TWI732885B - 用於含鋁之微電子基板的清潔組合物 - Google Patents
用於含鋁之微電子基板的清潔組合物 Download PDFInfo
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- TWI732885B TWI732885B TW106119387A TW106119387A TWI732885B TW I732885 B TWI732885 B TW I732885B TW 106119387 A TW106119387 A TW 106119387A TW 106119387 A TW106119387 A TW 106119387A TW I732885 B TWI732885 B TW I732885B
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- water
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- 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
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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Abstract
本發明利用新穎組合物及方法來剝除及清潔微電子基板。該組合物包含乙二醇丁醚、環丁碸、單乙醇胺、二甘醇、二羥基苯及水。在一較佳實施例中,該組合物係用於剝除且清潔含鋁之基板。該組合物亦較佳地實質上無N-甲基吡咯啶酮(NMP)及羥胺。
Description
本發明係關於用於微電子基板且特定言之用於自含鋁之微電子組件清除含金屬之殘留物而不引起不適當鋁腐蝕之清潔及剝除組合物。
在微電子裝置之製造期間,採用光阻劑將影像轉印至一微電子基板以建立所要電路層。用鋁金屬化許多微電子裝置。此等微電子基板亦可由諸如鈦、氮化鈦、鎢及類似者之金屬構成及/或採用該等金屬作為助黏劑及擴散障壁。 已提出許多鹼性微電子剝除及清潔組合物用於自此等微電子基板移除交聯且硬化光阻劑及其他殘留物(諸如蝕刻後殘留物)。然而,伴隨此剝除及清潔組合物之一個問題係由於使用此等清潔組合物而發生之金屬腐蝕之可能性。至少部分歸因於裝置基板中之金屬與採用之鹼性剝除劑之反應,此腐蝕導致金屬線之晶鬚、點蝕、切蝕。在美國專利第5,308,745號中揭示一種此鹼性微電子剝除及清潔組合物。雖然已在商業上採用該專利之剝除及清潔組合物以自基板剝除硬化且交聯光阻劑,但已發現,嘗試使用此專利之清潔組合物來清潔具有鋁金屬化且含有來自層(諸如鈦層、氮化鈦層、鎢層及類似者)之金屬之殘留物之微電子基板已導致顯著鋁腐蝕或金屬殘留物之不充分清潔。因此,在清潔穿通下伏鈦層、氮化鈦層、鎢層及類似者之導通孔中使用該專利之清潔組合物方面存在一限制。 當前,鋁技術之半導體清潔市場由基於羥胺(HA)及/或N-甲基吡咯啶酮(NMP)之化學物主導。出於安全、健康及成本原因,半導體產業正遠離NMP及HA化學物。在美國專利第8,178,482號中例示此技術,該專利揭示包含N-甲基吡咯啶酮(NMP)之剝除及清潔組合物。NMP在特殊健康危害物質清單上,且可在意外地吸入或吸收穿過皮膚時不利地影響一僱員,從而引起頭痛、胃痛、惡心及嘔吐。NMP亦可為一致畸物,即,可能導致孕婦之胎兒之畸形之一物質。因此,需要在自含Al之半導體裝置移除殘留物以及陰性及陽性塊狀光阻劑方面有效之無HA及NMP之清潔組合物及方法。 因此,需要微電子剝除及清潔組合物,其等可有效地移除此等金屬殘留物且如此做而無源自剝除及清潔組合物之任何顯著鋁腐蝕。亦需要剝除及清潔組合物,其等除清潔此等金屬殘留物以外,亦將有效地清潔來自其他導通孔及來自金屬線之灰化後殘留物,以及清潔來自基板之未灰化光阻劑殘留物。亦需要無NMP、HA及其他環境有害及/或有毒物質之此等組合物。
根據本發明,提供用於清潔微電子基板之剝除及清潔組合物,該組合物包含:約30重量%至約50重量%之乙二醇丁醚;約20重量%至約30重量%之環丁碸;約10重量%至約45重量%之單乙醇胺;約3重量%至約15重量%之二甘醇;約0.5重量%至約10重量%之二羥基苯;及約0.5重量%至約50重量%之水。組合物可額外地包括一或多種成分,諸如金屬絡合/耐腐蝕化合物、其他腐蝕抑制劑及表面活性劑。 在一實施例中,本發明之組合物用於剝除且清潔含鋁之基板。在一實施例中,基板包含具有導通孔且含有金屬殘留物之一鋁金屬化基板。在另一實施例中,金屬殘留物包含選自由鈦層及氮化鈦層組成之群組之至少一個層。在另一實施例中,剝除及清潔組合物包含:約35重量%至約45重量%之乙二醇丁醚;約24重量%至約27重量%之環丁碸;約13重量%至約15重量%之單乙醇胺;約4重量%至約10重量%之二甘醇;約3重量%至約8重量%之二羥基苯;及約9重量%至約13重量%之水。 在一實施例中,組合物用於剝除且清潔含鋁之基板。在一實施例中,本發明組合物實質上無羥胺。在其另一實施例中,本發明組合物實質上無N-甲基吡咯啶酮(NMP)。 在另一實施例中,本發明包含一種用於清潔微電子基板而不對一鋁基板產生任何實質腐蝕之方法,該程序包括使基板與一清潔組合物接觸達足以清潔基板之一時間,其中該清潔組合物包括:約30重量%至約50重量%之乙二醇丁醚;約20重量%至約30重量%之環丁碸;約10重量%至約45重量%之單乙醇胺;約3重量%至約15重量%之二甘醇;約0.5重量%至約10重量%之二羥基苯;及約0.5重量%至約50重量%之水。 根據本發明之用於清潔微電子基板之方法包括一種用於清潔微電子基板而不產生任何實質金屬腐蝕之方法,該基板含有至少一種光阻劑聚合材料、蝕刻殘留物及金屬殘留物,該程序包括使基板與一清潔組合物接觸達足以清潔基板之一時間,其中該清潔組合物包含:約30重量%至約50重量%之乙二醇丁醚;約20重量%至約30重量%之環丁碸;約10重量%至約45重量%之單乙醇胺;約5重量%至約15重量%之二甘醇;約0.5重量%至約10重量%之二羥基苯;及約0.5重量%至約50重量%之水。 組合物可額外地包括一或多種成分,諸如金屬絡合/耐腐蝕化合物、其他腐蝕抑制劑及表面活性劑。根據本發明之清潔微電子基板之方法尤其可用於清潔包括具有導通孔且含有金屬殘留物之鋁金屬化基板之基板,且在一實施例中金屬殘留物係來自鈦層及/或氮化鈦層之至少一者。
本發明亦係關於清潔穿通微電子組件之金屬層(諸如鈦層或氮化鈦層) 之導通孔,同時可與下伏鋁結構相容(即,於微電子組件中引起極少或無金屬腐蝕)。本發明進一步係關於亦能夠清潔來自其他導通孔及來自金屬線之灰化後殘留物以及清潔或剝除來自微電子基板之未灰化光阻劑之此等清潔組合物。本發明之一進一步態樣係一種清潔或剝除來自含鋁之微電子組件之光阻劑及殘留物而不引起不適當鋁腐蝕之程序。 如本文中使用之二羥基苯包含兒茶酚(亦稱為焦兒茶酚或1,2-二羥基苯),且具有C6
H4
(OH)2
之分子式。其係三種同分異構苯二醇之鄰位異構體。現在,每年合成產生約2000萬公斤作為商品有機化學品,主要作為農藥、香料及香精之前驅體。亦可使用兒茶酚之衍生物,包含3-甲基兒茶酚、4-甲基兒茶酚及4-第三丁基兒茶酚。 本發明之組合物亦可視需要含有其他額外成分。此等選用額外成分包含金屬絡合/耐腐蝕化合物、其他腐蝕抑制劑及表面活性劑。 有機或無機螯合或金屬絡合劑/腐蝕抑制劑並非必需,但可視需要包含於本發明之組合物中,但提供實質益處,諸如(舉例而言)在併入至本發明之水性清潔組合物中時之改良產品穩定性。適合螯合或絡合劑之實例包含(但不限於)反式-1,2-環己烷二胺四乙酸(CyDTA)、乙二胺四乙酸(EDTA)、錫酸鹽、焦磷酸鹽、亞烷基-二膦酸衍生物(例如,乙烷-1-羥基-1,1-二膦酸鹽)、含乙二胺之膦酸鹽、二亞乙基三胺或三亞乙基四官能部分[例如,乙二胺四(亞甲基膦酸)(EDTMP)、二亞乙基三胺五(亞甲基膦酸)、三亞乙基四胺六(亞甲基膦酸)]。螯合劑將基於組合物之重量以自0重量%至約5重量%、較佳地自約0.1重量%至約2重量%之量存在於組合物中。 本發明之水性清潔組合物亦可視需要含有微電子清潔劑組合物中採用之其他腐蝕抑制劑及類似非腐蝕性成分。化合物可包含間苯二酚、沒食子酸、沒食子酸丙酯、焦五倍子酚、對苯二酚、苯并三唑及苯并三唑之衍生物,及多官能羧酸(諸如檸檬酸、酒石酸、葡萄糖酸、糖酸、甘油酸、草酸、鄰苯二甲酸、馬來酸、扁桃酸、丙二酸、乳酸及水楊酸)。此等其他腐蝕抑制劑可以任何適合量(通常以自約0重量%至約5重量%、較佳地自約0.1重量%至約3重量%且更佳地自約0.2重量%至約2重量%之量)存在。 本發明之組合物亦可視需要含有任何適合之水溶性兩性、非離子、陽離子或陰離子表面活性劑。添加表面活性劑將減小配方之表面張力且改良待清潔表面之潤濕且因此改良組合物之清潔作用。若期望進一步的鋁腐蝕抑制,則亦可添加表面活性劑以降低鋁腐蝕速率。可用於本發明之組合物中之兩性表面活性劑包含:甜菜鹼及磺基甜菜鹼,諸如烷基甜菜鹼、醯胺基烷基甜菜鹼、烷基磺基甜菜鹼及醯胺基烷基磺基甜菜鹼;胺基羧酸衍生物,諸如兩性甘胺酸鹽、兩性丙酸鹽、兩性二甘胺酸鹽及兩性二丙酸鹽;亞胺基二酸,諸如烷氧基烷基亞胺基二酸或烷氧基烷基亞胺基二酸;胺氧化物,諸如烷基胺氧化物及烷醯胺基烷基胺氧化物;氟烷基磺酸鹽及氟化烷基兩性表面活性劑;及其混合物。 較佳地,兩性表面活性劑係椰油醯胺丙基甜菜鹼、椰油醯胺丙基二甲基甜菜鹼、椰油醯胺丙基羥基磺基甜菜鹼、辛醯基兩性二丙酸鹽、椰油醯胺基二丙酸鹽、椰油兩性丙酸鹽、椰油兩性羥基乙基丙酸鹽、異癸基氧基丙基亞胺基二丙酸、月桂基亞胺基二丙酸鹽、椰油醯胺基丙基胺氧化物及椰油胺氧化物及氟化烷基兩性表面活性劑。可用於本發明之組合物中之非離子表面活性劑包含炔二醇、乙氧基化炔二醇、氟化烷基烷氧化物、氟化烷基酯、氟化聚氧乙烯烷醇、多羥基醇之脂肪酸酯、聚氧乙烯單烷基醚、聚氧乙烯二醇、矽氧烷型表面活性劑及烷二醇單烷基醚。較佳地,非離子表面活性劑係炔二醇或乙氧基化炔二醇。可用於本發明之組合物中之陰離子表面活性劑包含羧酸鹽、N-醯基肌胺酸鹽、磺酸鹽、硫酸鹽,及正磷酸之單酯及二酯(諸如磷酸癸酯)。 較佳地,陰離子表面活性劑係無金屬之表面活性劑。可用於本發明之組合物中之陽離子表面活性劑包含胺乙氧基化物、二烷基二甲基銨鹽、二烷基嗎啉鎓鹽、烷基苄基二甲基銨鹽、烷基三甲基銨鹽及烷基吡啶鎓鹽。較佳地,陽離子表面活性劑係無鹵素之表面活性劑。特別適合表面活性劑之實例包含(但不限於) 3,5-二甲基-1-己炔-3-醇(Surfynol-61)、乙氧基2,4,7,9-四甲基-5-癸炔-4,7-二醇(Surfynol-465)、聚四氟乙烯環氧丙基甜菜鹼(Zonyl FSK)、Zonyl FSH、Triton X-100 (即,聚乙二醇辛基苯基醚)及類似者。表面活性劑將通常基於組合物之重量以自0重量%至約5重量%、較佳地0.001重量%至約3重量%之量存在。實例
藉由下列代表性實例進一步例示(但不限制)本發明,該等實例意欲圖解說明本發明且不應解釋為對其之限制。實例 1
本發明之配方A:
鋁相容性之重要成分係MEA及水。此外,兒茶酚係用於移除殘留物及光阻劑之一重要成分。實例 2
由美國專利第5,308,745號代表之最近先前技術包含一組合物,其包括一剝除溶劑、一親核胺及呈足以中和自約19重量%至約75重量%之親核胺之量之一非含氮弱酸。資料經收集以展示將酸(醋酸)添加至吾等發明之配方並不有助於光阻劑剝除效能。與具有兒茶酚之一組合物相比,尤其需要以有助於光阻劑及殘留物移除效能。 測試之晶圓包含鋁上之塊狀光阻劑。晶圓全部在65℃下、達20分鐘且按650 RPM之溶液中進行處理。經由SEM觀察清潔。測試之溶液:
A:40% EGBE、25.4%環丁碸、5% DEG、14% MEA、10.6%水、5%二羥基苯(本發明組合物) B:51% NMP;23% MEA;13.28% DEG;10%水;2.72%醋酸(先前技術比較實例) C:51% NMP;23% MEA;11.5% DEG;10%水;5.5%醋酸(先前技術比較實例) D.24% DMSO;46% MEA;10% DEG;10%水;10%醋酸(先前技術比較實例) E.24% DMSO;46% MEA;15% DEG;10%水;5%醋酸(先前技術比較實例)表 1
在表1中看見組合物效能之結果。不考慮溶劑,顯然二羥基苯對於清潔效能係必需的。僅將中和酸(諸如醋酸)添加至含NMP及DMSO之溶液導致不良清潔效能。實例 3
由美國專利第8,178,482號代表類似近先前技術,該專利描述由以下各者組成之組合物:約20重量%至約80重量%之N-甲基吡咯啶酮之組合物;基於組合物之重量呈自約10%至約45%之量之單乙醇胺;自約5重量%至約15重量%之二甘醇之組合物作為一金屬移除化合物;呈足以中和自約3重量%至約75重量%之單乙醇胺使得剝除組合物具有自約9.6至約10.9之一水性pH之量之兒茶酚;及水。以下資料展示藉由移除兒茶酚且使用EGBE及環丁碸之一混合物,可獲得可幸好剝除塊狀光阻劑,展示鋁基板之經改良清潔,且不具有與NMP相關聯之環境及健康危害之一清潔劑。 對於Al清潔,半導體產業通常要求一溶液能夠清潔許多各種不同程序。使用5個不同類型之晶圓來比較不同系統之清潔。此處之目標主要係考慮不同溶劑系統之影響。 測試之晶圓包含無金屬曝光之塊狀光阻劑、具有Al曝光之塊狀光阻劑、Al上之薄有機殘留物、Al上之厚有機殘留物及經由清潔之Al。晶圓全部在65℃下、達20分鐘、按650 RPM之溶液中進行處理。經由SEM觀察清潔。 測試之溶液: A.40% EGBE、25.4%環丁碸、5% DEG、14% MEA、10.6%水、5%二羥基苯 F.50%環丁碸、23% MEA、12% DEG、10%水、5%兒茶酚 G.50% EGBE、23% MEA、12% DEG、10%水、5%兒茶酚 H.46% NMP、23% MEA、10% DEG、15%水、5%兒茶酚表 2
高濃度之EGBE在清潔NMP及環丁碸化學物無法清潔之導通孔中之一些殘留物方面有效。塊狀PR移除要求存在環丁碸或NMP。用於塊狀PR以及大多數殘留物移除之最佳清潔溶液係高百分比之EGBE與若干環丁碸之一混合物。兒茶酚及MEA對於全部此等清潔係必需的。 因此,雖然已描述目前認為係本發明之最佳實施例之內容,但熟習此項技術者將瞭解,可對其作出改變及修改而不背離本發明之精神,且意欲將全部此等改變及修改主張為落在本發明之真實範疇內。
Claims (11)
- 一種用於清潔微電子基板之組合物,該組合物包括:約30重量%至約50重量%之乙二醇丁醚;約20重量%至約30重量%之環丁碸;約10重量%至約45重量%之單乙醇胺;約3重量%至約15重量%之二甘醇;約0.5重量%至約10重量%之二羥基苯;及約0.5重量%至約50重量%之水,其中該組合物不含額外的腐蝕抑制劑。
- 如請求項1之組合物,其包括:約35重量%至約45重量%之乙二醇丁醚;約24重量%至約27重量%之環丁碸;約13重量%至約15重量%之單乙醇胺;約4重量%至約10重量%之二甘醇;約3重量%至約8重量%之二羥基苯;及約9重量%至約13重量%之水。
- 如請求項1之組合物,其中該組合物係用於剝除且清潔含鋁之基板。
- 如請求項1之組合物,其中該基板包括具有導通孔且含有金屬殘留物之鋁金屬化基板。
- 如請求項4之組合物,其中該金屬殘留物包括選自由鈦層及氮化鈦層組成之群組之至少一個層。
- 如請求項1之組合物,其實質上不含羥胺。
- 如請求項1之組合物,其實質上不含N-甲基吡咯啶酮(NMP)。
- 一種用於清潔微電子基板而不對鋁基板產生任何實質腐蝕之方法,該程序包括使該基板與一清潔組合物接觸達足以清潔該基板之時間,其中該清潔組合物包括:約30重量%至約50重量%之乙二醇丁醚;約20重量%至約30重量%之環丁碸;約10重量%至約45重量%之單乙醇胺;約5重量%至約15重量%之二甘醇;約0.5重量%至約10重量%之二羥基苯;及約0.5重量%至約50重量%之水,其中該組合物不含額外的腐蝕抑制劑。
- 如請求項8之方法,其中該組合物包括約1.0重量%至約8重量%之二羥基苯,及約2重量%至約20重量%之水。
- 如請求項8之方法,其中該組合物實質上不含羥胺。
- 如請求項8之方法,其中該組合物實質上不含N-甲基吡咯啶酮(NMP)。
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TW201040674A (en) * | 2009-02-25 | 2010-11-16 | Mallinckrodt Baker Inc | Stripping compositions for cleaning ion implanted photoresist from semiconductor device wafers |
US20120073607A1 (en) * | 2010-09-27 | 2012-03-29 | Eastman Chemical Company | Polymeric or monomeric compositions comprising at least one mono-amide and/or at least one diamide for removing substances from substrates and methods for using the same |
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