KR101455951B1 - Adhesive composition, method for manufacturing semiconductor device, and semiconductor device - Google Patents
Adhesive composition, method for manufacturing semiconductor device, and semiconductor device Download PDFInfo
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- KR101455951B1 KR101455951B1 KR1020137009904A KR20137009904A KR101455951B1 KR 101455951 B1 KR101455951 B1 KR 101455951B1 KR 1020137009904 A KR1020137009904 A KR 1020137009904A KR 20137009904 A KR20137009904 A KR 20137009904A KR 101455951 B1 KR101455951 B1 KR 101455951B1
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- KR
- South Korea
- Prior art keywords
- adhesive composition
- semiconductor device
- semiconductor
- connection
- semiconductor chip
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 184
- 239000000853 adhesive Substances 0.000 title claims abstract description 116
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 238000007789 sealing Methods 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
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- 238000004381 surface treatment Methods 0.000 claims description 10
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- -1 and the like Substances 0.000 description 54
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- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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Abstract
본 발명은, 반도체칩 및 배선 회로 기판의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치 또는 복수의 반도체칩의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치에서 접속부를 밀봉하는 접착제 조성물로서, 에폭시 수지와, 경화제와, 아크릴계 표면 처리 충전재를 함유하는 접착제 조성물에 관한 것이다.The present invention is an adhesive composition for sealing a connection portion in a semiconductor device in which respective connection portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, , A curing agent, and an acrylic surface-treated filler.
Description
본 발명은, 접착제 조성물, 반도체 장치의 제조 방법 및 반도체 장치에 관한 것이다.The present invention relates to an adhesive composition, a method of manufacturing a semiconductor device, and a semiconductor device.
최근, 반도체칩을 기판에 실장하여 접속하기 위해서는, 금 와이어 등의 금속세선을 이용하는 와이어 본딩 방식이 널리 이용되고 있다. 한편, 반도체 장치에 대한 소형화, 박형화, 고기능, 고집적화, 고속화 등의 요구에 대응하기 위해, 반도체칩 및 기판간에 범프라 불리는 도전성 돌기를 형성하여, 반도체칩과 기판과 접속하는 플립 칩 접속 방식(FC 접속 방식)이 확대되고 있다.BACKGROUND ART [0002] In recent years, in order to mount and connect a semiconductor chip to a substrate, a wire bonding method using metal thin wires such as gold wire is widely used. On the other hand, in order to meet demands for miniaturization, thinness, high performance, high integration, and high speed of semiconductor devices, a conductive protrusion called a bump is formed between a semiconductor chip and a substrate, Connection method) is expanding.
예를 들면, 반도체칩 및 기판간의 접속에 대하여 BGA(Ball Grid Array), CSP(Chip Size Package) 등에 활발히 이용되고 있는 COB(Chip On Board)형의 접속 방식도 FC 접속 방식에 해당한다. 또한, FC 접속 방식은, 반도체칩 상에 접속부(범프나 배선)를 형성하여, 반도체칩간을 접속하는 COC(Chip On Chip)형의 접속 방식에도 널리 이용되고 있다(예를 들면, 특허문헌 1 참조).For example, a COB (Chip On Board) type connection method that is actively used for BGA (Ball Grid Array) and CSP (Chip Size Package) for connection between a semiconductor chip and a substrate corresponds to the FC connection method. The FC connection method is also widely used in a connection method of a COC (Chip On Chip) type in which a connection portion (bump or wiring) is formed on a semiconductor chip to connect between semiconductor chips (see, for example, Patent Document 1 ).
그러나, 한층 더 소형화, 박형화, 고기능화의 요구에 대응하기 위해, 상술한 접속 방식을 적층ㆍ다단화한 칩 스택형 패키지나 POP(Package On Package), TSV(Through-Silicon Via) 등도 널리 보급되기 시작하고 있다. 이러한 적층ㆍ다단화 기술은, 반도체칩 등을 삼차원적으로 배치하기 때문에, 이차원적으로 배치하는 방법에 비해 패키지를 작게 할 수 있다. 특히, TSV 기술은, 반도체의 성능 향상, 노이즈 감소, 실장 면적의 삭감, 전력 절약화에도 유효하며, 차세대 반도체 배선 기술로서 주목받고 있다.However, a chip stack type package, a package on package (POP), a through-silicon via (TSV), and the like, in which the above-described connection methods are stacked and multi-shaded, have also become widespread in order to meet demands for further miniaturization, thinning, . Such a stacking / multi-shrinking technique can reduce the size of a package as compared with a method of two-dimensionally arranging semiconductor chips or the like three-dimensionally. In particular, TSV technology is effective for improving the performance of semiconductors, reducing noise, reducing the mounting area, and saving power, and has been attracting attention as a next-generation semiconductor wiring technology.
그런데, 상기 접속부(범프나 배선)에 이용되는 주된 금속으로서는, 땜납, 주석, 금, 은, 구리, 니켈 등이 있으며, 이들 복수종을 포함한 도전 재료도 이용되고 있다. 접속부에 이용되는 금속은, 표면이 산화되어 산화막이 생성되거나, 표면에 산화물 등의 불순물이 부착됨으로써, 접속부의 접속면에 불순물이 발생하는 경우가 있다. 이러한 불순물이 잔존하면, 반도체칩 및 기판간이나 2개의 반도체칩간에서의 접속성ㆍ절연 신뢰성이 저하되어, 상술한 접속 방식을 채용하는 메리트가 손상될 염려가 있다.As a main metal used for the connecting portion (bump or wiring), there are solder, tin, gold, silver, copper, nickel, and the like, and a conductive material containing these plural kinds is also used. The metal used for the connecting portion may be oxidized to generate an oxide film or impurities such as oxides may adhere to the surface of the metal, so that impurities may be generated on the connecting surface of the connecting portion. If such impurities remain, the reliability of connection and insulation between the semiconductor chip and the substrate or between the two semiconductor chips deteriorates, and the merit of employing the above-described connection method may be damaged.
이들 불순물의 발생을 억제함과 함께 접속성을 향상시키는 방법으로서는, 접속 전에 기판이나 반도체칩의 표면에 전처리를 실시하는 방법을 들 수 있으며, OSP(Organic Solderbility Preservatives) 처리에 이용되는 프리플럭스나 방청 처리제를 실시하는 방법을 들 수 있다. 그러나, 전처리 후에 프리플럭스나 방청 처리제가 잔존하여 열화됨으로써, 접속성이 저하되는 경우도 있다.As a method of suppressing the generation of these impurities and improving the connectivity, there is a method of pretreating the surface of a substrate or a semiconductor chip before connection, and a method of pre-fluxing used for OSP (Organic Solderbility Preservatives) And a method of applying a treatment agent. However, after pre-treatment, the pre-flux or rust-preventive treatment agent remains and deteriorates, thereby reducing the connectivity.
한편, 반도체칩 및 기판간 등의 접속부를 반도체 밀봉 재료(반도체 밀봉용 접착제)로 밀봉하는 방법에 따르면, 반도체칩 및 기판이나 반도체칩끼리의 접속과 동시에 접속부를 밀봉하는 것이 가능해진다. 그 때문에, 접속부에 이용되는 금속의 산화나, 접속부로의 불순물의 부착을 억제하여, 접속부를 외부 환경으로부터 보호할 수 있다. 따라서, 효과적으로 접속성ㆍ절연 신뢰성, 작업성, 생산성을 향상시킬 수 있다.On the other hand, according to the method of sealing the connection portion such as between the semiconductor chip and the substrate with the semiconductor sealing material (adhesive for semiconductor sealing), it is possible to seal the connection portion simultaneously with the connection between the semiconductor chip and the substrate or the semiconductor chips. Therefore, oxidation of the metal used in the connection portion and adhesion of impurities to the connection portion can be suppressed, and the connection portion can be protected from the external environment. Therefore, the connection reliability, insulation reliability, workability, and productivity can be effectively improved.
또한, 플립 칩 접속 방식으로 제조된 반도체 장치에서는, 반도체칩과 기판과의 열팽창 계수차나 반도체칩끼리의 열팽창 계수차에서 유래하는 열 응력이 접속부에 집중되어 접속 불량을 일으키지 않도록 하기 위해, 반도체칩 및 기판간 등의 공극을 반도체 밀봉 재료로 밀봉할 필요가 있다. 특히, 반도체칩과 기판에서는 열팽창 계수가 상이한 성분이 이용되는 경우가 많고, 반도체 밀봉 재료에 의해 밀봉하여 내열충격성을 향상시키는 것이 요구된다.In the semiconductor device manufactured by the flip-chip bonding method, in order to prevent the thermal stress originating from the difference in thermal expansion coefficient between the semiconductor chip and the substrate or the thermal expansion coefficient difference between the semiconductor chips from concentrating on the connection portion, It is necessary to seal the gap between the substrates with the semiconductor sealing material. In particular, a component having a different coefficient of thermal expansion is often used for a semiconductor chip and a substrate, and sealing with a semiconductor sealing material is required to improve thermal shock resistance.
상술한 반도체 밀봉 재료에 의한 밀봉 방식에는 크게 나누어, 모세관-유동(Capillary-Flow) 방식과 예비-적용(Pre-applied) 방식을 들 수 있다(예를 들면, 특허문헌 2 내지 6 참조). 모세관-유동 방식이란, 반도체칩 및 기판의 접속 후에 반도체칩 및 기판간의 공극에 액상의 반도체 밀봉 재료를 모세관 현상에 의해 주입하는 방식이다. 예비-적용 방식이란, 반도체칩 및 기판의 접속 전에 반도체칩 또는 기판에 페이스트상이나 필름상의 반도체 밀봉 재료를 공급한 후, 반도체칩과 기판을 접속하는 방식이다. 이들 밀봉 방식에 대하여, 최근 반도체 장치의 소형화의 진전에 따라 반도체칩 및 기판간 등의 공극이 좁아지고 있으며, 모세관-유동 방식에서는 주입에 장시간 필요하여 생산성이 저하되는 경우나, 주입할 수 없는 경우, 또한 주입할 수 있더라도 미충전 부분이 존재하여 공극의 원인이 되는 경우가 있다. 그 때문에, 작업성ㆍ생산성ㆍ신뢰성의 관점에서 예비-적용 방식이 고기능ㆍ고집적ㆍ고속화 가능한 패키지의 제작 방법으로서 주류를 이루고 있다.Capillary-flow method and pre-applied method can be categorized largely into the sealing method by the above-mentioned semiconductor sealing material (for example, refer to Patent Documents 2 to 6). The capillary-flow method is a method in which a liquid semiconductor sealing material is injected into the gap between the semiconductor chip and the substrate by capillary phenomenon after the semiconductor chip and the substrate are connected. The pre-application method is a method in which a paste-like or film-like semiconductor sealing material is supplied to a semiconductor chip or a substrate before the semiconductor chip and the substrate are connected, and then the semiconductor chip and the substrate are connected. With respect to these sealing methods, the gap between the semiconductor chip and the substrate is becoming narrower due to the progress of miniaturization of the semiconductor device. In the capillary-flow system, productivity is deteriorated because it is required for injection for a long time, , And even if it can be injected, an uncharged portion exists, which may cause a gap. For this reason, the pre-application method has become mainstream as a method of producing a package capable of high performance, high integration, and high speed in terms of workability, productivity and reliability.
상술한 예비-적용 방식에서는, 가열 가압에 의한 접속과 동시에 반도체칩 및 기판간의 공극이 반도체 밀봉 재료에 의해 밀봉되기 때문에, 반도체 밀봉 재료의 함유 성분은 접속 조건을 고려하여 선택할 필요가 있다. 일반적으로 접속부끼리의 접속에는, 접속성ㆍ절연 신뢰성을 충분히 확보하는 관점에서 금속 접합이 이용되고 있다. 금속 접합은 고온(예를 들면 200℃ 이상)을 이용한 접속 방식이기 때문에, 반도체 밀봉 재료 중에 잔존하는 휘발 성분이나, 반도체 밀봉 재료의 함유 성분의 분해에 의해 새롭게 발생하는 휘발 성분에 기인하여 반도체 밀봉 재료가 발포되는 경우가 있다. 이에 따라, 공극이라 불리는 기포가 발생하여, 반도체 밀봉 재료가 반도체칩이나 기판으로부터 박리된다. 또한, 가열 가압시ㆍ압력 개방시에 상기 공극이나 반도체칩 등의 스프링백이 발생하면, 접속부끼리를 접속하는 접속 범프의 찢어짐에 의한 접속부의 파괴 등의 접속 불량이 발생한다. 이들에 기인하여, 종래의 반도체 밀봉 재료에서는 접속성ㆍ절연 신뢰성이 저하되는 것이 염려된다.In the pre-application method described above, since the gap between the semiconductor chip and the substrate is sealed by the semiconductor sealing material at the same time as the connection by heating and pressing, the contained component of the semiconductor sealing material needs to be selected in consideration of the connection conditions. Generally, metal bonding is used for connection between connection portions from the viewpoint of ensuring sufficient connection reliability and insulation reliability. Because the metal bonding is a connection method using a high temperature (for example, 200 DEG C or higher), the semiconductor sealing material can not be easily removed due to the volatile components remaining in the semiconductor sealing material and the volatile components newly generated by decomposition of the contained components of the semiconductor sealing material There is a case where the foam is foamed. As a result, a bubble called a gap is generated, and the semiconductor sealing material is peeled off from the semiconductor chip or the substrate. Further, when springback of the cavity or the semiconductor chip occurs at the time of heating and pressure-releasing the pressure, connection failure such as breakage of the connection portion due to tearing of the connection bump connecting the connection portions occurs. Due to these, it is feared that the reliability of connection and insulation is lowered in the conventional semiconductor encapsulating material.
또한, 반도체 밀봉 재료가 충분히 플럭스 활성(금속 표면의 산화막이나 불순물의 제거 효과)을 갖고 있지 않은 경우, 금속 표면의 산화막이나 불순물을 제거할 수 없으며, 양호한 금속-금속 접합이 형성되지 않고, 도통을 확보할 수 없는 경우가 있다. 또한, 반도체 밀봉 재료의 절연 신뢰성이 낮으면, 접속부의 협피치화에 대응하는 것이 곤란하고, 절연 불량이 발생한다. 이들에도 기인하여, 종래의 반도체 밀봉 재료에서는 접속성ㆍ절연 신뢰성이 저하되는 것이 염려된다.Further, when the semiconductor encapsulating material does not have sufficient flux activity (an oxide film or impurity removal effect on the metal surface), the oxide film and impurities on the metal surface can not be removed, no good metal-metal bond is formed, It may not be ensured. Further, if the insulation reliability of the semiconductor encapsulating material is low, it is difficult to cope with the narrowing of the connecting portion and insulation failure occurs. Due to these, it is feared that the reliability of connection and insulation is lowered in the conventional semiconductor encapsulation material.
반도체 밀봉 재료를 이용하여 제조되는 반도체 장치는, 신뢰성, 보다 구체적으로는 내열성, 내습성 및 내리플로우성의 면에서 충분한 레벨을 달성하는 것이 요구된다. 내리플로우성을 확보하기 위해서는, 260℃ 전후의 리플로우 온도에서 다이 본드층(접착제층)의 박리 또는 파괴를 억제할 수 있는 높은 접착 강도를 유지하는 것이 요구된다.A semiconductor device manufactured using a semiconductor encapsulating material is required to attain a sufficient level in terms of reliability, more specifically, heat resistance, moisture resistance, and floodability. It is required to maintain a high bonding strength capable of suppressing peeling or breakage of the die bond layer (adhesive layer) at a reflow temperature of about 260 캜.
본 발명은 상기 사정을 감안하여 이루어진 것이며, 내리플로우성 및 접속 신뢰성 및 절연 신뢰성이 우수한 반도체 장치의 제작을 가능하게 하는 접착제 조성물, 이 접착제 조성물을 이용한 반도체 장치의 제조 방법 및 반도체 장치를 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an adhesive composition capable of manufacturing a semiconductor device excellent in flow resistance, connection reliability and insulation reliability, a method of manufacturing a semiconductor device using the adhesive composition, and a semiconductor device The purpose.
본 발명은, 반도체칩 및 배선 회로 기판의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치 또는 복수의 반도체칩의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치에서 접속부를 밀봉하는 접착제 조성물로서, 에폭시 수지와, 경화제와, 하기 화학식 (1)로 표시되는 기를 갖는 화합물로 표면 처리된 아크릴계 표면 처리 충전재를 함유하는 접착제 조성물을 제공한다.The present invention is an adhesive composition for sealing a connection portion in a semiconductor device in which respective connection portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, And an acrylic surface-treated filler surface-treated with a curing agent and a compound having a group represented by the following formula (1).
(화학식 (1) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타냄)(In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R 2 represents an alkylene group having 1 to 30 carbon atoms)
또한, 본 발명은, 반도체칩 및 배선 회로 기판의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치 또는 복수의 반도체칩의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치에서 접속부를 밀봉하는 접착제 조성물로서, 에폭시 수지와, 경화제와, 하기 화학식 (1)로 표시되는 기를 갖는 충전재를 함유하는 접착제 조성물을 제공한다.The present invention also provides an adhesive composition for sealing a connection portion in a semiconductor device in which respective connection portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other or in a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, There is provided an adhesive composition comprising an epoxy resin, a curing agent and a filler having a group represented by the following formula (1).
(화학식 (1) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타냄)(In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R 2 represents an alkylene group having 1 to 30 carbon atoms)
상기 본 발명의 접착제 조성물은, 에폭시 수지 및 경화제를 함유한 후, 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재를 더 함유함으로써, 고온(예를 들면, 200℃ 이상)에서 금속 접합하는 플립 칩 접속 방식에서 반도체 밀봉용 접착제로서 적용한 경우에도 높은 내리플로우성, 접속 신뢰성 및 절연 신뢰성을 실현할 수 있다.The adhesive composition of the present invention may further contain a filler having an acrylic surface treatment filler or a group represented by the above formula (1) after containing an epoxy resin and a curing agent, Even when applied as an adhesive for semiconductor encapsulation in a flip-chip bonding method in which a bonding is performed, high flow-down property, connection reliability, and insulation reliability can be realized.
접착제 조성물의 내리플로우성을 향상시키기 위해서는, 고온에서의 흡습 후의 접착력을 향상시키는 것이 필요하다. 그러나, 종래부터 이용되고 있는 충전재는, 흡습률 및 열팽창률을 작게 하는 것이 가능하고, 접속성ㆍ절연 신뢰성을 향상시키기 위해서는 효과적이지만, 충전재 자체의 접착성은 통상 부족한 것이다.In order to improve the flow-down property of the adhesive composition, it is necessary to improve the adhesive force after moisture absorption at high temperature. However, the filler conventionally used can reduce the moisture absorption rate and the thermal expansion coefficient, and is effective for improving the connection property and insulation reliability, but the adhesion property of the filler itself is usually insufficient.
여기서, 실란 커플링제를 표면 처리하지 않은 충전재와 함께 수지 중에 함유시키면, 충전재의 표면이 실란 커플링 처리되어 실란 커플링제의 치환기에 의해 다양한 표면 상태의 충전재를 합성할 수 있다는 것이 알려져 있다. 그러나, 실란 커플링제의 휘발성은 높고, 고온 접속을 필요로 하는 금속 접합 등의 고온에서의 공정을 갖는 반도체 장치의 제조 공정에서는 공극이 발생하는 원인이 된다. 마찬가지로, 종래부터 이용되고 있는 충전재를 표면 처리하는 경우, 메탄올 등의 휘발성이 높은 유기물이 발생하는 경우가 있어, 공극이 발생하는 원인이 된다.It is known that when a silane coupling agent is contained in a resin together with a filler that has not been subjected to a surface treatment, the surface of the filler can be subjected to silane coupling treatment to synthesize fillers having various surface states by the substituent of the silane coupling agent. However, the volatility of the silane coupling agent is high, which causes pores in the process of manufacturing a semiconductor device having a process at a high temperature such as a metal junction requiring high-temperature connection. Likewise, when a conventionally used filler is surface-treated, highly volatile organic substances such as methanol may be generated, which may cause voids.
일반적으로, 반도체 기판 상에는 납땜 레지스트라 불리는 절연막이 형성되어 있으며, 납땜 레지스트는 아크릴계 재료를 포함하고 있는 경우가 많다. 따라서, 본 발명자들은, 상기 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재를 함유시킴으로써, 접착제 조성물의 고온에서의 탄성률과 흡습 후의 접착력을 향상시키고, 내리플로우성을 실현할 수 있다는 것을 발견하였다. 본 발명의 접착제 조성물에서는, 미리 표면 처리된 아크릴계 표면 처리 충전재 또는 상기 화학식 1로 표시되는 기를 갖는 충전재를 이용함으로써, 휘발성이 높은 물질의 발생을 억제할 수 있음과 함께, 아크릴계 화합물은 납땜 레지스트와의 접착성이 우수하기 때문에 기판과의 접속성을 향상시킬 수 있는 것으로 본 발명자들은 추측하고 있다. 또한, 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재는 접속부의 절연 신뢰성을 저하시키기 어렵고, 접착제 조성물의 경화물의 열팽창률 및 탄성률을 저하시키기 어렵기 때문에, 접속 신뢰성을 향상시킬 수 있는 것으로 본 발명자들은 추측하고 있다.Generally, an insulating film called a solder resist is formed on a semiconductor substrate, and a solder resist often contains an acrylic material. Accordingly, the inventors of the present invention have found that the inclusion of the above-mentioned acrylic surface-treating filler or a filler having the group represented by the above formula (1) improves the elastic modulus of the adhesive composition at high temperature and adhesion force after moisture absorption, Respectively. In the adhesive composition of the present invention, by using the acrylic surface treatment filler which has been surface-treated in advance or the filler having the group represented by the above-mentioned formula (1), the generation of the highly volatile substance can be suppressed, The inventors of the present invention have conjectured that the adhesiveness can be improved and the connection with the substrate can be improved. In addition, since the acrylic surface-treated filler or the filler having the group represented by the above formula (1) hardly deteriorates the insulation reliability of the connecting portion, and it is difficult to lower the thermal expansion coefficient and the elastic modulus of the cured product of the adhesive composition, The present inventors have speculated that there is.
아크릴계 표면 처리 충전재 또는 상기 화학식 1로 표시되는 기를 갖는 충전재는 수지 성분으로의 분산성이 우수하고, 본 발명의 접착제 조성물을 이용하여 제작한 반도체 장치에서의 패키지(기판-칩, 칩-칩 등) 말단부의 강도를 향상시킬 수 있다.The acrylic surface treatment filler or the filler having a group represented by the above formula (1) is excellent in dispersibility into a resin component and can be used as a package (substrate-chip, chip-chip, etc.) in a semiconductor device manufactured using the adhesive composition of the present invention. The strength of the distal end portion can be improved.
상술한 접착력 향상은 납땜 레지스트 상으로 제한되는 것은 아니며, 반도체칩간(SiO, SiN 등)에서도 발현한다.The above-described improvement in adhesion is not limited to a solder resist, but is also expressed between semiconductor chips (SiO, SiN, etc.).
상기 화학식 (1)로 표시되는 기를 갖는 화합물은, 하기 화학식 (2)로 표시되는 화합물인 것이 바람직하다.The compound having a group represented by the formula (1) is preferably a compound represented by the following formula (2).
(화학식 (2) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타내고, R3은 탄소수 1 내지 30의 알킬기를 나타냄)(Wherein R 1 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R 2 is an alkylene group having 1 to 30 carbon atoms, and R 3 is an alkyl group having 1 to 30 carbon atoms)
본 발명의 접착제 조성물은, 상기 화학식 (2)로 표시되는 화합물로 표면 처리된 충전재를 함유함으로써, 내리플로우성, 접속 신뢰성 및 절연 신뢰성을 더욱 향상시킬 수 있다.The adhesive composition of the present invention can further improve the flow resistance, connection reliability and insulation reliability by containing a filler surface-treated with the compound represented by the formula (2).
본 발명의 접착제 조성물에는, 접착제 조성물의 내열성 및 필름 형성성을 향상시키는 관점에서, 중량 평균 분자량이 10000 이상인 고분자 성분을 더 함유할 수 있다.The adhesive composition of the present invention may further contain a polymer component having a weight average molecular weight of 10,000 or more from the viewpoint of improving heat resistance and film formability of the adhesive composition.
접착제 조성물의 첩부성이나 필름 형성성을 더욱 향상시키는 관점에서 상기고분자 성분의 중량 평균 분자량은 30000 이상이고, 유리 전이 온도는 100℃ 이하인 것이 바람직하다.From the viewpoint of further improving the sticking property and film formability of the adhesive composition, the weight average molecular weight of the polymer component is preferably 30,000 or more, and the glass transition temperature is preferably 100 ° C or less.
본 발명의 접착제 조성물은, 플럭스 활성제를 더 함유함으로써 플럭스 활성을 높이고, 접속부의 금속 표면의 산화막이나 불순물을 제거하여, 양호한 금속-금속 접합을 형성할 수 있다.The adhesive composition of the present invention may further contain a flux activator to enhance the flux activity and remove the oxide film and impurities on the metal surface of the connecting portion to form a good metal-metal bond.
예비-적용 방식으로 반도체칩과 배선 회로 기판의 공극 또는 복수의 반도체칩간의 공극을 밀봉하는 경우의 작업성을 향상시킬 수 있기 때문에, 본 발명의 접착제 조성물은 형상이 필름상인 것이 바람직하다.It is preferable that the adhesive composition of the present invention is in the form of a film since it is possible to improve the workability in sealing the gap between the semiconductor chip and the wiring circuit board or the gap between the plurality of semiconductor chips by the preliminary application method.
또한, 본 발명은, 반도체칩 및 배선 회로 기판의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치 또는 복수의 반도체칩의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치의 제조 방법으로서, 접속부를 상기한 접착제 조성물을 이용하여 밀봉하는 공정을 구비하는 반도체 장치의 제조 방법을 제공한다.The present invention also provides a method of manufacturing a semiconductor device in which respective connecting portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other or each connecting portion of a plurality of semiconductor chips are electrically connected to each other, And a step of sealing with an adhesive composition.
본 발명의 반도체 장치의 제조 방법에 따르면, 상기 접착제 조성물을 이용함으로써, 반도체 장치의 내리플로우성, 접속 신뢰성 및 절연 신뢰성을 향상시킬 수 있다.According to the method for manufacturing a semiconductor device of the present invention, by using the above-mentioned adhesive composition, the flowability of the semiconductor device, the connection reliability, and the insulation reliability can be improved.
상기 접속부가 주성분으로서 금, 은, 구리, 니켈, 주석 및 납으로 이루어지는 군으로부터 선택되는 적어도 1종의 금속을 함유하면, 접속부의 전기 전도성, 열전도성, 접속 신뢰성을 더욱 향상시킬 수 있다.When the connecting portion contains at least one kind of metal selected from the group consisting of gold, silver, copper, nickel, tin and lead as a main component, the electrical conductivity, thermal conductivity and connection reliability of the connecting portion can be further improved.
또한, 본 발명은, 상기 반도체 장치의 제조 방법에 의해 얻어지는 반도체 장치를 제공한다.Further, the present invention provides a semiconductor device obtained by the above-described method for manufacturing a semiconductor device.
본 발명의 반도체 장치는 상기 반도체 장치의 제조 방법을 이용하여 제작되기 때문에, 내리플로우성, 접속 신뢰성 및 절연 신뢰성이 충분히 우수해진다.Since the semiconductor device of the present invention is manufactured by using the above-described method for manufacturing a semiconductor device, the flow resistance, connection reliability, and insulation reliability are sufficiently excellent.
본 발명에 따르면, 내리플로우성, 접속 신뢰성 및 절연 신뢰성이 우수한 접착제 조성물, 이 접착제 조성물을 이용한 반도체 장치의 제조 방법 및 반도체 장치를 제공할 수 있다.According to the present invention, it is possible to provide an adhesive composition excellent in flow resistance, connection reliability, and insulation reliability, a method of manufacturing a semiconductor device using the adhesive composition, and a semiconductor device.
[도 1] 본 발명의 반도체 장치의 한 실시 형태를 나타내는 모식 단면도이다.
[도 2] 본 발명의 반도체 장치의 다른 한 실시 형태를 나타내는 모식 단면도이다.
[도 3] 본 발명의 반도체 장치의 다른 한 실시 형태를 나타내는 모식 단면도이다.
[도 4] 본 발명의 반도체 장치의 제조 방법의 한 실시 형태를 모식적으로 나타내는 공정 단면도이다.
[도 5] 절연 신뢰성 시험용 샘플의 외관을 나타내는 모식도이다.1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention.
2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
4 is a process sectional view schematically showing an embodiment of a manufacturing method of a semiconductor device of the present invention.
5 is a schematic view showing the appearance of a sample for insulation reliability test.
이하, 경우에 따라 도면을 참조하면서 본 발명의 바람직한 실시 형태에 대하여 상세히 설명한다. 또한, 도면 중, 동일 또는 상당 부분에는 동일 부호를 붙여 중복된 설명은 생략한다. 또한, 상하 좌우 등의 위치 관계는 특별히 언급하지 않는 한, 도면에 나타내는 위치 관계에 기초하는 것으로 한다. 또한, 도면의 치수 비율은 도시한 비율로 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In addition, the positional relationships of the up, down, left, and right sides are based on the positional relationships shown in the drawings unless otherwise specified. In addition, the dimensional ratios in the drawings are not limited to the illustrated ratios.
<접착제 조성물>≪ Adhesive composition >
본 실시 형태의 접착제 조성물(반도체 밀봉용 접착제)은, 반도체칩 및 배선 회로 기판(이하, 경우에 따라 간단히 「기판」이라 함)의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치 또는 복수의 반도체칩의 각각의 접속부가 서로 전기적으로 접속된 반도체 장치에서 접속부를 밀봉하는 접착제 조성물로서, 에폭시 수지(이하, 경우에 따라 「(a) 성분」이라 함)와, 경화제(이하, 경우에 따라 「(b) 성분」이라 함)와, 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재(이하, 경우에 따라 「(c) 성분」이라 함)를 함유한다. 또한, 접착제 조성물은, 필요에 따라 중량 평균 분자량 10000 이상의 고분자 성분(이하, 경우에 따라 「(d) 성분」이라 함) 또는 플럭스 활성제(이하, 경우에 따라 「(e) 성분」이라 함)를 함유한다. 이하, 본 실시 형태의 접착제 조성물을 구성하는 각 성분에 대하여 설명한다.The adhesive composition (adhesive for semiconductor encapsulation) of the present embodiment is a semiconductor device in which respective connecting portions of a semiconductor chip and a wiring circuit substrate (hereinafter simply referred to as " substrate ") are electrically connected to each other, (Hereinafter, occasionally referred to as "component (a)") and a curing agent (hereinafter sometimes referred to as "(b)" in some cases) as an adhesive composition for sealing a connection portion in a semiconductor device, ) Component and an acrylic surface-treated filler or a filler having a group represented by the above formula (1) (hereinafter, sometimes referred to as "component (c)"). The adhesive composition may further contain, if necessary, a polymer component having a weight average molecular weight of 10000 or more (hereinafter referred to as "component (d)" in some cases) or a flux activator (hereinafter referred to as "component (e) . Hereinafter, each component constituting the adhesive composition of the present embodiment will be described.
(a) 성분: 에폭시 수지(a) Component: Epoxy resin
에폭시 수지로서는, 분자 내에 2개 이상의 에폭시기를 갖는 것이면 특별히 제한 없이 이용할 수 있다. (a) 성분으로서, 구체적으로는 비스페놀 A형, 비스페놀 F형, 나프탈렌형, 페놀노볼락형, 크레졸노볼락형, 페놀아르알킬형, 비페닐형, 트리페닐메탄형, 디시클로펜타디엔형 및 각종 다관능 에폭시 수지를 사용할 수 있다. 이들은 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule. Specific examples of the component (a) include bisphenol A, bisphenol F, naphthalene, phenol novolak, cresol novolak, phenol aralkyl, biphenyl, triphenylmethane, dicyclopentadiene, Various polyfunctional epoxy resins can be used. These can be used alone or as a mixture of two or more kinds.
(a) 성분은, 고온에서의 접속시에 분해되어 휘발 성분이 발생하는 것을 억제하는 관점에서, 접속시의 온도가 250℃인 경우에는 250℃에서의 열 중량 감소량률이 5% 이하인 에폭시 수지를 이용하는 것이 바람직하고, 300℃인 경우에는 300℃에서의 열 중량 감소량률이 5% 이하인 에폭시 수지를 이용하는 것이 바람직하다.The component (a) is preferably an epoxy resin having a thermogravimetric reduction rate of 5% or less at 250 캜 when the temperature at the time of connection is 250 캜 from the viewpoint of suppressing generation of volatile components upon decomposition at high temperature It is preferable to use an epoxy resin having a thermogravimetric reduction rate at 300 캜 of 5% or less at 300 캜.
(b) 성분: 경화제(b) Component: Curing agent
(b) 성분으로서는, 예를 들면 페놀 수지계 경화제, 산 무수물계 경화제, 아민계 경화제, 이미다졸계 경화제 및 포스핀계 경화제를 들 수 있다. (b) 성분이 페놀성 수산기, 산 무수물, 아민류 또는 이미다졸류를 포함하면, 접속부에 산화막이 발생하는 것을 억제하는 플럭스 활성을 나타내고, 접속 신뢰성ㆍ절연 신뢰성을 향상시킬 수 있다. 이하, 각 경화제에 대하여 설명한다.Examples of the component (b) include phenol resin-based curing agents, acid anhydride-based curing agents, amine-based curing agents, imidazole-based curing agents and phosphine-based curing agents. When the component (b) contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, it exhibits a flux activity that suppresses the generation of an oxide film at the connection portion and improves the connection reliability and insulation reliability. Each of the curing agents will be described below.
(i) 페놀 수지계 경화제(i) a phenol resin-based curing agent
페놀 수지계 경화제로서는, 분자 내에 2개 이상의 페놀성 수산기를 갖는 것이면 특별히 제한은 없으며, 예를 들면 페놀노볼락, 크레졸노볼락, 페놀아르알킬 수지, 크레졸나프톨포름알데히드 중축합물, 트리페닐메탄형 다관능 페놀 및 각종 다관능 페놀 수지를 사용할 수 있다. 이들은 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.The phenol resin-based curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule, and examples thereof include phenol novolak, cresol novolak, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, Phenol and various polyfunctional phenol resins can be used. These can be used alone or as a mixture of two or more kinds.
상기 (a) 성분에 대한 페놀 수지계 경화제의 당량비(페놀성 수산기/에폭시기, 몰비)는, 양호한 경화성, 접착성 및 보존 안정성의 관점에서 0.3 내지 1.5가 바람직하고, 0.4 내지 1.0이 보다 바람직하고, 0.5 내지 1.0이 더욱 바람직하다. 당량비가 0.3 이상이면 경화성이 향상되어 접착력이 향상되는 경향이 있고, 1.5 이하이면 미반응 페놀성 수산기가 과잉으로 잔존하지 않아, 흡수율이 낮게 억제되고, 절연 신뢰성이 향상되는 경향이 있다.The equivalent ratio (phenolic hydroxyl group / epoxy group, molar ratio) of the phenol resin-based curing agent to the component (a) is preferably from 0.3 to 1.5, more preferably from 0.4 to 1.0, and even more preferably from 0.5 To 1.0. When the equivalent ratio is 0.3 or more, the curing property is improved and the adhesion tends to be improved. When the equivalent ratio is not more than 1.5, unreacted phenolic hydroxyl groups do not remain excessively, so that the water absorption rate is suppressed to be low and the insulation reliability tends to be improved.
(ii) 산 무수물계 경화제(ii) an acid anhydride-based curing agent
산 무수물계 경화제로서는, 예를 들면 메틸시클로헥산테트라카르복실산 이무수물, 무수 트리멜리트산, 무수 피로멜리트산, 벤조페논테트라카르복실산 이무수물 및 에틸렌글리콜비스안히드로트리멜리테이트를 사용할 수 있다. 이들은 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.As the acid anhydride-based curing agent, for example, methylcyclohexanetetracarboxylic acid dianhydride, trimellitic anhydride, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride and ethylene glycol bisanhydrotrimellitate can be used . These can be used alone or as a mixture of two or more kinds.
상기 (a) 성분에 대한 산 무수물계 경화제의 당량비(산 무수물기/에폭시기, 몰비)는, 양호한 경화성, 접착성 및 보존 안정성의 관점에서 0.3 내지 1.5가 바람직하고, 0.4 내지 1.0이 보다 바람직하고, 0.5 내지 1.0이 더욱 바람직하다. 당량비가 0.3 이상이면, 경화성이 향상되어 접착력이 향상되는 경향이 있고, 1.5 이하이면 미반응 산 무수물이 과잉으로 잔존하지 않아, 흡수율이 낮게 억제되고, 절연 신뢰성이 향상되는 경향이 있다.The equivalent ratio (acid anhydride group / epoxy group, molar ratio) of the acid anhydride-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0 from the viewpoints of good curability, More preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted acid anhydride does not remain excessively, and the water absorption rate is suppressed to be low and the insulation reliability tends to be improved.
(iii) 아민계 경화제(iii) amine-based curing agent
아민계 경화제로서는, 예를 들면 디시안디아미드를 사용할 수 있다.As the amine-based curing agent, for example, dicyandiamide can be used.
상기 (a) 성분에 대한 아민계 경화제의 당량비(아민/에폭시기, 몰비)는, 양호한 경화성, 접착성 및 보존 안정성의 관점에서 0.3 내지 1.5가 바람직하고, 0.4 내지 1.0이 보다 바람직하고, 0.5 내지 1.0이 더욱 바람직하다. 당량비가 0.3 이상이면, 경화성이 향상되어 접착력이 향상되는 경향이 있고, 1.5 이하이면 미반응 아민이 과잉으로 잔존하지 않아, 절연 신뢰성이 향상되는 경향이 있다.The equivalent ratio (amine / epoxy group, molar ratio) of the amine-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and more preferably 0.5 to 1.0 in terms of good curability, Is more preferable. When the equivalent ratio is 0.3 or more, the curability is improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted amine does not remain excessively, and the insulation reliability tends to be improved.
(iv) 이미다졸계 경화제(iv) an imidazole-based curing agent
이미다졸계 경화제로서는, 예를 들면 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 1-벤질-2-메틸이미다졸, 1-벤질-2-페닐이미다졸, 1-시아노에틸-2-운데실이미다졸, 1-시아노-2-페닐이미다졸, 1-시아노에틸-2-운데실이미다졸트리멜리테이트, 1-시아노에틸-2-페닐이미다졸륨트리멜리테이트, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디아미노-6-[2'-운데실이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디아미노-6-[2'-에틸-4'-메틸이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진이소시아누르산 부가체, 2-페닐이미다졸이소시아누르산 부가체, 2-페닐-4,5-디히드록시메틸이미다졸, 2-페닐-4-메틸-5-히드록시메틸이미다졸 및 에폭시 수지와 이미다졸류의 부가체를 들 수 있다. 이들 중에서도, 우수한 경화성, 보존 안정성 및 접속 신뢰성의 관점에서, 1-시아노에틸-2-운데실이미다졸, 1-시아노-2-페닐이미다졸, 1-시아노에틸-2-운데실이미다졸트리멜리테이트, 1-시아노에틸-2-페닐이미다졸륨트리멜리테이트, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디아미노-6-[2'-에틸-4'-메틸이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진이소시아누르산 부가체, 2-페닐이미다졸이소시아누르산 부가체, 2-페닐-4,5-디히드록시메틸이미다졸 및 2-페닐-4-메틸-5-히드록시메틸이미다졸이 바람직하다. 이들은 단독으로 또는 2종 이상을 병용하여 이용할 수 있다. 또한, 이들을 마이크로 캡슐화한 잠재성 경화제로 할 수도 있다.Examples of the imidazole-based curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl- Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Ethyl-s-triazine, isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] Phenyl-4-methyl-5-hydroxymethylimidazole, and an adduct of an epoxy resin and imidazoles in a solvent such as tetrahydrofuran, . Among them, from the viewpoints of excellent curability, storage stability and connection reliability, it is preferable that 1-cyanoethyl-2-undecylimidazole, 1-cyano- Ethylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- Roximethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred. These may be used alone or in combination of two or more. In addition, they may be made into a latent curing agent microencapsulated.
이미다졸계 경화제의 함유량은 (a) 성분 100 질량부에 대하여 0.1 내지 20 질량부가 바람직하고, 0.1 내지 10 질량부가 보다 바람직하다. 이미다졸계 경화제의 함유량이 0.1 질량부 이상이면 경화성이 향상되는 경향이 있으며, 20 질량부 이하이면 금속 접합이 형성되기 전에 접착제 조성물이 경화되지 않아, 접속 불량이 발생하기 어려운 경향이 있다.The content of the imidazole-based curing agent is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the component (a). When the content of the imidazole-based curing agent is 0.1 parts by mass or more, the curing property tends to be improved. When the content of the imidazole-series curing agent is 20 parts by mass or less, the adhesive composition is not cured before the metal bonding is formed.
(v) 포스핀계 경화제(v) a phosphine-based curing agent
포스핀계 경화제로서는, 예를 들면 트리페닐포스핀, 테트라페닐포스포늄테트라페닐보레이트, 테트라페닐포스포늄테트라(4-메틸페닐)보레이트 및 테트라페닐포스포늄(4-플루오로페닐)보레이트를 들 수 있다.Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate.
포스핀계 경화제의 함유량은, (a) 성분 100 질량부에 대하여 0.1 내지 10 질량부가 바람직하고, 0.1 내지 5 질량부가 보다 바람직하다. 포스핀계 경화제의 함유량이 0.1 질량부 이상이면 경화성이 향상되는 경향이 있으며, 10 질량부 이하이면 금속 접합이 형성되기 전에 접착제 조성물이 경화되지 않아, 접속 불량이 발생하기 어려운 경향이 있다.The content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a). When the content of the phosphine-based curing agent is 0.1 parts by mass or more, the curing property tends to be improved. When the content of the phosphine-based curing agent is 10 parts by mass or less, the adhesive composition is not cured before the metal bonding is formed.
페놀 수지계 경화제, 산 무수물계 경화제 및 아민계 경화제는, 각각 1종을 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다. 이미다졸계 경화제 및 포스핀계 경화제는 각각 단독으로 이용할 수도 있지만, 페놀 수지계 경화제, 산 무수물계 경화제 또는 아민계 경화제와 함께 이용할 수도 있다.The phenol resin-based curing agent, acid anhydride-based curing agent and amine-based curing agent may each be used singly or as a mixture of two or more kinds. The imidazole-based curing agent and the phosphine-based curing agent may be used alone or in combination with a phenol resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent.
접착제 조성물이 (b) 성분으로서 페놀 수지계 경화제, 산 무수물계 경화제 또는 아민계 경화제를 포함하는 경우, 산화막을 제거하는 플럭스 활성을 나타내고, 접속 신뢰성을 보다 향상시킬 수 있다.When the adhesive composition contains a phenol resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent as the component (b), it exhibits flux activity for removing the oxide film and can further improve connection reliability.
(c) 성분: 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재(c) Component: Acrylic surface-treated filler or filler having a group represented by the above formula (1)
(c) 성분으로서는, 상기 화학식 (1)로 표시되는 기를 갖는 화합물로 표면 처리된 충전재이면 특별히 제한은 없으며, 예를 들면 절연성 무기 충전재, 휘스커 및 수지 충전재를 표면 처리한 것을 이용할 수 있다. 즉, (c) 성분으로서는, 상기 화학식 (1)로 표시되는 기를 갖는 충전재를 이용할 수 있다.The component (c) is not particularly limited as long as it is a filler surface-treated with a compound having a group represented by the above-mentioned formula (1), and for example, an insulating inorganic filler, whisker and resin filler can be used. That is, as the component (c), a filler having a group represented by the above formula (1) can be used.
여기서, 화학식 (1) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, 수소 원자, 메틸기 또는 에틸기인 것이 바람직하다. R1의 탄소수가 증가할수록 부피가 커지고, 탄소수가 2를 초과하면 반응성이 저하되는 경향이 있다. R2는 탄소수 1 내지 30의 알킬렌기를 나타내고, 탄소수 1 내지 15의 알킬렌기인 것이 바람직하다. R2의 탄소수가 30을 초과하면, 충전재를 표면 처리하기 어려워지는 경향이 있다.In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and is preferably a hydrogen atom, a methyl group or an ethyl group. As the number of carbon atoms in R 1 increases, the volume increases. When the number of carbon atoms exceeds 2, the reactivity tends to decrease. R 2 represents an alkylene group having 1 to 30 carbon atoms, and is preferably an alkylene group having 1 to 15 carbon atoms. When the carbon number of R 2 exceeds 30, the filler tends to be difficult to be surface-treated.
(c) 성분이 충전재 표면에 상기 화학식 (1)로 표시되는 기를 갖는지의 여부는, 예를 들면 이하와 같은 방법으로 확인할 수 있다.Whether or not the component (c) has a group represented by the above formula (1) on the surface of the filler can be confirmed, for example, by the following method.
본 실시 형태의 접착제 조성물을 가열하고, 가스 크로마토그래피(예를 들면, 시마즈(SHIMADZU) 제조, 제품명 「GC-17A」)를 이용하여 발생한 메탄올을 측정한다. 상기 메탄올의 양으로부터, 충전재 표면에 존재하는 상기 화학식 (1)로 표시되는 기를 갖는 것을 확인할 수 있다. 이 경우, (C) 성분을 포함하지 않는 접착제 조성물의 메탄올량을 마찬가지로 측정하여 기준으로 한다.The adhesive composition of the present embodiment is heated, and methanol generated by gas chromatography (for example, product name "GC-17A", manufactured by SHIMADZU) is measured. From the amount of methanol, it can be confirmed that the compound represented by the above formula (1) exists on the surface of the filler. In this case, the amount of methanol in the adhesive composition containing no component (C) is similarly measured and used as a reference.
절연성 무기 충전재로서는, 예를 들면 유리, 실리카, 알루미나, 산화티탄, 카본 블랙, 마이커 및 질화붕소를 들 수 있으며, 실리카, 알루미나, 산화티탄 및 질화붕소가 바람직하고, 실리카, 알루미나 및 질화붕소가 보다 바람직하다. 휘스커로서는, 예를 들면 붕산알루미늄, 티탄산알루미늄, 산화아연, 규산칼슘, 황산마그네슘 및 질화붕소를 들 수 있다. 수지 충전재로서는, 폴리우레탄, 폴리이미드를 들 수 있다. 이들 충전재 및 휘스커는 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다. 충전재의 형상, 입경 및 배합량은, 특별히 제한되지 않는다. 미세한 나노 실리카를 이용할 수도 있다. 이들 충전재 중에서도, 표면 처리의 간이성이나 수지 성분과의 상용성이 비교적 양호하다는 점에서 실리카 충전재가 바람직하다.Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica and boron nitride, and silica, alumina, titanium oxide and boron nitride are preferable, and silica, alumina and boron nitride More preferable. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. Examples of the resin filler include polyurethane and polyimide. These fillers and whiskers may be used alone or as a mixture of two or more thereof. The shape, particle size and blending amount of the filler are not particularly limited. Fine nanosilica may also be used. Among these fillers, a silica filler is preferable in view of the simplicity of surface treatment and the comparatively good compatibility with resin components.
(c) 성분으로서, 상기 화학식 (2)로 표시되는 화합물로 표면 처리된 충전재를 이용할 수 있다. 구체적으로는, 화학식 (2) 중, R1이 수소 원자인 아크릴계 화합물로 표면 처리된 실리카 충전재, R1이 메틸기인 메타크릴계 화합물로 표면 처리된 실리카 충전재, 및 R1이 에틸기인 에타크릴계 화합물로 표면 처리된 실리카 충전재를 사용할 수 있다. 반도체 접착제에 포함되는 수지 성분이나 반도체 기판 표면과의 반응성이나 결합 형성의 관점에서, 상기 화학식 (2) 중 R1이 부피가 크지 않은 기인 것이 바람직하고, R1이 수소 원자 또는 탄소수 1 또는 2의 알킬기이고, 수소 원자, 메틸기 또는 에틸기인 것이 바람직하다. R1의 탄소수가 증가할수록 부피가 커지고, 탄소수가 2를 초과하면 반응성이 저하되는 경향이 있다. 즉, (c) 성분으로서 아크릴계 화합물, 메타크릴계 화합물 또는 에타크릴계 화합물로 표면 처리된 실리카 충전재를 이용할 수 있다.As the component (c), a filler surface-treated with the compound represented by the formula (2) can be used. Specifically, a silica filler surface-treated with an acrylic compound wherein R 1 is a hydrogen atom, a silica filler surface-treated with a methacrylic compound wherein R 1 is a methyl group, and a silica filler whose R 1 is an ethyl group, A silica filler surface-treated with a compound can be used. It is preferable that R 1 in the above formula (2) is a non-bulky group in view of the reactivity with the resin component contained in the semiconductor adhesive or with the surface of the semiconductor substrate and bond formation, and R 1 is a hydrogen atom, An alkyl group, and is preferably a hydrogen atom, a methyl group or an ethyl group. As the number of carbon atoms in R 1 increases, the volume increases. When the number of carbon atoms exceeds 2, the reactivity tends to decrease. That is, as the component (c), a silica filler surface-treated with an acrylic compound, a methacrylic compound or an ethacrylic compound can be used.
상기 화학식 (1) 또는 (2)에서 R2는 탄소수 1 내지 30의 알킬렌기를 나타내고, 휘발 성분이 적기 때문에 탄소수 1 내지 15의 알킬렌기인 것이 바람직하다. 화학식 (2) 중, R3은 탄소수 1 내지 30의 알킬기를 나타내고, 표면 처리의 용이함에 따라 적절하게 선정할 수 있다. R3의 탄소수가 30 이하이면, 충전재를 표면 처리하기 쉬운 경향이 있다.In the above formula (1) or (2), R 2 represents an alkylene group having 1 to 30 carbon atoms and is preferably an alkylene group having 1 to 15 carbon atoms since the volatile component is small. In the formula (2), R 3 represents an alkyl group having 1 to 30 carbon atoms, and can be suitably selected in accordance with the ease of surface treatment. When the carbon number of R 3 is 30 or less, the filler tends to be easily surface-treated.
(c) 성분의 형상, 입경은, 접착제 조성물의 용도에 따라 적절하게 설정할 수 있으며, 특별히 제한되지 않는다.The shape and particle diameter of the component (c) can be appropriately set according to the use of the adhesive composition, and are not particularly limited.
(C) 성분의 평균 입경은, 충전재 형상이 구상인 경우, 평균 입경은 2 ㎛ 이하인 것이 바람직하고, 협피치화, 협갭화가 진행되는 패키지에서는, 트래핑에 의한 신뢰성 저하를 회피하기 위해 1.5 ㎛ 이하인 것이 보다 바람직하고, 1.0 ㎛ 이하인 것이 특히 바람직하다. 또한, 그의 하한은 취급성의 관점에서 0.005 ㎛ 이상인 것이 보다 바람직하고, 0.01 ㎛ 이하인 것이 특히 바람직하다.The average particle diameter of the component (C) is preferably not more than 2 占 퐉 when the filler has a spherical shape, and not more than 1.5 占 퐉 in order to avoid a decrease in reliability due to trapping in a package in which narrowing- More preferably 1.0 mu m or less. From the viewpoint of handling property, the lower limit thereof is more preferably 0.005 占 퐉 or more, and particularly preferably 0.01 占 퐉 or less.
(c) 성분의 배합량은, 접착제 조성물의 고형분 전체를 기준으로 5 내지 80 질량%가 바람직하고, 10 내지 70 질량%가 더욱 바람직하다. 5 질량% 이상이면 접착력의 향상이 강하게 발휘되기 쉬운 경향이 있으며, 80 질량% 이하이면 점도를 조정하기 쉽고, 접착제 조성물의 유동성의 저하나 접속부로의 충전재의 맞물림(트래핑)이 발생하기 어려워, 접속 신뢰성이 향상되는 경향이 있다.The blending amount of the component (c) is preferably from 5 to 80 mass%, more preferably from 10 to 70 mass%, based on the total solid content of the adhesive composition. When the amount is 80% by mass or less, the viscosity of the adhesive composition is easily adjusted, the fluidity of the adhesive composition is lowered, and the filling material (trapping) The reliability tends to be improved.
또한, 실란 커플링제를 미리 충전재와 표면 처리하지 않고, 접착제 조성물의 구성 성분으로서 첨가하여, 계 중에서 표면 처리를 행하면, 메탄올 등이 발생하여 고온 공정시에 발포의 원인이 된다.Further, when a silane coupling agent is added to the adhesive composition as a constituent component of the adhesive composition in advance of the surface treatment with a filler and the surface treatment is carried out in the system, methanol or the like may be generated to cause foaming at a high temperature process.
접착제 조성물의 260℃ 부근에서의 흡습 후의 접착력을 향상시키고, 260℃ 부근에서의 탄성률을 향상시킴으로써, 내리플로우성을 높이고, 리플로우 후의 박리나 접속 불량을 방지할 수 있다.By improving the adhesive force of the adhesive composition after moisture absorption at around 260 deg. C and improving the elastic modulus at around 260 deg. C, it is possible to improve the flow resistance and prevent detachment after reflow and poor connection.
(d) 성분: 중량 평균 분자량 10000 이상의 고분자 성분Component (d): a polymer component having a weight average molecular weight of 10,000 or more
(d) 성분으로서는, 예를 들면 페녹시 수지, 폴리이미드 수지, 폴리아미드 수지, 폴리카르보디이미드 수지, 시아네이트에스테르 수지, 아크릴 수지, 폴리에스테르 수지, 폴리에틸렌 수지, 폴리에테르술폰 수지, 폴리에테르이미드 수지, 폴리비닐아세탈 수지, 우레탄 수지 및 아크릴 고무를 들 수 있다. 이들 중에서도 내열성 및 필름 형성성이 우수하다는 관점에서, 페녹시 수지, 폴리이미드 수지, 아크릴 고무, 시아네이트에스테르 수지 및 폴리카르보디이미드 수지가 바람직하고, 페녹시 수지, 폴리이미드 수지 및 아크릴 고무가 보다 바람직하다. 이들 (d) 성분은 단독으로 또는 2종 이상의 혼합물이나 공중합체로서 사용할 수도 있다. 단, (d) 성분에는, (a) 성분인 에폭시 수지가 포함되지 않는다.Examples of the component (d) include a phenoxy resin, a polyimide resin, a polyamide resin, a polycarbodiimide resin, a cyanate ester resin, an acrylic resin, a polyester resin, a polyethylene resin, a polyether sulfone resin, Resins, polyvinyl acetal resins, urethane resins, and acrylic rubbers. Of these, phenoxy resins, polyimide resins, acrylic rubbers, cyanate ester resins and polycarbodiimide resins are preferable, and phenoxy resins, polyimide resins and acrylic rubbers are preferred from the viewpoint of excellent heat resistance and film formability desirable. These component (d) may be used singly or as a mixture or copolymer of two or more kinds. However, the component (d) does not include the epoxy resin as the component (a).
상술한 페녹시 수지, 폴리이미드 수지 등의 고분자 성분은 시판품을 이용할 수도 있고, 합성한 것을 이용할 수도 있다.The above-mentioned polymer components such as the phenoxy resin and the polyimide resin may be commercially available products or synthesized products.
폴리이미드 수지는, 예를 들면 테트라카르복실산 이무수물과 디아민을 공지된 방법으로 축합 반응시켜 얻을 수 있다. 보다 구체적으로는, 유기 용매 중에서 테트라카르복실산 이무수물과 디아민을 등몰 또는 거의 등몰 혼합하고(각 성분의 첨가 순서는 임의), 반응 온도를 80℃ 이하, 바람직하게는 0 내지 60℃로 설정하여 부가 반응시킬 수 있다. 또한, 접착제 조성물의 다양한 특성의 저하를 억제하기 위해, 상기한 테트라카르복실산 이무수물은 무수 아세트산으로 재결정 정제 처리되어 있는 것이 바람직하다.The polyimide resin can be obtained, for example, by a condensation reaction of a tetracarboxylic dianhydride and a diamine by a known method. More specifically, the tetracarboxylic dianhydride and the diamine are equimolarly or nearly equimolarly mixed in an organic solvent (the order of addition of each component is optional), the reaction temperature is set to 80 ° C or less, preferably 0 to 60 ° C Addition reaction can be carried out. Further, in order to suppress deterioration of various properties of the adhesive composition, it is preferable that the tetracarboxylic dianhydride is recrystallized and purified with acetic anhydride.
상기 부가 반응이 진행됨에 따라 반응액의 점도가 서서히 상승하고, 폴리이미드의 전구체인 폴리아미드산이 생성된다. 폴리이미드 수지는, 상기 폴리아미드산을 탈수 폐환시켜 얻을 수 있다. 탈수 폐환은, 가열 처리하는 열 폐환법이나, 탈수제를 사용하는 화학 폐환법으로 행할 수 있다. 상기 폴리아미드산은 50 내지 80℃에서 가열하여 해중합시킴으로써, 그의 분자량을 조정할 수 있다.As the addition reaction proceeds, the viscosity of the reaction solution gradually increases and polyamic acid, which is a precursor of polyimide, is produced. The polyimide resin can be obtained by subjecting the polyamide acid to dehydration ring closure. Dehydration ring closure can be performed by a thermal closure method in which a heat treatment is performed or a chemical closure method using a dehydrating agent. The molecular weight of the polyamic acid can be adjusted by heating at 50 to 80 DEG C to depolymerize.
폴리이미드 수지의 원료로서 이용되는 테트라카르복실산 이무수물로서는 특별히 제한은 없으며, 예를 들면 피로멜리트산 이무수물, 3,3',4,4'-비페닐테트라카르복실산 이무수물, 2,2',3,3'-비페닐테트라카르복실산 이무수물, 2,2-비스(3,4-디카르복시페닐)프로판 이무수물, 2,2-비스(2,3-디카르복시페닐)프로판 이무수물, 1,1-비스(2,3-디카르복시페닐)에탄 이무수물, 1,1-비스(3,4-디카르복시페닐)에탄 이무수물, 비스(2,3-디카르복시페닐)메탄 이무수물, 비스(3,4-디카르복시페닐)메탄 이무수물, 비스(3,4-디카르복시페닐)술폰 이무수물, 3,4,9,10-페릴렌테트라카르복실산 이무수물, 비스(3,4-디카르복시페닐)에테르 이무수물, 벤젠-1,2,3,4-테트라카르복실산 이무수물, 3,4,3',4'-벤조페논테트라카르복실산 이무수물, 2,3,2',3'-벤조페논테트라카르복실산 이무수물, 3,3,3',4'-벤조페논테트라카르복실산 이무수물, 1,2,5,6-나프탈렌테트라카르복실산 이무수물, 1,4,5,8-나프탈렌테트라카르복실산 이무수물, 2,3,6,7-나프탈렌테트라카르복실산 이무수물, 1,2,4,5-나프탈렌테트라카르복실산 이무수물, 2,6-디클로로나프탈렌-1,4,5,8-테트라카르복실산 이무수물, 2,7-디클로로나프탈렌-1,4,5,8-테트라카르복실산 이무수물, 2,3,6,7-테트라클로로나프탈렌-1,4,5,8-테트라카르복실산 이무수물, 페난트렌-1,8,9,10-테트라카르복실산 이무수물, 피라진-2,3,5,6-테트라카르복실산 이무수물, 티오펜-2,3,5,6-테트라카르복실산 이무수물, 2,3,3',4'-비페닐테트라카르복실산 이무수물, 3,4,3',4'-비페닐테트라카르복실산 이무수물, 2,3,2',3'-비페닐테트라카르복실산 이무수물, 비스(3,4-디카르복시페닐)디메틸실란 이무수물, 비스(3,4-디카르복시페닐)메틸페닐실란 이무수물, 비스(3,4-디카르복시페닐)디페닐실란 이무수물, 1,4-비스(3,4-디카르복시페닐디메틸실릴)벤젠 이무수물, 1,3-비스(3,4-디카르복시페닐)-1,1,3,3-테트라메틸디시클로헥산 이무수물, p-페닐렌비스(트리멜리테이트 무수물), 에틸렌테트라카르복실산 이무수물, 1,2,3,4-부탄테트라카르복실산 이무수물, 데카히드로나프탈렌-1,4,5,8-테트라카르복실산 이무수물, 4,8-디메틸-1,2,3,5,6,7-헥사히드로나프탈렌-1,2,5,6-테트라카르복실산 이무수물, 시클로펜탄-1,2,3,4-테트라카르복실산 이무수물, 피롤리딘-2,3,4,5-테트라카르복실산 이무수물, 1,2,3,4-시클로부탄테트라카르복실산 이무수물, 비스(엑소-비시클로〔2,2,1〕헵탄-2,3-디카르복실산 이무수물, 비시클로-〔2,2,2〕-옥트-7-엔-2,3,5,6-테트라카르복실산 이무수물, 2,2-비스(3,4-디카르복시페닐)프로판 이무수물, 2,2-비스〔4-(3,4-디카르복시페닐)페닐〕프로판 이무수물, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 이무수물, 2,2-비스〔4-(3,4-디카르복시페닐)페닐〕헥사플루오로프로판 이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐술피드 이무수물, 1,4-비스(2-히드록시헥사플루오로이소프로필)벤젠비스(트리멜리트산 무수물), 1,3-비스(2-히드록시헥사플루오로이소프로필)벤젠비스(트리멜리트산 무수물), 5-(2,5-디옥소테트라히드로푸릴)-3-메틸-3-시클로헥센-1,2-디카르복실산 이무수물, 테트라히드로푸란-2,3,4,5-테트라카르복실산 이무수물, 하기 화학식 (I)로 표시되는 테트라카르복실산 이무수물 및 하기 화학식 (II)로 표시되는 테트라카르복실산 이무수물을 들 수 있다.The tetracarboxylic acid dianhydride used as a raw material of the polyimide resin is not particularly limited and includes, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2, 3 '-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dianhydride, dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis Dianhydride, dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis Benzene-1,2,3,4-tetracarboxylic acid dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 2, 3, 3,2 ', 3'-benzophenone tetracarboxylic acid dianhydride, 3,3,3', 4'-benzo Nonatetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetra Carboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene -1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8, Tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, thiophene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3, 3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ', 3'-biphenyltetracarboxylic acid Dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis Bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3- 1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride Water, decahydronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6 - tetracarboxylic acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, 1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic acid dianhydride, bicyclo- [2,2,2] -2,3,5,6-tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- - Dicarb Phenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic acid) dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 1,4- (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene Tetracarboxylic dianhydride represented by the following formula (I) and a tetracarboxylic acid dianhydride represented by the following formula (II): < EMI ID = ). ≪ / RTI >
(화학식 (I) 중, a는 2 내지 20의 정수를 나타냄)(In the formula (I), a represents an integer of 2 to 20)
상기 화학식 (I)로 표시되는 테트라카르복실산 이무수물은, 무수 트리멜리트산모노크롬라이드 및 대응하는 디올로부터 합성할 수 있으며, 구체적으로는 1,2-(에틸렌)비스(트리멜리테이트 무수물), 1,3-(트리메틸렌)비스(트리멜리테이트 무수물), 1,4-(테트라메틸렌)비스(트리멜리테이트 무수물), 1,5-(펜타메틸렌)비스(트리멜리테이트 무수물), 1,6-(헥사메틸렌)비스(트리멜리테이트 무수물), 1,7-(헵타메틸렌)비스(트리멜리테이트 무수물), 1,8-(옥타메틸렌)비스(트리멜리테이트 무수물), 1,9-(노나메틸렌)비스(트리멜리테이트 무수물), 1,10-(데카메틸렌)비스(트리멜리테이트 무수물), 1,12-(도데카메틸렌)비스(트리멜리테이트 무수물), 1,16-(헥사데카메틸렌)비스(트리멜리테이트 무수물) 및 1,18-(옥타데카메틸렌)비스(트리멜리테이트 무수물)을 들 수 있다.The tetracarboxylic acid dianhydride represented by the above formula (I) can be synthesized from anhydrous trimellitic acid monochloride and the corresponding diol, and specifically includes 1,2- (ethylene) bis (trimellitate anhydride) (Trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride) 1,6-hexamethylene bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride) (Trimellitate anhydride), 1,12- (nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride) Hexadecamethylene) bis (trimellitate anhydride) and 1,18- (octadecamethylene) bis (trimellitate anhydride).
테트라카르복실산 이무수물로서는, 우수한 내습 신뢰성을 부여할 수 있다는 점에서 상기 화학식 (II)로 표시되는 테트라카르복실산 이무수물이 바람직하다. 상기 테트라카르복실산 이무수물은, 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.As the tetracarboxylic acid dianhydride, a tetracarboxylic acid dianhydride represented by the above-mentioned formula (II) is preferable in that it can give excellent moisture resistance reliability. The tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.
상기 화학식 (II)로 표시되는 테트라카르복실산 이무수물의 함유량은, 전체 테트라카르복실산 이무수물에 대하여 40 몰% 이상이 바람직하고, 50 몰% 이상이 보다 바람직하고, 70 몰% 이상이 더욱 바람직하다. 함유량이 40 몰% 이상이면, 상기 화학식 (II)로 표시되는 테트라카르복실산 이무수물을 사용함에 따른 내습 신뢰성의 효과를 충분히 확보하기 쉬운 경향이 있다.The content of the tetracarboxylic dianhydride represented by the above formula (II) is preferably at least 40 mol%, more preferably at least 50 mol%, still more preferably at least 70 mol%, based on the total tetracarboxylic dianhydride Do. When the content is 40 mol% or more, there is a tendency that the effect of moisture resistance reliability by the use of the tetracarboxylic acid dianhydride represented by the above formula (II) can be sufficiently ensured.
상기 폴리이미드 수지의 원료로서 이용되는 디아민으로서는 특별히 제한은 없으며, 예를 들면 o-페닐렌디아민, m-페닐렌디아민, p-페닐렌디아민, 3,3'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐에테르, 3,3'-디아미노디페닐메탄, 3,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐에테르메탄, 비스(4-아미노-3,5-디메틸페닐)메탄, 비스(4-아미노-3,5-디이소프로필페닐)메탄, 3,3'-디아미노디페닐디플루오로메탄, 3,4'-디아미노디페닐디플루오로메탄, 4,4'-디아미노디페닐디플루오로메탄, 3,3'-디아미노디페닐술폰, 3,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐술폰, 3,3'-디아미노디페닐술피드, 3,4'-디아미노디페닐술피드, 4,4'-디아미노디페닐술피드, 3,3'-디아미노디페닐케톤, 3,4'-디아미노디페닐케톤, 4,4'-디아미노디페닐케톤, 2,2-비스(3-아미노페닐)프로판, 2,2'-(3,4'-디아미노디페닐)프로판, 2,2-비스(4-아미노페닐)프로판, 2,2-비스(3-아미노페닐)헥사플루오로프로판, 2,2-(3,4'-디아미노디페닐)헥사플루오로프로판, 2,2-비스(4-아미노페닐)헥사플루오로프로판, 1,3-비스(3-아미노페녹시)벤젠, 1,4-비스(3-아미노페녹시)벤젠, 1,4-비스(4-아미노페녹시)벤젠, 3,3'-(1,4-페닐렌비스(1-메틸에틸리덴))비스아닐린, 3,4'-(1,4-페닐렌비스(1-메틸에틸리덴))비스아닐린, 4,4'-(1,4-페닐렌비스(1-메틸에틸리덴))비스아닐린, 2,2-비스(4-(3-아미노페녹시)페닐)프로판, 2,2-비스(4-(3-아미노페녹시)페닐)헥사플루오로프로판, 2,2-비스(4-(4-아미노페녹시)페닐)헥사플루오로프로판, 비스(4-(3-아미노에녹시)페닐)술피드, 비스(4-(4-아미노에녹시)페닐)술피드, 비스(4-(3-아미노에녹시)페닐)술폰, 비스(4-(4-아미노에녹시)페닐)술폰, 3,5-디아미노벤조산 등의 방향족 디아민, 1,3-비스(아미노메틸)시클로헥산, 2,2-비스(4-아미노페녹시페닐)프로판, 하기 화학식 (III) 또는 (IV)로 표시되는 지방족 에테르디아민, 하기 화학식 (V)로 표시되는 지방족 디아민 및 하기 화학식 (VI)으로 표시되는 실록산디아민을 들 수 있다.The diamine used as a raw material of the polyimide resin is not particularly limited and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'- (4-amino-3, 5-diisopropylphenyl) methane, 3,3'-diaminodiphenyl difluoromethane, 3,4'-diaminodiphenyl difluoromethane, 4,4'-diaminodiphenyl difluoromethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, '-Diaminodiphenylketone, 3,4'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 2,2-bis (3-amyl Phenyl) propane, 2,2 '- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane , 2,2- (3,4-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3- (1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, ) Bisaniline, 3,4 '- (1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4' - (1,4-phenylenebis (1-methylethylidene) Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoxy) phenyl) sulfone, 3,5-diaminobenzene (Aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, an aliphatic ether diamine represented by the following formula (III) or (IV) An aliphatic diamine represented by the formula (V) and a siloxane diamine represented by the following formula (VI).
(화학식 (III) 중, Q1, Q2 및 Q3은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기를 나타내고, b는 1 내지 80의 정수를 나타냄)(In the formula (III), Q 1 , Q 2 and Q 3 each independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 1 to 80)
(화학식 (IV) 중, Q4, Q5, Q6 및 Q7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기를 나타내고, c, d 및 e는 각각 독립적으로 1 내지 50의 정수를 나타냄)(IV), Q 4 , Q 5 , Q 6 and Q 7 each independently represent an alkylene group having 1 to 10 carbon atoms, and c, d and e each independently represent an integer of 1 to 50)
(화학식 (V) 중, f는 5 내지 20의 정수를 나타냄)(In the formula (V), f represents an integer of 5 to 20)
(화학식 (VI) 중, Q8 및 Q13은 각각 독립적으로 탄소수 1 내지 5의 알킬렌기 또는 치환기를 가질 수도 있는 페닐렌기를 나타내고, Q9, Q10, Q11 및 Q12는 각각 독립적으로 탄소수 1 내지 5의 알킬기, 페닐기 또는 페녹시기를 나타내고, g는 1 내지 5의 정수를 나타냄)(VI), Q 8 and Q 13 each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q 9 , Q 10 , Q 11 and Q 12 each independently represents a An alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and g is an integer of 1 to 5)
이들 중에서도, 저응력성, 저온 라미네이트성 및 저온 접착성을 부여할 수 있다는 점에서 상기 화학식 (III), (IV) 또는 (V)로 표시되는 디아민이 바람직하고, 저흡수성 및 저흡습성을 부여할 수 있다는 점에서 상기 화학식 (VI)으로 표시되는 디아민이 바람직하다. 이들 디아민은 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Of these, the diamines represented by the above-mentioned formulas (III), (IV) or (V) are preferable from the standpoint of low stressability, low temperature lamination property and low temperature adhesiveness, The diamine represented by the above formula (VI) is preferable. These diamines may be used alone or in combination of two or more.
상기 화학식 (III) 또는 (IV)로 표시되는 지방족 에테르디아민의 함유량은 전체 디아민의 1 내지 50 몰%인 것이 바람직하고, 상기 화학식 (V)로 표시되는 지방족 디아민의 함유량은 전체 디아민의 20 내지 80 몰%인 것이 바람직하고, 상기 화학식 (VI)으로 표시되는 실록산디아민의 함유량은 전체 디아민의 20 내지 80 몰%인 것이 바람직하다. 상기 함유량의 범위 내이면, 저온 라미네이트성 및 저흡수성의 부여 효과가 커지는 경향이 있다.The content of the aliphatic ether diamine represented by the formula (III) or (IV) is preferably 1 to 50 mol% of the total diamine, and the content of the aliphatic diamine represented by the formula (V) Mol%, and the content of the siloxane diamine represented by the formula (VI) is preferably 20 to 80 mol% of the total diamine. When the content is within the above range, the effect of imparting low temperature lamination property and low water absorption property tends to become large.
또한, 상기 화학식 (III)으로 표시되는 지방족 에테르디아민으로서는, 구체적으로는 하기 화학식 (III-1) 내지 (III-5)의 지방족 에테르디아민을 들 수 있다. 또한, 화학식 (III-4) 및 (III-5) 중, n은 1 이상의 정수를 나타낸다.Specific examples of the aliphatic ether diamines represented by the formula (III) include aliphatic ether diamines represented by the following formulas (III-1) to (III-5). In the formulas (III-4) and (III-5), n represents an integer of 1 or more.
상기 화학식 (III-4)로 표시되는 지방족 에테르디아민의 중량 평균 분자량은, 예를 들면 350, 750, 1100 또는 2100인 것이 바람직하다. 또한, 상기 화학식 (III-5)로 표시되는 지방족 에테르디아민의 중량 평균 분자량은, 예를 들면 230, 400 또는 2000인 것이 바람직하다.The weight average molecular weight of the aliphatic ether diamine represented by the formula (III-4) is preferably 350, 750, 1100 or 2100, for example. The weight average molecular weight of the aliphatic ether diamine represented by the formula (III-5) is preferably 230, 400 or 2000, for example.
상기 지방족 에테르디아민 중, 저온 라미네이트성과 유기 레지스트 부착 기판에 대한 양호한 접착성을 확보할 수 있다는 점에서 상기 화학식 (IV), 하기 화학식 (VII), (VIII) 또는 (IX)로 각각 표시되는 지방족 에테르디아민이 보다 바람직하다.(VII), (VIII) or (IX) represented by the above-mentioned formula (IV) in that the aliphatic ether diamine can secure low-temperature lamination property and good adhesion to the organic resist- Diamine is more preferable.
(화학식 (VII) 중, h는 2 내지 80의 정수를 나타내고, 2 내지 70인 것이 보다 바람직함)(In the formula (VII), h represents an integer of 2 to 80, more preferably 2 to 70)
(화학식 (VIII) 중, c, d 및 e는 1 내지 50의 정수를 나타내고, 2 내지 40인 것이 보다 바람직함)(In the formula (VIII), c, d and e represent an integer of 1 to 50, more preferably 2 to 40)
(화학식 (IX) 중, j 및 k는 각각 독립적으로 1 내지 70의 정수를 나타냄)(In the formula (IX), j and k each independently represent an integer of 1 to 70)
상기 화학식 (VII)로 표시되는 지방족 에테르디아민으로서는, 구체적으로는 선테크노 케미컬(주) 제조의 제파민 D-230, D-400, D-2000 및 D-4000, 바스프(BASF) 제조의 폴리에테르아민 D-230, D-400 및 D-2000을 들 수 있으며, 상기 화학식 (VIII)로 표시되는 지방족 에테르디아민으로서는, 구체적으로는 선테크노 케미컬(주) 제조의 제파민 ED-600, ED-900, ED-2001을 들 수 있으며, 상기 화학식 (IX)로 표시되는 지방족 에테르디아민으로서는 선테크노 케미컬(주) 제조의 제파민 EDR-148을 들 수 있다.Specific examples of the aliphatic ether diamines represented by the formula (VII) include Jefamin D-230, D-400, D-2000 and D-4000 manufactured by Suntechno Chemical Co., Specific examples of the aliphatic ether diamine represented by the above formula (VIII) include Zephamine ED-600 and ED-900 manufactured by Suntechno Chemical Co., And ED-2001. Examples of the aliphatic ether diamine represented by the above formula (IX) include Zephamine EDR-148 manufactured by Sun Techno Chemical Co., Ltd.
상기 화학식 (V)로 표시되는 지방족 디아민으로서는, 예를 들면 1,2-디아미노에탄, 1,3-디아미노프로판, 1,4-디아미노부탄, 1,5-디아미노펜탄, 1,6-디아미노헥산, 1,7-디아미노헵탄, 1,8-디아미노옥탄, 1,9-디아미노노난, 1,10-디아미노데칸, 1,11-디아미노운데칸, 1,12-디아미노도데칸 및 1,2-디아미노시클로헥산을 들 수 있다. 이들 중에서도, 1,9-디아미노노난, 1,10-디아미노데칸, 1,11-디아미노운데칸 및 1,12-디아미노도데칸이 바람직하다.Examples of the aliphatic diamines represented by the formula (V) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 - diaminododecane and 1,2-diaminocyclohexane. Among these, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane are preferable.
상기 화학식 (VI)으로 표시되는 실록산디아민으로서는, 화학식 (VI) 중의 g가 1인 경우에는 1,1,3,3-테트라메틸-1,3-비스(4-아미노페닐)디실록산, 1,1,3,3-테트라페녹시-1,3-비스(4-아미노에틸)디실록산, 1,1,3,3-테트라페닐-1,3-비스(2-아미노에틸)디실록산, 1,1,3,3-테트라페닐-1,3-비스(3-아미노프로필)디실록산, 1,1,3,3-테트라메틸-1,3-비스(2-아미노에틸)디실록산, 1,1,3,3-테트라메틸-1,3-비스(3-아미노프로필)디실록산, 1,1,3,3-테트라메틸-1,3-비스(3-아미노부틸)디실록산 및 1,3-디메틸-1,3-디메톡시-1,3-비스(4-아미노부틸)디실록산을 들 수 있다. g가 2인 경우에는, 1,1,3,3,5,5-헥사메틸-1,5-비스(4-아미노페닐)트리실록산, 1,1,5,5-테트라페닐-3,3-디메틸-1,5-비스(3-아미노프로필)트리실록산, 1,1,5,5-테트라페닐-3,3-디메톡시-1,5-비스(4-아미노부틸)트리실록산, 1,1,5,5-테트라페닐-3,3-디메톡시-1,5-비스(5-아미노펜틸)트리실록산, 1,1,5,5-테트라메틸-3,3-디메톡시-1,5-비스(2-아미노에틸)트리실록산, 1,1,5,5-테트라메틸-3,3-디메톡시-1,5-비스(4-아미노부틸)트리실록산, 1,1,5,5-테트라메틸-3,3-디메톡시-1,5-비스(5-아미노펜틸)트리실록산, 1,1,3,3,5,5-헥사메틸-1,5-비스(3-아미노프로필)트리실록산, 1,1,3,3,5,5-헥사에틸-1,5-비스(3-아미노프로필)트리실록산 및 1,1,3,3,5,5-헥사프로필-1,5-비스(3-아미노프로필)트리실록산을 들 수 있다.As the siloxane diamine represented by the formula (VI), when g in the formula (VI) is 1, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1, 3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl- , 1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis , 1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis , 3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane. When g is 2, 1,1,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl- 1, 5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1 , 1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy- , 5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis , 5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl- Aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane and 1,1,3,3,5,5- 1,5-bis (3-aminopropyl) trisiloxane.
상기 폴리이미드 수지는, 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.The polyimide resin may be used alone or as a mixture of two or more thereof.
(d) 성분의 유리 전이 온도(Tg)는, 접착제 조성물의 기판이나 칩으로의 첩부성이 우수하다는 관점에서 100℃ 이하가 바람직하고, 85℃ 이하가 보다 바람직하다. Tg가 100℃ 이하인 경우에는, 반도체칩에 형성된 범프나, 기판에 형성된 전극이나 배선 패턴 등의 요철을 접착제 조성물에 의해 매립하기 쉬워지며, 기포가 잔존하지 않고 공극이 발생하기 어려운 경향이 있다. 또한, 상기 Tg란, DSC(퍼킨 엘머사 제조 DSC-7형)를 이용하여 샘플량 10 mg, 승온 속도 10℃/분, 측정 분위기: 공기의 조건으로 측정했을 때의 Tg이다.The glass transition temperature (Tg) of the component (d) is preferably 100 占 폚 or lower, more preferably 85 占 폚 or lower, from the viewpoint of excellent adhesion of the adhesive composition to a substrate or a chip. When the Tg is 100 DEG C or less, the bump formed on the semiconductor chip and the irregularities such as electrodes and wiring patterns formed on the substrate can be easily filled with the adhesive composition, and the bubbles do not remain and voids tend to be hard to be generated. The Tg is a Tg measured using a DSC (DSC-7 type manufactured by Perkin Elmer Corp.) under the conditions of a sample amount of 10 mg, a heating rate of 10 ° C / min, and a measuring atmosphere: air.
(d) 성분의 중량 평균 분자량은 폴리스티렌 환산으로 10000 이상이지만, 단독으로 양호한 필름 형성성을 나타내기 때문에 30000 이상이 바람직하고, 40000 이상이 보다 바람직하고, 50000 이상이 더욱 바람직하다. 중량 평균 분자량이 10000 이상이면, 필름 형성성 및 내열성이 향상되는 경향이 있다. 또한, 본 명세서에서 중량 평균 분자량이란, 고속 액체 크로마토그래피(예를 들면, 시마즈 세이사꾸쇼 제조, 제품명 「C-R4A」)를 이용하여 폴리스티렌 환산으로 측정했을 때의 중량 평균 분자량을 의미한다.The weight average molecular weight of the component (d) is 10000 or more in terms of polystyrene, but is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more because it shows good film formability. When the weight average molecular weight is 10,000 or more, the film formability and heat resistance tend to be improved. In the present specification, the weight average molecular weight means a weight average molecular weight measured by polystyrene conversion using high performance liquid chromatography (for example, product name "C-R4A", manufactured by Shimadzu Corporation).
(d) 성분의 함유량은 특별히 제한되지 않지만, 필름상을 양호하게 유지하기 위해 (a) 성분 100 질량부에 대하여 1 내지 500 질량부인 것이 바람직하고, 5 내지 300 질량부인 것이 보다 바람직하고, 10 내지 200 질량부가 더욱 바람직하다. (d) 성분의 함유량이 1 질량부 이상이면, 필름 형성성의 향상 효과가 얻어지기 쉬운 경향이 있으며, 500 질량부 이하이면 접착제 조성물의 경화성이 향상되고, 접착력이 향상되는 경향이 있다.The content of the component (d) is not particularly limited, but it is preferably 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the component (a) More preferably 200 parts by mass. When the content of the component (d) is 1 part by mass or more, an effect of improving the film formability tends to be obtained. When the content is less than 500 parts by mass, the curing property of the adhesive composition is improved and the adhesive strength tends to be improved.
(e) 성분: 플럭스 활성제(e) Component: flux activator
본 발명의 접착제 조성물에는 (e) 성분, 즉 플럭스 활성(산화물이나 불순물을 제거하는 활성)을 나타내는 화합물인 플럭스 활성제를 함유할 수 있다. 플럭스 활성제로서는, 이미다졸류나 아민류와 같이 비공유 전자쌍을 갖는 질소 함유 화합물, 카르복실산류, 페놀류 및 알코올류를 들 수 있다.The adhesive composition of the present invention may contain a component (e), that is, a flux activator which is a compound that exhibits flux activity (activity to remove oxides or impurities). Examples of the flux activator include nitrogen-containing compounds, carboxylic acids, phenols, and alcohols having non-covalent electron pairs such as imidazoles and amines.
이들 중에서도 카르복실산류는 플럭스 활성이 강하고, (a) 성분인 에폭시 수지와 반응하여 접착제 조성물의 경화물 중에 유리된 상태로 존재하지 않기 때문에, 절연 신뢰성의 저하를 방지할 수 있다.Among them, carboxylic acids have strong flux activity and do not exist in the cured product of the adhesive composition in a free state in reaction with the epoxy resin as the component (a), so that deterioration in insulation reliability can be prevented.
카르복실산류로서는, 예를 들면 에탄산, 프로판산, 부탄산, 펜탄산, 헥산산, 헵탄산, 옥탄산, 노난산, 데칸산, 도데칸산, 테트라데칸산, 헥사데칸산, 헵타데칸산, 옥타데칸산 등의 지식(脂式) 포화 카르복실산; 올레산, 리놀레산, 리놀렌산, 아라키돈산, 도코사헥사엔산, 에이코사펜타엔산 등의 지식 불포화 카르복실산; 말레산, 푸마르산, 옥살산, 말론산, 숙신산, 글루타르산, 아디프산 등의 지식 디카르복실산; 벤조산, 프탈산, 이소프탈산, 테레프탈산, 트리멜리트산, 트리메스산, 헤미멜리트산, 피로멜리트산, 펜탄카르복실산, 멜리트산 등의 방향족 카르복실산을 들 수 있다. 또한, 히드록실기를 갖는 카르복실산으로서는, 예를 들면 락트산, 말산, 시트르산 및 살리실산을 들 수 있다.The carboxylic acids include, for example, ethane, propane, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, Saturated or unsaturated carboxylic acids such as octadecanoic acid; Unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid and eicosapentaenoic acid; Dicarboxylic acids such as maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; Aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, pentanecarboxylic acid and melitic acid. Examples of the carboxylic acid having a hydroxyl group include lactic acid, malic acid, citric acid and salicylic acid.
또한, 상기 방향족 카르복실산에 전자 흡인성 또는 전자 공여성 치환기가 있으며, 치환기에 따라 방향족 상의 카르복실산의 산성도를 변화시킨 방향족계 카르복실산을 이용할 수도 있다. 카르복실산의 산성도가 높을수록 플럭스 활성이 향상되는 경향이 있지만, 산성도가 지나치게 높으면 절연 신뢰성이 저하되는 경우가 있다. 카르복실산의 산성도를 높게 하는 전자 흡인성 치환기로서는, 니트로기, 시아노기, 트리플루오로메틸기, 할로겐기 및 페닐기를 들 수 있다. 카르복실산의 산성도를 약하게 하는 전자 공여성 치환기로서는, 메틸기, 에틸기, 이소프로필기, 터셔리부틸기, 디메틸아미노기 및 트리메틸아미노기를 들 수 있다. 또한, 상기 치환기의 수나 위치는, 플럭스 활성이나 절연 신뢰성이 저하되지 않으면 특별히 제한되지 않는다.An aromatic carboxylic acid having an electron attractive or electron attractive substituent on the aromatic carboxylic acid and an acidity of the aromatic carboxylic acid depending on the substituent may be used. The higher the acidity of the carboxylic acid is, the more the flux activity tends to be improved. However, if the acidity is too high, the insulation reliability may be lowered. Examples of the electron-withdrawing substituent for increasing the acidity of the carboxylic acid include a nitro group, a cyano group, a trifluoromethyl group, a halogen group and a phenyl group. Examples of the electron-donating substituent which weakens the acidity of the carboxylic acid include methyl, ethyl, isopropyl, tertiary butyl, dimethylamino and trimethylamino. The number or position of the substituent is not particularly limited as long as the flux activity and insulation reliability are not lowered.
(기타 성분)(Other components)
본 실시 형태의 접착제 조성물에는, 점도나 경화물의 물성을 제어하기 위해, 그리고 반도체칩 및 기판을 접속했을 때의 공극의 발생이나 흡습률의 상승을 억제하기 위해 (c) 성분 이외에 충전재를 더 배합할 수도 있다.The adhesive composition of the present embodiment may further contain a filler in addition to the component (c) in order to control the viscosity and the physical properties of the cured product and to suppress the generation of voids and increase in the moisture absorption rate when the semiconductor chip and the substrate are connected It is possible.
충전재로서는, 절연성 무기 충전재, 휘스커 또는 수지 충전재를 이용할 수 있다. 절연성 무기 충전재, 휘스커 또는 수지 충전재로서는, 상기 (c) 성분과 동일한 물질을 사용할 수 있다. 이들 충전재, 휘스커 및 수지 충전재는, 1종을 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다. 충전재의 형상, 평균 입경 및 함유량은 특별히 제한되지 않는다.As the filler, an insulating inorganic filler, a whisker, or a resin filler can be used. As the insulating inorganic filler, whisker or resin filler, the same material as the above-mentioned component (c) may be used. These fillers, whiskers and resin fillers can be used singly or as a mixture of two or more kinds. The shape, average particle diameter and content of the filler are not particularly limited.
또한, 본 실시 형태의 접착제 조성물에는, 산화 방지제, 실란 커플링제, 티탄 커플링제, 레벨링제, 이온 트랩제 등의 첨가제를 배합할 수도 있다. 이들은 1종을 단독으로 또는 2종 이상을 조합하여 이용할 수도 있다. 이들의 배합량에 대해서는, 각 첨가제의 효과가 발현되도록 적절하게 조정할 수 있다.Further, additives such as an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trap agent may be added to the adhesive composition of the present embodiment. These may be used singly or in combination of two or more. The blending amount of these additives can be appropriately adjusted so that the effect of each additive is exhibited.
본 실시 형태의 접착제 조성물은, 필름상으로 형성할 수 있다. 본 실시 형태의 접착제 조성물을 이용한 필름상 접착제의 제작 방법을 이하에 나타낸다. 우선, (a) 성분, (b) 성분 및 (c) 성분 및 필요에 따라 첨가되는 (d) 성분 또는 (e) 성분 등을 유기 용매 중에 가하고, 교반 혼합, 혼련 등에 의해 용해 또는 분산시켜 수지 바니시를 제조한다. 그 후, 이형 처리를 실시한 기재 필름 상에 수지 바니시를 나이프 코터, 롤 코터나 어플리케이터를 이용하여 도포한 후, 가열에 의해 유기 용매를 제거함으로써, 기재 필름 상에 필름상 접착제가 얻어진다.The adhesive composition of the present embodiment can be formed into a film. A method for producing a film-like adhesive using the adhesive composition of the present embodiment will be described below. First, the component (a), the component (b) and the component (c), and the component (d) or component (e) added as needed are added to an organic solvent and dissolved or dispersed by stirring, . Thereafter, the resin varnish is coated on the substrate film subjected to the release treatment by using a knife coater, a roll coater or an applicator, and then the organic solvent is removed by heating to obtain a film-like adhesive on the base film.
수지 바니시의 제조에 이용하는 유기 용매로서는, 각 성분을 균일하게 용해 또는 분산시킬 수 있는 특성을 갖는 것이 바람직하고, 예를 들면 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈, 디메틸술폭시드, 디에틸렌글리콜디메틸에테르, 톨루엔, 벤젠, 크실렌, 메틸에틸케톤, 테트라히드로푸란, 에틸셀로솔브, 에틸셀로솔브아세테이트, 부틸셀로솔브, 디옥산, 시클로헥사논 및 아세트산에틸을 들 수 있다. 이들 유기 용매는, 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 수지 바니시 제조시의 교반 혼합이나 혼련은, 예를 들면 교반기, 분쇄기, 3축 롤, 볼밀, 비드밀 및 호모디스퍼를 이용하여 행할 수 있다.The organic solvent used in the production of the resin varnish is preferably one having properties capable of uniformly dissolving or dispersing the components, and examples thereof include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, A solvent such as toluene, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, . These organic solvents may be used alone or in combination of two or more. Stirring mixing and kneading at the time of producing the resin varnish can be carried out, for example, using a stirrer, a pulverizer, a triple roll, a ball mill, a bead mill and a homodisper.
기재 필름으로서는, 유기 용매를 휘발시킬 때의 가열 조건에 견딜 수 있는 내열성을 갖는 것이면 특별히 제한은 없으며, 폴리프로필렌 필름, 폴리메틸펜텐 필름 등의 폴리올레핀 필름, 폴리에틸렌테레프탈레이트 필름, 폴리에틸렌나프탈레이트 필름 등의 폴리에스테르 필름, 폴리이미드 필름 및 폴리에테르이미드 필름을 예시할 수 있다. 기재 필름은, 이들 필름으로 이루어지는 단층의 것으로 한정되지 않으며, 2종 이상의 재료로 이루어지는 다층 필름일 수도 있다.The base film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions at the time of volatilization of the organic solvent. Examples of the base film include polyolefin films such as polypropylene film and polymethylpentene film, polyethylene terephthalate film and polyethylene naphthalate film A polyester film, a polyimide film, and a polyetherimide film. The base film is not limited to a single layer made of these films, and may be a multilayer film made of two or more kinds of materials.
기재 필름에 도포한 수지 바니시로부터 유기 용매를 휘발시킬 때의 건조 조건은, 유기 용매가 충분히 휘발되는 조건으로 하는 것이 바람직하고, 구체적으로는 50 내지 200℃, 0.1 내지 90분간의 가열을 행하는 것이 바람직하다.The drying conditions for volatilizing the organic solvent from the resin varnish applied to the base film are preferably set so that the organic solvent is sufficiently volatilized, specifically, the heating is preferably performed at 50 to 200 DEG C for 0.1 to 90 minutes Do.
또한, 본 실시 형태의 접착제 조성물은, 작업성을 향상시키는 관점에서 웨이퍼 상에 직접 스핀 코팅하고, 필요에 따라 건조한 후, 웨이퍼를 개편화함으로써도 사용할 수 있다.The adhesive composition of the present embodiment can also be used by directly spin-coating the wafer on the wafer from the viewpoint of improving workability, drying it if necessary, and then separating the wafer.
<반도체 장치><Semiconductor Device>
본 실시 형태의 반도체 장치에 대하여 도 1 및 2를 이용하여 이하 설명한다. 도 1은, 본 발명의 반도체 장치의 한 실시 형태를 나타내는 모식 단면도이다. 도 1(a)에 도시한 바와 같이, 반도체 장치 (100)은 서로 대향하는 반도체칩 (10) 및 기판(회로 배선 기판) (20)과, 반도체칩 (10) 및 기판 (20)의 서로 대향하는 면에 각각 배치된 배선 (15)와, 반도체칩 (10) 및 기판 (20)의 배선 (15)를 서로 접속하는 접속 범프 (30)과, 반도체칩 (10) 및 기판 (20) 사이의 공극에 간극 없이 충전된 접착제 조성물 (40)을 갖고 있다. 반도체칩 (10) 및 기판 (20)은, 배선 (15) 및 접속 범프 (30)에 의해 플립 칩 접속되어 있다. 배선 (15) 및 접속 범프 (30)은, 접착제 조성물 (40)에 의해 밀봉되어 있어 외부 환경으로부터 차단되어 있다.The semiconductor device of the present embodiment will be described below with reference to Figs. 1 and 2. Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. 1A, the
도 1(b)에 도시한 바와 같이, 반도체 장치 (200)은 서로 대향하는 반도체칩 (10) 및 기판 (20)과, 반도체칩 (10) 및 기판 (20)의 서로 대향하는 면에 각각 배치된 범프 (32)와, 반도체칩 (10) 및 기판 (20) 사이의 공극에 간극 없이 충전된 접착제 조성물 (40)을 갖고 있다. 반도체칩 (10) 및 기판 (20)은, 대향하는 범프 (32)가 서로 접속됨으로써 플립 칩 접속되어 있다. 범프 (32)는, 접착제 조성물 (40)에 의해 밀봉되어 있어 외부 환경으로부터 차단되어 있다.1B, the
도 2는, 본 발명의 반도체 장치의 다른 한 실시 형태를 나타내는 모식 단면도이다. 도 2(a)에 도시한 바와 같이, 반도체 장치 (300)은 2개의 반도체칩 (10)이 배선 (15) 및 접속 범프 (30)에 의해 플립 칩 접속되어 있는 점을 제외하고는, 반도체 장치 (100)과 동일하다. 도 2(b)에 도시한 바와 같이, 반도체 장치 (400)은 2개의 반도체칩 (10)이 범프 (32)에 의해 플립 칩 접속되어 있는 점을 제외하고는, 반도체 장치 (200)과 동일하다.2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. 2 (a), except that the two
반도체칩 (10)으로서는 특별히 한정은 없으며, 실리콘, 게르마늄 등의 동일 종류의 원소로부터 구성되는 원소 반도체, 갈륨비소, 인듐인 등의 화합물 반도체를 이용할 수 있다.The
기판 (20)으로서는 회로 기판이면 특별히 제한은 없으며, 유리 에폭시, 폴리이미드, 폴리에스테르, 세라믹, 에폭시, 비스말레이미드트리아진 등을 주된 성분으로 하는 절연 기판의 표면에, 금속막의 불필요한 개소를 에칭 제거하여 형성된 배선(배선 패턴) (15)를 갖는 회로 기판, 상기 절연 기판의 표면에 금속 도금 등에 의해 배선 (15)가 형성된 회로 기판, 상기 절연 기판의 표면에 도전성 물질을 인쇄하여 배선 (15)가 형성된 회로 기판을 이용할 수 있다.The
배선 (15)나 범프 (32) 등의 접속부는, 주성분으로서 금, 은, 구리, 땜납(주성분은, 예를 들면 주석-은, 주석-납, 주석-비스무트, 주석-구리, 주석-은-구리),니켈, 주석, 납 등을 함유하고 있으며, 복수의 금속을 함유하고 있을 수도 있다.The connecting portions such as the
상기 금속 중에서도, 접속부의 전기 전도성ㆍ열전도성이 우수한 패키지로 하는 관점에서 금, 은 및 구리가 바람직하고, 은 및 구리가 보다 바람직하다. 비용이 감소된 패키지로 하는 관점에서, 저렴하다는 것에 기초하여 은, 구리 및 땜납이 바람직하고, 구리 및 땜납이 보다 바람직하고, 땜납이 더욱 바람직하다. 실온에서 금속의 표면에 산화막이 형성되면 생산성이 저하되는 경우나 비용이 증가하는 경우가 있기 때문에, 산화막의 형성을 억제하는 관점에서 금, 은, 구리 및 땜납이 바람직하고, 금, 은, 땜납이 보다 바람직하고, 금, 은이 더욱 바람직하다.Among these metals, gold, silver and copper are preferable, and silver and copper are more preferable in view of the package having excellent electrical conductivity and thermal conductivity of the connecting portion. From the viewpoint of cost-reduced package, silver, copper and solder are preferable, copper and solder are more preferable, and solder is more preferable. Silver, copper, and solder are preferable from the viewpoint of suppressing the formation of an oxide film because the productivity may be lowered or the cost may increase when the oxide film is formed on the surface of the metal at room temperature More preferable is gold and silver.
상기 배선 (15) 및 범프 (32)의 표면에는, 금, 은, 구리, 땜납(주성분은, 예를 들면 주석-은, 주석-납, 주석-비스무트, 주석-구리), 주석, 니켈 등을 주된 성분으로 하는 금속층이, 예를 들면 도금에 의해 형성되어 있을 수도 있다. 이 금속층은 단일 성분만으로 구성되어 있을 수도, 복수의 성분으로 구성되어 있을 수도 있다. 또한, 상기 금속층은, 단층 또는 복수의 금속층이 적층된 구조를 하고 있을 수도 있다.The surface of the
또한, 본 실시 형태의 반도체 장치는, 반도체 장치 (100) 내지 (400)에 나타낸 바와 같은 구조(패키지)가 복수 적층되어 있을 수도 있다. 이 경우, 반도체 장치 (100) 내지 (400)은, 금, 은, 구리, 땜납(주성분은, 예를 들면 주석-은, 주석-납, 주석-비스무트, 주석-구리, 주석-은-구리), 주석, 니켈 등을 포함하는 범프나 배선으로 서로 전기적으로 접속되어 있을 수도 있다.Further, the semiconductor device of this embodiment may have a plurality of structures (packages) as shown in the
반도체 장치를 복수 적층하는 방법으로서는, 도 3에 도시한 바와 같이 예를 들면 TSV(Through-Silicon Via) 기술을 들 수 있다. 도 3은, 본 발명의 반도체 장치의 다른 한 실시 형태를 나타내는 모식 단면도이고, TSV 기술을 이용한 반도체 장치이다. 도 3에 도시한 반도체 장치 (500)에서는, 인터포저 (50) 상에 형성된 배선 (15)가 반도체칩 (10)의 배선 (15)와 접속 범프 (30)을 통해 접속됨으로써, 반도체칩 (10)과 인터포저 (50)은 플립 칩 접속되어 있다. 반도체칩 (10)과 인터포저 (50) 사이의 공극에는 접착제 조성물 (40)이 간극 없이 충전되어 있다. 상기 반도체칩 (10)에서의 인터포저 (50)과 반대측의 표면 상에는, 배선 (15), 접속 범프 (30) 및 접착제 조성물 (40)을 통해 반도체칩 (10)이 반복하여 적층되어 있다. 반도체칩 (10)의 표리에서의 패턴면의 배선 (15)는, 반도체칩 (10)의 내부를 관통하는 구멍 내에 충전된 관통 전극 (34)에 의해 서로 접속되어 있다. 또한, 관통 전극 (34)의 재질로서는, 구리, 알루미늄 등을 이용할 수 있다.As a method of laminating a plurality of semiconductor devices, for example, a TSV (Through-Silicon Via) technique is exemplified as shown in Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, and is a semiconductor device using TSV technology. 3, the
이러한 TSV 기술에 의해, 통상은 사용되지 않는 반도체칩의 이면으로부터도 신호를 취득하는 것이 가능해진다. 또한, 반도체칩 (10) 내에 관통 전극 (34)를 수직으로 통과시키기 때문에, 대향하는 반도체칩 (10) 사이나 반도체칩 (10) 및 인터포저 (50) 사이의 거리를 짧게 하고, 유연한 접속이 가능하다. 본 실시 형태의 접착제 조성물은, 이러한 TSV 기술에서 대향하는 반도체칩 (10) 사이나 반도체칩 (10) 및 인터포저 (50) 사이의 반도체 밀봉용 접착제로서 적용할 수 있다.Such a TSV technique makes it possible to acquire a signal from the underside of a semiconductor chip which is not normally used. Since the penetrating
또한, 에리어 범프 칩 기술 등의 자유도가 높은 범프 형성 방법에서는, 인터포저를 통하지 않고 그대로 반도체칩을 마더 보드에 직접 실장할 수 있다. 본 실시 형태의 접착제 조성물은, 이러한 반도체칩을 마더 보드에 직접 실장하는 경우에도 적용할 수 있다. 또한, 본 실시 형태의 접착제 조성물은, 2개의 배선 회로 기판을 적층하는 경우에 기판 사이의 공극을 밀봉할 때에도 적용할 수 있다.Further, in the bump forming method having a high degree of freedom such as the area bump chip technology, the semiconductor chip can be directly mounted on the mother board without passing through the interposer. The adhesive composition of the present embodiment can also be applied to the case where such a semiconductor chip is directly mounted on a mother board. Further, the adhesive composition of the present embodiment can be applied to sealing the gap between the substrates when two wiring circuit substrates are laminated.
<반도체 장치의 제조 방법><Method of Manufacturing Semiconductor Device>
본 실시 형태의 반도체 장치의 제조 방법에 대하여 도 4를 이용하여 이하 설명한다. 도 4는, 본 발명의 반도체 장치의 제조 방법의 한 실시 형태를 모식적으로 나타내는 공정 단면도이다.A method of manufacturing the semiconductor device of the present embodiment will be described below with reference to FIG. 4 is a process sectional view schematically showing an embodiment of a manufacturing method of a semiconductor device of the present invention.
우선, 도 4(a)에 도시한 바와 같이, 배선 (15)를 갖는 기판 (20) 상에 접속 범프 (30)을 형성하는 위치에 개구를 갖는 납땜 레지스트 (60)을 형성한다. 이 납땜 레지스트 (60)은 반드시 설치할 필요는 없다. 그러나, 기판 (20) 상에 납땜 레지스트를 설치함으로써, 배선 (15) 사이의 브릿지의 발생을 억제하여, 접속 신뢰성ㆍ절연 신뢰성을 향상시킬 수 있다. 납땜 레지스트 (60)은, 예를 들면 시판되는 패키지용 납땜 레지스트용 잉크를 이용하여 형성할 수 있다. 시판되는 패키지용 납땜 레지스트용 잉크로서는, 구체적으로는 SR 시리즈(히타치 가세이 고교 가부시끼가이샤 제조, 상품명) 및 PSR4000-AUS 시리즈(다이요 잉크 제조(주) 제조, 상품명)를 들 수 있다.First, as shown in Fig. 4 (a), a solder resist 60 having an opening is formed on the
이어서, 도 4(a)에 도시한 바와 같이, 납땜 레지스트 (60)의 개구에 접속 범프 (30)을 형성한다. 또한, 도 4(b)에 도시한 바와 같이, 접속 범프 (30) 및 납땜 레지스트 (60)이 형성된 기판 (20) 상에 필름상의 접착제 조성물(이하, 경우에 따라 「필름상 접착제」라 함) (40)을 첩부한다. 필름상 접착제 (40)의 첩부는, 가열 프레스, 롤 라미네이트, 진공 라미네이트 등에 의해 행할 수 있다. 필름상 접착제 (40)의 공급 면적이나 두께는, 반도체칩 (10) 및 기판 (20)의 크기나 접속 범프 (30)의 높이에 따라 적절히 설정된다.Then, as shown in Fig. 4A, the connection bumps 30 are formed in the openings of the solder resist 60. Then, as shown in Fig. 4 (b), a film-like adhesive composition (hereinafter sometimes referred to as a " film-like adhesive ") is formed on the
상기한 바와 같이 필름상 접착제 (40)을 기판 (20)에 첩부한 후, 반도체칩 (10)의 배선 (15)와 접속 범프 (30)을 플립 칩 본더 등의 접속 장치를 이용하여 위치 정렬한다. 이어서, 반도체칩 (10)과 기판 (20)을 접속 범프 (30)의 융점 이상의 온도에서 가열하면서 압착하고, 도 4(c)에 도시한 바와 같이, 반도체칩 (10)과 기판 (20)을 접속함과 함께 필름상 접착제 (40)에 의해 반도체칩 (10) 및 기판 (20) 사이의 공극을 밀봉 충전한다. 이상으로부터, 반도체 장치 (600)이 얻어진다.After the film-
본 실시 형태의 반도체 장치의 제조 방법에서는, 위치 정렬을 한 후에 임시 고정하고(반도체 접착제를 통하고 있는 상태), 리플로우로에서 가열 처리함으로써, 접속 범프 (30)을 용융시켜 반도체칩 (10)과 기판 (20)을 접속할 수도 있다. 임시 고정의 단계에서는, 금속 접합을 형성하는 것이 반드시 필요한 것은 아니기 때문에, 상기한 가열하면서 압착하는 방법에 비해 저하중, 단시간, 저온도에 의한 압착일 수 있으며, 생산성이 향상됨과 함께 접속부의 열화를 억제할 수 있다.In the method of manufacturing a semiconductor device according to the present embodiment, the connection bumps 30 are melted by temporarily heat-setting the
또한, 반도체칩 (10)과 기판 (20)을 접속한 후, 오븐 등으로 가열 처리를 행하여 접속 신뢰성ㆍ절연 신뢰성을 더 높일 수도 있다. 가열 온도는 필름상 접착제의 경화가 진행되는 온도가 바람직하고, 완전히 경화되는 온도가 보다 바람직하다. 가열 온도, 가열 시간은 적절히 설정된다.Further, after the
본 실시 형태의 반도체 장치의 제조 방법에서는, 필름상 접착제 (40)을 반도체칩 (10)에 첩부한 후에 기판 (20)을 접속할 수도 있다. 또한, 반도체칩 (10) 및 기판 (20)을 배선 (15) 및 접속 범프 (30)에 의해 접속한 후, 반도체칩 (10) 및 기판 (20) 사이의 공극에 페이스트상의 접착제 조성물을 충전할 수도 있다.In the semiconductor device manufacturing method of the present embodiment, the
생산성이 향상된다는 관점에서, 복수의 반도체칩 (10)이 연결된 반도체 웨이퍼에 접착제 조성물을 공급한 후, 다이싱하여 개편화함으로써 반도체칩 (10) 상에 접착제 조성물이 공급된 구조체를 얻을 수도 있다. 또한, 접착제 조성물이 페이스트상인 경우에는, 특별히 제한되는 것은 아니지만 스핀 코팅 등의 도포 방법에 의해 반도체칩 (10) 상의 배선이나 범프를 매립, 두께를 균일화시킬 수 있다. 이 경우, 수지의 공급량이 일정해지기 때문에 생산성이 향상됨과 함께, 매립 부족에 의한 공극의 발생 및 다이싱성의 저하를 억제할 수 있다. 한편, 접착제 조성물이 필름상인 경우에는, 특별히 제한되는 것은 아니지만 가열 프레스, 롤 라미네이트 및 진공 라미네이트 등의 첩부 방식에 의해 반도체칩 (10) 상의 배선이나 범프를 매립하도록 필름상의 수지 조성물을 공급할 수 있다. 이 경우, 수지의 공급량이 일정해지기 때문에 생산성이 향상되고, 매립 부족에 의한 공극의 발생 및 다이싱성의 저하를 억제할 수 있다.It is also possible to obtain a structure in which the adhesive composition is supplied to the
접속 하중은, 접속 범프 (30)의 수나 높이의 변동, 가압에 의한 접속 범프 (30), 또는 접속부의 범프를 받는 배선의 변형량을 고려하여 설정된다. 접속 온도는, 접속부의 온도가 접속 범프 (30)의 융점 이상인 것이 바람직하지만, 각각의 접속부(범프나 배선)의 금속 접합이 형성되는 온도일 수 있다. 접속 범프 (30)이 땜납 범프인 경우에는, 약 240℃ 이상이 바람직하다.The connection load is set in consideration of variations in the number or height of the connection bumps 30, the amount of deformation of the connection bumps 30 caused by the pressing, or the amount of deformation of the wirings receiving the bumps of the connection portions. The connection temperature is preferably the temperature at which the temperature of the connection portion is equal to or higher than the melting point of the
접속시의 접속 시간은 접속부의 구성 금속에 따라 상이하지만, 생산성이 향상되는 관점에서 단시간일수록 바람직하다. 접속 범프 (30)이 땜납 범프인 경우 접속 시간은 20초 이하가 바람직하고, 10초 이하가 보다 바람직하고, 5초 이하가 더욱 바람직하다. 구리-구리 또는 구리-금의 금속 접속인 경우에는, 접속 시간은 60초 이하가 바람직하다.The connection time at the time of connection differs depending on the constituent metal of the connection portion, but it is preferable to shorten the time from the viewpoint of improving the productivity. When the
상술한 다양한 패키지 구조의 플립 칩 접속부에서도, 본 발명의 접착제 조성물은 우수한 내리플로우성, 접속 신뢰성 및 절연 신뢰성을 나타낸다.Also in the flip chip connecting portions of the above-described various package structures, the adhesive composition of the present invention exhibits excellent bottom flowability, connection reliability and insulation reliability.
[실시예][Example]
이하, 실시예, 비교예를 이용하여 본 발명을 설명하지만, 본 발명은 이하의 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited by the following examples.
(폴리이미드 합성)(Polyimide synthesis)
온도계, 교반기 및 염화칼슘관을 구비한 300 mL 플라스크에 1,12-디아미노도데칸 2.10 g(0.035 몰), 폴리에테르디아민(바스프 제조, 상품명 「ED2000」, 분자량: 1923) 17.31 g(0.03 몰), 1,3-비스(3-아미노프로필)테트라메틸디실록산(신에쓰 가가꾸 제조, 상품명 「LP-7100」) 2.61 g(0.035 몰) 및 N-메틸-2-피롤리돈(간토 가가꾸 제조, 이하 「NMP」라 함) 150 g을 투입 교반하였다. 상기 디아민의 용해 후, 플라스크를 빙욕 중에서 냉각하면서 무수 아세트산으로 재결정 정제한 4,4'-(4,4'-이소프로필리덴디페녹시)비스(프탈산 이무수물)(알드리치(ALDRICH) 제조, 상품명 「BPADA」) 15.62 g(0.10 몰)을 소량씩 첨가하였다. 실온에서 8시간 반응시킨 후, 크실렌 100 g을 가하고, 질소 가스를 취입하면서 180℃에서 가열하고, 물과 함께 크실렌을 공비 제거하여 폴리이미드 수지를 얻었다. 얻어진 폴리이미드 수지로부터 용매(NMP)를 제거하고, 메틸에틸케톤(MEK)에 고형분 50 질량%가 되도록 용해한 것을 「폴리이미드 A」로 하였다. 폴리이미드 A의 Tg는 30℃, 중량 평균 분자량은 50000, SP값(용해도 파라미터)은 10.2였다.2.13 g (0.035 mol) of 1,12-diaminododecane and 17.31 g (0.03 mol) of polyether diamine (product name "ED2000", manufactured by BASF, molecular weight: 1923) were placed in a 300 mL flask equipped with a thermometer, a stirrer and a calcium chloride tube, , 2.61 g (0.035 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (trade name "LP-7100", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as " NMP ") was added and stirred. After dissolution of the diamine, 4,4 '- (4,4'-isopropylidene diphenoxy) bis (phthalic acid dianhydride) (manufactured by ALDRICH, manufactured by Aldrich), which was recrystallized and purified by acetic anhydride while cooling the flask in an ice bath, &Quot; BPADA ") were added in small portions. After reacting at room temperature for 8 hours, 100 g of xylene was added and heated at 180 캜 while blowing nitrogen gas, and xylene was removed together with water to remove the polyimide resin. The solvent (NMP) was removed from the obtained polyimide resin and dissolved in methyl ethyl ketone (MEK) so as to have a solid content of 50% by mass, to give " polyimide A ". Polyimide A had a Tg of 30 占 폚, a weight average molecular weight of 50,000, and an SP value (solubility parameter) of 10.2.
각 실시예 및 비교예에서 사용한 화합물은 이하와 같다.The compounds used in the respective Examples and Comparative Examples are as follows.
(a) 에폭시 수지(a) an epoxy resin
ㆍ트리페놀메탄 골격 함유 다관능 고형 에폭시(재팬 에폭시 레진 가부시끼가이샤 제조, 상품명 「EP1032H60」, 이하 「EP1032」라 함)&Quot; EP1032H60 ", hereinafter referred to as " EP1032 ", manufactured by Japan Epoxy Resin Co., Ltd.)
ㆍ비스페놀 F형 액상 에폭시(재팬 에폭시 레진 가부시끼가이샤 제조, 상품명 「YL983U」, 이하 「YL983」이라 함)- Bisphenol F type liquid epoxy (trade name: " YL983U ", hereinafter referred to as " YL983 ", manufactured by Japan Epoxy Resin Co.,
ㆍ유연성 에폭시(재팬 에폭시 레진 가부시끼가이샤 제조, 상품명 「YL7175」, 이하 「YL7175」라 함)Flexible Epoxy (trade name: "YL7175" manufactured by Japan Epoxy Resin Co., Ltd., hereinafter referred to as "YL7175")
(b) 경화제(b) Curing agent
ㆍ2-페닐-4,5-디히드록시메틸이미다졸(시코쿠 가세이 가부시끼가이샤 제조, 상품명 「2PHZ-PW」, 이하 「2PHZ」라 함)2-phenyl-4,5-dihydroxymethylimidazole (trade name "2PHZ-PW", hereinafter referred to as "2PHZ", manufactured by Shikoku Kasei Kabushiki Kaisha)
ㆍ2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진이소시아누르산 부가체(시코쿠 가세이 가부시끼가이샤 제조, 상품명 「2MAOK-PW」, 이하 「2MAOK」라 함)2'-methylimidazolyl- (1 ')] - ethyl-s-triazine was obtained by reacting isocyanuric acid adduct (trade name "2MAOK-PW" manufactured by Shikoku Kasei Kabushiki Kaisha, , Hereinafter referred to as " 2MAOK &
(c) 아크릴계 표면 처리 충전재 또는 상기 화학식 (1)로 표시되는 기를 갖는 충전재(c) an acrylic surface-treated filler or a filler having a group represented by the above formula (1)
ㆍ메타크릴 표면 처리 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「SE2050-SMJ」, 평균 입경 0.5 ㎛, 이하 「SM 실리카」라 함)(Hereinafter referred to as " SM silica ", trade name " SE2050-SMJ ", average particle diameter 0.5 mu m, manufactured by Adma Tech Co., Ltd.)
ㆍ메타크릴 표면 처리 나노 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「YA050C-SM」, 이하 「SM 나노 실리카」라 함)- Methacrylic surface-treated nano silica filler (trade name: YA050C-SM, manufactured by Adma Tech Co., Ltd., hereinafter referred to as SM nano silica)
(c') 기타 충전재(c ') Other filler
ㆍ미처리된 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「SE2050」, 평균 입경 0.5 ㎛, 이하, 「미처리 실리카」라 함)Untreated silica filler (trade name " SE2050 ", manufactured by Adma Tech Co., Ltd., average particle size 0.5 mu m, hereinafter referred to as " untreated silica "
ㆍ아미노실란 처리 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「SE2050-SXJ」, 평균 입경 0.5 ㎛, 이하 「SX 실리카」라 함)- Aminosilane-treated silica filler (trade name " SE2050-SXJ ", manufactured by Adma Tech Co., Ltd., average particle diameter 0.5 mu m, hereinafter referred to as " SX silica "
ㆍ에폭시실란 처리 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「SE2050-SEJ」, 평균 입경 0.5 ㎛, 이하 「SE 실리카」라 함)- Epoxysilane-treated silica filler (trade name " SE2050-SEJ ", manufactured by Admatechs Co., Ltd., average particle diameter 0.5 mu m, hereinafter referred to as " SE silica "
ㆍ페닐실란 처리 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「SE2050-SPJ」, 평균 입경 0.5 ㎛, 이하 「SP 실리카」라 함)(Hereinafter referred to as " SP silica ", trade name " SE2050-SPJ ", average particle size 0.5 mu m, manufactured by Adma Tech Co., Ltd.)
ㆍ페닐 표면 처리 나노 실리카 충전재(가부시끼가이샤 애드마테크스 제조, 상품명 「YA050C-SP」, 평균 입경 50 nm, 이하 「SP 나노 실리카」라 함)(Hereinafter referred to as " SP nano silica ", manufactured by Admatechs Co., Ltd., trade name: YA050C-SP,
ㆍ유기 충전재 (1)(미쯔비시 레이온 제조, 상품명 「W5500」, 이하 「W5500」이라 함)Organic filler 1 (manufactured by Mitsubishi Rayon, trade name " W5500 ", hereinafter referred to as " W5500 &
ㆍ유기 충전재 (2)(롬 앤드 하스 재팬(주)사 제조, 상품명 「EXL-2655」, 코어셸 타입 유기 미립자, 이하 「EXL2655」라 함)EXL-2655 ", core shell type organic fine particles, hereinafter referred to as " EXL2655 ", manufactured by Rohm and Haas Japan Co.,
(d) 분자량 10000 이상의 고분자 성분(d) a polymer component having a molecular weight of 10,000 or more
ㆍ페녹시 수지(도토 가세이 가부시끼가이샤 제조, 상품명 「ZX1356」, Tg: 약 71℃, Mw: 약 63000, 이하 「ZX1356」이라 함)(Trade name: " ZX1356 ", Tg: about 71 DEG C, Mw: about 63,000, hereinafter referred to as ZX1356)
ㆍ상술한 바와 같이 합성한 폴리이미드 AThe polyimide A synthesized as described above
(e) 플럭스 활성제(플럭스제)(e) flux activator (flux agent)
ㆍ디페놀산(도쿄 가세이 가부시끼가이샤 제조)- Diphenolic acid (manufactured by Tokyo Kasei Kabushiki Kaisha)
ㆍ아디프산(와코 준야꾸 고교 가부시끼가이샤 제조)Adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
<반도체 밀봉용 필름상 접착제의 제작>≪ Fabrication of adhesive agent for semiconductor encapsulation film &
(실시예 1)(Example 1)
에폭시 수지(EP1032) 100 질량부, 경화제(2PHZ) 7.5 질량부, 충전재(SM 실리카) 175 질량부, 플럭스 활성제(디페놀산) 25 질량부 및 MEK 용매를 고형분이 60 질량%가 되도록 투입하고, 직경 0.8 mm의 비드 및 직경 2.0 mm의 비드를 고형분과 동량 가하여, 비드밀(프리츠ㆍ재팬 가부시끼가이샤, 유성형 미분쇄기 「P-7」)로 30분간 교반하였다. 이어서, 폴리이미드 A를 100 질량부(고형분 환산) 가하고, 재차 비드밀로 30분간 교반한 후, 교반에 이용한 비드를 여과에 의해 제거하여, 수지바니시를 얻었다., 7.5 parts by mass of a curing agent (2PHZ), 175 parts by mass of a filler (SM silica), 25 parts by mass of a flux activator (diphenolic acid), and a MEK solvent were added so as to have a solid content of 60% A bead having a diameter of 0.8 mm and a bead having a diameter of 2.0 mm were added in the same amount as the solid portion and stirred for 30 minutes with a bead mill (Fritz Japan KK, planetary mill pulverizer "P-7"). Subsequently, 100 parts by mass (in terms of solid content) of polyimide A was added, and the mixture was stirred again with a bead mill for 30 minutes. Thereafter, the beads used for stirring were removed by filtration to obtain a resin varnish.
얻어진 수지 바니시를 기재 필름(데이진 듀퐁 필름 가부시끼가이샤 제조, 상품명 「퓨렉스 A53」)에 소형 정밀 도공 장치(야스이 세이끼 제조)로 도공하고, 클린 오븐(에스펙 가부시끼가이샤 제조) 중 70℃에서 10분간 건조하여, 필름상 접착제를 제작하였다.The resin varnish thus obtained was coated on a base film (trade name: "Purex A53", manufactured by Dejin DuPont Film Co., Ltd.) with a small precision coating apparatus (manufactured by Yasui Seiki Co., Ltd.) Lt; 0 > C for 10 minutes to prepare a film-like adhesive.
(실시예 2 내지 3 및 비교예 1 내지 6)(Examples 2 to 3 and Comparative Examples 1 to 6)
사용한 원재료의 조성을 하기의 표 1과 같이 변경한 것을 제외하고는, 실시예 1과 동일하게 하여 실시예 2 내지 3 및 비교예 1 내지 6의 필름상 접착제를 제작하였다.The film-like adhesives of Examples 2 to 3 and Comparative Examples 1 to 6 were prepared in the same manner as in Example 1, except that the composition of the raw materials used was changed as shown in Table 1 below.
이하, 실시예 및 비교예에서 얻어진 필름상 접착제의 평가 방법을 나타낸다.Hereinafter, evaluation methods of the film-like adhesive obtained in Examples and Comparative Examples are shown.
<260℃에서의 탄성률의 측정>≪ Measurement of elastic modulus at 260 캜 >
필름상 접착제를 소정의 크기(세로 37 mm×가로 4 mm×두께 0.13 mm)로 잘라내고, 클린 오븐(에스펙 가부시끼가이샤 제조) 중 180℃에서 3시간 유지하여 경화하였다. 경화 후, 점탄성 측정 장치(레오메트릭스(Rheometrics) 제조, 상품명 「RASII」)를 이용하여, 내리플로우성의 평가시의 리플로우로의 도달 온도인 260℃에서의 탄성률을 측정하였다. 측정은, 온도 범위 -30 내지 270℃, 승온 속도 5℃/분, 측정 파장 10 Hz로 행하였다.The adhesive agent on the film was cut into a predetermined size (37 mm in length x 4 mm in width x 0.13 mm in thickness) and cured in a clean oven (manufactured by Espace KK) at 180 DEG C for 3 hours. After curing, the elastic modulus at 260 占 폚, which is the temperature reached by reflow at the time of evaluating the flow resistance, was measured using a viscoelasticity measuring apparatus (manufactured by Rheometrics, trade name "RASII"). The measurement was carried out at a temperature range of -30 to 270 DEG C, a heating rate of 5 DEG C / min, and a measurement wavelength of 10 Hz.
<흡습 후의 260℃에서의 접착력의 측정>≪ Measurement of Adhesive Force at 260 캜 after Moisture Absorption >
필름상 접착제를 소정의 크기(세로 5 mm×가로 5 mm×두께 0.025 mm)로 잘라내고, 실리콘칩(세로 5 mm×가로 5 mm×두께 0.725 mm, 산화막 코팅)에 60℃에서 첩부하고, 열압착 시험기(히타치 카세이 테크노 플랜트 가부시끼가이샤 제조)를 이용하여 납땜 레지스트(타이요 잉크 제조, 상품명 「AUS308」)가 코팅된 유리 에폭시 기판(두께 0.02 mm)에 압착하였다(압착 조건: 필름상 접착제의 도달 온도 180℃/10초간/0.5 MPa, 이어서 필름상 접착제의 도달 온도 245℃/10초간/0.5 MPa). 이어서, 클린 오븐(에스펙 가부시끼가이샤 제조) 중에서 후경화하였다(180℃/3시간). 그 후, 85℃, 상대 습도 60%의 항온 항습기(에스펙 가부시끼가이샤 제조, 상품명 「PR-2KP」)에 48시간 방치하고, 취출 후, 260℃의 핫 플레이트 상에서 접착력 측정 장치(DAGE사 제조, 만능형 본드 테스터 DAGE4000형)를 사용하여 기판으로부터의 툴 높이 0.05 mm, 툴 속도 0.05 mm/초의 조건으로 측정하였다.The film adhesive was cut into a predetermined size (5 mm in length × 5 mm in width × 0.025 mm in thickness) and attached to a silicon chip (5 mm in length × 5 mm in width × 0.725 mm in thickness, oxide film coating) at 60 ° C., (Thickness: 0.02 mm) coated with a solder resist (manufactured by TAIYO INK, trade name "AUS308") using a compression tester (Hitachi Kasei Techno Plant Co., Ltd.) Temperature: 180 占 폚 / 10 seconds / 0.5 MPa, then the film-shaped adhesive reached 245 占 폚 / 10 seconds / 0.5 MPa). Subsequently, post-curing was performed in a clean oven (manufactured by Espec Corp.) (180 DEG C / 3 hours). Thereafter, the sample was left in a thermo-hygrostat (product name: "PR-2KP" manufactured by Espec Co., Ltd.) at 85 ° C. and a relative humidity of 60% for 48 hours. , Universal bond tester DAGE 4000 type) at a tool height of 0.05 mm from the substrate and a tool speed of 0.05 mm / sec.
<초기 접속성의 평가><Evaluation of Initial Connectivity>
제작한 필름상 접착제를 소정의 크기(세로 8 mm×가로 8 mm×두께 0.025 mm)로 잘라내고, 유리 에폭시 기판(유리 에폭시 기재: 420 ㎛ 두께, 구리 배선: 9 ㎛두께, 80 ㎛ 피치) 상에 첩부하고, 땜납 범프 부착 반도체칩(칩 크기: 세로 7 mm×가로 7 mm×높이 0.15 mm, 범프: 구리 필러(pillar) 및 땜납, 80 ㎛ 피치)를 플립 칩 실장 장치 「FCB3」(파나소닉 제조, 상품명)으로 실장하였다(실장 조건: 필름상 접착제의 도달 온도 180℃, 10초간, 0.5 MPa, 이어서 필름상 접착제의 도달 온도 245℃, 10초간, 0.5 MPa). 이에 따라, 도 4와 마찬가지로 상기 유리 에폭시 기판과, 땜납 범프 부착 반도체칩이 데이지 체인 접속된 반도체 장치를 얻었다.The produced film-like adhesive was cut into a predetermined size (8 mm in length x 8 mm in width x 0.025 mm in thickness), and a glass epoxy substrate (glass epoxy substrate: 420 m thick, copper wiring: 9 m thick, 80 m pitch) (Chip size: 7 mm length x 7 mm width x 0.15 mm height, bump: copper pillar and solder, pitch of 80 mu m) with a solder bump was mounted on a flip chip mounting apparatus "FCB3" (Mounting conditions: the temperature of the film adhesive reached 180 占 폚 for 10 seconds, 0.5 MPa, and then the film adhesive reached 245 占 폚 for 10 seconds, 0.5 MPa). Thus, a semiconductor device in which the glass epoxy substrate and the semiconductor chip with a solder bump were connected in a daisy chain was obtained as in Fig.
얻어진 반도체 장치의 접속 저항값을 멀티미터(어드반테스트(ADVANTEST) 제조, 상품명 「R6871E」)를 이용하여 측정함으로써, 실장 후의 초기 도통의 가부를 평가하였다. 접속 저항값이 11 내지 14Ω인 경우를 접속성 양호 「A」로 하고, 그 이외의 접속 저항값인 경우 또는 접속 불량(Open)이 발생하여 저항값이 표시되지 않은 경우를 「B」로 하여 평가하였다.The connection resistance value of the obtained semiconductor device was measured using a multimeter (manufactured by ADVANTEST, trade name " R6871E ") to evaluate the initial conductivity after mounting. A case where the connection resistance value is 11 to 14 OMEGA is evaluated as "B" where the connection property is good "A" and the other is the connection resistance value or the connection failure (Open) Respectively.
<내리플로우성의 평가>≪ Evaluation of flowability &
상술한 반도체 장치를 밀봉재(히타치 가세이 고교 가부시끼가이샤 제조, 상품명 「CEL9700HF10K」)를 이용하여 180℃, 6.75 MPa, 90초간의 조건으로 소정의 형상으로 몰드하고, 클린 오븐(에스펙 가부시끼가이샤 제조) 중 175℃에서 5시간 경화시켜 패키지를 얻었다. 이어서, 이 패키지를 JEDEC 레벨(level) 2 조건으로 고온 흡습 후, IR 리플로우로(후루카와 일렉트릭(FURUKAWA ELECTRIC) 제조, 상품명 「SALAMANDER」)에 패키지를 통과시켰다. 리플로우 후의 패키지의 접속성을 후술하는 초기 접속성의 평가와 동일한 방법으로 평가하여, 내리플로우성의 평가로 하였다. 박리가 없고, 접속 양호한 경우를 「A」, 박리나 접속 불량이 발생하여 저항값이 표시되지 않은 경우를 「B」로 하였다.The above semiconductor device was molded into a predetermined shape at 180 占 폚 and 6.75 MPa for 90 seconds by using a sealing material (trade name: CEL9700HF10K, manufactured by Hitachi Kasei Kogyo Co., Ltd.) ) At 175 ° C for 5 hours to obtain a package. Then, the package was subjected to high-temperature moisture absorption at a JEDEC level (level 2), and then the package was passed through an IR reflow furnace (manufactured by FURUKAWA ELECTRIC, trade name "SALAMANDER"). The connectivity of the package after the reflow was evaluated in the same manner as the evaluation of the initial connectability to be described later to evaluate the underflow performance. &Quot; A " when no peeling was observed and good connection, and " B " when no connection resistance was detected due to detachment or connection failure.
<접속 신뢰성의 평가(내TCT 평가)>≪ Evaluation of connection reliability (My TCT evaluation) >
상술한 반도체 장치를 밀봉재(히타치 가세이 고교 가부시끼가이샤 제조, 상품명 「CEL9700HF10K」)를 이용하여 180℃, 6.75 MPa, 90초간의 조건으로 소정의 형상으로 몰드하고, 클린 오븐(에스펙 가부시끼가이샤 제조) 중 175℃에서 5시간 경화시켜 패키지를 얻었다. 이어서, 이 패키지를 냉열 사이클 시험기(ETAC 제조, THERMAL SHOCK CHAMBER NT1200) 내에 방치하고, 1 mA의 전류를 흘려 25℃ 2분간/-55℃ 15분간/25℃ 2분간/125℃ 15분간/25℃ 2분간을 1 사이클로 하여 접속 저항을 측정하고, 1000 사이클 반복한 후의 접속 저항의 변화를 평가하였다. 초기의 저항값 파형에 비해 1000 사이클 후에도 큰 변화가 없었던 경우를 「A」, 1Ω 이상의 차가 발생한 경우를 「B」로 하였다.The above semiconductor device was molded into a predetermined shape at 180 占 폚 and 6.75 MPa for 90 seconds by using a sealing material (trade name: CEL9700HF10K, manufactured by Hitachi Kasei Kogyo Co., Ltd.) ) At 175 ° C for 5 hours to obtain a package. Then, the package was placed in a thermal cycle tester (manufactured by ETAC, THERMAL SHOCK CHAMBER NT1200), and a current of 1 mA was applied thereto. The temperature was 25 ° C for 2 minutes / -55 ° C for 15 minutes / 25 ° C for 2 minutes / 125 ° C for 15 minutes / The connection resistance was measured with one cycle for 2 minutes, and the change of the connection resistance after repeating 1000 cycles was evaluated. &Quot; A ", and " B " when a difference of 1? Or more was generated after 1,000 cycles compared with the initial resistance value waveform.
<절연 신뢰성의 평가(내HAST 평가)><Evaluation of insulation reliability (my HAST evaluation)>
제작한 필름상 접착제를 소정의 크기(세로 10 mm×가로 5 mm×두께 25 ㎛)로 잘라내고, 폴리이미드 기판 상에 배선 구리 배선을 형성한 빗형 전극 기판(배선 피치: 0.05 mm)에 첩부하고, 도 5에 도시한 바와 같이 빗형 전극 (90)이 형성된 기판 (20) 상에 필름상 접착제 (40)이 적층된 샘플을 제작하였다. 또한, 도 5에서는, 편의상 필름상 접착제의 도시를 생략하였다. 이어서, 샘플을 클린 오븐(에스펙 가부시끼가이샤 제조) 중 185℃에서 3시간 유지하여 경화하였다. 경화 후, 각 샘플을 취출하고, 가속 수명 시험 장치(히라야마(HIRAYAMA)사 제조, 상품명 「PL-422R8」, 조건: 130℃/상대 습도 85%/200시간/5 V 인가)에 설치하여 절연 저항을 측정하였다. 200시간을 통과시켜 절연 저항이 108Ω 이상인 경우를 「A」, 108Ω 미만인 경우를 「B」로 하여 평가하였다.The film-like adhesive thus prepared was cut into a predetermined size (10 mm in length x 5 mm in width x 25 m in thickness), and the resultant was affixed to a comb-shaped electrode substrate (wiring pitch: 0.05 mm) having wiring copper wirings formed on the polyimide substrate , A sample in which a film-like
각 실시예 및 비교예의 접착제 조성물의 원재료의 조성(단위: 질량부)을 표 1에, 각 시험 결과를 표 2에 나타낸다.Table 1 shows the composition (unit: parts by mass) of the raw materials of the adhesive compositions of Examples and Comparative Examples, and Table 2 shows the results of each test.
아크릴계 표면 처리 충전재를 이용한 실시예 1 내지 3은 흡습 후의 260℃에서의 접착력이 높고, 내리플로우성, 내TCT성 및 내HAST성 중 어떠한 특성도 우수하다는 것이 확인되었다.It was confirmed that Examples 1 to 3 using an acrylic surface treatment filler had high adhesion at 260 ° C. after moisture absorption and excellent properties such as flow resistance, TCT resistance and HAST resistance.
10…반도체칩, 15…배선(접속부), 20…기판(배선 회로 기판), 30…접속 범프, 32…범프(접속부), 34…관통 전극, 40…접착제 조성물(필름상 접착제), 50…인터포저, 60…납땜레지스트, 90…빗형 전극, 100, 200, 300, 400, 500, 600…반도체 장치.10 ... Semiconductor chip, 15 ... Wiring (connection part), 20 ... Substrates (wiring circuit boards), 30 ... Connection bump, 32 ... Bump (connection part), 34 ... Through electrode, 40 ... Adhesive composition (adhesive on film), 50 ... Interposer, 60 ... Solder resist, 90 ... Interdigital electrodes, 100, 200, 300, 400, 500, 600 ... A semiconductor device.
Claims (10)
에폭시 수지와, 경화제와, 하기 화학식 (1)로 표시되는 기를 갖는 화합물로 표면 처리된 아크릴계 표면 처리 충전재와, 중량 평균 분자량이 10000 이상인 고분자 성분을 함유하는 접착제 조성물.
[화학식 (1) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타냄]An adhesive composition for sealing a connecting portion of a semiconductor chip and a wiring circuit board in a semiconductor device electrically connected to each other or a connecting portion of a plurality of semiconductor chips electrically connected to each other,
An adhesive composition comprising an acrylic surface-treatment filler surface-treated with an epoxy resin, a curing agent, and a compound having a group represented by the following formula (1), and a polymer component having a weight average molecular weight of 10,000 or more.
Wherein R 1 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms and R 2 is an alkylene group having 1 to 30 carbon atoms,
[화학식 (2) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타내고, R3은 탄소수 1 내지 30의 알킬기를 나타냄]The adhesive composition according to claim 1, wherein the compound is a compound represented by the following formula (2).
Wherein R 1 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R 2 is an alkylene group having 1 to 30 carbon atoms, and R 3 is an alkyl group having 1 to 30 carbon atoms.
에폭시 수지와, 경화제와, 하기 화학식 (1)로 표시되는 기를 갖는 충전재와, 중량 평균 분자량이 10000 이상인 고분자 성분을 함유하는 접착제 조성물.
[화학식 (1) 중, R1은 수소 원자 또는 탄소수 1 또는 2의 알킬기를 나타내고, R2는 탄소수 1 내지 30의 알킬렌기를 나타냄]An adhesive composition for sealing a connecting portion of a semiconductor chip and a wiring circuit board in a semiconductor device electrically connected to each other or a connecting portion of a plurality of semiconductor chips electrically connected to each other,
An adhesive composition comprising an epoxy resin, a curing agent, a filler having a group represented by the following formula (1), and a polymer component having a weight average molecular weight of 10,000 or more.
Wherein R 1 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms and R 2 is an alkylene group having 1 to 30 carbon atoms,
상기 접속부를 제1항 내지 제3항 중 어느 한 항에 기재된 접착제 조성물을 이용하여 밀봉하는 공정을 구비하는 반도체 장치의 제조 방법.There is provided a method of manufacturing a semiconductor device in which respective connecting portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other or each connecting portion of a plurality of semiconductor chips are electrically connected to each other,
And a step of sealing the connecting portion with the adhesive composition according to any one of claims 1 to 3.
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TWI554530B (en) * | 2012-10-08 | 2016-10-21 | 國立臺灣大學 | Polymer, gel electrolyte made of the polymer and the preparing method thereof |
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JP5373192B2 (en) | 2013-12-18 |
KR101728203B1 (en) | 2017-04-18 |
TW201414795A (en) | 2014-04-16 |
KR20130143667A (en) | 2013-12-31 |
KR20130133762A (en) | 2013-12-09 |
JP2012149266A (en) | 2012-08-09 |
CN103642441A (en) | 2014-03-19 |
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CN103222040A (en) | 2013-07-24 |
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