TWI629351B - 用於光刻法的光阻劑清潔組合物及以其處理基材的方法 - Google Patents

用於光刻法的光阻劑清潔組合物及以其處理基材的方法 Download PDF

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TWI629351B
TWI629351B TW105124840A TW105124840A TWI629351B TW I629351 B TWI629351 B TW I629351B TW 105124840 A TW105124840 A TW 105124840A TW 105124840 A TW105124840 A TW 105124840A TW I629351 B TWI629351 B TW I629351B
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Taiwan
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mass
mixture
photoresist
cleaning composition
photoresist cleaning
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TW105124840A
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TW201712111A (zh
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張禮凱
郡 艾韋拉德 沛瑞斯
陳秀美
李翊嘉
劉文達
天牛 陳
羅拉Ｍ 梅特茲
羅立章
孟令人
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慧盛材料美國責任有限公司
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
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Abstract

本發明揭示一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其含有(a)氫氧化季銨，(b)水溶性有機溶劑混合物，(c)至少一腐蝕抑制劑，及(d)水；及以其處理基材之方法。

Description

用於光刻法的光阻劑清潔組合物及以其處理基材的方法 相關申請案之交互參照
本專利案請求2015年8月5日申請的美國臨時專利案序號第62/201,352號的權益，在此以引用的方式將其全文併入本文。
本發明關於一種用於剝離厚光阻劑圖案的光刻法的光阻劑清潔組合物及以其處理基材的方法。本發明的光阻劑清潔組合物尤其適用於製造半導體裝置，例如IC及LSI時形成凸塊或柱體或再分配層(redistribution layer；RDL)。在製造半導體裝置，例如IC及LSI時其也可在蝕刻製程，例如Bosch蝕刻製程，之後用於將貫穿矽通孔(TSVs)形成於矽或玻璃基材上。
最近幾年，隨著半導體裝置例如IC及LSI的高 集積度及晶片尺寸縮減，必需得減小金屬配線的尺寸並且使在基材上高度為20μm或更高之充當連接端部(微細突出電極)的凸塊或柱體以高精確度對齊。未來，隨著晶片尺寸進一步減小，又更需要高精確度的金屬配線及凸塊。
該凸塊形成係藉由以下方式進行，舉例來說，將金屬薄膜提供於基材上，藉由光刻技術使厚光阻劑圖案形成於該金屬薄膜上，將導電層提供於該基材的光阻劑圖案沒覆蓋的區域(亦即，露出金屬薄膜的區域)以形成凸塊、柱體或RDLs而且接著移除該光阻劑圖案。
該光阻劑圖案可能是厚膜，通常為約3至150μm的膜厚度，而且該光阻劑可為正向作用型光阻劑材料，因為負向作用型光阻劑有許多常見的剝離化學藥品會嚴重蝕刻或損壞基材材料例如銅、鎳、銅或鎳與不同金屬的合金、錫-銀合金(也被稱作組成變動的SAC)、TiN或其他鈍化材料例如SiN、聚醯胺、BCB等等。
因為該光阻劑圖案可能是厚的，通常為約3至150μm的膜厚度，所以就耐鍍敷、圖案形狀特性等等的觀點來看該光阻劑可能是負向作用型光阻劑材料。與由正向作用型光阻劑材料製作的光阻劑圖案相比要移除由負向作用型光阻劑材料製作的光阻劑圖案通常更困難，因此，相對於厚的正向作用型光阻劑材料要移除由負向作用型光阻劑材料製作的厚光阻劑圖案又更困難。
再者，該厚光阻劑圖案可能由於其厚重的膜厚度而在該形成製程期間變形或崩塌。在此案例中，必須中斷其 後的製程而且藉由從該基材完全地移除變形的光阻劑圖案並且重複用以形成該光阻劑圖案的步驟才能進行再製。
在該凸塊形成之後的光阻劑圖案移除或有關再製的光阻劑圖案移除之後，通常在光阻劑清潔組合物槽中發生以快迅而且完全地剝離該光阻劑圖案(固化材料)。重要的是在清潔該光阻劑的時候該光阻劑清潔組合物不會侵蝕該金屬薄膜，而且重要的是得完全移除該光阻劑。除此之外，在該基材上形成凸塊時，該光阻劑圖案與該凸塊之間的界面處可能會形成再產生變質的膜。因此必須防止該金屬膜腐蝕並且保護該凸塊不受腐蝕影響的凸塊及任何其他存在而不想被該光阻劑清潔組合物移除的材料。
JP-A-08-301911描述拿供凸塊形成用途用的輻射敏感性樹脂組合物當成圖案形成材料並且在[0032]及[0043]段中揭示當成用於剝離光固化圖案的剝離液之季銨、二甲基亞碸及水的混合物(明確地說，0.5質量%氫氧化四甲基銨(含有1.5質量%的水)的二甲基亞碸溶液)。然而，此剝離液涉及多數問題使其得花時間將該光固化圖案溶解，該光固化圖案在該剝離液中自該基材被剝離，而且使原料處理量在低值。另外，該剝離液造成這些應用中使用的不同金屬基材的高度蝕刻。
JP-A-10-239865描述當成用於剝離供形成凸塊用的負向作用型光阻劑的剝離液之含有指定量的二甲基亞碸、1,3-二甲基-2-咪唑啶酮、氫氧化四烷基銨水的配方。就像在以上JP-A-08-301911的案例中，JP-A-10-239865同樣涉及 多數問題使其得花時間將該光固化圖案溶解，該光固化圖案在該剝離液中自該基材被剝離，而且使原料處理量在低值。同樣重要的是，此剝離液造成這些應用中使用的不同金屬基材的高度蝕刻。再者，該JP-A-10-239865中的剝離溶液含有1,3-二甲基-2-咪唑啶酮當成基本組分。此化合物造成Cu的變色或腐蝕。
在該光刻領域中，JP-A-2001-324823、JP-A-07-028254等等揭示含有氫氧化季銨及水溶性有機溶劑例如二甲基亞碸的剝離液。然而，那些完全沒有任一者述及移除適用於供形成凸塊用的厚圖案的厚正向或負向作用型光阻劑之難題的排除方法。
其他已知的組合物可剝離該光阻劑，而且也會侵蝕存於基材上要被清潔的金屬及其他材料。需要的組合物得能徹底清潔而且幾乎不會或不會造成該基材上的金屬及/或鈍化材料的腐蝕。
本發明的目的在於提供一種不僅能自基材剝離厚光阻劑圖案(其可用於凸塊形成)的光阻劑清潔組合物，及一種使用該光阻劑清潔組合物處理基材的方法。
在本發明之一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或0.5至4或0.5至3或1至5或1至4或1至3或1至2或1.5至3或1.8至2.3或1.25至4.5質量%的至少一氫 氧化季銨或二或更多氫氧化季銨的混合物；(b)60至97.5或60至96或73至98或75至96或90至96或89至95或78至85或64至69或80.5至82.5或82至97.5或80至83或85至96或89至94或85至97.5或86至97或91至96質量%的水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑；(c)0.5至15或0.5至14或0.5至12或0.5至10或10.5至15或11至14或11至13 or10至20或0.5至5或0.5至4或0.5至3或1至10或1至5或1至4或1至3或3至4質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)0.5至25或0.5至10或1至10或1至8或1至7或2至5或1至5或1至2或3至7或4至6質量%的水。
注意無論在本文述及“包含”、“含有”或“具有”等的任何之處，其包括“基本上由...所組成”及“由...所組成”在內。
在本發明之另一態樣中，本發明提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或0.5至4或0.5至3或1至5或1至4或1至3或1至2或1.5至3或1.8至2.3或1.25至4.5質量%的至少一氫氧化季銨，例如氫氧化四甲基銨及/或氫氧化四乙基銨或任何其他氫氧化季銨(其可選自以下列舉者)，或其混合物，(b)60至97.5或60至96或73至98或75至96或90至96或89至95或78至85或64至69或80.5至82.5或82至 97.5或80至83或85至96或89至94或85至97.5或86至97或91至96質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一(或二或更多)其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、其他二醇類、二元醇類、三元醇類、環狀醇類、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺或其他烷醇胺類(通常為C1至C6烷醇胺類，例如二乙醇乙基胺)、胺基丙基嗎啉及其混合物所組成的群組；(c)0.5至15或0.5至14或0.5至12或0.5至10或10.5至15或11至14或11至13或10至20或0.5至5或0.5至4或0.5至3或1至10或1至5或1至4或1至3或3至4質量%的至少一腐蝕抑制劑，該至少一腐蝕抑制劑係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)、二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物或任何該等腐蝕抑制劑的混合物所組成的群組；而且(d)0.5至25或0.5至10或1至10或1至7或2至5或1至5或1至2或3至7或4至6質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或0.5至4或0.5至3或1至5或1至4或1至3或1至2或1.5至3或1.8至2.3或1.25至4.5質量%的至少一氫氧化季銨，該至少一氫氧化季銨係選自由氫氧化四甲基 銨或氫氧化四乙基銨及其混合物所組成的群組；(b)60至97.5或60至96或73至98或75至96或90至96或89至95或78至85或64至69或80.5至82.5或82至97.5或80至83或85至96或89至94或85至97.5或86至97或91至96質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺或胺基丙基嗎啉及其混合物所組成的群組；(c)0.5至15或0.5至14或0.5至12或0.5至10或10.5至15或11至14或11至13或10至20或0.5至5或0.5至4或0.5至3或1至10或1至5或1至4或1至3或3至4質量%的至少一腐蝕抑制劑，該至少一腐蝕抑制劑係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物及/或二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物所組成的群組；及(d)0.5至25或0.5至10或1至10或1至8或1至7或2至5或1至5或1至2或3至7或4至6質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或0.5至4或0.5至3或1至5或1至4或1至3或1至2或1.5至3或1.8至2.3或1.25至4.5質量%的一或更多氫氧化季銨，(b)60至97.5或60至96或73至98或75 至96或90至96或89至95或78至85或64至69或80.5至82.5或82至97.5或80至83或85至96或89至94或85至97.5或86至97或91至96質量%的二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及至少一其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺、二乙醇胺、胺基丙基嗎啉或其他溶劑或其混合物所組成的群組；(c)0.5至15或0.5至14或0.5至12或0.5至10或10至20或10.5至15或11至14或11至13或0.5至5或0.5至4或0.5至3或1至10或1至5或1至4或1至3或3至4質量%的二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物及至少一其他腐蝕抑制劑，該至少一其他腐蝕抑制劑係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組；及(d)0.5至25或0.5至10或1至10或1至8或1至7或2至5或1至5或1至2或3至7或4至6質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或1至5或1.25至4.5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)82至97.5或85至96或89-94質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有 機溶劑或二或更多其他有機溶劑；(c)1至5或1至4或1至3質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或1至8或1至7質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或1至5或1.25至4.5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)水溶性有機溶劑之混合物，包含80至96或83至94或87至92質量%二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及1至4或2至3或2質量%的至少一其他有機溶劑或二或更多其他有機溶劑；(c)1至5或1至4或1至3質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或1至8或1至7質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或1至5或1.25至4.5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)82至97.5或85至96或89至94質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑；(c)1至5或1至4或1至3質量%的包含PEI之二或更多腐蝕抑制劑的混合物；及(d)1至10或1至8或1至7質量%的水。1至2或1質量%。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含 (a)0.5至5或1至5或1.25至4.5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)水溶性有機溶劑之混合物，包含80至96或83至94或87至92質量%二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及1至4或2至3或2質量%的至少一其他有機溶劑或二或更多其他有機溶劑；(c)1至5或1至4或1至3質量%的包含PEI之至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或1至8或1至7質量%的水。在該光阻劑清潔組合物中前述PEI可能存有1至2或1質量%。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或1至5或1至2質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)85至97.5或86至97或91至96質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑；(c)1至10或1至5或3至4質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或1至5或1至2質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5或1至5或1至2質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)水溶性有機溶劑之混合物含35至50或38至45或41至44質量%二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物的及45至58或48至54或50 至52質量%的其他有機溶劑或二或更多其他有機溶劑；(c)1至10或1至5或3至4質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或1至5或1至2質量%的水。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5或1.5至3或1.8至2.3質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)78至85或80至83或80.5至82.5質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑；(c)10.5至15或11至14或11至13質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或3至7或4至6質量%的水。該光阻劑清潔組合物可包含胺或烷醇胺當成其他有機溶劑。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5或1.5至3或1.8至2.3質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)59至84或65至81或63至67質量%的二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及1至20或1至15或2至15質量%的至少一其他有機溶劑或二或更多其他有機溶劑；(c)10.5至15或11至14或11至13質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至10或3至7或4至6質量%的水。在任何態樣中，該光阻劑清潔組合物可包含胺或烷醇胺當成 其他有機溶劑。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5或1.5至3或1.8至2.3質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)78至85或80至83或80.5至82.5質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑；(c)10至20或5至14.5或7至12或9至11質量%的二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物及0.5至5或1至4或1至3質量%的至少一腐蝕抑制劑或二或更多其他腐蝕抑制劑的混合物；及(d)1至10或3至7或4至6質量%的水。該光阻劑清潔組合物可包含胺或烷醇胺當成其他有機溶劑。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5或1.5至3或1.8至2.3質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)59至84或65至81或63至67質量%的二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及1至20或1至15或2至15質量%的至少一其他有機溶劑或二或更多其他有機溶劑；(c)10至20或5至14.5或7至12或9至11質量%的二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物及0.5至5或1至4或1至3質量%的至少一腐蝕抑制劑或二或更多其他腐蝕抑制劑的混合物，及(d)1至10或3至7或4至6質量%的水。該光 阻劑清潔組合物可包含胺或烷醇胺當成其他有機溶劑。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5或1.5至3或1.8至2.3質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)64至69質量%的一水溶性有機溶劑之混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑，該至少一其他有機溶劑或二或更多其他有機溶劑包含烷醇胺類，通常為C1至C6烷醇胺類，舉例來說單乙醇胺；(c)10.5至15或11至14或11至13質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；(d)1至10或3至7或4至6質量%的水。
在本發明的任何態樣中，單獨或與其他態樣一起，該水溶性有機溶劑可包含二甲基亞碸及至少一其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組。在本發明的任何態樣中，單獨或與其他態樣一起，該光阻劑清潔組合物可包含選自由氫氧化四甲基銨或氫氧化四乙基銨及其混合物所組成的群組之氫氧化季銨。
在本發明之另一態樣中提供一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至3質量%的氫氧化季銨，例如氫氧化四甲基銨或氫氧化四乙基銨；(b)90至95質量%的二甲基亞碸及1至6質量% 的至少一其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組；(c)0.5至3質量%的至少一腐蝕抑制劑，該至少一腐蝕抑制劑係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組；及(d)2至5質量%的水。
在本發明的任何態樣中，單獨或與其他態樣一起，該(等)其他有機溶劑係選自由丙二醇、其他二醇類、二元醇類、三元醇類、環狀醇類、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺或其他烷基烷醇胺類(例如二乙醇乙基胺)、胺基丙基嗎啉及其混合物所組成的群組。在本發明的任何態樣中，該至少一腐蝕抑制劑係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)、二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物或任何該等腐蝕抑制劑的混合物所組成的群組。
在本發明的任何態樣中，該腐蝕抑制劑，單獨或與本發明其他態樣聯合，可包含PEI，該PEI可存有1至2或1質量%。在任何態樣中，該組分(b)，單獨或與本發明其他態樣聯合，可包含丙二醇及/或二甲基亞碸。在其他態樣中，單獨或與本發明其他態樣聯合，該組分(b)可包含乙二醇或二丙 二醇甲基醚。
在該光阻劑清潔組合物之一態樣中，組分(c)，單獨或與本發明其他態樣聯合，係選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組；或其中組分(c)，單獨或與本發明其他態樣聯合，係選自由苯磷二酚、第三丁基苯磷二酚、沒食子酸、單-或二-羥基苯甲酸或其混合物所組成的群組；或其中組分(c)，單獨或與本發明其他態樣聯合，係選自由苯磷二酚、第三丁基苯磷二酚、單-或二-羥基苯甲酸或其混合物所組成的群組；或其中組分(c)，單獨或與本發明其他態樣聯合，係選自由苯磷二酚、第三丁基苯磷二酚或其混合物所組成的群組；或其中組分(c)，單獨或與本發明其他態樣聯合，係選自由檸檬酸、聚乙烯亞胺(PEI)或其混合物所組成的群組。根據任何前述具體實施例的光阻劑清潔組合物，單獨或與本發明其他態樣聯合，該光阻劑圖案可能是使用靠輻射照射而聚合的正向或負向作用型光阻劑組合物形成的光固化圖案。
在本發明的其他態樣中，該腐蝕抑制劑，單獨或與本發明其他態樣聯合，包含或另外包含DEHA，或其中該腐蝕抑制劑包含或另外包含PEI。在本發明的其他態樣中，單獨或與本發明其他態樣聯合，該其他有機溶劑包含或另外包含丙二醇，或另外包含烷醇胺，例如單乙醇胺。
在本發明的其他態樣中，任何具體實施例及/或用於任何方法的光阻劑清潔組合物，單獨或與其他態樣一起， 可不含醯胺類，或不含內醯胺類，或不含咪唑啶酮類，或不含碸類，或不含醚類，或不含烷醇胺類，或不含羥基胺類，或不含酸類。在另一態樣中，用於本發明任何方法的本發明的任何組合物，單獨或與其他態樣一起，的pH可為9，或高於9.5，或9.5至12.5，或9.5至13，或10至12，或10.5至11.5，或11至12.5。
另外，在另一態樣中，本發明提供一種用於處理基材之方法，其包含將膜厚度為3至150μm的光阻劑圖案形成於上面有金屬薄膜的基材上，將導電層提供於露出金屬薄膜的區域或光阻劑圖案沒覆蓋的區域上，而且使該光阻劑圖案與該光阻劑清潔組合物接觸以利用本文揭示的任何光阻劑清潔組合物剝離該光阻劑圖案。
在本發明的其他態樣中，本發明提供一種用於處理基材之方法，其包含以下步驟：將膜厚度為3至150μm的光阻劑圖案形成於上面有金屬薄膜的基材上，將非導電性鈍化層提供於露出金屬薄膜的區域或光阻劑圖案沒覆蓋的區域上，使該光阻劑圖案與本文揭示的任何光阻劑清潔組合物接觸以剝離該光阻劑圖案。
在本發明的其他態樣中，提供一種用於處理基材之方法，其包含將膜厚度為3至150μm的光阻劑圖案形成於上面有金屬薄膜的基材上，將導電層提供於露出金屬薄膜的區域或光阻劑圖案沒覆蓋的區域上，而且使該光阻劑圖案與本文揭示的任何光阻劑清潔組合物接觸以剝離並且溶解該光阻劑圖案。
在該方法的其他態樣中，該光阻劑圖案係利用靠輻射照射而聚合的正向或負向作用型光阻劑組合物形成的光固化圖案。
在本發明的其他態樣中提供一種用於處理基材之方法，其包含將膜厚度為3至150μm的光阻劑圖案形成於上面有金屬薄膜的基材上，使該光阻劑圖案與本文所述的任何光阻劑清潔組合物接觸以剝離並且溶解該光阻劑圖案，而沒將導電層提供於露出金屬薄膜的區域或光阻劑圖案沒覆蓋的區域上。
在本發明的其他態樣中提供，單獨或與其他態樣一起，本發明用於處理基材之方法，其中該光阻劑圖案可為利用靠輻射照射而聚合的正向或負向作用型光阻劑組合物所形成的光固化圖案。
本發明的清潔組合物及方法提供一或更多下列益處：該等光阻劑清潔組合物組分的改良可剝離性和溶解度及該光阻劑於該光阻劑清潔組合物中的溶解度，及對銅和其他金屬的低腐蝕速率及存於該基材上的鈍化材料或其他材料的低腐蝕作用。
本發明的光阻劑清潔組合物係用於剝離膜厚度為3至150μm的光阻劑圖案，該光阻劑圖案係形成於上面有金屬薄膜的基材上。該光阻劑清潔組合物的組分(a)可為選自由氫氧化四甲基銨(TMAH)或氫氧化四乙基銨(TEAH)或其混 合物所組成的群組之氫氧化季銨。在可供選擇的具體實施例中，該氫氧化季銨可為或可包括氫氧化四乙基銨(TEAH)。在另一實例中，該組合物可包括氫氧化四甲基銨(TMAH)。在其他實例中，該組合物可包括下列一或多者：TEAH、TMAH、氫氧化二甲基二丙基銨、氫氧化四丙基銨、氫氧化苯甲基三甲基銨、氫氧化二甲基二乙基銨及/或氫氧化四丁基銨。在其他實例中，該組合物可包括TEAH、TMAH、氫氧化二甲基二丙基銨、氫氧化四丙基銨、氫氧化四丁基銨，或其組合。組分(a)的其他實例包括氫氧化四丙基銨、氫氧化四丁基銨、氫氧化甲基三丙基銨及氫氧化甲基三丁基銨。組分(a)可單獨或依其二或更多者的混合物使用。
該被當成(a)組分的一或更多季銨化合物的總量可為本發明的光阻劑清潔組合物之0.5至5或0.5至4或0.5至3或1至5或1至4或1至3或1至2或1.5至3或1.8至2.3或1.25至4.5質量%。
該被當成(b)組分的水溶性有機溶劑混合物可包含二甲基亞碸(DMSO)、環丁碸或二甲基碸中的一或多者及至少一可與水混溶的有機溶劑。該其他有機溶劑可選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組。
在一些具體實施例中，本發明的光阻劑清潔組合物不含某些有機溶劑或其他有機溶劑，其可依任何組合包括下列任一或多者：胺類(季銨化合物以外的)、烷醇胺、醯胺類、 嗎啉類、內醯胺類、咪唑類、咪唑啶酮類、碸類、酮類、酸類、醇類(例如單醇類、二元醇類、三元醇類)、酯類、亞胺類及/或醚類。在一些具體實施例中，該組合物或該其他有機溶劑不是及/或該組合物不含環丁碸及/或N-甲基-2-吡咯烷酮及/或其他N-烷基-吡咯啶類及/或其他吡咯啶類。另外，該組合物可舉例來說不含“烷醇胺”，或舉其他例子可另外包含其他不含“醇”及/或不含“二元醇”的溶劑。任何前述組分皆可換成剛才列舉的實例，例如不含“酮”而且不含“咪唑”來描述本發明任何方法所用的本發明的任何光阻劑組合物。
至於本發明的組分(b)，可使用二甲基亞碸(DMSO)、環丁碸或二甲基碸中的一或多者及一或更多其他有機溶劑之混合溶劑，該一或更多其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、其他二醇醚類、γ-丁內酯、γ-戊內酯、二甲基乙醯胺、單乙醇胺或其他烷醇胺類及胺基丙基嗎啉及其混合物所組成的群組。至於本發明的組分(b)，可使用二甲基亞碸及丙二醇的混合溶劑。可使用二甲基亞碸及乙二醇的混合溶劑。另外可使用二甲基亞碸及乙二醇及烷醇胺的混合溶劑。
在一些具體實施例中，該二甲基亞碸(DMSO)、環丁碸或二甲基碸中的一或多者對該其他水溶性有機溶劑或複數個有機溶劑之混合比較佳為高於2：1，或高於5：1，或高於10：1，或高於15：1，或高於20：1，或高於25：1，或高於30：1，或高於35：1，或高於40：1，或高於45：1。組分(b)可以三或更多有機溶劑的混合物被使用。該二甲基亞 碸(DMSO)、環丁碸或二甲基碸或其混合物中的一或多者存於該光阻劑剝離劑(光阻劑清潔組合物)的量可為80至96或83至94或87至92或90至95質量%而且該(等)溶劑的其餘部分存在的量可為該光阻劑剝離劑組合物的1至4或2至3或2或1至6質量%。在可供選擇的具體實施例中，二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物中的一或多者存在的量可為58至84或65至81或63至67質量%而且該(等)有機溶劑的其餘部分存在的量可為該光阻劑清潔組合物的1至10或1至5或1.5至3質量%。
在可供選擇的具體實施例中，該二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物中的一或多者的質量%對該(等)其他有機溶劑的質量%之比率可為低於1：2。在一些具體實施例中該二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物中的一或多者的質量%對該(等)其他有機溶劑的質量%之比率可為約1：0.9至1.5。在一些具體實施例中，該二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物中的一或多者可為35至50或38至45或41至44質量%而且該(等)其他有機溶劑可為該光阻劑清潔組合物的45至58或48至54或50至52質量%。在可供選擇的具體實施例中，二甲基亞碸(DMSO)、環丁碸或二甲基碸中的一或多者存在的量可為34至59或35至53或40至50質量%而且該其他有機溶劑，可為一或更多溶劑，存有該光阻劑清潔組合物的40至65或46至60或48至55質量%。
該其他一或更多溶劑可選自以上列舉的溶劑或 其可為一或更多二醇醚類及/或一或更多二醇類。若二醇醚及二醇與該二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物一起用於該清潔組合物中時，該二醇醚使用的量可高於該二醇使用之量的15：1，或高於20：1，或大約25：1。
該溶劑組分(b)的總量可為本發明的光阻劑清潔組合物的60至97.5或60至96或73至98或75至96或90至96或89至95或78至85或64至69或80.5至82.5或82至97.5或80至83或85至96或89至94或85至97.5或86至97或91至96質量%。
在一些具體實施例中，該溶劑組分(b)的總量可為該光阻劑清潔組合物的78至85或64至69或80至83或82至97.5或80.5至82.5或85至96或89至94或85至97.5或86至97或91至96質量%。
當組分(c)的腐蝕抑制劑的量可為0.5至15或0.5至14或0.5至12或0.5至10或10.5至15或11至14或11至13或0.5至5或0.5至4或0.5至3或1至10或1至5或1至4或1至3或3至4質量%。該腐蝕抑制劑使該金屬薄膜或鈍化材料或介電材料的腐蝕作用降低。該腐蝕抑制劑可選自由苯磷二酚、第三丁基苯磷二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、沒食子酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組。在一些具體實施例中，較佳的腐蝕抑制劑係4-羥基苯甲酸(4BHA)；或2,4-二羥基苯甲酸；或3,4-二羥基苯甲酸或3,5-二羥基苯甲酸，或檸檬酸與聚乙烯亞胺(PEI)的組合。在可供選擇的具體實施例 中，該光阻劑清潔組合物包含DEHA(當成該等腐蝕抑制劑中之至少其一)及二醇(當成至少一其他有機溶劑)而且可另外包含胺或烷醇胺。
任何具體實施例中的腐蝕抑制劑可包含或可附帶地另外包含2至20或10至20或5至14.5或5至15或7至12或8至12或9至11質量%或約10質量%的量之羥基胺類或其酸鹽類，舉例來說，二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物。該二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物可單獨被用作該腐蝕抑制劑或可另外再使用一或更多其他腐蝕抑制劑。該二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物可依上述量用於該一或更多腐蝕抑制劑。在一些包含二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物的具體實施例中，該光阻劑清潔組合物可包含60至94質量%溶劑。該溶劑可包含59至84或65至81或63至67質量%的二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及1至10或1至5或1至4質量%的其他有機溶劑。
當組分(d)的水的量可為本發明光阻劑清潔組合物中的0.5至25或0.5至10或1至10或1至8或1至7或2至5或1至5或1至2或3至7或4至6質量%的水。
該清潔組合物的pH，當使用pH計於室溫下在去離子水將該組合物稀釋成5質量%之後測量時，應該高於9，或高於9.5或9.5至12.5或10至12或10.5至11.5或11至12.5。
該光阻劑清潔組合物也可包括量達於以該組合物的總重量為基準總共5重量%的下列任意添加物中的一或多者，附帶條件為這些添加物不會不利地影響該組合物的剝離和清潔效應，也不會損壞下方的基材表面：表面活性劑、螯合劑、化學改質劑、染料、殺生物劑及/或其他添加物。代表性添加物的一些實例包括炔屬醇類及其衍生物、炔屬二元醇類(非離子型烷氧基化及/或可自乳化型炔屬二元醇表面活性劑)及其衍生物，及螯合劑例如β-二酮類、β-酮亞胺類、以蘋果酸和酒石酸為基礎的酯類及二酯類及其衍生物，及三級胺類、二胺類及三胺類。在可供選擇的具體實施例中，本發明的光阻劑清潔組合物可個別地或總括性地不含此段落中列舉的任何添加物。舉例來說，該清潔組合物可不含表面活性劑及/或螯合劑及/或化學改質劑及/或染料及/或殺生物劑及/或胺類及/或炔屬醇類等等。
關於該厚光阻劑圖案，其係能被本發明的方法中之本發明的光阻劑清潔組合物剝離並且溶解的物體，可使用用於供凸塊形成用的厚圖案之任任何光阻劑組合物。
光聚合型負向作用型光阻劑組合物及化學放大型負向作用型光阻劑組合物現在主要被用於形成厚圖案用途之類的光阻劑組合物。本發明的光阻劑清潔組合物應該顯現相對於以上目前主要利用的光阻劑組合物的有益效應，但是不限於此。預期本發明的光阻劑清潔組合物也顯現其相對於用於i-射線的正向作用型光阻劑組合物及化學放大型正向作用型光阻劑組合物的有益效應。
在前述不同光阻劑組合物當中，據說該光聚合型負向作用型光阻劑組合物，其靠照射來聚合而且可能變成不溶於鹼中，在光刻製程時最難以被剝離而且難以被溶於清潔溶液。本發明的光阻劑清潔組合物能有效地剝離而且在許多案例中溶解這樣的光聚合型負向作用型光阻劑組合物。
該等光聚合型負向作用型光阻劑組合物的實例包括含有聚合物組分(例如(甲基)丙烯酸酯、含環狀烷基的(甲基)丙烯酸酯及以苯乙烯為基礎的聚合物)、光聚合起始劑、溶劑及交聯劑當主要組分者。
該化學放大型負向作用型光阻劑組合物的實例包括含有聚合物組分(例如酚醛(novolak)樹脂)、交聯劑、光酸產物劑及溶劑當構成組分者。
以下將描述本發明的光阻劑清潔組合物的用途及利用該光阻劑清潔組合物來處理基材的方法；然而，本發明並不限於此。舉例來說曾有人述及負向作用型光阻劑塗層，也可取而代之地使用正向作用型光阻劑。
負向作用型光阻劑塗佈液，其靠照射來聚合而且可能變成不溶於鹼中，係藉由已知方法(例如旋塗法及輥塗法)塗佈(於塗佈步驟)於上面有金屬薄膜的基材上而且接著乾燥(其可以乾燥步驟)以製造光阻劑層。
該金屬薄膜的實例包括Cu、Cu合金、Al、Al合金、Ni、Au、Pd、TI、V、Cr及其合金或成層的結構，包括TiCu合金、TiCuNi合金及Cr：Cu或Cu：Ni：Au成層材料。該金屬薄膜的形成(於形成步驟)係藉由，舉例來說，CVD氣 相沉積法、濺鍍法、電鍍法等等進行，但不限於此。
接著，該光阻劑層透過遮罩圖案照射(於照射步驟)而且經選擇性地曝光。在以上的負向作用型光阻劑中，該曝光區域係藉由光聚合反應固化而變成光固化區域。(就正向作用型光阻劑而言，沒曝光的區域固化了。)輻射的類型包括紫外線、可見光、遠紫外線、X-射線及電子束等。輻射源包括低壓水銀蒸氣燈、高壓水銀蒸氣燈、超高壓水銀蒸氣燈、KrF、ArF及F2準分子雷射。
在那之後，進行顯影(於顯影步驟)，藉以將該光阻劑層未曝光的區域除去以形成膜厚度為3至150μm的光阻劑圖案(光固化圖案)。(關於正向作用型光阻劑，移除曝光區域。)該顯影能藉由常用方法進行。在前述負向作用型光阻劑中，使用鹼性水溶液當成顯影溶液。其特定實例包括氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、正丙基胺、二乙基胺、二正丙基胺、三乙基胺、甲基二乙基胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯、六氫吡啶、1,8-二氮雜二環[5.4.0]-7-十一烯及1,5-二氮雜二環[4.3.0]-5-壬烷。顯影時間並沒有特別限制，但是通常為約30至360秒。習用方法皆可用於該顯影，例如浸漬法、攪槽法(paddle method)及噴霧法。
其後，該基材上未覆蓋光阻劑的區域(露出金屬薄膜的區域；亦即，未經照射的區域)係填充導電金屬以形成導電層(凸塊形成物)。為了填料該導電金屬，儘管能運用任意方法，但是主要都使用電鍍法。從而形成具有期望高度的凸 塊。該等凸塊通常具有20μm或更高的高度。至於用於該凸塊形成物的導電金屬，任意金屬例如Cu、Cu合金、Al、Al合金、Ni、Au及焊料皆可運用。本發明的光阻劑清潔組合物尤其能使用Cu或焊料當該導電金屬而有效防止基材腐蝕。
在該凸塊形成製程中，該光阻劑圖案厚厚地形成，而且因此，與形成薄膜圖案的案例相比該圖案免不了可能造成其外形的變形，例如崩塌及變形。若在該凸塊形成完成之前形成該等光阻劑圖案時造成變形或崩塌時，必須從該基材移除此等變形的光阻劑圖案然後再從一開始施敷該基材以便形成該凸塊("再製")。
本發明的光阻劑清潔組合物尤其能在該凸塊形成之後有效移除該光阻劑圖案，或移除變形的光阻劑圖案以便進行該再製製程。
也就是說，使本發明的光阻劑清潔組合物與形成該凸塊之後的光阻劑圖案或得進行再製製程且尚未形成凸塊的變形光阻劑圖案接觸，從而移除那些圖案。
在使該光阻劑清潔組合物與該等光固化圖案接觸時，較佳為將該基材完全漬於光阻劑清潔組合物槽。藉由使該基材與該光阻劑清潔組合物接觸，使該光固化圖案從該基材被剝離同時被部分溶解，而且再者在本發明中，其顯現良好的清潔作用使因此被剝離的固化圖案被迅速溶解。即使是該固化圖案從該基材被剝離，若該經剝離的固化圖案仍然留在該光阻劑清潔組合物槽中而沒被迅速溶解，則得擔心該經剝離的光固化圖案或其殘餘物再黏附於該基材或隨後在該 清潔槽中加工的基材。
本發明的光阻劑清潔組合物使該光固化圖案能從該基材被完全剝離而且即使是當該圖案係由負向作用型可光聚合的光阻劑製造時也能被溶解，該負向作用型可光聚合的光阻劑至今仍被認為難以完全移除或得花長時期來移除，而且當該圖案厚(例如，3至150μm)的時候又更難以移除。本發明顯現多數效應例如籨基材迅速剝離。另外本發明能有效地防止該基材上的金屬薄膜及凸塊(導電層)的腐蝕。再者，本發明能防止再生膜形成於該凸塊與該光阻劑圖案之間的界面處。
該基材的浸漬時間可為足敷從該基材剝離該光阻劑圖案的時間而且沒有特別限制，但是通常為約10秒至20分鐘。該製程溫度較佳為約25至90℃，而且特別為約40至80℃。在本發明的光阻劑清潔組合物中，固化材料可在約5至60分鐘的時間內完全被溶解。
此外，在本發明的方法中，在使上面具有該光固化圖案的基材與本發明的光阻劑清潔組合物接觸之前，該基材可先與臭氧水溶液及/或過氧化氫水溶液接觸。再者，在本發明的方法中，上面具有該光固化圖案的基材可以循環方式與下列者接觸：(1)臭氧或過氧化氫水溶液，(2)本文所述的光阻劑清潔組合物中的一或多者，(3)以去離子水沖洗，及(4)步驟1至3重複1至10次。也可以，僅步驟2及3可重複1至10次而無使該基材與臭氧或過氧化氫水溶液接觸。該循環式製程重複1至10次那麼多以達到該基材的完全清潔。
實施例
本發明將參照下列實施例在下文詳細加以描述，但是其不得被視為將本發明限於此。除非另行指明，否則在以下本案所有實施例中的所有量皆以質量%來表示。
光阻劑清潔組合物的製備
如以下表中所示的光阻劑清潔組合物係藉由在攪拌板上的玻璃燒杯中於室溫下將個別組分數量合併製備而成。
關於各自組分在該等表中的縮寫具有下列意義：
4BHA：4-羥基苯甲酸
DIW：去離子水
DMSO：二甲基亞碸
PG：丙二醇
PEI：聚乙烯亞胺
TBC：第三丁基苯磷二酚
TMAH：氫氧化四甲基銨
該等組合物的pH係在該組合物於去離子水(DIW)中稀釋成5質量%之後藉由於室溫下使用pH測量該等組合物而求出。
鋁和銅和該等鈍化材料的腐蝕(蝕刻)速率係藉由使用該等金屬或鈍化材料的空白晶圓來測試。若該等蝕刻速率高於約20至30埃/分鐘(Å/min)則將該等試驗設定成持續20分鐘，或若該等蝕刻速率低於約20Å/min則持續60分鐘。以 Å為單位的厚度測量在時間0、3、5、10及20分鐘，或0、10、20、40及60分鐘之後做3次。將該等蝕刻速率的數值平均值記錄於此。金屬厚度測量利用ResMap四點探針完成。鈍化材料的膜厚度測量使用Filmtek橢圓儀。
該等清潔試驗按照下列方式進行。具有預先固化且顯影的光阻劑的試驗晶圓，及已經形成在其上面的微凸塊(microbump)係自德國的Fraunhofer IZM獲得。該等晶圓中某些具有50μm的凸塊直徑，其餘者具有25μm的凸塊直徑。凸塊直徑為50μm的晶圓當中的各晶圓上具有110、150、300及600μm的凸塊間距。凸塊直徑為25μm的晶圓當中的各晶圓上具有55、75、150及300μm的凸塊間距。該等晶圓用兩類型的金屬堆疊體形成該等凸塊：(a)Cu及SnAg，及(b)Cu、Ni及SnAg。用於所有晶圓的基材皆具有50nm Ti及300nm Cu的塗層。該光阻劑係AZ IPS-528，50μm厚。將該基材的各自2” x 2”試片浸於500ml玻璃燒杯中的330ml示範清潔溶液中經過2至10分鐘，同時在攪拌板上於300rpm下攪拌該溶液。加熱該溶液並且記錄溫度。溫度係約40至65℃。經過浸漬之後藉著去離子水於周遭環境下沖洗該等基材3分鐘並且藉著氮來乾燥。該經處理的基材使用SEM照像而且用目視檢查該等像片並且利用下列分級定等級：
√√√√=完全清潔
√√√=意指稍有殘餘物
√√=意指部分清潔
√=意指微弱至沒有清潔作用
如以上詳細描述的，藉由使用本發明的光阻劑清 潔組合物，不僅可從基材剝離用於形成凸塊的厚光阻劑圖案，也能溶解該光阻劑清潔組合物中已剝離的光阻劑圖案而不會造成再黏附於該基材。另外，可改善生產效率。

Claims (16)

  1. 一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)0.5至5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)60至97.5質量%的一水溶性有機溶劑的混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑，該其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二醇醚、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組；(c)0.5至15質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物，該腐蝕抑制劑係選自由鄰苯二酚、第三丁基鄰苯二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組；及(d)0.5至25質量%的水。
  2. 如申請專利範圍第1項之光阻劑清潔組合物，其包含(b)91至96質量%；(c)0.5至5質量%的至少一腐蝕抑制劑或二或更多腐蝕抑制劑的混合物；及(d)1至8質量%的水。
  3. 如申請專利範圍第1項之光阻劑清潔組合物，其中該組合物不含烷醇胺。
  4. 如申請專利範圍第2項之光阻劑清潔組合物，其中前述(c)包含含PEI之二或更多腐蝕抑制劑的混合物。
  5. 如申請專利範圍第1項之光阻劑清潔組合物，其中前述(c)包含PEI。
  6. 如申請專利範圍第1項之光阻劑清潔組合物，其中前述(b)包含35至50質量%二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及45至58質量%的其他有機溶劑或二或更多其他有機溶劑。
  7. 如申請專利範圍第1項之光阻劑清潔組合物，其中前述(a)係1至5質量%；前述(b)係78至85質量%；前述(c)係10.5至15質量%；而且前述(d)係1至10質量%。
  8. 如申請專利範圍第1項之光阻劑清潔組合物，其中前述(a)係1至5質量%；前述(b)係59至84質量%二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物及1至20質量%的至少一其他有機溶劑或二或更多其他有機溶劑；前述(c)10.5至15質量%；而且前述(d)係1至10質量%。
  9. 一種用於剝離膜厚度為3至150μm的光阻劑圖案之光阻劑清潔組合物，其包含(a)1至5質量%的至少一氫氧化季銨或二或更多氫氧化季銨的混合物；(b)78至85質量%的一水溶性有機溶劑的混合物，包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物，及至少一其他有機溶劑或二或更多其他有機溶劑，該其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二醇醚、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組；(c)10至20質量%的二乙基羥基胺(DEHA)、羥基胺或二丙基羥基胺或其鹽類或其混合物及0.5至5質量%的至少一腐蝕抑制劑或二或更多其他腐蝕抑制劑的混合物，該腐蝕抑制劑係選自由鄰苯二酚、第三丁基鄰苯二酚、苯甲酸銨、鄰胺苯甲酸、苯甲酸、水楊酸、檸檬酸、單-或二-羥基苯甲酸、聚乙烯亞胺(PEI)或其混合物所組成的群組；及(d)1至10質量%的水。
  10. 如申請專利範圍第9項之光阻劑清潔組合物，其中前述(c)係10至20質量%的二乙基羥基胺(DEHA)、羥基胺或其鹽類、二丙基羥基胺或其鹽類、或其混合物，及1至4質量%的至少一腐蝕抑制劑或二或更多其他腐蝕抑制劑的混合物。
  11. 如申請專利範圍第9項之光阻劑清潔組合物，其中前述(b)係64至69質量%的包含二甲基亞碸(DMSO)、環丁碸或二甲基碸或其混合物的水溶性有機溶劑的混合物；及9至21質量%的包含烷醇胺的至少一其他有機溶劑或二或更多其他有機溶劑。
  12. 如申請專利範圍第9項之光阻劑清潔組合物，其中該組合物不含烷醇胺。
  13. 如申請專利範圍第6項之光阻劑清潔組合物，其中前述其他有機溶劑包含二丙二醇甲基醚。
  14. 如申請專利範圍第1項之光阻劑清潔組合物，其中前述(b)係90至95質量%的二甲基亞碸及1至6質量%的至少一其他有機溶劑，該至少一其他有機溶劑係選自由丙二醇、四氫呋喃甲醇、二丙二醇甲基醚、單乙醇胺及胺基丙基嗎啉及其混合物所組成的群組；前述(c)係0.5至3質量%；而且前述(d)係0.5至8.5質量%。
  15. 如申請專利範圍第10項之光阻劑清潔組合物，其中前述至少一其它腐蝕抑制劑或二或更多其他腐蝕抑制劑係選自由鄰苯二酚、第三丁基鄰苯二酚、單-或二-羥基苯甲酸、或其混合物所組成的群組。
  16. 一種用於處理基材之方法，其包含將膜厚度為3至150μm的光阻劑圖案提供於上面有金屬薄膜的基材上，將導電層提供於露出金屬薄膜的區域或光阻劑圖案沒覆蓋的區域上，而且使該光阻劑圖案與請求項1至15中任一項所述的光阻劑清潔組合物接觸，以剝離並且溶解該光阻劑圖案。
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