TWI235892B - Cleaning composition for removing resists and manufacturing method of semiconductor device - Google Patents
Cleaning composition for removing resists and manufacturing method of semiconductor device Download PDFInfo
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- TWI235892B TWI235892B TW092118959A TW92118959A TWI235892B TW I235892 B TWI235892 B TW I235892B TW 092118959 A TW092118959 A TW 092118959A TW 92118959 A TW92118959 A TW 92118959A TW I235892 B TWI235892 B TW I235892B
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- film
- component
- acid
- cleaning solution
- mass
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- 238000004140 cleaning Methods 0.000 title claims abstract description 86
- 239000004065 semiconductor Substances 0.000 title claims abstract description 27
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- 238000005260 corrosion Methods 0.000 claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 claims abstract description 69
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 67
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- 238000000034 method Methods 0.000 claims abstract description 23
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
-
- 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
- G03F7/425—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
-
- 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
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76807—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics for dual damascene structures
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
Landscapes
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
1235892 王久、:發明說明 [發明所屬之技術領域] 本發明係有關將半導體基板上以銅為主成分之金屬佈 線之成型過程之乾蝕刻後所殘存的抗蝕膜、抗蝕膜殘渣物 以及其他與蝕刻氣體之反應殘渣物(蝕刻殘渣物)加以剝離 去除的蝕刻去除用清洗液,以及使用此清洗液的半導體之 製造方法。 [先前技術] 、.、二阿檟肢化的半導體元件之製造過程,通常係採用名 作為導電用佈線素材的金屬膜等之佈線材料或以佈線間之 絕料目的之層間絕緣膜材料等之上,塗佈抗蝕膜並依夫 刻過程成型所需抗蝕膜圖型後,以此抗蝕膜為遮罩而實摊 ::蝕刻丄以去除所殘存的抗蝕膜的製程。去除此抗蝕膜的 f程而言,一般係在實施電浆抛光(Plasma ashlng)後,^ :使用π洗液將佈線材料或層間絕緣材料上所殘存的抗姓 膜殘渣物加以剝離去除的濕式處理。 2 ’佈線材料—般係使用Α](㈣佈線材料,而此 液可例舉如:以氟系化合物作為基質的清洗 二㈣1 794號公報侧平㈣觸號公報、 4寸開平1 1 -271 985號公郝)、人〜甘〜 5334332 人/虎么報)3經基胺之清淨液(美國專利 ? 9 5〇、3乳氧化四級銨之清淨液(日本專利特開平 '247498號公報)等。 竹開千 层,Π二年來隨著半導體元件之微細化、高速化的進 、 之製造過程方面正進行著大幅度地改變。 314857(修正本) 6 1235892 值膜4乾蝕刻至氮化矽膜能露 h〇Ie)21。此時 ,'、,止以形成介層洞(via 了 乾钱刻所用的氣體盥 反應生成物將 '值膜與抗#膜之 竹成為殘渣以致介層洞 渣物6。 内堆積著抗蝕膜殘 “ 篸考第3B圖及第3C圖,依备將私一 膜5。此時因枷亦 兒水拋光去除抗蝕 了 U拋先所引起的熱及電浆 值膜表面4形成變質層7。 ]之反應而將在低k 其—人’參考第3C圖及第3D圖,實h 系化合物為美皙的、主、土、六^ 貝知使用以習用之氟 土貝的 >月洗液的處理,以土 6。如有殘留兮 无除抗蝕膜殘渣物 間之電氣接觸y $ n 、,成為爾後與上部佈線 ^伐月蜀不良之原因。於是, 殘渣物,俜推田μ 為確實去除抗蝕膜 π、使用對絕緣膜亦具有蝕刻作 上述低k #胺n j作用的清洗液,因此, _k值膜表面之變質層7或低k 以致產生介岸、,n 7 1 + & 俚腠4本身被蝕刻, μ噌洞2 1之内徑之擴大。 接著,參考第3Ε圖,為形成與 在低k佶勝/1 "" s 1連接的佈線, - 值無4上形成經圖型構成準 立A 再成木溝形成用的抗蝕膜5。 〆、_人’翏考第3F圖,以抗 值膜柷蝕胰5作為遮罩,將低k 值肤軋蝕刻至低k值膜4之 22。μ· η* Π位置為止,以形成渠溝 守’乾飯刻所用的氣體與低k值膜與抗姓膜之反應 匆的抗餘膜殘逢物6堆積在介層、;同21與渠溝Μ内部。 其:欠’參考第奸圖及帛3G圖’依電衆拋光去除抗钮 '。此時,因拋光所引起的熱與電毁間之反應而在低k 值腠4表面形成變質層7。 其次,參考第3G圖及第3H圖,實施使用以習用之a 314857(修正本) 8 1235892 系化°物為基的清洗液的處理,以去除抗蝕胺 6。此時,在習用之生、土十 去陈抗蝕胰殘渣物 π冼液的情形,與抗蝕殘渣物 同時,低k值臌本工 〜太丨示心 值杈表面之變質層7經蝕刻而 内徑及渠溝22寬幅之擴大。 "層况21 其次,參考第31圖’依乾姓刻去除氮化 第-銅佈、線。此時m “ ’胰3以路出 h ^ J 抗蝕殘渣物堆積在介層洞21内。 ^ 考第3 J圖,為清洗銅佈線表面,實施使用、f 洗液的處理。在習用之嶋化合物為基質的清::; 形,如欲提升抗钱膜、抗姓膜殘渣物 = 之去除作用時’第—銅佈線"更有受細問題。=物 為防…銅佈線之腐姓,添加有苯并三唾(bta)等之銅 2腐U (日本專利特開2__83712號公報)。然而,即 使在如此的清洗劑中,如欲再加強抗钱膜殘渔物之去除作 用日彳’而便有銅之抗腐蝕效果降低的問題。 ' 、、其-人’茶考弟3Κ圖,依電鐘將銅埋入介層洞2】及渠 溝22中’再依化學機械式研磨(CMp:ch咖⑶⑽ P〇Hs^ 用之滑洗液所腐钱時’由於第二銅佈線1〇不能完全埋入於 介層洞21内,以致引获筮— x 銅佈、、泉1與第二銅佈線1 0間 之接合電阻的提高、或斷線等之問題。 隨著元件之微細化,佈線與佈線間之間隔^設計的愈 狭窄’故在上述步驟中如採用以往之清洗液時,則低k值 膜表面之變質層7及低k值膜4本身即被钮刻,以致佈線 與佈線間之間隔η將更狹窄。因此,具有因佈線間之電容 3]4857(修正本) 9 1235892 重上升時鸦:e j 、 JN 、 & ϋ半導體元件之驅動速度之低落等的特性 + 或佈線與佈線間之短路等之不良情況的問題。又, 習用之、'主、朱、 , ’夜尚未‘元全具備滿足去除抗姓膜殘渣物、銅 之抗腐蝕以及低k值膜之抗腐蝕等性能。 [發明内容] 之目的在於供·在銅佈線過程中,在去除乾 姓刻後之抗I虫膜與飯刻殘渣物以及拋光後之抗㈣殘逢物 與蝕刻殘渣物時,兼備有優異的去除效果與對銅及層間絕 緣膜的耐腐姓效果,且能在安全、溫和的條件下使用的抗 蝕膜去除用清洗液以及使用此去除用清洗液的半導體製造 方法。 、 為達成上述目@,本發明之抗㈣去除用清洗液之特 么為.含有;氫I酸與不含金屬的驗所生成之鹽(A成分 :溶性有機溶劑⑻成分)、選自有機酸及無機酸而成的群 之1種以上之酸(C成分)以及水(D成分),且氣離子濃度 p,為4至8°再者,本發明之抗㈣去除用清洗液,除上 述A成分、B1成分、c成分以及D成分 銨鹽(E1成分)。 〇」3有 又,本發明之另一抗姓膜去除用清洗液之特徵為:含 有;氫氟酸與不含金屬的驗所生成之鹽(α成分)、水溶性 有機溶劑’分、膦酸⑹成分)、水⑺成分)以及不含金 屬的鹼(E成分),且氫離子濃度pH為2至 丹考' ’本發 :之抗钮膜去除用清洗液’除上“成分、B成分、C] 成分、D成分以及E成分之外,尚可含有Cu防姓劑成 3]4857(修正本) 10 1235892 分)。 又,本發明之半導體裝置之製造方法之特徵為:在於 半導體基板上進行以銅為主成分的金屬膜之成膜的步驟、 及於其上面形成絕緣膜的步驟、及再於其上面形成抗姓膜 的步驟、及以該抗姓膜作為遮罩而實施乾兹刻以在該 ^以置洞❹溝的步驟、以及藉由使用氣體的電浆處理 一加熱處理以去除該抗蝕膜的步驟之後,將在乾蝕刻時因 虫刻風體與抗姓膜與值膜等之絕緣膜之間的反 生的讓殘逢物,使用前偏膜去除用清洗液加以: 除。在此,本發明之姓刻氣體中含有作為主成分之敦碳, 而因蚀刻氣體與抗姓膜與低k值膜等之絕緣膜間之 生成的抗蝕刻膜殘渣物中’含有抗蝕 此等之複合物。 奴殘邊以及 又’本發明之半導體裝置之其他製造 在半導體基板上,將以銅為主成分 ^文為. 爲认甘,,、 戚刀的金屬膜成膜的步驟、 及於其上面形成絕緣膜的步驟、及 的步驟、以及以該抗姓膜為遮罩而實^上面形成抗飯膜 膜中設置洞或渠溝的步驟之後 ^ L虫刻以在該絕緣 心俊將所殘存的抗蝕刻膜另户 乾蝕刻時因蝕刻氣體與抗蝕刻膜與低k 、及在 V pg -值膜寺之絕緣性膜 ㈠反應所產生的抗㈣膜殘逢物,、 除用清洗液以去除。 ^ M k ϋ Μ去 ”Γ,本發明之之抗餘膜去除用清洗液,由於1有古 度去除性之抗㈣殘逢物與對鋼佈線膜及絕緣編”; 耐腐蝕性,因而在上述半導體乂 fe的呵度 衣免中,可防止銅佈線間 314857(修正本) 11 1235892 之間隔變狹窄,而* t隹:^日也丨、 元件之驅 路等不良 月匕貝現製造不會發生如半導體 動速度低洛等特性次、彳μ 1.. JU y. 竹注免化’或如佈線與佈線間之短 之半導體製造裝置。 …再者’本發明之半導體裝置之又另外之製造方法之特 斂為.在衣半導體基板上將以銅為主成分的金屬膜成膜的 步驟、及於其上面形成絕緣膜的步驟、以及藉由乾姓刻於 該絕緣膜中設置到達該金屬膜洞的步驟之後,將在乾蝕刻 時因蝕刻氣體與絕緣膜間的反應所產生的抗蝕膜殘逢物: 以使用前述抗蝕膜去除用清洗液以去除。 本發明中所使用的钱刻氣體,係以說碳為主成分的氣 版’由方;因乾蝕刻氣體與絕緣膜或與以銅為主成分的金屬 膜之反應所產生的飯刻殘渣物之主成分係碳殘渣物,因 而:本發明之抗姓膜去除用清洗液不僅能去除抗姓膜及抗 餘膜m ’肖a去除未含有抗钱膜及其殘潰物的姓刻殘 潰物。 在此,以銅為主成分的金屬,係指例如該金屬中之銅 含量在90質量%以上者之意。 本發明之上述以及其他目的、特徵、形態以及優點, 可在苓考所附圖面之下,由下述詳細說明更為明瞭。 [實施方式] (實施形態1) 本申請案之一種抗蝕膜去除用清洗液,含有:氫氟酸 舁不3金屬的鹼所生成之鹽(A成分)、水溶性有機溶劑(B】 成分)、選自有機酸及無機酸而成的群中之i種以上之酸(c 314857(修正本) 12 1235892 成分)以及水(D成分),且氫離子濃度pHg ‘至8。 本4 S之A $刀,係、氯亂酸與不含金屬的驗所生成之 鹽。不含金屬的驗適合使用經基胺類、一級、二級或二級 脂肪族胺、脂環族胺、雜環胺、芳香族胺等有機胺化合物、 氨、低級四級錄驗等。 經基胺類可例舉如··經基胺、N-甲基經基胺、N算二 甲基經基、N,N-—乙基經基胺等。 -級脂肪族胺可例舉如:甲胺、乙胺、丙胺、丁胺 乙醇胺、單異丙醇胺、2-(2_胺基乙胺基)乙醇等。二級脂肪 族胺可例舉…甲胺、二乙胺、二丙胺、二丁胺方 曱基乙醇^乙基乙醇胺等。三級脂肪族胺可 ㈣如.三甲胺、三乙胺、三丙胺、三丁胺、聯二甲美 乙%月女、N,N-二乙基乙醇胺、Ν·甲基二乙醇胺、 : 乙醇胺、三乙醇胺等。 土— ^㈣胺可例舉如:環己胺、二環己胺等。雜環胺可 噻二㈣ '吼。定、嗎琳、•秦、脈。定、^坐、 Ν-乙基节:曰广:可例舉如:苄胺、二节胺、ν-甲基苄胺、 氯氧n級四級銨驗可例舉如:氫氧化四甲錢、 ν &乙基)三曱錄等。 化四=rr中,較佳為可舉如:氨、乙醇胺、氣氧 甲叙寺。其中以氨為最佳。 上述 Α 士八 姓膜之去j刀’關於乾關後之化學放大型愛克斯瑪抗 中所含的=而言’係藉由與化學增幅型愛克斯瑪抗飯膜 九氧弓丨發劑反應而改善去除性,對拋光後之抗蝕 314857(修正本) ]3 1235892 膜K渣物而p則藉由促進抗姓膜殘渣物中之化學結合之 開裂而顯著改善去除性。 又,A成分之含量為0·01質量%至}質量%、較佳為 0’05質量%至0.5質量%。如在〇·〇】質量%以下,則抗蝕膜' 抗蝕膜殘漬物以及其他蝕刻殘逢物之刻離性降低,而如超 過1質量%時’則對銅佈線及低k值膜等之層間絕緣膜的 腐钱轉劇故不宜。
:發明之B1 &分,係水溶性有機溶劑。祇要是水溶 ::容劑則並不特別限定’惟適宜使用胺類、多元醇或 ^甲丁^類。胺類可例舉如:甲酸胺、N•甲基甲醒胺、n,n_ '甲:胺、N-乙基曱醯胺、N,N•二乙基甲酸胺、乙I 乙酿胺、N,N_二甲基乙酿胺U基乙酿胺、 一乙基乙醯胺等。 多兀醇或其衍生物類可例舉如: 醚、乙一醇、乙二醇單甲 一释單乙醚、乙二醇單丙醚、 醇單甲— G —醇早丁醚、乙二 ^乙酸酯、乙二醇單乙醚乙酸 ^ 酸酯、7 — ··曰、乙二醇單丙峻乙 —醇單丁醚乙酸酯、二乙二醇、_ 二乙二醆⑽ 子一乙二醇早曱醚、 醉早乙醚、二乙二醇單丙醚、― 二。 乙二醇置 一乙一醇單丁 、二 早曱乙酸酉旨、二乙-西拿显 單丙_乙阶匕—— > 乙一酉子早乙醚乙酸酉旨、二乙二醇 丙 丙 •义酉日、一乙一醇單丁 _乙酸、二—> 口 醇、工 ·一乙二醇單曱_、 二丙二醇單甲醚、丙二醇單乙醚、 酉亨i 子單丙醚、二丙二醇單丁醚 丙二醇單乙醚乙酸酯 丙二醚單丙醚、 二丙二醇單乙醚、二丙 丙一醇單甲醚乙酸酯、 丙二醇單丙喊乙酸醋、二丙二 平丁醚、二丙二醇單甲醚、 314857(修正本) 】4 1235892 醇單丁醚乙酸酯、二乙二醇— ^ 籽—甲醚、二乙二醇二乙醚、二 乙一醇一丙驗、二乙二醇-τ㈣ ^ 子—丁醚'二丙二醇二甲醚、二丙 二醇二乙&$、二丙二醇-呙㈣ 内卿一丙醚、二丙二醇二丁醚等。 又,作為本發明之B1成公 风刀 以使用上述醯胺類與多 元醇或其衍生物類之混合物為祛 钓1土 胺類與多元醇或其衍 生物頌之耽*合質置比並不特別限 w J丨艮疋’惟彳之乾姓刻後之化學 放大型愛克斯瑪抗姓膜去除性髮
1牙'丨王 < 規點來看,如欲去除KrF 用抗姓膜(the KrF resist)(KrF愛克斯瑪雷射用抗㈣)時, 由於其主骨架為苯紛骨架之聚經基苯乙浠之故,以對此溶 解性高的醯胺類之比例高者為佳,而如欲去除W用抗姓 膜㈣e ArF reS1St)(ArF愛克斯瑪雷射用抗姓膜)時,則由於 其主架為丙烯酸系之故,以對此溶解性高的多元醇或其衍 生物類之比例高者為佳。又,對乾姓刻及拋光後之抗姓膜 殘㈣亦具有與上述同樣傾向。亦即,對應於乾㈣前所 使用的抗蝕膜之種類以決定醯胺類與多元醇或其衍生物類 之混合質量比即可。 又’特別是在一個半導體裝置之製造時,如欲併用入^ 用抗蝕膜與KrF用抗蝕膜時,m成分,以使用醯胺 類與多元醇或其衍生物類之混合物較為㈣。彳(兩姓刻膜 之溶解性來看’ B1成分中之醯胺類之混合質量比在〇·3至 0 · 5者為最佳。 上述Β!成分之含量較佳為5〇質量%至98質量%,更 佳為60質量%至95 »量%。如在5〇質量%以下時,則抗 峨漬物之去除性降低之同時,對銅佈線之腐钱將轉 3]4857(修正本) 15 1235892 :二:Γ,即使超過98質量%,對抗姓膜、抗峨 /一 4 去除性因降低而不理想。 中的T::明之C成分可使用選自有機酸及無機酸而成的群 …以上之酸。有機酸可例舉如:甲酸、乙酸、丙酸、 丁酉夂、草酸、乙醇酸 《酒石H棣酸等之脂肪族酸;安 心曰酉夂本乙酸、對苯二甲酸箄之:¾:夭#减〜 例舉如:硫酸、睡酸H ^ 。無機酸可 1馱硝酸、磷酸等。此種C成分,係作 整抗㈣去除用清洗液之顺氫離子濃度)者,其 添加里並不特別限定。 本♦明之抗姓腺麥哈_、,主、土、产 為5.5至75,更:A “液之PH值為4至8,較佳 且有… 至7·5。本發明中,清洗液之沖 為重要的影響。如阳在4以下時, 之腐蝕轉劇,而如pH超過 一屬膜 物以及其他蝕刿焱、本仏χ 机蚀腰歹欠屋 蝕刻殘渣物之去除性降低,以 低k值膜之腐钱增大之故不宜。 U屬膑及 本發明之〇成分,可徒用匕^ *不含金J _ 使^水可使A成分之氫氟酸 ’ ”屬的知所生成之鹽離子化,以增高尸為胺我冰从 以及其他蝕刻殘渣物去 液之引火點、4曰 舌除^之问妗,亦具有提高清洗 人.·、、占亚使易於操作處理的角色。 (實施形態2) :發明之其他抗蝕膜去除用清洗液,含有 不含金屬的鹼所生成之躂 a軋-夂… 成分)、w白古Jfe |(A成刀)、水溶性有機溶劑(B1 遣自有機酸及無機酸而成的群 成分I水⑴成分)以及㈣(E1成八^ U之_
汉KE1成刀),且氫離子濃度pH 3]4857(修正本) 36 1235892 广亦即’本實施形態係在上述實施形態1中的抗 =去除用清洗液之A成分、B1成分、c成分以… 刀中,再添加E1成分,以使PH作成4至8者。 在此,錢鹽(E1成分)具有抑制 I好 丨制乡巴緣肤之腐蝕的作用, 而其含量較佳為0·01質量%至5 Λ/ 貝里/〇,更佳為0.05質量 /〇至3質量。/。。如在〇 〇 1質量。/ C.M 貝里/〇以下時,則如TEOS、SiN、
SiON、S!〇2等的絕緣膜之腐蝕轉 二“ f寻剔,而如超過5質量%時, 則抗蝕膜以及抗蝕膜殘渣物等之去除性降低。 作為本發明之 E1成分祐| θ ^ * 要疋釦鹽則並不限定其使 用。可例舉如··甲酸銨、乙酸銨、 /、 丙酉欠叙、丁酸銨等之脂 肪酸單羧酸銨鹽、乙醇酸銨鹽、 早酼鉍、丙二酸銨、琥珀 I銨、馬來酸銨、戊二酸銨、 敲釦專之脂肪族多元羧 酸銨鹽;乳酸銨、葡萄酸銨、酒 _ ^ ㈡七馱釦、頻果酸銨、檸檬 酸鈹寻之羥酸銨鹽;胺基碏酸銨 ”夂钕寺之胺基膦酸錄鹽箄。 (實施形態3)
本發明之再其他抗蝕膜去除用清洗液,含有:氫默酸 =含t屬的驗所生成之鹽(A &分)、水溶性有機溶劑(B v、 ^ (成刀)以及不含金屬的鹼(E成 且氮離子濃2至8。由於添加膦酸⑹成分) 及不含金屬㈣0Β❹)而可提升㈣金屬膜抗钱性之 故,可使用廣泛的pH區域(pH為9 ㈣m u)者作為抗㈣去 本發明之A成分,係氫氟酸與 卜3孟/蜀的驗所生成之 鹽,而其詳細内容係如於實施形態】所說明者。 3]4S57(修正本) 1235892 本♦明之B成分,係水溶性有機溶劑。祇要是水溶性 =機溶劑則並不特別限定,而適宜使用醯胺類、吡咯烷酮 六、、燒基脲類、亞楓類、楓類、咪唑啉二酮 夕—二 复^ jlL λ 、夕兀醇或 /、’了生物類、内酯類 '羧酸衍生物類等。 胺類可例舉如:甲醯胺、Ν-甲基曱醯胺、Νν__ 曱醯胺、Ν-乙基甲醯胺、Ν,Ν_二乙基曱醯 乙:土 甲基乙酿胺、Ν,二甲基乙酸胺、Ν_ 广月女1- 7 ^ 泰乙醯胺、ΝΝ- I乙醯胺等。吡咯烷酮類可例舉如:Ν 5 一一 二I乙基。’略烧w、Ν’己基_2,卜各烷二t:各烷 土 吡咯烷嗣等。烷基脲類可例舉如:四 ° m 亞楓類可例舉如:二m二乙亞 ㈣、四乙脲等。 二甲碉、二乙碉、雙(2_經乙基)碉。磾類可例舉如·· 啉二酉同類可例舉如 甲基碉等。咪唑 ,J 一 T基-2-咪峻酿 多元醇或其衍生物可例舉如:乙二酽二鲷等。 乙二醇單乙醚、乙二醇單丙醚、乙二rl、乙二醇單甲_、 罗_乙酸酯、乙—σσ 子畢丁 _、乙-含 6 一知早乙醚乙酸酯、 1 乙一%早 乙二醇單丁醚乙酸酯、- 〜醇單丙醚乙酸酯、 醇單T醚、二 、千円醚、一 7 一 醇單甲醚乙酸酯、-7 一 醇單丁醚、二乙 Μ —乙二醇單乙醚乙酴紙 一 趑乙酸酯、二乙二醇單 知、二乙二醇單g 一%、丙二醇單甲 —乙二醇單f醚、戸 -於。。 丙二醇單乙醚、兩 一 S子早丁醚、二丙— 丙二醇單丙醚、 οσ %早尹醚、二丙-啦 、 醇早丙醚、二丙二醇單丁 4、_内—知單乙醚、二丙二 丙二醇單乙醚乙酴 醚、一丙二醇單尹醚乙酸酯、二 ~丙二醇單丙醚 G醆酯、二丙二醇 ~ L· 二醇、一 r 二醇單乙醚、- 一乙 —乙一醇單丙醚、二乙 3]4857(修正本) 18 1235892 醇二甲醚、- 7 一 ^ ^ 一乙一醇二乙醚、二乙 丁醚、二丙二醇二甲醚、二丙二 丙醚、二丙二醇二丁醚等 單丁醚乙酸酯、二乙 二醇二丙醚、二乙二 醇二乙、二丙二醇 —卩 -J 啤哥 〇 内酯可例舉如:^ •丁内 物·^ 門®曰、戊内酯等。羥酸衍生 物了例舉如.乙酸曱酯、乙 等。 _夂乙知、乳酸甲酯、乳酸乙酯 又,本發明之B成分,較佳 ^ ^ ^ ^ . 权佳為使用上述亞碉類或楓類 铷盥夕_ ^ 飞/生物之混合物。含磺化合 物與夕7L 或其衍生物之混 " 弘“ a 1 貝里比亚不特別限定,惟從 乾姓X彳後之化學放大型愛 a 克埘瑪抗蝕膜去除性之觀點來 看’如-去除KrF用抗蝕膜時 之聚羥基笨乙橋,田士 …, -王月木為本鉍月木 比例古去反 ,以對此溶解性高的含硫化合物之 骨;丙:佳,而如欲去除ArF用抗㈣時,,'lj由於其主 ==酸系,目此,以對此溶解性高的多元醇或其衍 生物之比例;t; & & y+ 渣物亦具有*4 ==對乾㈣及拋紐之抗姓膜殘 用的抗姓膜之種:亦gp ’對應於刪前所使 ^ ,θ ^ ^ θ Λ' 1决疋含硫化合物與多元醇或其衍生物 之混合質量比即可。 V述:Β 成 刀之έ里,較佳為5 0質量%至9 5質量%, 钱二抗Λ量至9 0質量%。如在5 〇質量%以下時,則抗 將鋅&几殘渣物之去除性降低之同時,對銅佈線之腐姓
將轉劇,另〜士I _ 面’即使超過95質量%,由於對抗蝕膜、 _之去除性降低而不理想。 本發明之Γ ^丄成分為膦酸。本發明中所使用的膦酸可 19 314857(修正本) 1235892 例舉如··二乙稀三胺基五(亞甲基膦酸)、苯基鱗酸 基二膦酸、伸乙基二膦酸、】,基伸乙基]丄二膦酸、1 經基伸丙基-u-二膦酸、卜經基伸丁基]山二膦酸、 胺基雙(亞甲基鱗酸)、十二烧基胺基雙(亞甲基、乙I 胺雙(亞甲基膦酸)、乙二胺肆(亞甲基膦酸)、六亞甲基二: 四(亞曱基鱗酸)、異丙二胺雙(亞f基膦酸)、異丙二胺二 甲基膦酸)、氰基參(亞曱基膦酸)等。 本發明所使用的膦酸(C1成分),係由於與不含金屬的 鹼(E成分)之併用而具有對作為佈線材料之銅系金屬膜、 或低k值膜等之絕緣膜的抗蝕劑的功能之同時’且有作為 PH調整劑的功能。在此,C1成分之含量較佳為nf% 至20質% ’更佳為〇 5質量%至15質量%。如。成分之 含量為(M質量%以下,則對銅系金屬膜或低k值膜的耐 腐蝕性將降低,而如超過2〇質量%,則由於對抗蝕膜、抗 蝕膜殘渣物或蝕刻殘渣物之去除性因降低而不理想。几 本發明之D成分係使用水,而其詳細内容係如於實 形態1所說明者。 ' 本發明之E成分,係不含金屬的鹼。本發明中所使用 的不含金屬之鹼並不特別限定,而適合使用羥基胺類'一 級、二級或三級脂肪族胺、脂環族胺、雜環胺、芳香族胺 等之有機胺化合物、氨、低級四級銨鹼等。 經基胺類可例舉如··羥基胺、曱基羥基胺、n,n-二 曱基羥基胺、N,N-二乙基羥基胺等。 一級脂肪族胺,可例舉如··甲胺、乙胺、丙胺、丁胺、 20 3】4857(修正本) J235892 醇胺、:伽基乙胺基)… 乙醇胺、N-甲美乙旷二月女、一乙胺、二丙胺、二丁胺、二 可例舉如::;胺乙Γ基乙醇胺等。三級脂肪族胺 Am 胺、三丙胺、三丁胺、Ν,Ν-二甲 土 _ 、Ν,Ν-二乙基乙醇胺、Ν_甲 二ΓW r基一乙醇胺、Ν-乙基 —乙S手胺、三乙醇胺等。 μ胺可例舉如:環己胺'二環己胺等。雜環胺可例 二:吡咯、吡咯烷、吡啶、嗎琳、吡嗪、哌啶、噚唑、 土唾寺。芳香族胺可例舉如:〒胺、— Ν . —卞月女、I曱基▼胺、 基卞私寺。低級四級錄驗可例舉如:氯氧化四甲敍、 氧虱化(2-羥乙基)三曱錄等。 ^發明所使用的不含金屬的驗(Ε &分),係由於與麟 成分)之併用而具有對作為佈線材料之鋼系金屬膜、 3低k值膜等之絶緣膜的抗姓劑的功, b具同時,具有作 為PH調整劑的功能。在此,E成分之含量較佳為〇1所旦 …。質量%,更佳為。.5質量%至15質量%。如二 ,含量為0.1質”。以下,則對銅系金屬膜及低让值膜之 腐钱增大,而如超過20質量%,則由於對抗姓膜、抗姓膜 殘渣物以及其他姓刻殘渣物之去除性因降低而不理想。 本實施形態之抗蝕膜去除用清洗液之pH為2 ^ 佳為2.5至7.5。如PH在2以下時,則鋼系金屬膜至之^ 轉劇’而如PH超過8時’則對抗姓膜、抗姓膜殘逢物以 及其他姓刻殘潰物之去除性降低,並且鋼系金屬膜及低让 值膜之腐蝕增大因而不宜。另外’本實施形態中,由於添 3]*4857(修正本) 21 1235892 加膦酸(Cl成分)及不含今展 孟屬的鹼(E成分),而改善金屬膜 防蝕性,所以,比較實 t 、也九恶1及實施形態2中之抗蝕膜 去除用清洗液之pH區域达
一MpH為4至8),可使用廣泛的pH 區域(pH為2至8)者作為浐总^ l 為抗姓fe去除用清洗液。 (實施形態4) 本發明之再其他抗腹\ 、去除用清洗液’含有:氫氟酸 铃不含金屬的驗所生成蹄
嚴(A成分)、水溶性有機溶劑(B 成分)、膦酸(C1成分)、水⑺士、八、 a ^ ( 成刀)、不含金屬的驗(E成分) 成分且氯離子濃度邱為2至8。亦 即’本貫施形態,係在上述實施形態3之抗蝕膜去除用清 夜之A成刀、B成分、Cl成分、D成分以及£成分中, 再添加F成分,並將pH作成2至8者。 在此,Cu杬蝕劑(F成分),具有抑制銅系金屬膜之腐 ^作用,其含量較佳為〇·〇1質%至5質量%,更佳為〇 〇5 質量。/〇至3質量%。如在〇.〇1質量%以下時,銅系金屬膜 之腐蝕轉劇,而如超過5質量%,則對抗蝕膜以及抗蝕膜 殘渣物等之去除性因而降低。 本鲞明之F成分適合使用三唑類、脂肪族羧酸類、芳 香族羧酸類或胺基羧酸類。又,亦可併用2種以上之此等 F成分。三唑類可例舉如:笨并三唑、鄰曱苯基三唑 '間 曱苯基三唑、對甲苯基三唑、羧基苯并三唑、卜羥基苯并 三。坐、琐基苯并三唑、二羥丙基苯并三D坐等。脂肪族㈣ 可例舉如:草酸、丙二酸、丙烯酸、甲基丙烯酸 '馬來酸、 富馬酸、琥拍酸、衣康酸、戊二酸、己二酸、乳酸、韻果 3]4857(修正本) 22 1235892 酸、棒、 丁豕-义、酒石酸等。芳族香羧酸可例舉如:安息香酸、 欧酸、偏笑二m ^ 、一美— 一曱酉夂、均苯四曱酸、5-磺基水揚酸、2,4-二 匕基女息香酸等。胺基羧酸可例舉如:胺基乙㉟、二羥乙 基胺基乙酴、& ^ ^ " 丙月女馱、纈胺酸、白胺酸、天冬醯胺、谷胺 酿胺、夭夂^ ^ ;胺黾、麩胺酸、離胺酸、精胺酸、亞胺二乙酸、 亂基二乙酸、乙撐二胺四乙酸、丨,2_環己基二胺四 二乙撐三胺五乙酸等。 去除其=,以銅佈線過程為例’將就使用本發明之抗蝕膜 .π洗液以去除抗蝕膜、抗蝕膜殘渣物以及其他蝕刻 殘渣物為特徵 干V版展置之製造方法之實施形態,說 (貫施形態5) 翏考第1Α圖至第1Κ圖’就使用本發明之清洗液的顏 :過%之一種實施形態加以說明。第ια圖至第W圖係 二知步驟之第3A_ 3C圖之情形相同者。在此,參 考第1C圖及第则,使用本發明之清洗液以去除介層洞 入1形成時所產生的抗蝕膜殘渣物6。本發明之清洗液,由 於對低k值膜4及其變質膜7的蝕刻量極小,而不致於發 生介層洞2 1内徑之放大。 " 又,第1E圖至第1G圖係與習知步驟之第3e圖至第 ::圖相同者。其次’參考第〗G圖及第m圖,使用本發 广青洗液以去除渠溝22形成時所產生的抗飯膜殘逢 。本發明之清洗液’由於對低让值膜4及其變質層7的 姓刻量極小,而不致於發生介層洞内徑及渠溝寬幅之:大。 3】4857(修正本) 23 1235892 圖’藉由乾I虫刻而去除氮化石夕膜3 以露出第一銅佈線。此時 ' ^ ^在弟一銅佈線1表面將堆積因 敍刻氣體與氮化矽間之 、 # 反亡所生成的蝕刻殘渣物8。接 者,參考第II圖及第U圖 θ 使用本發明之清洗液以清洗 弟一銅佈線1之表面。此4 7 本赍明之清洗液,係與以往 以月洗液不同而不致於腐钱第一銅佈線i之表面。其次, 蒼考第1J圖及第1K圖,藉由採 猎由抹用電鍍法、迴銲濺鍍法或 :機金屬化合物的化學氣相沈積(cvd: ch⑽…-: 山。η)的-種金屬有機化學氣相沈積(M〇cvD: Mew 哪㈣Chemical Vap〇r Dep〇siti〇n)法將銅埋入介層洞 渠溝22之中,並依CMp去除不需要部份以形成第二 銅佈線1 0。由於本發明之、生 之α洗液不致於腐蝕第一銅佈線表 面’因此第一銅佈線1盘笙— 一乐一銅佈線10間之接合良好,而 不會產生接合電阻增高或斷線等之問題。X,本發明之清 洗液’由於對低k值膜4及其變質層7之姓刻極少,因而 銅佈線與銅佈線間之間隔11不致於變窄,所以不會產生半 導體兀件之特性低落或佈線間之短路等之問題。 (實施形態6) 參考弟2A圖至第2TIS1,丄 ^ 弟21圖就使用本發明之清洗液的銅 佈線過程之其他實施形態加以說明。第2a圖及第2b圖係 細主步驟之第3A圖及第3B圖相同者。參考第2B圖及 2圖u洞2 i之乾名虫刻後,不實施或不充分實施 電漿拋光處理而使抗蝕膜5殘存的狀態下,使用本發明之 清洗液以去除抗蝕M 5及抗餘膜殘渣物6。本實施形態, 3]4857(修正本) 24 1235892 由於在低k值膜4表面不形成變_ ^ _制 第圖及第2Ε圖 心的形態。 丄. 彺步驟之第3Ε圖及第π同 相同者。參考第2Ε圖及第2F圖 及弟邛圖 實施或不充分實施電㈣光/在…乾姓刻後,不 …κ拋先處理而使抗蝕 + 月洗液以去除抗蝕膜5及抗蝕 6。本實施形態,由於在低 、'澧物 隹低k值膜4表面不形 為一種理想的形態。 夂貝層,而 、•其Ϊ ’參考第2G目’藉由乾㈣而去除氮化石夕膜3 以硌出第一銅佈線。此時, 一 、 長弟一鋼佈線1表面將雄 钱刻氣體與氮化石夕間之反庫所u A 卸將堆積因 车“ Μ 反應所生成的钱刻殘渣物8。接 者,簽考弟2G圖及第2Η圖 第一銅佈線i表面。本發明之Ϊ = Γ月之清洗液以清洗 不同,而不致於腐钱第-銅佈線!之表面。其次, 2Η圖及第21圖,盥上述闾婷 > 考第 準、、聋22…土 ‘方式’將銅埋入介層洞幻及 ^ 中,亚去除不需要部份以形成第二銅佈線10。由 ;本發明之清洗液因不腐蝕第-銅佈線!之表面,使第一 銅佈線1與第二銅佈線10間之接合良好,而不會產 電阻增高或斷線等之問題。又’本發明之清洗液,由於= 氐k值膜4之蝕刻極小’而銅佈線與銅佈 不致於變窄,因此不致於發生半導麵門^ 11 線間之短路等之問題。“月豆兀件之特性低落或佈 、、以下’再具體說明本發明。本發明之抗姓膜去除用清 洗液之藉由乾蝕刻的抗蝕膜殘渣物之去除性、因蝕刻氣2 與無機質模間之反應所.產生㈣刻殘逢物之去除性、對= 3】4S57(修正本) 25 1235892 膜或低k值膜之耐腐蝕性,係按下述方式加以評估。 (1)抗敍膜去除用清洗液之調製 作為實施形態1之抗蝕膜去除用清洗劑之實施例而調 製貫施例1至實施例2丨之抗蝕膜去除用清洗液、作為實施 例2之抗姓膜去除用清洗液之實施例而調製實施例u至實 施例25之抗蝕膜去除用清洗液、作為實施形態3之抗蝕膜 去除用清洗液之實施例而調製實施例26至實施例56之抗 蝕膜去除用清洗液、以及作為實施形態4之抗蝕膜去除用 清洗液之實施例而調製實施例57至實施例61之抗蝕膜去 除用清洗液。 ' 實施形態1之抗蝕膜去除用清洗液,係混合表丨至表 3内所示的特定質量%之a成分、β1成分、以及所需要的 D成分(水)分量全體之95質量%,再添加少量作為c成分 之確酸及丙酸並調整為特定之pH,再添加D成分作成ι〇〇 質量%以調製。又,實施形態、2之抗蝕膜去除用清洗液, 係提合表4内所示的特定質量%之A成分、Bi成分、£1 成分以及所需要的D成分分量全體之95質量%,再添加少 量作為c成分之硝酸及丙酸並調整為特定之pH,再添加d 成分作成1〇〇質量%以調製。所添加的c成分之量,係隨 所調整的pH而有所變化,為〇·3質量%至3質量%。 實施形態3之抗蝕膜去除用清洗液,係對表$至表8 内所示的特定質量。之A成分、B成分、C1成分以及£、成 分中添加D成分以作成100質量%,並在確認pH之下所 ㈣者。X,實施形態4之抗蝕膜去除用清洗液,係對表 3]4857(修正本) 26 1235892 9八内所不的特定質量°/。之A成A,B成分、Cl成分、E成 /刀以及F成分中添加D成分以作& 1〇〇質量。/。,並在確認 pH之下所調製者。 (2)抗蝕膜殘渣物去除性 /考第1A圖’採用通常之金屬鑲嵌過程,將埋入型 之第-銅佈線1形成在本身為卜絕緣膜2的氧化石夕膜之 間亚在其上面作為第一鋼佈線之保護膜依序形成厚度 6〇請之氮化矽膜3及本身為低k值膜4之厚纟咖聰之 cvd-Si0N膜(介電常數2 8),並於其上面形成經圖型構成 的厚度400nm之正型抗㈣5。在此,ArF用抗姓膜係使 用本身為含丙稀酸樹脂的化學放大型ArF愛克斯瑪抗㈣ 之PAR 1〇1(住友化學社製)' KrF用抗蝕膜係使用本身為含 苯酚樹脂的化學放大型KrF愛克斯瑪抗蝕膜2 SEPR-43 0(信越化學社製)。 其次,筝考第1B圖,使用並行平板RIE以處理壓力 l〇Pa、RF(射頻)電力300W、氟碳與Al•之混合氣體將:身 為低k值膜4之CVD_Si0N膜加以乾蝕刻,並形成介層洞 2 1以露出氮化矽膜3。此時,在介層洞内確認有抗蝕膜殘 渣物6。 其次’參考第1C圖,依使用氧氣的電漿,在室溫下 實施乾蝕刻後之抗蝕膜圖型之拋光處理9 〇秒鐘。此時,在 低k值膜表面形成有變質層7之同時,在其表面及介層洞 21内確認有抗蝕膜殘渣物6。 其次,將上述之附著有抗蝕膜殘渣物之晶片(尺寸 3]4857(修正本) 27 1235892 20mmx 20mm),在24。(:下浸潰在具有表1、表2、表3、 表4、表5、表6、表8或表9所示的組成之抗蝕膜去除用 清洗液200cm3中30分鐘後,水洗後加以乾燥。將使用實 施形態1中之抗蝕膜去除用清洗液時之ArF用抗姓膜及其 抗姓膜殘潰物去除性示於表1 ’將KrF用抗蝕膜殘渣物去 除性示於表2。又,將使用實施形態2中之抗蝕膜去除用 清洗液時之ArF用抗蝕膜及其抗蝕膜殘渣物去除性示於夺 4。又,將使用實施形態3中之抗蝕膜去除用清洗液時之 ArF用抗蝕膜及其抗蝕膜殘渣物去除性示於表$及表8, 將KrF用抗蝕膜及其抗蝕膜殘渣物去除性示於表6及表 8再者,將使用貫施形態4中之抗蝕膜去除用清洗液時^ ArF用抗蝕膜及其抗蝕膜殘渣物去除性以及用抗蝕膜 及其抗蝕膜殘渣物去除性示於表9。在上述各表中 及〇表示未經確認為抗蝕殘渣物者(〇〇之表面狀態係較 〇者為佳)、X表示經確認為抗蝕膜殘渣物者。 :著,參考第1£圖至第10圖,按與上述同樣步驟, 巴㈣4部分形成渠溝部22,參考第1G圖及第⑴ :二:上述同樣步驟去除所殘存的抗姓膜殘渣物。此時 杬姓版之去除性,係與表1、表2、表4、表5…、 表8、或表9者同樣。 又 3)餘刻I體及無機質膜對反應殘渣物之去除性 接著,參考第1Ϊ圖,使用' 1〇ρ, 使用亚仃板RIE,以處理壓 〇Pa、RF電力3〇(m i碳盥 加以虱及,、^之^合氣體將氮化矽膜 刀乂导乙儀刻,以霞屮楚 。出弟一銅佈線】。此時,由於在第一^ 3】仙57(修正本) 28 1235892 佈線表面上因上述乾钱刻所生成的㈣氣 之反應而堆積有㈣殘渣物8。 氮化石夕膜間 其次,參考第u圖及第u圖, 表8或表9之組成的抗_去除用 ^表3、表7、 法去除上述蝕q ^按與(2)同樣方 4挪刻胰殘渣物8。蔣1社里-中。表3、# 7主 將其、结果不於所對應的表 〒表3表7、表8或表9中之〇f)、n 同樣基準所表示者。 、><係按與表1 接著,參考第1K圖,依泰供、土收^ , 泪雀”击、, ㈡依书鑛法將銅埋入介層洞21及 木/ ,並將不需要部份依CMP以形成第_ # # ⑷銅佈線之耐歧 銅佈線10。 銅佈線之耐腐純,係將銅板晶片(厚度5〇〇麵、2〇職 = 〇mm),在24t下浸潰在具有表1至表9所示的組成之 /月洗液中30分鐘後並水洗後乾燥時之銅板之蝕刻量(厚度 之減J )’使用本身為依螢光χ線之膜厚測定裝置之4 Pr〇be(福地面雄社製)加以測定。將蝕刻量為1 nm以下者以 〇〇表示,將2nm以下者以〇、2mm以上者以χ示於表i 至表9。 (5)低k值膜之耐腐蝕性 低k值膜之耐腐姓性,係將CVD_Si〇N膜晶片(厚度 5〇〇nm、20mmx 20mm),在24t:下浸潰在具有表}至表9 所不的组成之抗蝕膜去除用清洗液中3 〇分鐘之後,並加以 水洗後乾燥時之CVD-SiON膜晶片之蝕刻量(厚度之減 少)’使用本身為光干擾式膜厚測定裝置的NanoSpec(奈諾 米特克斯社製)加以測定。將蝕刻量為]nrn以下者以〇〇 29 314857(修正本) 1235892 表示,將2nm以下者以〇、2mm以上者以X示於表1至表 9 〇 在此,表1至表9中,NH4F表示氟化銨、DMAC表 示Ν,Ν·二曱基乙醯胺、DGBE表示二乙二醇單丁醚、DMSO 表示二曱亞楓、DGME表示二乙二醇單甲醚、MDP表示亞 曱基二膦酸、DEEA表示Ν,Ν-二乙基乙醇胺、DMAC表示 Ν,Ν-二甲基乙醯胺、PGME表示丙二醇單甲醚、PGBE表 示丙二醇單丁醚、ΜΕΑ表示單乙醇胺、ΒΤΑ表示苯并三唑 之意。 30 314857(修正本) 1235892 【LS |比較例3 1 τ- Ο § CO 〇 〇 LO 〇〇 | oo I X X |比較例2 I ▼ 〇 § CO 〇 卜 〇 LO CO X X 〇 實施例4 1 LO 〇 § CO 〇 r- 〇 LO CO L 〇〇I 〇 ο 實施例8 | f— 〇 § τ~ ο ιο 卜*· 〇 〇 〇 實施例3 τ— 〇 § CO 〇 卜 〇 LO I __〇〇 I 〇 〇 實施例7 〇 § ο co Ο LO 卜· 〇 〇 Ο |實施例2 | Ύ— 〇 § 〇 〇 LO CO 〇 〇 ο 實施例6 τ~ 〇 § ΙΟ ο LO Ο LO 卜·· I —..…Q〇 I 〇 〇 實施例1 〇 § CO 〇 Γ-* 〇 LO to 〇 〇 〇 I實施例3 | ο g CO ο 卜 Ο ΙΟ 卜· 〇 〇ΓΊ 〇 〇 I比較例1| 〇 〇 § CO 〇 r- 〇 LO C〇 X 〇 〇 |實施例5 | τ— ο § ο LO 卜·· L〇〇—I 〇 〇 Α成分:NH4F (質量%) DMAC+DGBE (質量 %) i DMAG混合質量比 DGBE混合質量比 工 a ArF用抗蝕膜去除性 C LJ膜耐腐蝕性 低k値耐腐蝕性 Α成分:NH4F (質量%) DMAG+DGBE (質量 %) DMAG混合質量比 DGBE混合質量比I 工 a ArF用抗蝕膜去除性 C U膜耐腐蝕性 低k値膜耐腐蝕性 5 <R £ 液 洗 清 用 除 去 膜 姓 抗 之 中 8 例 施 實 至 IX 例 施 實 由 31 314857(修正本) 1235892 含有A成分、B1成分、C成分以及D成分之全部成分, 而其pH在4至8之範圍内,因此,ArF用抗蝕膜去除性、 Cu膜耐腐蝕性以及低k值膜耐腐蝕性均大。相對於此,由 於比較例1不含A成分,因此,ArF用抗蝕膜去除性變小。 由於比較例2之pH較4為小,因此,ArF用抗姓膜去除 性及Cu膜耐腐蚀性便降低。由於比較例3之pH較8為大, 因此,Cu膜耐腐蝕性及低k值膜耐腐蝕性便降低。 又,從實施例3及實施例5至實施例8可知,b 1成分 中之二乙二醇單丁醚含量愈多者,愈能去除多含丙稀酸樹 脂的ArF用抗姓膜及其殘渣物者。 32 3M857(修正本) 1235892 【cvls
1比較例6 1 T— 〇 § 卜 ο CO ο in od X X X 1比較例5 1 τ- Ο § 卜 ο CO ο LO CO 〇〇 X 〇 實施例12 i in ο § 卜 ο CO ο 〇 卜·· 1 oo 〇 〇 實施例16 r— 〇 § ο r— to CD 〇 〇 〇 實施例11 | τ— ο § r*^ Ο CO Ο LO 1 oo Ο 〇 實施例15 | ο § CO ο 〇 LO CO oo 〇 〇 實施例10 ▼— ο § 卜 ο CO ο LO cd L〇〇 J Ο 〇 實施例14 r~ ο § ur> Ο LO Ο LO CQ L oo I 〇 〇 |實施例9 ! ο § 卜 ο CO ο in LO* 〇 〇 實施例10 τ— ο § r- ο CO O’ LO cd l__ . 〇〇 _ I 〇 〇 |比較例4 | ο ο § 1 ο CO ο 〇 r-· X 〇 〇 實施例13 ο § τ— o LO cd L _.〇〇Π 〇 〇 Α成分:NH4F (質量%) DMAG+DGBE (質量 %) DMAC混合質量比 i DGBE混合質量比 1_ 工 a KrF用抗蝕膜去除性 C L1膜耐腐蝕性 低k値耐腐蝕性 Α成分·· NH4F (質董%) DMAC+DGBE (質量 %) DMAC混合質量比 DGBE混合質量比 工 a KrF用抗蝕膜去除性 C U膜耐腐蝕性 低k値膜耐腐蝕性 S S <R 33 3]4857(修正本) 1235892 實施例9至實施例1 6中之抗蝕膜去除用清洗液,由於 含有A成份、成分、C成分以及D成分之全部成分, 而其pH在4至8之範圍内,因此,KrF用抗蝕膜去除性、 Cu膜耐腐蝕性以及低k值膜耐蝕性均大。相對於此,由於 比較例4不含A成分,因此,KrF用抗蝕膜去除性變小。 由於比較例5之較4為小,因此,Cu膜耐腐钱性便降 低。由於比較例6之PH較8為大,因此,KrF用抗蝕膜 去除性、Cu膜耐腐蝕性以及低k值膜耐腐蝕性均降低。 又,從實施例1 0及實施例丨3至實施例丨6可知,B i 成分中之N,N-二甲基乙酿胺含量愈多者,愈能去除多含笨 西分樹脂的KrF用抗姓膜及其殘渣物者。 3]4857(修正本) 34 1235892
1比較例9 1 〇 § CO o 卜 ο LO CO 〇 X X 比較例8 ί T— 〇 § CO o r- ο LO CO 〇 X 〇 實施例21 LO 〇 § CO o 卜 ο LO CJD 〇〇 〇 〇 實施例20 , 〇 g 卜 o CO ο LO 卜· o 〇 〇 實施例19 ο g CO o 卜 ο to 〇 Ο 〇 實施例18 r— ο § CO o 卜 ο LO CJO o 〇 〇 實施例17 r— ο § CO o 卜 ο LO LO 〇 〇 〇 比較例7 ο ο § CO o 卜 d to CO X Ο 〇 Α成分·· ΝΗ^(質董。/〇) DMAC+DGBE (質量 %) DMAC混合質量比 DGBE混合質量比 I a 蝕刻殘渣物 驾’ 產 m 3 〇 低k値膜耐腐蝕性 S <R 35 3M857(修正本) 1235892 實施例1 7至實施例2 1中之抗蝕膜去除用清洗液,由 於含有A成分、b 1成分、C成分以及D成分之全部成分, 而其PH在4至8之範圍内,因此,蝕刻殘渣物去除性、
Cu膜耐腐蝕性以及低k值膜耐腐蝕性均大。本蝕刻殘逢物 中’雖未含有上述抗蝕膜及抗蝕膜殘渣物,惟由於多含有 源自蝕刻氣體的碳殘渣,因此,可適用本發明之抗蝕膜去 除用清洗液。 相對於此,由於比較例7中未含有A成分,因此,蝕 刻殘逢物去除性變小。由於比較例8《#較4為小,因 此,CU膜耐腐蝕性便降低。由於比較例9之PH較8為大, 因此’ Cu膜耐腐㈣及低k值膜耐腐錄便降低’ 3]4857(修正本) 36 1235892
【寸S τ— ο § LO 〇 LO 〇 1 LO r— LO 卜· o o 〇 Ο m m w τ— ο § CO o 卜 d 1 LO LO o o o 〇 琢 m Μ Τ Ο g LO 〇 LO o LO T^9 i LO 〇 〇 o 〇 U ^— ο § CO O’ Γ- o LO 1 LO r-· 〇 〇 〇 〇 ? S LL· X ζ <R < ? Djlil g UJ § Q + o _ _ u 〇 M D_ U <!〇 ΨΜ LU CO CD u 鴆 氍 κ) |i| a 繼 m ii 稍 工 a m' 遄 :跽 LL· έΗ w. 鶴 D Ο Μ m is i ^ <R m ^ r (R LU链 實施例22至實施例25中之抗蝕膜去除用清洗液,由 於含有A成分、B1成分、C成分以及E1成分之全部成分, 而其pH在4至8之範圍,因此,ArF用抗蝕膜去除性、 Cu膜耐腐蝕性以及低k值膜耐腐蝕性均大。又,與未含有 E 1成分的實施例3、實施例6相比較時,雖然表中之符號 37 314857(修正本) 1235892 同為〇 於該改 渣物去 性亦可 惟可確認低k值膜耐腐蝕性更能改善的傾向。對 ϋ傾向’不僅應證於對ArF用抗#膜及其抗飯膜殘 除性’並且對KrF用抗蝕膜及其抗蝕膜殘渣物去除 見證到。 38 314857(修正本) 1235892 【Los
比較例12 〇 〇 CO Ο 1 〇 LO r- LO CO* o X X 覽施例35 〇 S CO ο 卜 ο ο r~ r- O <JD Γ 〇〇 〇 00 比較例11 V— 〇 〇 CO Ο r- 〇 1 LO ^r— 〇 X οο 實施例Μ Υ— 〇 § co ο r- Ο LO CO 〇 〇〇 Ο οο 實施例29 〇 〇 CO ο 〇 CJD uo 〇 cxi L 〇〇」 Ο Γ〇〇^ 實施例33 Τ"— 〇 ο ο Υ— ο ο LO CO 〇 CD 〇 〇 Γ 00 I 實施例28 〇 〇 CO ο 〇 to LO LO l—oo 1 Ο 1 1 實施例32 τ~ 〇 ο Γ- ο CO ο L〇 ro o <x> 〇〇 I 〇 ΟΟ ! 實施例27 一 » 〇 〇 CO ο 1 〇 to CO 〇 CO L—⑽ _ .1 〇 L〇Q—…」 實施例31 〇 ο Γ— LO ο LO Ο LO CO o <·〇· oo ο ΟΟ 實施例26 V— Q· 〇 ro Ο Γ— 〇· LO to r~ o rp 〇 〇 οο 實施例27 V— 〇 ο Γ^· CO Ο r- Ο lO c〇 o CD 00 ο ο 〇 比較例10 〇 〇 〇 CO Ο 1— 〇 ΙΓ> ro 〇 cd X Ο 〇〇Ί 實施例30 •r— ο ο Ο Ο Ο LO cr> o cd oo ο οο Α成分:N&F (質量%) DMS0+DGME (質量 %) DMSO混合質量比 | DGME混合質量比 1成分:MDP (質量%) E成分fDEEA (質量%〉 I a | ArF用抗蝕膜去除性 C υ膜耐腐蝕性 低k値膜耐腐蝕性 Α成分:_/(質量%); DMS0+DGME (質量%) DMS0混合質量比 DGME混合質量比 C 1成分:MDP (質量%) I | E成分:DEEA (質跫%) ! X Q ArF用抗蝕膜去除性 C U膜耐腐蝕性 低k値耐腐蝕性 CD τ- Ο CD <R 39 314857(修正本) 1235892 實施例26至丧 於含有A成分貝施例35中之抗蝕膜去除用清洗液,由 部成分,而心:成分、C1成分、D成分以及£成分之全 膜去除性、Cur在2至8之範圍内’因此’ArF用抗姓 ^ 果耐腐蝕性以及低k值膜耐腐蝕性均大。相 對於此,由於卜卜私 备 、权例1〇不含有Α成分,因此,ArF用抗 敍膜去除性變,丨 又4 °由於比較例11之pH較2為小,因此, υ膜耐腐餘性便降低。由於比較例12之pH較8為大, 因此’ CU膜耐腐蝕性及低k值膜耐腐蝕性便降低。 又’從實施例27及實施例30至實施例33可知,B成 分中之二乙二醇單曱醚含量愈多者,愈能去除多含丙烯酸 樹月曰的ArF用抗钱膜及其殘渣物者。 40 314857(修正本) 1235892 【9搬〕
I ·比較例15 〇 〇 卜 Ο co ο LO r- LO CO· X X X 實施例45 r— 〇 g ο co O’ O τ— 卜 ο cd r〇〇~i 〇 oo 比較例14 r— 〇 〇 r- 卜 Ο CQ Ο 卜 r~ LO >- r〇Q„j X 丨一οο I 實施例44 y~ ο g 卜 ο CO o LO Γ〇 Ο cd 〇〇 〇 o 實施例39 ιο 〇· ο Γ-' Ο CO Ο CO LO o cd l 〇〇. I Ο I 〇〇 I 實施例43 r—. ο ο ο r— o o LO CO Ο CO L〇〇 〇 oo 1 實施例38 〇 ο r- 卜 ο CO Ο LO LO LO 卜》 o 〇 L—.〇〇」 實施例37 ο ο ι— Ο ro o LO ro ο CO 〇〇 〇 〇〇i 實施例37 〇 ο Γ'- Γ- ο CO o’ LO CO o <JD L00」 〇 L„ 〇〇 _J |實施例42 | ο Ο ιη Ο LO o LO CO Ο cd 〇〇 〇 oo 実施例36 一 〇 ο 卜 r- ο CO o LO to r~ o CO Ο m 實施例41 τ— ο Ο Γ〇 Ο r- 〇 m ro ο CO 〇〇 Ο 〇〇 比較例13 〇 〇 ο Γ— Ο CO o L〇 o iJD X 〇 l·.—〇〇」 實施例40. ο ο ο ο 〇 r~ m CO Ο cd 〇 Ο 〇〇 Α成分:ΝΗ/(質量%〉 DMSODGME (質量 %〉 DMS0混合質量比 DGME混合質量比 I成分:MDP (質量%) E成分::DEEA (質量%) I a KrF用抗蝕膜去除性 C υ膜耐腐蝕性 低k値膜耐腐蝕性 Α成分:NH<F (質量%) DMS0+DGME (質量 %) DMS0混合質量比 DGME混合質董比1 C 1成分:MDP (質量%) E成分:0[[八(質量%) X Q KrF用抗蝕膜去除性 C Li膜耐腐蝕性 :' ι ' ' .......i i 低k値膜耐腐蝕性 CD 链: 厂 Ο CQ ;R 41 3M857(修正本) 1235892 貫施例3 6至實施例4 5中之抗名虫膜去除用清洗液,由 於含有A成分、B成分、C1成分、D成分以及E成分之全 部成分,而其pH在2至8之範圍内’因此,KrF用抗|虫 膜去除性、Cii膜耐腐蝕性以及低k值膜耐腐蝕性均大。相 對於此,由於比較例13未含有A成分,因此,Krp用抗 蝕膜去除性變小。由於比較例14之pH較2為小,因此, Cu膜耐腐姓性便降低。由於比較例15之pH較$為大
Cu膜耐腐蝕性以及低k值膜 因此,KrF用抗姓膜去除性、 耐腐钱性均降低。 40至實施例43可知,B成 愈能去除多含苯酚樹脂的 又’從實施例3 7及實施例 分中之二甲基亞楓含量愈多者, KrF用抗蝕膜及其殘渣物者。 3]4857(修正本) 42 1235892 【卜ffi
比較例T8 yr ο ο r- ΓΟ ο ο LO r- LO CO* 〇 X X 1比較例Π ] Ol Ο CO ο 卜 ο 卜 T 一 LO X X 〇 實施例50 ΙΟ o’ ο CO ο r- ο LO L〇 c6 LO VO L〇Q I 〇 I 〇〇 1 實施例49 r~ Ο ο 卜 ο co ο Ο r丨·— 卜 〇 CO L〇〇 J 〇 1 〇〇 1 實施例48 γ— ο ο Γ— Γ- ο CO ο ir> CO o to· 〇〇 〇 1 〇〇 1 τ— ο ο CO ο ο in 〇〇 o UD L〇〇丨 〇 1 〇〇 1 實施例46 τ—^ ο ο CO ο r- ο LO LO o CO op…一 〇 1 〇〇 1 |比較例16 i ο ο ο Γ— CO ο 卜 ο 1-0 CO o tjd X Ο 1 〇〇 1 Α成分:NH<F(質量%) | DMS0+DGME (質量%) DMS0混合質量比 | DGME混合質量比 .C 1成分:MDP (質量%) E成分:’DEEA(質量%) X a Μ C U膜耐腐蝕性 低k値膜耐腐蝕性 CQ 43 3 ]4857(修正本) 1235892 汽苑例46至實施例5〇中之抗蝕膜去除用清 於含右 ^ :、A成分、B成分、C1成分、D成分以及E成分之全 成刀,而其pH在2至8之範圍内,因此,蝕刻殘渣物 、“ 、Cu膜耐腐蝕性以及低k值耐腐蝕性均大。本姓 殘 >查物中 s奋土 r 雖未含有上述抗蝕膜及抗蝕膜殘渣物,惟由於 夕s有源自蝕刻氣體的碳殘渣,因此,可適用本發明之抗 钱膜去除用清洗液。 相對於此,由於比較例丨6中未含有A成分,因此, 飯刻殘渣物去除性變小。由於比較例1 7之pH較2為小, 因此’蝕刻殘渣物去除性及Cu膜耐腐蝕性便降低。由於 比較例18之pH較8為大,因此,Cu膜耐腐蝕性及低k 值膜耐腐蝕性便降低。 44 3]4857(修正本) 1235892 〔8術〕 |比較例20 1 〇 〇 CO ο Γ Ο LO DEEEA 7 LO οό 〇〇 X .......〇〇' X X 比較例19 Y— 〇 〇 ΓΟ ο ο r- DEEA 1 LO f _ o ΟΟ ΟΟ X I〇〇 實施例56 〇 〇 CO ο r- ο LO -< LO LU S CVJ Ο CJO I 〇〇 I Γ οο Γ〇〇.......Ί 〇 Γ 〇〇 I 實施例55 〇 ο 1 CO ο Γ— Ο UD DEEA 3 Ο to 〇 o ο ο L〇〇 _ι 〇 I 00 I |實施例54 | Τ Ο ο ΓΟ ο 〇 LO DEEA 3 Ο CJO* L—qo] L〇〇__ I L盖丨 〇 I 〇〇 I 實施例53 〇 ο r*- CO ο Ο LO DEEA 3 Ο CO lq〇... 〇〇—_ οο 〇 I 〇〇 ] 實施152 V—— 〇 Ο CO ο j^ ο LO DEEA 3 Q CO _〇〇_ 〇〇 L〇Q_J 〇 I 〇〇 I 實施例51 τ-~ 〇 Ο r- 〇〇 ο r^ Ο LO DEEA 3 o CJD L-QP-J Loo......... L〇Q_ 〇 I 〇〇 I Α成分:NH<F (質量%) |β成分(質董%) DMS0混合質置比 DMAC混合質量比 DGME混合質量比 DGBE混合質量比 PGME混合質量比 PGBE混合質量比 C 1成分:MDP (質量%) E成分:化合物名 (質量%) X a ArF闲抗蝕膜去除性 KrF闲抗蝕膜去除性 刻殘渣物去除性 C U膜耐腐蝕性 低k値膜耐腐蝕性 m链次 45 314857(修正本) 1235892 實施例5 1至實施例5 6中之抗蝕膜去除用清洗液,由 於含有A成分、B成分、C1成分、D成分以及£成分之全 部成分,而其pH在…之範圍内,因此,⑽用抗二 朕去除性、KrF用抗蝕膜去除性、#岁丨 膜耐腐H u w士 1虫刻殘清物去除性、Cu 、生以及低k值膜耐腐蝕性始士 _ 係在表示以與B成分之含硭 :大。又,前述實施例 或胺類(例如,ν,ν-二甲美;?合物(例如’二甲基亞楓) 如,二乙二醇單曱醚、二:_ )與多元醇或其衍生物(例 醇單丁醚等)之混合物為佳者。 314857(修正本) 46 1235892 【6鄕】 比較例23 1— 〇 〇 ΓΟ 〇 卜 〇 L〇 < »— T— CD LO 〇〇· 〇 X 〇 X’ X |比較例22 | 〇 〇 〇 〇 一 •C LO 〇 〇 〇 X X 〇 〇 |實施例61 | 〇 〇 ro 〇 〇 LO CO 胺基乙酸 1 〇 <〇· 〇 Ο 〇 〇 〇 〇 〇 〇 〇 〇 |實施例60 r— 〇 〇 CT) 〇 1 〇 to CO 安息香酸 1 〇 CD 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 實施例59 〇 〇 ΓΟ 〇 卜 〇 m CO 草酸1 〇 cd 〇 ο 〇 〇 〇 〇 〇 〇 〇 〇 l·實施例58 r— 〇 〇 CO ο 〇 LO CO QQ ο CO ο 〇 〇 〇 〇 〇 〇 〇 〇 〇 實施例57 r— 〇 〇 CO ο 〇 LO LO CD Ο CO 〇 〇 〇 〇 〇 〇 〇 〇 〇 比較例2彳 〇 〇 〇 CO ο r^ Ο LO ro CO ο CO X X X 〇 〇 〇 〇 A成分:NH<F(質量。/〇) DMS0+DGME (質量 %) DMSO混合質量比 DGME混合質董比 .C 1成分:MDP (質董%) E成分: DEEA(質量%) F成分:化合物名 (質量%) 工 Q ArF用抗蝕膜去除性 KrF用抗蝕fl莫去除性 β出刻殘渣物去除性 C U膜耐腐蝕性 低kM膜耐腐蝕性 〇□链 47 3 ]4857(修正本) 1235892 實施例57至實施例61中之抗蝕膜去除用清洗液,由 於含有A成分、B成分、C1成分、D成分、E成分以及f 成分之全部成分,而其pH在2至8之範圍内,因此,Αβ 用抗蝕膜去除性、KrF用抗蝕膜去除性、蝕刻殘渣物去除 性、CU膜耐腐蝕性以及低k值膜耐蝕性均大。本蝕刻殘渣 物中’由於未含有上述抗蝕膜及抗蝕膜殘渣物,又由於多 含有源自蝕刻氣體的碳殘渣,因此,可適用本發明之抗2 膜去除用清洗液。 相對於此,由於比較例21中未含有A成分,因此
ArF用抗蝕膜去除性、KrF用抗蝕膜去除性以及蝕刻殘渣 物去除性變小。由於比較例22之pH較2為小,因此,蝕 刻殘渣物去除性及Cu膜耐腐蝕性便降低。由於比較例U 之pH較8為大,因此,KrF用抗蝕膜去除性、Cu膜耐腐 Ί虫性以及低]值膜财腐蚀性便降低。 解 限 所 以上,係就本發明所作之詳細說明,惟應可明白理 該說明僅供為例示之用,故本發明並不因該實施例所 定,而發明之精神與範圍,僅由所添附之巾請專利範圍 限定。 [圖式簡單說明] 第1A圖至f 1K® ’係使用本發明之清洗液的銅佈線 過程之另一實施形態之各步驟中的剖面圖。 第2A圖至第21圖’係使用本發明之清洗液的銅佈線 過程之另一貝施形怨之各步驟中的剖面圖。 第3A圖至f 3K圖,係使用以往之清洗液的代表性銅 314857(修正本) 48 1235892 佈線 1 過程之各步驟中 第一銅佈線 的剖面圖。 2 第一絕緣膜 3 氮化矽膜 4 低k值膜 5 抗1虫膜 6 抗#膜殘渣物 7 變質層 8 蝕刻殘渣物 10 第二銅佈線 11 間隔 21 介層洞 22 渠溝 49 314857(修正本)
Claims (1)
1235892 第921 1 8959號專利申請案 申請專利範圍修正本 1 . 一種抗I虫膜去除用、.主.先液^ (94年4月18曰) 含金屬的鹼所生成之臨(八&八1 ^ ^ ^鼠1與不 •分)、膦酸(C1成分)、水⑴成八、 ^(B成 … 欣刀)水(D成分)以及銨鹽(Ει 而上述水溶·性有機溶劑(B成分 物艿夕-^^ 3啕1^月女犬員、含硫化合 物以及夕兀醇或其衍生物之至 為4至8-者。 裡且心隹子濃度pH 2·如申請專利範圍第!項之抗姓膜去除用清洗液, Π:::卿:成分):係—醇或其街生 ::。月專利乾圍第;!項之抗蝕膜去除用清洗液,其 氫氟酸與不含金屬的鹼所生成 用之X人八ρ 风之ι(Α成分)於形成時所 用之不3金屬的鹼,係選自有機胺化合物、氨 級四級銨鹼而成之群中之至少】種鹼。 民 (^申請專利範圍第!項之抗钱膜去除用清洗液, 氫氟酸與不含金屬的驗所生成之鹽(Α成分)之含有’ 0 · 0 1質量%至1質量%。 …為 5·:種抗㈣去除用清洗液,其特徵為:含有氫I酸虚不 3金屬的驗所生成之鹽(Α成分)、水溶性有機溶 分)、膦酸(α成分)、水(D成分)以及不含金屬的驗(Ε 成为),且氫離子濃度pH為2至8者。 6·如申4專利乾圍第5項之抗钱膜去除用清洗液,其中, 3M857修正木 l235892 水溶性有機溶劑(B成分) 其衍生物之混合物 7·:種抗㈣去除用清洗液,其特徵為··含有氫氟 ;金屬的驗所生成之鹽(A成分)、水溶性有機溶劑(二 膦酸(C1成分)、水(D成分)、不含金屬的驗二成 ^)。以及Cu抗姓劑(F.成分),且氫離子濃度_為2至8 如申凊專利範圍第7頂$ y “ 含有選V二=二除^ 酸類以及胺基羧酸矢羧U、方香族羧 9· 1半導體裝置之=Γ::至少1種類者。 上進行以銅為主成/Π:屬=徵為:在半導體基板 面形成絕緣膜的膜的步驟、及於其上 驟、及以該抗兹膜作為二二其上面形成抗 *設置洞或渠溝的牛:貫施乾姓刻以在該絕緣膜 或加敎處理以本/ 及藉由使用氣體的電焚處理 餘膜殘膜的步驟之後,將所殘存的抗 主I 用申δ月專利範圍第5項之抗蝕膜去除用 β冼液加以去除者。 、玄丨示用 1 〇·如申請專利範圍第9項之 , 刻步驟中,作為乾姓刻之^ 在前述乾蝕 大型準分子抗j虫膜/ ^ W钱膜,係使用化學放 L種半導體裝置之繫 上進行以銅為主成二二Γ 為:在半導體基板 面形成絕缘^ 刀、孟屬肤之成膜的步驟、及於其上 成、痛的步驟、及再於其上面形成抗姓膜的步 3M857修正本 1235892 驟、以及以該抗姓膜作為遮罩而薈 ^ φ ^ 貝、&乾餘刻以在該絕緣 膜中設置洞或渠溝的步驟之後,將 ^ 歹乂存的抗姓膜及在 乾姓刻犄所產生的抗蝕膜殘渣物, ,s ^ ^ 使用申請專利範圍第 12 5項之杬蝕膜去除用清洗液加以去除者。 一種半導體裝置之製造方法,其 卜4 〜* 、4寸试為:在半導體基板 品r』、 腰之成朕的步驟、及於豆上 面形成絕緣膜的步驟、以及藉 ’ 抓罟糾、去# 由乾餘刻而在該絕緣膜中 6又置到達該金屬膜之洞 、〒 生的姓刻殘洁物,使用後將在乾姓刻時所產 除用、、主、#申M專利乾圍第5項之抗蝕膜去 除用π洗液加以去除者。 联云 3]4857修正本
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-
2003
- 2003-06-19 JP JP2003174816A patent/JP4443864B2/ja not_active Expired - Fee Related
- 2003-07-11 TW TW092118959A patent/TWI235892B/zh not_active IP Right Cessation
- 2003-07-11 US US10/617,128 patent/US7250391B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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US7250391B2 (en) | 2007-07-31 |
TW200406650A (en) | 2004-05-01 |
JP2004094203A (ja) | 2004-03-25 |
US20040106531A1 (en) | 2004-06-03 |
JP4443864B2 (ja) | 2010-03-31 |
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