TW201834089A - 半導體裝置之製造方法 - Google Patents

半導體裝置之製造方法 Download PDF

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Publication number
TW201834089A
TW201834089A TW106145686A TW106145686A TW201834089A TW 201834089 A TW201834089 A TW 201834089A TW 106145686 A TW106145686 A TW 106145686A TW 106145686 A TW106145686 A TW 106145686A TW 201834089 A TW201834089 A TW 201834089A
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Taiwan
Prior art keywords
fine particles
silver fine
resin composition
silver
semiconductor element
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TW106145686A
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English (en)
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TWI655693B (zh
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藤原正和
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日商京瓷股份有限公司
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
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Abstract

本發明之半導體裝置之製造方法具有如下步驟：塗佈步驟，其將含有熱硬化性樹脂、及於表面具有有機化合物之保護層且平均粒徑為10～200 nm之銀微粒子的接著用樹脂組合物塗佈於半導體元件支持構件上；半燒結步驟，其以低於熱硬化性樹脂之反應起始溫度且50℃以上之溫度，以銀微粒子成為半燒結狀態之方式加熱塗佈之接著用樹脂組合物；及接合步驟，其將半導體元件載置於含有半燒結狀態之銀微粒子之接著用樹脂組合物上，且於無加壓狀態下，以高於熱硬化性樹脂之反應起始溫度之溫度進行加熱，而將半導體元件接合於半導體支持構件上。

Description

半導體裝置之製造方法
本發明之一態樣係關於一種於半導體裝置之製造時，能夠對支持構件與半導體元件之接合部賦予優異之導熱性及導電性的半導體裝置之製造方法。
伴隨半導體製品之大電容化、高速處理化及微細配線化，半導體製品作動中所產生之熱逐漸變得顯著，自半導體製品散熱、即所謂之熱管理越發受到關注。 因此，一般採用有於半導體製品安裝散熱片、散熱器等散熱構件之方法等，期待將半導體元件與散熱構件接著之接著材料本身亦為導熱率較高者。 進而，由於對環境之意識之提高，電力用半導體裝置不僅用於一般產業用途、電氣化鐵路用途，亦廣泛用於車載用途。尤其是車載用零件由於容許尺寸有限，故而將各零件縮小、變輕與車輛之性能直接關聯，故而對於電力用半導體裝置而言，尺寸之縮小化亦受到關注。 此種半導體裝置例如係於DBC(Direct Bonded Copper，直接覆銅(註冊商標))基板之晶片座上經由耐熱性較高之高鉛焊料而安裝電力用半導體元件。然而，含有鉛之有害物質之使用受到限制，從而要求無鉛化。 因此，研究有將奈米級之銀填料作為高鉛焊料以外之高耐熱之無鉛接合材料以熔點以下之溫度進行接合的使用燒結型之銀漿之接合方法。燒結型之銀漿為高導熱，對處理大電流之電力用半導體元件之接合有效。 然而，由於高鉛漿料及焙燒型銀漿會形成填角及產生向元件上表面電極之爬升(kerf creep)等，故而其會成為封裝尺寸之縮小化之妨礙因素之一。因此，提出一種例如利用多孔金屬膜之半導體元件與DBC基板之接合方法(參照專利文獻1)。 進而，於專利文獻2中亦揭示一種半導體裝置之製造方法，其於使含有錫銅合金粒子及錫鉍合金粒子之熔結晶粒接合材料進行B-階段化之後，搭載半導體元件而進行後續硬化。 [先前技術文獻] [專利文獻] [專利文獻1]美國專利申請公開第2013/0256894號說明書 [專利文獻2]美國專利申請公開第2014/0131898號說明書
[發明所欲解決之問題] 然而，於專利文獻1所記載之方法中，有存在於接合層之空隙對導熱性及可靠性產生不良影響之可能性變高之情況。 進而，專利文獻2所記載之熔結晶粒接合材料由於製成半燒結狀態而使用，故而導熱性優異，但由於使用焊料化合物，故而有高溫放置特性降低之虞。 因此，本發明之一態樣提供一種半導體裝置之製造方法，其係為了解決上述課題而成者，能夠發揮優異之導熱性及導電性，且能夠實現半導體元件與半導體元件支持構件之高密度接合。 [解決問題之技術手段] 於使用含有於表面具有包含有機化合物之保護層之銀微粒子及熱硬化性樹脂的接著用樹脂組合物接合半導體元件之情形時，發現，藉由進行使附著於銀微粒子之表面之保護層之一部分分解，且使銀微粒子成為半燒結狀態的加熱處理，能夠使接合部分之導熱性及導電性良好。 即，本發明之一態樣之半導體裝置之製造方法至少包括下述步驟。 (1)第一步驟為塗佈步驟，其將含有熱硬化性樹脂、及於表面具有有機化合物之保護層且平均粒徑為10～200 nm之銀微粒子的接著用樹脂組合物塗佈於半導體元件支持構件上。 (2)第二步驟為半燒結步驟，其以低於上述熱硬化性樹脂之反應起始溫度且50℃以上之溫度，以上述銀微粒子成為半燒結狀態之方式加熱上述塗佈之接著用樹脂組合物。 (3)第三步驟為接合步驟，其將半導體元件載置於含有上述半燒結狀態之銀微粒子之接著用樹脂組合物上，且於無加壓狀態下，以高於上述熱硬化性樹脂之反應起始溫度之溫度進行加熱，而將上述半導體元件接合於上述半導體元件支持構件上。 [發明之效果] 根據本發明之一態樣之半導體裝置之製造方法，藉由使用含有特定之銀微粒子之接著用樹脂組合物，且預先使含有之銀微粒子成為半燒結狀態，其後，能夠於無加壓下將半導體元件與半導體元件支持構件接合。 又，以此種方式接合半導體元件之接著用樹脂組合物之硬化物即便未形成填角，亦能夠表現出良好之接著力。藉此，能夠將半導體元件穩定地接合，並且亦能夠實現小型化，而能夠製造高密度安裝型之半導體裝置。
本發明之一態樣之半導體裝置之製造方法係藉由實施上述各步驟而進行者。以下，對於本發明之一態樣一面參照一實施形態之半導體裝置之製造方法一面進行說明。 [半導體裝置之製造方法] 本實施形態之半導體裝置之製造方法如上所述，係具有特定之塗佈步驟、半燒結步驟及接合步驟而構成。以下，一面參照圖式一面對該等各步驟進行詳細說明。圖1係用於說明該半導體裝置之製造方法之圖。 (塗佈步驟) 於第一步驟(塗佈步驟)中，將特定之接著用樹脂組合物塗佈於半導體元件支持構件上。藉由該塗佈，接著用樹脂組合物之塗膜12形成於半導體元件支持構件11上(圖1(a))。該塗膜12係根據要製造之半導體裝置之構成而形成於半導體元件之配置部位，可形成於任意之部位。 此處，作為所形成之塗膜12，其厚度亦可為10 μm～120 μm。藉由以成為該範圍之厚度之方式進行塗佈，半導體元件之接著性及半導體裝置之可靠性變良好。 又，該塗佈步驟只要為先前公知之塗佈方法，則能夠無任何限制地進行。作為此處所使用之塗佈方法，例如可列舉：網版印刷、輥塗印刷、噴霧方式、棒式塗佈法、噴墨法、分注器法、戳印法、轉印法等方法。 以下，對此處所使用之半導體元件支持構件及半導體元件接著用樹脂組合物進行說明。 ＜半導體元件支持構件＞ 作為本實施形態中所使用之半導體元件支持構件，只要為能夠穩定地搭載半導體元件之構件，則能夠並無特別限定地使用。作為該半導體元件支持構件，例如可列舉：42合金引線框架、銅引線框架等引線框架；聚醯亞胺樹脂、環氧樹脂、聚醯亞胺系樹脂等塑膠膜；將包含聚醯亞胺樹脂、環氧樹脂、聚醯亞胺系樹脂等之樹脂組合物含浸於玻璃不織布等基材並使其硬化而成者(預浸體)；氧化鋁等陶瓷製之支持構件等。 ＜接著用樹脂組合物＞ 本實施形態中所使用之接著用樹脂組合物係含有熱硬化性樹脂及特定之銀微粒子而成者。該接著用樹脂組合物藉由加熱而使銀微粒子成為半燒結狀態。進而，係由不使接著用樹脂組合物之硬化進行之組合構成者。 此處所使用之熱硬化性樹脂只要為用於半導體元件之接著用途之熱硬化性樹脂即可，可使用公知之熱硬化性樹脂。作為該熱硬化性樹脂，例如可列舉：丙烯酸系樹脂、氰酸酯樹脂、環氧樹脂、馬來醯亞胺樹脂等。 又，此處所使用之銀微粒子只要為於表面具有有機化合物之保護層(被膜層)者即可。其形狀並無特別限定，例如可示例：板型、薄片狀、鱗片狀、樹枝狀、桿狀、線狀、球狀等。該銀微粒子之平均粒徑為10～200 nm之範圍。球狀粒子以外之平均粒徑係指短邊(短徑或厚度)之平均直徑。 若設為此種形態，則由於能夠使所含有之銀微粒子彼此之金屬面不直接接觸，故而不會形成銀微粒子凝集而成之塊，而能夠於使銀微粒子各自分散之狀態下保持。即，只要於板型、薄片狀、鱗片狀中其厚度滿足上述範圍，又，於樹枝狀、桿狀、線狀中垂直於其長軸之截面直徑中之最短直徑滿足上述範圍即可。 再者，該平均粒徑係利用穿透式電子顯微鏡(TEM)或掃描式電子顯微鏡(SEM)，對隨機地抽選之100個左右之試樣之粒徑藉由算術平均進行測定。滿足上述範圍之大小之銀微粒子能夠藉由150～250℃左右之加熱而進行自燒結，從而能夠使導熱性及導電性變良好。 又，成為保護層之有機化合物只要能夠藉由加熱進行分解、去除，使銀微粒子之半燒結狀態處於適當之狀態(Appropriately)即可。進而，成為保護層之有機化合物亦可作為相對較薄之膜而設置於銀微粒子之表面。進而，亦可以銀微粒子分散於有機化合物中之狀態相對較厚地設置保護層。 作為此處所使用之有機化合物，例如可列舉分子量20000以下之具有氮、碳、氧作為構成要素之有機化合物。於將亦包含該有機化合物在內之銀微粒子設為100質量%時，具有該有機化合物之銀微粒子中所包含之有機化合物可為0.1～2.5質量%。即，該有機化合物於後述之半燒結步驟之前，控制銀微粒子之燒結。藉由利用半燒結步驟使該有機化合物分解、去除，能夠實現銀微粒子之燒結。 (半燒結步驟) 於第二步驟(半燒結步驟)中，藉由對塗佈於半導體元件支持構件11上之接著用樹脂組合物(塗膜12)進行加熱，而使接著用樹脂組合物中之銀微粒子成為半燒結狀態，從而製成接著用樹脂組合物12s(圖1(b))。 接著用樹脂組合物藉由以此種方式使銀微粒子處於半燒結狀態，能夠使於後述之接合步驟中硬化而獲得之硬化物之導熱性、導電性變良好。 於該半燒結步驟中，不使接著用樹脂組合物之硬化進行。為了設為此種狀態，於該半燒結步驟中，以低於所使用之熱硬化性樹脂之反應起始溫度且50℃以上之溫度進行加熱。加熱能夠使用加熱器等公知之加熱機構而進行，但就加熱條件略微溫和而言，亦可如圖1所示般藉由準備加熱板30並於其上進行加熱而進行(圖1(b))。 該半燒結步驟中之加熱溫度係以低於銀微粒子之自燒結溫度之溫度進行，例如，可為50～150℃，進而可為60～100℃，亦可為60～80℃。半燒結步驟之加熱時間以成為所需之半燒結狀態之方式而適當設定。再者，該加熱時間就作業效率之觀點而言，亦可設為30分鐘以下。 再者，於本說明書中，所謂銀微粒子之半燒結狀態，係作為存在於銀微粒子之表面之保護層的有機化合物中之一部分保護層分解而被去除，而使銀微粒子彼此、或銀微粒子與其他金屬粒子融合(部分燒結)的狀態。於該狀態下，燒結並未完結。係指藉由加熱能夠進一步進行燒結之狀態。 銀微粒子之半燒結狀態由於與覆蓋銀微粒子之表面之保護層之質量%處於良好之相關關係，故而能夠藉由控制保護層之質量%而進行管理。具體而言，若銀微粒子之由有機物所形成之保護層為0.1～2.5質量%，則能夠維持良好之半燒結狀態。 此處，半燒結狀態以半燒結程度而言可為1%以上且未達50%，亦可未達25%。若未達1%，則有形成填角及發生向元件上表面電極爬升(kerf creep)等之虞，故而不適於高密度接合，若燒結進行至50%以上，則有樹脂組合物之活性降低之虞。 於本實施形態中，半燒結狀態係根據銀微粒子表面之由有機化合物所形成之保護層之種類、量等、形成於半導體元件支持構件上之接著用樹脂組合物(塗膜)之種類、接合之加熱條件等而決定。 此處，所謂半燒結程度，係根據加熱後之銀微粒子之SEM圖像，以鄰接之粒子彼此鍵結之個數之比率獲得。具體而言，能夠藉由自30,000倍至100,000倍之SEM圖像中任意地抽選100個銀微粒子，對於該100個粒子中鄰接之粒子彼此融合(部分燒結)之個數進行計數並求出燒結粒子之比率而進行評價。 (接合步驟) 於第三步驟(接合步驟)中，將半導體元件13載置於含有第二步驟(半燒結步驟)中形成之半燒結狀態之銀微粒子的接著用樹脂組合物上(圖1(c-1))，進而進行加熱，藉此，使接著用樹脂組合物硬化。如此，半導體元件13經由接著用樹脂組合物之硬化物21而接合於半導體元件支持構件11上(圖1(c-2))。 該接合步驟中之加熱係以高於樹脂組合物之反應起始溫度之溫度進行。藉由以此種溫度進行加熱，能夠進一步進行樹脂之硬化。又，於進行該加熱時，銀微粒子之燒結進一步進行，硬化物之導電性及導熱性變良好。再者，於該接合步驟中，即便於無加壓狀態下亦能夠使上述接合成為充分之接合，而獲得穩定且可靠性較高之半導體裝置。 該接合步驟中之加熱溫度例如可為150～300℃，進而亦可為200～250℃。接合步驟之加熱時間以半導體元件穩定地接合之方式而適當設定。 再者，該接合步驟中之加熱只要不影響安裝組裝步驟，則亦可與用於密封半導體元件之密封材料之後續硬化步驟一併實施。 藉由本實施形態之半導體裝置之製造方法，能夠獲得具有導熱性及導電性優異之接合部的半導體裝置。此處所製造之半導體裝置可列舉與公知之半導體裝置相同構造者。作為代表性之半導體裝置，例如係具有於支持基板上形成有特定之配線之半導體元件搭載用基板、黏晶層、半導體元件、將上述配線與半導體元件之端子連接之導線、至少密封導線連接部之密封材料而構成。 又，作為本實施形態之半導體裝置之製造方法所使用之接著用樹脂組合物，可使用上述所說明者，亦可為以下所記載之接著用樹脂組合物。 作為該接著用樹脂組合物，具體而言，可列舉含有(A)具有羥基之(甲基)丙烯酸酯化合物或(甲基)丙烯醯胺化合物、(B)自由基起始劑、(C)銀微粒子、(D)銀粉、(E)溶劑而成之接著用樹脂組合物。以下，對該等各成分進行詳細說明。 此處所使用之(A)成分之具有羥基之(甲基)丙烯酸酯化合物或(甲基)丙烯醯胺化合物係分別於1個分子中具有1個以上之(甲基)丙烯醯基的(甲基)丙烯酸酯或(甲基)丙烯醯胺，且含有羥基。 具有羥基之(甲基)丙烯酸酯能夠藉由使多元醇化合物與(甲基)丙烯酸及其衍生物進行反應而獲得。該反應可使用公知反應，通常使用相對於多元醇化合物為0.5～5倍莫耳之丙烯酸酯或丙烯酸。 又，具有羥基之(甲基)丙烯醯胺可藉由使具有羥基之胺化合物與(甲基)丙烯酸及其衍生物進行反應而獲得。作為使(甲基)丙烯酸酯與胺化合物進行反應而製造(甲基)丙烯醯胺類之方法，由於(甲基)丙烯酸酯之雙鍵極其富有反應性，故而通常預先於雙鍵上加成胺、環戊二烯、醇等作為保護基，並於醯胺化結束後進行加熱，使保護基脫離而製造。藉由如此含有羥基，而促進由還原作用而得之燒結性，並且提高接著性。 又，此處所述之羥基係脂肪族烴基之氫原子經取代之醇性之基。該羥基之含量可於1個分子中為1至50個，若羥基之含量處於該範圍，則無由硬化過多而引起之燒結性之妨礙。 作為具有此種羥基之丙烯酸系樹脂化合物，例如可列舉下述通式(I)～(IV)所表示之化合物。 [化1](式中，R1 表示氫原子或甲基，R2 表示碳數1～100之2價之脂肪族烴基或具有環狀結構之脂肪族烴基) [化2](式中，R1 及R2 分別表示與上述相同者) [化3](式中，R1 表示與上述相同者，n表示1～50之整數) [化4](式中，R1 及n分別表示與上述相同者) 作為該(甲基)丙烯酸酯或(甲基)丙烯醯胺，可將上述化合物單獨使用或將2種以上組合使用。再者，通式(I)及(II)中之R2 之碳數可為1～100，進而亦可為1～36。若R2 之碳數處於此種範圍，則無由硬化過多而引起之燒結性之妨礙。 作為此處所使用之(B)成分之自由基起始劑，可使用通常用於自由基聚合之觸媒，並無特別限定。例如，急速加熱試驗(於將1 g試樣置於電熱板之上，且以4℃/分鐘進行升溫時之分解起始溫度之測定試驗)中之分解溫度可為100～190℃。若該分解溫度未達100℃，則由於銀微粒子之半燒結狀態與熱硬化性樹脂之半硬化狀態並列地進行，而變得難以控制半導體元件接合狀態，若超過190℃，則熱硬化性樹脂之硬化時間可能會變得極長。再者，此處分解起始溫度係設為相對於試樣之加熱前之質量減少1%質量時之溫度。 作為分解起始溫度滿足上述條件之自由基起始劑，例如可列舉1,1-雙(第三丁基過氧基)-2-甲基環己烷、過氧化新癸酸第三丁酯、過氧化二異丙苯等。 該(B)成分之自由基起始劑可單獨使用，或為了控制硬化性而將2種以上混合使用。進而，為了提高晶粒接合漿料之保存性，亦可預先添加各種聚合抑制劑。 該(B)成分之自由基起始劑之調配量相對於(A)成分100質量份可為0.1～10質量份。若超過10質量份，則晶粒接合漿料之黏度之經時變化有可能變大，若未達0.1質量份，則硬化性有可能顯著降低。 此處所使用之(C)成分之銀微粒子如上文所說明，於表面具有有機化合物之保護層(被膜層)。其平均粒徑為10～200 nm之範圍。作為設置於該(C)成分之銀微粒子之表面作為保護層之有機化合物，具體而言，可為包含胺基、羧基等官能基之有機化合物。 作為此處所使用之含有羧基之有機化合物，可列舉選自分子量為110～20000之有機羧酸中之1種以上之有機化合物，例如可列舉己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、十二烷酸、十四烷酸、二十烷酸、二十二烷酸、2-乙基己酸、油酸、亞麻油酸、次亞麻油酸、末端為二丙酸之聚環氧乙烷之類之羧酸。進而，作為上述有機化合物，亦可使用上述羧酸之羧酸衍生物。 又，作為此處所使用之含有胺基之有機化合物，可列舉烷基胺等，例如有：丁胺、甲氧基乙基胺、2-乙氧基乙基胺、己胺、辛胺、3-丁氧基丙基胺、壬胺、十二烷基胺、六-十二烷基胺、十八烷基胺、椰油胺、牛脂胺、氫氧化牛脂胺、油胺、月桂胺、及硬脂胺、3-胺基丙基三乙氧基矽烷等之類之一級胺，二椰油胺、二氫化牛脂胺、及二硬脂胺等之類之二級胺，以及十二烷基二甲基胺、二(十二烷基)單甲基胺、十四烷基二甲基胺、十八烷基二甲基胺、椰油二甲基胺、十二烷基十四烷基二甲基胺、及三辛胺等之類之三級胺，此外，有萘二胺、硬脂基丙二胺、辛二胺、壬二胺、末端為二胺之聚環氧乙烷、末端為三胺之聚環氧丙烷、末端為二胺之聚環氧丙烷等之類之二胺。 若附著於銀微粒子之表面之有機化合物之分子量大於20000，則不易發生有機化合物自銀微粒子表面之脫離，而可能難以獲得所需之半燒結狀態。因此，就該觀點而言，被覆表面之有機化合物之分子量可較小。又，分子量可為50以上，若分子量未達50，則有機化合物變得容易自金屬粒子表面脫離，而使粒子彼此容易凝集，故而亦可能會變得難以獲得所需之半燒結狀態。 若被覆或分散(C)成分之銀微粒子之有機化合物處於上述範圍，則相較於(C)成分之銀微粒子彼此之凝集，與(D)成分之銀粉之部分燒結更為進展，故而獲得穩定之半燒結狀態。 該(C)成分之銀微粒子之由有機物所形成之保護層可為0.1～2.5質量%。若該保護層少於0.1質量%，則凝集之控制變得不充分，而使樹脂組合物內之燒結優先進行，因此有接著力降低或因黏度上升而形成孔隙之虞，若保護層多於2.5質量%，則有因在焙燒後之硬化物內殘存上述有機化合物而導致產生孔隙之虞，可能會引起導電性之降低。 又，(C)成分之銀微粒子之形狀亦如上所述，並無特別限定，其中，其形狀可包含選自(C1)板型銀微粒子及(C2)球狀銀微粒子中之至少1種之銀微粒子。 此處所使用之(C1)成分之板型銀微粒子與球狀之奈米粒子不同，係使一個金屬結晶面大幅度生長而獲得之厚度均勻的板狀之薄片狀粒子，可列舉能夠調配至樹脂組合物之公知之板型銀微粒子。通常，大小為微米級且厚度為數奈米左右，且具有三角形板狀、六角形板狀、切頂三角形板狀等形狀。又，其上表面亦可被[111]面廣泛覆蓋。 藉由使樹脂組合物含有(C1)成分之板型銀微粒子，導熱率高於僅填充通常之銀粉者。又，由於主要於厚度方向進行燒結，故而與使用球狀之銀奈米微粒子者相比，內部應力較小。又，藉由使銀微粒子進行高配向而成為反射率優異之接合材料。進而，該(C1)成分之板型銀微粒子與通常之銀微粒子(銀奈米粒子)不同，不易受到氧之有無之影響，故而能夠進行在氮等惰性氣體氛圍下之燒結。 該(C1)成分之板型銀微粒子可中心粒徑為0.3～15 μm。藉由使板型銀微粒子之中心粒徑處於該範圍，能夠提高向樹脂成分之分散性。進而，藉由使板型銀微粒子之中心粒徑處於該範圍，能夠控制噴嘴之堵塞、半導體元件之組裝時之晶片之變形等。此處，所謂中心粒徑係指利用雷射繞射式粒度分佈測定裝置進行測定而獲得之體積基準之粒度分佈曲線中的50%累計值(50%粒徑)。即，該中心粒徑與上述短邊之平均粒徑之不同之處在於，亦一併考慮長邊而算出。 又，厚度亦可為10～200 nm。該厚度係藉由對利用穿透式電子顯微鏡(TEM)或掃描式電子顯微鏡(SEM)而取得之觀察圖像進行資料處理而測得者。該平均厚度係如下所述以個數平均厚度算出。 將根據板型銀微粒子之[n＋1]個(n＋1例如為50至100左右)觀察圖像測得之厚度從厚至薄依序排列，且對其範圍(最大厚度：x1 、最小厚度：xn ＋ 1 )進行n分割，並將各厚度之區間設為[xj 、xj ＋ 1 ](j＝1，2，……，n)。此情形時之分割成為對數刻度上之均等分割。又，基於對數刻度，將各厚度區間中之代表厚度以下述式進行表示。 [數1]進而，將rj (j＝1，2，……，n)設為與區間[xj 、xj ＋ 1 ]對應之相對量(差分%)，若將整個區間之合計設為100%，則對數刻度上之平均值μ能夠根據下述式進行計算。 [數2]該μ為對數刻度上之數值，不具有作為厚度之單位，因此，為了恢復厚度之單位，計算10μ 即10之μ次方。將該10μ 設為個數平均厚度。 又，與厚度方向垂直之方向之長邊可為厚度之8～150倍之範圍內，亦可為10～50倍。進而，與厚度方向垂直之方向之短邊可為厚度之1～100倍之範圍內，亦可為3～50倍。 該(C1)成分之板型銀微粒子能夠以100～250℃進行自燒結。藉由如此含有以100～250℃進行自燒結之銀微粒子，於熱硬化時銀微粒子之流動性提高，其結果為，銀微粒子彼此之接點變得更多，並且接點之面積變大，導電性顯著提高。因此，板型銀微粒子之燒結溫度可為100～200℃。再者，此處所謂能夠自燒結係指即便不施加加壓或不添加添加劑等，亦藉由在低於熔點之溫度下之加熱而燒結。 進而，(C1)成分之板型銀微粒子可為單晶。藉由設為單晶，能夠確保低溫硬化中之導電性。 (C1)成分之板型銀微粒子於塗佈膜中向水平方向配向，具有更多之接點，從而能夠提高導電性。其原因在於，由於藉由在熱硬化時因晶片之自重而產生之壓縮、樹脂組合物之揮發成分之減少、硬化收縮等而使體積收縮的體積排除，於塗佈膜中以厚度方向積層之方式自然配向，而能夠較大程度地確保銀微粒子彼此之接點。 此處所使用之(C2)成分之球狀銀微粒子之粒徑為10～200 nm。再者，該粒徑係藉由對利用穿透式電子顯微鏡(TEM)或掃描式電子顯微鏡(SEM)取得之觀察圖像進行資料處理而測得者。進而，(C2)成分之球狀銀微粒子之平均粒徑亦可為上述範圍內。該平均粒徑係以自球狀銀微粒子之50個至100個觀察圖像中測得之粒徑之個數平均粒徑算出。該個數平均粒徑只要以與上述平均厚度之算出相同之方式算出平均值即可。 此處所使用之(D)成分之銀粉係平均粒徑超過0.25 μm且為30 μm以下之銀粉，通常，只要係作為用於賦予導電性而添加於樹脂接著劑中之無機填充材料的銀粉即可。藉由除上述(C)成分之銀微粒子以外，添加如該(D)成分之銀粉般之微米級之銀粒子，能夠進一步提高半導體元件與支持構件之接合強度。又，作為此處所使用之銀粒子之形狀，例如可列舉：薄片狀、鱗片狀、樹枝狀、桿狀、線狀、球狀、板狀等者。再者，該平均粒徑係藉由雷射繞射法而算出者。 此處，(C)成分之銀微粒子與(D)成分之銀粉如上所述，於將該等之合計量設為100質量份時，以上述(A)成分成為1～20質量份之方式進行調配。若(A)成分未達1質量份，則由於銀成分過多，故而可能黏度過高而變得難以處理，若超過20質量份，則由於銀成分之比率降低，故而可能無法充分確保高導熱性而降低散熱性。 再者，該等(C)成分與(D)成分之比率於將該等之合計量設為100質量份時，(C)成分：(D)成分之質量比可為10：90～90：10。若(C)成分相對於(D)成分過少，則難以確保高導熱性，若(C)成分過多，則與非金屬體之接著力可能會變差。 此處所使用之(E)成分之溶劑只要係發揮作為還原劑之功能之溶劑，則可使用公知之溶劑。作為該溶劑，可為醇，例如可列舉脂肪族多元醇。作為脂肪族多元醇，例如可列舉：乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、甘油、聚乙二醇等二醇類等。該等溶劑可單獨使用或將兩種以上組合使用。 發揮作為還原劑之功能之醇溶劑藉由漿料硬化(燒結)時之熱處理而成為高溫，藉此增大醇之還原力。藉此，(C)成分之銀微粒子及(D)成分之銀粉中存在之一部分之氧化銀及金屬基板上之氧化金屬(例如，氧化銅)被醇還原，而成為純粹之金屬。其結果為，認為能夠形成更緻密、導電性更高、且與基板之密接性更高之硬化膜。又，藉由被半導體元件與金屬基板所夾持，而於漿料硬化時之熱處理中，一部分醇成為回流狀態，作為溶劑之醇不會因揮發而自系統中消失，氧化金屬以沸點以上之漿料硬化溫度更有效率地被還原。 該溶劑之沸點具體而言，可為100～300℃，亦可為150～290℃。若沸點未達100℃，則即便於常溫下揮發性亦變高，故而容易因分散介質之揮發而產生還原能力之降低，可能會無法獲得穩定之接著強度。又，若沸點超過300℃，則不易產生導電膜之燒結，可能會缺乏緻密性，溶劑不揮發而殘存於膜中。 該(E)成分之溶劑之調配量於將(C)成分與(D)成分之合計量設為100質量份時，可為7～20質量份。若未達7質量份，則有黏度變高，作業性降低之虞，若超過20質量份，則有黏度變低，漿料中之銀下沈及可靠性降低之虞。 於此處所示之接著用樹脂組合物中，除以上之各成分以外，於不妨礙本發明之內容之範圍內，可視需要調配通常向此種組合物中調配之硬化促進劑、橡膠或矽酮等低應力化劑、偶合劑、消泡劑、界面活性劑、著色劑(顏料、染料)、及其他各種添加劑。該等各添加劑均可單獨使用1種，亦可將2種以上混合使用。 本實施形態之接著用樹脂組合物之調整可藉由如下方式而製備：首先將上述(A)成分至(E)成分、及視需要調配之偶合劑等添加劑等充分地混合。繼而，藉由分散機、捏合機、三輥磨機等對經混合之樹脂組合物進行混練處理。最後，將經混練之樹脂組合物消泡。 又，此時所獲得之樹脂組合物之黏度(25℃)可為5～300 Pa・s。半燒結狀態與黏度之變化率有相關關係，藉由對黏度之變化率進行管理，能夠對半燒結狀態進行管理。若黏度為5以上，則藉由利用印刷法之塗佈，容易控制供給至基板上之接著用樹脂組合物之塌邊等之產生而良好地保持印刷形狀。又，若黏度為300 Pa・s以下，則藉由利用印刷法進之塗佈，容易控制供給至基板上之接著用樹脂組合物之「缺損」、「擦痕」等之產生。 [實施例] [銀微粒子之製備] (合成例1) 將硝酸銀(關東化學股份有限公司製造，一級)203 g與草酸銨一水合物(關東化學股份有限公司製造，特級)82 g依序溶解於純水，於室溫下攪拌混合12小時，而獲得草酸銀180 g。將草酸銀238 mg(0.78 mmol)與正丁胺(關東化學股份有限公司製造)348 mg(3.12 mmol)混合，於室溫下攪拌1分鐘，而製備草酸銀-烷基胺錯合物。 若向其中加入6 mL之1-丁醇(關東化學股份有限公司製造)與0.141 mg之NaCl，並於100℃下加熱攪拌15分鐘，則完成伴隨CO2 之發泡之反應，且生成銀色之沈澱物。向其中加入甲醇(關東化學股份有限公司製造，一級)10 mL，將藉由離心分離所獲得之沈澱物自然乾燥，而獲得厚度20 nm、長徑100 nm左右之板型之銀微粒子1。 為了調查於合成例1中所獲得之銀微粒子粉體之保護分子之含有質量，進行熱重量示差熱同步分析(TG-DTA)。藉由自室溫加熱至250℃，可見到2階段之質量減少。又，若超過400～500℃，則質量減少停止，質量成為固定，此時之質量減少率之1.5質量%成為覆蓋銀微粒子之表面之有機保護分子之質量。 (合成例2) 除對銀色之沈澱物添加甲醇15 mL以外，藉由與合成例1相同之操作獲得銀微粒子2。此處所獲得之銀微粒子2與銀微粒子1大小及形狀相同。不同之處僅為覆蓋其表面之有機保護層達到1.2質量%。 (合成例3) 除對銀色之沈澱物添加甲醇20 mL以外，藉由與合成例1相同之操作獲得銀微粒子3。此處所獲得之銀微粒子3與銀微粒子1大小及形狀相同。不同之處僅為覆蓋其表面之有機保護層達到0.8質量%。 (合成例4) 除對銀色之沈澱物添加甲醇40 mL以外，藉由與合成例1相同之操作獲得銀微粒子4。此處所獲得之銀微粒子4與銀微粒子1大小及形狀相同。不同之處僅為覆蓋其表面之有機保護層達到0.05質量%。 (合成例5) 除對銀色之沈澱物添加甲醇5 mL以外，藉由與合成例1相同之操作獲得銀微粒子5。此處所獲得之銀微粒子5與銀微粒子1大小及形狀相同。不同之處僅為覆蓋其表面之有機保護層達到3質量%。 (實施例1～3、比較例1～4) 依據表1之組成而將各成分混合，藉由輥進行混練，而獲得樹脂組合物A～E。 使用所獲得之接著用之樹脂組合物A～E於以下之條件下進行處理，藉此製造半導體裝置，並分別進行評價。將其結果彙總示於表2。 再者，實施例及比較例中使用之材料除於上述合成例1～5中製備之銀微粒子以外，使用如下所述之市售品。 [(A)成分] 熱硬化性樹脂：羥基乙基丙烯醯胺(興人(股)製造，商品名：HEAA) [(B)成分] 聚合起始劑：過氧化二異丙苯(日本油脂(股)製造，商品名：Percumyl D，急速加熱試驗中之分解溫度：126℃) [(C)成分] (C1)板型銀微粒子 銀微粒子1(於合成例1中所獲得之板型銀微粒子；厚度20 nm，長徑100 nm，有機保護層 1.5質量%) 銀微粒子2(於合成例2中所獲得之板型銀微粒子；厚度20 nm，長徑100 nm，有機保護層 1.2質量%) 銀微粒子3(於合成例3中所獲得之板型銀微粒子；厚度20 nm，長徑100 nm，有機保護層 0.8質量%) 銀微粒子4(於合成例4中所獲得之板型銀微粒子；厚度20 nm，長徑100 nm，有機保護層 0.05質量%) 銀微粒子5(於合成例5中所獲得之板型銀微粒子；厚度20 nm，長徑100 nm，有機保護層 3質量%) (C2)球狀銀微粒子 銀微粒子6(Mitsuboshi Belting(股)製造，商品名：MDot；平均粒徑：50 nm，有機保護層 1.5質量%) [(D)成分] 銀粉(福田金屬箔工業(股)製造，商品名：AgC-212D；平均粒徑 5 μm) [(E)成分] 溶劑：二乙二醇(東京化成(股)製造) [表1] [表2] ＜評價方法＞ [黏度] 樹脂組合物之黏度係藉由東機產業(股)製造之E型黏度計，使用直徑19.4 mm、3°之圓錐，於25℃下測得(轉數0.5 min-1 )。 [外觀之評價程序] (1)將樹脂組合物以60 μm之厚度塗佈於PPF(Pre-plated frames，預電鍍框架，鍍覆有Ni-Pd/Au之銅框架)。 (2)將所塗佈之樹脂組合物於半燒結處理條件為40℃(比較例3)、70℃(實施例1～4、比較例1～2)、150℃(比較例4)之各溫度下加熱15分鐘。 (3)將6 mm×6 mm之矽晶片、及於接合面設有金蒸鍍層之背面金晶片安裝於PPF。 (4)將安裝有晶片之PPF於200℃之烘箱中加熱1小時而使其硬化，獲得半導體裝置。 (5)對所獲得之半導體裝置進行觀察，確認填角產生之有無、及向晶片側面爬升(kerf creep)之有無，並基於下述基準進行判定。 ○：無填角之產生及向晶片側面之爬升(kerf creep) ×：確認出填角之產生、或向晶片側面之爬升 [熱時接著強度之評價程序] (1)將樹脂組合物以60 μm之厚度塗佈於PPF(鍍覆有Ni-Pd/Au之銅框架)。 (2)將所塗佈之樹脂組合物於半燒結處理條件為40℃(比較例3)、70℃(實施例1～4、比較例1～2)、150℃(比較例4)之各溫度下加熱15分鐘。 (3)安裝6 mm×6 mm之矽晶片、及於接合面設有金蒸鍍層之背面金晶片。 (4)於200℃之烘箱中加熱1小時而使其硬化，獲得半導體裝置。 (5)對該半導體裝置進行吸濕處理(85℃，相對濕度85%，72小時)。 (6)利用安裝強度測定裝置，測定260℃下之熱時晶片剪切強度(切斷)。 [電阻之評價程序] (1)將樹脂組合物以10 mm×10 mm之面積、60 μm之厚度塗佈於玻璃基板(厚度1 mm)。 (2)將所塗佈之樹脂組合物於半燒結處理條件為40℃(比較例3)、70℃(實施例1～4、比較例1～2)、150℃(比較例4)之各溫度下加熱15分鐘。 (3)以200℃加熱60分鐘而使樹脂組合物硬化。 (4)使用MCP-T600(三菱化學股份有限公司製造，商品名)，藉由四端子法，對所獲得之硬化後之樹脂組合物測定體積電阻(Ω・cm)。 [導熱率之評價程序] (1)將樹脂組合物以1 mm之厚度塗佈於鐵氟龍(註冊商標)片材(厚度1 mm)。 (2)於半燒結處理條件為40℃(比較例3)、70℃(實施例1)之各溫度下加熱15分鐘。 (3)於200℃之烘箱中硬化1小時而製作試片。 (4)藉由雷射閃光法(測定方法：JIS R 1611-1997)測定試片之導熱率。 [耐封裝龜裂性] [耐IR(Infrared，紅外線)回焊性之評價程序] (1)將上述樹脂組合物以60 μm之厚度塗佈於PPF(鍍覆有Ni-Pd/Au之銅框架)。 (2)於半燒結處理條件為40℃(比較例3)、70℃(實施例1)之各溫度下加熱15分鐘。 (3)於無加壓下安裝6 mm×6 mm之矽晶片、及於接合面設有金蒸鍍層之背面金晶片。 (4)於200℃之烘箱中加熱1小時而使樹脂組合物硬化，獲得半導體裝置。 (5)使用Kyocera Chemical股份有限公司製造之環氧密封材料(商品名：KE-G3000D)，於下述條件下藉由樹脂密封成形半導體裝置。 (6)對所成形之半導體裝置以85℃、相對濕度85%、168小時進行吸濕處理。 (7)對吸濕後之半導體裝置進行IR回焊處理(260℃，10秒)。 (8)對5個樣品利用超音波顯微鏡觀察半導體裝置之內部龜裂產生之有無。 (9)對產生龜裂之樣品進行計數。 [耐冷熱衝擊性之評價程序] (1)使用與於上述IR回焊性中使用者相同之試片。 (2)進行冷熱循環處理(將自-55℃升溫至150℃，又，冷卻至-55℃之操作設為1個循環，進行1000個循環)。 (3)利用超音波顯微鏡對5個樣品觀察封裝之內部龜裂產生之有無。 (4)對產生龜裂之樣品進行計數。 [供試於耐IR回焊性、耐冷熱衝擊性之半導體裝置之製作條件] 封裝：80pQFP(14 mm×20 mm×2 mm厚) 晶片：矽晶片及背面鍍金晶片 引線框架：PPF及銅 密封材料之成形：175℃，2分鐘 後固化(Post Mold Cure)：175℃，8小時 根據本發明之一態樣之半導體裝置之製造方法(實施例1～3)，藉由使用含有特定之銀微粒子之接著用樹脂組合物，且預先使所含有之銀微粒子成為半燒結狀態，其後，能夠於無加壓下將半導體元件與半導體元件支持構件接合。 又，以此種方式將半導體元件接合之接著用樹脂組合物之硬化物即便未形成填角，亦能夠表現出良好之接著力。藉此，能夠將半導體元件穩定地接合，並且亦能夠實現小型化，而能夠製造高密度安裝型之半導體裝置。 如比較例1般使用含有在有機保護層較少之合成例4中獲得之銀微粒子4作為(C)成分的樹脂組合物D之情形時，由於保護層容易脫落，故而保存穩定性較差，而有於樹脂組合物內部過度進行燒結之傾向。因此，於在無加壓下進行接合之情形時，接著強度變低。 又，如比較例2般使用含有有機保護層較多之合成例5之銀微粒子5作為(C)成分的樹脂組合物E之情形時，由於銀微粒子之保護層難以脫落，故而難以進行燒結，而於在無加壓下進行接合之情形時，接著強度變低且體積電阻變高。 如比較例3般即便(C)成分之有機保護層為適當範圍內，但半燒結步驟之加熱溫度未達50℃之情形時，若於無加壓下進行接合，則樹脂組合物中之溶劑之揮發性較弱，故而容易產生孔隙。 如比較例4般即便(C)成分之有機保護層為適當範圍內，但半燒結步驟之加熱溫度高於反應起始溫度之情形時，由於在半燒結步驟中進行銀微粒子之燒結，故而無法獲得PPF與晶片之接合。
11‧‧‧半導體元件支持構件
12‧‧‧塗膜
12s‧‧‧接著用樹脂組合物
13‧‧‧半導體元件
21‧‧‧接著用樹脂組合物之硬化物
30‧‧‧加熱板
圖1(a)、(b)、(c-1)、(c-2)係用於說明本發明之一態樣之一實施形態之半導體裝置之製造方法的圖。

Claims (4)

  1. 一種半導體裝置之製造方法，其特徵在於至少包括下述(1)至(3)之步驟： (1)第一步驟為塗佈步驟，其將含有熱硬化性樹脂、及於表面具有有機化合物之保護層且平均粒徑為10～200 nm之銀微粒子的接著用樹脂組合物塗佈於半導體元件支持構件上； (2)第二步驟為半燒結步驟，其以低於上述熱硬化性樹脂之反應起始溫度且50℃以上之溫度，以上述銀微粒子成為半燒結狀態之方式加熱上述塗佈之接著用樹脂組合物；及 (3)第三步驟為接合步驟，其將半導體元件載置於含有上述半燒結狀態之銀微粒子之接著用樹脂組合物上，且於無加壓狀態下，以高於上述熱硬化性樹脂之反應起始溫度之溫度進行加熱，而將上述半導體元件接合於上述半導體元件支持構件上。
  2. 如請求項1之半導體裝置之製造方法，其中於將具有上述保護層之銀微粒子設為100質量%時，於上述銀微粒子中含有形成上述保護層之有機化合物0.1～2.5質量%。
  3. 如請求項1或2之半導體裝置之製造方法，其中上述接著用樹脂組合物以下述成分作為必需成分： (A)具有羥基之(甲基)丙烯酸酯化合物或(甲基)丙烯醯胺化合物、 (B)自由基起始劑、 (C)於表面具有由有機化合物所形成之保護層且平均粒徑為10～200 nm之銀微粒子、 (D)平均粒徑為0.25～30 μm之銀粉、及 (E)溶劑。
  4. 如請求項1至3中任一項之半導體裝置之製造方法，其中上述(B)自由基起始劑之分解溫度為100～180℃，且以60～80℃加熱上述接著用樹脂組合物。
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