TW202244104A - 非導電性助焊劑、連接構造體及連接構造體之製造方法 - Google Patents

非導電性助焊劑、連接構造體及連接構造體之製造方法 Download PDF

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TW202244104A
TW202244104A TW111102441A TW111102441A TW202244104A TW 202244104 A TW202244104 A TW 202244104A TW 111102441 A TW111102441 A TW 111102441A TW 111102441 A TW111102441 A TW 111102441A TW 202244104 A TW202244104 A TW 202244104A
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electrode
mentioned
conductive flux
flux
conductive
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TW111102441A
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保井秀文
松下清人
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日商積水化學工業股份有限公司
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Publication of TW202244104A publication Critical patent/TW202244104A/zh

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Abstract

本發明提供一種可提高所獲得之連接構造體之生產性及耐衝擊性，且抑制焊料溢料之發生之非導電性助焊劑。 本發明之非導電性助焊劑包含環氧化合物、酸酐硬化劑、及有機磷化合物。

Description

非導電性助焊劑、連接構造體及連接構造體之製造方法
本發明係關於一種非導電性助焊劑。又，本發明係關於一種使用上述非導電性助焊劑之連接構造體及連接構造體之製造方法。
近年來，伴隨資料伺服器、個人電腦(PC)及移動終端等電子機器之小型化、輕量化、及高功能化，不斷推進印刷配線板等中之配線之微間距化。因此，配線向晶片之正下方延伸之球柵陣列(BGA)或超小型晶片級封裝(CSP)等表面安裝型封裝引人注目。
然而，於BGA等表面安裝型封裝中，與先前之針插入型封裝不同，配線基板之表面之電極彼此係由焊球連接，因此存在接著性變低，於掉落時容易破損(耐衝擊性較低)之問題。
因此，有時於表面安裝型封裝與配線基板之間填充底部填充材後使其硬化，藉此補強接合部分。
下述專利文獻1中揭示有一種將半導體晶片覆晶安裝於一面而成之半導體封裝基板。該半導體封裝基板係從該半導體封裝基板之另一面側安裝於印刷配線板。上述半導體封裝基板具備芯基材、增層、及應力緩衝層。上述增層係交替地積層有配線圖案與絕緣樹脂層之多層配線層，增層之最上層係配線圖案。又，上述應力緩衝層配備於上述另一面側且位於增層之表面上。上述應力緩衝層具備第一應力緩衝層、及該第一應力緩和層上之第二應力緩衝層，上述第一應力緩衝層及上述第二應力緩衝層分別具備通孔及配線圖案。在將半導體晶片安裝於上述半導體封裝基板之一面上之後，於半導體晶片與半導體封裝基板之間封入底部填充材。 [先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2018-186121號公報
[發明所欲解決之問題]
於如專利文獻1般使用底部填充材作為密封劑之情形時，可提高半導體晶片與半導體封裝基板之接著性，提高所獲得之連接構造體(半導體封裝)之耐衝擊性。
然而，於連接構造體之生產步驟中，為了連接電極彼此而進行回焊步驟後，需要再次進行回焊步驟，該回焊步驟之目的在於使底部填充材利用毛細管現象滲透並填充於半導體晶片與半導體封裝基板之間，以使底部填充材硬化。即，於先前之使用底部填充材之連接構造體之製造方法中，需要進行2次回焊步驟，因此存在生產性較低之問題。進而，於先前之使用底部填充材之連接構造體中，在第2次回焊步驟時，由於連接了電極彼此之焊料會熔融，故有時會發生焊料破壞底部填充材與零件(或基板)之界面並不斷發展之現象(焊料溢料(solder flash))。當發生焊料溢料時，有時會發生短路或開路不良。
本發明之目的係提供一種可提高所獲得之連接構造體之生產性及耐衝擊性，且抑制焊料溢料之發生之非導電性助焊劑。又，本發明之目的係提供一種使用上述非導電性助焊劑之連接構造體及連接構造體之製造方法。 [解決問題之技術手段]
根據本發明之廣泛態樣，提供一種包含環氧化合物、酸酐硬化劑、及有機磷化合物之非導電性助焊劑。
於本發明之非導電性助焊劑之某一特定態樣中，25℃下之接著力為100000 N/m 2以上210000 N/m 2以下。
於本發明之非導電性助焊劑之某一特定態樣中，25℃下之黏度為400 Pa·s以下。
於本發明之非導電性助焊劑之某一特定態樣中，25℃下之黏度為50 Pa·s以下。
於本發明之非導電性助焊劑之某一特定態樣中，相對於上述酸酐硬化劑100重量份，上述有機磷化合物之含量為0.5重量份以上10重量份以下。
於本發明之非導電性助焊劑之某一特定態樣中，上述非導電性助焊劑100重量%中，上述酸酐硬化劑之含量為5重量%以上50重量%以下。
於本發明之非導電性助焊劑之某一特定態樣中，上述非導電性助焊劑為焊膏(paste)。
根據本發明之廣泛態樣，提供一種連接構造體，其具備：第1連接對象構件，其於表面具有第1電極；第2連接對象構件，其於表面具有第2電極；及樹脂部，其將上述第1連接對象構件與上述第2連接對象構件進行連接；上述第1電極具備第1電極本體、及上述第1電極本體之表面上之焊料粒子，上述第1電極本體與上述第2電極電性連接，上述樹脂部之材料為上述非導電性助焊劑。
根據本發明之廣泛態樣，提供一種連接構造體之製造方法，其具備：第1配置步驟，使用第1連接對象構件，並且使用上述非導電性助焊劑，於上述第1連接對象構件中之焊料粒子之表面上配置上述非導電性助焊劑，上述第1連接對象構件於表面具有第1電極，且上述第1電極具備第1電極本體及上述第1電極本體之表面上之上述焊料粒子；第2配置步驟，將配置有上述非導電性助焊劑之上述第1連接對象構件與表面具有第2電極之第2連接對象構件，以上述第1電極與上述第2電極對向之方式配置；以及如下步驟，藉由對上述焊料粒子及上述非導電性助焊劑進行加熱，而將上述第1電極與上述第2電極電性連接，且由上述非導電性助焊劑形成將上述第1連接對象構件與上述第2連接對象構件連接之樹脂部。
於本發明之連接構造體之製造方法之某一特定態樣中，在上述第1配置步驟中，以浸漬方式配置上述非導電性助焊劑。 [發明之效果]
本發明之非導電性助焊劑包含環氧化合物、酸酐硬化劑、及有機磷化合物。本發明之非導電性助焊劑由於具備上述構成，故可提高所獲得之連接構造體之生產性及耐衝擊性，抑制焊料溢料之發生。
以下，對本發明之詳細情況進行說明。
(非導電性助焊劑) 本發明之非導電性助焊劑包含環氧化合物、酸酐硬化劑、及有機磷化合物。上述非導電性助焊劑不具有導電性。上述非導電性助焊劑較佳為不含導電性物質。上述非導電性助焊劑較佳為不含導電性粒子。上述非導電性助焊劑較佳為不含焊料。上述非導電性助焊劑較佳為不含焊料粒子。又，上述非導電性助焊劑能夠熱硬化。上述非導電性助焊劑具有藉由加熱而硬化之特性。
於如先前之使用底部填充材進行密封之情形時，為了進行焊料接合及底部填充材之硬化，會進行2次回焊步驟，存在生產性較低之問題。
本發明之非導電性助焊劑由於具備上述構成，故於使用上述非導電性助焊劑製作連接構造體時，藉由1次回焊步驟，可使焊料熔融而連接電極彼此，並且可使上述非導電性助焊劑硬化。因此，無需進行2次回焊步驟。即，本發明之非導電性助焊劑於製作連接構造體時可實現一次安裝，故可提高生產性。
本發明之非導電性助焊劑亦可於為了使焊料熔融而連接電極彼此所進行之回焊步驟之前，配置於焊料粒子之表面上而使用。即，本發明之非導電性助焊劑亦可用作先放入(first in)之底部填充材。本發明之非導電性助焊劑較佳為用作先放入之底部填充材。於此情形時，與在用以連接電極彼此之回焊步驟後填充底部填充材並再次進行回焊步驟之情形相比，可減少回焊步驟之次數。即，於本發明之非導電性助焊劑用作先放入之底部填充材之情形時，在製作連接構造體時能夠實現一次安裝，因此可更進一步提高生產性。
又，本發明之非導電性助焊劑由於具備上述構成，故例如在以浸漬方式將非導電性助焊劑配置於封裝體時，可配置充足之量。其結果為，於對使用本發明之非導電性助焊劑之連接構造體施加掉落等衝擊時，可降低發生連接不良等導致連接構造體故障之概率。即，可提高所獲得之連接構造體之耐衝擊性。又，在將非導電性助焊劑配置於連接對象構件時，可將連接對象構件容易地從浸漬槽中提拉。
進而，本發明之非導電性助焊劑由於具備上述構成，故可抑制所獲得之連接構造體之焊料溢料之發生，可提高耐焊料溢料性。其結果為，於使用本發明之非導電性助焊劑之連接構造體中，可抑制短路及開路不良之發生。
進而，本發明之非導電性助焊劑由於具備上述構成，故可降低所獲得之連接構造體中之上下電極間之連接電阻，結果可提高導通可靠性。尤其是於本發明中，藉由併用酸酐硬化劑與有機磷化合物，可很大程度地提高助焊效果。
於本發明中，非導電性係指絕緣電阻為1.0×10 6Ω以上。非導電性助焊劑之絕緣電阻例如可藉由以下方法進行測定。於表面具有銅電極之櫛齒狀基板之表面上，以100 μm之厚度塗佈非導電性助焊劑，而獲得試樣。針對所獲得之試樣，使用回焊模擬器(Reflow simulator)(例如Cores公司製造之「Core9046a」)，於氮氣氛圍下(氧濃度100 ppm以下)以2℃/秒升溫至160℃後，冷卻至室溫(23℃)。其後，施加5 V之電壓，使用測定裝置(例如ESPEC公司製造之「電化學遷移(electrochemical migration)評價系統」)，測定絕緣電阻。
於本發明中，助焊劑係指以下焊料潤濕性試驗中之焊料潤濕直徑為600 μm以上之組合物。於鍍金印刷基板之表面上，以150 μm之厚度塗佈組合物，於該組合物之表面上，配置SnBi焊料粒子(粒徑500 μm，熔點139℃)，而獲得試樣。針對所獲得之試樣，使用回焊模擬器(例如Cores公司製造之「Core9046a」)，於氮氣氛圍下(氧濃度100 ppm以下)以2℃/秒升溫至160℃，保持3分鐘後，冷卻至室溫(23℃)。其後，將潤濕擴散之焊料之形狀近似為橢圓，將該橢圓之短徑與長徑之平均((短徑＋長徑)/2)設為組合物之焊料潤濕直徑。再者，上述橢圓之概念中包括正圓，於上述橢圓為正圓之情形時，組合物之焊料潤濕直徑為正圓之直徑。
本發明之非導電性助焊劑可適宜地用於表面安裝型封裝與配線基板之連接。作為上述表面安裝型封裝，可例舉BGA、及CSP等。
上述非導電性助焊劑於25℃下之接著力(黏著力)較佳為50000 N/m 2以上，更佳為100000 N/m 2以上，進而較佳為120000 N/m 2以上，特佳為140000 N/m 2以上。上述非導電性助焊劑於25℃下之接著力(黏著力)較佳為250000 N/m 2以下，更佳為210000 N/m 2以下，進而較佳為170000 N/m 2以下，特佳為160000 N/m 2以下。當上述非導電性助焊劑於25℃下之接著力為上述下限以上時，在以浸漬方式將上述非導電性助焊劑配置於封裝體時，可配置充足之量。結果可更進一步有效地提高所獲得之連接構造體之耐衝擊性。又，當上述非導電性助焊劑於25℃下之接著力為上述上限以下時，可容易地從浸漬槽中提拉封裝體。
上述非導電性助焊劑於25℃下之接著力(黏著力)如下所述地進行測定。將上述非導電性助焊劑以50 μm之厚度塗佈於不鏽鋼板之表面上，獲得積層體。使用黏性試驗機，向上述積層體壓入探針(直徑8 mm，10 g)10秒後，以0.1 mm/秒之速度提拉探針，測定提拉探針時之負載。作為黏性試驗機，可例舉UBM公司製造之「TA-500」等。
就更進一步有效地提高所獲得之連接構造體之耐衝擊性之觀點而言，上述非導電性助焊劑於25℃下之黏度(η25)較佳為5 Pa·s以上，更佳為25 Pa·s以上，並且，較佳為400 Pa·s以下，更佳為300 Pa·s以下，進而較佳為50 Pa·s以下，特佳為40 Pa·s以下。上述黏度(η25)可根據調配成分之種類及調配量進行適當調整。
上述黏度(η25)例如可使用E型黏度計(東機產業公司製造之「TVE22L」)等，於25℃及10 rpm之條件下進行測定。
就提高所獲得之連接構造體之耐衝擊性之觀點而言，上述非導電性助焊劑較佳為於25℃下為液狀，較佳為焊膏。
就更進一步有效地提高所獲得之連接構造體之耐衝擊性之觀點而言，上述非導電性助焊劑之熔點較佳為40℃以上，更佳為70℃以上，並且，較佳為350℃以下，更佳為310℃以下。
上述非導電性助焊劑之熔點可藉由示差掃描熱分析(DSC)求出。作為示差掃描熱分析(DSC)裝置，可例舉SII公司製造之「EXSTAR DSC7020」等。
就提高導通可靠性之觀點而言，上述非導電性助焊劑之反應起始溫度較佳為50℃以上，更佳為70℃以上，進而較佳為80℃以上，並且，較佳為250℃以下，更佳為200℃以下，進而較佳為150℃以下，特佳為140℃以下。
＜環氧化合物＞ 上述環氧化合物係具有至少1個環氧基之化合物。作為上述環氧化合物，可例舉：聯二甲苯酚型環氧化合物、雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、苯酚酚醛清漆型環氧化合物、聯苯型環氧化合物、聯苯酚醛清漆型環氧化合物、聯苯酚型環氧化合物、萘型環氧化合物、茀型環氧化合物、苯酚芳烷基型環氧化合物、萘酚芳烷基型環氧化合物、二環戊二烯型環氧化合物、蒽型環氧化合物、具有金剛烷骨架之環氧化合物、具有三環癸烷骨架之環氧化合物、伸萘基醚型環氧化合物、及骨架上具有三𠯤核之環氧化合物等。上述環氧化合物可僅使用1種，亦可併用2種以上。
就提高浸漬性之觀點而言，上述環氧化合物較佳為聯二甲苯酚型環氧化合物、雙酚F型環氧化合物或骨架上具有三𠯤核之環氧化合物，更佳為聯二甲苯酚型環氧化合物或雙酚F型環氧化合物。上述環氧化合物進而較佳為聯二甲苯酚型環氧化合物。
就更進一步提高所獲得之連接構造體之耐衝擊性之觀點而言，上述環氧化合物較佳為於25℃下為液狀。
就更進一步提高所獲得之連接構造體之耐衝擊性之觀點而言，上述非導電性助焊劑100重量%中，上述環氧化合物之含量較佳為15重量%以上，更佳為30重量%以上，進而較佳為50重量%以上，並且，較佳為70重量%以下，更佳為60重量%以下，進而較佳為55重量%以下。
＜酸酐硬化劑＞ 上述酸酐硬化劑使上述環氧化合物熱硬化。藉由併用上述酸酐硬化劑與下述有機磷化合物，可很大程度地提高上述非導電性助焊劑之助焊效果。結果可良好地去除所獲得之連接構造體中之電極及焊料表面之氧化膜。
作為上述酸酐硬化劑，可例舉：鄰苯二甲酸酐、四氫鄰苯二甲酸酐、三烷基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基丁烯基四氫鄰苯二甲酸酐、鄰苯二甲酸衍生物之酐、馬來酸酐、耐地酸酐、甲基耐地酸酐、戊二酸酐、琥珀酸酐、甘油雙偏苯三甲酸酐單乙酸酯、及乙二醇雙偏苯三甲酸酐等二官能之酸酐硬化劑、偏苯三甲酸酐等三官能之酸酐硬化劑、以及均苯四甲酸二酐、二苯甲酮四羧酸二酐、甲基環己烯四羧酸二酐、及聚壬二酸酐等四官能以上之酸酐硬化劑等。上述酸酐硬化劑可僅使用1種，亦可併用2種以上。
就提高浸漬性之觀點而言，上述酸酐硬化劑較佳為四氫鄰苯二甲酸酐或六氫鄰苯二甲酸酐，更佳為六氫鄰苯二甲酸酐。就更進一步提高浸漬性之觀點而言，上述六氫鄰苯二甲酸酐較佳為甲基六氫鄰苯二甲酸酐。
上述非導電性助焊劑100重量%中，上述酸酐硬化劑之含量較佳為5重量%以上，更佳為10重量%以上，進而較佳為25重量%以上，並且，較佳為60重量%以下，更佳為50重量%以下，進而較佳為45重量%以下。當上述酸酐硬化劑之含量為上述下限以上及上述上限以下時，可更進一步提高所獲得之連接構造體之耐衝擊性及耐焊料溢料性。
相對於上述環氧化合物100重量份，上述酸酐硬化劑之含量較佳為50重量份以上，更佳為60重量份以上，進而較佳為70重量份以上，並且，較佳為120重量份以下，更佳為110重量份以下，進而較佳為100重量份以下。當上述酸酐硬化劑之含量為上述下限以上及上述上限以下時，可更進一步提高所獲得之連接構造體之耐衝擊性及耐焊料溢料性。
＜有機磷化合物＞ 藉由併用上述有機磷化合物與上述酸酐硬化劑，可提高非導電性助焊劑之助焊性。結果可良好地去除所獲得之連接構造體中之電極及焊料表面之氧化膜。又，可提高所獲得之連接構造體之耐衝擊性。
作為上述有機磷化合物，可例舉：有機鏻鹽、有機磷酸、有機磷酸酯、有機膦酸、有機膦酸酯、有機次膦酸、及有機次膦酸酯等。上述有機磷化合物可僅使用1種，亦可併用2種以上。
就提高導通可靠性之觀點而言，上述有機磷化合物較佳為有機鏻鹽、有機磷酸或有機磷酸酯，更佳為有機鏻鹽。
作為上述有機鏻鹽，可例舉包含鏻離子及其抗衡離子之有機鏻鹽。
就提高導通可靠性之觀點而言，上述有機鏻鹽較佳為甲基三丁基鏻磷酸二甲酯鹽、三丁基甲基鏻磷酸雙(2-乙基己基)酯鹽、或溴化四丁基鏻，更佳為甲基三丁基鏻磷酸二甲酯鹽。
作為上述有機鏻鹽之市售品，可例舉日本化學工業公司製造之「Hishicolin」系列等。
上述有機磷酸、上述有機磷酸酯、上述有機膦酸、上述有機膦酸酯、上述有機次膦酸、及上述有機次膦酸酯並無特別限定，可使用先前公知之化合物或市售品。
就更進一步提高所獲得之連接構造體之耐衝擊性之觀點而言，上述有機磷化合物較佳為於25℃下為液狀。
就更進一步提高所獲得之連接構造體之耐衝擊性及耐焊料溢料性之觀點而言，上述非導電性助焊劑100重量%中，上述有機磷化合物之含量較佳為0.5重量%以上，更佳為0.8重量%以上，並且，較佳為10重量%以下，更佳為8.0重量%以下，進而較佳為4.0重量%以下。
就更進一步提高所獲得之連接構造體之耐衝擊性及耐焊料溢料性之觀點而言，相對於上述酸酐硬化劑100重量份，上述有機磷化合物之含量較佳為0.5重量份以上，更佳為1重量份以上，進而較佳為2重量份以上，並且，較佳為10重量份以下，更佳為5重量份以下。
＜其他成分＞ 上述非導電性助焊劑視需要亦可包含例如填充劑、增量劑、軟化劑、塑化劑、觸變劑、調平劑、聚合觸媒、硬化觸媒、著色劑、抗氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、抗靜電劑及阻燃劑等各種添加劑。
就更進一步提高助焊性之觀點而言，上述非導電性助焊劑可包含具有羧基之化合物，亦可包含羧酸化合物。由於上述非導電性助焊劑之助焊性優異，故上述非導電性助焊劑可不含具有羧基之化合物，亦可不含羧酸化合物。
(連接構造體及連接構造體之製造方法) 本發明之非導電性助焊劑可適宜地用於獲得連接構造體。本發明之非導電性助焊劑可適宜地用於塗佈於焊料之表面上(非導電性助焊劑對焊料表面之應用)。本發明之非導電性助焊劑可適宜地用於塗佈於焊料粒子之表面上(非導電性助焊劑對焊料粒子表面之應用)。本發明之非導電性助焊劑亦可為焊料之被覆材料。本發明之非導電性助焊劑亦可為焊料粒子之被覆材料。本發明之非導電性助焊劑亦可適宜地用於塗佈於電極之表面上(非導電性助焊劑對電極表面之應用)。本發明之非導電性助焊劑亦可適宜地用於塗佈於導電性粒子之表面上(非導電性助焊劑對導電性粒子表面之應用)。本發明之非導電性助焊劑亦可為電極之被覆材料。本發明之非導電性助焊劑亦可為導電性粒子之被覆材料。
本發明之連接構造體具備：第1連接對象構件，其於表面具有第1電極；第2連接對象構件，其於表面具有第2電極；以及樹脂部，其將上述第1連接對象構件與上述第2連接對象構件進行連接。於本發明之連接構造體中，上述第1電極具備第1電極本體、及上述第1電極本體之表面上之焊料粒子。於本發明之連接構造體中，上述第1電極本體與上述第2電極電性連接。於本發明之連接構造體中，上述樹脂部之材料為上述非導電性助焊劑。
於本發明之連接構造體之製造方法中，使用表面具有第1電極之第1連接對象構件，上述第1電極具備第1電極本體、及上述第1電極本體之表面上之焊料粒子。本發明之連接構造體之製造方法具備第1配置步驟，該步驟係使用上述第1連接對象構件，且使用上述非導電性助焊劑，於上述第1連接對象構件中之上述焊料粒子之表面上配置上述非導電性助焊劑。本發明之連接構造體之製造方法具備第2配置步驟，該步驟係將配置有上述非導電性助焊劑之上述第1連接對象構件與表面具有第2電極之第2連接對象構件，以上述第1電極與上述第2電極對向之方式配置。本發明之連接構造體之製造方法具備如下步驟，該步驟係藉由對上述焊料粒子及上述非導電性助焊劑進行加熱，而將上述第1電極與上述第2電極電性連接，且由上述非導電性助焊劑形成將上述第1連接對象構件與上述第2連接對象構件連接之樹脂部。
於本發明之連接構造體之製造方法中，在上述第1配置步驟中，對於上述非導電性助焊劑，可以點膠方式進行配置，可藉由網版印刷進行配置，可藉由噴墨裝置之噴出進行配置，亦可以浸漬方式進行配置。就更進一步提高生產性之觀點而言，較佳為於上述第1配置步驟中以浸漬方式配置上述非導電性助焊劑。
於先前之使用底部填充材之連接構造體之製造方法中，在進行用以連接電極彼此之回焊步驟後，需要再次進行使底部填充材利用毛細管現象滲透並填充至連接對象構件間，以使底部填充材硬化之回焊步驟。即，於先前之使用底部填充材之連接構造體之製造方法中，需要進行2次回焊步驟，因此存在生產性較低之問題。進而，於先前之使用底部填充材之連接構造體中，有時會發生焊料溢料。當發生焊料溢料時，有時會發生短路或開路不良。
於本發明之連接構造體及連接構造體之製造方法中，由於使用特定之非導電性助焊劑，故可藉由1次回焊步驟，將電極彼此電性連接，且使上述非導電性助焊劑硬化。因此，無需進行2次回焊步驟。即，於本發明之連接構造體及連接構造體之製造方法中，能夠實現一次安裝，因此，結果可更進一步提高生產性。又，於本發明之連接構造體及連接構造體之製造方法中，由於使用特定之非導電性助焊劑，故例如在以浸漬方式將非導電性助焊劑配置於封裝體時，可配置充足之量。其結果為，於對連接構造體施加掉落等衝擊時，可降低發生連接不良等導致連接構造體故障之概率(提高耐衝擊性)。進而，於本發明之連接構造體及連接構造體之製造方法中，由於使用特定之非導電性助焊劑，故可抑制焊料溢料之發生。結果可抑制所獲得之連接構造體中發生短路或開路不良。
以下，參照圖式，對本發明之具體實施方式進行說明。
圖1係模式性地表示使用本發明之一實施方式之非導電性助焊劑所獲得之連接構造體的剖視圖。
圖1所示之連接構造體1具備第1連接對象構件2、第2連接對象構件3、及將第1連接對象構件2與第2連接對象構件3連接之樹脂部4。樹脂部4由非導電性助焊劑4Xa(參照圖2(a)～(d))所形成。樹脂部4之材料為非導電性助焊劑4Xa。於本實施方式中，非導電性助焊劑4Xa包含環氧化合物、酸酐硬化劑、及有機磷化合物。於本實施方式中，非導電性助焊劑4Xa為焊膏。
樹脂部4係非導電性助焊劑4Xa被熱硬化而成之硬化物部。
第1連接對象構件2於表面(下表面)具有複數個第1電極。上述第1電極具備第1電極本體2a、及第1電極本體2a之表面上之焊料部2B(焊料粒子)。上述第1電極係第1電極本體2a與焊料部2B之複合電極。第2連接對象構件3於表面(上表面)具有複數個第2電極3a。於連接構造體1中，第1電極本體2a與第2電極3a電性連接。於連接構造體1中，第1電極本體2a與第2電極3a藉由焊料部2B電性連接。
如圖1所示，於連接構造體1中，在第1電極本體2a與第2電極3a之間，焊料粒子之至少與第2電極3a相接之部分熔融後，焊料粒子固化，而形成焊料部2B。因此，焊料部2B與第2電極3a之連接面積變大。於上述連接構造體中，可殘存焊料粒子。於上述連接構造體中，可存在焊料粒子及焊料部。
其次，利用圖2(a)～(d)，對連接構造體之製造方法之一例進行具體說明。圖2(a)～(d)係用以對使用本發明之一實施方式之非導電性助焊劑來製造連接構造體的方法之一例之各步驟進行說明之剖視圖。
首先，如圖2(a)及圖2(b)所示，準備於表面(下表面)具有第1電極之第1連接對象構件2。上述第1電極具備第1電極本體2a、及第1電極本體2a之表面上之焊料粒子2b。又，準備非導電性助焊劑4Xa。非導電性助焊劑4Xa填充於浸漬槽4X內。於第1連接對象構件2之焊料粒子2b之表面上，配置非導電性助焊劑4Xa(第1配置步驟)。非導電性助焊劑4Xa包含環氧化合物、酸酐硬化劑、及有機磷化合物。
於第1配置步驟中，以浸漬方式將非導電性助焊劑4Xa配置於第1連接對象構件2之焊料粒子2b之表面上。使第1連接對象構件2浸漬於填充有非導電性助焊劑4Xa之浸漬槽4X中，於第1連接對象構件2之焊料粒子2b之表面上配置非導電性助焊劑4Xa。非導電性助焊劑4Xa被覆焊料粒子2b之表面，為被覆層。作為被覆層之非導電性助焊劑4Xa沿焊料粒子2b之表面配置。
配置於焊料粒子表面上之非導電性助焊劑之量較佳為可於所獲得之連接構造體中填埋第1連接對象構件與第2連接對象構件之空隙之量。
又，準備於表面(上表面)具有第2電極3a之第2連接對象構件3。其次，如圖2(b)及(c)所示，將配置有非導電性助焊劑4Xa之第1連接對象構件2、及第2連接對象構件3以第1電極(第1電極本體2a及焊料粒子2b)與第2電極3a對向之方式配置(第2配置步驟)。從第2電極3a側朝第1連接對象構件2之第1電極側配置第2連接對象構件3。此時，使第1電極本體2a與第2電極3a對向。
其次，如圖2(d)所示，對焊料粒子2b及非導電性助焊劑4Xa進行加熱(第3步驟)。較佳為將上述非導電性助焊劑加熱至上述焊料粒子之與第2電極相接之部分之熔融溫度以上。更佳為將非導電性助焊劑4Xa加熱至上述環氧化合物之硬化溫度以上。藉由該加熱，第1電極(第1電極本體2a、及焊料粒子2b或焊料部2B)與第2電極2a電性連接。又，非導電性助焊劑4Xa熱硬化。結果如圖2(d)所示，由非導電性助焊劑4Xa形成將第1連接對象構件2與第2連接對象構件3連接之樹脂部4。藉由非導電性助焊劑4Xa熱硬化，而形成樹脂部4。又，如圖2(d)所示，由焊料粒子2b形成焊料部2B，第1電極本體2a與第2電極3a藉由焊料部2B電性連接。
如此，獲得圖1所示之連接構造體1。再者，亦可連續地進行上述第2步驟及上述第3步驟。又，於進行上述第2步驟後，亦可使第1連接對象構件2、非導電性助焊劑4Xa及第2連接對象構件3之積層體移動至加熱部，進行上述第3步驟。為了進行上述加熱，可於加熱構件上配置上述積層體，亦可於經加熱之空間內配置上述積層體。
上述第3步驟中之上述加熱溫度較佳為140℃以上，更佳為160℃以上，並且，較佳為450℃以下，更佳為250℃以下，進而較佳為200℃以下。上述第3步驟中之上述加熱溫度較佳為加熱至上述焊料粒子之熔點以上。上述第3步驟中之上述加熱溫度較佳為加熱至上述環氧化合物之硬化溫度以上。上述第3步驟中之上述加熱溫度較佳為上述焊料粒子之與第2電極相接之部分之熔融溫度以上，更佳為上述環氧化合物之硬化溫度以上。
作為上述第3步驟中之加熱方法，可例舉使用回焊爐或使用烘箱對上述積層體整體進行加熱之方法、或僅對上述積層體之焊料部(焊料粒子)及樹脂部(非導電性助焊劑)進行局部加熱之方法。
作為進行局部加熱之方法所使用之器具，可例舉加熱板、吹送熱風之熱風槍、烙鐵、及紅外線加熱器等。
又，於利用加熱板進行局部加熱時，較佳為對於焊料部(焊料粒子)及樹脂部(非導電性助焊劑)正下方，由導熱性較高之金屬形成加熱板上表面，對於其他不應加熱之部位，由氟樹脂等導熱性較低之材質形成加熱板上表面。
連接構造體中之焊料部之厚度較佳為10 μm以上，更佳為20 μm以上，並且，較佳為100 μm以下，更佳為80 μm以下。
連接構造體中之樹脂部之厚度較佳為10 μm以上，更佳為20 μm以上，並且，較佳為100 μm以下，更佳為80 μm以下。
焊料粒子之熔點下之非導電性助焊劑之黏度(ηmp)較佳為0.1 Pa·s以上，更佳為0.2 Pa·s以上，並且，較佳為50 Pa·s以下，更佳為10 Pa·s以下，進而較佳為1 Pa·s以下。若上述黏度(ηmp)為上述下限以上及上述上限以下，則可使導通可靠性更良好。
上述黏度(ηmp)例如可使用Thermo Fisher Scientific公司製造之流變儀「HAAKE MARS III」，於頻率2 Hz、升溫速度0.11℃/秒、測定溫度範圍25℃～200℃(其中，於焊料粒子之熔點超過200℃之情形時，將溫度上限作為焊料粒子之熔點)之條件下進行測定。根據測定結果，評價焊料粒子之熔點(℃)下之黏度。
於非導電性助焊劑為焊膏(液狀)之情形時，根據非導電性助焊劑之塗佈量，會容易調整樹脂部之厚度。
上述第1、第2連接對象構件並無特別限定。作為上述第1、第2連接對象構件，具體而言，可例舉：半導體晶片、半導體封裝、LED(light emitting diode，發光二極體)晶片、LED封裝、電容器及二極體等電子零件、以及樹脂膜、印刷基板、軟性印刷基板、軟性扁平電纜、剛性軟性基板、玻璃環氧基板及玻璃基板等電路基板等電子零件等。上述第1、第2連接對象構件較佳為電子零件。
作為設置於上述連接對象構件之電極，可例舉：金電極、鎳電極、錫電極、鋁電極、銅電極、鉬電極、銀電極、SUS(Steel Use Stainless，日本不鏽鋼標準)電極、及鎢電極等金屬電極。於上述連接對象構件為軟性印刷基板之情形時，上述電極較佳為金電極、鎳電極、錫電極、銀電極或銅電極。於上述連接對象構件為玻璃基板之情形時，上述電極較佳為鋁電極、銅電極、鉬電極、銀電極或鎢電極。再者，於上述電極為鋁電極之情形時，可為僅由鋁形成之電極，亦可為於金屬氧化物層之表面積層有鋁層之電極。作為上述金屬氧化物層之材料，可例舉摻雜有3價金屬元素之氧化銦及摻雜有3價金屬元素之氧化鋅等。作為上述3價金屬元素，可例舉Sn、Al及Ga等。
以下，舉出實施例及比較例，對本發明進行具體說明。本發明並不僅限定於以下實施例。
環氧化合物： 環氧化合物1(雙酚F型環氧化合物，新日鐵住金化學公司製造之「YDF-8170C」) 環氧化合物2(聯二甲苯酚型環氧化合物，Mitsubishi Chemical公司製造之「YX-4000HK」)
硬化劑： 酸酐硬化劑1(六氫鄰苯二甲酸酐與甲基六氫鄰苯二甲酸酐之混合物，新日本理化公司製造之「RIKACID MH-700」) 酸酐硬化劑2(四氫鄰苯二甲酸酐，新日本理化公司製造之「RIKACID TH」) 咪唑硬化劑(四國化成工業公司製造之「2E4MZ-A」)
有機磷化合物： 有機磷化合物1(溴化四丁基鏻，日本化學工業公司製造之「Hishicolin PX-4B」，熔點：110℃) 有機磷化合物2(甲基三丁基鏻磷酸二甲酯鹽，日本化學工業公司製造之「Hishicolin PX-4MP」，熔點：10℃)
(實施例1～8及比較例1、2) (1)非導電性助焊劑或組合物之製作 以下述表1～3所示之調配量調配下述表1～3所示之成分，獲得非導電性助焊劑或組合物。
(2)連接構造體之製作 將剛製作好之非導電性助焊劑(組合物)填充至浸漬槽中。準備BGA(0.8 mm間距，100個電極)作為表面具有第1電極之第1連接對象構件(封裝體)。準備與第1連接對象構件對應之表面具有第2電極(金電極)之印刷基板(材質：FR4；厚度：1 mm)作為第2連接對象構件。將上述第1連接對象構件於浸漬槽中浸漬1秒，將非導電性助焊劑(組合物)配置於第1電極本體表面上之焊料粒子(第1配置步驟)。其次，以電極彼此對向之方式，於非導電性助焊劑(組合物)之下表面積層第2連接對象構件(第2配置步驟)。第2連接對象構件之重量施加於焊料粒子及非導電性助焊劑(組合物)。從該狀態開始，以焊料粒子及非導電性助焊劑之溫度在開始升溫之50秒後達到焊料粒子之熔點的方式進行加熱。進而，以在開始升溫之65秒後，焊料粒子(焊料部)及非導電性助焊劑(樹脂部)之溫度達到160℃的方式進行加熱。其後，於160℃下保持120秒鐘，使非導電性助焊劑(組合物)硬化，而獲得連接構造體。加熱時不進行加壓。
(評價) (1)黏度 針對所獲得之非導電性助焊劑(組合物)0.1 mL，使用E型黏度計(東機產業公司製造之「TVE22L」)，於25℃及10 rpm之條件下測定25℃下之黏度(η25)。再者，錐形轉子使用3°×R7.7之錐形轉子。
(2)接著力 將所獲得之非導電性助焊劑(組合物)以50 μm之厚度塗佈於不鏽鋼板之表面上，獲得積層體。使用黏性試驗機(UBM公司製造之「TA-500」)，向上述積層體壓入探針(直徑8 mm，10 g)10秒後，以0.1 mm/秒之速度提拉探針，測定提拉探針時之負載作為25℃下之接著力。
(3)耐衝擊性(掉落可靠性) 使所獲得之連接構造體以1500 G之加速度掉落300次。將掉落試驗後之20個連接構造體中發生了開路不良之連接構造體之數量作為故障數量。按以下基準判定耐衝擊性。
[耐衝擊性之判定基準] ○○：故障數量為0個 ○：故障數量為1個 △：故障數量為2個 ×：故障數量為3個以上
(4)焊料溢料發生之抑制性 針對所獲得之連接構造體，以在開始升溫50秒後達到焊料粒子之熔點之方式進行加熱。進而，以在開始升溫75秒後，焊料部及樹脂部之溫度達到180℃之方式進行加熱，並於180℃下保持60秒鐘。其後，進行冷卻，將20個連接構造體中發生了開路不良或短路之連接構造體之個數作為開路不良或短路之發生數量。按以下基準判定焊料溢料發生之抑制性。
[焊料溢料發生之抑制性之判定基準] ○：開路不良或短路之發生數量為0個 ×：開路不良或短路之發生數量為1個以上
(5)導通可靠性(上下電極間) 針對所獲得之20個連接構造體，利用2端子之電阻計，對上下電極間之100處連接電阻進行測定，算出連接電阻之平均值。再者，根據電壓＝電流×電阻之關係，測定流過定電流時之電壓，藉此可求出連接電阻。按以下基準判定導通可靠性。
[導通可靠性之判定基準] ○：連接電阻之平均值為0.9 mΩ以下 ×：連接電阻之平均值超過0.9 mΩ、或發生了連接不良
(6)浸漬性 於上述連接構造體之製作中，將第1連接對象構件於浸漬槽中浸漬1秒後，提拉出第1連接對象構件。藉由目視確認附著於焊料粒子上之非導電性助焊劑(組合物)之量。按下述基準判定浸漬性。
[浸漬性之判定基準] ○：可從浸漬槽中提拉出第1連接對象構件，且可於焊料粒子之表面配置對填埋連接對象構件間之空隙而言充足量之非導電性助焊劑(組合物) ×：無法從浸漬槽中提拉出第1連接對象構件，或無法於焊料粒子之表面配置對填埋連接對象構件間之空隙而言充足量之非導電性助焊劑(組合物)
(7)助焊性 於鍍金印刷基板之表面上，以150 μm之厚度塗佈所獲得之非導電性助焊劑(組合物)，於該組合物之表面上，配置SnBi焊料粒子(粒徑500 μm，熔點139℃)，而獲得試樣。針對所獲得之試樣，使用回焊模擬器(Cores公司製造之「Core9046a」)，於氮氣氛圍下(氧濃度100 ppm以下)以2℃/秒升溫至160℃，保持3分鐘後，冷卻至室溫(23℃)。其後，將潤濕擴散之焊料形狀近似為橢圓，將該橢圓之短徑與長徑之平均((短徑＋長徑)/2)設為非導電性助焊劑(組合物)之焊料潤濕直徑。按下述基準判定助焊性。再者，於上述橢圓為正圓之情形時，非導電性助焊劑(組合物)之焊料潤濕直徑設為正圓之直徑。
[助焊性之判定基準] ○：焊料潤濕直徑為600 μm以上 ×：焊料潤濕直徑未達600 μm
(8)非導電性 於表面具有銅電極之櫛齒狀基板之表面上，以100 μm之厚度塗佈非導電性助焊劑(組合物)，而獲得試樣。針對所獲得之試樣，使用回焊模擬器(Cores公司製造之「Core9046a」)，於氮氣氛圍下(氧濃度100 ppm以下)以2℃/秒升溫至160℃後，冷卻至室溫(23℃)。其後，施加5 V之電壓，使用測定裝置(ESPEC公司製造之「電化學遷移評價系統」)，測定絕緣電阻。按下述基準判定非導電性。
[非導電性之判定基準] ○：絕緣電阻為1.0×10 6Ω以上 ×：絕緣電阻未達1.0×10 6Ω
將結果示於下述表1～3。
[表1]
   實施例1 實施例2 實施例3 實施例4
非導電性助焊劑 環氧化合物1 重量份    45      
環氧化合物2 重量份 58    51 58
硬化劑 酸酐硬化劑1 重量份 42    49 42
酸酐硬化劑2 重量份    55      
咪唑硬化劑 重量份            
有機磷化合物1 重量份 2 2 2   
有機磷化合物2 重量份          4
評價 黏度 Pa·s 35 45 25 42
接著力 N/m 2 170000 250000 100000 210000
耐衝擊性 ○○ △ ○○ ○
焊料溢料發生之抑制性 ○ ○ ○ ○
導通可靠性 ○ ○ ○ ○
浸漬性 ○ ○ ○ ○
助焊性 ○ ○ ○ ○
非導電性 ○ ○ ○ ○
[表2]
   實施例5 實施例6 實施例7 實施例8
非導電性助焊劑 環氧化合物1 重量份          54
環氧化合物2 重量份 58 58 58   
硬化劑 酸酐硬化劑1 重量份 42 42 42 46
酸酐硬化劑2 重量份            
咪唑硬化劑 重量份            
有機磷化合物1 重量份          2
有機磷化合物2 重量份 2 1 0.5   
評價 黏度 Pa·s 33 28 27 5
接著力 N/m 2 150000 130000 120000 50000
耐衝擊性 ○○ ○○ ○ △
焊料溢料發生之抑制性 ○ ○ ○ ○
導通可靠性 ○ ○ ○ ○
浸漬性 ○ ○ ○ ○
助焊性 ○ ○ ○ ○
非導電性 ○ ○ ○ ○
[表3]
   比較例1 比較例2
組合物 環氧化合物1 重量份    45
環氧化合物2 重量份 47   
硬化劑 酸酐硬化劑1 重量份 53   
酸酐硬化劑2 重量份    55
咪唑硬化劑 重量份 5 5
有機磷化合物1 重量份      
有機磷化合物2 重量份      
評價 黏度 Pa·s 20 20
接著力 N/m 2 190000 230000
耐衝擊性 × ×
焊料溢料發生之抑制性 ○ ×
導通可靠性 ○ ×
浸漬性 ○ ×
助焊性 × ×
非導電性 ○ ○
再者，所有實施例中，回焊步驟均僅為1次。
1:連接構造體 2:第1連接對象構件 2a:第1電極本體 2b:焊料粒子 2B:焊料部 3:第2連接對象構件 3a:第2電極 4:樹脂部 4X:浸漬槽 4Xa:非導電性助焊劑
圖1係模式性地表示使用本發明之一實施方式之非導電性助焊劑所獲得之連接構造體的剖視圖。 圖2(a)～(d)係用以對使用本發明之一實施方式之非導電性助焊劑來製造連接構造體的方法之一例之各步驟進行說明之剖視圖。

Claims (10)

  1. 一種非導電性助焊劑，其包含環氧化合物、酸酐硬化劑、及有機磷化合物。
  2. 如請求項1之非導電性助焊劑，其於25℃下之接著力為100000 N/m 2以上210000 N/m 2以下。
  3. 如請求項1或2之非導電性助焊劑，其於25℃下之黏度為400 Pa·s以下。
  4. 如請求項3之非導電性助焊劑，其於25℃下之黏度為50 Pa·s以下。
  5. 如請求項1或2之非導電性助焊劑，其中相對於上述酸酐硬化劑100重量份，上述有機磷化合物之含量為0.5重量份以上10重量份以下。
  6. 如請求項1或2之非導電性助焊劑，其中非導電性助焊劑100重量%中，上述酸酐硬化劑之含量為5重量%以上50重量%以下。
  7. 如請求項1或2之非導電性助焊劑，其為焊膏。
  8. 一種連接構造體，其具備：第1連接對象構件，其於表面具有第1電極； 第2連接對象構件，其於表面具有第2電極；以及 樹脂部，其將上述第1連接對象構件與上述第2連接對象構件進行連接； 上述第1電極具備第1電極本體、及上述第1電極本體之表面上之焊料粒子， 上述第1電極本體與上述第2電極電性連接， 上述樹脂部之材料為如請求項1至7中任一項之非導電性助焊劑。
  9. 一種連接構造體之製造方法，其具備：第1配置步驟，使用第1連接對象構件，並且使用如請求項1至7中任一項之非導電性助焊劑，於上述第1連接對象構件中之焊料粒子之表面上配置上述非導電性助焊劑，上述第1連接對象構件於表面具有第1電極，且上述第1電極具備第1電極本體及上述第1電極本體之表面上之上述焊料粒子； 第2配置步驟，將配置有上述非導電性助焊劑之上述第1連接對象構件與表面具有第2電極之第2連接對象構件，以上述第1電極與上述第2電極對向之方式配置；以及 如下步驟，藉由對上述焊料粒子及上述非導電性助焊劑進行加熱，而將上述第1電極與上述第2電極電性連接，且由上述非導電性助焊劑形成將上述第1連接對象構件與上述第2連接對象構件連接之樹脂部。
  10. 如請求項9之連接構造體之製造方法，其中於上述第1配置步驟中，以浸漬方式配置上述非導電性助焊劑。
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