TW201718841A - 半導體元件之洗淨用液體組成物、半導體元件之洗淨方法及半導體元件之製造方法 - Google Patents
半導體元件之洗淨用液體組成物、半導體元件之洗淨方法及半導體元件之製造方法 Download PDFInfo
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- TW201718841A TW201718841A TW105129192A TW105129192A TW201718841A TW 201718841 A TW201718841 A TW 201718841A TW 105129192 A TW105129192 A TW 105129192A TW 105129192 A TW105129192 A TW 105129192A TW 201718841 A TW201718841 A TW 201718841A
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- cobalt
- copper
- mass
- cleaning
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Classifications
-
- 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
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
- C11D3/048—Nitrates or nitrites
-
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Abstract
[課題] 提供於半導體元件製造中,抑制銅或銅合金、或鈷或鈷合金之損傷且同時將氮化鈦硬遮罩予以去除之洗淨用液體組成物、使用該洗淨用液體組成物之洗淨方法、及半導體元件之製造方法。 [解決方法] 本發明之於半導體元件之製造中所使用之洗淨用液體組成物含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水。
Description
本發明係關於半導體積體電路之製造步驟中所使用之半導體元件之洗淨用液體組成物、使用該洗淨用液體組成物之半導體元件之洗淨方法及半導體元件之製造方法。
於經高積體化之半導體元件的製造中,一般而言採用一系列之步驟:通常於矽晶圓等元件上,形成了成為導電用佈線材料之金屬膜等導電薄膜、或目的為使導電薄膜之間絕緣之層間絕緣膜之後,於其表面均勻地塗布光阻設置感光層,對其實施選擇性的曝光及顯影處理而製成期望之光阻圖案。接著藉由將該光阻圖案作為遮罩,對於層間絕緣膜實施乾式蝕刻處理而於該薄膜形成期望之圖案。然後,將因為光阻圖案及乾式蝕刻處理而產生之殘渣(以下稱為「乾式蝕刻殘渣」。)藉由以氧電漿之灰化或洗淨液等完全地予以去除。
近年來,隨著設計規則之微細化之進展,信號傳輸延遲會支配高速演算處理之極限。因此,層間絕緣膜逐漸從矽氧化膜改變為低介電係數層間絕緣膜(比介電係數小於3之膜。以下稱為「低介電係數層間絕緣膜」)。此外,形成0.2μm以下之圖案時,就膜厚1μm之光阻而言會有其圖案之縱橫比(aspect ratio)(將光阻膜厚除以光阻線寬之比)過大,圖案崩塌等問題產生。為了解決上述情事,有人使用:於想實際形成之圖案與光阻膜之間插入鈦(Ti)系或矽(Si)系之膜(以下稱為「硬遮罩」。),先將光阻圖案藉由乾式蝕刻轉移至硬遮罩並去除光阻之後,將該硬遮罩作為蝕刻遮罩,藉由乾式蝕刻將圖案轉移於想實際形成之膜的硬遮罩法。該方法因為可更換將硬遮罩進行蝕刻時之氣體、及將實際想形成之膜進行蝕刻時之氣體,且可於將硬遮罩進行蝕刻時取得光阻與硬遮罩之選擇比,將實際之膜進行蝕刻時能選擇確保硬遮罩與實際進行蝕刻之膜之選擇比的氣體,故有盡可能地減少對於實際之膜造成之損傷,可形成圖案之優點。
另外,因為設計規則之微細化之進展致使金屬佈線之電流密度增大,有對於在金屬佈線材料流通電流時金屬佈線材料會移動而於金屬佈線造成孔洞的電遷徙(electromigration)之對策的強大需求。作為該對策,有人提出於銅佈線上形成鈷或鈷合金作為帽蓋金屬之方法、或如專利文獻1所記載,使用鈷或鈷合金作為金屬佈線材料之方法。因此以往之銅佈線以外,鈷或鈷合金也為抑制損傷之對象。
因此,於半導體元件製造中,有抑制銅或銅合金、及鈷或鈷合金之損傷且同時將硬遮罩予以去除之方法的需求。對此,有人提出各式各樣之技術。
於專利文獻2,提出藉由含有過氧化氫、胺基聚亞甲基膦酸類、氫氧化鉀及水之洗淨用組成物的洗淨方法。
於專利文獻3,提出一種蝕刻用組成物,於水性溶劑中含有選自於由氨、具有胺基之化合物及具有含氮原子之環狀結構之化合物構成之群組中之至少1種及過氧化氫,且pH超過8.5。
於專利文獻4,提出一種洗淨用組成物,含有: 選自於由二甲基哌啶酮、碸類及環丁碸類等構成之群組中之極性有機溶劑; 選自於由四烷基氫氧化銨、氫氧化膽鹼、氫氧化鈉及氫氧化鉀等構成之群組中之鹼; 水; 及選自於反式-1,2-環己烷二胺四乙酸、乙烷-1-羥基-1,1-二膦酸鹽及乙二胺四(亞甲基膦酸)等構成之群組中之螯合化或金屬錯合物化劑。
於專利文獻5,提出一種半導體元件之洗淨方法,藉由以70℃以上之硫酸水溶液洗淨,將氮化鈦(TiN)膜予以去除且不蝕刻鈷(Co)化矽。
於專利文獻6,提出一種蝕刻液,含有六氟矽酸化合物與氧化劑。
於專利文獻7,提出一種蝕刻液,含有選自於鹽酸等鹵素化合物、氧化劑、含氮雜環芳香族化合物及四級鎓(Onium)化合物等之金屬層抗蝕劑。
於專利文獻8,提出一種蝕刻方法,採用含有氟酸等氟化合物及氧化劑之蝕刻液而將含有氮化鈦(TiN)之層予以去除且不去除過渡金屬層。
於專利文獻9,提出一種蝕刻方法,採用含有有機鎓化合物及氧化劑之蝕刻液,將含有氮化鈦(TiN)之層予以去除且不去除過渡金屬層。
於專利文獻10,提出一種蝕刻方法,藉由使用含有選自於由氫氟酸之金屬鹽及氫氟酸之銨鹽構成之群組中之特定之氟化合物及氧化劑且pH1以上的蝕刻液,相對於含有過渡金屬之層優先地去除含有氮化鈦(TiN)之層。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2013-187350號公報 [專利文獻2]國際公開第2008/114616號 [專利文獻3]日本特開2010-232486號公報 [專利文獻4]日本特表2005-529363號公報 [專利文獻5]日本特開2003-234307號公報 [專利文獻6]日本特開2014-84489號公報 [專利文獻7]日本特開2014-93407號公報 [專利文獻8]日本特開2014-99498號公報 [專利文獻9]日本特開2014-99559號公報 [專利文獻10]日本特開2014-146623號公報
[發明所欲解決之課題] 然而,近年來,設計規則之微細化進一步地進展,對於抑制對金屬佈線材料之損傷的要求也變得更嚴格。對於如此要求,本案發明者深入研究之結果,得知於專利文獻2~10中記載之組成物或方法有如下述之各種技術上之課題及問題點。 專利文獻2中記載之洗淨用液體組成物(一種洗淨用組成物,含有過氧化氫、胺基聚亞甲基膦酸類、氫氧化鉀及水),無法充分地抑制銅及鈷之損傷,於本目的中無法使用(參照比較例1)。 專利文獻3中記載之蝕刻用組成物(一種蝕刻用組成物,於水性溶劑中含有選自於由氨、具有胺基之化合物及具有含氮原子之環狀結構之化合物構成之群組中之至少1種及過氧化氫,且pH超過8.5),去除TiN硬遮罩之性能不夠充分,且無法充分地抑制銅之損傷,於本目的中無法使用(參照比較例2)。 專利文獻4中記載之洗淨用組成物(一種洗淨用組成物,含有:選自於由二甲基哌啶酮、碸類及環丁碸類等構成之群組中之極性有機溶劑;選自於由四烷基氫氧化銨、氫氧化膽鹼、氫氧化鈉及氫氧化鉀等構成之群組中之鹼;水;及選自於由反式-1,2-環己烷二胺四乙酸、乙烷-1-羥基-1,1-二膦酸鹽及乙二胺四(亞甲基膦酸) 等構成之群組中之螯合化或金屬錯合物化劑。),無法充分地抑制銅及鈷之損傷,於本目的中無法使用(參照比較例3)。 專利文獻5中記載之硫酸水溶液(70℃以上之硫酸水溶液),去除TiN硬遮罩之性能並不夠充分,且無法充分地抑制銅及鈷之損傷,於本目的中無法使用(參照比較例4)。 專利文獻6中記載之蝕刻液(含有六氟矽酸及氧化劑之蝕刻液),去除TiN硬遮罩之性能並不充分,且無法充分地抑制銅及鈷之損傷,於本目的中無法使用(參照比較例5)。 專利文獻7中記載之蝕刻液(一種蝕刻液,含有選自於鹽酸等鹵素化合物、氧化劑、含氮雜環芳香族化合物及四級鎓化合物等之金屬層抗蝕劑。),去除TiN硬遮罩之性能並不充分,且無法充分地抑制銅及鈷之損傷,於本目的無法使用。(參照比較例6)。 專利文獻8中記載之蝕刻方法(使用含有氟酸等氟化合物及氧化劑之蝕刻液。),無法充分地抑制銅及鈷之損傷,於本目的無法使用(參照比較例7)。 專利文獻9中記載之蝕刻方法(使用含有有機鎓化合物及氧化劑之蝕刻液),無法充分地抑制銅及鈷之損傷,於本目的無法使用(參照比較例8)。 專利文獻10中記載之蝕刻液(一種蝕刻液,含有選自於由氫氟酸之金屬鹽及氫氟酸之銨鹽構成之群組中之特定之氟化合物及氧化劑,且為pH1以上),去除TiN硬遮罩之性能並不充分,於本目的無法使用(參照比較例9)。
本發明之目的係提供於半導體元件製造中,抑制銅或銅合金、或鈷或鈷合金之損傷,且同時將TiN硬遮罩予以去除之洗淨用液體組成物、使用該洗淨用液體組成物之洗淨方法及使用該方法而獲得之半導體元件。 [解決課題之手段]
本發明係提供解決上述課題之方法。本發明如同下述。 1.一種洗淨用液體組成物,其抑制選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除; 含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水。 2.如第1項之洗淨用液體組成物,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。 3.如第1項之洗淨用液體組成物,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。 4.如第1項之洗淨用液體組成物,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。 5.如第1項之洗淨用液體組成物,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。 6.一種洗淨方法,係使用洗淨用液體組成物,抑制含有鈷元素之材料及含有銅元素之材料中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除;該洗淨用液體組成物係含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水。也就是說為一種洗淨方法,係抑制具有選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之至少1種以上之材料與氮化鈦硬遮罩之半導體元件中的選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除; 包括以下步驟: 使該半導體元件接觸含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水之洗淨用液體組成物。 7.如第6項之洗淨方法,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。 8.如第6項之洗淨方法,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。 9.如第6項之洗淨方法,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。 10.如第6項之洗淨方法,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。 11.一種半導體元件之製造方法,係製造具有選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之半導體元件之方法, 包括以下步驟: 使用含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水之洗淨用液體組成物,來抑制選自於由該含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除。 12.如第11項之半導體元件之製造方法,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。 13.如第11項之半導體元件之製造方法,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。 14.如第11項之半導體元件之製造方法,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。 15.如第11項之半導體元件之製造方法,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。 [發明之效果]
藉由使用本發明之洗淨用液體組成物及洗淨方法,於半導體元件之製造步驟中,可抑制金屬佈線及由鈷(Co)構成之帽蓋金屬的損傷且同時將被處理物表面之由氮化鈦(TiN)構成之硬遮罩予以去除,可以良好之產率來製造高精度、高品質之半導體元件。
本發明之洗淨用液體組成物(以下有時簡稱為「洗淨液」)含有過氧化氫、氫氧化鉀、胺基聚亞甲基膦酸、具有13族元素之化合物、及水。
本發明中用於去除TiN硬遮罩之半導體元件之洗淨用液體組成物因為係於製造半導體元件之步驟中所使用者,必須抑制金屬佈線之損傷。
本發明中使用之過氧化氫的濃度範圍為1~30質量%,宜為3~25質量%、尤其宜為10~25質量%。若為上述範圍內可有效地去除TiN硬遮罩且抑制金屬佈線之損傷。
本發明中使用之氫氧化鉀的濃度範圍為0.01~1質量%,宜為0.05~0.7質量%,尤其宜為0.07~0.5質量%。若為上述範圍內可有效地去除TiN硬遮罩且抑制金屬佈線之損傷。
就本發明中使用之胺基聚亞甲基膦酸之例而言,可舉例如胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、1,2-丙二胺四(亞甲基膦酸)等。此等之胺基聚亞甲基膦酸可單獨摻合或組合2種類以上摻合。
本發明中使用之胺基聚亞甲基膦酸的濃度範圍為0.0001~0.05質量%,宜為0.0003~0.01質量%,尤其宜為0.0005~0.005質量%。若為上述範圍內可有效地抑制金屬佈線之損傷。
就本發明中使用之具有13族元素之化合物之例而言,可舉例如鋁或鎵之硫酸鹽、硝酸鹽、鹽酸鹽或乳酸鹽等,宜為硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁或硝酸鎵。此等具有13族元素之化合物可單獨摻合或組合2種類以上摻合。
本發明中使用之具有13族元素之化合物的濃度範圍為0.00005~0.5質量%,宜為0.0001~0.1質量%,尤其宜為0.01~0.07質量%。若為上述範圍內可有效地抑制金屬佈線之損傷。
於本發明之洗淨用液體組成物,根據期望於不妨害本發明之目的之範圍可摻合以往於半導體元件之洗淨用液體組成物所使用之添加劑。例如,就添加劑而言可添加界面活性劑、消泡劑等。
於本發明之洗淨用液體組成物,根據期望於不妨害本發明之目的之範圍內可摻合唑類。 就唑類而言特別是選自於1-甲基咪唑、1-乙烯咪唑、2-苯基咪唑、2-乙基-4-咪唑、N-苄基-2-甲基咪唑、2-甲基苯并咪唑、吡唑、4-甲基吡唑、3,5-二甲基吡唑、1,2,4-三唑、1H-苯并三唑、5-甲基-1H-苯并三唑、及1H-四唑中之1種以上之唑較為理想,尤其宜為3,5-二甲基吡唑,但並沒有限定為此等。
本發明之洗淨方法係抑制具有選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之材料及氮化鈦硬遮罩之半導體元件中的選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之材料的腐蝕,且同時將氮化鈦硬遮罩予以去除者,包含使上述半導體元件接觸本發明之洗淨用液體組成物之步驟。此處「抑制選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之材料的腐蝕」係指上述材料之蝕刻速率為0.1埃/min(0.01nm/min)以下之含意。 使半導體元件接觸本發明之洗淨用液體組成物之方法沒有特別之限制。例如,可採用將半導體元件浸漬於本發明之洗淨用液體組成物之方法或藉由滴液或噴霧等來跟洗淨用液體組成物接觸之方法等。 使用本發明之洗淨用液體組成物之溫度宜為20~80℃,更宜為25~70℃,尤其宜為40~60℃之範圍,根據蝕刻之條件或使用之半導體基體適當地選擇即可。 本發明之洗淨方法因應需求可併用超音波。 使用本發明之洗淨用液體組成物之時間宜為0.3~30分鐘,更宜為0.5~20分鐘,尤其宜為1~10分鐘之範圍,根據蝕刻之條件或使用之半導體基體適當地選擇即可。 就使用了本發明之洗淨用液體組成物後之沖洗液而言,也可使用如醇之有機溶劑,但僅以水進行沖洗亦有足夠之效果。
圖1係具有阻隔金屬1、金屬佈線2、帽蓋金屬3、阻隔絕緣膜4、低介電係數層間絕緣膜5及硬遮罩6之半導體元件之概略的截面圖,為展示藉由本發明之洗淨用液體組成物所洗淨之半導體元件的一例。此處為於具有阻隔金屬1、金屬佈線2、帽蓋金屬3及低介電係數層間絕緣膜5之基板上,按阻隔絕緣膜4、低介電係數層間絕緣膜5及硬遮罩6之順序進行疊層,形成指定之圖案。
一般而言半導體元件及顯示元件係包含:矽、非晶矽、多晶矽、玻璃等基板材料、 氧化矽、氮化矽、碳化矽及此等之衍生物等絕緣材料、 鉭、氮化鉭、釕、氧化釕等阻隔材料、 銅、銅合金、鈷、鈷合金等佈線材料、 鎵-砷、鎵-磷、銦-磷、銦-鎵-砷、銦-鋁-砷等化合物半導體、 及氧化鉻等氧化物半導體等。
就一般之低介電係數層間絕緣膜而言,使用羥基矽倍半氧烷(hydroxysilsesquioxane)(HSQ)系或甲基矽倍半氧烷(methylsilsesquioxane)(MSQ)系之OCD(商品名,東京應化工業公司製)、碳摻雜氧化矽(carbon doepd silicon oxide)(SiOC)系之Black Diamond(商品名,Applied Materials公司製)、Aurora(商品名,ASM International公司製)、Coral(商品名,Novellus systems公司製)等。低介電係數層間絕緣膜沒有限定為此等。
就一般之阻隔金屬而言,使用鉭、氮化鉭、釕、錳、鎂、鈷及此等之氧化物等。阻隔金屬沒有限定為此等。
就一般之阻隔絕緣膜而言,使用氮化矽、碳化矽、氮化碳化矽等。阻隔絕緣膜沒有限定為此等。
就可適用本發明之硬遮罩而言,使用鈦或氮化鈦等。於本發明中尤其使用氮化鈦。
就可適用本發明之金屬佈線而言,使用銅或銅合金、於銅或銅合金上形成了鈷或鈷合金作為帽蓋金屬者、鈷或鈷合金等。此處之「銅合金」係指以質量基準,含有銅50%以上,宜為60%以上,更宜為70%以上之合金的含意。「鈷合金」係指以質量基準,含有鈷50%以上,宜為60%以上,更宜為70%以上之合金的含意。
於半導體元件之製造步驟之一例中,首先,於具有阻隔金屬、金屬佈線、低介電係數層間絕緣膜、因應需求之帽蓋金屬的基板上,疊層了阻隔絕緣膜、低介電係數層間絕緣膜、硬遮罩及光阻後,對於該光阻施以選擇性的曝光及顯影處理,形成光阻圖案。接著,將該光阻圖案藉由乾式蝕刻轉印於硬遮罩上。之後,去除光阻圖案,將該硬遮罩作為蝕刻遮罩於低介電係數層間絕緣膜及阻隔絕緣膜施以乾式蝕刻。接著,去除硬遮罩而可獲得具有期望之金屬佈線圖案之半導體元件。在以如此方式形成期望之金屬佈線圖案後,除去不再需要之硬遮罩時適用本發明之洗淨用液體組成物。 根據本發明之理想態樣,藉由使用本發明之洗淨用液體組成物洗淨半導體元件,因為可抑制金屬佈線之損傷且同時將氮化鈦硬遮罩予以去除,故可以良好之產率製造高精度、高品質之半導體元件。 [實施例]
接著藉由實施例及比較例更具體地說明本發明。但本發明沒有因為此等之實施例而有任何之限制。
[使用晶圓] 於本實施例中,使用了於矽晶圓上具有氮化鈦層之「附氮化鈦膜之晶圓」(表中以TiN表示。Advantech Co.製。)、於矽晶圓上具有銅層之「附銅膜之晶圓」(表中以Cu表示。Advantech Co.製。)、及於矽晶圓上具有鈷層之「附鈷膜之晶圓」(表中以Co表示。Advantech Co.製。)。
[氮化鈦膜厚測定] 附氮化鈦膜之晶圓之氮化鈦膜厚係使用SII Nanotechnology公司製X射線螢光裝置SEA1200VX進行測定。
[氮化鈦之蝕刻速率之測定及判定] 氮化鈦之蝕刻速率之評價係將附氮化鈦膜之晶圓之洗淨液處理前後之膜厚的差除以處理時間而得之值定義為蝕刻速率並將其算出。將氮化鈦之蝕刻速率為100埃/min(10nm/min)以上判定為合格。
[銅及鈷之蝕刻速率之測定及判定] 使用Thermo Scientific公司製感應耦合電漿發射光譜分析裝置iCAP6300測定附銅或鈷膜之晶圓處理後之洗淨液中之銅或鈷之濃度。由測定結果之濃度及使用之洗淨液量算出已溶解之銅或鈷量,將該已溶解之銅或鈷量除以密度算出已溶解之銅或鈷之體積。將該已溶解之銅或鈷之體積除以經處理之附膜晶圓的面積及處理時間所得之值定義為蝕刻速率並將其算出。銅或鈷之蝕刻速率為0.1埃/min(0.01nm/min)以下判定為合格。
實施例1~15 使用附氮化鈦膜之晶圓,檢查去除氮化鈦之性能。使用於表1記載之1A~1O之洗淨用液體組成物,以表2所示之溫度浸漬3分鐘,之後藉由超純水沖洗,藉由噴射乾燥氮氣進行乾燥。以X射線螢光裝置求得浸漬前後之膜厚,算出蝕刻速率,結果整理於表2。
接著,使用附銅及鈷膜之晶圓,使用表1中記載之1A~1O之洗淨用液體組成物,檢查銅及鈷之抗蝕性。以表2所示之溫度浸漬30分鐘,之後,藉由超純水沖洗,藉由噴射乾燥氮氣進行乾燥。以感應耦合電漿發射光譜分析裝置求出浸漬後之洗淨液中的銅或鈷之濃度,算出蝕刻速率,結果整理於表2。
使用了實施例1之洗淨用液體組成物1A(過氧化氫15質量%、氫氧化鉀0.1質量%、二乙烯三胺五(亞甲基膦酸)(DTPP)0.05質量%、硫酸鋁0.01質量%之水溶液)之情況,就氮化鈦之蝕刻速率為220埃/min(22nm/min),判定為合格,就銅及鈷之蝕刻速率為0.1埃/min(0.01nm/min)以下,判定為合格。 使用了於實施例2~15之表2所示之本發明之洗淨用液體組成物之情況,氮化鈦之蝕刻速率為100埃/min(10nm/min)以上,判定為合格,可知其可良好地去除氮化鈦。此外,銅及鈷之蝕刻速率為0.1埃/min(0.01nm/min)以下,也知其可抑制銅及鈷之損傷。
比較例1~21 使用記載於表3之洗淨液2A~2U,以表4所示之溫度浸漬附氮化鈦、附銅、附鈷膜之晶圓以外,進行與實施例1~15同樣之操作,算出氮化鈦、銅、鈷各自之蝕刻速率。 比較例1、3、7、8、10~12、15~21中氮化鈦之蝕刻速率為100埃/min(10nm/min)以上,但銅及鈷之蝕刻速率超過0.1埃/min(0.01nm/min)。使用洗淨液2A、2C、2G、2H、2J、2K、2L、2O、2P、2Q、2R、2S、2T、2U之洗淨方法可良好地去除氮化鈦,係因為對於銅及鈷造成損傷,於本案之目的無法使用。 比較例2、4、5、6、9、13、14中氮化鈦之蝕刻速率未達100埃/min(10nm/min)。使用洗淨液2B、2D、2E、2F、2I、2M、2N之洗淨方法無法良好地去除氮化鈦,故於本案之目的無法使用。
【表1】其中,於表中DTPP係指二乙烯三胺五(亞甲基膦酸),PDTP係指1,2-丙二胺四(亞甲基膦酸),ATP係指胺基三(亞甲基膦酸),EDTP係指乙二胺四(亞甲基膦酸)。
【表2】
【表3】其中,於表中DTPP係指二乙烯三胺五(亞甲基膦酸),PDTP係指1,2-丙二胺四(亞甲基膦酸),ATP係指胺基三(亞甲基膦酸),EDTP係指乙二胺四(亞甲基膦酸),TMAH係指氫氧化四甲基銨,EDTA係指乙二胺四乙酸、DGME係指二乙二醇單甲醚。
【表4】
1‧‧‧阻隔金屬
2‧‧‧金屬佈線
3‧‧‧帽蓋金屬
4‧‧‧阻隔絕緣膜
5‧‧‧低介電係數層間絕緣膜
6‧‧‧硬遮罩
2‧‧‧金屬佈線
3‧‧‧帽蓋金屬
4‧‧‧阻隔絕緣膜
5‧‧‧低介電係數層間絕緣膜
6‧‧‧硬遮罩
[圖1]為含有阻隔金屬、金屬佈線、帽蓋金屬、阻隔絕緣膜、低介電係數層間絕緣膜及硬遮罩之半導體元件的概略截面圖。
1‧‧‧阻隔金屬
2‧‧‧金屬佈線
3‧‧‧帽蓋金屬
4‧‧‧阻隔絕緣膜
5‧‧‧低介電係數層間絕緣膜
6‧‧‧硬遮罩
Claims (15)
- 一種洗淨用液體組成物,其抑制選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除; 含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水。
- 如申請專利範圍第1項之洗淨用液體組成物,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。
- 如申請專利範圍第1項之洗淨用液體組成物,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。
- 如申請專利範圍第1項之洗淨用液體組成物,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。
- 如申請專利範圍第1項之洗淨用液體組成物,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。
- 一種洗淨方法,係抑制至少具有選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料與氮化鈦硬遮罩之半導體元件中的選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除; 包括以下步驟: 使該半導體元件接觸含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水之洗淨用液體組成物。
- 如申請專利範圍第6項之洗淨方法,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。
- 如申請專利範圍第6項之洗淨方法,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。
- 如申請專利範圍第6項之洗淨方法,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。
- 如申請專利範圍第6項之洗淨方法,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。
- 一種半導體元件之製造方法,係製造具有選自於由含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之半導體元件之方法, 包括以下步驟: 使用含有過氧化氫1~30質量%、氫氧化鉀0.01~1質量%、胺基聚亞甲基膦酸0.0001~0.05質量%、具有13族元素之化合物0.00005~0.5質量%及水之洗淨用液體組成物,來抑制選自於由該含有鈷元素之材料及含有銅元素之材料構成之群組中之1種以上之材料之腐蝕且同時將氮化鈦硬遮罩予以去除。
- 如申請專利範圍第11項之半導體元件之製造方法,其中,該具有13族元素之化合物係選自於由鋁之鹽及鎵之鹽構成之群組中之1種以上。
- 如申請專利範圍第11項之半導體元件之製造方法,其中,該具有13族元素之化合物係選自於由硫酸鋁、硝酸鋁、氯化鋁、乳酸鋁、及硝酸鎵構成之群組中之1種以上。
- 如申請專利範圍第11項之半導體元件之製造方法,其中,該胺基聚亞甲基膦酸係選自於由胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、及1,2-丙二胺四(亞甲基膦酸)構成之群組中之1種以上。
- 如申請專利範圍第11項之半導體元件之製造方法,其中,該含有鈷元素之材料為鈷或鈷合金,該含有銅元素之材料為銅或銅合金。
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