TW201542730A - 半導體封裝的製造方法 - Google Patents

半導體封裝的製造方法 Download PDF

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Publication number
TW201542730A
TW201542730A TW104103750A TW104103750A TW201542730A TW 201542730 A TW201542730 A TW 201542730A TW 104103750 A TW104103750 A TW 104103750A TW 104103750 A TW104103750 A TW 104103750A TW 201542730 A TW201542730 A TW 201542730A
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Taiwan
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die
meth
compound
semiconductor package
semiconductor
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TW104103750A
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English (en)
Inventor
Hiroto Kouka
Yui Ozawa
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Showa Denko Kk
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Publication of TW201542730A publication Critical patent/TW201542730A/zh

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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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Abstract

本發明係提供一種維持塗佈性同時藉由B階段化可抑制塗佈後之濕潤蔓延，而且晶粒結著時即使不加熱，亦可得到充分之接著性，可製造信賴性高之半導體封裝之半導體封裝之製造方法。將包含光聚合起始劑(1)、熱自由基產生劑(2)、含有聚烯烴構造之樹脂(3)、及自由基聚合性化合物(4)之半導體用晶粒黏著糊塗佈於支持構件，照射紫外線於經塗佈之半導體用晶粒黏著糊而進行B階段化。然後，於經B階段化之半導體用晶粒黏著糊上配置晶粒進行壓著，接合晶粒與支持構件，進行晶粒結著。

Description

半導體封裝的製造方法
本發明係關於使用半導體用晶粒黏著糊之半 導體封裝之製造方法。
作為接合IC、LSI等之半導體晶片(以下記為「晶粒」)、與引線框架或絕緣性支持基板等之支持構件，密封而製造半導體封裝時之接合材料，除了Au-Si共晶合金、焊接之外，自以往已知有將樹脂作為主要原料之糊、薄膜等。
Au-Si共晶合金雖耐熱性及耐濕性高，但由於彈性率大，因熱履歴造成其他構件的膨脹、收縮的應力易破裂、且高價。焊接雖便宜，但耐熱性不夠充分，彈性率亦高且同樣易破裂。
將樹脂作為主要原料之糊(以下記為「晶粒黏著糊」)，具備充分之耐熱性與耐濕性、彈性率，且可緩和因熱履歴造成之膨脹、收縮之應力，因而被廣泛使用。惟，晶粒黏著糊成為考慮塗佈性之黏度時，易濕潤蔓延，同一封裝實裝複數之晶粒的封裝(以下記為「多晶粒封 裝」)的情況，由於有必要取得晶粒彼此的距離，故有難以對應多晶粒封裝的高積體化之缺點。
作為解決如此之晶粒黏著糊所具有之缺點的方法，提案有B階段化。所謂B階段化，係指藉由使包含在晶粒黏著糊之溶劑揮發，僅使硬化成分之一部分硬化等之方法，並藉由進行塗佈後晶粒黏著糊之增黏或賦予觸變性、或成為可保持形狀之硬度之固體，而防止晶粒黏著糊塗佈後之濕潤蔓延的製程。
例如專利文獻1中，揭示有使用含有硬化性化合物、光自由基起始劑、及熱自由基起始劑之電子零件用連接材料，B階段化電子零件用連接材料後，利用加熱壓縮使其熱硬化而得到連接構造體之方法。然而，專利文獻1所揭示之方法中，於得到連接構造體時，由於有必要加熱壓縮(熱壓著)電子零件用連接材料，有藉由於該加熱壓縮之熱的負荷，對晶粒給予熱履歴，而使半導體封裝的信賴性降低的問題。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開2013-001712號公報
本發明係鑑於上述之以往技術所具有之課題而完成者，係以提供一種維持塗佈性同時將由B階段化可抑制塗佈後之濕潤蔓延，而且晶粒結著時即使不加熱，亦可得到充分之接著性，可製造信賴性高之半導體封裝之半導體封裝之製造方法為目的。
本發明者們對解決上述課題經重複研究的結果，發現使用包含光聚合起始劑、熱自由基產生劑、含有聚烯烴構造之樹脂、及自由基聚合性化合物之半導體用晶粒黏著糊，藉由通過B階段化進行晶粒結著，可抑制塗佈後之濕潤蔓延，而且晶粒結著時即使不加熱，亦可得到充分之接著性，可得到信賴性高之半導體封裝，而終至完成本發明。
亦即本發明之態樣係如以下之[1]~[11]所述。
[1]一種半導體封裝之製造方法，其係包含接合晶粒與支持該晶粒之支持構件的晶粒結著步驟之半導體封裝之製造方法，其特徵為前述晶粒結著步驟係將包含光聚合起始劑(1)、熱自由基產生劑(2)、含有聚烯烴構造之樹脂(3)、及自由基聚合性化合物(4)之半導體用晶粒黏著糊塗佈於前述晶粒及前述支持構件之一者，於被塗佈之前述半導體用晶粒黏著糊照射光，進行B階段化後，於被B階段化之前述半導體用晶粒黏著糊上配置前述晶粒及前述支 持構件之另一者進行壓著，接合前述晶粒與前述支持構件的步驟。
[2]如[1]之半導體封裝之製造方法，其中，前述自由基聚合性化合物(4)為含(甲基)丙烯醯基之化合物。
[3]如[2]之半導體封裝之製造方法，其中，前述含(甲基)丙烯醯基之化合物的至少一部分為將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物。
[4]如[1]~[3]中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)係烷基苯酮系光聚合起始劑及醯基膦氧化物系光聚合起始劑中之至少一種。
[5]如[1]~[3]中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)係α-胺基烷基苯酮系光聚合起始劑及單醯基膦氧化物系光聚合起始劑中之至少一種。
[6]如[1]~[3]中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)為下述式(1)所表示之化合物及下述式(2)所表示之化合物中之至少一種；惟，下述式(1)中之R1為氫原子或碳數1~3之烷基；
[7]如[1]~[6]中任一項之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為有機過氧化物。
[8]如[7]之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為二烷基過氧化物或過氧化酯。
[9]如[7]之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為下述式(3)所表示之化合物；惟，下述式(3)中之R2及R3為碳數1~3之伸烷基。
[10]如[7]~[9]中任一項之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)之1分鐘半衰期溫度為120℃以上且200℃以下。
[11]如[1]~[10]中任一項之半導體封裝之製造方法，其中，在前述B階段化之前述光的照射量，係經B階段化之前述半導體用晶粒黏著糊的以溫度25℃、頻率1Hz的條件所測定之複合黏度成為100~1000Pa．s之範圍 的量。
本發明之半導體封裝之製造方法，由於可維持半導體用晶粒黏著糊之塗佈性，同時藉由B階段化可抑制塗佈後之濕潤蔓延，而且晶粒結著時即使不加熱，亦可得到充分之接著性，可得到信賴性高之半導體封裝。
以下，詳細說明本發明之實施形態。尚，本發明中，所謂「(甲基)丙烯醯基」，係指丙烯醯基及/或甲基丙烯醯基。
<半導體用晶粒黏著糊>
本發明之半導體封裝之製造方法中所使用之半導體用晶粒黏著糊，係包含光聚合起始劑(1)、熱自由基產生劑(2)、含有聚烯烴構造之樹脂(3)、及自由基聚合性化合物(4)。
首先，對於光聚合起始劑(1)進行說明。
光聚合起始劑(1)若為藉由近紅外線、可見光線、紫外線等之光的照射，而產生有助於自由基聚合性化合物(4)之自由基聚合開始之自由基的化合物，則並未特別限制。
又，作為光聚合起始劑(1)，亦可使用二茂金屬 (Metallocene)化合物。作為二茂金屬化合物，可使用中心金屬為Fe、Ti、V、Cr、Mn、Co、Ni、Mo、Ru、Rh、Lu、Ta、W、Os、Ir等所代表之過渡元素者，例如可列舉雙(η5-2,4-環戊二烯-1-基)-雙[2,6-二氟-3-(吡咯-1-基)苯基]鈦。
作為本發明所使用之光聚合起始劑(1)更佳者，係烷基苯酮系光聚合起始劑、醯基膦氧化物系光聚合起始劑，此等之光聚合起始劑可單獨使用，或是可適當組合2種以上使用。作為烷基苯酮系光聚合起始劑，可列舉苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、二乙氧基苯乙酮、1-羥基環己基苯基酮、1,2-羥基-2-甲基-1-苯基丙烷-1-酮、α-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙酮、2-羥基-2-甲基-1-(4-異丙基苯基)丙酮、2-羥基-2-甲基-1-(4-十二烷基苯基)丙酮、2-羥基-2-甲基-1-[(2-羥基乙氧基)苯基]丙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基(Morpholinyl)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮、安息香、安息香醚類(例如安息香甲基醚、安息香乙基醚、安息香丙基醚、安息香異丙基醚、安息香異丁基醚、安息香苯基醚、苄基二甲基縮酮)等。
又，作為醯基膦氧化物系光聚合起始劑，可列舉2,4,6-三甲基苯甲醯基二苯基膦氧化物、2,6-二甲氧基苯甲醯基二苯基膦氧化物、2,6-二氯苯甲醯基二苯基膦氧化物、2,4,6-三甲基苯甲醯基甲氧基苯基膦氧化物、2,4,6-三 甲基苯甲醯基乙氧基苯基膦氧化物、2,3,5,6-四甲基苯甲醯基二苯基膦氧化物、雙-(2,6-二氯苯甲醯基)苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-2,5-二甲基苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-4-丙基苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-1-萘基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)苯基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)-2,5-二甲基苯基膦氧化物、雙-(2,4,6-三甲基苯甲醯基)苯基膦氧化物、(2,5,6-三甲基苯甲醯基)-2,4,4-三甲基戊基膦氧化物等。
作為本發明所使用之光聚合起始劑再更佳者，係α-胺基烷基苯酮系光聚合起始劑、單醯基膦氧化物系光聚合起始劑。作為α-胺基烷基苯酮系光聚合起始劑，雖可列舉2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮及式(1)所表示之化合物等，但特佳為式(1)所表示之化合物。惟，下述式(1)中之R1為氫原子或碳數1~3之烷基。此等可單獨使用，或是可適當組合2種以上使用。
作為式(1)所表示之化合物，例如可列舉2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-乙基苯基)甲基]1-[4-(4-嗎啉基苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-n-丙基苯基)甲基]-1-[4-(4-嗎啉基苯基]-1-丁酮及2-(二甲基胺基)-2-[(4-異丙基苯基)甲基]-1-[4-(4-嗎啉基苯基]-1-丁酮。
又，作為單醯基膦氧化物系光聚合起始劑，可列舉2,4,6-三甲基苯甲醯基二苯基膦氧化物、2,6-二甲氧基苯甲醯基二苯基膦氧化物、2,6-二氯苯甲醯基二苯基膦氧化物、2,4,6-三甲基苯甲醯基甲氧基苯基膦氧化物、2,4,6-三甲基苯甲醯基乙氧基苯基膦氧化物、2,3,5,6-四甲基苯甲醯基二苯基膦氧化物。此等之單醯基膦氧化物系聚合起始劑系起始劑當中最佳者，係下述式(2)所表示之2,4,6-三甲基苯甲醯基二苯基膦氧化物。
而且，考慮半導體用晶粒黏著糊的保存穩定性時，式(2)所表示之化合物亦較式(1)所表示之化合物者為佳。
作為α-胺基烷基苯酮系光聚合起始劑之市售品，例如可列舉Irgacure 369、Irgacure 379EG(皆為BASF公司製)等。又，作為單醯基膦氧化物系光聚合起始劑之 市售品，例如可列舉DAROCUR TPO(BASF公司製)、Micure TPO(MIWON公司製)等。
半導體用晶粒黏著糊中之光聚合起始劑(1)的使用量，相對於全自由基聚合性化合物(4)(例如含(甲基)丙烯醯基之化合物)100質量份，較佳為0.01~5質量份的範圍，更佳為0.05~3質量份，再更佳為0.1~1質量份。
光聚合起始劑(1)的使用量，相對於全自由基聚合性化合物(4)(例如含(甲基)丙烯醯基之化合物)100質量份，若為0.01~5質量份，易表現藉由半導體用晶粒黏著糊之B階段化的濕潤蔓延抑制，又，半導體用晶粒黏著糊之B階段化物不會變過硬，由壓著可輕易進行晶粒結著。
其次，對於熱自由基產生劑(2)進行說明。
熱自由基產生劑(2)若為藉由加熱而產生有助於自由基聚合性化合物(4)之自由基聚合的開始之自由基的化合物，並未特別限制。
作為熱自由基產生劑，例如可列舉偶氮系化合物、有機過氧化物，作為用在半導體用晶粒黏著糊之熱自由基產生劑，較佳為有機過氧化物。
作為有機過氧化物，例如可列舉過氧化酮、過氧化縮酮、過氧化氫、二烷基過氧化物、二醯基過氧化物、過氧化二碳酸酯、過氧化酯等。此等當中，較佳係1分鐘半衰期溫度為120~200℃之物。更佳係1分鐘半衰期溫度為120~200℃之二烷基過氧化物、過氧化酯，再 更佳係一般而言為式(3)所表示之化合物。惟，下述式(3)中之R2及R3為碳數1~3之伸烷基。
作為1分鐘半衰期溫度為120~200℃之二烷基過氧化物、過氧化酯之市售品，例如可列舉Perocta O(日油股份有限公司製)、Perbutyl O(日油股份有限公司製)、Perhexa25Z(日油股份有限公司製)、Percumyl D(日油股份有限公司製)等。
半導體用晶粒黏著糊中之熱自由基產生劑(2)的使用量，相對於全自由基聚合性化合物(4)(例如含(甲基)丙烯醯基之化合物)100質量份，較佳為0.1~10質量份的範圍，更佳為0.5~6質量份，再更佳為1~3質量份。熱自由基產生劑(2)的使用量，相對於全自由基聚合性化合物(4)100質量份，若為0.1質量份以上，可使半導體用晶粒黏著糊之硬化物的彈性率成為良好者。又，熱自由基產生劑(2)的使用量，相對於全自由基聚合性化合物(4)100質量份，若為10質量份以下，使半導體用晶粒黏著糊之熱硬化時或半導體封裝製造步驟當中難以產生放氣。
其次，對於含有聚烯烴構造之樹脂(3)進行說明。
含有聚烯烴構造之樹脂(3)，若為包含藉由不飽和烴的聚合所得之構造之樹脂，並未特別限制。作為不飽和 烴，例如可列舉α-烯烴或二烯烴等之烯烴，作為α-烯烴，可列舉乙烯、丙烯、1-丁烯，作為二烯烴，可列舉丁二烯、異戊二烯，可為選自此等當中之2種以上的共聚合物。
又，為了賦予接著性或與其他成分的反應性，尤其是與後述之含有環氧乙烷環構造或環氧丙烷(Oxetane)環構造之含環構造之化合物的反應性，含有聚烯烴構造之樹脂(3)較佳為具有羥基、羧基、酸酐基、環氧基、酯構造等。例如酸酐基可藉由接枝馬來酸酐、苯二甲酸酐、衣康酸酐等於前述之烯烴的聚合物，導入於含有聚烯烴構造之樹脂(3)。
作為含有聚烯烴構造之樹脂(3)更佳之例，可列舉不飽和烴與馬來酸酐的共聚物之馬來酸酐改質聚烯烴。與馬來酸酐共聚合之不飽和烴，從半導體用晶粒黏著糊之硬化物的應力緩和性的觀點來看，較佳為具有共軛雙鍵之化合物，更佳為預先聚合丁二烯或異戊二烯者、或預先共聚合丁二烯與異戊二烯者。又，此馬來酸酐改質聚烯烴，較佳為具有不飽和之2價烴基者。而且，此馬來酸酐改質聚烯烴係包含於預先聚合丁二烯或異戊二烯者、或預先共聚合丁二烯與異戊二烯者，使馬來酸酐接枝之化合物。
作為馬來酸酐改質聚烯烴之市售品，可列舉DIACARNA(三菱化學股份有限公司製)、M-1000-80(日本石油化學股份有限公司製)、Ricon MA(CRAYVALLEY公 司製)等。
含有聚烯烴構造之樹脂(3)之數平均分子量，較佳為大於2000，更佳為大於5000。含有聚烯烴構造之樹脂(3)之數平均分子量若大於2000，可使半導體用晶粒黏著糊之硬化物的應力緩和性成為良好者。
半導體用晶粒黏著糊中之含有聚烯烴構造之樹脂(3)的使用量，相對於全硬化成分，較佳為20~80質量%，更佳為30~70質量%。含有聚烯烴構造之樹脂(3)的使用量，相對於全硬化成分，若為20質量%以上，可使半導體用晶粒黏著糊之硬化物的應力緩和性成為良好者。又，含有聚烯烴構造之樹脂(3)的使用量相對於全硬化成分，若為80質量%以下，可使半導體用晶粒黏著糊的黏度成為良好者，並使操作變容易。
其次，對於自由基聚合性化合物(4)進行說明。
自由基聚合性化合物(4)若為具有自由基聚合性之化合物，並未特別限制，例如可列舉具有乙烯基之化合物、具有(甲基)丙烯醯基之化合物等，更佳為含(甲基)丙烯醯基之化合物。惟，後述之矽烷偶合劑當中具有(甲基)丙烯醯基者除外。亦即，半導體用晶粒黏著糊包含矽烷偶合劑的情況下，矽烷偶合劑當中包含具有(甲基)丙烯醯基者時，具有(甲基)丙烯醯基之矽烷偶合劑，成為包含在矽烷偶合劑者，成為未包含於自由基聚合性化合物(4)者。
作為含(甲基)丙烯醯基之化合物，可列舉多元 醇聚(甲基)丙烯酸酯、環氧基(甲基)丙烯酸酯、胺基甲酸乙脂(甲基)丙烯酸酯、(甲基)丙烯酸酯單體等。
所謂多元醇聚(甲基)丙烯酸酯，係指多元醇、與丙烯酸或甲基丙烯酸的酯化合物。於此所選之多元醇雖並未特別限制，但例如可列舉鏈狀之氫化二聚二醇、1,3-丙烷二醇、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、新戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、2-乙基-2-丁基-1,3-丙烷二醇、2,4-二乙基-1,5-戊二醇、1,10-癸烷二醇、1,12-十二烷二醇、聚烯烴多元醇、氫化聚烯烴多元醇等之鏈狀脂肪族多元醇。
作為多元醇，進而可列舉具有脂環構造之氫化二聚二醇、氫化雙酚A烯烴氧化物加成物、氫化雙酚F烯烴氧化物加成物、氫化雙酚烯烴氧化物加成物、1,4-環己烷二甲醇、1,3-環己烷二甲醇、三環[5.2.1.02,6]癸烷二甲醇、2-甲基環己烷-1,1-二甲醇等之具有脂環構造之多元醇。
作為多元醇，進而可列舉三聚物三醇、p-苯二甲醇、雙酚A烯烴氧化物加成物、雙酚F烯烴氧化物加成物、雙酚烯烴氧化物加成物等之具有芳香環之多元醇，進而可列舉聚乙二醇、聚丙二醇、聚四亞甲基二醇等之聚醚多元醇，進而可列舉聚六亞甲基己二酸酯、聚六亞甲基琥珀酸酯、聚己內酯等之聚酯多元醇。
作為多元醇，進而可列舉α,ω-聚(1,6-伸己基碳酸酯)二醇、α,ω-聚(3-甲基-1,5-伸戊基碳酸酯)二醇、 α,ω-聚[(1,6-伸己基：3-甲基-五亞甲基)碳酸酯]二醇、α,ω-聚[(1,9-伸壬基：2-甲基-1,8-伸辛基)碳酸酯]二醇等之(聚)碳酸酯二醇，進而可列舉具有從氫化二聚酸所衍生之構造單元及從氫化二聚二醇所衍生之構造單元之聚酯多元醇。此等之多元醇可單獨使用，或是可適當組合2種以上使用。
又，從主要為確保硬化後之彈性率的觀點來看，較佳為具有脂環構造之多元醇、具有芳香環之多元醇、(聚)碳酸酯二醇、聚酯多元醇。更佳為具有芳香環之多元醇。作為從具有芳香環之多元醇所衍生之多元醇聚(甲基)丙烯酸酯之市售品，例如可列舉M-208(東亞合成股份有限公司製)、M-211B(東亞合成股份有限公司製)、FA-321A(日立化成股份有限公司製)、FA-324A(日立化成股份有限公司製)、Light AcrylateBP-4EAL(共榮社化學股份有限公司製)、Light AcrylateBP-4PA(共榮社化學股份有限公司製)等。
又，所謂環氧基(甲基)丙烯酸酯，係指藉由於環氧樹脂末端環氧基，使丙烯酸或甲基丙烯酸加成而得之化合物。於此時所選之環氧樹脂並無特別限制。具體而言，例如可列舉雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、氫化酚醛清漆型環氧樹脂、縮水甘油基酯型環氧樹脂、聯苯型環氧樹脂、氫化聯苯型環氧樹脂等。此等之環氧基(甲基)丙烯酸酯可單獨使用，或是可適 當組合2種以上使用。
作為環氧基(甲基)丙烯酸酯之市售品，例如可列舉環氧基酯3000A(共榮社化學股份有限公司製)、EBECRYL600(Daicel-Cytec股份有限公司製)、EBECRYL6040(Daicel-Cytec股份有限公司製)等。
又，所謂胺基甲酸乙脂(甲基)丙烯酸酯，係指藉由使多元醇與聚異氰酸酯與含有羥基之(甲基)丙烯酸酯進行反應、或使多元醇與含有異氰酸酯基之(甲基)丙烯酸酯進行反應所得之化合物。於此時所選之多元醇、聚異氰酸酯、含有羥基之(甲基)丙烯酸酯、及含有異氰酸酯基之(甲基)丙烯酸酯並無特別限制。
多元醇係與在多元醇聚(甲基)丙烯酸酯中所使用之多元醇相同。作為聚異氰酸酯，例如可列舉1,4-環己烷二異氰酸酯、異佛爾酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、1,3-雙(異氰酸酯甲基)環己烷、1,4-雙(異氰酸酯甲基)環己烷、2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、1,3-苯二甲基二異氰酸酯、1,4-苯二甲基二異氰酸酯、賴胺酸三異氰酸酯、賴胺酸二異氰酸酯、六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、2,2,4-三甲基己烷亞甲基二異氰酸酯及降莰烷二異氰酸酯等。此等可單獨使用，或是可適當組合2種以上使用。
作為含有羥基之(甲基)丙烯酸酯，例如可列舉2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯、3-羥基丙基 丙烯酸酯、2-羥基丁基丙烯酸酯、4-羥基丁基丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、2-羥基-3-(o-苯基苯氧基)丙基丙烯酸酯、2-羥基乙基丙烯醯胺、2-羥基乙基甲基丙烯酸酯、2-羥基丙基甲基丙烯酸酯、3-羥基丙基甲基丙烯酸酯、2-羥基丁基甲基丙烯酸酯、4-羥基丁基甲基丙烯酸酯、2-羥基-3-苯氧基丙基甲基丙烯酸酯、2-羥基-3-(o-苯基苯氧基)丙基甲基丙烯酸酯等。此等可單獨使用，或是可適當組合2種以上使用。
作為含有異氰酸酯基之(甲基)丙烯酸酯，可列舉2-異氰酸酯乙基丙烯酸酯、2-異氰酸酯乙基甲基丙烯酸酯等。此等可單獨使用，或是可適當組合2種以上使用。
胺基甲酸乙脂(甲基)丙烯酸酯於如二丁基錫二月桂酸酯、二辛基錫二月桂酸酯之周知的胺基甲酸乙脂化觸媒的存在下或非存在下，可藉由使多元醇與聚異氰酸酯與含有羥基之(甲基)丙烯酸酯、或使多元醇與含有異氰酸酯基之(甲基)丙烯酸酯進行反應予以合成，但於觸媒之存在下使其反應者，在縮短反應時間的意義上較佳。惟，半導體用晶粒黏著糊最終實際使用時，雖作為硬化膜使用，但過度大量使用觸媒時，由於有對硬化膜之物性值造成不良影響的可能性。因此，觸媒的使用量，相對於多元醇與聚異氰酸酯與含有羥基之(甲基)丙烯酸酯、或多元醇與含有異氰酸酯基之(甲基)丙烯酸酯的總量100質量份，較佳為0.001~1質量份。
又，本發明之半導體用晶粒黏著糊中包含烷 氧基矽烷基時，前述胺基甲酸乙脂化觸媒係觸媒烷氧基矽烷基之水解反應。如此的情況中，有必要考慮本發明之半導體用晶粒黏著糊之時間穩定性與對支持構件(例如引線框架或基板)之密著性的平衡，此時的使用量，相對於多元醇與聚異氰酸酯與含有羥基之(甲基)丙烯酸酯、或多元醇與含有異氰酸酯基之(甲基)丙烯酸酯的總量100質量份，較佳為0.003~0.2質量份，更佳為0.005~0.15質量份。觸媒量若為0.001質量份以上，適當表現觸媒之添加效果，若為1質量份以下，如先前所述，最終作為硬化膜實際使用之物性值成為良好者。
在本說明書之(甲基)丙烯酸酯單體，係從前述之含(甲基)丙烯醯基之化合物(1)，去除前述多元醇聚(甲基)丙烯酸酯、前述環氧基(甲基)丙烯酸酯及前述胺基甲酸乙脂(甲基)丙烯酸酯之化合物。
作為(甲基)丙烯酸酯單體，例如可列舉縮水甘油基丙烯酸酯、四氫糠基丙烯酸酯、縮水甘油基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯等之具有環狀醚基之含(甲基)丙烯醯基之化合物、環己基丙烯酸酯、異莰基丙烯酸酯、二環戊烯基丙烯酸酯、二環戊烯基氧基乙基丙烯酸酯、二環戊烷基丙烯酸酯、二環戊烷基乙基丙烯酸酯、4-tert-丁基環己基丙烯酸酯、環己基甲基丙烯酸酯、異莰基甲基丙烯酸酯、二環戊烯基甲基丙烯酸酯、二環戊烯基氧基乙基甲基丙烯酸酯、二環戊烷基甲基丙烯酸酯、二環戊烷基乙基甲基丙烯酸酯、4-tert-丁基環己基甲基丙烯酸酯等之具有環 狀脂肪族基之含單官能(甲基)丙烯醯基之化合物、月桂基丙烯酸酯、異壬基丙烯酸酯、2-乙基己基丙烯酸酯、異丁基丙烯酸酯、tert-丁基丙烯酸酯、異辛基丙烯酸酯、異戊基丙烯酸酯、月桂基甲基丙烯酸酯、異壬基甲基丙烯酸酯、2-乙基己基甲基丙烯酸酯、異丁基甲基丙烯酸酯、tert-丁基甲基丙烯酸酯、異辛基甲基丙烯酸酯、異戊基甲基丙烯酸酯等之具有鏈狀脂肪族基之含單官能(甲基)丙烯醯基之化合物、苄基丙烯酸酯、苯氧基乙基丙烯酸酯、苄基甲基丙烯酸酯、苯氧基乙基甲基丙烯酸酯、2-羥基-3-苯氧基丙基甲基丙烯酸酯等之具有芳香環之含單官能(甲基)丙烯醯基之化合物、聚乙二醇二丙烯酸酯、癸烷二醇二丙烯酸酯、壬烷二醇二丙烯酸酯、己二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等之含多官能(甲基)丙烯醯基之化合物。尚，所謂上述含單官能(甲基)丙烯醯基之化合物，係指含有1個(甲基)丙烯醯基之含(甲基)丙烯醯基之化合物，所謂上述含多官能(甲基)丙烯醯基之化合物，係指含有複數之(甲基)丙烯醯基之含(甲基)丙烯醯基之化合物。
半導體用晶粒黏著糊中之自由基聚合性化合物(4)的使用量，相對於全硬化成分，較佳為含有5~80質量%，更佳為10~60質量%，再更佳為15~50質量%。自由基聚合性化合物(4)的使用量，相對於全硬化成 分，若為80質量%以下，使半導體用晶粒黏著糊之硬化物對支持構件之密著性成良好者。又，自由基聚合性化合物(4)的使用量，相對於全硬化成分，若為5質量%以上，可使半導體用晶粒黏著糊的黏度成為良好者，並使操作變容易。
尚，所謂本說明書所記載之「硬化成分」，係意指藉由自由基聚合而可聚合之化合物及/或後述之含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物及/或可與環氧乙烷環構造或環氧丙烷環構造進行反應之化合物，所謂「全硬化成分」係意指硬化成分的總量。自由基聚合性化合物(4)(例如含(甲基)丙烯醯基之化合物)、含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物、馬來酸酐改質聚烯烴全部包含在硬化成分。
後述之矽烷偶合劑中之p-苯乙烯基三甲氧基矽烷、p-苯乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷之具有自由基聚合性不飽和基之矽烷偶合劑亦包含在硬化成分。
本發明所使用之含(甲基)丙烯醯基之化合物，較佳為包含將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙 烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)。將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)，若為將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之化合物，並未特別限制。
惟，將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)，未包含在後述之含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物。亦即，於半導體用晶粒黏著糊，包含將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方，含有於同一分子內之含(甲基)丙烯醯基之化合物(5)時，將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方，含有於同一分子內之含(甲基)丙烯醯基之化合物(5)，係成為包含在含(甲基)丙烯醯基之化合物者，成為未包含在含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物者。
所謂將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方，含有於同一分子內之含(甲基)丙烯醯基之化合物(5)，可列舉前述之多元醇聚(甲基)丙烯酸酯、環氧基(甲基)丙烯酸酯、胺基甲酸乙脂(甲基)丙烯酸酯、(甲基)丙烯酸酯單體之內，含有環氧乙烷環構造或環氧丙烷環構造之物等。
例如可列舉從含有環氧乙烷環構造或環氧丙 烷環構造之多元醇所衍生之多元醇聚(甲基)丙烯酸酯或胺基甲酸乙脂(甲基)丙烯酸酯、或從含有環氧乙烷環構造或環氧丙烷環構造之環氧樹脂所衍生之環氧基(甲基)丙烯酸酯等。此等例如，可藉由將所含有之環氧乙烷環構造或環氧丙烷環構造的總數，對於使其反應之丙烯酸或甲基丙烯酸的總數之比設為大於1而獲得。又例如，作為含有環氧乙烷環構造或環氧丙烷環構造之(甲基)丙烯酸酯單體，可列舉縮水甘油基丙烯酸酯、縮水甘油基甲基丙烯酸酯、4-羥基丁基丙烯酸酯縮水甘油基醚等。
半導體用晶粒黏著糊中，將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)的使用量，相對於全含(甲基)丙烯醯基之化合物(1)100質量份，較佳係成為10質量份以上，更佳為20質量份以上，再更佳為30質量份以上。將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)的使用量，相對於全含(甲基)丙烯醯基之化合物100質量份，若為10質量份以上，可使本發明之半導體用晶粒黏著糊之硬化物的彈性率成為良好者。
本發明中，半導體用晶粒黏著糊，由於較佳係包含含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物，故有時添加含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物。含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物，若為含有環氧乙烷環構造 或環氧丙烷環構造之化合物，則並未特別限制。
作為含有環氧乙烷環構造或環氧丙烷環構造之化合物，可列舉醇、胺、羧酸等之表氯醇加成物、烯烴氧化物、酮與烯烴之環狀加成物、環氧丙烷醇衍生物等，具體而言，可列舉前述之環氧基(甲基)丙烯酸酯所使用之環氧樹脂、或2-乙基己基環氧丙烷、苯二甲基雙環氧丙烷、環氧丙烷樹脂。從半導體用晶粒黏著糊硬化物之交聯密度的觀點來看，含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物較佳為2官能以上，其中較佳為環氧樹脂。
半導體用晶粒黏著糊中之含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物的使用量，較佳為環氧乙烷環構造或環氧丙烷環構造的總數對於源自後述之馬來酸酐改質聚烯烴之馬來酸酐的羧酸酐構造的總數之比成為2.8~0.4的量，更佳係成為2.0~1.2的量。環氧乙烷環構造或環氧丙烷環構造的總數對於源自馬來酸酐之羧酸酐構造的總數之比若為2.8~0.4，可使半導體用晶粒黏著糊之硬化物的彈性率成為良好者。
又，本發明中，半導體用晶粒黏著糊，由於較佳係包含熱硬化促進劑，故有時添加熱硬化促進劑。熱硬化促進劑若為促進環氧乙烷環構造或環氧丙烷環構造、和可與該等反應之化合物的反應之化合物，則並未特別限制。
作為熱硬化促進劑，例如可列舉烷基膦化合物、咪唑 化合物、脂肪族胺、脂環族胺、環狀脒、此等之四苯基硼酸酯鹽等之嵌段化合物、具有酚性羥基之化合物、聚醯胺、羧酸酐、雙氰胺、有機酸二醯肼等。
從硬化性與保存穩定性之平衡的觀點來看，較佳為咪唑化合物及其嵌段化合物、環狀脒之嵌段化合物。作為此等之市售品之例，可列舉Curezol 2E4MZ(四國化成工業股份有限公司製)、Curezol 2PZ-PW(四國化成工業股份有限公司製)、Curezol2P4MZ(四國化成工業股份有限公司製)、CurezolC11Z-CNS(四國化成工業股份有限公司製)、U-CAT SA102(SANAPRO股份有限公司製)、U-CAT SA506(SANAPRO股份有限公司製)、U-CAT 5002(SANAPRO股份有限公司製)等。
半導體用晶粒黏著糊中之熱硬化促進劑的使用量，相對於含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物、及將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)的合計之100質量份，較佳為0.5質量份以上且10質量份以下之範圍，更佳為1質量份以上且6質量份以下。
熱硬化促進劑的使用量，相對於含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物、及將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)的合計之100質量份，若為0.5質量份以上，可使半導體用晶 粒黏著糊之硬化物的彈性率成為良好者。又，熱硬化促進劑的使用量，相對於含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物、及將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物(5)的合計之100質量份，若為10質量份以下，使半導體用晶粒黏著糊之熱硬化時或半導體封裝製造步驟當中難以產生放氣。
又，本發明中，半導體用晶粒黏著糊由於較佳為為了增加保存穩定性，而添加聚合抑制劑，故有時添加聚合抑制劑。作為此聚合抑制劑，雖非特別限定者，但例如適合使用對苯二酚、p-甲氧基酚、p-苯醌、萘醌、菲醌(phenan thraquinone)、甲苯醌、2,5-二乙醯氧基-p-苯醌、2,5-二己酸基(caproic acid)-p-苯醌、2,5-醯氧基-p-苯醌、p-tert-丁基鄰苯二酚、2,5-二-tert-丁基對苯二酚、p-tert-丁基鄰苯二酚、單-tert-丁基對苯二酚、2,5-二-tert-戊基對苯二酚、二-tert-丁基-p-甲酚對苯二酚單甲基醚及吩噻嗪。此等可單獨使用，或是可適當組合2種以上使用。
通常此聚合抑制劑，相對於全含(甲基)丙烯醯基之化合物(4)100質量份，較佳為添加0.01~10質量份。
本發明中，半導體用晶粒黏著糊以賦予對支持構件的密著性為目的，進而可包含矽烷偶合劑。
矽烷偶合劑係於分子內具有與有機材料反應鍵結之官能基、及與無機材料反應鍵結之官能基的雙方之有機矽化合物，一般而言其構造係如下述式(4)所示。
於此，Y係與有機材料反應鍵結之官能基，可列舉乙烯基、環氧基、胺基、取代胺基、(甲基)丙烯醯基、巰基等作為其代表例。又，X係與無機材料反應鍵結之官能基，由水或是濕氣受到水解，而生成矽醇基，此矽醇基係與無機材料反應鍵結。作為X之代表例，可列舉烷氧基、乙醯氧基、氯原子等。R4為2價有機基，R5表示烷基。i表示1~3之整數，j表示0~2之整數。惟，i與j之和為3。
如此之矽烷偶合劑當中，較佳者係Y為與自由基聚合性化合物(4)(例如含(甲基)丙烯醯基之化合物)及/或含有環氧乙烷環構造或環氧丙烷環構造之含環構造之化合物及/或馬來酸酐改質聚烯烴具有反應性的化合物，其中，較佳為p-苯乙烯基三甲氧基矽烷、p-苯乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷2-(3,4-環氧基環己基)乙基三甲氧 基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷。
再更佳係於熱硬化反應時，以易被併入硬化物中之2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷較佳。
本發明中，相對於半導體用晶粒黏著糊中之全硬化成分，矽烷偶合劑的量較佳為0.01質量%以上且8質量%以下的範圍，更佳為0.1質量%以上5質量%以下的範圍。相對於半導體用晶粒黏著糊中之全硬化成分，若為 0.01質量%以上，可充分表現對支持構件的密著性。又，相對於半導體用晶粒黏著糊之全硬化成分，若為8質量%以下，無論所使用之矽烷偶合劑的種類，可使保存穩定性成為良好者。
又，本發明中，半導體用晶粒黏著糊由於較佳係包含填料，故有時添加填料。
填料例如可列舉銀粉、金粉、銅粉、鎳粉等之金屬填料、或氧化鋁、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、結晶性二氧化矽、非晶性二氧化矽、氮化硼、二氧化鈦、玻璃、氧化鐵、陶瓷等之無機填料、或碳、橡膠系填料等之有機填料等，包含種類、形狀等並未特別限制。此等可單獨使用，或是可適當組合2種以上使用。
此等之填料可因應目的分開使用。例如金屬填料主要是以賦予半導體用晶粒黏著糊導電性為目的而添加，無機填料主要是以賦予半導體用晶粒黏著糊低熱膨脹性為目的而添加，有機填料主要是以賦予半導體用晶粒黏著糊應力緩和性為目的而添加，又除此之外，可依熱傳導性、低吸濕性、絕緣性等各種目的進行不同種類填料的添加。
填料較佳係平均粒子徑為20μm以下且最大粒子徑為60μm以下，更佳為平均粒子徑為10μm以下且最大粒子徑為30μm以下。平均粒子徑若為20μm以下且最大粒子徑為60μm以下，使半導體用晶粒黏著糊的保存穩 定性及塗佈性成為良好者。
填料的摻合量，相對於半導體用晶粒黏著糊中之全硬化成分100質量份，較佳為5質量份以上且80質量份以下。填料的摻合量為5質量份以上時，半導體用晶粒黏著糊之硬化物的彈性率良好，熱膨脹．收縮率的控制亦容易。另外，填料的摻合量為80質量份以下時，半導體用晶粒黏著糊的黏度為適當。
本發明之半導體用晶粒黏著糊，較佳係於25℃的黏度為50000mPa．s以下。更佳係於25℃的黏度為25000mPa．s以下。於25℃的黏度若為50000mPa．s以下，將半導體用晶粒黏著糊配合晶粒的尺寸而定量性良好地進行塗佈變得容易。
在本發明中，使用黏彈性測定裝置，測定半導體用晶粒黏著糊之剪斷黏度。說明使用黏彈性測定裝置進行黏度測定時之代表性條件。將半導體用晶粒黏著糊的試料，裝入黏彈性測定裝置(Anton-Paar公司製、型式：MCR301)，使用型號CP-25之錐板型心軸，以溫度25.0℃、剪斷速度10s-1之條件測定剪斷黏度。
<半導體封裝之製造方法>
本發明之半導體封裝之製造方法，係將半導體用晶粒黏著糊塗佈於晶粒或支持構件，其次，於半導體用晶粒黏著糊之塗佈部分照射例如紫外線，藉由產生自光聚合起始劑(1)之自由基，使自由基聚合性化合物(4)等之硬化成分 的一部分進行光聚合，B階段化半導體用晶粒黏著糊。此後，係進行於例如25℃等常溫下的晶粒結著、與經B階段化之半導體用晶粒黏著糊的熱硬化(藉由產生自熱自由基產生劑(2)之自由基，而使自由基聚合性化合物(4)等之硬化成分的殘餘熱聚合)，進而進行密封者。藉此，可得到信賴性高且經高積體化之半導體封裝。尚，亦可同時進行熱硬化與密封。
半導體用晶粒黏著糊之塗佈方法雖並未特別限定，但可列舉浸漬法、刷塗法、噴塗法、連線塗佈法、沖壓法、印刷法、噴射點膠法、噴墨法等。對半導體用晶粒黏著糊之塗佈部分的紫外線等之光的照射方法雖並未特別限定，但可列舉將可撓式導光管以手或機械進行保持．操作，並照射於半導體用晶粒黏著糊之塗佈部分之方法、或於輸送帶放上經塗佈半導體用晶粒黏著糊之晶粒或支持構件，使其通過照射紫外線等之光的區域進行照射之方法等。
半導體用晶粒黏著糊之B階段化，較佳為使用黏彈性測定裝置之振動模式，以頻率1Hz的條件所測定在25℃之複合黏度成為100Pa．s以上且1000Pa．s以下來實施。複合黏度若為100Pa．s以上且1000Pa．s以下，抑制熱硬化的步驟中，半導體用晶粒黏著糊之B階段化物的濕潤蔓延，易達成半導體封裝的高積體化，進而，不需要在晶粒結著之加熱，而對不需對晶粒給予多餘的熱履歴並易使信賴性提昇。
具體而言，將半導體用晶粒黏著糊塗佈成厚度50μm，照射波長365nm之紫外線使其B階段化，將此經B階段化之半導體用晶粒黏著糊以抹刀等刮取者作為樣品，進行黏彈性測定。黏彈性測定使用黏彈性測定裝置之振動模式，以溫度25℃、頻率1Hz的條件測定複合黏度。而且，較佳為求得複合黏度成為100~1000Pa．s的範圍之紫外線照射量，並將其作為半導體用晶粒黏著糊之B階段化時的紫外線照射線量。
半導體用晶粒黏著糊之B階段化物，較佳為在熱硬化的步驟，不會濕潤蔓延，而抑制加熱時的濕潤蔓延。具體而言，於支持構件之矽基板上，將半導體用晶粒黏著糊塗佈成厚度200μm、直徑2mm大小之圓狀，將照射1000mJ/cm2紫外線使其B階段化的試驗片投入烤箱，以昇溫速度4℃/分鐘昇溫至170℃，其後直接使其硬化1小時。而且，將硬化後之試驗片上的半導體用晶粒黏著糊硬化物在顯微鏡下觀察測定直徑，算出照射1000mJ/cm2紫外線後立即之直徑的增加率。此時，較佳為直徑的增加率未達10%，更佳為未達5%。
進而，B階段化時之紫外線照射量，較佳為用以B階段化之紫外線照射後立即之半導體用晶粒黏著糊的直徑與加熱硬化後之半導體用晶粒黏著糊硬化物的直徑的變化率成為未達10%般的紫外線照射量。
半導體用晶粒黏著糊之B階段化後，進行晶粒結著後之熱硬化的方法雖並未特別限定，但可列舉將晶 粒與支持構件已進行晶粒結著者投入烤箱之方法、或將晶粒與支持構件已進行晶粒結著者放上輸送帶，使其通過加熱至特定溫度之區域之方法等。
對於依本發明之半導體封裝之製造方法，進行晶粒結著及熱硬化時之晶粒抗剪強度的評價方法進行說明。晶粒抗剪強度的評價，例如依MIL-STD-883G、IEC-60749-22、EIAJ-ED-4703等之規格進行。作為具體例，使用Dage-4000(剪斷接著力試驗機、Dage公司製)，將經接合之晶粒的側面以附傳感器之治具推擠，測量破壞晶粒與支持構件的接合所需要的力量。尚，晶粒抗剪強度在接合2mm平方之正方形的晶片與支持構件的情況下，較佳為58.8N以上。若為成為如58.8N以上之接合材料或接合法，可使半導體封裝的信賴性成為良好者。
<半導體封裝>
本發明之態樣中，亦有使用半導體用晶粒黏著糊所製造之半導體封裝。作為半導體封裝，可列舉插入形(Pin insertion type)之DO封裝(Diode Outline)、TO封裝(Transistor Outline)、DIP(Dual Inline Package)、SIP(Single Inline Package)、ZIP(Zigzag Inline Package)、PGA(Pin Grid Array)、表面實裝形之SOP(Small Outline Package)、SOJ(Small Outline J-leaded)、CFP(Ceramic Flat Package)、SOT(Small Outline Transistor)、QFP(Quad Flat Package)、PLCC(Plastic Leaded Chip Carrier)、BGA(Ball Grid Array)、LGA(Land Grid Array)、LLCC(LeadLess Chip Carrier)、TCP(Tape Carrier Package)、LLP(Leadless Leadframe Package)、DFN(Dual Flatpack No-leaded)、COB(Chip On Board)等。
半導體封裝，係將半導體用晶粒黏著糊塗佈於晶粒或支持構件，其次，於半導體用晶粒黏著糊之塗佈部分，照射例如紫外線進行B階段化，此後進行晶粒結著與熱硬化，進而可藉由進行密封而製造。如此進行所製造之本發明之半導體封裝係信賴性高。
[實施例]
以下雖由實施例，更具體說明本發明，但本發明並非僅被限制於以下之實施例者。
(實施例1)
將10.3g雙酚A烯烴氧化物加成物二丙烯酸酯(共榮社化學股份有限公司製BP-4EAL、化合物名稱為2,2’-雙[4-(丙烯醯氧基聚乙氧基)苯基]丙烷)、41.4g馬來酸酐改質聚丁二烯(CRAYVALLEY公司製Ricon131MA17)、6.9g縮水甘油基甲基丙烯酸酯(日油股份有限公司製BlemmerGH)、10.3g氫化雙酚A型環氧樹脂(三菱化學股份有限公司製YX-8000)、0.1g 2,4,6-三甲基苯甲醯基二苯基膦氧化物(BASF公司製DAROCUR TPO)、0.3g過氧化二異丙苯(日油股份有限公司製PercumylD)、0.7g二氮雜 雙環十一烯-四苯基硼酸酯鹽(SANAPRO股份有限公司製U-CAT5002)、29.5g球狀二氧化矽凝膠(三菱Rayon股份有限公司製QS-2)、0.3g 3-縮水甘油氧基丙基三甲氧基矽烷(信越矽股份有限公司製KBM-403)，投入自轉．公轉混合機(THINKY股份有限公司製泡取練太郎ARE-310)並進行混合，而得到晶粒黏著糊。
(實施例2~4、比較例1~5)
除了將各成分之種類及量如表1所示進行變更之外，其他與實施例1進行同樣之操作，而得到晶粒黏著糊。
表1中、Acryester M係三菱Rayon股份有限公司製甲基甲基丙烯酸酯，SR-349係Sartomer公司製之乙氧基化雙酚A二丙烯酸酯，FA-512M係日立化成工業股份有限公司製之二環戊烯基氧基乙基甲基丙烯酸酯，EBECRYL3702係Daicel-Cytec股份有限公司製環氧基丙烯酸酯，CTBN-1300X8係宇部興產股份有限公司製羧基末端丙烯腈丁二烯共聚物，EXA-4850-150係大日本油墨化學工業股份有限公司製環氧樹脂(環氧基當量450)，PB-4700係Daicel化學股份有限公司製環氧基化聚丁二烯，UC-203係Kuraray股份有限公司製甲基丙烯醯基改質聚異戊二烯。
又，Irgacure(註冊商標)369係BASF製2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1，V-65係和光純藥工業公司製2,2’-偶氮雙-2,4-二甲基戊腈，DICY係雙氰胺，AEROSIL R972係以日本Aerosil股份有限公司製之二甲基二氯矽烷進行表面處理之疏水性二氧化矽填料，SFP-20M係電氣化學工業股份有限公司製球狀二氧化矽凝膠，ASFP-20係電氣化學工業股份有限公司製球狀氧化鋁，MicropearlAU係積水化學工業股份有限公司製金鍍覆導電性粒子。
<濕潤蔓延抑制的評價>
晶粒黏著糊之濕潤蔓延抑制係藉由以下之方法評價。
將晶粒黏著糊於矽基板上塗佈成厚度200μm、直徑 2mm大小之圓狀，照射1000mJ/cm2紫外線使其B階段化，而得到試驗片。之後，將試驗片投入烤箱，以昇溫速度4℃/分鐘昇溫至170℃，其後直接使其硬化1小時。
將硬化後的試驗片上之晶粒黏著糊在顯微鏡進行觀察並測定直徑，算出從塗佈時之直徑的增加率，並藉由直徑的增加率，評價濕潤蔓延抑制。將結果示於表1。直徑的增加率未達5%時，濕潤蔓延抑制評價為非常良好，在表1中顯示為◎印。又，直徑的增加率為5%以上未達10%時，濕潤蔓延抑制評價為良好，在表1中顯示為○印。進而，直徑的增加率為10%以上時，濕潤蔓延抑制評價為不佳，在表1中顯示為×印。
<晶粒抗剪強度的評價>
晶粒抗剪強度係藉由以下之方法評價。
於一邊5mm正方形狀之PPF引線框架(於Cu基板上依Ni、Pd、Au順序實施3層鍍覆者)上，將晶粒黏著糊塗佈成一邊2mm之正方形狀(厚度80μm)，照射1000mJ/cm2紫外線使其B階段化。而且，使用晶粒接合器MD-P200(Panasonic股份有限公司製)，以溫度25℃、荷重10N、時間1秒的條件，將一邊2mm之正方形狀的矽晶片(厚度0.7mm)接著於晶粒黏著糊上。之後，於170℃之烤箱使其硬化1小時。
將如此進行所得者在溫度25℃之剪斷強度(N/晶片)，使用剪斷接著力試驗機Series4000(Dage公司製) 測定。將結果示於表1。剪斷強度之測定值為58.8N/晶片以上時，晶粒抗剪強度評價為良好，在表1中顯示為○印。又，剪斷強度之測定值未達58.8N/晶片時，晶粒抗剪強度評價為不佳，在表1中顯示為×印。
<B階段化物之複合黏度的評價>
將晶粒黏著糊之B階段化物的複合黏度藉由以下之方法評價。將晶粒黏著糊塗佈成厚度50μm，以1000mJ/cm2之條件照射紫外線使B階段化，將此使B階段化之晶粒黏著糊以抹刀刮取，成為樣品。將此樣品的複合黏度，使用黏彈性測定裝置之振動模式，以溫度25℃、頻率1Hz的條件測定。
複合黏度為100~1000Pa．s的範圍時，在表1表示為「A」。此情況下，晶粒黏著糊之B階段化進行良好，濕潤蔓延與晶粒抗剪強度皆為良好。又，複合黏度超過1000Pa．s時，在表1表示為「B」。此情況下，無加熱的接著變困難，晶粒黏著糊的濕潤蔓延雖良好，但成為晶粒抗剪強度不良的結果。進而，複合黏度未達100Pa．s時，在表1表示為「C」。此情況下，晶粒黏著糊之濕潤蔓延的抑制變困難。
<保存穩定性的評價>
將晶粒黏著糊的保存穩定性由以下之方法評價。將晶粒黏著糊在溫度25℃靜置3天。而且，將靜置初期及3 天後之晶粒黏著糊的剪斷黏度，使用黏彈性測定裝置的旋轉模式以溫度25℃、剪斷速度10s-1的條件測定。算出靜置3天後之剪斷黏度自靜置初期之剪斷黏度的增黏率，藉由此增黏率評價晶粒黏著糊的保存穩定性。將結果示於表1。
增黏率未達40%時，晶粒黏著糊的保存穩定性評價為非常良好，在表1中顯示為◎印。又，增黏率為40%以上未達100%時，保存穩定性評價為良好，在表1中顯示為○印。進而，增黏率為100%以上以上時，晶粒黏著糊的保存穩定性評價為不佳，在表1中顯示為×印。
由表1，判斷含有光聚合起始劑與熱自由基產生劑與含有聚烯烴構造之樹脂與自由基聚合性化合物的晶粒黏著糊之實施例1~4係抑制濕潤蔓延，且具有高度晶粒抗剪強度。又，使用醯基膦氧化物系光聚合起始劑(DAROCUR TPO)之實施例1，係較使用烷基苯酮系光聚合起始劑(Irgacure(註冊商標)369)之實施例2~4保存穩定性更佳。
另外，判斷未含有熱自由基產生劑之晶粒黏著糊之比較例1~2，以25℃進行晶粒結著時，由於未接合於支持構件，故晶粒抗剪強度不良。又，判斷未含有含有聚烯烴構造之樹脂的晶粒黏著糊之比較例3，晶粒抗剪強度亦不良。亦即，判斷含有光聚合起始劑與熱自由基產生劑與含有聚烯烴構造之樹脂與自由基聚合性化合物的晶粒黏著糊，與以往的晶粒黏著糊相比較，藉由B階段化可抑制濕 潤蔓延，又具有高度晶粒抗剪強度。
進而，比較例4之晶粒黏著糊，除了取代含有聚烯烴構造之樹脂，將四氫酞酐(Tetrahydrophthalic anhydride)(DIC股份有限公司製B-570H)以酸酐構造成為相同莫耳量的摻合量而使用的點之外，其他為與實施例1相同者。四氫酞酐雖具有與實施例1之含有聚烯烴構造之樹脂之馬來酸酐改質聚丁二烯相同的酸酐構造，但由於未含有聚烯烴構造，晶粒抗剪強度不夠充分。
進而，比較例5之晶粒黏著糊，雖除了未摻合含有聚烯烴構造之樹脂的點之外，其他係與實施例1相同者，但由於未含有含有聚烯烴構造之樹脂，晶粒抗剪強度不夠充分。
[產業上之可利用性]
根據本發明之半導體封裝之製造方法，由於可維持半導體用晶粒黏著糊之塗佈性同時由B階段化可抑制塗佈後之濕潤蔓延，可製造高積體之多晶粒封裝。又，由於晶粒結著時即使不加熱，亦可得到充分之接著性，可製造不需熱壓著，信賴性高之半導體封裝。因此藉由本發明之半導體封裝之製造方法所製造之半導體封裝，係有用於各種裝置。

Claims (11)

  1. 一種半導體封裝之製造方法，其係包含接合晶粒與支持該晶粒之支持構件的晶粒結著步驟之半導體封裝之製造方法，其特徵為前述晶粒結著步驟係將包含光聚合起始劑(1)、熱自由基產生劑(2)、含有聚烯烴構造之樹脂(3)、及自由基聚合性化合物(4)之半導體用晶粒黏著糊塗佈於前述晶粒及前述支持構件之一者，於被塗佈之前述半導體用晶粒黏著糊照射光，進行B階段化後，於被B階段化之前述半導體用晶粒黏著糊上配置前述晶粒及前述支持構件之另一者進行壓著，接合前述晶粒與前述支持構件的步驟。
  2. 如請求項1之半導體封裝之製造方法，其中，前述自由基聚合性化合物(4)為含(甲基)丙烯醯基之化合物。
  3. 如請求項2之半導體封裝之製造方法，其中，前述含(甲基)丙烯醯基之化合物的至少一部分為將(甲基)丙烯醯基與環氧乙烷環構造或環氧丙烷環構造的雙方含有於同一分子內之含(甲基)丙烯醯基之化合物。
  4. 如請求項1~3中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)係烷基苯酮系光聚合起始劑及醯基膦氧化物系光聚合起始劑中之至少一種。
  5. 如請求項1~3中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)係α-胺基烷基苯酮系光聚合起始劑及單醯基膦氧化物系光聚合起始劑中之至少一種。
  6. 如請求項1~3中任一項之半導體封裝之製造方法，其中，前述光聚合起始劑(1)為下述式(1)所表示之化合物及下述式(2)所表示之化合物中之至少一種；惟，下述式(1)中之R1為氫原子或碳數1~3之烷基；
  7. 如請求項1~6中任一項之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為有機過氧化物。
  8. 如請求項7之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為二烷基過氧化物或過氧化酯。
  9. 如請求項7之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)為下述式(3)所表示之化合物；惟，下述式(3)中之R2及R3為碳數1~3之伸烷基；
  10. 如請求項7~9中任一項之半導體封裝之製造方法，其中，前述熱自由基產生劑(2)之1分鐘半衰期溫度為120℃以上且200℃以下。
  11. 如請求項1~10中任一項之半導體封裝之製造方法，其中，在前述B階段化之前述光的照射量，係經B階段化之前述半導體用晶粒黏著糊的以溫度25℃、頻率1Hz的條件所測定之複合黏度成為100~1000Pa．s之範圍的量。
TW104103750A 2014-02-12 2015-02-04 半導體封裝的製造方法 TW201542730A (zh)

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