TW201305747A - 從基板除去光阻劑之方法 - Google Patents
從基板除去光阻劑之方法 Download PDFInfo
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- TW201305747A TW201305747A TW101133536A TW101133536A TW201305747A TW 201305747 A TW201305747 A TW 201305747A TW 101133536 A TW101133536 A TW 101133536A TW 101133536 A TW101133536 A TW 101133536A TW 201305747 A TW201305747 A TW 201305747A
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- Prior art keywords
- stripper solution
- solution
- photoresist
- substrate
- stripper
- Prior art date
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- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 21
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- 125000001424 substituent group Chemical group 0.000 claims description 5
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/3218—Alkanolamines or alkanolimines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Landscapes
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Physics & Mathematics (AREA)
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
本發明提供一種用來從基板上除去一、二或更多層光阻層的改良無水(dry)剝除劑溶液。該剝除劑溶液包含二甲亞碸、四級氫氧化銨及烷醇胺、可選擇的輔助溶劑及少於約3重量%的水,及/或乾度係數為至少約1。本發明額外提供一種該改良無水剝除溶液之製備及使用方法。
Description
此申請案為2005年10月28日所提出之美國申請案號11/260,912的部分接續申請案,該美國申請案以參考之方式併於本文。
本揭示廣泛關於一種具有可從基板有效除去光阻劑的能力之組成物及其使用方法。所揭示的組成物為用來除去光阻劑之剝除劑溶液,其具有可在低於正常室溫及在運輸與倉儲時常會遇到的溫度下保持為液體之能力,且其額外對已除去之光阻材料具有優良的負載力。已證明具有減少的水含量之剝除劑溶液在乾淨地除去光阻劑、提供低銅蝕刻速率及增加光阻劑在剝除劑溶液中的溶解度(如由較少的顆粒計數所證明者)上特別有效。
與本揭示相關的先前技術包括本田(Honda)等人之美國專利案號5,648,324、本田等人之美國專利案號5,798,323、沙荷巴里(Sahbari)等人的美國專利案號6,319,835、池本(Ikemoto)等人之美國專利案號6,372,410、沙荷巴里等人的美國專利案號6,531,436、巴依克(Baik)等人之美國專利案號6,579,668、池本等人的美國專利案號6,638,694、錢(Chien)等人之美國專利案號6,846,748、岡田(Okada)的美國專利案號6,872,663及拉特(Rutter)二世等人之美國專利案號6,878,500。
廣泛來說,本揭示的第一觀點提供一種可從基板上有效除去或剝除光阻劑之光阻剝除劑溶液,其具有對該光阻材料特別高的負載力,以及當遭遇到典型在運輸、倉儲及在使用於某些製造設備時遇到之低於正常室溫的溫度時保持為液體之能力。根據本揭示之組成物典型可在低如約-20℃至約+15℃之溫度下保持為液體。根據本揭示的組成物典型包含二甲亞碸(DMSO)、四級氫氧化銨及烷醇胺。一個較佳具體實例包含約20%至約90%的二甲亞碸、約1%至約7%之四級氫氧化銨及約1%至約75%具有至少二個碳原子、至少一個胺基取代基及至少一個羥基取代基的烷醇胺,該胺基及羥基取代基接附至二個不同的碳原子。較佳的四級基團有(C1-C8)烷基、芳烷基及其組合。特別佳的四級氫氧化銨為氫氧化四甲基銨。特別佳的1,2-烷醇胺包括下式之化合物:
其中R1可為H、C1-C4烷基或C1-C4烷胺基。對特別佳的式I烷醇胺來說,R1為H或CH2CH2NH2。根據本揭示之進一步具體實例包含附加或輔助溶劑。較佳的輔助溶劑包括二醇類、二醇醚類及其類似物。
本揭示之第二觀點提供一種使用上述新穎剝除劑溶液從基板除去光阻劑及相關聚合材料之方法。光阻劑可從一上面具有光阻劑的經選擇基板除去如下:讓基板與剝除溶液
接觸一段足以除去所欲光阻劑量之時間,從剝除溶液中移出基板,以溶劑從基板沖洗掉溶液及乾燥基板。
本揭示的第三觀點包括經由所揭示之新穎方法製造的電子元件。
本揭示之第四觀點包括一種較佳的剝除劑溶液,其包含二甲亞碸、四級氫氧化銨、烷醇胺、可選擇的輔助溶劑與減低的水量。該較佳溶液之乾度係數為至少約1,且更佳溶液的乾度係數為至少約1.8,其中該乾度係數(DC)可由下列方程式來定義:
本揭示之第五觀點包括用該新穎無水(dry)剝除劑溶液從基板除去光阻劑的方法。該方法包括選擇上面已沉積有光阻劑之基板,讓該包含光阻劑的基板與一包含二甲亞碸、四級氫氧化銨、烷醇胺、可選擇的輔助溶劑之剝除劑溶液接觸,其中該剝除劑溶液的乾度係數為至少約1,移出基板使其不與剝除劑溶液接觸且從該基板沖洗掉剝除劑溶液。
本揭示的第六觀點包括一種部分經由上述方法所製備之電子元件。
本揭示之第七觀點包括一種提供無水組成物的方法,該組成物包含二甲亞碸、四級氫氧化銨、烷醇胺、可選擇的輔助溶劑,其中該溶液之乾度係數為至少約1。
本揭示之第八觀點包括一種獲得具有減低的水含量之四
級氫氧化銨的方法,其係藉由形成四級氫氧化銨、不想要的水與犧牲性溶劑的溶液且讓該溶液接受減壓與稍微加熱來獲得。在該處理期間,移除部分的犧牲性溶劑及水。在該方法期間,應該避免過度加熱以防止氫氧化物分解。可按需要重覆加入及移除犧牲溶劑與水,直到水含量足夠減低為止。
本揭示的第九觀點包括一種維持剝除劑溶液低水含量的方法。該方法包括選擇無水剝除劑溶液,在該剝除劑溶液與分子篩間建立接觸,及維持與該篩接觸直到用到該剝除劑溶液。此方法在於製造後、在儲存及/或裝運期間及在溶液容器已經打開後維持剝除劑溶液呈無水形式上特別有用。
為了促進對所請求發明之了解,現在將參考所闡明的具體實例且將使用具體文字來描述之。然而需了解的是,不意欲因此限制所請求發明的範圍,諸如於此所闡明的改變及進一步修改及其原理之進一步應用係設想在內,如熟知與此揭示相關技藝之人士通常會設想到者。
根據本揭示之組成物包括二甲亞碸(DMSO)、四級氫氧化銨及烷醇胺。較佳的烷醇胺具有至少二個碳原子、至少一個胺基取代基及至少一個羥基取代基,該胺基及羥基取代基接附至二個不同碳原子。較佳的四級取代基包括(C1-C8)烷基、苄基及其組合。較佳組成物的凝固點為低於約-20℃至最高約+15℃,及負載力為約15立方公分/升至最高
約90立方公分/升。對無水剝除劑溶液來說,較佳的四級取代基包括C1-C4烷基、芳烷基或其組合。
比起其它剝除劑溶液,具有增加烷醇胺含量之調配物對碳鋼特別無腐蝕性且對典型的廢棄物處理系統及附屬設備較無害。特別佳的組成物包含具有下式之1,2-烷醇胺:
其中R1為氫、(C1-C4)烷基或(C1-C4)烷胺基。某些較佳調配物額外包含輔助溶劑。特別佳的調配物包含約2%至約75%之輔助溶劑。特別有用的輔助溶劑包括以下更詳細描述的二醇類及其烷基或芳基醚類。較佳調配物具有充分低於25℃的凝,以使在運輸及倉儲期間的固化減到最小。更佳調配物的凝固點為低於約15℃。因為較佳剝除劑溶液在低溫下保持為液體,故消除或減少在溶液可供使用前將在冷天氣期間所接收或於未加熱倉庫所貯存之固化剝除劑溶液鼓狀物之需求。使用鼓狀加熱器來熔化固化的剝除劑溶液是耗時的、需要額外處理且會造成不完全熔化及熔化的溶液組成物變性。
此外,根據本揭示之組成物顯示出高負載力,使得該組成物能除去較高程度的光阻劑而沒有固體沉澱。負載力係定義為在材料再沉積於晶圓上之前或在殘餘物殘留在晶圓上之前,每升剝除劑溶液可除去的光阻劑或雙層材料之立方公分數。例如,若在再沉積發生或殘餘物殘留在晶圓上
之前,20升的剝除劑溶液可除去300立方公分之光阻劑時,負載力為300立方公分/20升=15立方公分/升。
組成物典型包含約55%至約95%的溶劑,其全部或大部分為DMSO及約2%至約10%之四級氫氧化銨。較佳的四級取代基包括(C1-C8)烷基、苄基及其組合。當使用時,輔助溶劑典型上構成組成物之約2%至約35%。剝除調配物亦可包含可選擇的界面活性劑,其含量範圍典型為約0.01%至約3%。所需烷醇胺之合適含量範圍可為該組成物的約2%至約75%。因為剝除劑溶液的某些組分可以水溶液提供,故組成物可選擇性包含小量的水。於本文中所提供之全部%皆為重量百分比。
較佳的烷醇胺具有至少二個碳原子,且在不同碳原子上具有胺基及羥基取代基。合適的烷醇胺包括但不限於乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、異丙醇胺、二異丙醇胺、三異丙醇胺、N-甲基異丙醇胺、N-乙基異丙醇胺、N-丙基異丙醇胺、2-胺基丙烷-1-醇、N-甲基-2-胺基丙烷-1-醇、N-乙基-2-胺基丙烷-1-醇、1-胺基丙烷-3-醇、N-甲基-1-胺基丙烷-3-醇、N-乙基-1-胺基丙烷-3-醇、1-胺基丁烷-2-醇、N-甲基-1-胺基丁烷-2-醇、N-乙基-1-胺基丁烷-2-醇、2-胺基丁烷-1-醇、N-甲基-2-胺基丁烷-1-醇、N-乙基-2-胺基丁烷-1-醇、3-胺基丁烷-1-醇、N-甲基-3-胺基丁烷-1-醇、N-乙基-3-胺基丁烷-1-醇、1-胺基丁烷-4-醇、N-甲基-1-胺基丁烷-4-醇、N-
乙基-1-胺基丁烷-4-醇、1-胺基-2-甲基丙烷-2-醇、2-胺基-2-甲基丙烷-1-醇、1-胺基戊烷-4-醇、2-胺基-4-甲基戊烷-1-醇、2-胺基己烷-1-醇、3-胺基庚烷-4-醇、1-胺基辛烷-2-醇、5-胺基辛烷-4-醇、1-胺基丙烷-2,3-二醇、2-胺基丙烷-1,3-二醇、三(氧基甲基)胺基甲烷、1,2-二烷基丙烷-3-醇、1,3-二烷基丙烷-2-醇及2-(2-胺基乙氧基)乙醇。
適當的二醇醚溶劑包括但不限於乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、二乙二醇單異丁基醚、二乙二醇單苄基醚、二乙二醇二乙基醚、三乙二醇單甲基醚、三乙二醇二甲基醚、聚乙二醇單甲基醚、二乙二醇甲基乙基醚、三乙二醇、醋酸乙二醇單甲基醚酯、醋酸乙二醇單乙酯、丙二醇單甲基醚、丙二醇二甲基醚、丙二醇單丁基醚、二丙二醇單甲基醚、二丙二醇單丙基醚、二丙二醇單異丙基醚、二丙二醇單丁基醚、二丙二醇二甲基醚、二丙二醇二丙基醚、二丙二醇二異丙基醚、三丙二醇及三丙二醇單甲基醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基-2-丁醇、3-甲氧基-3-甲基-1-丁醇、二烷、三烷、1,1-二甲氧基乙烷、四氫呋喃、冠醚類及其類似物。
該組成物亦可選擇性包括一或多種腐蝕抑制劑。合適的腐蝕抑制劑包括但不限於:芳香族羥基化合物,諸如兒茶酚;烷基兒茶酚類,諸如甲基兒茶酚、乙基兒茶酚及三級
丁基兒茶酚、酚類及焦棓酚;芳香族三唑類,諸如苯并三唑;烷基苯并三唑類;羧酸類,諸如蟻酸、醋酸、丙酸、丁酸、異丁酸、草酸、丙二酸、琥珀酸、戊二酸、馬來酸、反丁烯二酸、苯甲酸、酞酸、1,2,3-苯三羧酸、乙醇酸、乳酸、蘋果酸、檸檬酸、醋酸酐、酞酸酐、馬來酸酐、琥珀酸酐、水楊酸、沒食子酸及沒食子酸酯類,諸如沒食子酸甲酯及沒食子酸丙酯;上述含羧基有機化合物之有機鹽類;鹼性物質,諸如乙醇胺、三甲胺、二乙胺;及吡啶類,諸如2-胺基吡啶及其類似物;及螯合物化合物,諸如以磷酸為基礎的螯合物化合物,包括1,2-丙二胺四亞甲基膦酸及羥基乙烷膦酸,以羧酸為基礎的螯合物化合物,諸如乙二胺四乙酸及其鈉與銨鹽、二羥基乙基甘胺酸及氮基三醋酸,以胺為基礎的螯合物化合物,諸如聯吡啶、四苯基卟啉及啡啉,及以肟為基礎的螯合物化合物,諸如二甲基乙二肟及二苯基乙二肟。可使用單一腐蝕抑制劑或可使用腐蝕抑制劑的組合。已證明該腐蝕抑制劑的有用含量範圍為約1 ppm至約10%。
較佳可選擇的界面活性劑包括氟界面活性劑。較佳的氟界面活性劑之一個實例為杜邦(duPont)FSO(含聚乙二醇(50%)、乙二醇(25%)、1,4-二烷(<0.1%)、水(25%)之氟化短鏈聚合物B單醚)。
與基板接觸的較佳溫度為至少50℃較佳,然而對多數應用來說,約50℃至約75℃的溫度更佳。對基板具敏感性或需要較長除去時間之特別應用來說,較低的接觸溫度是適
當的。例如,當再加工基板時,可為適當的是將剝除劑溶液維持在至少20℃的溫度下一段較長的時間,以除去光阻劑及避免損傷該基板。若需要較長的接觸時間來完全除去光阻劑時,在剝除劑溶液上放置乾燥的氮覆蓋層可減低從環境中吸收水及維持該無水剝除劑溶液之改善性能。
當浸泡基板時,攪動組成物額外促進光阻劑之去除。可使用機械攪拌、循環或利用吹入惰性氣體氣泡通過該組成物來達成攪動。在去除想要量的光阻劑後,將基板移出使其不與剝除劑溶液接觸,且以水或醇來沖洗之。DI水為較佳的水形式及異丙醇為較佳的醇。對具有會遭受氧化之組分的基板來說,在惰性環境下進行該沖洗較佳。根據本揭示之較佳剝除劑溶液對光阻材料具有比目前商業產物改善的負載力,且能夠以既定體積的剝除劑溶液處理較大量的基板。
在此揭示中所提供的剝除劑溶液可用來除去以單層存在的聚合光阻材料或某些類型之雙層光阻劑。例如,雙層光阻劑典型具有被第二聚合層所覆蓋的第一無機層,或可具有二層聚合層。使用下列所教導的方法,可從一具有單層聚合物的標準晶圓有效地除去該單層聚合光阻劑。亦可使用相同方法,從具有由第一無機層與第二或外部聚合物層組成之雙層的晶圓除去單一聚合物層。最後,可從具有由二層聚合層所組成的雙層之晶圓有效地除去二層聚合物層。此新穎無水剝除劑溶液可用來除去一、二或更多層光阻層。
較佳的無水剝除劑溶液包含二甲亞碸、四級氫氧化銨、烷醇胺、可選擇的輔助溶劑及少於約3重量%的水。較佳的輔助溶劑為二醇醚類。更佳的無水剝除劑溶液包含二甲亞碸、四級氫氧化銨、烷醇胺、二醇醚溶劑,且其乾度係數為至少約1.8。
無水光阻剝除劑溶液的用途類似於上述就具有低凝固點的剝除劑溶液所述者。但是,有益的是在使用前維持剝除劑溶液呈無水形式及藉由在涉及光阻劑去除的區域中維持乾燥環境而在其使用期間使水吸收減到最小。藉由在儲存、運輸期間及在打開容器後,於其使用之前保持剝除劑溶液與活性分子篩間之接觸,可讓剝除劑溶液維持在無水狀態。
描述於本文的無水剝除劑溶液應該從無水組分製備至可能的程度。因為四級氫氧化銨類具吸濕性且通常以水溶液或其水合物獲得,故通常必需除去包含在該溶液中或與該水合物結合的水,以提供乾度係數至少約1之無水剝除劑溶液。在高溫下乾燥四級氫氧化銨類且至乾燥狀態的努力通常會造成該氫氧化物分解。已驚人地發現,可將在揮發性溶劑中之四級氫氧化銨類預先乾燥,以提供具有減少的水含量但沒有分解之溶劑溼糊狀物。藉由預先乾燥四級氫氧化銨且將其與其它實質上無水的組分結合來維持低水含量,或藉由隨後乾燥從含水組分形成之最初形成的溼剝除劑溶液,可製備包含四級氫氧化銨的無水剝除劑溶液。
預先乾燥形式的四級氫氧化銨可藉由讓水合或其它潮溼
形式的四級氫氧化銨接受減壓與非常輕微的加熱來獲得。水去除可經由在讓氫氧化物接受減壓前將四級氫氧化銨溶解在諸如醇的溶劑中來促進。基於到目前為止所進行的工作,較佳的醇為甲醇。在此處理期間,除去實質部分的水及醇以提供該四級氫氧化銨之醇潮溼糊狀物。依想要之乾燥程度而定,可將額外的無水醇加至最初處理的氫氧化物,且將在減壓下處理重覆一或多次。可在約0.001至約30毫米汞柱的壓力及最高至少約35℃的溫度下進行該處理,而沒有四級氫氧化銨的實質分解。更佳的處理可在約0.01至約10毫米汞柱的壓力下進行。
對含或不含輔助溶劑的潮溼調配物來說,可在加入全部組分後,藉由讓剝除劑溶液與固體乾燥劑,諸如例如分子篩、氫化鈣、硫酸鈣或乾燥劑組合接觸,而對剝除劑溶液進行乾燥。較佳的乾燥劑為一種活化的3A或4A分子篩。對包含輔助溶劑的無水剝除劑溶液來說,較佳的是結合四級氫氧化銨(及任何其它潮溼組分),讓所產生的溶液與活性乾燥劑如分子篩接觸,分離無水溶液與廢乾燥劑,以及將任何剩餘的無水組分加至無水溶液。與分子篩或其它固體乾燥劑之接觸,可藉由任何已知的方法,諸如漿化該溶液與乾燥劑及過濾該無水漿料。類似地,上述描述的任何潮溼溶液可藉由讓潮溼溶液通過在管柱中的粒化活化分子篩或其它乾燥劑來乾燥。合適的分子篩包括型式3A、4A及5A篩。
分子篩亦為將剝除劑溶液維持在無水狀態的較佳乾燥劑
或去濕劑。小粒形式最佳,因為其允許藉由簡單的傾析來移出無水剝除劑溶液。但是,對於傾析無法提供適當分離之應用中,可將分子篩(不論是粉末或丸粒)摻入"茶包"設備中,其將允許與溶液平衡,但不會讓任何篩顆粒污染溶液。包含分子篩的無水剝除劑溶液可在容器已經打開後維持於無水狀態一段延長的時間,此端視剝除劑溶液所包含的分子篩量、環境濕度及容器打開之時間量來決定。
在攪拌下分別結合列在表I中的反應物,以提供13種均勻剝除劑溶液之各者。測量凝固點且亦將資料提供在表I中。可選擇性將實施例1-13的組成物配製成不含界面活性劑及配製成包含腐蝕抑制劑。
將上面具有光阻劑的矽晶圓浸入來自實施例1之剝除溶液中,伴隨攪拌維持在約70℃的溫度約30至約60分鐘。移出該晶圓,以DI水沖洗及乾燥。晶圓之檢驗將說明實質上全部的光阻劑已經除去。對某些應用來說,可藉由將晶圓浸入剝除溶液而沒有攪拌及/或浸漬該晶圓歷時至高達150分鐘來獲得優異的結果。從晶圓除去光阻劑的較佳方式可容易地決定而無需過度實驗。此方法可用來除去存在於具有二層聚合物層的雙層光阻劑中之單層聚合光阻劑或二層聚合層。
將上面具有光阻劑的矽晶圓安置在一標準噴灑裝置中,且以來自實施例2之剝除劑溶液噴灑,並維持在約50℃下。可選擇性在惰性氣氛中或選擇性於活性氣體如例如氧、氟或矽烷存在下進行該噴灑。可週期性移出及檢查該晶圓,以測定何時已經除去足夠的光阻劑。當已經除去足
夠的光阻劑時,可使用異丙醇來沖洗晶圓及乾燥。此方法可用來除去存在於具有二層聚合物層之雙層光阻劑中的單層聚合光阻劑或二層聚合層。
描述在實施例14及15中的方法可與此揭示之剝除劑溶液一起使用,以從由多種材料(包括GaAs)所構成晶圓除去光阻劑。此外,正型與負型光阻劑二者都可用這二種方法除去。
在實施例14、15及16中所描述的方法可類似地與描述於本文之無水剝除劑溶液一起使用。
使用在實施例14中所描述的方法從描述在下表II中之晶圓除去光阻劑。使用20升體積的三種剝除劑溶液,直到光阻聚合物之殘餘物殘留在晶圓上,或直到發生聚合物或其降解產物再沉積到該晶圓上,在此點即到達該溶液的負載力。使用此方法,對在上述實施例1及2中所描述的二種剝除劑溶液及對一般為目前商業剝除劑溶液代表之比較例測定負載力。
結合二甲亞碸(85.5克)、二乙二醇單甲基醚(6.0克)、胺基乙基乙醇胺(2.7克)及氫氧化四甲基銨五水合物(5.5克),以提供一包含約3重量%的水及乾度係數約0.9之剝除劑溶液。藉由稍微攪拌該混合物來促進氫氧化物五水合物之溶解。在該溶液中約3重量%的水實質上來自該五水合物。
將活性3A分子篩加至根據實施例17之方法所製備的三種不同剝除劑溶液樣品中,且在周溫下維持與剝除劑溶液接觸72小時。藉由過濾除去該篩,且使用卡爾費雪(Karl Fischer)方法來測定初始及乾燥溶液之水分含量。將乾燥的剝除劑溶液貯存在封閉容器中。可將廢篩乾燥以供重複利用,或可將其扔掉。此實驗的具體細節表列在下表III中。
在此實施例中可以變化量的氫化鈣和其它固體去濕劑來取代分子篩,以提供具有類似減低水含量之剝除劑溶液。
將三片上面有負型以丙烯酸酯聚合物為基礎的乾膜光阻劑(120微米)置於銅區域上之矽晶圓分別浸入在實施例18中所製備的三種無水剝除劑溶液中且維持在70℃下60分鐘。移出樣品且以去離子水沖洗一分鐘。使用(LiQuilaz SO5顆粒分析器分析懸浮於所產生的剝除劑溶液中之光阻劑顆粒數,且對每片晶圓測定銅蝕刻速率。結果列在下文所提供的表IV中。LiQuilaz為顆粒測量系統公司(Particle Measuring Systems,Inc.,5475 Airport Blvd.,Boulder,Colorado,80301)之註冊商標。
如上所述之光阻劑去除可在範圍從約70℃至約80℃之溫度下進行而無需採用任何排除水分的措施。但是,當在低
於約70℃的較低溫度下進行光阻劑去除時,採用使水分從大氣中吸收減到最小的措施可為有益的。在維持在低於約70℃之剝除劑溶液上提供乾燥氮覆蓋層已證明可有效使因剝除劑溶液較長時間曝露至潮濕大氣所致的水吸收減到最小。上述無水剝除劑溶液可溶解較大量光阻劑且使分散於剝除劑溶液中之顆粒數減到最小的能力可延長剝除劑溶液之有效壽命及減低整體成本。
製備氫氧化四甲基銨五水合物在甲醇中的25重量%溶液,且在水浴中將40.8克的該溶液升溫至約30℃並將壓力維持在約0.01毫米汞柱下約75分鐘。在以液態氮冷卻的杜耳(Dewar)燒瓶中收集冷凝物。在約75分鐘後,將水浴的溫度提昇至約35℃且維持在此溫度下額外105分鐘。產生白色糊狀物。中斷真空且加入85.8克的無水DMSO以溶解該白色固體,在此之後,加入6.0克之二乙二醇單甲基醚及2.7克之胺基乙基乙醇胺,以提供描述在實施例1之表I中的剝除劑溶液之實質上無水形式。藉由卡爾費雪方法實測出該無水剝除劑溶液的水含量為0.71%,且該溶液包含少於1%的甲醇。可藉由將額外的甲醇加至白色糊狀物且將所產生的溶液維持在減壓下額外2至5小時來獲得較低的水含量。
將適當量在實施例18中所描述類型之無水剝除劑溶液與活性分子篩一起包裝,以將該剝除劑溶液維持在無水狀態
下一段較長的時間。每100克維持在封閉及密封容器中之剝除劑溶液加入約5至約10克的活性篩。呈丸粒形式之分子篩較佳。但是,若在使用前藉過濾除去或若小量微粒物質不會干擾無水剝除劑溶液之使用時,可使用粉末化的篩。
雖然已參考上述之特定具體實例來提供申請人的揭示,但需了解的是,熟知技藝之人士對所揭示的具體實例可做出修改及改變而不脫離本發明之精神及範圍。本發明意欲涵蓋全部的此類修改及改變。
Claims (16)
- 一種從基板除去光阻劑的方法,該方法包括:(a)選擇上面具有光阻劑的基板;(b)讓基板與剝除劑溶液接觸一段足以除去所欲光阻劑量之時間,其中該剝除劑溶液包括:i)自約20%至約90%之二甲亞碸;ii)自約1%至約7%之四級銨氫氧化物;iii)自約1%至約75%之烷醇胺,其具有至少二個碳原子、至少一個胺基取代基及至少一個羥基取代基,該胺基及羥基取代基係接附至不同碳原子;及iv)自約0.01重量%至約3重量%之界面活性劑;及(c)從基板沖洗掉剝除劑溶液。
- 如申請專利範圍第1項之方法,其中該四級銨氫氧化物具有為(C1-C8)烷基、芳烷基或其組合的取代基。
- 如申請專利範圍第1項之溶液,其中四級銨氫氧化物為氫氧化四甲基銨。
- 如申請專利範圍第1項之方法,其中烷醇胺為下式的化合物:
- 如申請專利範圍第4項之方法,其中R1為氫。
- 如申請專利範圍第4項之方法,其中R1為CH2CH2NH2。
- 如申請專利範圍第1項之方法,其中該剝除劑溶液額外包含自約2至約35重量%的輔助溶劑。
- 如申請專利範圍第7項之方法,其中該輔助溶劑為二醇醚。
- 如申請專利範圍第8項之方法,其中該二醇醚為二乙二醇單甲基醚。
- 如申請專利範圍第1項之方法,其中該接觸包括將該基板浸入該剝除劑溶液中。
- 如申請專利範圍第1項之方法,其中在接觸期間該剝除劑溶液維持在至少約20℃的溫度。
- 如申請專利範圍第11項之方法,其中在接觸期間該剝除劑溶液維持在至少約50℃的溫度。
- 如申請專利範圍第1項之方法,其中該沖洗係使用水。
- 如申請專利範圍第1項之方法,其中該沖洗係使用醇。
- 如申請專利範圍第10項之方法,其中該接觸進一步包括在浸入期間攪動該剝除劑溶液。
- 如申請專利範圍第15項之方法,其中該攪動係藉由機械攪拌該剝除劑溶液、藉由循環該剝除劑溶液或藉由吹入惰性氣體氣泡通過該剝除劑溶液來達成。
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TW200736856A (en) | 2007-10-01 |
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EP3043209A1 (en) | 2016-07-13 |
EP2657770A1 (en) | 2013-10-30 |
MY180725A (en) | 2020-12-07 |
KR101362527B1 (ko) | 2014-02-13 |
US20090186793A1 (en) | 2009-07-23 |
JP5306817B2 (ja) | 2013-10-02 |
WO2007053363A3 (en) | 2009-04-30 |
US9069259B2 (en) | 2015-06-30 |
US20130172225A1 (en) | 2013-07-04 |
KR20080080280A (ko) | 2008-09-03 |
EP2657771A1 (en) | 2013-10-30 |
US20070111912A1 (en) | 2007-05-17 |
US8263539B2 (en) | 2012-09-11 |
JP2009514026A (ja) | 2009-04-02 |
SG180047A1 (en) | 2012-05-30 |
EP1941018B1 (en) | 2013-09-11 |
WO2007053363A2 (en) | 2007-05-10 |
SG2013081401A (en) | 2015-05-28 |
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