JP6475612B2 - 電子部品実装用接着剤及びフリップチップ実装用接着フィルム - Google Patents
電子部品実装用接着剤及びフリップチップ実装用接着フィルム Download PDFInfo
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- JP6475612B2 JP6475612B2 JP2015513541A JP2015513541A JP6475612B2 JP 6475612 B2 JP6475612 B2 JP 6475612B2 JP 2015513541 A JP2015513541 A JP 2015513541A JP 2015513541 A JP2015513541 A JP 2015513541A JP 6475612 B2 JP6475612 B2 JP 6475612B2
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- C—CHEMISTRY; METALLURGY
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/93—Batch processes
- H01L2224/94—Batch processes at wafer-level, i.e. with connecting carried out on a wafer comprising a plurality of undiced individual devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
Description
しかしながら、近年、半導体チップの小型化が進行するとともに電極間のピッチもますます狭くなっており、また、これらに伴って半導体チップ同士又は半導体チップと基板との間のギャップが狭くなっていることから、アンダーフィルの注入時に空気が巻き込まれ、ボイドが発生しやすくなっている。
しかしながら、このような方法では、接着剤の硬化が遅いと、半田溶融時点で接着剤が充分に硬化せず、溶融した半田が接着剤の流動によって押し流されること(半田流れ)があった。また、実装時に接着剤が充分に硬化していないと、実装後の冷却過程でボイドが発生しやすくなっていた。フリップチップ実装では生産性を上げるためにも実装時間を短くすることが求められているが、従来の接着剤又は接着フィルムでは、短い実装時間の中で半田流れを抑えつつ充分に半田接合することが困難であった。
以下、本発明を詳述する。
これまでに、例えば、アクリル重合体を含む接着剤組成物(特開2010−126617号公報)、ジエン系化合物の重合体または共重合体で両末端に重合可能な炭素−炭素2重結合を有する化合物を含む樹脂組成物(特許第5228419号公報)等が知られているが、これらの組成物は、電子部品の接着の際の接合信頼性(例えば、耐熱性、耐湿熱安定性等)の維持を目的としたものであり、フリップチップ実装において短い実装時間の中で半田流れを抑えつつ充分に半田接合することは困難であった。
これに対して、本発明者は、側鎖に(メタ)アクリロイル基を有する二重結合当量1〜5meq/gのアクリルポリマーと、3官能以上の多官能(メタ)アクリレート化合物と、ラジカル重合開始剤とを含有する電子部品実装用接着剤であれば、短い実装時間の中で半田流れを抑えつつ充分に半田接合でき、ボイドを抑制し、耐リフロー性にも優れることを見出し、本発明を完成させるに至った。
これらの成分を含有することにより、本発明の電子部品実装用接着剤は、ラジカル重合反応により硬化し、短い実装時間の中で半田流れを抑えつつ充分に半田接合できるものとなり、また、実装時に充分に硬化し、実装後の冷却過程でのボイドの発生を抑制することができる。また、本発明の電子部品実装用接着剤は、接合信頼性にも優れたものとなり、耐リフロー性が向上する。
なお、側鎖に(メタ)アクリロイル基を有するとは、最も長い炭素鎖である「主鎖」の片末端又は両末端ではなく、主鎖から分岐した「側鎖」中に(メタ)アクリロイル基を有することを意味する。
なお、本明細書における二重結合当量とは、側鎖に(メタ)アクリロイル基を有するアクリルポリマー1g当たりの(メタ)アクリロイル基の平均個数に関する指標を意味し、具体的には、下記式(a)から算出される。
二重結合当量(meq/g)
=[側鎖に(メタ)アクリロイル基を有するアクリルポリマー1分子中の(メタ)アクリロイル基の平均個数]×1000/[側鎖に(メタ)アクリロイル基を有するアクリルポリマーの数平均分子量] (a)
なお、二重結合当量はヨウ素価を測定することにより算出できる。
なお、必ずしも官能基含有アクリルポリマーの官能基の全てが、その官能基と反応可能であり、かつ、(メタ)アクリロイル基を有する化合物と反応している必要はない。
(1)水酸基含有アクリルポリマーに対しては、アミド基、イソシアネート基、エポキシ基及びカルボキシル基からなる群より選択される少なくとも1つを有し、かつ、(メタ)アクリロイル基を有する化合物を反応させればよい。
(2)カルボキシル基含有アクリルポリマーに対しては、エポキシ基又はイソシアネート基を有し、かつ、(メタ)アクリロイル基を有する化合物を反応させればよい。
(3)エポキシ基含有アクリルポリマーに対しては、カルボキシル基又はアミド基を有し、かつ、(メタ)アクリロイル基を有する化合物を反応させればよい。
(4)アミノ基含有アクリルポリマーに対しては、エポキシ基を有し、かつ、(メタ)アクリロイル基を有する化合物を反応させればよい。
(5)イソシアネート基含有アクリルポリマーに対しては、水酸基又はカルボキシル基を有し、かつ、(メタ)アクリロイル基を有する化合物を反応させればよい。
なお、重量平均分子量(Mw)は、ゲルパミエーションクロマトグラフィ(GPC)法によりポリスチレン換算分子量として測定される。具体的には、重量平均分子量(Mw)は、アクリルポリマーをテトラヒドロフラン(THF)によって50倍希釈して得られた希釈液をフィルターで濾過し、得られた濾液を用いてGPC法によりポリスチレン換算分子量として測定される。GPC法では、例えば、2690 Separations Model(Waters社製)等を使用できる。
なお、3官能以上の多官能(メタ)アクリレート化合物とは、1分子中に(メタ)アクリレート部分を3以上有する化合物である。1分子中に(メタ)アクリレート部分が2以下であると、半田流れが生じやすくなって半田接合性が低下し、また、実装後の冷却過程でボイドが発生しやすくなる。また、本明細書中、1分子中に(メタ)アクリレート部分に加えてエポキシ基を有する化合物は「3官能以上の多官能(メタ)アクリレート化合物」には含まず、後述する「エポキシ樹脂」であるものとする。
また、上記過酸化物のうち、有機過酸化物の市販品として、例えば、パーロイル355(10時間半減期温度:59.4℃)、パーロイルL(10時間半減期温度:61.6℃)、パーオクタO(10時間半減期温度:65.3℃)、パーロイルSA(10時間半減期温度:65.9℃)、パーヘキサ25O(10時間半減期温度:66.2℃)、パーヘキシルO(10時間半減期温度:69.9℃)、ナイパーPMB(10時間半減期温度:70.6℃)、パーブチルO(10時間半減期温度:72.1℃)、ナイパーBMT(10時間半減期温度:73.1℃)、ナイパーBW(10時間半減期温度:73.6℃)、パーヘキサMC(10時間半減期温度:83.2℃)、パーヘキサTMH(10時間半減期温度:86.7℃)、パーヘキサHC(10時間半減期温度:87.1℃)、パーヘキサC(10時間半減期温度:90.7℃)、パーテトラA(10時間半減期温度:94.7℃)、パーヘキシルI(10時間半減期温度:95.0℃)、パーブチルMA(10時間半減期温度:96.1℃)、パーブチル355(10時間半減期温度:97.1℃)、パーブチルL(10時間半減期温度:98.3℃)、パーブチルI(10時間半減期温度:98.7℃)、パーブチルE(10時間半減期温度:99.0℃)、パーヘキシルZ(10時間半減期温度:99.4℃)、パーヘキサ25Z(10時間半減期温度:99.7℃)、パーブチルA(10時間半減期温度:101.9℃)、パーヘキサ22(10時間半減期温度:103.1℃)、パーブチルZ(10時間半減期温度:104.3℃)、パーヘキサV(10時間半減期温度:104.5℃)、パーブチルD(10時間半減期温度:123.7℃)、パークミルD(10時間半減期温度116.4℃)、パーヘキシン25B(10時間半減期温度:128.4℃)(以上、日油社製)等が挙げられる。
これらの過酸化物は、単独で用いてもよく、2種以上を併用してもよい。
上記イミダゾール系硬化剤は特に限定されず、例えば、フジキュアー7000、フジキュアー7001、フジキュアー7002(以上、T&K TOKA社製、常温(25℃)で液状)、イミダゾールの1位をシアノエチル基で保護した1−シアノエチル−2−フェニルイミダゾール、イソシアヌル酸で塩基性を保護したイミダゾール系硬化剤(商品名「2MA−OK」、四国化成工業社製、常温(25℃)で固体)、2MZ、2MZ−P、2PZ、2PZ−PW、2P4MZ、C11Z−CNS、2PZ−CNS、2PZCNS−PW、2MZ−A、2MZA−PW、C11Z−A、2E4MZ−A、2MAOK−PW、2PZ−OK、2MZ−OK、2PHZ、2PHZ−PW、2P4MHZ、2P4MHZ−PW、2E4MZ・BIS、VT、VT−OK、MAVT、MAVT−OK(以上、四国化成工業社製)等が挙げられる。これらのイミダゾール系硬化剤は、単独で用いてもよく、2種以上を併用してもよい。
上記無機フィラーは単独で使用してもよいし、複数種の無機フィラーを混合して使用してもよい。
上記混合の方法は特に限定されず、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー等を使用する方法が挙げられる。
なかでも、本発明の電子部品実装用接着剤からなる接着剤層を有するフリップチップ実装用接着フィルムを、基板又は半導体チップに予め貼付しておき、加熱により電極接合と接着剤の硬化とを同時に行って半導体チップを実装することが好ましい。
本発明のフリップチップ実装用接着フィルムを製造する方法は特に限定されず、例えば、上記側鎖に(メタ)アクリロイル基を有するアクリルポリマーと、上記3官能以上の多官能(メタ)アクリレート化合物と、上記ラジカル重合開始剤とに、必要に応じてその他の成分と溶媒とを所定量配合して混合し、得られた接着剤溶液を離型フィルム上に塗工し、乾燥させてフィルムを製造する方法等が挙げられる。
(1)接着フィルムの作製
表1に記載の材料を用いた(表1中、MMAはメチルメタクリレート、BAはブチルアクリレート、HEMAはヒドロキシエチルメタクリレートを意味する)。表2又は3に記載の配合組成に従って、各材料を溶媒としてのメチルエチルケトン(MEK)に添加し、ホモディスパーを用いて攪拌混合することにより接着剤溶液を製造した。得られた接着剤溶液を、アプリケーターを用いて離型PETフィルム上に乾燥後の厚みが30μmとなるように塗工し、乾燥させることにより、接着フィルムを製造した。使用時まで、得られた接着剤層の表面を離型PETフィルム(保護フィルム)で保護した。
先端部が半田からなるバンプが50μmピッチでペリフェラル状に形成されたウエハ(WALTS−TEG MB50−0101JY、半田溶融点235℃、ウォルツ社製)を用意した。接着フィルムの片面の保護フィルムを剥がし、真空ラミネーター(ATM−812M、タカトリ社製)を用いて、ステージ温度80℃、真空度100Paでウエハのバンプが形成された面に接着フィルムを貼り合わせた。
接着フィルムの他面の離型PETフィルムを剥がし、露出した接着剤面に、研削用保護テープ(エレップホルダーBT3100P、日東電工社製)をラミネートした。次いで、研削装置(DFG8560、ディスコ社製)を用いて、厚みが100μmとなるまでウエハの裏面を研削した。ウエハの研削した面にダイシングテープを貼り付け、研削用保護テープを剥離した。その後、ダイシング装置(DFD651、ディスコ社製)を用いて、送り速度20mm/秒でウエハをダイシングして、厚みが30μmの接着剤層が付着した接着剤層付き半導体チップ(7.6mm×7.6mm)を得た。
Ni/Au電極を有する基板(WALTS−KIT MB50−0101JY、ウォルツ社製)を用意した。フリップチップボンダ(FC−3000、東レエンジニアリング社製)を用いて、ボンディングステージ温度100℃の条件下で、120℃接触で280℃まで2秒かけて昇温し、280℃、0.8MPaで2秒間荷重をかけ、得られた接着剤層付き半導体チップを基板上に熱圧着した。その後、常圧190℃オーブンで30分間保持することにより、接着剤層を完全に硬化させて、半導体パッケージを得た。
実施例、比較例で得られた半導体パッケージについて以下の評価を行った。結果を表2又は3に示した。
半導体パッケージの半田接合部をX透過装置(MF100C、日立エンジニアリング・アンド・サービス社製)により観察し、半田流れの有無を確認した。半田が半田接合部にのみ存在した場合を良品(○)、接合時に押し流された半田が、半田接合部以外の箇所に島状に存在した場合を不良品(×)とした。
研磨機を用いて半導体パッケージを断面研磨し、マイクロスコープを用いて半田接合部の接合状態を観察した。上下電極間に樹脂(接着剤)の噛み込み及び半田流れによる半田流失がなく、接合状態が良好であった場合を良品(○)、上下電極間にわずかに樹脂(接着剤)の噛み込みがあるものの、半田流れによる半田流失がなく、接合状態が比較的良好であった場合を良品(△)、上下電極間に樹脂(接着剤)の噛み込み又は半田流れによる半田流失があり、上下電極が全く接合していなかった場合を不良品(×)とした。
超音波探査映像装置(C−SAM D9500、日本バーンズ社製)を用いて半導体パッケージを観察し、ボイドの有無を評価した。半導体チップの接着面積に対するボイド発生部分の面積が0.5%未満であった場合を良品(〇)、半導体チップの接着面積に対するボイド発生部分の面積が0.5%以上1%未満であった場合を良品(△)、半導体チップの接着面積に対するボイド発生部分の面積が1%以上であった場合を不良品(×)とした。なお、良品か不良品かの判断は、n数を5個として、半導体チップの接着面積に対するボイド発生部分の面積が最も小さかった半導体パッケージについて行った。
半導体パッケージを85℃、60RH%に168時間放置して吸湿させた後、半田リフロー炉(プレヒート150℃×100秒、リフロー[最高温度260℃])に4回通過させた。n数を20個として、半導体チップの基板からの剥離が発生した半導体パッケージの個数を確認した。20個の半導体パッケージのうち、剥離が発生した半導体パッケージが0個であった場合を○、1〜3個であった場合を△、4〜20個であった場合を×とした。
Claims (7)
- 半田からなる突起電極を有する半導体チップの該突起電極と、他の半導体チップ又は基板の電極とを接合する際に、前記半導体チップ又は基板に予め電子部品実装用接着剤を供給しておき、加熱により電極接合と接着剤の硬化とを同時に行って半導体チップを実装するフリップチップ実装方法に用いられる電子部品実装用接着剤であって、
側鎖に(メタ)アクリロイル基を有する二重結合当量1.2〜5meq/gのアクリルポリマーと、3官能以上の多官能(メタ)アクリレート化合物と、熱ラジカル重合開始剤とを含有することを特徴とする電子部品実装用接着剤。 - 更に、エポキシ樹脂と、エポキシ硬化剤とを含有することを特徴とする請求項1記載の電子部品実装用接着剤。
- エポキシ樹脂は、1分子中にエポキシ基と(メタ)アクリロイル基とを有するエポキシ化合物を含有することを特徴とする請求項2記載の電子部品実装用接着剤。
- 更に、無機フィラーを含有することを特徴とする請求項1、2又は3記載の電子部品実装用接着剤。
- 更に、(メタ)アクリル基を有するシランカップリング剤を含有することを特徴とする請求項1、2、3又は4記載の電子部品実装用接着剤。
- 側鎖に(メタ)アクリロイル基を有する二重結合当量1.2〜5meq/gのアクリルポリマーは、側鎖にのみ(メタ)アクリロイル基を有することを特徴とする請求項1、2、3、4又は5記載の電子部品実装用接着剤。
- 請求項1、2、3、4、5又は6記載の電子部品実装用接着剤からなる接着剤層を有することを特徴とするフリップチップ実装用接着フィルム。
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US20160272854A1 (en) | 2016-09-22 |
KR20160130372A (ko) | 2016-11-11 |
TW201538657A (zh) | 2015-10-16 |
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