 필름성이 담보되므로, 특히 접착 필름 용도로 이용할 때에 바람직하다.
본 발명의 도전성 조성물을 접착 용도로 이용하는 경우, 필름 모양인 점에서, 예를 들면 파워 반도체 소자가 형성된 웨이퍼 이면에 붙이고, 웨이퍼를 소자별로 분할·칩화하는 다이싱 공정에서 접착 필름을 웨이퍼별로 분할하는 것이 가능하며, 이에 따라 땜납의 젖음성, 즉 젖어서 퍼지거나 밀려나오는 등, 액체이기 때문에 발생하는 문제와는 관계없이, 과부족 없이 소자의 이면 전체에 접착 필름을 용이하게 실장할 수 있다. 또한, 미리 소정의 두께로 접착 필름을 조정함으로써, 종래의 땜납이나 도전 페이스트보다 다이 본딩 후 소자의 높이 제어를 정밀도 좋게 실시할 수도 있다.
본 발명의 도전성 접착 필름은, 상기 본 발명의 도전성 조성물을 기재에 막 형상으로 성형하여 이루어진다. 성형 방법으로서는, 도전성 조성물을 용매에 용해·분산시킨 니스를 기재상에 도포한 후 건조시키는 방법, 도전성 조성물을 고온하에서 용해한 후 기재에 도포하는 용융 도포법, 도전성 조성물을 기재와 함께 고압으로 프레스 하는 방법, 도전성 조성물을 용융한 후 압출기를 이용해서 밀어낸 후에 연신하는 압출법, 스크린 메시(스크린 인쇄)나 금속판(그라비어판) 등에 상기 니스를 충전해서 전사하는 인쇄법 등, 공지의 방법을 들 수 있지만, 이것들로 한정되는 것은 아니다.
또한, 본 발명의 도전성 접착 필름을 다이싱 테이프와 조합해서 다이싱 다이 본딩 필름화 함에 따라, 접착 필름과 다이싱 테이프를 한 번에 웨이퍼에 첩합할 수 있어서 공정을 생략화 할 수 있다.
상기 양태에 대해서, 도면에 근거하여 설명한다.
도 1은 본원 발명에 관련된 다이싱 다이 본딩 필름(10)을 나타내는 단면도이다. 다이싱 다이 본딩 필름(10)은, 주로 다이싱 테이프(12), 접착 필름(13)으로 구성되어 있다. 다이싱 다이 본딩 필름(10)은, 반도체 가공용 테이프의 일례로서, 사용 공정이나 장치에 맞추어 미리 소정의 형상으로 절단(프리컷)되어 있어도 좋고, 반도체 웨이퍼 1매 분마다 절단되어 있어도 좋으며, 길이가 긴 롤 형상을 하고 있어도 좋다.
다이싱 테이프(12)는, 지지 기재(12a)와, 그 위에 형성된 점착제층(12b)으로 구성되어 있다.
박리 처리 PET(11)는, 다이싱 테이프(12)를 덮고 있어 점착제층(12b)과 접착 필름(13)을 보호하고 있다.
지지 기재(12a)로서는, 방사선 투과성인 것이 바람직하고, 구체적으로는, 통상, 플라스틱, 고무 등을 이용하여 방사선을 투과하는 한, 특히 제한되는 것은 아니다.
점착제층(12b)의 점착제 베이스 수지 조성물은, 특별히 한정되는 것은 아니고, 통상의 방사선 경화성 점착제가 이용된다. 바람직하게는 수산기 등의 이소시아네이트기와 반응할 수 있는 관능기를 가지는 아크릴계 점착제가 있다. 특히 제한되는 것은 아니지만, 아크릴계 점착제는 요오드가 30 이하이고, 방사선 경화성 탄소-탄소 이중결합 구조를 가지는 것이 바람직하다.
본 발명에 관련된 접착 필름(13)의 구성으로는, 상술한 바와 같이, 금속 입자와, 열경화성 수지와, 루이스 산성을 갖는 화합물 또는 열산 발생제를 포함하는 도전성 접착 필름인 것이, 반도체 파워 소자를 금속 리드 프레임에 접합할 때, 내열성과 실장 신뢰성이 뛰어나고, 또 환경에 대한 부하가 작은 점에서 매우 바람직하다.
(다이싱 다이 본딩 필름의 사용 방법)
반도체 장치의 제조에, 본 발명의 다이싱 다이 본딩 필름(10)을 적합하게 사용할 수가 있다.
우선, 다이싱 다이 본딩 필름(10)으로부터 박리 처리 PET(11)를 제거하고, 도 2에 나타내는 바와 같이, 반도체 웨이퍼(1)에 접착 필름(13)을 부착하여 다이싱 테이프(12)의 측부를 링 프레임(20)으로 고정한다. 링 프레임(20)은 다이싱용 프레임의 일 예이다. 접착 필름(13)은 다이싱 테이프(12)의 반도체 웨이퍼(1)가 첩합되는 부위에 적층되어 있다. 다이싱 테이프(12)의 링 프레임(20)과 접하는 부위에는 접착 필름(13)은 없다.
그 후, 도 3에 나타내는 바와 같이, 다이싱 테이프(12)의 아래쪽 면을 흡착 테이블(22)로 흡착·고정하면서, 다이싱 블레이드(21)를 이용하여 반도체 웨이퍼(1)를 소정의 사이즈로 다이싱하고, 복수의 반도체 칩(2)을 제조한다.
그 후, 도 4에 나타내는 바와 같이, 링 프레임(20)에 의해 다이싱 테이프(12)를 고정한 상태로, 테이프 압력 링(30)을 상승시켜서, 다이싱 테이프(12)의 중앙부를 위쪽으로 휘게 하는 동시에, 자외선 등의 방사선을 다이싱 테이프(12)에 조사하여 다이싱 테이프(12)의 점착력을 약화시킨다. 그 후, 반도체 칩마다 이에 대응한 위치에서 압력 핀(31)을 상승시키고, 반도체 칩(2)을 흡착 콜릿(32)으로 픽업한다.
그 후에는, 도 5에 나타내는 바와 같이, 픽업한 반도체 칩(2)을, 리드 프레임(4) 등의 지지 부재나 다른 반도체 칩(2)에 접착(다이 본딩 공정)하여, 도 6에 나타내는 바와 같이, Al 와이어의 부설이나, 수지 몰드, 가열 경화, 소결 등의 공정을 거쳐서 반도체 장치를 얻을 수 있다.
(도전성 페이스트)
상기 실시형태에 있어서는, 본원 발명의 도전성 조성물을, 도전성 접착제 조성물로서 접착 필름(13)의 형태로 이용하는 예를 제시했지만, 도전성 조성물에 배합하는 열경화성 수지의 양을 줄이거나, 혹은 열경화성 수지를 배합하지 않고, 땜납 등의 용도로 페이스트 모양의 형태로 이용할 수도 있다. 구체적으로는, 스크린 인쇄나 디스펜서 등으로 도포함으로써, 전자 부품의 접속에 제공할 수가 있다.
실시예
이하, 실시예에 의해 본 발명을 구체적으로 설명하지만, 본 발명은 그 실시예에 의해 한정·구속되어야 하는 것은 아니다. 또한, wt%는 중량%를 나타낸다.
<실시예 1~4>
표 1의 조성에서, 금속 입자 92wt%, 수지 4.5wt%, 플럭스 3.5wt%의 혼합물에, 톨루엔을 추가하여 슬러리화 한 것을 플랜터리 믹서에서 교반한 후, 이형 처리된 PET 상에 얇게 도포하여 120℃에서 건조시켜서, 두께 40㎛의 접착 필름을 얻었다. 또한, 표 중, BMI-3000이란, 하기 구조(n=1~10)이다.
[화학식 5]
<비교예 1, 2>
표 1의 조성에서, 금속 입자 85wt%, 수지 8wt%, 플럭스 7wt%의 조성으로 한 것 외에는, 실시예와 같은 방법으로 접착 필름을 제작했다.
<지지 기재>
시판하는 저밀도 폴리에틸렌으로 이루어지는 수지 비즈(일본 폴리에틸렌(주) 제 노바테크 LL)를 140℃에서 용융하고, 압출기를 이용하여 두께 100㎛의 긴 필름 형상으로 성형했다.
<점착제 조성물>
n-옥틸아크릴레이트, 2-하이드록시에틸아크릴레이트, 메타크릴산, 중합 개시제로서 과산화벤조일의 200:10:5:2(중량비) 혼합물을 적정량의 톨루엔 중에 분산하고, 반응 온도 및 반응 시간을 조정하여, 관능기를 가지는 아크릴 수지 용액을 얻었다. 그 다음, 이 아크릴 수지 용액에, 폴리이소시아네이트로서 코로네이트 L(일본 폴리우레탄제)를 상기 아크릴 수지 용액 100중량부에 대해서 2중량부와, 추가 용매로서 적량의 톨루엔을 더해서 교반하여 점착제 조성물 1을 얻었다.
<다이싱 테이프>
지지 기재 상에 점착제 조성물 1의 건조 후 두께가 5㎛가 되도록 상기 점착제 조성물을 도공하고, 120℃에서 3분간 건조시켜서 다이싱 테이프를 작성했다.
실시예 1~4, 비교예 1, 2에 의해 얻어진 접착 필름, 및 그것을 다이싱 테이프와 첩합하여 이루어지는 다이싱 다이 본딩 테이프에 있어서, 이하에 기재하는 항목에 대해 평가를 실시한 결과에 대해서, 마찬가지로 표 1에 나타낸다.
·체적 저항율 … JIS-K7194에 준거한 4탐침법으로 측정
·DSC … DSC 측정 장치(히타치 하이테크제 DSC7000)를 이용하여, 소결 전의 각 샘플에 대해서 200~250℃의 온도 영역에서 흡열 피크의 유무를 확인했다. 그 다음, 각 샘플을 질소 하에 250℃에서 4시간 소결한 것에 대해서도 같은 측정을 실시했다.
·접착력 … 접착 필름을 다이싱 테이프와 맞붙여서 다이 본딩 필름을 조정하고, 이면을 Au 도금된 Si 웨이퍼에 100℃에서 첩합한 후, 5mm사방으로 다이싱하여, 개편화(個片化)한 칩 및 접착 필름을 얻었다. Ag 도금된 금속 리드 프레임 상에 140℃에서 다이 본딩한 후, 230℃에서 3시간 소결하여 작성한 샘플에 대해서, 다이 쉐어 측정기(아크테크제 시리즈 4000)로 260℃에서의 전단 접착력을 측정했다.
· TCT 후의 접착력…상기와 같이 샘플을(-40⇔+150℃)×200 사이클의 냉열 충격(TCT) 처리 후에, 260℃에서의 전단 접착력을 측정했다.
· MSL-Lv1, Lv2, Lv3 후의 PKG 박리 유무 … 접착력과 같은 샘플을 에폭시계 몰드 수지로 밀봉한 후, JEDEC J-STD-020 D1에 정하는 흡습 후 리플로우 시험(무연 땜납 준거)의 MSL-Lv1, Lv2, Lv3(표 2 참조)로 처리한 후, 초음파 화상 장치(히타치 파워 솔루션제 SAT)로 내부에 박리가 생기지 않는지를 관찰했다.
[표 1]
또한, 표 1 중,
Cu:미쓰이 금속광업제 미립 구리 분말
SnBi 합금:미쓰이 금속광업제 미립 땜납 분말 Sn72Bi28
에폭시:신닛테츠스미킨화학제 YD-128 + YD-013 + YP-50 + 시코쿠가세이제 2PHZ의 15:5:10:1 혼합물
비스말레이미드(C9):1,6'-비스말레이미드(2,2,4-트리메틸)헥산 + 일유제 퍼부틸O의 100:5 혼합물
비스말레이미드(C10):1,10-비스말레이미드노르말데칸 + 일유제 퍼부틸O의 100:5 혼합물
비스말레이미드(C36):DMI 사제 BMI-3000 + 니치유제 퍼부틸O의 100:5 혼합물
술피드 1:페닐술피드 Mw=186.3
술피드 2:티안트렌 Mw=216.3
술피드 2:비스(4-메타크릴로일티오페닐)술피드 Mw=386.6
이다.
[표 2]
상기 결과로부터, 금속 입자와, 플럭스로서 상기 일반식 (1)로 나타나는 술피드 화합물을 포함하는 실시예 1~4의 도전성 접착 필름은, 환경에 대한 부하가 높은 땜납을 이용하지 않고, 내열성, 흡습 신뢰성, 결합 신뢰성을 겸비하는, 종래 기술에 없는 현저한 효과를 나타내는 점이 증명되었다.
특히, 플럭스로서 아크릴로일기를 갖는 술피드 화합물을 이용한 실시예 3, 또한, 상기 아크릴로일기를 갖는 술피드 화합물에 더하여, 열경화성 수지로서 탄소수 30 이상의 지방족 아민에 유래하는 골격을 포함하는 말레산 이미드 수지를 이용한 실시예 4는 매우 뛰어난 성능을 갖는다는 것을 알 수 있다.
이에 대해서, 플럭스로서 술피드 화합물이 아닌 테트라에틸렌글리콜을 이용한 비교예 1, 아비에트산을 이용한 비교예 2에서는, TCT 후의 접착력이 낮고, 또한 흡습하기 쉽기 때문에, MSL 시험 후에도 내부 박리를 나타내는 등, 흡습 신뢰성, 결합 신뢰성에 어려움이 있다는 것이 증명되었다. 또한, 아비에트산은 카르본산의 질량별 당량이 작기 때문에, 실시예와 같은 비교적 소량의 첨가로는 산화막을 제거할 수 없다. 따라서 산화막이 장벽이 되어, 금속간 확산 반응이 진행되지 않기 때문에, 소결 후에도 흡열 피크가 남아 버리는 결과가 되었다.
1:반도체 웨이퍼
1a:이면 Au 도금층
2:반도체 칩
4:금속 리드 프레임
4a:Ag 도금층
5:몰드 수지
6:Al 와이어
10:다이싱 다이 본딩 필름
11:박리 처리 PET
12:다이싱 테이프
12a:지지 기재
12b:점착제층
13:접착 필름
20:링 프레임
21:다이싱 블레이드
22:흡착 스테이지
30:테이프 압력 링
31:압력 핀
32:흡착 콜릿
1a:이면 Au 도금층
2:반도체 칩
4:금속 리드 프레임
4a:Ag 도금층
5:몰드 수지
6:Al 와이어
10:다이싱 다이 본딩 필름
11:박리 처리 PET
12:다이싱 테이프
12a:지지 기재
12b:점착제층
13:접착 필름
20:링 프레임
21:다이싱 블레이드
22:흡착 스테이지
30:테이프 압력 링
31:압력 핀
32:흡착 콜릿
Claims (16)
- 제1항에 있어서,
상기 술피드 화합물이 1분자 중에 황 원자를 2개 이상 포함하는 화합물인, 도전성 조성물. - 제1항 또는 제2항에 있어서,
상기 술피드 화합물이 비닐기, 아크릴로일기, 1급 아미노기, 2급 아미노기, 페놀성 수산기, 티올기, 히드로실릴기, 히드로붕소기, 말레산 에스테르기, 말레산 아미드기, 말레산 이미드기 중 적어도 어느 하나를 갖는 화합물인, 도전성 조성물. - 삭제
- 제1항 또는 제2항에 있어서,
적어도 상기 일반식 (1)로 나타나는 술피드 화합물, 금속 입자 및 열경화성 수지를 포함하는, 도전성 조성물. - 제5항에 있어서,
상기 열경화성 수지가 이미드기를 1분자에 2단위 이상 포함하는 말레산 이미드 화합물을 포함하는 것을 특징으로 하는, 도전성 조성물. - 제6항에 있어서,
상기 말레산 이미드 화합물이, C10 이상의 지방족 아민에 유래하는 골격을 포함하는 것을 특징으로 하는, 도전성 조성물. - 제6항에 있어서,
상기 말레산 이미드 화합물의 수평균 분자량이 3000 이상인, 도전성 조성물. - 제5항에 있어서,
상기 열경화성 수지가 에폭시 수지인, 도전성 조성물. - 제1항 또는 제2항에 있어서,
상기 금속 입자 중 적어도 일부가, Cu, Ag, Au, Ni, Sn 중 어느 하나를 포함하는 것을 특징으로 하는, 도전성 조성물. - 제1항 또는 제2항에 있어서,
상기 금속 입자가, 서로 금속간 화합물 형성이 가능한 조합을 포함하는 2종 이상 금속의 혼합물인 것을 특징으로 하는, 도전성 조성물. - 제11항에 있어서,
상기 2종 이상의 금속 입자 중 적어도 2종이 Cu, Ag, Ni, Ti, Al, Sn, Zn, Au, In으로부터 선택되는 것을 특징으로 하는, 도전성 조성물. - 제1항 또는 제2항에 있어서,
소결 전은 DSC(시차주사열량 측정)에 의해 관측되는 흡열 피크가 100℃~250℃에서 적어도 1개 존재하고, 또한, 소결 후는 그것이 관측되지 않게 되는 것을 특징으로 하는, 도전성 조성물. - 제1항 또는 제2항 중 어느 한 항에 기재된 도전성 조성물을 이용하여 이루어지는, 도전성 접착제 조성물.
- 제14항에 기재된 도전성 접착제 조성물을 기재에 막 형상으로 성형한, 도전성 접착 필름.
- 제15항에 기재된 도전성 접착 필름과, 점착 테이프를 첩합하여 이루어지는, 다이싱 다이 본딩 필름.
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