TWI538930B - 半導體密封用環氧樹脂組成物，其硬化體及半導體裝置 - Google Patents

半導體密封用環氧樹脂組成物，其硬化體及半導體裝置 Download PDF

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Publication number
TWI538930B
TWI538930B TW099142334A TW99142334A TWI538930B TW I538930 B TWI538930 B TW I538930B TW 099142334 A TW099142334 A TW 099142334A TW 99142334 A TW99142334 A TW 99142334A TW I538930 B TWI538930 B TW I538930B
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Prior art keywords
epoxy resin
resin composition
semiconductor
group
copper wire
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TW099142334A
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English (en)
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TW201129601A (en
Inventor
伊藤慎吾
前佛伸一
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住友電木股份有限公司
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Publication of TW201129601A publication Critical patent/TW201129601A/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
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Description

半導體密封用環氧樹脂組成物，其硬化體及半導體裝置
本發明係關於半導體密封用環氧樹脂組成物、其硬化體及具有該等之半導體裝置。
近年來，作為取代金線之廉價接合導線，已提案有銅導線。
專利文獻1中記載有一種接合導線，其具有以銅為主成分的芯材，與在該芯材上、含有與芯材之成分或組成之一者或兩者相異的導電性金屬與銅的外皮層。其記載著：於此接合導線中，藉由將外皮層厚度設為0.001~0.02μm，而可提供材料費便宜，焊球接合性、導線接合性等優越，且迴路形成性亦良好，亦適合用於狹間距用細線化、電源系IC用途之粗徑化的銅系接合導線。
[先行技術文獻] [專利文獻]
專利文獻1：日本專利特開2007-12776號公報
然而，若將連接著上述銅導線之半導體元件以環氧樹脂進行密封，則有高溫保管性(HTSL，High Temperature Storage Life)降低的情形。根據本發明者等人的見解，在高溫保管性不良的半導體裝置中，因為半導體元件上之金屬墊與銅導線間之接合部的腐蝕(氧化劣化)，將造成接合部之電阻上升或接合部之斷線發生。從而，若可防止此種接合部之電阻上升或接合部之斷線，則期待可提升半導體裝置之高溫保管性。
本發明係有鑑於上述情況而形成者，其目的在於提供一種使高溫保管時之半導體元件上之金屬墊與銅導線間之接合部的腐蝕(氧化劣化)減低，可提升半導體裝置之可靠性的半導體密封用樹脂組成物、其硬化體及具有該等之半導體裝置。
根據本發明，提供一種半導體密封用環氧樹脂組成物，係含有環氧樹脂(A)及硬化劑(B)，並對銅導線及上述銅導線所連接之半導體元件進行密封者，其特徵為，上述半導體密封用環氧樹脂組成物之硬化體經200℃10小時加熱時，含有對上述銅導線具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下。
另外，根據本發明，提供一種上述半導體密封用環氧樹脂組成物之硬化體。
再者，根據本發明，提供一種半導體裝置，其具有：具有晶粒墊部之引線框架；搭載於上述晶粒墊部之半導體元件；將上述引線框架與上述半導體元件電性連接之銅導線；與密封樹脂，係由環氧樹脂組成物之硬化體所構成，且密封著上述半導體元件與上述銅導線；上述密封樹脂經200℃ 10小時加熱時，含有對上述銅導線具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下。
根據本發明，使半導體裝置經200℃ 10小時加熱時之由密封樹脂所產生之含有硫化合物的第一腐蝕性氣體的產生量成為70ppm以下。藉此，由於可使半導體元件上之金屬墊與銅導線間之接合部的腐蝕(氧化劣化)減低，故可減低接合部之電阻上升或接合部斷線。因此，可實現提升了高溫保管特性之高可靠性的半導體裝置。
根據本發明，提供一種提升了高溫保管特性之高可靠性的半導體裝置。
以下，針對本發明實施形態，使用圖式進行說明。又，所有圖式中，對相同構成元件係加註相同符號，並適當省略說明。
本發明之半導體密封用環氧樹脂組成物係含有環氧樹脂(A)及硬化劑(B)，並對銅導及該銅導線所連接之半導體元件進行密封者。此環氧樹脂組成物中，該環氧樹脂組成物之硬化體經200℃ 10小時加熱時，含有對銅導線具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下。
作為本發明之半導體密封用環氧樹脂組成物所使用的環氧樹脂(A)，係於1分子內具有2個以上環氧基之所有單體、寡聚物、聚合物，其分子量、分子構造並無特別限定，可舉例如：聯苯型環氧樹脂、雙酚型環氧樹脂、茋型環氧樹脂等之結晶性環氧樹脂；酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂；三酚甲烷型環氧樹脂、烷基改質三酚甲烷型環氧樹脂等之多官能環氧樹脂；具有伸苯基骨架之酚芳烷基型環氧樹脂、具有伸聯苯基骨架之酚芳烷基型環氧樹脂等之芳烷基型環氧樹脂；二羥基萘型環氧樹脂、將二羥基萘之2聚物予以環氧丙基醚化而得的環氧樹脂等之萘酚型環氧樹脂；三環氧丙基三聚異氰酸酯、單烯丙基二環氧丙基三聚異氰酸酯等之含三核環氧樹脂；二環戊二烯改質酚型環氧樹脂等之有橋環狀烴化合物改質酚型環氧樹脂；此等可單獨使用1種，亦可併用2種以上。
作為環氧樹脂(A)，較佳可使用含有選自由下述式(2)所示之環氧樹脂、下述式(3)所示之環氧樹脂及下述式(4)所示之環氧樹脂所組成群之至少1種者。
[化1]
[式(2)中，Ar1表示伸苯基或伸萘基，在Ar1為伸萘基的情況，環氧丙基醚基可鍵結於α位、β位之任一者，Ar2表示伸苯基、伸聯苯基及伸萘基中之任一種基，R5及R6分別獨立表示碳數1~10之烴基，g為0~5之整數，h為0~8之整數，n3表示聚合度，其平均值為1~3之正數。]
[化2]
[式(3)中，複數存在之R9分別獨立表示氫原子或碳數1~4之烴基，n5表示聚合度，其平均值為0~4之正數。]
[化3]
[式(4)中，複數存在之R10及R11分別獨立表示氫原子或碳數1~4之烴基，n6表示聚合度，其平均值為0~4之正數。]
作為環氧樹脂(A)之調配比例的下限值並無特別限定，較佳係相對於半導體密封用環氧樹脂組成物整體，為3質量%以上、更佳5質量%以上。若環氧樹脂(A)之調配比例為上述範圍內，則發生因黏度上升所造成之導線斷線之疑虞較少。又，作為環氧樹脂(A)之調配比例之上限值並無特別限定，較佳係相對於半導體密封用環氧樹脂組成物整體，為20質量%以下、更佳18質量%以下。若環氧樹脂(A)之調配比例之上限值為上述範圍內，則發生因吸水率增加所造成之耐濕可靠性降低等之疑虞較少。
作為本發明之半導體密封用環氧樹脂組成物所使用的硬化劑(B)，可大致分為例如聚加成型之硬化劑、觸媒型之硬化劑、縮合型之硬化劑3種類型。
作為聚加成型之硬化劑，可舉例如：二乙三胺(DETA)、三乙四胺(TETA)、間茬二胺(MXDA)等之脂肪族多胺；二胺基二苯基甲烷(DDM)、間苯二胺(MPDA)、二胺基二苯基碸(DDS)等之芳香族多胺；二氰二醯胺(DICY)、含有有機酸二肼等之多胺化合物；六氫酞酸酐(HHPA)、甲基四氫酞酸酐(MTHPA)等之脂環族酸酐；包含偏苯三甲酸酐(TMA)、均苯四酸酐(PMDA)、二苯基酮四羧酸(BTDA)等之芳香族酸酐等之酸酐；酚醛清漆型酚樹脂、酚聚合物等之多酚化合物；多硫化物、硫酯、硫醚等之多硫醇化合物；異氰酸酯預聚物、嵌段化異氰酸酯等之異氰酸酯化合物；含羧酸之聚酯樹脂等之有機酸類等。
作為觸媒型之硬化劑，可舉例如：苄基二甲基胺(BDMA)、2,4,6-參二甲基胺基甲基酚(DMP-30)等之3級胺化合物；2-甲基咪唑、2-乙基-4-甲基咪唑(EMI24)等之咪唑化合物；BF3錯合物等之路易斯酸等。
作為縮合型之硬化劑，可舉例如：酚醛清漆型酚樹脂、可溶酚醛型酚樹脂等之酚樹脂系硬化劑；含羥甲基之尿素樹脂般之尿素樹脂；含羥甲基之三聚氰胺樹脂般之三聚氰胺樹脂等。
此等之中，由耐燃性、耐濕性、電氣特性、硬化性、保存安定性等之均衡的觀點而言，較佳為酚樹脂系硬化劑。酚樹脂系硬化劑係指一分子內具有2個以上酚性羥基之所有單體、寡聚物、聚合物，其分子量、分子構造並無特別限定，可舉例如酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等之酚醛清漆型樹脂；三酚甲烷型酚樹脂等之多官能型酚樹脂；萜烯改質酚樹脂、二環戊二烯改質酚樹脂等之改質酚樹脂；具有伸苯基骨架及/或伸聯苯基骨架之酚芳烷基樹脂、具有伸苯基及/或伸聯苯基骨架之萘酚芳烷基樹脂等之芳烷基型樹脂；雙酚A、雙酚F等之雙酚化合物等，此等可單獨使用1種或併用2種以上。
較佳可使用選自由下式(5)所示之化合物所組成群之至少1種硬化劑作為硬化劑(B)。
[化4]
[式(5)中，Ar3表示伸苯基或伸萘基，在Ar3為伸萘基的情況，羥基可鍵結於α位、β位之任一者，Ar4表示伸苯基、伸聯苯基及伸萘基中之任一種基，R7及R8分別獨立表示碳數1~10之烴基，i為0~5之整數，j為0~8之整數，n4表示聚合度，其平均值為1~3之正數。]
關於硬化劑(B)之調配比例之下限值並無特別限定，較佳係於半導體密封用環氧樹脂組成物中為0.8質量%以上，更佳為1.5質量%以上。若調配比例之下限值在上述範圍內，則可得到充分之流動性。又，關於硬化劑(B)之調配比例之上限值並無特別限定，較佳係於半導體密封用環氧樹脂組成物中為16質量%以下、更佳14質量%以下。若調配比例之上限值為上述範圍內，則發生因吸水率增加所造成之耐濕可靠性降低的疑慮較少。
另外，作為在使用酚樹脂系硬化劑作為硬化劑(B)時之環氧樹脂與酚樹脂系硬化劑的調配比率，較佳係總環氧樹脂之環氧基數(EP)與總酚樹脂系硬化劑之酚性羥基數(OH)的當量比(EP)/(OH)為0.8以上且1.3以下。若當量比為此範圍內，則發生半導體密封用環氧樹脂組成物之硬化性降低、或樹脂硬化物之物性降低等的疑慮較少。
另外，本發明之半導體密封用環氧樹脂組成物亦可含有無機填充材及視需要之中和劑或硬化促進劑。
作為無機填充材，可使用一般之半導體密封用環氧樹脂組成物所使用者。可舉例如熔融球狀二氧化矽、熔融破碎二氧化矽、結晶二氧化矽、滑石、氧化鋁、鈦白、氮化矽等；其中，特佳為熔融球狀二氧化矽。此等無機填充材可單獨使用1種或併用2種以上無妨。又，作為無機填充材之形狀，為了抑制半導體密封用環氧樹脂組成物之熔融黏度上升、進而提高無機填充材之含量，最好儘可能為正球狀，且粒度分佈寬廣。又，無機填充材亦可藉偶合劑予以表面處理。再者，視需要亦可藉環氧樹脂或酚樹脂對無機填充材事先進行處理；作為處理方法，有如在使用溶媒予以混合後將溶媒去除的方法；或直接添加至無機填充材中、使用混合機予以混合處理的方法等。
無機填充材之含有比例並無限定，若考慮到半導體密封用環氧樹脂組成物之填充性、半導體裝置之可靠性，較佳係相對於半導體密封用環氧樹脂組成物整體，為60質量%以上、更佳65質量%以上。若為不低於上述下限值之範圍，則因為可得到低吸濕性、低熱膨脹性，故耐濕可靠性不足的疑慮較少。又，關於無機填充材之含有比例的上限值，若考慮到成形性，則相對於半導體密封用環氧樹脂組成物整體，較佳為92質量%以下、更佳89質量%以下。若為不超過上述上限值之範圍，則流動性降低而在成形時發生填充不良等、或因高黏度化造成半導體裝置內之導線流動等不良情形的疑慮較少。
本發明所使用之環氧樹脂組成物中，為了抑制銅導線與半導體元件之鋁製電極墊間之接合部的腐蝕(氧化劣化)，亦可含有中和劑，以中和因加熱環氧樹脂組成物之硬化體所產生之酸性腐蝕性氣體。具體而言，較佳係含有選自由鹼性金屬鹽、尤其是含有鈣元素之化合物、含有鋁元素之化合物及含有鎂元素之化合物所組成群之至少1種中和劑。
作為上述含有鈣元素之化合物，可舉例如碳酸鈣、硼酸鈣、偏矽酸鈣等；其中，由雜質含量、耐水性及低吸水率的觀點而言，較佳為碳酸鈣，更佳為藉碳酸氣體反應法所合成之沉澱性碳酸鈣。
作為上述含鋁元素之化合物，可舉例如氫氧化鋁、水鋁石等。其中，較佳為氫氧化鋁；氫氧化鋁中，更佳為藉2階段拜耳法所合成之低鈉鹼氫氧化鋁。
作為上述含鎂元素之化合物，可舉例如水滑石、氧化鎂、碳酸鎂等；其中，由雜質含量及低吸水率之觀點而言，較佳為下式(1)所示之水滑石。
MaAlb(OH)2a+3b-2c(CO3)c‧mH2O　(1)
[式(1)中，M表示至少含有Mg之金屬元素，a、b、c分別為滿足2≦a≦8、1≦b≦3、0.5≦c≦2之數，m為0以上之整數。]
作為具體之水滑石，可舉例如Mg6Al2(OH)16(CO3)‧mH2O、Mg3ZnAl2(OH)12(CO3)‧mH2O、Mg4.3Al2(OH)12.6(CO3)‧mH2O等。
本發明所使用之環氧樹脂組成物中，作為中和劑之含有率，較佳係相對於組成物整體為0.01質量%以上且10質量%以下。若中和劑之含有率未滿上述下限，則無法充分得到中和劑添加效果，尤其有無法防止銅導線與半導體元件之鋁製電極墊間之接合部的腐蝕(氧化劣化)而使半導體裝置之高溫保管特性降低的傾向；另一方面，若超過上述上限，則吸濕率變高，有耐焊裂性降低之傾向。尤其在使用碳酸鈣或水滑石作為抗腐蝕劑的情況，由上述相同觀點而言，其含有率係相對於組成物整體，較佳為0.05質量%以上且2質量%以下。
本發明之半導體密封用環氧樹脂組成物中，可進一步使用硬化促進劑。硬化促進劑只要為可促進環氧樹脂之環氧基與硬化劑(例如酚樹脂系硬化劑之酚性羥基)間之交聯反應者即可，可使用一般半導體密封用環氧樹脂組成物所使用者。可舉例如：1,8-二氮雜雙環(5.4.0)十一烯-7等之二氮雜雙環烯及其衍生物；三苯基膦、甲基二苯基膦等之有機膦類；2-甲基咪唑等之咪唑化合物；四苯基鏻‧四苯基硼酸酯等之四取代鏻‧四取代硼酸酯；膦化合物與醌化合物之加成物等；此等可單獨使用1種或併用2種以上無妨。
作為硬化促進劑之調配比例之下限值並無特別限定，係相對於半導體密封用環氧樹脂組成物整體，較佳為0.05質量%以上、更佳0.1質量%以上。若硬化促進劑之調配比例之下限值為上述範圍內，則發生硬化性降低之疑慮較少。又，硬化促進劑之調配比例之上限值並無特別限定，係相對於半導體密封用環氧樹脂組成物整體，較佳為1質量%以下、更佳0.5質量%以下。若硬化促進劑之調配比例之上限值為上述範圍內，則發生流動性降低之疑慮較少。
本發明之半導體密封用環氧樹脂組成物中，視需要可進一步適當調配：氫氧化鋯等之抗鋁腐蝕劑；氧化鉍水合物等之無機離子交換體；γ-環氧丙氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷等之偶合劑；碳黑、鐵丹等之著色劑；聚矽氧橡膠等之低應力成分；棕櫚蠟等之天然蠟、合成蠟、硬脂酸鋅等之高級脂肪酸及其金屬鹽類或石蠟等之脫模劑；氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅、磷腈(phosphazene)等之難燃劑；抗氧化劑等之各種添加劑。
本發明之半導體裝置中所使用的半導體密封用環氧樹脂組成物，可使用將上述各成分，例如使用混合機等依15℃~28℃予以混合，其後再藉輥、捏合機、擠出機等之混練機予以熔融混練，冷卻後予以粉碎者等，視需要適當調整了分散度或流動性等者。
本發明之半導體密封用環氧樹脂組成物之硬化體，可藉由將上述環氧樹脂組成物依轉移模製、壓縮模製、射出模製等習知成形方法進行成形硬化而獲得。藉轉移模製等成形方法所成形硬化之環氧樹脂組成物之硬化體，視需要亦可依80℃~200℃左右的溫度，歷時10分鐘~10小時左右之時間使其完全硬化而獲得。
如此所得之本發明之半導體密封用環氧樹脂組成物之硬化體，於乾燥空氣環境下經200℃ 10小時加熱時，由該硬化體所產生之第一腐蝕性氣體的產生量為70ppm以下。本說明書中，所謂「乾燥空氣」係指由大氣去除了水分及二氧化碳者；具體而言係指使大氣中水分量成為0.1容量%以下、且二氧化碳濃度成為0.04容量%以下者。關於第一腐蝕性氣體，若為含有硫元素且對銅導線等具有腐蝕性之化合物，則無特別限定，可舉例如亞硫酸氣體(二氧化硫，SO2)、硫化氫(H2S)、三氧化硫(SO3)；此等可單獨產生1種或產生2種以上。
由本發明之半導體密封用環氧樹脂組成物之硬化體所產生的第一腐蝕性氣體之產生量只要為70ppm以下即可，若為60ppm以下，則由可確保150℃中之高溫保管性的觀點而言屬較佳，若為35ppm以下，則由於可提升更高溫之175℃中之高溫保管特性，故更佳。
另外，本發明之半導體密封用環氧樹脂組成物之硬化體，在乾燥空氣環境下經200℃ 10小時加熱時，亦可產生對銅導線具有腐蝕性的第二、第三腐蝕性氣體。此時，若第一、第二及第三腐蝕性氣體之產生量合計為230ppm以下，則由可確保150℃中之高溫保管性的觀點而言屬較佳，若為200ppm以下，則由於可提升更高溫之175℃中之高溫保管特性，故更佳。
第二腐蝕性氣體係含有對銅導線具有腐蝕性之鹵化合物，具體可舉例如氟化氫、氯化氫、溴化氫、碘化氫；此等可單獨產生1種或產生2種以上不同之鹵化合物。
第三腐蝕性氣體係含有對銅導線具有腐蝕性之有機酸，具體可舉例如碳數1~4之脂肪族羧酸。更具體可舉例如甲酸、乙酸、丙酸、丁酸等；此等可單獨產生1種或產生2種以上不同之有機酸。
第一、第二及第三腐蝕性氣體之產生量，可藉由將使上述硬化體經200℃ 10小時加熱時所產生之腐蝕性氣體，直接或採集至液體中並利用離子層析法進行分析。
分析條件係如下述。
‧分析裝置：DIONEX公司製「ICS2000型」
‧管柱：DIONEX公司製「AS17」
‧流速：1.5ml/min
‧檢測器：電傳導度檢測器
‧溶媒：氫氧化鉀(梯度1mL~35mM)
‧保持時間：亞硫酸離子12.7分鐘，氯化物離子6.0分鐘，甲酸3.6分鐘，乙酸2.9分鐘
接著，使用圖1說明本發明之半導體裝置。本發明之半導體裝置係具有：具有晶粒墊部3a之引線框架3；搭載於晶粒墊部3a之半導體元件1；將引線框架3與半導體元件1電性連接之銅導線4；與密封樹脂5，係由上述環氧樹脂組成物之硬化體所構成，且密封著半導體元件1與銅導線4。
作為半導體元件1，並無特別限定，可舉例如集體電路、大規模集體電路、固態影像元件等。
作為本發明所使用之引線框架3並無特別限制，亦可取代引線框架3而使用電路基板。具體而言可使用雙列直插式封裝(DIP)、塑膠晶粒承載封裝(PLCC)、四方扁平封裝(QFP)、低剖面四方扁平封裝(LQFP)、小外型J型引腳封裝(SOJ)、薄型小外型封裝(TSOP)、薄型四方扁平封裝(TQFP)、捲帶式載體封裝(TCP)、球柵列陣(BGA)、晶片尺寸封裝(CSP)、四方扁平無引腳封裝(QFN)、小外型無引腳封裝(SON)、引線框架‧BGA(LF-BGA)、模製陣列封裝型之BGA(MAP-BGA)等之習知半導體裝置所使用的引線框架或電路基板。
半導體元件1亦可為複數之半導體元件所積層者。此時，第一階之半導體元件係經由薄膜接黏劑、熱硬化性接黏劑等之黏晶材硬化體2而接黏至晶粒墊部3a。第二階以後之半導體元件可藉由絕緣性之薄膜接黏劑依序予以積層。然後，於最上層形成電極墊6。
電極墊6係以鋁作為主成分。作為電極墊6所使用之鋁之純度並無特別限定，較佳為99.5質量%以上。電極墊6可藉由於下層之銅電路端子之表面上形成一般之鈦製隔離層，再應用將鋁進行蒸鍍、濺鍍、無電解鍍敷等一般半導體元件之電極墊形成方法而製作。
銅導線4係用於將引線框架3與引線框架3之晶粒墊部3a上所搭載之半導體元件1予以電性連接。銅導線4之表面上，係自然地或製程上不可避免地形成氧化膜。本發明中，所謂銅導線4，亦包括具備如此形成於導線表面上之氧化膜者。
銅導線4之導線徑較佳為30μm以下、更佳25μm以下且15μm以上。若為此範圍，則銅導線前端之球形狀穩定，可提升接合部分之連接可靠性。又，可減低因銅導線本身之硬度所造成的導線流動。
銅導線4並無特別限定，較佳為銅純度99.99質量%以上，更佳為99.999質量%以上。一般而言，藉由對銅添加各種元素(摻雜物)可達到接合時之銅導線前端之球側形狀穩定化，但若添加大於0.01質量%之大量摻雜物，則因導線接合時球部分變硬而對半導體元件1之電極墊6側造成損傷，而發生接合不足所起因的耐濕可靠性降低、高溫保管特性降低、電阻值增大等不良情形。相對於此，若為銅純度99.99質量%以上之銅導線4，則由於球部分具有充分柔軟性，故於接合時沒有對墊側造成損傷之虞。尚且，本發明之半導體裝置中可使用之銅導線4，可藉由於芯線之銅中摻雜0.001質量%~0.003質量%之Ba、Ca、Sr、Be、Al或稀土族金屬以進而改善球形狀與接合強度。
另外，銅導線4較佳係於其表面上具有由含鈀之金屬材料所構成的被覆層。藉此，可使銅導線前端之球形狀穩定，提升接合部分之連接可靠性。又，亦可得到防止芯線之銅的氧化劣化之效果，且可提升接合部分之高溫保管特性。
作為銅導線4中之由含鈀之金屬材料所構成的被覆層的厚度，較佳為0.001μm~0.02μm，更佳為0.005μm~0.015μm。若超過上述上限值，則導線接合時芯線之銅與被覆材之含鈀之金屬材料未充分熔融而使球形狀不穩定，有接合部分之耐濕性、高溫保管特性降低之虞。又，若小於上述下限值，則無法充分防止芯線之銅的氧化劣化，同樣地有接合部分之耐濕性、高溫保管特性降低之虞。
銅導線4可藉由將銅合金在熔解爐進行鑄造，對其鑄塊進行輥軋延，進而使用眼模進行抽線加工，並實施一邊連續性地對導線進行掃掠、一邊進行加熱的後熱處理即可獲得。又，本發明之半導體裝置中可使用的銅導線4中之由含鈀之金屬材料所構成的被覆層，係預先準備所需的導線徑之線，將其浸漬於含鈀之電解溶液或無電解溶液，連續性地進行掃掠並予以鍍敷，使可形成被覆層。此時，被覆之厚度可藉由掃掠速度而調整。又，亦可採用準備較所需更粗的線，將其浸漬於電解溶液或無電解溶液中並連續性地掃掠以形成被覆層，再進行抽線至既定徑的手法。
引線框架3之引線部3b與半導體元件1之間，亦可藉導線之逆打線法予以接合。逆打線時，首先係於半導體元件1之電極墊6上接合形成於銅導線4前端的球，切斷銅導線4以形成針腳式接合用的凸塊。其次，對引線框架3之經金屬鍍敷的引線部3b接合形成於導線前端的球，並予以針腳式接合至半導體元件之凸塊上。逆打線時，由於可較正打線更加減低半導體元件1上之導線高度，故可減低半導體元件1之接合高度。
本發明之半導體裝置係使用半導體密封用環氧樹脂組成物，對半導體元件等電子零件進行密封，並依轉移模製、壓縮模製、射出模製等習知成形方法予以硬化成形而獲得。藉轉移模製等成形方法所密封之半導體裝置，係直接、或依80℃~200℃左右的溫度歷時10分鐘~10小時左右的時間使其完全硬化後，搭載於電子機器等中。
密封樹脂5係上述說明之環氧樹脂組成物之硬化體。因此，密封樹脂5於乾燥空氣環境下經200℃10小時加熱時，含有對銅導線4具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下。又，密封樹脂5於乾燥空氣環境下經200℃10小時加熱時，亦可產生含有鹵化合物之第二腐蝕性氣體、以及含有有機酸之第三腐蝕性氣體，而第一、第二及第三腐蝕性氣體之產生量合計較佳為230ppm以下。
因密封樹脂5之熱處理所產生之第一、第二及第三腐蝕性氣體的產生量，亦與上述說明之環氧樹脂組成物之硬化體同樣地可藉由離子層析法進行分析。
接著，針對本發明之作用效果，使用圖1予以具體說明。根據本發明，使半導體裝置經200℃ 10小時加熱時之由密封樹脂5所產生之二氧化硫的產生量成為70ppm以下。藉此，由於可減低銅導線4與半導體元件之鋁製電極墊間之接合部的腐蝕(氧化劣化)，故可實現不易發生接合部之電阻上升或接合部斷線的高可靠性半導體裝置。
銅導線4由於價廉，故有助於半導體裝置之低成本化。然而，若對連接了銅導線4之半導體元件1藉習知環氧樹脂組成物進行密封，則有高溫保管性降低的情形。
銅導線4與半導體元件1之鋁製電極墊6間之接合部的腐蝕(氧化劣化)的機制，一般認為如下述。在銅導線4與半導體元件1之鋁性電極墊6的接合界面係形成銅鋁合金。銅鋁合金係一般耐腐蝕性較低。在高溫保管時，由構成密封樹脂5之環氧樹脂組成物之硬化體因熱分解而產生微量之腐蝕性氣體(酸性氣體)。由於此腐蝕性氣體而使耐腐蝕性低之銅鋁合金層發生乾蝕(腐蝕、氧化劣化)，並發生接合部之電阻上升或斷線。
因此，使半導體裝置經熱處理時，由密封樹脂5所產生之含有硫化合物之第一腐蝕性氣體之產生量成為70ppm以下。藉此，可避免銅導線4與半導體元件1之鋁製電極墊6間之接合部的腐蝕(氧化劣化)。又，使由密封樹脂5所產生之含有硫化合物之第一腐蝕性氣體、含有鹵化合物之第二腐蝕性氣體、含有有機酸之第三腐蝕性氣體的產生量合計成為230ppm以下。藉此，可有效防止銅導線4與半導體元件1之鋁製電極墊6間之接合部的腐蝕(氧化劣化)。因此，根據本發明之半導體裝置，可使高溫保管特性優越。亦即，將本發明之半導體裝置保管於150℃環境下，將佈線間之電阻值相對於初期值係增加了20%之半導體裝置判定為不良時，即使經2000小時之高溫保管仍未發生不良。又，將本發明之半導體裝置保管於175℃環境下，並同樣地判定不良時，即使經200小時之高溫保管仍未發生不良。
通常，半導體裝置若具有於150℃中2000小時以上、於175℃中200小時以上之耐性，即可確保充分之可靠性。因此，藉由使環氧樹脂組成物之硬化體經200℃ 10小時熱處理時之腐蝕性氣體之產生量成為上述範圍，則可充分確保半導體裝置之高溫保管特性。
如以上所述，根據本發明之環氧樹脂組成物，可得到高溫保管特性高之半導體裝置，故可實現不易發生斷線的高可靠性半導體裝置。
以上，參照圖式敘述了本發明之實施形態，但此等僅為本發明之例示，亦可採用上述以外的各種構成。
(實施例)
以下，根據實施例及比較例更具體說明本發明，但本發明並不限定於以下實施例。實施例及比較例中所使用之環氧樹脂組成物的各成分如以下所示。
<環氧樹脂>
BA-1：具有伸聯苯基骨架之酚芳烷基型環氧樹脂(上式(2)中，Ar1為伸苯基、Ar2為伸聯苯基、g為0、h為0之環氧樹脂，日本化藥(股)製「NC3000」，軟化點58℃，環氧當量276，水解氯230ppm)。
BA-2：具有伸聯苯基骨架之酚芳烷基型環氧樹脂(BA-1的通用品，軟化點55℃，環氧當量283，水解氯3000ppm)。
BP-1：聯苯型環氧樹脂(上式(3)中，3位、3’位及5位、5’位之R9為甲基，2位、2’位及6位、6’位之R9為氫原子的環氧樹脂，Japan Epoxy Resin(股)製「YX4000H」，熔點105℃，環氧當量191，水解氯150ppm)。
BP-2：聯苯型環氧樹脂(上式(3)中，3位、3’位及5位、5’位之R9為甲基，2位、2’位及6位、6’位之R9為氫原子的環氧樹脂，Japan Epoxy Resin(股)製「YX4000」，熔點105℃，環氧當量185，水解性氯670ppm)。
BP-3：聯苯型環氧樹脂(將上式(3)中，3位、3’位及5位、5’位之R9為甲基，2位、2’位及6位、6’位之R9為氫原子的環氧樹脂藉再結晶法予以精製的環氧樹脂，三菱化學(股)製「YX4000UH」，熔點113℃，環氧當量177，水解性氯未滿15ppm)。
<硬化劑>
HA-1：具有伸聯苯基骨架之酚芳烷基樹脂(上式(5)中，i為0、j為0、Ar3為伸苯基、Ar4為伸聯苯基之酚芳烷基樹脂，明和化成(股)製「MEH-7851SS」，軟化點65℃，羥基當量203)
HB-1：酚芳烷基樹脂(上式(5)中，i為0、j為0、Ar3為伸苯基、Ar4為伸苯基之酚芳烷基樹脂，三化學(股)製「XLC-2L」，羥基當量175，150℃之熔融黏度360mPa‧s)
<填充材>
熔融球狀二氧化矽(平均粒徑26.5μm，105μm以上之粒子為1%以下，電氣化學工業(股)製「FB-820」
<中和劑>
水滑石(上式(1)中，a為4.3、b為2、c為1之水滑石，協和化學工業(股)製「DHT-4A(註冊商標)」
<硬化促進劑>
A：三苯基膦(TPP，K‧I化成(股)製「PP360」之1,4-苯醌加成物
B：三苯基膦(TPP，K‧I化成(股)製「PP360」)
<偶合劑>
C-1：γ-環氧丙氧基丙基三甲氧基矽烷
C-2：γ-巰基丙基三乙氧基矽烷
<難燃劑>
氫氧化鋁(住友化學(股)製，CL-310，平均粒徑9.6μm，比表面積1.1m2/g)
上述各成分之外，尚使用碳黑作為著色劑，使用棕櫚蠟作為脫模劑。
環氧樹脂組成物之製造： (實施例1)
將環氧樹脂BA-1(5.91質量份)、硬化劑HA-1(4.34質量份)、作為填充材之熔融球狀二氧化矽(86.40質量份)、作為中和劑之水滑石(0.30質量份)、硬化促進劑A(0.50質量份)、偶合劑C-1(0.25質量份)、作為著色劑之碳黑(0.30質量份)、作為脫模劑之棕櫚蠟(0.50質量份)與作為難燃劑之氫氧化鋁(1.50質量份)，使用混合機依15~28℃進行混合，接著依70℃~100℃進行輥混練。冷卻後，予以粉碎而得到環氧樹脂組成物。
(實施例2~5、比較例1~3)
依表1記載之半導體密封用環氧樹脂組成物配方，與實施例1同樣地進行而得到半導體密封用環氧樹脂組成物。表1中，各成分的單位為質量份。
(實施例6~12、比較例4~6)
依表2記載之半導體密封用環氧樹脂組成物配方，與實施例1同樣地進行而得到半導體密封用環氧樹脂組成物。表2中，各成分的單位為質量份。
半導體裝置之製造：
將具備鋁製電極墊之TEG(TEST ELEMENT GROUP，測試元件組)晶片(3.5mmx3.5mm)，接黏至352引腳BGA(基板係厚0.56mm，雙順丁烯二醯亞胺‧三樹脂/玻璃布基板，封裝尺寸為30mmx30mm，厚1.17mm)的晶粒墊部上，依使TEG晶片之鋁製電極墊與基板之電極墊成為菊鍊連接之方式，使用銅導線4N依導線間距80μm進行導線接合。使用低壓轉移成形機(TOWA製「Y系列」)，對其依模具溫度175℃、注入壓力6.9MPa、硬化時間2分鐘之條件藉實施例1~12或比較例1~6之任一環氧樹脂組成物進行密封成形，製作352引腳BGA封裝。將此封裝依175℃、4小時之條件進行後硬化而得到半導體裝置。
評價方法：
(1)　環氧樹脂組成物之物性評估
將所得之環氧樹脂組成物之物性藉以下方法進行測定。其結果示於表1、2。
<螺旋流動(SF)>
使用低壓轉移成形機(Kohtaki精機(股)製「KTS-15」)，對根據EMMI-1-66之螺旋流動測定用之模具，依模具溫度175℃、注入壓力6.9MPa、硬化時間120秒之條件，分別注入實施例1~12、比較例1~6之環氧樹脂組成物，測定流動長(單位：cm)。若為80cm以下，則有發生封裝未填充等之成形不良的情形。
<凝膠時間(GT)>
於加熱至175℃之熱板上分別使實施例1~12、比較例1~6之環氧樹脂組成物熔融後，一邊以攪棒予以混練、一邊測定硬化為止的時間。
<腐蝕性氣體量之測定>
將實施例1~12、比較例1~6之環氧樹脂組成物依175℃、4小時進行硬化後，將其以振動磨粉碎。將所得硬化體粉末以公制孔徑74μm(200網目)之篩去除粗粒子，將所得樣本試料2g設置於圖2所示之玻璃製管狀爐的試料板101上。接著，使水分量0.1容量%以下之空氣A通過CO2捕捉器(通氣孔過濾器)102，而將二氧化碳濃度成為0.04容量%以下之乾燥空氣投入至試料板101中，於該乾燥空氣環境下(流量10ml/分鐘)藉加熱爐103對硬化物粉末依200℃加熱10小時。所產生之腐蝕性氣體係被捕集至由冰水105所冷卻之捕集液104中而使總量成為25mL之檢液。具體而言，作為所產生之亞硫酸氣體之捕集液104，係使用稀薄之過氧化氫溶液(於超純水25ml中加入了濃度35%之過氧化氫水0.1ml者)。又，作為氯化氫及有機酸(甲酸及乙酸)之捕集液105，係使用稀薄之氫氧化鉀溶液(8mmol/L)。將所得檢液導入至離子層析裝置(DIONEX公司製「ICS2000型」)中。分析條件係如上述所說明般，設為[流速：1.5ml/min，檢測器：電傳導度檢測器，溶媒：氫氧化鉀(梯度1~35mM)]。藉檢量曲線法定量出各離子，換算成由試料所產生之離子量。結果示於表1、2。
(2)半導體裝置之特性評估
將所製作之半導體裝置之高溫保管性(HTSL)藉以下方法進行測定。其結果示於表1、2。
<HTSL1>
將所得之半導體裝置保管於150℃環境下，每24小時測定佈線間之電阻值，將該值相對於初期值係增加了20%的半導體裝置判定為不良，測定成為不良為止的時間(單位：小時)。測定係針對5個半導體裝置進行，其中，將最早成為不良的時間示於表1、2。又，在所有半導體裝置即使經2000小時高溫保管仍未發生不良的情況記載為「>2000」。
<HTSL2>
將所得之半導體裝置保管於175℃環境下，每24小時測定佈線間之電阻值，將該值相對於初期值係增加了20%的半導體裝置判定為不良，測定成為不良為止的時間(單位：小時)。測定係針對5個半導體裝置進行，其中，將最早成為不良的時間示於表1、2。
<判定>
將HTSL1中，即使經2000小時高溫保管仍未發生不良，且HTSL2中，即使經200小時高溫保管仍未發生不良的情形判定為良(○)，將其以外判定為不良(╳)。
如表1、2所示般，在具備使實施例1~12之環氧樹脂組成物硬化而成之密封樹脂的半導體裝置中，係於150℃環境下，即使經2000小時高溫保管仍未發生不良。又，將其保管於175℃環境下時，即使經200小時高溫保管仍未發生不良。從而，表示藉由使用使硬化體依200℃ 10小時加熱時之SO2產生量成為70ppm以下，並使SO2、氫化氫(HCl)、甲酸及乙酸之產生量成為230ppm以下的環氧樹脂組成物，則可提升半導體裝置之高溫保管性。
1．．．半導體元件
2．．．黏晶材硬化體
3．．．引線框架
3a．．．晶粒墊部
3b．．．引線部
4．．．銅導線
5．．．密封樹脂
6．．．電極墊
101．．．試料板
102．．．CO2捕捉器
103．．．加熱爐
104．．．捕集液
105．．．冰水
A．．．空氣
圖1為表示實施形態中之半導體裝置的概略剖面圖。
圖2為表示用於本發明之半導體密封用環氧樹脂組成物之評估的裝置之一例的圖。
1．．．半導體元件
2．．．黏晶材硬化體
3．．．引線框架
3a．．．晶粒墊部
3b．．．引線部
4．．．銅導線
5．．．密封樹脂
6．．．電極墊

Claims (19)

  1. 一種半導體密封用環氧樹脂組成物，係含有環氧樹脂(A)及硬化劑(B)，並對銅導線及上述銅導線所連接之半導體元件進行密封者，其特徵為，上述半導體密封用環氧樹脂組成物之硬化體經200℃ 10小時加熱時，含有對上述銅導線具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下；上述環氧樹脂(A)係含有聯苯型環氧樹脂；該半導體密封用環氧樹脂組成物係含有水滑石。
  2. 如申請專利範圍第1項之半導體密封用環氧樹脂組成物，其中，上述第一腐蝕性氣體為亞硫酸氣體。
  3. 如申請專利範圍第1或2項之半導體密封用環氧樹脂組成物，其中，含有鹵化合物之第二腐蝕性氣體及含有有機酸之第三腐蝕性氣體係對上述銅導線具有腐蝕性，上述半導體密封用環氧樹脂組成物之硬化體經200℃ 10小時加熱時後，上述第一、第二及第三腐蝕性氣體之產生量合計為230ppm以下。
  4. 如申請專利範圍第3項之半導體密封用環氧樹脂組成物，其中，上述第二腐蝕性氣體為氯化氫氣體。
  5. 如申請專利範圍第3項之半導體密封用環氧樹脂組成物，其中，上述第三腐蝕性氣體係含有二種以上不同之有機酸。
  6. 如申請專利範圍第3項之半導體密封用環氧樹脂組成物，其中，上述第三腐蝕性氣體係含有甲酸及/或乙酸。
  7. 如申請專利範圍第1項之半導體密封用環氧樹脂組成物，其中，上述水滑石為下式(1)所示化合物；MaAlb(OH)2a+3b-2c(CO3)c．mH2O (1)[式(1)中，M表示至少含有Mg之金屬元素，a、b、c分別為滿足2≦a≦8、1≦b≦3、0.5≦c≦2之數，m為0以上之整數]。
  8. 如申請專利範圍第1或2項之半導體密封用環氧樹脂組成物，其中，上述環氧樹脂(A)係含有選自由下式(2)所示之環氧樹脂、下式(3)所示之環氧樹脂及下式(4)所示之環氧樹脂所組成群之至少一種； [式(2)中，Ar1表示伸苯基或伸萘基，在Ar1為伸萘基的情況，環氧丙基醚基可鍵結於α位、β位之任一者，Ar2表示伸苯基、伸聯苯基及伸萘基中之任一種基，R5及R6分別獨立表示碳數1~10之烴基，g為0~5之整數，h為0~8之整 數，n3表示聚合度，其平均值為1~3之正數]； [式(3)中，複數存在之R9分別獨立表示氫原子或碳數1~4之烴基，n5表示聚合度，其平均值為0~4之正數]； [式(4)中，複數存在之R10及R11分別獨立表示氫原子或碳數1~4之烴基，n6表示聚合度，其平均值為0~4之正數]。
  9. 如申請專利範圍第1或2項之半導體密封用環氧樹脂組成物，其中，上述環氧樹脂組成物係含有選自由下式(5)所示化合物所組成群之至少1種硬化劑； [式(5)中，Ar3表示伸苯基或伸萘基，在Ar3為伸萘基的情 況，羥基可鍵結於α位、β位之任一者，Ar4表示伸苯基、伸聯苯基及伸萘基中之任一種基，R7及R8分別獨立表示碳數1~10之烴基，i為0~5之整數，j為0~8之整數，n4表示聚合度，其平均值為1~3之正數]。
  10. 如申請專利範圍第1或2項之半導體密封用環氧樹脂組成物，其中，上述銅導線之銅純度為99.99質量%以上。
  11. 如申請專利範圍第1項之半導體密封用環氧樹脂組成物，其中，進一步含有氫氧化鋁。
  12. 如申請專利範圍第1或2項之半導體密封用環氧樹脂組成物，其中，上述第一腐蝕性氣體的產生量為30ppm以上且70ppm以下。
  13. 一種硬化體，係申請專利範圍第1或2項之半導體密封用環氧樹脂組成物的硬化體。
  14. 一種半導體裝置，其具有：具有晶粒墊部之引線框架；搭載於上述晶粒墊部之半導體元件；將上述引線框架與上述半導體元件電性連接之銅導線；與密封樹脂，係由環氧樹脂組成物之硬化體所構成，且密封著上述半導體元件與上述銅導線；上述密封樹脂經200℃ 10小時加熱時，含有對上述銅導線具有腐蝕性之硫化合物的第一腐蝕性氣體的產生量為70ppm以下； 上述環氧樹脂組成物係含有環氧樹脂(A)；上述環氧樹脂(A)係含有聯苯型環氧樹脂；該半導體密封用環氧樹脂組成物係含有水滑石。
  15. 如申請專利範圍第14項之半導體裝置，其中，含有鹵化合物之第二腐蝕性氣體及含有有機酸之第三腐蝕性氣體係對上述銅導線具有腐蝕性，上述密封樹脂經200℃ 10小時加熱時，上述第一、第二及第三腐蝕性氣體之產生量合計為230ppm以下。
  16. 如申請專利範圍第14項之半導體裝置，其中，進一步含有水滑石。
  17. 如申請專利範圍第14或15項之半導體裝置，其中，上述環氧樹脂組成物係進一步含有氫氧化鋁。
  18. 如申請專利範圍第14或15項之半導體裝置，其中，上述第一腐蝕性氣體的產生量為30ppm以上且70ppm以下。
  19. 如申請專利範圍第14或15項之半導體裝置，其中，上述第一腐蝕性氣體為亞硫酸氣體。
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