TWI304315B - - Google Patents
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- TWI304315B TWI304315B TW092123058A TW92123058A TWI304315B TW I304315 B TWI304315 B TW I304315B TW 092123058 A TW092123058 A TW 092123058A TW 92123058 A TW92123058 A TW 92123058A TW I304315 B TWI304315 B TW I304315B
- Authority
- TW
- Taiwan
- Prior art keywords
- forming
- solder bump
- film
- substrate
- layer
- Prior art date
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
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- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
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Description
1304315 (1) 玫、發明說明 【發明所屬之技術領域】 本發明爲關於對多層印刷電路基板裝配1C晶片時所使 用之焊料凸點等之低熔點金屬焊料凸點的形成方法。 【先前技術】 於1C晶片側形成焊料凸點之例有BGA ( Ball Grid Array,焊球網格陣列),其一般而指封裝基板上己搭載 1C晶片的形態。 最近之高密度化裝配之一形態爲稱爲WL - CSP ( Wafer Level Chip Size Package,晶圓級晶片大小封裝) 之技術。此WL — CSP爲於一枚晶圓上形成數個1C晶片的電 路後,以晶圓之狀態,一倂實施電極形成、封裝、及初始 運行(burn— in )試驗後,將1C晶片以封裝型式予以切分 之技術。 於WL - CSP中一倂進行電極形成之技術可列舉電鍍法 ,將金屬漿料埋入後進行逆流之方法,將金屬球載置後進 行逆流之方法。 隨著1C晶片的高集成化,1C晶片的焊料凸點乃發展成 高密度化及小型化。於上述之WL - C S P之裝配技術中,乃 進行可令接續信賴性、加工費用降低兩相成立之焊料凸點 的檢討及實用化。具體而言,將液狀之正/負型光阻物或 乾式薄膜形成5 0 // m以上之膜厚,其次予以圖案化,並 將其做爲光罩材料進行電鍍之方法等。 (2) 1304315 另一*力面,於多層印刷電路基板側形成焊料凸點時, 因爲此些焊料凸點彼此未熔黏,故於電路基板上施以焊料 光阻層。於此焊料光阻層上,於電極底座之對應位置設置 開□部。於焊料光阻層上形成焊料凸點時,進行焊錫漿料 的光罩印刷。光罩印刷中所用之光罩爲在焊料光阻層開口 部的對應位置配置圖案(開口圖案)。進行光罩印刷時, 將此光罩令光罩圖案與焊料光阻層開口部對應載置。其後 ,透過此光罩,將焊錫漿料印刷至電極底座上的焊料光阻 層開口部。其後,令焊錫漿料逆流,於電極底座上形成焊 料凸點。 以焊料光阻上再將可剝離的焊料光阻物(特開平 1 0 - 3 5 02 3 0號公報)疊層,並再於前述焊料光阻物將乾式 薄膜予以疊層,於電極底座之對應位置設置開口部,並供 給焊錫漿料,逆流後,將乾式薄膜予以剝離之方法(特開 2000 — 2089 1 1號公報)等,進行應付焊料凸點狹間距化的 檢討。 於上述之焊料凸點之形成步驟中,使用正型光阻物時 ,一般可輕易剝離,難以控制開口圖案的形狀,於焊料凸 點大小之均勻性上易發生問題。 相對地使用負型光阻物時’雖較容易控制圖案形狀, 但因係爲光交聯型,故一般爲剝離困難。特別於漿料埋入 後進行逆流形成焊料凸點時’經由逆流時的熱而進一步進 行負型光阻物的交聯反應’故更難將光阻物由基板上剝離 .-6 - (3) 1304315 光阻膜的剝離i般爲以使用氫氧化鈉或碳酸鈉水溶液 的噴霧剝離,但於使用乾式薄膜狀或液狀之負型光阻物時 ,乃使用在高極性溶劑中添加有機鹼之剝離液予以浸漬剝 離。前者之方法雖爲廉價,但於焊料凸點密集之部分易發 生剝離殘留物,有時易發生令焊料凸點惡化等問題,後者 之方法則具有剝離液本身爲昂貴,若爲了提升每一定剝離 液量的剝離處理枚數,而提高有機鹼濃度,並提高剝離液 之溫度,則令焊料凸點之金屬表面惡化,並且具有令頭道 基板表面腐蝕等之問題點。 【發明內容】 發明之揭示 本發明爲了解決上述問題點,乃如圖1 ( a )或圖5 ( a )般於電路基板上,形成下層爲由鹼可溶性且非感放射線 性樹脂組成物所構成,上層爲由負型感放射性樹脂組成物 所構成的雙層層合薄膜後,經由暫時的曝光/顯像操作, 則可於電極底座之對應位置形成焊料凸點形成用的開口圖 案。 又,本發明爲在使用特性不同的雙層層合薄膜下,令 高解像性和易剝離性可兩相成立。即,經由使用具有酚性 羥基之化合物做爲下層,則達成如下述之效果。 (1 )對下層賦與適當的鹼顯像性,並且以曝光/顯 像操作可暫時予以圖案化。 (2 )經由下層樹脂組成物所具有之酚性羥基令光自 (4) 1304315 由基失活之效果,即使於上下層之界面,及上下層進行內 部混合時,亦可抑制下層與基板界面的硬化反應,可保持 雙層層合薄膜的良好剝離性。 藉此,可使用直到目前剝離性低且難應用的負型光阻 物做爲上層。又,使用負型光阻物做爲上層,則可在圖1 (b )或圖5 ( b )所示之焊料凸點形成開口圖案內導入低 熔點金屬之步驟中,確保必要之光阻圖案的機械強度。 又,下層因爲剝離性優良,故即使以單獨之二甲基亞 硕或N -甲基吡咯烷酮等之高極性有機溶劑亦可剝離,並 且,進行交聯反應之上層部分的剝離片因爲於此些高極性 有機溶劑中爲難溶,故產生易經由沈降分離或循環過濾將 剝離片除去的優點。 又,於使用具有多段浸漬槽之剝離設備時,於第一槽 爲經由有機溶劑而完成大部分負型光阻膜的剝離,於第二 槽以後則經由含有驗性成分的剝離液,於選擇移除下層之 剝離殘留物之步驟下,則可不提高剝離液的鹼性濃度即可 提升剝離處理能力,並且可將焊料凸點及頭道基板的損傷 壓至最低限度。 【實施方式】 實施發明之最佳形態 以下,參照圖面說明本發明之焊料凸點的形成方法。 關於根據本發明之第一實施形態之電極底座上形成焊 料凸點之方法,爲使用圖2更加詳細說明。於本實施形態 (5) 1304315 中,電路基板爲由做爲基材的矽晶圓203、和其表面所設 置之多數電極底座2 0 1所構成,且於形成焊料凸點用之開 口部2 2 0內導入低熔點金屬之步驟係爲使用充塡代表焊錫 漿料之低熔點金屬漿料的方法。還有,於電極底座2 0 1之 兩側面及該底座之兩側端面上,形成鈍化膜2 02。 於半導體全面以區域狀配置電極底座2 〇丨之半導體晶 片晶圓的截面構造示於圖2 (a)。於砂晶圓203之表面上 形成電極底座2 0 1,且於電極底座2 0 1表面爲露出之狀態下 ,於電路基板表面,例如覆蓋1 // m的鈍化膜2 0 2。 如圖2 ( b )所示般,於電極底座201及鈍化膜202之全 部表面上,以賤鍍法、澱積法等形成電極金屬的防止金屬 擴散膜204。防止金屬擴散膜204爲使用Ni、Cr、TiN、 TaN、Ta、Nb、WN任一者,例如形成1 // m之膜厚。此 防止金屬擴散膜204可爲單層膜或層合膜。 如圖2 ( c )所示般,於形成防止金屬擴散膜204之電 路基板全體表面上,例如將Ti、Ni、Pd、Cii等之阻擋金屬 膜,使用濺鍍裝置、電子束澱積裝置等分別疊層散千A的 膜厚,形成阻擋金屬層205。 如圖2 ( d )所示般,於形成阻擋金屬層205之電路基 板的表面上,形成由鹼可溶性且非感放射性樹脂組成物所 構成之下層2 0 6,由負型感放射線性樹脂組成物所構成之 上層207的雙層層合薄膜。 例如將液狀下層材料以2〜3 // m之膜厚塗佈形成下 層206。更且,於下層206上,將液狀之負型光阻物或乾式 (6) 1304315 薄膜狀之負型光阻物任一者以5 0 // m以上之膜厚塗佈或 層合,形成上層2 0 7。對於下層2 0 6和上層2 0 7所構成的雙 層層合薄膜,透過光罩照射放射線後顯像,於電極底座 20 1上之形成焊料凸點用場所_之對應位置,形成焊料凸點 形成用之開口部2 2 0。 包含上述方法之雙層層合薄膜的形成方法有 ① 下層爲液狀,上層爲液狀光阻物
② 下層爲液狀,上層爲乾式薄膜光阻物 ③ 下層爲乾式薄膜,上層爲液狀光阻物 ④ 下層爲乾式薄膜,上層爲乾式薄膜光阻物 ⑤ 具有下層/上層二層構造之乾式薄膜 等之組合。 如圖2 ( e )所示般,於上述焊料凸點形成用之開口部 220使用滑移板209等,埋入例如焊錫漿料般的低熔點金屬 漿料2 0 8。
如圖2 ( f )及(g )所示般,將埋入金屬漿料之電路 基板於氮氣環境氣體中加熱,將金屬漿料逆流形成焊料凸 點 2 1 0 〇 如圖2 ( h )所示般,將層合膜剝離。其後,進行電性 試驗,並進行塑模,分割成晶片,進行倒裝片裝配。 本實施形態中,雖例示低熔點金屬漿料做爲焊錫漿料 ,但即使使用混合 Sn、Pb、Ag、Bi、Zn、In、Sb、Cu、
Bi、Ge等金屬之混合金屬,亦可取得良好的信賴性。還有 ,於形成低熔點金屬凸點,較佳爲焊料凸點時,除了使用 -10> (7) 1304315 滑移板埋入焊料凸點形成用之開口部22 0之方法以外,亦 可使用搭載祗熔點金屬球(焊料球)3 0 8之第二實施形態 (圖3 )、和以電鍍形成低熔點金屬膜4〇8之第三實施形態 (圖4 )予以形成。 又,將金屬漿料逆流後,進行鬆化洗淨。 圖5 ( a )〜(d )爲於所謂的多層印刷電路基板上, 根據本發明形成焊料凸點時的說明圖。此圖5之層間樹脂 絕緣層之下方爲分別形成各一層之導體電路和層間樹脂絕 緣層,而其通常形態爲交互形成多層。 關於本發明第四實施形態之電極底座上形成焊料凸點 之方法,爲使用圖6予以說明。於本實施形態中,電路基 板爲由玻璃環氧樹脂或BT (雙馬來醯亞胺-三哄)樹脂 6 1 5所構成之基材、和於其上所設置之層間樹脂絕緣層6 0 2 、和複數之電極底座605、和於電極底座60 5之側面所形成 之焊料光阻物6 1 1所構成,且於焊料凸點形成用之開口部 608內導入低熔點金屬61 1所構成,且於焊料凸點形成用之 開口部6 0 8內導入低熔點金屬之步驟,乃使用以滑移板充 塡代表焊錫漿料之低熔點金屬漿料6 1 0之方法。 於半導體全面以區域狀配置電極底座6 0 5之電路基板 的截面構造示於圖6 ( a )。於玻璃環氧樹脂6 1 5上具有層 間樹脂絕緣層602和導體電路6 03之多層層合板的電路基板 ,爲藉由鍍層形成的雙孔604,確保上下導通。於層間樹 脂絕緣層60 2上塗佈焊料光阻物61 1,且於底部於電極底座 之對應位置形成開口部。於此開口部之底部露出一部分的 -11 - (8) 1304315 導體電路6 0 3,於此導體電路6 0 3上以無電場鍍層等形成電 極底座6 0 5。 如圖6 ( b )所示般,於焊料光阻物6 1 1上,形成由鹼 可溶性且非感放射線性樹脂組成物所構成之下層606、由 負型感放射線性樹脂組成物所構成之上層607的雙層層合 薄膜。 例如將液狀下層材料以2〜3 // m之膜厚塗佈形成下 層6 0 6。更且,於下層6 0 6上,將液狀之負型光阻物或乾式 薄膜狀之負型光阻物任一者以40 // m以上之膜厚塗佈或 層合,形成上層607。其次將此層合薄膜予以圖案曝光後 ,顯像,則可於電極底座605上之形成焊料凸點用場所之 對應位置,形成焊料凸點形成用之開口部608。 包含上述方法之雙層層合薄膜的形成方法爲與矽晶圓 做爲基材之情況同樣地,可爲 ① 下層爲液狀,上層爲液狀光阻物 ② 下層爲液狀,上層爲乾式薄膜光阻物 ③ 下層爲乾式薄膜,上層爲液狀光阻物 ④ 下層爲乾式薄膜,上層爲乾式薄膜光阻物 ⑤ 具有下層/上層二層構造之乾式薄膜 等之組合。 如圖6 ( c )所示般,於上述焊料凸點形成用之開口部 60 8使用滑移板609等,埋入例如焊錫漿料般的低熔點金屬 漿料6 1 0。 其次,如圖6 ( d )及(e )所示般,將埋入金屬漿料 -12、 (9) 1304315 之電路基板於氮氣環境氣體中加熱,將金屬漿料逆流形成 焊料凸點。 ‘ 其後,如圖6 ( f)所示般,將層合膜剝離。 本實施形態中,雖例示低熔點金屬漿料做爲焊錫漿料 ,但即使使用混合 Sn、Pb、Ag、Bi、Zn、In、Sb、Cu、 B i、G e等金屬之混合金屬,亦可取得良好的信賴性。還有 ,於形成低熔點金屬凸點,較佳爲焊料凸點時,除了使用 滑移板埋入焊料凸點形成用之開口部60 8之方法以外,亦 可使用搭載低熔點金屬球(焊料球)7 0 8之第五實施形態 (圖7 )、和以電鍍形成低熔點金屬膜8 0 8之第六實施形態 (圖8 )予以形成。 又,將金屬漿料逆流後,進行鬆化洗淨。 以下,詳細說明本發明之下層材料和上層材料。 下層 本發明所用之下層,除了含有鹼可溶性化合物,較佳 爲具有酚性羥基之鹼可溶性化合物以外,並無特別限制, 但以如下組成爲佳。 還有,形成下層時,使用由鹼可溶性且非感放射線性 樹脂組成物所構成的下層材料,且下層材料可爲液狀或乾 式薄膜狀。 〔具有酚性羥基之鹼可溶性化合物:A成分〕 本發明所用之上述化合物(以下稱爲化合物(A )) -13 - (10) 1304315 大致可分成苯酚骨架爲1 0個以下的低分子量化合物、和酚 醛樹脂或聚(4 -羥基苯乙烯)等之高分子量聚合物。 於使用低分子量之化合物(A )之情形中,形成開口 部時所使用的顯像液以碳酸鈉等之鹼性較弱的顯像液爲佳 。又’於使用高分子量之聚合物之情形中,形成開口部時 所使用的顯像液以氫氧化四甲基銨等之鹼性較強的顯像液 爲佳。 低分子量化合物之例可列舉4,4,〔 1〔 4〔 1 一( 4 一 羥苯基)一 1 一甲基乙基〕苯基〕亞乙基〕二苯酚、2,2 —雙(1,5 —二甲基一 4一羥苯基)丙酸甲酯、4,6 —雙 〔1一(4 一羥苯基)一1 一甲基乙基〕一1,3 —苯二醇等 〇 又,此外熱聚合抑制劑亦可使用一般所用的化合物。 可列舉例如鄰苯二酚、苯醌、氫醌、甲基藍、第三丁基鄰 苯二酚、單苄醚、甲基氫醌、戊醌、戊氧基氫醌、正丁基 苯酚、苯酚、氫醌單丙醚、4,I 一 (1—甲基亞乙基) 雙(2—甲基苯酚)、4,一 (1 一甲基亞乙基)雙(2 ,6 —二甲基苯酚)、4,4,,4" 一亞乙基三(2—甲基 苯酚)、4,4,,4々一亞乙基三苯酚、1,1,3—(2,5 一二甲基一4一羥苯基)—3—苯基丙烷等。 高分子量化合物之例爲具有酚性羥基之聚合物,可列 舉下列所示之酚醛樹脂、聚羥苯乙烯及其衍生物。彼等可 單獨使用,亦可混合使用。 -14- (11) 1304315 (酚醛樹脂) 本發明所用之鹼可溶性酚醛樹脂爲令間-甲酚與其他 一種以上之酚類與醛化合物縮合所得之樹脂,若間-甲酚 之比例爲全酚類中之50〜90莫耳%之鹼可溶性酚醛樹脂即 可,並無特別限制。 酚醛樹脂之原料所使用之該其他酚類具體而言可列舉 例如2,3—二甲苯酚、2,4 —二甲苯酚、2,5 —二甲苯酚 、3,4一二甲苯酚、3,5 —二甲苯酚及2,3,5 —三甲基 苯酚等。彼等可單獨或組合使用二種以上。 其中,較佳可列舉2,3 —二甲苯酚、2,4 —二甲苯酚 、3,4一二甲苯酚及2,3,5—三甲基苯酚。 又,間-甲酚與其他一種以上酚類之較佳組合可列舉 間一甲酚/ 2,3 —二甲苯酚、間一甲酚/ 2,4 —二甲苯酚 、間一甲酚/ 2,3 —二甲苯酚/ 3,4 一二甲苯酚、間一甲 酚/ 2,3,5 —三甲基苯酚及間一甲酚/ 2,3 —二甲苯酚 /2,3,5—三甲基苯酚等。 又,被縮合之醛化合物可列舉例如甲醛、對甲醛、乙 醛、苯甲醛、鄰一羥基苯甲醛、間一羥基苯甲醛、對一羥 基苯甲醛、乙二醛、戊二醛、對酞醛、間酞醛等。其中, 特別以甲醛、鄰-羥基苯甲醛爲適於使用。 此些醛類可單獨或組合使用二種以上。此類醛化合物 相對於酚類1莫耳,較佳使用0.4〜2莫耳,更佳爲0.6〜15 吴耳之份量。 於酚類與醛化合物之縮合反應上,通常使用酸性觸媒 -15- (12) 1304315 。此酸性觸媒可列舉例如鹽酸、硝酸、硫酸、甲酸、草酸 、醋酸、甲烷磺酸、對-甲苯磺酸等。此類酸性觸媒通常 相對於酚類1莫耳,可使用1 X 1 0 — 5〜5 X 1 〇 - 1莫耳之份 量。 於縮合反應中,通常使用水做爲反應介質,由反應初 期變成不均勻系之情況可使用例如甲醇、乙醇、丙醇、丁 醇、丙二醇單甲醚等之醇類、四氫呋喃、二哼烷等之環狀 醚類、乙基甲基酮、甲基異丁基酮、2—庚酮等之酮類做 爲反應介質。此些反應介質通常爲反應原料每100重量份 ,使用20〜1,00 0重量份之份量。 縮合反應之溫度爲根據原料的反應性而適當調整,但 通常爲10〜200 °C。 反應方法爲適當採用將酚類、醛化合物、酸性觸媒等 一倂裝入之方法,及於酸性觸媒存在下將酚類、醛化合物 等隨著反應之進行而加入之方法等。 縮合反應終了後,爲了除去系統內存在的未反應原料 、酸性觸媒、反應介等,乃將反應溫度上升至130 °C〜230 °C,並於減壓下除去揮發成分,回收酚醛樹脂之方法,和 將所得之酚醛樹脂於乙二醇單甲醚醋酸酯、3 -甲氧基丙 酸甲酯、乳酸乙酯、甲基異丁基酮、2 —庚酮、二Df烷、 甲醇、醋酸乙酯等之良溶劑中溶解後,混合水、正己烷、 正庚烷等之貧溶劑,其次,將析出之樹脂溶液層予以分離 ,回收高分子量之酚醛樹脂之方法。 又,前述酚醛樹脂之換算成聚苯乙烯的重量平均分子 -16- (13) 1304315 量(以下,稱爲「Mw」),由製膜組成物時之作業性, 使用做爲光阻物時之顯像性、感度及耐熱性之觀點而言, 以2,000〜20,000爲佳,且以3,000〜15,000爲特佳。 (聚羥基苯乙烯) 本發明可使用之聚羥基苯乙烯類可列舉以 Marucalinker M Marucalinker CMM、Marucalinker CHM、 Marucalinker MB、Marucalinker PHM— C、Marucalinker CTS、Marucalinker CBA(九善石油化學(株)製)等名 稱販售的樹脂。 〔溶劑:B成分〕
將上述成分A溶解、塗佈之目的下可使用溶劑。溶劑 若爲可良好溶解化合物A者即可,並無特別限制。溶劑之 例可列舉乙二醇單甲醚、乙二醇單乙醚、乙二醇單甲醚醋 酸酯、乙二醇單乙醚醋酸酯、二甘醇單甲醚、二甘醇單乙 醚、丙二醇單甲醚、丙二醇單丙醇醋酸酯、甲苯、二甲苯 、甲基乙基酮、2 —庚酮、3 —庚酮、4 —庚酮、環己酮、2 一羥基丙酸乙酯、2 -羥基一 2 一甲基丙酸乙酯、乙氧基醋 酸乙酯、羥基醋酸乙酯、2 —經基一 3 —甲基丁酸甲酯、3 一甲氧基丙酸甲酯、3—乙氧基丙酸乙酯、3 一甲氧基丙酸 乙酯、醋酸丁酯、丙酮酸甲酯、丙酮酸乙酯等。更且,亦 可添加N —甲基甲醯胺、n,N—二甲基甲醯胺、N—甲基 甲醯替苯胺、N—甲基乙醯胺、n,N —二甲基乙醯胺、N …17- (14) 1304315 一甲基吡咯烷酮、二甲基亞硕、苄基乙醚、二苄醚、乙腈 丙酮、異佛爾'酮、乙酸、辛酸、1 一辛酸、1 一壬酸、苄醇 、醋酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙 酯、r 一丁內酯、碳酸伸乙酯、碳酸丙酯、乙二醇單苯醚 醋酸酯等之高沸點溶劑。此些溶劑可單獨或組合使用二種 以上。其中以2 —羥基丙酸乙酯和丙二醇單甲醚醋酸酯爲 佳。 〔丙烯酸樹脂:C成分〕 特別於使用低分子量之具有酚性羥基之化合物做爲a 成分時,於提高塗佈性,令塗膜性狀安定之目的下,可添 加如下所示之鹼可溶性丙烯酸樹脂。 丙烯酸樹脂之組成並無特別限制,可爲(甲基)丙烯 酸酯所導出的單位,加上含有用以賦與鹼可溶性而具有笑至 基和/或酚性羥基之自由基聚合性化合物所導出的單位。 具有殘基之自由基聚合性化合物,可使用例如丙稀酸 、甲基丙烯酸等。 具有酚性羥基之自由基聚合性化合物可使用對一經基 苯乙烯、間一羥基苯乙烯、鄰一羥基苯乙燒、α —甲基— 對一羥基苯乙烯、α —甲基一間一羥基苯乙烯、α 一甲基 一鄰-羥基苯乙烯、4 一異丙烯基苯酚、2 一乙烯丙基苯酉分 、4 一烯丙基苯酚、2-烯丙基一 6-甲基苯酚、2-烯丙基 一 6 —甲氧基苯酚、4 一烯丙基一 2-甲氧基苯酚、4一烯两 基一 2,6—二甲氧基苯酚、4一烯丙氧基一 2一羥基二苯酮 -18- (15) 1304315 等之具有酚性羥基的乙·烯系單體等。此些化合物可單獨或 組合使用二種以上。其中以對一羥基苯乙烯、4 一異丙烯 基苯酌爲佳。 於此類丙烯酸共聚物中結合具有羧基之自由基聚合性 化合物和/或具有酚性羥基之自由基聚合性化合物所導出 的單位爲單獨或組合以1〜60重量%,較佳爲5〜50重量% 。若未滿5重量%,則丙烯酸共聚物於鹼性顯像液中難溶 解,故於顯像後產生膜殘留並且無法取得充分的解像度。 相反地,若超過5 0重量%,則丙烯酸共聚物對於鹼性顯像 液之溶解性變爲過大,於雙層化時易變成下切(undercut )形狀。 〔界面活性劑:D成分〕 於此組成物中,在提高塗佈性、消泡性、勻塗性之目 的下,亦可配合界面活性劑。界面活性劑可使用以B Μ -1 000、ΒΜ— 1100 ( BM CHEMY公司製)、MEGAFAC F 142D、同F 172、同F 173、同F 183 (大曰本油墨化學( 株)製)、FLORADE FC— 135、同 FC-170C、同 FC — 430、同 FC— 431 (住友 3Μ (株)製)、SARFURON S — 112、同 s— 113、同 S— 131、同 S— 141、同 S— 145 (旭硝 子(株)製)、SH— 289Α、同—190、同—193、SZ — 603 2、SF — 8 42 8 (東雷Silicone (株)製)等之名稱所販 售的氟系界面活性劑。此些界面活性劑之使用量相對於共 聚物(A ) 1 0 0重量份較佳以5重量份以下。 -19- (16) 1304315 於本發明所用之下層材料中,可含有其他成分。具體 而言’可列舉苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂 、雙酚型環氧樹脂、三酚型環氧樹脂、四酚型環氧樹脂、 苯酚一伸二甲苯型環氧樹脂、苯酚-伸二甲苯型環氧樹脂 、苯酚-萘酚型環氧樹脂、苯酚一二環戊二烯型環氧樹脂 、月曰式氧樹脂等。又’亦可添加無機充塡劑,具體而 言可列舉矽石、氫氧化鋁、硫酸鋇等。更且,亦可含有高 分子添加劑、反應性稀釋劑、勻塗劑、濕潤性改良劑、可 塑劑、抗氧化劑、抗靜電劑、防黴劑、調濕劑、難燃劑等 上層 形成上層時,使用由負型感放射線性樹脂組成物所構 成的上層材料,且上層材料可爲液狀或乾式薄膜狀。 此類負型感放射線性樹脂組成物可使用例如特開平 8 - 3 0 1 9 1 1號公報所記載之感放射性樹脂組成物。 本發明所用之負型感放射線性樹脂組成物爲由丙_酸 樹脂(上述C成分)、交聯劑(E成分)、引發劑(F成 分)、溶劑(上述B成分)、界面活性劑(上述D成分) 等所構成。 〔交聯劑:E成分〕 交聯劑(E )可列舉例如三羥甲基丙烷三(甲基)西 烯酸酯 '季戊四醇三(甲基)丙烯酸酯、乙二醇二(甲基 , -20 - (17) 1304315 )丙烯酸酯 '四甘醇二(甲基)丙烯酸酯、聚乙二醇二( 甲基)丙烯酸酯、1,4 - 丁二醇二(甲基)丙烯酸酯、丁 二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、 三羥甲基丙烷二(甲基)丙烯酸酯、丨,6 一己二醇二(甲 基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基 丙i:兀二(甲基)丙烯酸酯、三(2 一羥乙基)異氰脲酸酯 三(甲基)丙烯酸酯、三(2 —羥乙基)異氰脲酸酯二( 甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、 雙ffij A之一縮水甘油醚中加成(甲基)丙燒酸的環氧(甲 基)丙烯酸酯、雙酚A二(甲基)丙烯醯氧基乙醚、雙酚 A二(甲基)丙烯醯氧乙氧基乙醚、雙酚a二(甲基)丙 烯醯氧基氧甲基乙醚、四羥甲基丙烷四(甲基)丙烯酸酯 、季戊四醇三(甲基)丙烯酸酯 '季戊四醇四(甲基)丙 烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六 (甲基)丙烯酸酯等。
此些交聯劑(E成分)可直接使用市售之化合物。市 售化合物之具例可列舉ARONIX M— 210、同M— 309、同 Μ — 310、同 Μ — 400、同 Μ — 7100、同 Μ — 80 30、同 Μ — 8060、同 Μ— 8100、同 Μ— 9050、同 Μ— 240、同 Μ— 245、 同 Μ— 6100、同 Μ— 6200、同 Μ— 6250、同 Μ— 63 00、同 Μ— 6400、同M— 6500 (以上,東亞合成(株)製、 KAYARAD、R — 551、同 R— 712、同 TMPTA、同 HDDA、 同 TPGDA、同 PEG400DA、同 MANDA、同 HX— 200、同 HX — 620、同 R— 640、同 DPCA — 20、同 DPCA— 30、同 DPCA -21 - (18) 1304315 —60、同DPCA — 120 (以上,臼本化藥(株)製)、 BISCOAT #295、同 3 00、’同 26 0、同 312、' 同 3 5 5 HP、同 3 6 0、同GPT、同3PA、同400 (以上,大阪有機化學工業 (株)製)等。 此些交聯劑(E成分)可單獨或倂用二種以上,相對 於丙烯酸樹脂(分成分)1 〇 〇重量份較佳以丨〇〜2 5 〇重量份 ,更佳爲20〜200重量份,特佳爲25〜15〇重量%。若未滿 1 〇重量份,則曝光時之感度易降低,若超過2 5 〇重量份則 與共聚物(A )之相溶性變差,保存安定性降低,且有時 難形成2 0 // m以上的厚膜。 〔放射線自由基聚合引發劑:F成分〕 放射線自由基聚合引發劑(以下,稱爲引發劑:F成 分)可列舉例如苄基、二乙醯基等之α 一二酮類;苯偶姻 等之偶姻類;苯偶姻甲醚、苯偶姻乙醇、苯偶姻丙醇等之 偶姻醚類;噻吨酮、2,4 一二乙基噻吨酮、噻吨酮一 4 — 5風酸、二苯酮、4,I 一雙(二甲胺基)二苯酮、4,4, 〜雙(二乙胺基)二苯酮等之二苯酮類;乙醯苯、對一二 甲胺基乙醯苯、α ,α —二甲氧基一 α —乙醯氧基二苯酮 、α ,α —二甲氧基一 α 一苯基乙醯苯、對一甲氧基乙醯 苯、1一 〔2—甲基一 4 一甲硫苯基〕一 2—嗎啉基一 1 一丙 酮、α ,α —二甲氧基—α 一嗎啉基一甲硫苯基乙醯苯、 2 —卡基—2 — 一甲胺基一 1 一 (4一嗎琳苯基)一丁院一 1 一酮等之乙醯苯類;蒽醌、1,4 -萘醌等之醌類;苯醯甲 - 22- (19) 1304315 基氯、三溴甲基苯基硕、三(三氯甲基)- S-三畊等之 鹵素化合物;—雙咪唑〕—3,3/,4,,4^一 四苯基、〔1,2,—雙咪唑〕一 1,-二氯苯基—3,3 > ,4> ,4 / 一四苯基等之雙咪唑類、二一第三丁基過氧 化物等之過氧化物;2,4,6 -三甲基苯偶姻二苯膦氧化 物等之醯膦氧化物類等,又,市售品可列舉IRGACURE 184、 651、 500、 907 、 CGI 1369、 CS 24—61 (以上, Ciba Specialty Chemicals (股)製)、RUSILIN、LR 8 72 8 、 RUSILIN ΤΡΟ (以上,BASF (株)製、 DAR0CURE 1116 、 1173 (以上,Ciba Specialty
Chemicals (股)製)、U B E C RILIR P 3 6 ( U C B (股)製) 等。又,視需要亦可將氫硫基苯並噻唑、氫硫基苯並鸣唑 等之具有氫供給性的化合物與上述光自由基聚合引發劑倂 用。 上述各種放射線自由基聚合引發劑中較佳之化合物可 列舉1 一 〔 2 —甲基一 4 —甲硫苯基〕一 2 —嗎啉基一1 一丙 酮、2_节基一2—二甲胺基—1— (4一嗎啉苯基)一丁院 —1—酮、α ,α —二甲氧基一 α —苯基乙酿苯等之乙醯 苯類、苯甲醯基氯、三溴甲基苯基硕、2,4,6—三甲基 苯偶姻二苯膦氧化物、1,2 / -雙咪唑類與4,4 / 一二乙 胺基二苯酮與氫硫基苯並噻唑倂用,RUSILIN ΤΡ0、 IRGACURE 651等。此些化合物可單獨或組合使用二種以 上。其使用量爲相對於鹼可溶性共聚物(A ) 1 0 0重量份 ,較佳以〇 · 1〜6 0重量份,更佳爲5〜5 0重量份,特佳爲} 〇 -23 - (20) 1304315 〜40重量份。其使用量若爲1重量%以下,則自由基易受 到氧氣的影響而失活(感度降低),又,若超過60重量% ’則相溶性變差,且保存安定性有降低之傾向。又,此些 放射線自由聚合引發劑與放射線增感劑倂用亦可。 下層及上層之形成方法 本發明爲於具有指定電路圖案之基板上,首先將下層 塗佈或層合,其次將上層塗佈或層合後,形成所欲的雙層 層合薄腠。於基板上之形成方法’於材料爲液狀時,可採 用浸漬法、旋塗法、輥塗法、網版印刷法、塗佈輥祛、幕 塗法等之方法。又,於材料爲薄膜狀時,可採用層合法、 真空層合法等之方法。還有,下層及上層之乾燥條件爲依 據組成物中之各成分的種類、配合比例、塗佈膜厚等而異 ,但通常爲於70〜12(TC下以5〜20分鐘左右,較佳爲8〇〜 1 0 0 C。乾燥日寸間若過短,則顯像時之密黏狀態變差,又 ,若過長,則因過熱導致解像度降低。 又’作成以下層材料與上層材料爲首之雙層構造的乾 式薄膜’並且暫時層合,則可於基板上形成雙層層合薄膜 〇 放射線照射方法 對所得之層合薄膜透過指定圖案的光罩,照射波長爲 3 0 0〜5 OOnm的紫外線或可見光線。此些放射線之光源可 使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵素 燈、氳氣雷射等。此處所謂之放射線爲意指紫外線、可見 -24- (21) 1304315 光線、遠紫外線、X射線、電子射線等。放射線照射量爲 依據組成物中之各成分的種類、配合量、層合薄膜之膜厚 等而異’例如於使用超高壓水銀燈時,爲1〇〇〜5〇〇mJ/ cm2 ° 顯像方法 方夕Ιί線照射後之顯像方法爲使用鹼性水溶液做爲顯像 液’並將不要的部分予以溶解、除去,僅殘存放射線照射 方法。顯像液可使用例如氫氧化鈉、氫氧化鉀、碳酸鈉、 矽酸鈉、偏矽酸鈉、氨水、乙胺、正丙胺、二乙胺、二正 丙胺、三乙胺、甲基二乙胺、二乙基乙醇胺、二乙醇胺、 氫氧化四甲基銨、氫氧化四乙基銨、吡咯、哌啶、1,8 一 二卩丫雙環〔5 · 4 · 0〕一 7 —十一碳烯、1,5 -二吖雙環〔 4.3 · 0〕一 5 —壬烷等之鹼類水溶液。又,於上述鹼類水溶 液中適量添加甲醇、乙醇等之水溶性有機溶劑和界面活性 劑之水溶液亦可使用做爲顯像液。顯像時間爲依據組成物 各成分之種類、配合比例、組成物之乾燥膜厚而異,通常 爲3 0〜3 6 0秒鐘。顯像方法可爲滿液法、漬浸法' 槳葉法 、噴霧顯像法等任一種。顯像後,以流水洗淨3 〇〜9 0秒鐘 ,使用空氣槍等令其風乾,並於烘爐中乾燥。 若使用如上述之顯像液進行顯像,則上層爲僅殘存放 射線照射部分,下層爲僅將對應上層中被除去部分(放射 非照射部)之部分予以溶解除去。 其後對殘存的光阻膜,經由後曝光和加熱再令光阻膜 -25- (22) 1304315 硬化亦可。 焊料凸點之形成 其次對如上述的開口圖案,例如導入焊 熔點金屬,並且加熱逆流形成焊料凸點。又 導入低熔點金屬之其他方法例如爲直接搭載 、或電鍍等。 剝離處理 於形成焊料凸點後,將基板上殘存之硬 的方法爲將該基板於5 0〜8 0 °C中攪拌之剝离1 3 0分鐘,則可將硬化膜(光阻膜)剝離。此 離液以使用單獨之二甲基亞碾或四級銨鹽與 水的混合溶液爲佳。 更具體而言,由基板上將雙層層合薄膜 去上,爲準備具有多段浸漬槽的剝離設備, 適當的有機溶劑將雙層層合薄膜剝離並且將 灑後’於弟一槽以後爲以含有有機鹼成分之 該層合薄膜的剝離殘留物予以剝離。 更且’準備具有多段浸漬槽之剝離設備 用二甲基亞碾將雙層層合薄膜剝離並且將剝 後’於弟一槽以後爲以含有有機驗成分和二 離液將該層合薄膜的剝離殘留物予以剝離爲 錫漿料等之低 ,對開口圖案 焊料球之方法 化物予以剝離 ^液中浸漬5〜 時所使用之剝 二甲基亞碾與 予以剝離、除 於第一槽使用 剝離片循環過 剝離液即可將 ,於第一槽使 離片循環過濾、 甲基亞碾之剝 佳0 -26- (23) 1304315 實施例 以下,根據實施例具體說明本發明,但本發明並非限 定於此。又,只要無特別指明,則份爲表示重量份、%爲 表示重量%。 以下列述下層材料與上層材料的原料。 (A成分:具有酚性羥基之化合物) A — 1 :將間〜甲酚與對—甲酚以重量比4〇 : 6〇之比 例混合’於其中加入甲醛水,使用草酸觸媒依常法縮合取 得甲酚酚醛。對於此樹脂施以分級處理,將低分子區域切 割取得重量平均分子量1 2 0 0 0的酚醛樹脂。 A— 2:4,4〆〔1— 〔4— ( 1 - (4 一 羥苯基)一1 — 甲基乙基〕苯基〕亞乙基〕二苯酚 (B成分:溶劑) B — 1 :丙二醇單甲醇 B — 2 : 2 —羥基丙酸乙酯 B — 3 : 2 —庚酮 (C成分:丙烯酸樹脂) C 一 1 :將附有乾冰/甲醇迴流器和溫度計之燒瓶以氮 氣進行更換後,裝入做爲聚合引發劑的2,2 / -偶氮雙異 丁腈4.0克,做爲溶劑的2 -羥基丙酸乙酯]2 0克,並且攬 拌直到聚合引發劑溶解爲止。接著,裝入丙烯酸2 0 · 0克、 -27- (24) 1304315 對一異丙烯基苯酚1 0.0克、甲基丙烯酸正-丁酯3 0 · 0克、 甲基丙烯酸甲酯2 0 · 0克、丙烯酸正丁酯2 0.0克後,慢慢開 始攪拌。其後,令溶液溫度上升至8 0 °C,以此溫度聚合4 小時,再升溫至1 〇(TC並以此溫度進行1小時聚合。其後, 於冷至室溫,將燒瓶內以空氣進行更換。將反應產物滴入 大量的甲醇中令反應物凝固。將此凝固物水洗後,於凝固 物同重量之四氫呋喃中再溶解,並以大量的甲醇令其再度 凝固。將此再溶解-凝固操作共計進行3回後,所得之凝 固物於4 0 °C下真空乾燥4 8小時,取得丙烯酸樹脂c — 1。 C - 2 :將附有乾冰/甲醇迴流器和溫度計之燒瓶以氮 氣進行更換後,裝入做爲聚合引發劑的2 ’ 2 / —偶氮雙異 丁腈4 · 0克,做爲溶劑的2 —羥基丙酸乙酯1 0 0克,並且攪 拌直到聚合引發劑溶解爲止。接著,裝入甲基丙烯酸1 0.0 克、對一異丙烯基苯酚15.0克、8 —三環〔5·2·1·0·02·6〕 癸基-甲基丙烯酸酯25.0克、丙烯酸異次片酯20克、丙儲 酸正丁酯3 0.0克後,慢慢開始攪拌。其次,令溶液溫度上 升至8 0 °C,以此溫度聚合3小時,添加2,2 / 一偶氮雙異 丁腈1克,並再以8 (TC聚合3小時,其後,升溫至1 0 0 °C並 以此溫度進行1小時聚合。放冷至室溫,將燒瓶內以空氣 進行更換。將反應產物滴入大量的甲醇中令反應物凝固。 將此凝固物水洗後,於凝固物同重量之四氫13夫喃中再溶解 ,並以大量的甲醇令其再度凝固。將此再溶解一凝固操作 共計進行3回後,所得之凝固物於4 0 T:下真空乾燥4 8小時 ,取得丙烯酸樹脂C 一 2。 * - 28 - (25) 1304315 C - 3 :將附有乾冰/甲醇迴流器和溫度計之燒瓶以氮 氣進行更換後,裝入做爲聚合引發劑的2,2 / -偶氮雙異 丁腈3.0克,做爲溶劑的2 一羥基丙酸乙酯1 5 0克,並且攪 持直到聚合引發劑溶解爲止。接著,裝入4 -異丙烯基苯 酉分4 3克、丙烯酸正丁酯3 〇 . 8克、丙烯酸2.9克、丙烯酸2 -經乙酯23 ·3克後,慢慢開始攪拌。其後,令溶液溫度上升 至7 〇 °C ’並以此溫度進行3小時聚合。其次添加做爲聚合 引發劑的2,2 / -偶氮雙異丁腈1 · 5克,再以7 0 °C繼續聚 合3小時。其後,放冷至室溫,將燒瓶內以空氣進行更換 後,加入對一甲氧基苯酌1 5 0毫克。將反應產物滴入大量 的甲醇中令反應物凝固。將此凝固物水洗後,於凝固物同 重量之四氫呋喃中再溶解,並以大量的甲醇令其再度凝固 。將此再溶解一凝固操作共計進行3回後,所得之凝固物 於4 0 °C下真空乾燥4 8小時,取得丙烯酸樹脂C — 3。 (D成分:界面活性劑) D - 1 ·· NBX — 15 (Neos公司製) D - 2: SF— 8428 (東雷 Silicone (股)製) (E成分:交聯劑) E—l: AR0NIXM - 8060 (東亞合成(股)) (F成分:引發劑) F — 1 : IRGACURE 651 ( Ciba Geigy公司製) -29- (26) 1304315 F — 2 : CACURE DETX — S (日本化藥(股))、 下層材料A— L、B—L、C—L之調製 如表1所示般,將A — 1以35份、!以65份、D — 1以 〇·1份攪拌、溶解後,使用孔徑3从m的膜濾器( ADVANTE(公司製 Capsuie cartridge Filter CCP—FX — CIB)予以過濾。調製下層材料A— L。同樣處理,調製下 層材料B— L、C— L。 下層材料B—D、C—D之製作 使用下層材料B - L或C 一 L製作乾式薄膜。對厚度50 // m ' 1 1公分正方的聚對酞酸乙二酯(ρΕτ )薄膜,使用 旋塗器將下層材料B - L,以烘烤後之膜厚爲5 // m般進行 塗佈後’以對流式烘爐於1 1 0 T:中烘烤1 0分鐘,製作下層 材料B - D。同樣處理,製作下層材料c 一 〇。
-30- 1304315 (27) 表1 ^^ 樣品$ A成分 B成分 C成分 D成分 形態 下層材料 A-1 B-1 — D-1 液狀 A‘L —___ 3 5份 65份 0.1份 、--- 下層材料 A-2 D-2 C-1 一 液狀 B^L 2 0份 90份 10份 --- 下層材料 A-2 B-2 C-1 一 乾式薄膜 20份 90份 10份 一----- 下層材料 A-2 B-2 C-3 D- 1 液狀 C-L 20份 9 0份 20份 〇·ΐ份 下層材料 A-2 B-2 C-3 D- 1 乾式薄膜 C-D 2 0份 9 0份 20份 0.1份 上層材料A—L、B - L、C—L之調製 使用表2所示之成分以下層材料A - L同樣之手續調製 上層材料A— D、B— D之製作 使用上層材料A - L或B - L製作乾式薄膜。對厚度5 0 // m ' 1 1公分正方的聚對酞酸乙二酯(PET )薄膜,使用 旋塗器將上層材料A - L,以烘烤後之膜厚爲40 // m般進 行塗佈後,以對流式烘爐於1 1 0 °C中烘烤1 〇分鐘,製作上 層材料A — D。同樣處理,製作上層材料B - D。 -31 - 1304315 (28) 表2 樣品名 B 成 分 C成分 D成分 E成分 F成分 形態 上層材料 B -1 C-2 D-1 E-1 F -1 1 8 · 6 份 液狀 A-L 8 8份 1〇〇份 0.1份 51.7 份 F-2 4.0份 上層材料 B-1 C-2 D-1 E-1 F -1 1 8 · 6 份 液狀 A - D 88份 1 0 0份 0.1份 51.7 份 F - 2 4 · 0 份 上層材料 B-2 C-1 D-2 E-1 F-1 乾式薄 B-L 122份 1 0 0份 0.3份 45份 30份 膜 上層材料 B-2 C-1 D-2 E-1 F-1 乾式薄 B-D 122份 1.00 份 〇·3份 45份 3〇份 膜 上層材料 B-3 C-2 D-1 E-1 F-1 18.6份 液狀 C-L 88份 1 00份 0.1份 51.7 份 F-2 4.0份 雙層乾式薄膜A、B之製作 以表3之組合製作雙層乾式薄膜。對厚度5 〇 # m、 1 1公分正方的聚對酞酸乙二酯(PET )薄膜,使用旋塗器 將上層材料B 一 L,以烘烤後之膜厚爲4 〇 μ 1Ώ般進行塗佈 後’以對流式烘爐於丨丨〇它中烘烤丨〇分鐘,其次對此塗佈 基板上使用旋塗器將下層材料B 一 L,以烘烤後之膜厚爲 40 “ m般進行塗佈後,以對流式烘爐於1 1 〇°C中烘烤10 分鐘,製作雙層乾式薄膜A。同樣處理製作雙層乾式薄膜 B。 -32- (29) 1304315
樣品名 '—------ 上層材料 下層林 雙層乾式薄膜 上層材料FUT. —__料 下層材粗D τ 雙層乾式薄膜 上層材料C-L —---L 下層材料r L 剝離液之調製 剝離液:於二甲基亞硕4 9 〇 〇克中添加氫氧化四甲基錢 水溶液(2 5重量% ) 1 0 0克後,攪拌,作成剝離液1。 評價基板A之製作 於4吋矽晶圓上以濺鍍形成〗〇 〇 〇 A鉻層,再於其上形 成銅層1 0 0 0人,作成評價基板A。 評價基板B之製作 對表面粗化之貼銅玻璃環氧層合板(基板厚:〇. 6 、大小;1 〇公分正方),塗佈(i )間—甲酚/對—甲醇 = 6 0 / 40 (莫耳比)所構成的甲酚酚醛樹脂(換算成聚苯 乙烯之重量平均分子量8 7 00) 、 (ii)六甲氧基甲基蜜胺 、(iii )交聯微粒子、(iv )苯乙烯基—雙(三氯甲基) 一 S —三畊及(v )含有乳酸乙酯做爲溶劑的焊料光阻物( JSR (股)製)、特願2000 — 3 3 4 3 4 8號中記載之實施例1的 感光性絕緣樹脂組成物),並以對流式烘爐於9(TC,加熱 1小時,製作3 0 // m厚的均勻塗膜。其後,使用校準器( Suss Microtech公司製MA — 15 0),透過圖案光罩,將來 -33- (30) 1304315 自高壓水銀燈之紫外線以波長3 5 0 li m中之曝光量爲3 0 0〜 5 00 nU/cm 2般進行曝光,並以對流式烘爐於90 °C,進行 1 5分鐘PEB (烘烤後曝光),且使用1重量%氫氧化鈉水 溶液以30°C淋洗顯像(壓力;3 kgf · cm2 ) 2〜3分鐘。其 後,使用高壓水銀燈以波長3 5 0 nm中之曝光量爲1〇〇〇 mJ / cm2般進行曝光。其次,以對流式烘爐於150°C,加熱2 小時,再於1 7 〇 °C加熱2小時取得硬化膜。 此基板爲於第一開口圖案中混合存在下列圖案。 • 1 5 0 // m間距且開口徑9 5 // m的孔圖案 • 1 2 5 // m間距且開口徑8 0 // m的孔圖案 • 1 0 0 // m間距且開口徑6 0 // m的孔圖案 對上述基板之開口部以Ni/ Αιι施行無電電鍍,作成 評價基板B。 旋塗法 將液狀之下層材料或上層材料對上述評價用基板直接 滴下,並使用旋塗器以烘烤後之膜厚爲40 // m般進行塗佈 後,以對流式烘爐於1 1 (TC烘烤1 0分鐘。將此塗佈基板慢 慢放冷至室溫度,將塗佈面以厚度50 // m之PET薄膜,使 用層合器予以覆蓋。 層合條件爲如下。 輥溫度:8 0 t 輥壓·· 0.4MPa 搬送速度·· 〇 . 5 m / m i η -34- (31) j304315 層合法 將乾式薄膜狀之下層材料、上層材料、或雙層乾式薄 膜使用層合器予以層合。使用做爲支撑體的PET薄膜爲就 其原樣之狀態。 層合條件爲如下。 輥溫度:120°C 車毘壓:0 · 4 Μ P a 搬送速度:〇.5m/ min
〔實施例1〕 <塗佈> 對評價基板A旋塗下層材料A - L,並以熱板於1 2 〇。〇 下烘烤5分鐘,形成膜厚5 // m的下層。於此下層之上方旋 塗上層材料A — L,並以熱板於1 2 0 °C下烘烤5分鐘,形成 膜厚6 5 // m的上層。
<曝光> 使用校準器(Suss Microtec公司製MA— 150),透過 附有圖案的玻璃光罩令來自高壓水銀燈之紫外線以波長 420 nm中之曝光量爲1〇〇〇 mj/ cm2般進行曝光。玻璃光 罩爲密合至以PET薄膜覆蓋的基板並且曝光。 <顯像> 經曝光之基板,以含有2.3 8 %氫氧化四甲基錢之水溶 -35- (32) 1304315 液(以下,簡稱爲TMAH顯像液)進行槳葉顯像 之滿液時間爲以90秒鐘爲中心並以1 5秒鐘間隔進 顯像後,以離子交換水漂洗60秒鐘。 此圖案化基板爲存在許多具有7 5 // m X 7 5 // 孔圖案。 顯像後,以光學顯微鏡和掃描型電子顯微鏡 ’並以下列基準評價。結果示於表4。 圖案形狀〇:具有7 5 // m X 7 5 // m開口之孔 無顯像殘留的地顯像,且未察見圖案浮起、剝落 像時間。 圖案形狀X :具有7 5 // m X 7 5 // m開口之孔 像殘留物、或者察見圖案浮起、剝落,且顯像時 <焊料凸點之埋入> 其後,對雙層層合薄膜之全體表面,使用滑 錫漿料塗佈,且於凹狀之焊料凸點形成用之開口 充塡焊錫漿料。還有,此處充塡的焊錫漿料爲 Ag以重量比96.5 : 3.5配合爲主之粒徑5〜20# m 且其黏度被調整至200Pa · S。其次,將焊料凸點 開0部所充塡之焊錫漿料以外之焊錫漿料,首先 板予以除去,其後,使用淸潔紙(cleaning paf 完全除去,令焊錫漿料的表面平坦化。 。顯像時 行調製。 m開口的 確認圖案 圖案爲以 寺具有顯 圖案有顯 間無界限 移板將焊 部中完全 含有Sn、 的焊料, 形成用之 使用滑移 ,e r )將其 -36- (33) 1304315 <逆流> 其後,將上述步驟所印刷之焊錫漿料以2 5 0 °C逆流 再進洗鬆化洗淨。 <剝離〉
於約1公升二甲基亞硕或剝離液1加溫至約6 〇。(:之剝離 槽中’逆流後’冷卻至室溫的基板以1 0分鐘浸瀆/攪拌下 ,將雙層層合薄膜剝離。 以剝離槽進行剝離處理之基板爲以異丙醇予以漂洗後 ,水洗並以空氣槍乾燥。 剝離處理後,以光學顯微鏡和掃描型電子顯微鏡觀察 基板表面、焊料凸點,並以下列基準進行評價。結果示於 表4。 評價基準 對於D M S Ο之剝離性〇:大部分之雙層層合薄膜爲剝 離。 對於DMSO之剝離性X :完全未剝離。 對於剝離液1之剝離性〇:於基板面上無剝離殘留物 〇 對於剝離液1之剝離性X :於基板面上觀察到剝離殘 留物。 〔實施例2〕 -37- (34) 1304315 <塗佈> 對評價基板A旋塗下層材料a - L,並以熱板於1 2 0 ΐ: 下烘烤5分鐘,形成膜厚5 // m的下層。於此下層之上方將 上層材料A — D (膜厚6 5 // m )層合。 以下之操作,以實施例1同樣之手續實施。 〔實施例3〕 對評價基板B旋塗下層材料B - L,並以乾淨爐於1 1 0 °C下烘烤1 〇分鐘,形成膜厚2 // m的下層。於此下層之上 方旋塗上層材料B — L,並於1 1 〇 °C下烘烤1 0分鐘,形成膜 厚4 0 // m的上層。 使用校準器(Suss Microtec公司製MA — 150),透過 附有圖案的玻璃光罩令來自高壓水銀燈之紫外線以波長 3 5 0 ηηι中之曝光量爲400 mJ/ cm2般進行曝光。玻璃光罩 爲密合至以PET薄膜覆蓋的基板並且曝光。 曝光時,於評價基板之孔圖案(第一開口圖案)上令 感放射線性樹脂組成物之第二開口圖案爲以相同位置般, 對準並且曝光。 經曝光之基板,使用1重量%碳酸鈉水溶液於3 0 °C下 以4 5秒鐘爲中心並以1 5秒鐘間隔進行淋洗顯像(壓力, 1 k g f · cm2 ) ° 此基板爲具有如下之第一開口圖案和第二開口圖案。 第一開口圖案 第二開口圖案 1 5 0 // m間距開口直徑9 5 Μ ni之孔開口直徑1 0 0 // m之 -38- (35) 1304315 孔 125 /i m間距開口直徑8〇 g m之孔開口直徑90 之孔 1 0 0 " m間距開口直徑6 0 // m之孔開口直徑8 〇 # m之孔 顯像後,以光學顯微鏡和掃描型電子顯微鏡確認圖案 形狀,並以下列基準進行評價。結果示於表4。 續像性〇:第二開口圖案爲以無顯像殘留物地顯像, 且未察見圖案浮起,剝落等並具有顯像時間。 顯像性X :於第二開口圖案有顯像殘留物,或者察見 圖案浮起、剝落,且顯像時間無界限。 以下之步驟爲與實施例1相同。 〔實施例4〕 <塗佈> 對δ平價基板B旋塗下層材料b - L,並以熱板於1 2 0 °C 下供烤5分鐘’形成膜厚2 # m的下層。於此下層之上方將 上層材料B— D (膜厚4〇//m)層合。 以下之操作爲以實施例3同樣之手續實施。 〔實施例5〕 對評價基板β旋塗下層材料B 一 L,並以乾淨爐於1 1 0 °C Τ供;烤1 0分鐘’形成膜厚2 // m的下層。於此下層之上 方旋塗上層材料A〜L,並以乾淨爐於1 1 〇。(:下烘烤1 0分鐘 ’开夕成膜厚4 0 // in的上層。 …39 - (36)1304315 以下之操作除了顯像,爲以實施例4同樣之手 續實施 <顯像> 經曝光之基板,以含有1 %氫氧化鈉之水溶液 ,簡稱爲N aO Η顯像液)於3 0 °C下以4 5秒鐘爲中心 秒鐘間隔進行淋洗顯像(壓力;1 kg f · cm 2 )。顯 以離子交換水漂洗6 0秒鐘。 (以下 並以15 ί象後, 〔實施例6〕 對評價基板B旋塗下層材料b - L,並以熱板方 下烘烤5分鐘’形成膜厚2 // πι的下層。於此下層之 上層材料B— D (膜厚40// m)層合。 以下之操作爲以實施例5同樣之手續實施。 ^ 1 2 0 °C 上方將 〔實施例7〕 對評價基板B層合下層材料β 一 D,形成膜厚2 下層。於此下層之上方旋塗上層材料B — l,並以 於下烘烤1〇分鐘,形成膜厚4〇v m的上層。 以下之操作爲以實施例3同樣之手續實施。 // m的 乾淨爐 〔實施例8〕 對評價基板B層合下層材料B〜〇 下層 。於此下層之上方層合上
層材料B 形成膜厚2 一 D (膜厚 // m的 4 0// m (37) 1304315 以下之操作爲以實施例3同樣之手續實施。 〔實施例9〕 對評價基板B層合雙層乾式薄膜A。 以下之操作爲以實施例3同樣之手續實施。
〔實施例1 〇〕 對評價基板B層合雙層乾式薄膜B。 以下之操作爲以實施例5同樣之手續實施。 〔比較例1〜4〕 比較例1〜4除了未形成下層材料以外,全部與對應編 號之實施例同樣實施。
-41 - (38)1304315 表4
實施例 膜 B Na2C03 〇 〇 實施例 10 雙乾式薄膜
B
NaOH 〇 〇 〇 比較例
A— L
A TMAH 〇 x x 比較例2
A - D
A TMAH 〇 x 比較例 B ~~ L b Na2C03 〇 比較例4 B - D B Na2C03 〇
X 【圖式簡單說明】 圖1爲示出本發明之焊料凸點之形成方法的截面模型 圖。 圖2爲示出本發明之焊料凸點之形成方法的截面模型 -42 - (39) 1304315 圖 圖 圖 圖 圖 圖 圖
圖3爲示出本發明之焊料凸點之形成方法的截面模型 圖4爲示出本發明之焊料凸點之形成方法的截面模型 圖5爲示出本發明之焊料凸點之形成方法的截面模型 圖6爲示出本發明之焊料凸點之形成方法的截面模型 圖7爲示出本發明之焊料凸點之形成方法的截面模型 圖8爲示出本發明之焊料凸點之形成方法的截面模型
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Claims (1)
- (1) 1304315 拾、申請專利範圍 1. 一種電極底座上形成焊料凸點之方法,其特徵爲於 基材、與複數電極底座所構成的電路基板上,至少進行下 述(a )〜(d )之步驟; (a )於電路基板上,形成下層爲由鹼可溶性且非感 放射線性樹脂組成物所構成,上層爲由負型感放射性樹脂 組成物所構成的雙層層合薄膜後,於電極底座的對應位置 形成開口圖案之步驟、 (b )於該開口圖案內導入低熔點金屬之步驟、 (c )於加壓或加熱處理下令該低熔點金屬逆流並且 形成焊料凸點之步驟、及 (d )將該雙層層合薄膜由基板上剝離、除去之步驟 〇 2. 如申請專利範圍第1項之焊料凸點形成方法,其中 該非感放射線性樹脂組成物爲含有具有酚性羥基的化合物 〇 3. 如申請專利範圍第1項或第2項之焊料凸點形成方法 ,其中該非感放射線性樹脂組成物爲含有丙烯酸樹脂。 4. 如申請專利範圍第1項之焊料凸點形成方法,其中 該雙層層合薄膜之下層爲由液狀或乾式薄膜狀之非感放射 線性樹脂組成物所形成。 5 ·如申請專利範圍第1項之焊料凸點形成方法,其中 該雙層層合薄膜之上層爲由液狀或乾式薄膜狀之負型感放 射線性樹脂組成物所形成。 6.如申請專利範圍第1項之焊料凸點形成方法,其中 _44 - (2) 1304315 該雙層層合薄膜爲由具有下層及上層雙層構造的乾式薄膜 所形成。 7. 如申請專利範圍第1項之焊料凸點形成方法,其中 該(d )步驟爲由準備具有多段浸漬槽之剝離設備,且於 第一槽使用有機溶劑將雙層層合薄膜予以剝離並且將剝離 片予以循環過濾後’於第二槽以後將該層合薄膜以含有有 機鹼成分之剝離液予以剝離所構成。 8. 如申請專利範圍第1項之焊料凸點形成方法,其中 該(d )步驟爲由準備具有多段浸漬槽之剝離設備,且於 第一槽使用二甲基亞硕將雙層層合薄膜予以剝離並且將剝 離片予以循環過濾後,於第二槽以後將該層合薄膜以含有 機鹼成分和二甲基亞硕之剝離液予以剝離所構成。 9. 如申請專利範圍第1項之焊料凸點形成方法,其中 該電路基板爲由矽晶圓所構成之基材、與該基材表面所設 置之多數的電極底座所構成。 10. 如申請專利範圍第1項之焊料凸點形成方法,其中 該電路基板爲由矽晶圓所構成之基材、與該基材表面所設 置之多數的電極底座、與該電極底座之側面及側端面上所 形成的鈍化膜所構成。 11. 如申請專利範圍第1項之焊料凸點形成方法,其中 該電路基板爲由玻璃環氧樹脂或雙馬來醯亞胺-三畊樹脂 所構成之基材、與複數的電極底座所構成。 12. 如申請專利範圍第1項之焊料凸點形成方法,其中 該電路基板爲由玻璃環氧樹脂或雙馬來醯亞胺-三畊樹脂 所構成之基材、與該基材上所設置之層間樹脂絕緣層及導 - 45… (3) 1304315 體電路、與該導體電路上所設置之複數電極底座所構成。 1 3 .如申請專利範圍第1項〜第1 2項中任一項之焊料凸 點形成方法,其中該低熔點金屬爲焊錫。_ 46 -
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JP2003023602A JP2004140313A (ja) | 2002-08-22 | 2003-01-31 | 二層積層膜を用いた電極パッド上へのバンプ形成方法 |
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EP (1) | EP1542520A4 (zh) |
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EP1542520A4 (en) | 2008-12-03 |
EP1542520A1 (en) | 2005-06-15 |
CN100463587C (zh) | 2009-02-18 |
TW200405784A (en) | 2004-04-01 |
KR100756151B1 (ko) | 2007-09-05 |
CN1675968A (zh) | 2005-09-28 |
US7265044B2 (en) | 2007-09-04 |
WO2004019667A1 (ja) | 2004-03-04 |
JP2004140313A (ja) | 2004-05-13 |
AU2003257647A1 (en) | 2004-03-11 |
US20050277245A1 (en) | 2005-12-15 |
KR20050058390A (ko) | 2005-06-16 |
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