TWI754777B - 剝除劑溶液及使用剝除劑溶液的方法 - Google Patents
剝除劑溶液及使用剝除劑溶液的方法 Download PDFInfo
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- TWI754777B TWI754777B TW107134523A TW107134523A TWI754777B TW I754777 B TWI754777 B TW I754777B TW 107134523 A TW107134523 A TW 107134523A TW 107134523 A TW107134523 A TW 107134523A TW I754777 B TWI754777 B TW I754777B
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- Prior art keywords
- stripper solution
- weight
- stripper
- solution
- acid
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
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- UKLQXHUGTKWPSR-UHFFFAOYSA-M oxyphenonium bromide Chemical compound [Br-].C=1C=CC=CC=1C(O)(C(=O)OCC[N+](C)(CC)CC)C1CCCCC1 UKLQXHUGTKWPSR-UHFFFAOYSA-M 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
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- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- G—PHYSICS
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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
- G03F7/42—Stripping or agents therefor
- 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
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/42—Stripping or agents therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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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Abstract
本發明提供一種可置換蝕刻光阻灰化方法的剝除溶液。該剝除溶液係在用於半導體積體電路的半導體裝置上製造電路及/或形成電極及/或封裝/凸塊應用有用，其具有好的光阻移除效率及具有低氧化矽蝕刻速率及低金屬蝕刻速率。類似地，提供其使用方法。較佳的剝除試劑包括極性非質子溶劑、水、羥胺、腐蝕抑制劑、氫氧化四級銨及選擇性界面活性劑。本發明進一步提供根據這些方法製備的積體電路裝置及電子互連結構。
Description
相關申請案之相互參照
本申請案在35 U.S.C.§119(e)下主張2017年9月29日提出的美國臨時專利申請案案號62/565,939之優先權，其全文係以參考之方式併入本文。
發明領域
本揭示係關於一種剝除劑，其可係一使用在用於半導體積體電路或液晶顯示器的半導體裝置上來製造電路或形成電極及/或封裝/凸塊應用的方法之後段製程剝除劑；使用該新型剝除劑所製得的半導體裝置；及進一步關於使用該剝除劑來製造半導體裝置之方法及用以製造該剝除劑之方法。
發明背景
半導體積體電路的製造技術已進步到關於可在單一積體電路晶片上製造出一定數目的電晶體、電容器及其它電子元件。此增加的積體程度大部分係產生自降低該積體電路的最小外貌尺寸及增加構成該積體電路的層數目。至今的設計外貌通常指為「次微米」，其已降低至低於0.25微米。具有此減小尺寸的積體電路構件之製造及減少製造步驟的需求已在其製造的全部態樣上寄予新的需求，包括以化學剝除劑溶液來移除光阻及相關材料。
用於半導體積體電路或液晶顯示器的半導體裝置通常藉由一包括下列步驟之方法進行製造：使用一或多層聚合物光阻材料來塗佈一基材以提
供一光阻膜；藉由曝露至光及隨後顯影來圖形化該感光性光阻膜；使用該經圖形化的光阻膜作為遮罩來蝕刻該基材之曝露出的部分以形成微電路；及從該無機基材移除該光阻膜。任擇地，在形成微電路後，可灰化該蝕刻後殘餘物及使用蝕刻後殘餘物移除劑從該基材移除剩餘的光阻殘餘物。此電路製造部分指為後段製程(BEOL)製造。所需要者為一可在單一步驟中移除殘餘光阻及蝕刻後殘餘物之剝除劑溶液。
優異的剝除劑溶液應該提供下列一或多種利益：(a)在中至低溫下快速而乾淨地移除全部光阻殘餘物、蝕刻殘餘物及相關材料而不需要最後灰化或蝕刻後移除步驟；(b)在該基材之曝露的構件特別是氧化矽及金屬上具有可接受的效應；(c)具有實質上溶解及/或懸浮光阻及/或蝕刻後殘餘物的能力，以防止固體析出及/或再沈積到晶圓上，因此需要較早丟棄剝除劑溶液；(d)從欲清潔的基材或晶圓之全部表面及邊緣完全移除光阻；(e)在製造環境下安全地使用；(f)具有可接受的閑置壽命；及(g)向後與較低的技術結相容。優異的剝除劑溶液應該亦在重加工製程中快速移除光阻殘餘物而沒有損傷基材。最後，優異的剝除劑溶液應該具有最小毒性。本揭示滿足及解決這些需求而可使用在BEOL中。
發明概要
本發明的普遍目標為提供一種可使用在後段製程操作中來移除光阻、殘餘物及相關材料的組合物；將該組合物使用於半導體結構製造的方法；及使用該組合物所製造之半導體結構。可使用該組合物的較佳具體實例而沒有蝕刻或其它方面損傷到包含在欲清潔的基材之半導體結構中或上的金屬及/或介電材料。如於本文中所使用，用語「光阻」指為光阻或光阻材料、蝕刻後殘餘物或其組合。
本揭示的一個態樣為一種剝除劑組合物，其包括一種或多於一種
有機溶劑、水、一種或多於一種羥胺及/或羥胺之衍生物或其混合物、一種或多於一種氫氧化四級銨、一種或多於一種腐蝕抑制劑、及選擇性一種或多於一種界面活性劑。合適的氫氧化四級銨由下列提供的式表示：
其中R1、R2、R3及R4各自獨立地係集體具有至少5個碳的烷基、芳基或其組合。較佳的剝除劑溶液實質上不包括氫氧化四甲基銨，也就是說，它們實質上無或無氫氧化四甲基銨。該剝除劑溶液亦包含羥胺或其衍生物。對某些剝除劑溶液來說，該有機溶劑係極性非質子溶劑，例如，二甲亞碸(DMSO)。
該較佳溶液的水含量範圍通常為約1至約30重量%，或約7至約25重量%，或約1至約15重量%，或約3至約9重量%。但是，最理想的水量可依其它組分之選擇及其比例而變化。
該一種或多於一種腐蝕抑制劑可係任何保護銅的腐蝕抑制劑，包括芳香族羥基化合物、炔系醇、含羧基有機化合物及其酐、三唑化合物及咪唑化合物或其混合物。該腐蝕抑制劑可係苯并三唑、羧基苯并三唑、胺基-苯并三唑、D-果糖、三級丁基兒茶酚、L-抗壞血酸、香草精、水楊酸、二乙基羥胺、聚(伸乙基亞胺)、鄰-甲苯基三唑、間-甲苯基三唑、對-甲苯基三唑、或2-巰基苯并咪唑、或其混合物。該剝除劑可包含約0.1至約15重量%、約0.1至約10重量%、約0.5至約5重量%、或約0.1至約1重量%的一種或多於一種腐蝕抑制劑。
在本發明的另一個態樣中，單獨或與其它態樣，於該組合物中之一或多種界面活性劑若存在時可係任何已知的界面活性劑，諸如兩性鹽、陽離
子界面活性劑、陰離子界面活性劑、兩性離子界面活性劑、非離子界面活性劑及其組合。數個有用的界面活性劑之實施例包括雙(2-乙基己基)磷酸酯、全氟庚酸、全氟癸酸、三氟甲烷磺酸、膦醯基醋酸、十二碳烯基琥珀酸、磷酸氫雙十八烷酯、磷酸二氫十八烷酯、十二烷胺、十二碳烯基琥珀酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、杜松酸、12-羥基硬脂酸及磷酸十二烷酯。有用的界面活性劑量之實施例包括約0.001至約15重量%、或約0.1至約1重量%、或約0.001至約1重量%、或約0.5至約5重量%之該一種或多於一種界面活性劑。
對某些具體實例來說，該組合物之pH將大於7、或大於8、或大於9、或大於10、或大於11。在某些具體實例中，該pH可大於7、8、9、10或11及小於或等於12.2或12。
於本文中所描述的剝除劑溶液可使用在多種應用中來移除光阻、蝕刻殘餘物及其類似物，包括但不限於：(i)高劑量植入物光阻移除，(ii)在閘極形成時的蝕刻後殘餘物，(iii)在浮置閘極形成時的蝕刻後殘餘物，(iv)再加工應用，及(v)後段製程應用。
本揭示的另一個目標為提供一種用以在一製程中從一基材移除一光阻膜的方法，其中該方法可係一後段製程(BEOL)方法。該方法包括下列步驟：提供一上面具有選自於由光阻、光阻殘餘物及其類似物所組成之群的組分之基材；及讓該基材與一包括該剝除劑溶液的組合物接觸，其中該剝除劑溶液可係一BEOL剝除劑溶液，以實現移除光阻及相關材料。光阻、正或負光阻、光阻殘餘物及其類似物於本文中集體地指為「光阻」。該光阻可係單層或雙層。除了光阻外，亦可移除蝕刻殘餘物。在該接觸步驟中所使用的較佳剝除劑溶液包括上述那些。該接觸步驟可包括將一基材沈浸在一剝除劑溶液中或使用噴灑工具將一剝除劑溶液噴灑到該基材上，含或不含其它清洗輔助，諸如例如，兆聲波(megasonics)。在接觸後之進一步步驟可包括移出該基材使其不與該剝除劑
溶液接觸及/或以適當的溶劑或水沖洗該基材的額外步驟。在該接觸步驟期間，較佳為將該剝除劑溶液的溫度維持在至少約10℃，及更佳的溫度範圍係約15℃至約25℃，或10℃至80℃。在某些具體實例中，該剝除劑組合物在沒有加熱該剝除劑組合物下係有效，也就是說，該剝除劑組合物在該接觸步驟期間的溫度可低於40℃，或低於35℃，或低於30℃。
本揭示的另一個目標為提供一種電子互連結構，其在某種程度上係根據上述方法藉由從具有金屬組分的基材上移除光阻、光阻殘餘物及其類似物來製備，以便使用減少的蝕刻製程數目及對該結構提供減少的損傷來製造出該互連結構。圖4闡明典型的電子互連結構之一個實施例，其在二個由障壁層4分隔開的介電層5及6中具有溝槽1及2且其經由通道3互連。該溝槽1及2及通道3典型係以金屬諸如銅、鋁或包括這些金屬的合金填充。當在該電子互連之製備時使用該較佳剝除劑溶液時，這些金屬的腐蝕及/或蝕刻典型會減少。
本揭示的另一個目標為提供一種積體電路裝置，其在某種程度上可根據上述方法藉由處理包括金屬組分的晶圓(基材)來移除光阻殘餘物與減少金屬蝕刻而獲得。圖5闡明一典型的積體電路裝置，其具有複數個經由晶片路由器20互連的電腦晶片10。
本揭示的又進一步目標為提供一種用以製備本發明之剝除劑溶液的方法，其係藉由提供一容器；提供該剝除劑溶液的組分；及將該等組分加入至該容器以在該容器內提供內容物。該提供組分可包括提供各別組分、包括多種組分的組合物或其組合。再者，該加入剝除劑溶液的組分可包括加入各別組分、以實質上任何順序預混合的組分及/或預形成包括所提供的組分之剝除劑溶液。較佳組分包括一種或多於一種有機溶劑(其可係極性非質子有機溶劑)、水、一種或多於一種羥胺或羥胺之衍生物或其混合物、一種或多於一種腐蝕抑制劑、選擇性一種或多於一種界面活性劑、及一種或多於一種氫氧化四級銨，
其中該氫氧化四級銨具有下式：
其中R1、R2、R3及R4係集體具有至少5個碳的烷基、芳基或其組合。該容器可包括實質上任何能容納剝除劑溶液的容器及包括典型使用來裝運或運輸液體產物的容器、使用來包括剝除劑溶液以使用來處理基材而移除光阻及/或蝕刻殘餘物之設備。如於本文中所使用，該容器包括在基材加工期間使用來容納及/或運輸剝除劑溶液的設備，及包括但不限於容納及轉移容器，包括使用來運輸剝除劑溶液的任何輸送管系統。
1,2:溝槽
3:通道
4:障壁層
5,6:介電層
10:電腦晶片
20:晶片路由器
圖1A提供一在不成功的清洗程序後之晶圓邊緣表面的光學顯微圖(OM)(俯視圖)，其將視為不乾淨(NC)。
圖1B提供一在不成功的清洗程序後之晶圓邊緣表面的OM(俯視圖)，其將視為不乾淨(NC)。
圖2A提供一在不成功的清洗程序後之晶圓邊緣表面的OM(俯視圖)，其將視為不乾淨(NC)。
圖2B提供一在不成功的清洗程序後之晶圓邊緣表面的OM(俯視圖)，其將視為不乾淨(NC)，但是比圖2A所顯示的清洗結果好。
圖2C提供一在不成功的清洗程序後之晶圓邊緣表面的OM(俯視圖)，其將視為乾淨(C)。
圖2D提供一在不成功的清洗程序後之晶圓邊緣表面的OM(俯視
圖)，其將視為乾淨(C)。
圖3A提供一在不成功的清洗程序後之晶圓邊緣側壁的SEM(斜視圖(tilt view))，其將視為不乾淨(NC)。
圖3B提供一在成功的清洗程序後之晶圓邊緣側壁的SEM(斜視圖)，其將視為清潔(C)。
圖4闡明一電子互連結構。
圖5闡明一包括複數個電子互連結構的電子裝置。
圖6係使用來製得在實施例中所使用的測試試樣之晶圓的俯視圖(A)及側視圖(B)。
較佳實施例之詳細說明
除非其它方面於本文中有指示出或於上下文中有明確矛盾，否則在描述出本發明之上下文中(特別在下列申請專利範圍的上下文中)所使用的用語「一」及「一種」及「該」及類似指示用字欲解釋為涵蓋單數及複數二者。除非其它方面有提到，否則用語「包含(comprising)」、「具有(having)」、「包括(including)」及「包括(containing)」係解釋為開放式用語(即，意謂著「包括但不限於」)及包括額外的組分及方法步驟。除非其它方面於本文中有指示出，否則於本文中的值範圍之列舉全然意欲提供作為各別指出每個分別值係落在該範圍內的速記方法，及每個分別值係併入該專利說明書中如若其各別於本文中敘述般。除非其它方面於本文中有指示出或其它方面於上下文中有明確矛盾，否則於本文中所描述的全部方法可以任何合適的順序進行。除非其它方面有主張，否則於本文中所提供的任何及全部實施例或範例性文字(例如，「諸如」)之使用全然意欲較好地闡明本發明及不在本發明之範圍上引起限制。在本專利說明書中並無文字應該解釋為指示出任何未主張的元素作為實行本發明之基本。在本專利說明書
及申請專利範圍中所使用來描述該組合物及方法的用語「包含」包括「基本上由...組成」及「由...組成」之更窄義的文字，如若它們被提出般。
將要了解的是，當用語「矽」係以一材料沈積在微電子裝置上時，其將包括多晶矽。
為了參照容易，「基材」包括用於微電子裝置的任何基材，及與經製造以使用於微電子、積體電路或電腦晶片應用的半導體基材例如晶圓、平板顯示器、相位改變記憶元件、太陽能面板及包括太陽能基材的其它產品、光電伏特計及微電機系統(MEMS)相應。該太陽能基材包括但不限於矽、非晶矽、多晶矽、單晶矽、CdTe、硒化銅銦、硫化銅銦及在鎵上的砷化鎵。該太陽能基材可經摻雜或未摻雜。要瞭解的是，用語「基材」不意欲以任何方式限制及包括最終將變成或係微電子裝置、微電子組合或積體電路的部分之任何基材。該基材可在以本發明的組合物清洗前或後於其上面具有電子互連結構。該基材可包括任何數目存在於不導電支撐物上的材料或層或部分的層。該等材料可包含介電質(諸如，高K介電質及/或低K介電質)，及/或障壁材料，及/或覆蓋材料，及/或金屬層，及/或由熟悉人士已知的其它。該基材可在不導電支撐物上包含銅及/或氧化矽。
如於本文中所定義，「低K介電材料」係與在積層的微電子裝置中使用作為介電材料之任何材料相應，其中該材料具有介電常數低於約3.5。較佳的是，該低K介電材料包括低極性材料，諸如含矽的有機聚合物、含矽的混雜有機/無機材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化的矽酸鹽玻璃(FSG)、二氧化矽及摻雜碳的氧化物(CDO)玻璃。要瞭解的是，該低K介電材料可具有不同的密度及不同的多孔洞性。
如於本文中所定義，「高K介電材料」指為具有高介電常數K的材料(如與二氧化矽比較)。該高K介電質可使用來置換微電子裝置的二氧化矽閘
極介電質或其它介電質層。該高K材料可係二氧化鉿(HfO2)、氧氮化鉿(HfON)、二氧化鋯(ZrO2)、氧氮化鋯(ZrON)、氧化鋁(Al2O3)、氧氮化鋁(AlON)、氧化鉿矽(HfSiO2)、氧化鉿鋁(HfAlO)、氧化鋯矽(ZrSiO2)、二氧化鉭(Ta2O5)、氧化鋁、Y2O3、La2O3、氧化鈦(TiO2)、摻雜鋁的二氧化鉿、鉍鍶鈦(BST)或鉑鋯鈦(PZT)。
如於本文中所定義，用語「障壁材料」與在技藝中使用來密封該金屬線例如銅互連線，以最小化該金屬例如銅擴散進該介電材料中之任何材料相應。較佳的障壁層材料包括鉭、鈦、釕、鉿及其它耐火性金屬、及其氮化物及矽化物。
「實質上無」於本文中係定義為少於0.001重量%。「實質上無」亦包括0.000重量%。用語「無」意謂著0.000重量%或較少。
如於本文中所使用，「約」意欲與所描述的值之±5%相應。
在全部此等組合物中，其中該組合物的特定組分係就包括零下限之重量百分比範圍來進行討論，將要了解的是，此等組分可於該組合物的多個特定具體實例中存在或缺乏，及在此等組分係存在的例子中，它們可以低如0.001重量百分比之濃度呈現，以使用此等組分之組合物的總重量為基準。除非其它方面有定義，否則於本文中所報導的全部量皆以重量百分比計，以該組合物的總重量為基準，也就是說，100%。
如於本文中所使用，後段製程指為積體電路製造的部分，其中電晶體、電阻器及其類似元件係與該配線互連。該製造的部分典型係從圖形化該第一金屬接觸或將該第一層金屬沈積到晶圓上開始。
根據本揭示之組合物包括剝除劑溶液，其可係一後段製程剝除劑溶液，其包含一種或多於一種有機溶劑(其可係一種或多於一種極性非質子溶劑)、水、羥胺或一種或多於一種羥胺之衍生物或其混合物、一種或多於一種選擇性界面活性劑、一種或多於一種腐蝕抑制劑、及一種或多於一種氫氧化四級
銨。較佳的剝除劑溶液包含二甲亞碸、水、羥胺、界面活性劑、腐蝕抑制劑及由下列式表示的氫氧化四級銨：
其中R1、R2、R3及R4係相同或不同的烷基、芳基或那些基團之任何組合。在某些具體實例中，R1、R2、R3及R4非全部皆甲基。較佳的R1、R2、R3及R4各自獨立地選自於(C1-C8)烷基、苄基、芳基及其組合。在某些具體實例中，在R1、R2、R3及R4中所包括的碳數係至少5。
可使用在本發明的組合物中之氫氧化四級銨的實施例包括下列一種或多於一種：氫氧化乙基三甲基銨、氫氧化苄基三甲基銨、氫氧化四乙基銨及氫氧化四丁基銨。較佳的氫氧化四級銨係氫氧化四乙基銨。特別佳的剝除劑溶液包括少於0.1重量%的TMAH，或亦實質上無或無氫氧化四甲基銨(「TMAH」)。包括少於0.001重量%TMAH的剝除劑溶液係視為實質上無TMAH。無TMAH係一包括少於0.000重量%TMAH的剝除劑組合物。TMAH被懷疑會對人體造成傷害。「實質上無」亦包括「無」。下列將使用具有僅所描述的相同重量%意義之用語「實質上無」或「無」來描述在本發明的剝除劑組合物中不存在有或可僅存在有小量之其它組分。
在本發明的組合物中所使用之一種或多於一種氫氧化四級銨(純淨)量可係約1重量%至約10重量%，或約1重量%至約20重量%，或約1至約7重量%，或約1至約5重量%，或約1.2至約4.5重量%，或約1.5至約4重量%，或約1.75至約3.75重量%之一種或多於一種氫氧化四級銨，以該組合物整體重量為基準。
在本發明的組合物中有用之額外的氫氧化四級銨(純淨)總量範圍可係具有終點係選自於下列列出的那些範圍：0.5、1、1.2、1.5、1.6、1.75、2、2.5、3、3.5、3.75、3.9、4、4.5、5、5.5、7、10、12、15及20。在某些具體實例中，本發明的態樣之一係可以相當低的氫氧化四級銨量達成好的清洗結果。
可在本發明的組合物中使用羥胺或一種或多於一種羥胺之衍生物或羥胺及其衍生物之混合物。該羥胺之衍生物包括N,N-二乙基羥胺(DEHA)、異丙基羥胺；或羥胺的鹽，諸如氯化羥銨或硫酸羥銨。在某些具體實例中，該羥胺之衍生物及本發明的組合物係無或實質上無羥胺的鹽。可於該組合物中存在有合適程度之所需要的羥胺或羥胺之衍生物或其混合物(純淨)，如約0.1重量%至約10重量%，或約0.1至約5重量%，或約0.1至約3重量%，或約0.1至約1.8重量%，或約0.4至約1.7重量%，或約0.5至約1.5重量%，或約0.3至約1.3重量%，以該組合物的總重量為基準。該羥胺或一種或多於一種羥胺之衍生物或其混合物可以大於或等於0.001重量%及少於2重量%之量(總量)存在於該組合物中。除了上述範圍外，存在於本發明的組合物中之羥胺及/或一種或多於一種羥胺之衍生物或其混合物(純淨)的(總)量可係具有開始及結束點係來自下列所列出的重量百分比之任何範圍：0.1、0.2、0.3、0.5、0.7、0.8、1、1.3、1.5、1.7、1.8、2、2.4、2.6、3、3.3、3.6、4、4.3、4.6、5、5.5、6、6.5、7、7.5、8、8.5、9及10。
本發明的組合物包含水(DI水或其它純水)，約1%至約15%的水，或約1%至約30重量%，或約1至約10重量%，或約1至約8重量%，或約3.5至約9重量%，或約4至約8.5重量%，或約4.4至約8重量%，或約4.8至約7.6重量%，以該組合物的總重量為基準。存在於該剝除劑組合物中的水之總量(加入及/或來自任何來源，諸如，來自加入至該組合物的組分之水溶液)可係具有開始及結束點係來自下列列出的重量百分比之任何範圍：0.1、0.2、0.3、0.5、0.7、0.8、1、1.3、1.5、1.7、1.8、2、2.4、2.6、3、3.3、3.6、4、4.3、4.6、5、5.5、6、6.5、
7、7.5、8、8.5、9、10、15、20、25及30。
本發明的組合物包含一種或多於一種有機溶劑。有用的溶劑之實施例包括下列列出的溶劑：二甲基亞碸、N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基咪唑、γ-丁內酯、環丁碸、2-吡咯啶酮、1-甲基-2-吡咯啶酮、1-乙基-2-吡咯啶酮、1-丙基-2-吡咯啶酮、1-羥乙基-2-吡咯啶酮、1-羥丙基-2-吡咯啶酮、二甘醇單烷基醚、二烷基碸、四氫噻吩-1,1-二氧化物、或聚乙二醇、或其混合物。較佳的溶劑係極性非質子溶劑，例如，二甲基亞碸。該剝除組合物可包括約20至約95重量%，或約40至約90重量%的溶劑，或約60至約90重量%的溶劑。任擇地，該一種或多於一種有機溶劑的濃度範圍可係約80至約98重量%，或約82至約96重量%，或約85至約95重量%，或約86至約94重量%。除了上述範圍外，加入至本發明的組合物之一或多種溶劑的(總)量可係具有開始及結束點係來自下列列出的重量百分比之任何範圍：20、30、40、50、60、70、80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、97、98及98.5。
本發明的組合物進一步包含一種或多於一種腐蝕抑制劑。該腐蝕抑制劑提供與曝露在欲蝕刻的基材表面上之任何金屬特別是銅或非金屬反應，以鈍化該表面及防止在清洗期間過量蝕刻。
可使用在技藝中已知用於類似應用的任何腐蝕抑制劑作為在本發明之組合物中的一或多種腐蝕抑制劑。該腐蝕抑制劑的實施例包括芳香族羥基化合物、炔系醇、含羧基的有機化合物及其酐、及三唑化合物、及咪唑化合物。
範例性芳香族羥基化合物包括酚、甲酚、二甲苯酚、焦兒茶酚、間苯二酚、氫醌、焦棓酚、1,2,4-苯三醇，水楊基醇、對-羥基苄基醇、鄰-羥基苄基醇、對-羥基苯乙基醇、對-胺基酚、間-胺基酚、二胺基酚、胺基間苯二酚、
對-羥基苯甲酸、鄰-羥基苯甲酸、2,4-二羥基苯甲酸、2,5-二羥基苯甲酸、3,4-二羥基苯甲酸及3,5-二羥基苯甲酸。
範例性炔系醇包括2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4-7,9-四甲基-5-癸炔-4,7-二醇及2,5-二甲基-3-己炔2,5-二醇。
範例性含羧基的有機化合物及其酐包括蟻酸、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、羥乙酸、乳酸、馬來酸、醋酸酐及水楊酸。
範例性三唑化合物包括苯并三唑、鄰-甲苯基三唑、間-甲苯基三唑、對-甲苯基三唑、羧基苯并三唑、1-羥基苯并三唑、硝基苯并三唑及二羥基丙基苯并三唑。
範例性咪唑化合物包括苯并咪唑及2-巰基苯并咪唑。
在範例性具體實例中，於本發明的組合物中之一種或多於一種腐蝕抑制劑包括下列之一或多種：苯并三唑、羧基苯并三唑、胺基-苯并三唑、D-果糖、三級丁基兒茶酚、L-抗壞血酸、香草精、水楊酸、二乙基羥胺、及聚(伸乙基亞胺)、2-巰基苯并咪唑。
在其它具體實例中，該一種或多於一種腐蝕抑制劑係三唑及係下列之至少一種：苯并三唑、鄰-甲苯基三唑、間-甲苯基三唑及對-甲苯基三唑；更佳的腐蝕抑制劑包含苯并三唑。
咸信對大部分應用來說，若存在時，該組合物將包含一種或多於一種腐蝕抑制劑(純淨)，其量係該組合物之約0.1至約15重量%；較佳的是，其包含該組合物之約0.1至約10重量%，較佳的是，約0.5至約5重量%，及最佳的是，約0.1至約1重量%，或約0.5至約5重量%。除了上述範圍外，本發明的組合物可包含量(總量)在具有開始及結束點係來自下列列出的重量百分比之範圍內的一
種或多於一種腐蝕抑制劑(純淨)：0.1、0.2、0.25、0.4、0.5、1、1.5、2、2.5、3、4、5、6、7、8、9、10及15。
本發明的組合物可包含一種或多於一種選擇性界面活性劑。在本文描述之組合物中有用的界面活性劑包括但不限於兩性鹽、陽離子界面活性劑、陰離子界面活性劑、兩性離子界面活性劑、非離子界面活性劑及其組合，包括但不限於雙(2-乙基己基)磷酸酯、全氟庚酸、全氟癸酸、三氟甲烷磺酸、膦醯基醋酸、十二碳烯基琥珀酸、磷酸氫雙十八烷酯、磷酸二氫十八烷酯、十二烷胺、十二碳烯基琥珀酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、杜松酸、12-羥基硬脂酸、磷酸十二烷酯。
在該組合物中有用的非離子界面活性劑包括但不限於乙炔二醇界面活性劑，包括Surfynol® 104、104E、104H、104A、104BC、104DPM、104PA、104PG-50、104S、420、440、465、485、SE、SE-F、504、61、DF37、CT111、CT121、CT131、CT136、GA及DF110D。Surfynol®係Evonik，GmbH的註冊商標；聚氧基伸乙基月桂基醚(Emalmin® NL-100(Sanyo的商品名)、Brij® 30、Brij 98、Brij 35)、十二碳烯基琥珀酸單二乙醇醯胺(DSDA，Sanyo)、乙二胺四(乙氧基化物-嵌段-丙氧基化物)四醇(Tetronic® 90R4)、聚乙二醇(例如，PEG 400)、聚丙二醇、聚伸乙基或聚伸丙基二醇醚、以環氧乙烷及環氧丙烷為主的嵌段共聚物(Newpole® PE-68(Sanyo)、Pluronic L31、Pluronic 31R1、Pluronic L61、Pluronic F-127)、聚氧基伸丙基蔗糖醚(SN008S，Sanyo)、三級辛基苯氧基聚乙氧基乙醇(Triton® X100)、10-乙氧基-9,9-二甲基癸-1-胺(TRITON® CF-32)、分枝的聚氧基伸乙基(9)壬基苯基醚(IGEPAL® CO-250)、分枝的聚氧基伸乙基(40)壬基苯基醚(IGEPAL CO-890)、聚氧基伸乙基山梨糖醇六油酸酯、聚氧基伸乙基山梨糖醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯(Tween® 80)、脫水山梨糖醇單油酸酯(Span 80)、Tween 80與Span 80之組合、醇烷氧基化物(例如，Plurafac® RA-20)、
烷基-多糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降冰片烯-2-基)乙基]三矽氧烷；單體的十八烷基矽烷衍生物，諸如SIS6952.0(Siliclad®，Gelest®)；經矽氧烷修改的聚矽氮烷，諸如PP1-SG10 Siliclad Glide 10(Gelest)；聚矽氧-聚醚共聚物，諸如Silwet® L-77(Setre Chemical Company)、Silwet ECO Spreader(Momentive)；及乙氧基化的氟界面活性劑(ZONYL® FSO-100、ZONYL® FSN-100)。
可單獨或與其它界面活性劑使用在本發明的組合物中之陽離子界面活性劑的實施例包括但不限於溴化鯨蠟基三甲基銨(CTAB)、十七烷氟辛烷磺酸、四乙基銨、氯化硬脂基三甲基銨(Econol TMS-28，Sanyo)、溴化4-(4-二乙基胺基苯基偶氮)-1-(4-硝基苄基)吡錠、氯化鯨蠟基吡錠單水合物、氯化苄烷銨、氯化苄乙氧銨、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲基銨、氯化二甲基雙十八烷基銨、氯化十二烷基三甲基銨、對-甲苯磺酸十六烷基三甲基銨、溴化雙十二烷基二甲基銨、氯化二(氫化獸脂)二甲基銨、溴化四庚基銨、溴化四(癸基)銨、Aliquat® 336及奧芬溴銨(oxyphenonium bromide)；胍鹽酸(C(NH2)3Cl)或三氟甲基磺酸鹽，諸如三氟甲烷磺酸四丁基銨；氯化二甲基雙十八烷基銨、溴化二甲基雙十六烷基銨及氯化二(氫化獸脂)二甲基銨(例如，Arquad 2HT-75，Akzo Nobel)。
可單獨或與其它界面活性劑使用在本發明的組合物中之陰離子界面活性劑的實施例包括但不限於聚丙烯酸銨(例如，DARVAN® 821A)、經修改在水中的聚丙烯酸(例如，SOKALAN CP10S)、磷酸鹽聚醚酯(例如，TRITON H-55)、癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、十八烷基膦酸、十二烷基苯磺酸、聚(丙烯酸鈉鹽)、聚氧基伸乙基月桂基醚鈉、二己基磺基琥珀酸鈉、二環己基磺基琥珀酸鈉鹽、硫酸7-乙基-2-甲基-4-十一烷基鈉(Tergitol 4)、SODOSIL RM02；及磷酸鹽氟界面活性劑，諸如Zonyl FSJ及ZONYL®
UR。
可單獨或與其它界面活性劑使用在本發明的組合物中之兩性離子界面活性劑的實施例包括但不限於炔系雙醇或經修改的炔系雙醇(例如，SURFONYL® 504)、椰油醯胺基丙基甜菜鹼、環氧乙烷烷基胺(AOA-8，Sanyo)、N,N-二甲基十二烷基胺N-氧化物、椰油胺丙酸鈉(sodium cocaminpropinate)(LebonApl-D，Sanyo)、3-(N,N-二甲基肉豆蔻基銨基)丙烷磺酸鹽及(3-(4-庚基)苯基-3-羥丙基)二甲基銨基丙烷磺酸鹽。較佳的是，該一種或多於一種界面活性劑包含十二烷基苯磺酸、十二烷基膦酸、磷酸十二烷酯、Triton® X-100、SOKALAN ® CP10S、PEG 400及Pluronic® F-127。
該較佳的一種或多於一種界面活性劑係非離子表面活性劑；及更佳的界面活性劑係Surfynol 420、440、465、485；及最佳的界面活性劑係Surfynol 485。
當存在時，該界面活性劑(純淨)的量範圍可在約0.001至約1重量%內，較佳為約0.1至約1重量%，以該組合物的總重量為基準。任擇地，咸信對某些應用來說，若存在時，所包含的一種或多於一種界面活性劑將係該組合物之約0.1至約15重量%、或該組合物之約0.1至約10重量%、或約0.5至約5重量%、或約0.1至約1重量%、或約0.5至約5重量%。在任擇的具體實例中，於該組合物中之界面活性劑(純淨)的(總)重量百分比可在具有開始及結束點係選自於下列之任何範圍內，以該組合物的總重量為基準：0.001、0.01、0.025、0.05、0.08、0.1、0.15、0.2、0.5、1、2、5、10及15。
在某些具體實例中，若已經存在於該組合物中時，本發明的組合物將無或實質上無下列之一種或多於一種或無任何額外的下列：烷醇胺、烷醇胺之烷基醚、醚、醇、含氟化合物、含金屬化合物、氧化物、有機酸及TMAH。在其它具體實例中，該組合物將實質上無(或無)鈉、及/或鈣、及/或胺基羧酸、
及/或醇、及/或二醇、及/或二醇醚、及/或乙二胺、及/或伸乙基三胺、及/或苯硫酚。在某些具體實例中，於本文中所揭示出的組合物係調配成實質上無下列化學化合物之至少一種：無機酸、烷基硫醇及有機矽烷。在某些具體實例中，於本文中所揭示出的組合物係調配成實質上無或無無機鹼。在某些具體實例中，該組合物可實質上無或無氫氧化物、金屬氫氧化物之一或多種，諸如KOH、或LiOH、或NaOH。在其它具體實例中，該組合物可實質上無或無含鹵化物化合物，例如，其可實質上無或無下列之一或多種：含氟、溴、氯或碘化合物。在其它具體實例中，該組合物可實質上無或無磺酸、及/或磷酸、及/或硫酸、及/或硝酸、及/或鹽酸。在其它具體實例中，該組合物可實質上無或無硫酸鹽、及/或硝酸鹽、及/或亞硫酸鹽、及/或亞硝酸鹽。在其它具體實例中，該組合物可實質上無或無氫氧化銨及/或乙基二胺。在其它具體實例中，該組合物可實質上無或無含鈉化合物、及/或含鈣化合物、及/或含錳化合物、或含鎂化合物、及/或含鉻化合物、及/或含硫化合物、及/或含矽烷化合物、及/或含磷化合物。某些具體實例可實質上無或無界面活性劑。某些具體實例可實質上無或無兩性鹽、及/或陽離子界面活性劑、及/或陰離子界面活性劑、及/或兩性離子界面活性劑、及/或非離子界面活性劑。某些具體實例可實質上無或無烷醇胺、及/或咪唑、及/或酐。某些具體實例可實質上無或無吡咯啶酮類及/或乙醯胺類。某些具體實例可除了羥胺或其衍生物外實質上無或無任何胺。某些具體實例可實質上無或無氧化試劑。某些具體實例可實質上無或無過氧化合物、及/或過氧化物、及/或過硫酸鹽、及/或過碳酸鹽、及其酸、及其鹽。某些具體實例可實質上無或無碘酸鹽、及/或過硼酸、及/或硼酸鹽、及/或過碳酸鹽、及/或過氧酸、及/或鈰化合物、及/或氰化物、及/或過碘酸、及/或鉬酸銨、及/或硝酸、及/或氨。本發明的組合物可無之組分可呈組分的任何組合，如若全部組合係於本文中提出般。
本發明的蝕刻組合物亦可包括一或多種下列添加劑：螯合劑、化
學改質劑、染料、滅菌劑及其它添加劑。該添加劑可加入的程度為它們不會相反地影響該組合物之性能，其量典型最高係總共該組合物之約5重量%。在其它具體實例中，該組合物將實質上無或無螯合劑、染料、滅菌劑及其它添加劑。
對接觸該基材來說，至少30℃的較佳溫度係較佳，然而對多數應用來說，溫度約40℃至約50℃係更佳。對該基材係較敏感或需要較長的移除時間之特別應用來說，較低的接觸溫度係適當。例如，當再加工基材時，可適當地將該剝除劑溶液維持在較低溫度下一段較長的時間以移除光阻及避免損傷基材，諸如較早描述的較低溫度。若需要較長的接觸時間來完全移除光阻時，在該剝除劑溶液上放置一乾氮覆蓋層可減低從環境中吸收水及維持該乾剝除劑溶液之改良的性能。
當沈浸一基材時，額外攪動該組合物會使得光阻移除容易。該攪動可藉由機械攪拌、循環、藉由將惰性氣體氣泡吹過該組合物或其任何組合實現。在移除想要的光阻膜量後，移出該基材使其不與該剝除劑溶液接觸及可在一或多個步驟中以包含水、醇或其混合物之液體沖洗。DI水係較佳的水形式及異丙醇係較佳的醇。對具有會遭受氧化的組分之基材來說，該一或多個沖洗步驟可在惰性環境下進行。與現在商業產品比較，根據本揭示的較佳剝除劑溶液對光阻材料具有改良的負載容量及能夠以所提供的剝除劑溶液體積處理較多的基材數目。如於本文中所使用，負載容量指為剝除劑溶液溶解、懸浮、或其它方面避免固體析出及/或再沈積到晶圓上之清潔能力。
除了沈浸技術外，該晶圓亦可使用噴灑裝置與剝除劑溶液接觸且將該剝除劑溶液維持在想要的溫度下。該噴灑可選擇性使用額外的清洗輔助來進行，包括超音波及/或在惰性環境下或選擇性於活性氣體諸如例如氧或臭氧存在下。可定期移出該晶圓及進行檢驗以決定何時已發生足夠的清洗。可如上所述以一或多個沖洗步驟來沖洗該乾淨晶圓，例如，以異丙醇，然後乾燥。可使
用此方法來移除多重光阻層及作為一清洗步驟。
在製造晶圓時所使用的典型方法可包含下列步驟：在單一晶圓工具或多晶圓槽中接觸(藉由沈浸或噴灑或二者)欲清潔的晶圓，其中該組合物在接觸步驟期間之溫度可如較早描述般，或如在一個具體實例中，約40℃、或約40至50℃。該接觸步驟應該進行5分鐘或較少，或30秒至5分鐘，或30秒至10分鐘。藉由從該清洗組合物移出該晶圓或停止噴灑及以DI水沖洗晶圓例如約2分鐘來結束該晶圓接觸該組合物，然後，藉由在晶圓處直接吹氮氣(N2)或旋轉晶圓或同時或連續地二者來乾燥晶圓。想要的結果為完全移除光阻及在較佳的具體實例中，該氧化矽蝕刻速率應該少於0.2埃/分鐘，及該銅蝕刻速率應該少於5埃/分鐘。
在150毫升燒杯中，於600rpm下，以½”圓鐵弗龍攪拌棒混合該等組分來製備本實施例主題之全部組合物。該等材料加入該燒杯的順序如下：去離子(DI)水，若分別加入時，然後一種或多於一種溶劑，然後一種或多於一種氫氧化四級銨，然後羥胺或一種或多於一種羥胺之衍生物或其混合物，然後一種或多於一種選擇性界面活性劑，然後一種或多於一種腐蝕抑制劑。
對銅及氧化矽蝕刻速率測試來說，在本實施例中使用2公分乘以3公分的試樣。該試樣包含具有銅層(用於銅蝕刻速率)或氧化矽層(用於矽蝕刻速率)的矽基材。第三組2公分乘以3公分測試試樣具有顯示在圖6中的截面，其具有一上面已顯影的光阻頂層及在如所顯示的晶圓上之各別晶片間的溝槽1中之已顯影的光阻。從該溝槽移除光阻對清洗組合物係特別的挑戰。
在150毫升燒杯中，以設定在600rpm之½”圓鐵弗龍攪拌棒，使用100克剝除劑/清洗組合物來進行蝕刻速率及清洗性能測試二者。在加熱板上將該組合物加熱至溫度約40℃。將該測試試樣沈浸在該組合物中約5分鐘，同時攪
拌。然後，在DI水槽中或噴灑沖洗該等斷片3分鐘，隨後藉由在該試樣處直接吹拂經過濾的氮氣流進行乾燥。
從蝕刻前後之厚度變化來估計銅及氧化矽蝕刻速率，銅係藉由4點探針電阻率測量來進行度量，及氧化矽係藉由NanoSpec反射計來度量。對銅來說，典型的起始層厚度係1000埃，及對SiO2來說係7000埃。藉由光學顯微鏡(OM)及掃描電子顯微鏡(SEM)檢查圖案晶圓清潔性能。使用比較例1組合物所產生之不成功的清洗結果係顯示在圖1A中，其係使用比較例1清潔的測試試樣之光學放大的邊緣表面。使用比較例2組合物所產生之不成功的清洗結果係顯示在圖1B中，其係使用比較例2清潔的測試試樣之光學放大的邊緣表面。使用比較例3組合物所產生之不成功的清洗結果係顯示在圖2A中，其係使用比較例3清潔的測試試樣之光學放大的邊緣表面。
使用實施例A組合物所產生的清洗結果係顯示在圖2B中，其係使用實施例A清潔的測試試樣之光學放大的邊緣表面。實施例A未完全清潔，但是比使用比較例的清洗組合物之結果好。使用實施例B組合物所產生之成功的清洗結果係顯示在圖2C中，其係使用實施例B清潔的測試試樣之光學放大的邊緣表面。使用實施例C組合物所產生之成功的清洗結果係顯示在圖2D中，其係使用實施例C清潔的測試試樣之光學放大的邊緣表面。圖3A顯示出一使用實施例B清洗組合物清潔的晶圓側壁，其未完全清潔；但是圖3B顯示出使用實施例C清洗組合
物完全清潔的晶圓側壁。
當描述出本發明之組合物及方法時，開放式用語「包含、具有及包括」之使用並未限制至各別列出的組分或方法步驟，及可包括額外的組分及/或步驟。包含及其它開放式用語包括更多限制的「實質上由...組成」及封閉式用語「由...組成」；因此，另一方面，任何地方的包含係包括用語「實質上由...組成」及「由...組成」。
雖然本發明已於上述參照特定具體實例進行詳細描述，將要了解的是，可由實行技藝人士在所揭示出的具體實例中製得修改及改變而沒有離開本發明之精神及範圍。除非其它方面於本文中有指示出或其它方面於上下文中有明確矛盾，否則意欲涵蓋全部此等修改及改變和上述組分及步驟以全部可能的變化之任何組合。此外，於本文中所引用的全部公告係技藝之技能水平象徵，及藉此其全文以參考方式併入本文如若各者已經各別以參考方式併入本文及完整提出般。
Claims (22)
- 一種用以從一基材移除一光阻之剝除劑溶液，其包含下列成分：60重量%至90重量%的二甲基亞碸；水；0.1重量%至5.0重量%的羥胺；約1.0重量%的苯并三唑；及1重量%至20重量%的一種氫氧化四級銨，其中該氫氧化四級銨具有下式：
- 如請求項1之剝除劑溶液，其中R1、R2、R3及R4係C1-C8烷基、C1-C8苄基、C1-C8芳基或其組合。
- 如請求項1的剝除劑溶液，其中該氫氧化四級銨係選自於由下列所組成之群：氫氧化乙基三甲基銨、氫氧化苄基三甲基銨、氫氧化四乙基銨及氫氧化四丁基銨。
- 如請求項1的剝除劑溶液，其中該剝除劑溶液實質上不含有氫氧化四甲基銨。
- 如請求項1的剝除劑溶液，其中該剝除劑溶液包含1重量%至15重量%的該氫氧化四級銨。
- 如請求項5的剝除劑溶液，其中該剝除劑溶液包含1重量%至7重量%的該氫氧化四級銨。
- 如請求項6的剝除劑溶液，其中該剝除劑溶液包含1.5重量%至4重量%的該氫氧化四級銨。
- 如請求項7的剝除劑溶液，其中該剝除劑溶液包含1.75重量%至3.75重量%的該氫氧化四級銨。
- 如請求項1的剝除劑溶液，其中該氫氧化四級銨為四乙基銨氫氧化物。
- 如請求項1的剝除劑溶液，其進一步包含0.001重量%至1重量%的非離子界面活性劑。
- 如請求項1的剝除劑溶液，其進一步包含一附加的腐蝕抑制劑。
- 如請求項1的剝除劑溶液，其基本上由該等成分所組成。
- 如請求項1的剝除劑溶液，其由該等成分所組成。
- 如請求項1的剝除劑溶液，其包含1重量%至2重量%的羥胺。
- 如請求項1的剝除劑溶液，其包含1重量%至2重量%的羥胺，及3.5重量%至13重量%的四乙基銨氫氧化物。
- 如請求項15的剝除劑溶液，其包含約60重量%的二甲基亞碸。
- 如請求項15的剝除劑溶液，其包含約87重量%的二甲基亞碸。
- 如請求項1至13項任一項的剝除劑溶液，其包含1重量%至26重量%的水。
- 如請求項18的剝除劑溶液，其包含1重量%至15重量%的水。
- 如請求項11的剝除劑溶液，其中該附加的腐蝕抑制劑係選自於由下列所組成之群：羧基苯并三唑、胺基苯并三唑、D-果糖、三級丁基兒茶酚、L-抗壞血酸、香草精、水楊酸、二乙基羥胺、聚(伸乙基亞胺)、鄰-甲苯基三唑、間-甲苯基三唑、對-甲苯基三唑及2-巰基苯并咪唑。
- 如請求項10的剝除劑溶液，其中該非離子界面活性劑係選自於由下列所組成之群：乙炔二醇界面活性劑、聚氧基伸乙基月桂基醚、十二碳烯基琥珀酸單二乙醇醯胺)、乙二胺四(乙氧基化物-嵌段-丙氧基化物)四醇、聚乙二醇、聚丙二醇、聚伸乙基或聚伸丙基二醇醚、以環氧乙烷及環氧丙烷為主的嵌段共聚物、聚氧基伸丙基蔗糖醚、三級辛基苯氧基聚乙氧基乙醇、10-乙氧基-9,9-二甲基癸-1-胺、分枝的聚氧基伸乙基(9)壬基苯基醚、分枝的聚氧基伸乙基(40)壬基苯基醚、聚氧基伸乙基山梨糖醇六油酸酯、聚氧基伸乙基山梨糖醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯、山梨糖醇單油酸酯、醇烷氧基化物、烷基-多糖苷、1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降冰片烯-2-基)乙基]三矽氧烷、單體的十八烷基矽烷衍生物、經矽氧烷修改的聚矽氮烷及聚矽氧-聚醚共聚物。
- 一種使用一剝除劑溶液從一基材移除一光阻的方法，其包含：(a)提供一上面具有一光阻的基材；(b)讓該基材與如請求項1至21中任一項之剝除劑溶液接觸一段足夠的時間以移除該光阻；(c)將該基材移出該剝除溶液；及(d)以一溶劑從該基材沖洗掉該剝除劑溶液。
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| US11456170B2 (en) * | 2019-04-15 | 2022-09-27 | Taiwan Semiconductor Manufacturing Co., Ltd. | Cleaning solution and method of cleaning wafer |
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| IL273542B2 (en) | 2024-03-01 |
| IL273542A (en) | 2020-05-31 |
| EP3688132B1 (en) | 2023-06-28 |
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