TW201408768A - 微影用洗淨液及配線形成方法 - Google Patents
微影用洗淨液及配線形成方法 Download PDFInfo
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- TW201408768A TW201408768A TW102118407A TW102118407A TW201408768A TW 201408768 A TW201408768 A TW 201408768A TW 102118407 A TW102118407 A TW 102118407A TW 102118407 A TW102118407 A TW 102118407A TW 201408768 A TW201408768 A TW 201408768A
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- cleaning solution
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- 238000004140 cleaning Methods 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 title abstract description 22
- 238000001459 lithography Methods 0.000 title abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- -1 hydrazine compound Chemical class 0.000 claims description 80
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 21
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 3
- 150000001785 cerium compounds Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 6
- 125000005372 silanol group Chemical group 0.000 abstract 1
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 45
- 239000000463 material Substances 0.000 description 45
- 238000005260 corrosion Methods 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 25
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
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- 239000003960 organic solvent Substances 0.000 description 13
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- 229910052707 ruthenium Inorganic materials 0.000 description 9
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
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- 238000001556 precipitation Methods 0.000 description 5
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- 238000007654 immersion Methods 0.000 description 4
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- VPLKXGORNUYFBO-UHFFFAOYSA-N C1(CC2C(CC1)O2)CCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(CC2C(CC1)O2)CCC(C(OC)(OC)OC)CCCCCCCC VPLKXGORNUYFBO-UHFFFAOYSA-N 0.000 description 3
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- XJDCHDFUMGSEHD-UHFFFAOYSA-N NCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound NCCCC(C(OC)(OC)OC)CCCCCCCC XJDCHDFUMGSEHD-UHFFFAOYSA-N 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
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Classifications
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
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- C11D7/5022—Organic solvents containing oxygen
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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
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- 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
- C11D7/50—Solvents
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
-
- 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
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
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Abstract
本發明之課題在於提供對Low-k材料的腐蝕抑制機能優異,而且由於在蝕刻處理後所殘留的殘渣物之去除性能亦優異,而可以一步驟有效果地去除上述殘渣物之微影用洗淨液,及使用該微影用洗淨液之配線形成方法。本發明之微影用洗淨液含有鹼或酸、溶劑、與因水解而生成矽烷醇基的矽化合物。本發明之配線形成方法係藉由在形成於半導體多層層合體的低介電體層之蝕刻空間中埋入金屬而形成金屬配線層者,於此配線形成方法中,在上述蝕刻空間之形成後,使用本發明之微影用洗淨液來洗淨上述半導體多層層合體。
Description
本發明關於微影用洗淨液,更詳細地關於不腐蝕低介電體材料等的易腐蝕性材料,可有效果地去除蝕刻處理後所殘留的殘渣物之微影用洗淨液。再者,本發明關於使用上述微影用洗淨液之配線形成方法。
半導體裝置係在矽晶圓等的基板上層合金屬配線層、低介電體層、絕緣層等而形成者,如此的半導體裝置係藉由以抗蝕圖型作為遮罩,施予蝕刻處理之微影法,將上述各層加工而製造。
上述微影法中使用的抗蝕膜、暫時的層合膜(亦稱為犧牲膜)、更且蝕刻步驟中所產生的殘渣物,係為了不成為半導體裝置的障礙,而且為了不成為下一步驟之妨礙,而使用洗淨液來去除。
又,近年來隨著半導體裝置之高密度化、高積體化,採用使用鑲嵌(damascene)法的配線形成方法。於如此的配線形成方法中,作為構成半導體裝置的金屬配線層之金屬配線材料,採用容易發生腐蝕的銅,再者關於構成低
介電體層的低介電體材料(亦稱為Low-k材料),愈來愈往低介電常數化進展,而採用容易發生腐蝕的Low-k材料。因此,於基板的洗淨時,要求開發出對於此等的易腐蝕性材料不發生腐蝕之洗淨液。
特別地,介電常數(k)為2.5以下的Low-k材料亦稱為ULK(ultra low-k)材料,非常容易受到作為洗淨液使用的鹼或酸所造成的損傷,容易發生尺寸的變動、k值之變化、接觸角之變化等。如此的損傷係不僅在洗淨液所致的洗淨步驟中發生,而且在CMP步驟、蝕刻步驟、灰化步驟中亦發生。再者,作為ULK材料,使用多孔質的SiO2膜等。
以往,為了抑制ULK材料之損傷,使用降低pH而成為弱鹼性之洗淨液進行洗淨。藉此,的確可抑制ULK材料之損傷,但殘渣物的去除性亦降低。
為了減低ULK材料在洗淨中的損傷,有提案用超臨界矽烷化劑及超臨界溶劑來處理在蝕刻處理中已損傷的ULK材料表面之方法(專利文獻1)。藉由此方法,由於ULK材料表面係至少部分地不動態化,其後即使以洗淨液來處理ULK材料,也將ULK材料的損傷抑制在最小限度。
[專利文獻1]特開2005-522737號公報
專利文獻1之處理方法,為了去除蝕刻處理後所殘留的殘渣物,需要洗淨步驟與使ULK材料表面成為不動態化之步驟的二步驟。因此,希望能以一步驟也可有效果地去除上述殘渣物之微影用洗淨液。
本發明係鑒於如此以往的實情而完成者,目的在於提供對Low-k材料的腐蝕抑制機能優異,而且由於在蝕刻處理後所殘留的殘渣物之去除性能亦優異,而可以一步驟來去除上述殘渣物之微影用洗淨液,及使用該微影用洗淨液之配線形成方法。
本發明者們為了解決上述問題,重複專心致力的研究。結果發現藉由在微影用洗淨液中添加因水解而生成矽烷醇基的矽化合物,可解決上述問題,終於完成本發明。具體地,本發明提供以下者。
本發明的第一態樣係一種微影用洗淨液,其含有鹼或酸、溶劑、與因水解而生成矽烷醇基的矽化合物。
本發明的第二態樣係一種配線形成方法,其係藉由在形成於半導體多層層合體的低介電體層之蝕刻空間中埋入金屬而形成金屬配線層之配線形成方法,其中於上述蝕刻空間之形成後,使用本發明之微影用洗淨液來洗淨上述半導體多層層合體。
依照本發明,可提供對Low-k材料的腐蝕抑制機能優異,而且由於在蝕刻處理後所殘留的殘渣物之去除性能亦優異,而可以一步驟有效果地去除上述殘渣物之微影用洗淨液,及使用該微影用洗淨液之配線形成方法。
本發明之微影用洗淨液含有鹼或酸、溶劑、與因水解而生成矽烷醇基的矽化合物。本發明之微影用洗淨液例如可用於具備低介電體層的層合體之洗淨。作為上述層合體,例如可舉出具備低介電體層的半導體多層層合體。於上述洗淨中,取決於層合體的加工狀態,上述洗淨液有直接接觸低介電體層之情況,但即使為如此的情況下,也抑制低介電體層之腐蝕。上述層合體之洗淨亦可不以低介電體層之洗淨作為主要目的,例如也可以去除低介電體層上所設置的金屬硬遮罩層者作為目的。
以下,詳細說明本發明,惟對於各材料只要沒有特別預先指明,則可以使用市售者。
作為鹼,只要是可去除蝕刻處理後所殘留的殘渣物
者,則沒有特別的限定。鹼係可單獨使用,也可組合2種以上使用。
作為鹼,例如可使用四級銨氫氧化物。作為四級銨氫氧化物,較佳為下述通式(2)所示的化合物。
上述通式(2)中,R3~R6各自獨立地表示碳數1~16的烷基、芳基、芳烷基或羥烷基。
於上述通式(2)所示的化合物之中,從取得容易性之點來看,特佳為選自由氫氧化四甲銨、氫氧化四乙銨、氫氧四丙銨、氫氧化四丁銨、氫氧化甲基三丙基銨、氫氧化甲基三丁基銨、氫氧化乙基三甲基銨、氫氧化二甲基二乙基銨、氫氧化苄基三甲基銨、氫氧化十六基三甲基銨及氫氧化(2-羥基乙基)三甲基銨所成之群組中的至少1種。再者,從對於蝕刻處理後所殘留的殘渣物之溶解性高之點來看,較佳為氫氧化四甲銨及/或氫氧化四乙銨。
又,作為鹼,可使用烷醇胺。作為烷醇胺,例如可舉出單乙醇胺、二乙醇胺、三乙醇胺、2-(2-胺基乙氧基)乙醇、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、N-甲基二乙醇胺、單異丙醇胺、二異丙醇胺、三異丙醇胺等。
另外,作為鹼,例如亦可併用無機鹼與四級銨氫氧化
物。作為無機鹼,較佳為氫氧化鉀、氫氧化鈉、氫氧化銣等之鹼金屬的氫氧化物,更佳為氫氧化鉀。
相對於微影用洗淨液全量,鹼之含量就四級銨氫氧化物而言較佳為0.05~10質量%,更佳為0.1~5質量%,就烷醇胺而言較佳為0.05~20質量%,更佳為0.1~10質量%。藉由成為如此的含量,可一邊抑制Low-k材料等的腐蝕,一邊有效果地去除蝕刻處理後所殘留的殘渣物。再者,併用無機鹼與四級銨氫氧化物時,相對於微影用洗淨液全量,無機鹼之含量較佳為0.1質量ppm~1質量%,更佳為1質量ppm~1000質量ppm。藉由成為如此的含量,可一邊抑制Low-k材料等的腐蝕,一邊提高對蝕刻處理後所殘留的殘渣物之去除性能。
作為酸,只要可去除蝕刻處理後所殘留的殘渣物,則沒有特別的限定,例如可舉出氫氟酸。酸係可單獨使用,也可組合2種以上使用。
相對於微影用洗淨液全量,酸之含量較佳為1質量ppm~10質量%,更佳為100質量ppm~5質量%。藉由成為如此的含量,可一邊抑制Low-k材料等的腐蝕,一邊有效果地去除蝕刻處理後所殘留的殘渣物。
作為溶劑,可使用該領域中慣用的化合物。溶劑係大致區分為有機溶劑與水,可適宜選擇或組合使用。
作為有機溶劑,例如可舉出二甲亞碸等的亞碸類;二
甲基碸、二乙基碸、雙(2-羥基乙基)碸、四亞甲基碸等的碸類;N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等的醯胺類;N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-羥基甲基-2-吡咯啶酮、N-羥基乙基-2-吡咯啶酮等的內醯胺類;β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、ε-己內酯等的內酯類;1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、1,3-二異丙基-2-咪唑啉酮等的咪唑啉酮類;乙二醇、丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、丙三醇、二乙二醇等的多元醇類;乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單烯丙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、3-甲氧基-3-甲基-1-丁醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇單苄基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單丙基醚、三乙二醇單丁基醚、三丙二醇單丁基醚、乙二醇二甲基醚、二乙二醇二甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚等的二醇醚系溶劑;乙二醇單乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單乙酸酯等的二醇酯系溶劑等。
其中作為較佳的有機溶劑所選擇者,係選自由3-甲氧
基-3-甲基-1-丁醇、二甲亞碸、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、二乙二醇單乙基醚、二乙二醇單丁基醚及三乙二醇單丁基醚所成之群組中的至少1種。有機溶劑亦可按照需要適宜地混合2種以上而使用。
併用有機溶劑與水作為溶劑時,較佳為使用水溶性有機溶劑作為有機溶劑。作為水溶性有機溶劑,可舉出上述的亞碸類、碸類、醯胺類、內醯胺類、內酯類、咪唑啉酮類、多元醇類、二醇醚系溶劑、二醇酯系溶劑。
相對於微影用洗淨液全量,溶劑之含量較佳為1~99.7質量%,更佳為2~99.5質量%。藉由成為如此的含量,可一邊抑制Low-k材料等的腐蝕,一邊有效果地去除蝕刻處理後所殘留的殘渣物。
併用有機溶劑與水時,相對於微影用洗淨液全量,水之含量較佳為10~80質量%,更佳為15~70質量%。又,有機溶劑之含量係在由有機溶劑與水所構成的溶劑全體之含量中,被視為水的剩餘部分。又,於本發明中,亦可僅使用有機溶劑作為溶劑。
於ULK材料等的Low-k材料之表面,由於在CMP步驟、蝕刻步驟、灰化步驟、洗淨步驟等中受到的損傷,而切斷Si-O-Si鍵,生成矽烷醇基Si-OH。推測此等的矽烷醇基由於受到洗淨液中的鹼或酸之攻擊,而Low-k材料的腐蝕進行。
因水解而生成矽烷醇基的矽化合物,係在本發明的微影用洗淨液中因水解而生成矽烷醇基。此等的矽烷醇基係互相脫水縮合而使上述矽化合物聚合,同時與Low-k材料表面受到損傷所生成的矽烷醇基亦鍵結而脫水縮合。結果,判斷Low-k材料表面係被由上述矽化合物的聚合物所構成之膜覆蓋,保護其防止被微影用洗淨液中的鹼或酸所損傷。
作為因水解而生成矽烷醇基的矽化合物,並沒有特別的限定,例如可使用烷氧基矽烷或其部分水解縮合物,較佳為下述式(1)所示的烷氧基矽烷或其部分水解縮合物。
R1 4-nSiOR2 n (1)
(式中,R1表示有機基,R2表示碳數1~4的烷基,n為1~4之整數)。
作為R1的有機基,例如可舉出可具有取代基的烴基。烴基的碳數較佳為1~20。作為如此的烴基,例如可舉出烷基、環烷基、烯基、芳基、芳烷基,此等之基亦可具有取代基。
作為取代基,例如可舉出3,4-環氧基環己基、環氧丙氧基、3-丙烯醯氧基、3-甲基丙烯醯氧基、2-胺基乙基胺基、胺基、甲基丁基酮亞胺基、苯基胺基、脲基、巰基、異氰酸酯基、鹵素原子(例如氟原子、氯原子)等。具有取代基時,其數可為1個或複數個。
作為上述烷基,較佳為碳數1~20者,例如可舉出甲
基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、己基、辛基、癸基、十二基、十四基、十六基、十八基、二十基、3,3,3-三氟丙基、2-(3,4-環氧基環己基)乙基、3-環氧丙氧基丙基、3-丙烯醯氧基丙基、3-甲基丙烯醯氧基丙基、N-2-(胺基乙基)-3-胺基丙基、3-胺基丙基、3-甲基丁基酮亞胺基丙基、N-苯基-3-胺基丙基、3-脲基丙基、3-巰基丙基、3-異氰酸酯基丙基等。
作為上述環烷基,較佳為碳數3~20者,例如可舉出環戊基、環己基等。
作為上述烯基,較佳為碳數2~20者,例如可舉出乙烯基、烯丙基等。
作為上述芳基,較佳為碳數6~20者,例如可舉出苯基、甲苯基、乙烯基苯基、萘基等。
作為上述芳烷基,較佳為碳數7~20者,例如可舉出苯甲基、苯乙基等。
作為R2的烷基,例如可舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基。其中,從上述矽化合物的取得容易性之點來看,較佳為甲基及乙基。
從經本發明的微影用洗淨液所洗淨的半導體多層層合體之表面狀態成為良好的容易性來看,n較佳為1~3之整數,更佳為1或2。
因水解而生成矽烷醇基的矽化合物係可單獨使用或組
合2種以上使用,作為其具體例,可舉出甲基三甲氧基矽烷、二甲基二甲氧基矽烷、三甲基甲氧基矽烷、苯基三甲氧基矽烷、二甲氧基甲基苯基矽烷、四乙氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、癸基三甲氧基矽烷、三氟丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、對乙烯基苯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、丙烯醯氧基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷的鹽酸鹽、3-脲基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基矽烷基丙基)四硫化物、3-異氰酸酯基丙基三乙氧基矽烷等。其中,從上述矽化合物的取得容易性之
點或對Low-k材料的影響小之點等來看,較佳為甲基三甲氧基矽烷、二甲基二甲氧基矽烷、三甲基甲氧基矽烷、二甲氧基甲基苯基矽烷、正丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、及3-胺基丙基三甲氧基矽烷,其中由於特性優異,特佳為甲基三甲氧基矽烷、二甲基二甲氧基矽烷、三甲基甲氧基矽烷及二甲氧基甲基苯基矽烷。
相對於微影用洗淨液全量而言,因水解而生成矽烷醇基的矽化合物之含量較佳為5質量%以下,更佳為1質量%以下。藉由成為如此的含量,上述矽化合物的聚合不過度進行,可防止來自矽化合物的膜在低介電體層表面過剩地形成,不易發生尺寸的粗大或缺損。又,所得之微影用洗淨液係不易發生白濁,保存安定性良好。再者,相對於微影用洗淨液全量,上述矽化合物之含量較佳為0.01質量%以上,更佳為0.1質量%以上。藉由成為如此的含量,可一邊抑制Low-k材料等的腐蝕,一邊有效果地去除蝕刻處理後所殘留的殘渣物。
於本發明的微影用洗淨液中,亦可添加其它成分。作為其它成分,例如可舉出防蝕劑、界面活性劑等。
作為防蝕劑,可使用由咪唑系化合物、苯并三唑系化合物及含有巰基的化合物中選出的至少1種防蝕劑。
作為上述咪唑系化合物,可舉出下述通式(3)所示的化合物。
上述通式(3)中,R7表示碳數1~17的烷基或芳基,R8表示碳數1~13的烷基。R7較佳為碳數1~11的烷基或芳基,更佳為碳數1~6的烷基或苯基。又,R8較佳為碳數1~6的烷基,更佳為甲基或乙基。再者,烷基可為直鏈狀、支鏈狀、環狀之任一者。
於上述通式(3)所示的化合物之中,較佳為選自由2-乙基-4-甲基咪唑、2-甲基-4-乙基咪唑、2,4-二甲基咪唑、2-正丁基-4-甲基咪唑、2-環己基-4-甲基咪唑及2-苯基-4-甲基咪唑所成之群組中的至少1種。
相對於微影用洗淨液全量,上述通式(3)所示的化合物之含量較佳為0.1~10質量%,更佳為0.5~5質量%。藉由成為如此的含量,可一邊抑制金屬的腐蝕,一邊有效果地去除蝕刻處理後所殘留的殘渣物。
作為上述苯并三唑系化合物,可舉出下述通式(4)所示的化合物。
上述通式(4)中,R9、R10各自獨立地表示氫原子、可具有取代基的碳數1~10的烴基、羧基、胺基、羥基、氰基、甲醯基、磺醯基烷基或磺基,Q表示氫原子、羥基、可具有取代基的碳數1~14的烴基(惟,該烴基係可被醯胺鍵或酯鍵所中斷)、或下述通式(5)所示的基。
上述通式(5)中,R11表示碳數1~6的伸烷基,R12、R13各自獨立地表示氫原子、羥基、或碳數1~6的羥烷基或烷氧基烷基。
再者,於上述通式(4)中,R9、R10、Q的各定義中之烴基係可為芳香族烴基及脂肪族烴基之任一者,也可具有不飽和鍵,或可為直鏈狀、支鏈狀、環狀之任一者。作為芳香族烴基,例如可舉出苯基、對甲苯基等。作為直鏈狀的脂肪族烴基,例如可舉出甲基、正丙基、乙烯基等。作為支鏈狀的脂肪族烴基,例如可舉出異丁基、第三丁基等。作為環狀的脂肪族烴基,例如可舉出環戊基、環己基等。作為具有取代基的烴基,例如可舉出羥烷基、烷氧基烷基等。
又,於上述通式(4)中,作為Q,較佳為上述通式
(5)所示的基。尤其在上述通式(5)所示的基之中,R12、R13各自獨立地較佳為選擇碳數1~6的羥烷基或烷氧基烷基。
再者,Q較佳係以上述通式(4)所示的化合物成為水溶性之方式來選擇。具體地,較佳為氫原子、碳數1~3的烷基(即甲基、乙基、丙基、異丙基)、碳數1~3的羥烷基、羥基等。
作為苯并三唑系化合物,具體地例如可舉出苯并三唑、5,6-二甲基苯并三唑、1-羥基苯并三唑、1-甲基苯并三唑、1-胺基苯并三唑、1-苯基苯并三唑、1-羥基甲基苯并三唑、1-苯并三唑羧酸甲基、5-苯并三唑羧酸、1-甲氧基-苯并三唑、1-(2,2-二羥基乙基)-苯并三唑、1-(2,3-二羥基丙基)苯并三唑;作為「IRGAMET」系列之由CIBA特殊化學品公司所市售的2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(5-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙烷、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙丙烷等。於此等之中,較宜使用1-(2,3-二羥基丙基)-苯并三唑、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(5-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇等。此等的苯并三唑化合物係可單獨使用,也可組合2種以上使用。
作為上述含有巰基的化合物,較佳為在鍵結於巰基的
碳原子之α位、β位之至少一位置,具有羥基及/或羧基之化合物。作為如此的化合物,具體地可舉出1-硫甘油、3-(2-胺基苯硫基)-2-羥基丙基硫醇、3-(2-羥基乙硫基)-2-羥基丙基硫醇、2-巰基丙酸、3-巰基丙酸等。於此等之中,特佳為使用1-硫甘油。
又,作為上述含有巰基的化合物,較佳為下述式(6)所示的化合物。
(式(6)中,R係選自由羥基、碳數1~4的烷基、碳數1~4的烷氧基、碳數1~4的烷硫基、碳數1~4的羥烷基、碳數1~4的巰基烷基、碳數1~4的鹵烷基及鹵素原子所成之群組中的基,p為1~3之整數,q為0~3之整數,當p為2或3時,R可相同或相異)。
作為R為碳數1~4的烷基時之具體例,可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基及第三丁基。於此等的烷基之中,由於在溶劑的溶解性適宜,較佳為甲基或乙基,由於防蝕效果更高,更佳為甲基。
作為R為碳數1~4的烷氧基時之具體例,可舉出甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基及第三丁氧基。於此等的烷氧基之中,由於在溶劑的溶解性適宜,較佳為甲氧基或乙氧基,由於防蝕效果更高,更佳為甲氧基。
作為R為碳數1~4的烷硫基時之具體例,可舉出甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、第二丁硫基及第三丁硫基。於此等的烷硫基之中,由於在溶劑的溶解性適宜,較佳為甲硫基或乙硫基,由於防蝕效果更高,更佳為甲硫基。
作為R為碳數1~4的羥烷基時之具體例,可舉出羥甲基、2-羥乙基、1-羥乙基、3-羥基-正丙基、4-羥基-正丁基等。於此等的羥烷基之中,由於在溶劑的溶解性適宜,較佳為羥基甲基、2-羥乙基或1-羥乙基,由於防蝕效果更高,更佳為羥甲基。
作為R為碳數1~4的巰基烷基時之具體例,可舉出巰基甲基、2-巰基乙基、1-巰基乙基、3-巰基-正丙基、4-巰基-正丁基等。於此等的巰基烷基之中,由於在溶劑的溶解性適宜,較佳為巰基甲基、2-巰基乙基或1-巰基乙基,由於防蝕效果更高,更佳為巰基甲基。
當R為碳數1~4的鹵烷基時,作為鹵烷基中所含有的鹵素原子,可舉出氟原子、氯原子、溴原子、碘原子等。作為R為碳數1~4的鹵烷基時之具體例,可舉出氯甲基、溴甲基、碘甲基、氟甲基、二氯甲基、二溴甲基、二氟甲基、三氯甲基、三溴甲基、三氟甲基、2-氯乙基、2-溴乙基、2-氟乙基、1,2-二氯乙基、2,2-二氟乙基、1-氯-2-氟乙基、3-氯-正丙基、3-溴-正丙基、3-氟-正丙基及4-氯-正丁基等。於此等的鹵烷基之中,較佳為氯甲基、溴甲基、碘甲基、氟甲基、二氯甲基、二溴甲基、二氟甲
基、三氯甲基、三溴甲基或三氟甲基,由於防蝕效果更高,更佳為氯甲基、二氯甲基、三氯甲基或三氟甲基。
作為R為鹵素原子時的具體例,可舉出氟原子、氯原子、溴原子或碘原子。
於式(6)中,p為1~3之整數,更佳為1。當p為2或3時,R可相同或相異。
於式(6)所示的化合物中,苯環上的R之取代位置係沒有特別的限定。從容易得到高的防蝕效果之點來看,苯環上的R之取代位置係相對於-(CH2)q-SH的鍵結位置而言較佳為間位或對位。
作為式(6)所示的化合物,從對易腐蝕性材料的防蝕性優異,而且在微影用洗淨液中的安定性優異來看,較佳為具有至少1個選自由烷基、羥烷基及巰基烷基所成之群組中的基作為R之化合物,更佳為具有1個選自由烷基、羥烷基及巰基烷基所成之群組中的基作為R之化合物。當式(6)所示的化合物具有1個選自由烷基、羥烷基及巰基烷基所成之群組中的基作為R時,烷基、羥烷基或巰基烷基在苯環上的取代位置係相對於-(CH2)q-SH的鍵結位置而言較佳為間位或對位,更佳為對位。
式(6)中,q為0~3之整數。從化合物之調製或取得容易來看,q較佳為0或1,更佳為0。
作為式(6)所示的化合物之具體例,可舉出對巰基苯酚、對硫代甲酚、間硫代甲酚、4-(甲硫基)苯硫醇、4-甲氧基苯硫醇、3-甲氧基苯硫醇、4-乙氧基苯硫醇、4-
異丙氧基苯硫醇、4-第三丁氧基苯硫醇、3,4-二甲氧基苯硫醇、3,4,5-三甲氧基苯硫醇、4-乙基苯硫醇、4-異丙基苯硫醇、4-正丁基苯硫醇、4-第三丁基苯硫醇、3-乙基苯硫醇、3-異丙基苯硫醇、3-正丁基苯硫醇、3-第三丁基苯硫醇、3,5-二甲基苯硫醇、3,4-二甲基苯硫醇、3-第三丁基-4-甲基苯硫醇、3-第三4-甲基苯硫醇、3-第三丁基-5-甲基苯硫醇、4-第三丁基-3-甲基苯硫醇、4-巰基苯甲醇、3-巰基苯甲醇、4-(巰基甲基)苯酚、3-(巰基甲基)苯酚、4-氟苯硫醇、3-氟苯硫醇、4-氯苯硫醇、3-氯苯硫醇、4-溴苯硫醇、4-碘苯硫醇、3-溴苯硫醇、3,4-二氯苯硫醇、3,5-二氯苯硫醇、3,4-二氟苯硫醇、3,5-二氟苯硫醇、4-巰基兒茶酚、2,6-二-第三丁基-4-巰基苯酚、3,5-二-第三丁基-4-甲氧基苯硫醇、4-溴-3-甲基苯硫醇、4-(三氟甲基)苯硫醇、3-(三氟甲基)苯硫醇、3,5-雙(三氟甲基)苯硫醇、4-甲硫基苯硫醇、4-乙硫基苯硫醇、4-正丁硫基苯硫醇及4-第三丁硫基苯硫醇等。於此等的化合物之中,從對於易腐蝕性材料的防蝕效果高、取得容易來看,更佳為對巰基苯酚、對硫代甲酚、間硫代甲酚、4-(甲硫基)苯硫醇、4-甲氧基苯硫醇、4-乙基苯硫醇、4-異丙基苯硫醇、4-氟苯硫醇、4-氯苯硫醇及4-溴苯硫醇。又,從對於易腐蝕性材料的防蝕效果高,而且在微影用洗淨液中的安定性優異來看,亦較佳為4-巰基苯甲醇及4-(巰基甲基)苯酚。
式(6)所示的化合物在微影用洗淨液中的含量,只
要不妨礙該洗淨液之洗淨效果,式(6)所示的化合物能均勻溶解在該洗淨液中,則沒有特別的限定。微影用洗淨液中之式(6)所示的化合物之含量,相對於該洗淨液的質量,較佳為0.05~5.0質量%,更佳為0.1~1.0質量%。將式(6)所示的化合物以該範圍之量加到微影用洗淨液時,一邊得到對於易腐蝕性材料的良好防蝕效果,一邊在藉由水等沖洗由該洗淨液所洗淨後的被洗淨物時,容易抑制式(6)所示的化合物之析出。再者,於微影用洗淨液中,式(6)所示的化合物亦可組合2種以上而使用。
又,作為上述含有巰基的化合物,較佳為下述式(7)所示的直鏈巰基醇化合物。
HS-(CH2)x-OH (7)
(式(7)中,x為3以上之整數)。
式(7)中,x為3以上之整數,其上限只要是不妨礙本發明目的之範圍,則沒有特別的限定。從可良好地抑制微影用洗淨液所致的腐蝕之點來看,x較佳為3以上10以下之整數,更佳為3以上9以下之整數。使用x為該範圍的化合物作為防蝕劑時,由於防蝕劑容易溶解在微影用洗淨液中,而容易得到良好的防蝕效果。又,此時當藉由水來沖洗洗淨後的被洗淨物時,可抑制防蝕劑之式(7)所示的化合物之析出。
x未達3之整數的化合物,雖然容易溶解在微影用洗淨液中,但防蝕效果差。x超過10之整數的化合物,雖
然顯示良好的防蝕效果,但使用含有該化合物的微影用洗淨液時,由於因洗淨後之水的沖洗,有析出至被洗淨物的表面之情況。因此,使用含有x超過10之整數的化合物之微影用洗淨液時,洗淨後較佳為在藉由有機溶劑的沖洗後,接著視需要進行藉由水的沖洗。
作為式(7)所示的化合物之合適例,可舉出:HS-(CH2)3-OH
HS-(CH2)4-OH
HS-(CH2)5-OH
HS-(CH2)6-OH
HS-(CH2)7-OH
HS-(CH2)8-OH
HS-(CH2)9-OH,及HS-(CH2)10-OH。
式(7)所示的化合物在微影用洗淨液中之含量,只要不妨礙該洗淨液的洗淨效果,式(7)所示的化合物能均勻溶解在該洗淨液中,則沒有特別的限定。微影用洗淨液中之式(7)所示的化合物之含量,相對於該洗淨液的質量,較佳為0.05~5.0質量%,更佳為0.1~1.0質量%。將式(7)所示的化合物以該範圍之量加到微影用洗淨液時,一邊得到對於易腐蝕性材料的良好防蝕效果,一邊在藉由水等沖洗由該洗淨液所洗淨後的被洗淨物時,容易抑制式(7)所示的化合物之析出。再者,於微影用洗淨液中,式(7)所示的化合物亦可組合2種以上而使
用。
本發明的微影用洗淨液視需要亦可含有界面活性劑。藉由在本發明的微影用洗淨液中添加界面活性劑,可提高微影用洗淨液中的四級銨氫氧化物或防蝕劑之溶解性,可抑制微影用洗淨液中的四級銨氫氧化物或防蝕劑之析出。如此的效果尤其在微影用洗淨液為濃縮狀態時為顯著。又,若在微影用洗淨液中添加界面活性劑,則微影用洗淨液的潤濕性升高,得到抑制蝕刻殘渣等之效果
界面活性劑係沒有特別的限定,可使用習知的界面活性劑。具體地,可使用非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑及兩性界面活性劑。
陰離子系界面活性劑係沒有特別的限定,可使用具有陰離子性基的習知界面活性劑。作為如此的陰離子系界面活性劑,例如可舉出具有羧酸基、磺酸基或磷酸基作為陰離子性基之界面活性劑。
具體地,可舉出碳數8~20的烷基之高級脂肪酸、高級烷基硫酸酯、高級烷基磺酸、高級烷基芳基磺酸、具有磺酸基的其它界面活性劑、或高級醇磷酸酯、或彼等之鹽等。此處,上述陰離子系界面活性劑所具有的烷基係可為直鏈狀或支鏈狀之任一者,在支鏈中也可插入伸苯基或氧原子等,烷基所具有的氫原子之一部分亦可被羥基或羧基取代。
作為上述高級脂肪酸之具體例,可舉出十二酸、十四酸、硬脂酸等,作為高級烷基硫酸酯之具體例,可舉出硫酸癸酯、硫酸十二酯等。又,作為上述高級烷基磺酸之例,可舉出癸烷磺酸、十二烷磺酸、十四烷磺酸、十七烷磺酸、硬脂酸磺酸等。
又,作為高級烷基芳基磺酸之具體例,可舉出十二基苯磺酸、癸基萘磺酸等。
再者,作為具有磺酸基的其它界面活性劑,例如可舉出十二基二苯基醚二磺酸等之烷基二苯基醚二磺酸,磺基二辛基琥珀酸酯等之磺基二烷基琥珀酸酯等。
作為高級醇磷酸酯之例,例如可舉出棕櫚基磷酸酯、蓖麻油烷基磷酸酯、椰子油烷基磷酸酯等。
於以上的陰離子性界面活性劑之中,較佳為使用具有磺酸基的界面活性劑,具體地可舉出烷基磺酸、烷基苯磺酸、油基磺酸、烷基二苯基醚磺酸、烷基萘磺酸、磺基二烷基琥珀酸酯等。於此等之中,較佳為使用烷基磺酸、烷基苯磺酸、烷基二苯基醚二磺酸、磺基二烷基琥珀酸酯。烷基磺酸的烷基之平均碳數較佳為9~21,更佳為12~18。又,烷基苯磺酸的烷基之平均碳數較佳為6~18,更佳為9~15。烷基二苯基醚二磺酸的烷基之平均碳數較佳為6~18,更佳為9~15。再者,磺基二烷基琥珀酸酯的烷基之平均碳數較佳為4~12,更佳為6~10。
於以上的陰離子性界面活性劑之中,較佳為使用具有平均碳數15的烷基之烷基磺酸及具有平均碳數12的烷基
的烷基苯磺酸。
作為非離子系界面活性劑,可例示炔屬醇系界面活性劑等的炔系非離子界面活性劑、聚氧乙烯烷基醚等。作為非離子系界面活性劑,宜為具有水溶性者。宜為HLB7~17之範圍。於HLB小而水溶性不足之情況,可與其它界面活性劑混合等而使具有水溶性。
再者,於微影用洗淨液中,作為界面活性劑,可添加1種或2種以上之各種界面活性劑。
微影用洗淨液中的界面活性劑之含量較佳為0.01~10質量%。藉由界面活性劑之含量為0.01質量%以上,而有效果地抑制微影用洗淨液中的四級銨氫氧化物或防蝕劑之析出。此效果係在微影用洗淨液為濃縮狀態時顯著。又,藉由界面活性劑之含量為10質量%以下,可減低界面活性劑對矽基板或蝕刻遮罩造成損傷等之影響。微影用洗淨液中的界面活性劑之含量更佳為0.02~1質量%,最佳為0.03~0.5質量%。再者如上述,此處所言的界面活性劑之含量,係指顯像處理時實際使用的微影用洗淨液中之濃度,不是指濃縮狀態的微影用洗淨液中之濃度。
本發明的配線形成方法係藉由在形成於半導體多層層合體的低介電體層之蝕刻空間中埋入金屬而形成金屬配線層,使用鑲嵌法之配線形成方法,其中於上述蝕刻空間之形成後,使用本發明之微影用洗淨液至少洗淨上述半導體
多層層合體。
使用鑲嵌法的配線形成方法,更具體地係以在半導體多層層合體的低介電體層上所形成的抗蝕圖型作為遮罩,將上述低介電體層予以蝕刻處理而形成蝕刻空間,藉由在此蝕刻空間中埋入金屬,而形成金屬配線者。再者,於蝕刻空間中,有暫時地埋入犧牲膜之情況。
本發明之微影用洗淨液係可有效果地去除上述蝕刻處理後所殘留之殘渣物。作為蝕刻處理後所殘留的殘渣物,例如可舉出來自抗蝕膜的殘渣物、來自犧牲膜的殘渣物、由來自蝕刻處理所發生的低介電體層或金屬配線層的殘渣物。
作為蝕刻處理後所殘留的殘渣物之去除方法,只要是通常進行的去除方法,則沒有特別的限定。具體地,例如藉由使用浸漬法、浸液法、噴淋法等,使本發明之微影用洗淨液接觸基板1~40分鐘而處理。為了提高去除效果,通常為室溫,亦可將微影用洗淨液升溫到85℃左右為止而進行去除處理。
此處,作為形成上述抗蝕膜之材料,可依照常用方法使用(KrF、ArF、F2、EUV)準分子雷射或電子線用所慣用之抗蝕材料。
使用如此慣用的抗蝕材料,係在層間絕緣層或其上層的障壁層上形成抗蝕膜,通過遮罩進行圖型曝光後,進行顯像處理而形成抗蝕圖型。其次,將此抗蝕圖型當作遮罩,進行蝕刻後之抗蝕圖型殘渣物,係與其它之來自犧牲
膜及來自因蝕刻處理所發生的低介電體層或金屬配線層之殘渣物一起,藉由本發明之微影用洗淨液來去除。
作為上述低介電體層,具體地例如是由摻雜有碳的氧化物(SiOC)系、甲基倍半矽氧烷(MSQ)系、氫倍半矽氧烷(HSQ)系之材料所形成之層。為了不對金屬配線層的電氣特性造成影響,介電常數(k)較佳為3.0以下,更佳為2.5以下之低介電體層。
此等低介電體層係可形成在上述金屬配線層上,也可形成在金屬配線層上形成有障壁層之上。低介電體層的焙燒溫度通常在350℃以上之高溫進行。
形成如此低介電體層之材料,即低介電體材料(Low-k材料),具體地可舉出上述摻雜有碳的氧化物系之Black Diamond(商品名:Apllied Materials公司製)、Coral(商品名:Novelus Systems公司製)、Aurora(商品名:日本ASM公司製)、上述甲基倍半矽氧烷系之OCL T-31、OCL T-37、OCL T-39(皆商品名:東京應化工業公司製)、氫倍半矽氧烷系之OCD T-12、OCL T-32(皆商品名:東京應化工業公司製)等。
又,作為上述障壁層,例如可舉出SiC、SiN、SiCN、Ta、TaN等。如此的障壁層亦可形成在低介電體層與低介電體層之間。
另外,作為鑲嵌法中使用的形成金屬配線層之金屬材料,主要為Cu,但Cu以外的Al、Ti、W等之導電體材料亦可層合在同一基板上。藉由本發明之微影用洗淨液,
即使洗淨液與此等金屬材料接觸時,也可有效果地抑制腐蝕。
本發明之微影用洗淨液係於鑲嵌法之內,在所形成的蝕刻空間內暫時設置犧牲膜之鑲嵌法的配線形成方法中亦有用,但作為形成如此的犧牲膜之材料(埋入材料),具體地較宜為藉由縮合反應所得之旋塗式玻璃材料。
以下,顯示本發明之實施例來更詳細說明本發明,惟本發明不受下述實施例所限定。
根據下述表1中所示的組成及配合量,調製微影用洗淨液。再者,對於各試藥,沒有特別的記載者,係使用一般市售的試藥。又,表中之數值只要沒有特別預先指明,則以質量%之單位表示。
於矽基板上將低介電體材料Aurora ULK(日本ASM公司製)成膜,得到具備1500Å的低介電體層之矽基板。將此矽基板浸漬於經加溫到60℃的上述微影用洗淨液中30分鐘。浸漬結束後,用純水沖洗矽基板,測定低介電體層的膜厚,自浸漬前後的膜厚之差求得低介電體層之蝕刻速度。表1中顯示結果。
將碳系硬遮罩(以下稱為「C-HM」)形成用樹脂組成物(東京應化工業(股)製TBLM-800 EM)滴下至矽基板上,將矽基板以2000rpm旋轉,而使組成物擴展於矽基板全面,形成均勻的膜。然後,在220℃進行以乾燥及樹脂的交聯為目的之熱處理90秒,得到膜厚1400Å的C-HM。
其次,於以下的條件下,對於上述C-HM進行乾蝕刻,得到C-HM的蝕刻殘渣物(即在矽基板上殘留的薄膜狀之C-HM)。乾蝕刻後的膜厚約400Å。
裝置:TCA-3822(東京應化工業(股)製)
功率:800W
壓力:40Pa
平台溫度:40℃
氣體:CF4,300ml/分鐘
時間:3分鐘
將乾蝕刻後的矽基板浸漬於經加溫到60℃的上述微影用洗淨液中15分鐘。浸漬結束後,用純水沖洗矽基板,對於矽基板的主平面呈垂直地切斷矽基板。用SEM觀察切斷面,確認是否去除蝕刻殘渣物。當蝕刻殘渣物被完全去除時,殘渣去除性係評價為良好。另一方面,當蝕刻殘渣物殘留時,殘渣去除性係評價為不良。表1中顯示結果。
TMAH:氫氧化四甲銨
MMEA:單甲基乙醇胺
HF:氟化氫
混合溶劑:3-甲氧基-3-甲基-1-丁醇(商品名:Solfit(註冊商標)、(股)KURARAY製)與二甲亞碸之混合溶劑(質量比6:4)
矽烷1:三甲基甲氧基矽烷
矽烷2:二甲基二甲氧基矽烷
矽烷3:甲基三甲氧基矽烷
矽烷4:丙基三乙氧基矽烷
矽烷5:二甲氧基甲基苯基矽烷
矽烷6:2-(3,4-環氧基環己基)乙基三甲氧基矽烷
矽烷7:3-胺基丙基三甲氧基矽烷
矽烷8:N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷
矽烷9:苯基三甲基矽烷
1)更含有丙二醇0.8質量%。
2)所調製的微影用洗淨液為白濁,無法評價。
如由表1可知.使用含有因水解而生成矽烷醇基的矽化合物之實施例1~14的微影用洗淨液時,可一邊抑制低介電體層的腐蝕,一邊有效果地去除C-HM的蝕刻殘渣物。
另一方面,於比較例1中,雖然可有效果地去除C-HM的蝕刻殘渣物,但由於上述矽化合物存在,而在低介電體層發生腐蝕。又,於比較例2中,所調製的微影用洗淨液係白濁,無法評價低介電體層之蝕刻速度及蝕刻殘渣物之去除性。再者,於比較例3中,存在於微影用洗淨液中的矽化合物,由於不是因水解而生成矽烷醇基的矽化合物,故在低介電體層發生腐蝕。
Claims (6)
- 一種微影用洗淨液,其含有鹼或酸、溶劑、與因水解而生成矽烷醇基的矽化合物。
- 如請求項1之微影用洗淨液,其中前述矽化合物係下述式(1)所示的烷氧基矽烷或其部分水解縮合物,R1 4-nSiOR2 n (1)(式中,R1表示有機基,R2表示碳數1~4的烷基,n為1~4之整數)。
- 如請求項1之微影用洗淨液,其中前述矽化合物之添加量為5質量%以下。
- 如請求項1之微影用洗淨液,其中前述酸包含氫氟酸。
- 如請求項1之微影用洗淨液,其係使用於具備低介電體層的半導體多層層合體之洗淨。
- 一種配線形成方法,其係藉由在形成於半導體多層層合體的低介電體層之蝕刻空間中埋入金屬而形成金屬配線層之配線形成方法,其中於前述蝕刻空間之形成後,使用如請求項1至5中任一項之微影用洗淨液來洗淨前述半導體多層層合體。
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US20130330927A1 (en) | 2013-12-12 |
US9920286B2 (en) | 2018-03-20 |
US20160208201A1 (en) | 2016-07-21 |
KR102088535B1 (ko) | 2020-03-12 |
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KR20130138681A (ko) | 2013-12-19 |
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