TW201435083A - 半導體元件用清洗液及利用此清洗液之清洗方法 - Google Patents

半導體元件用清洗液及利用此清洗液之清洗方法 Download PDF

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TW201435083A
TW201435083A TW102144061A TW102144061A TW201435083A TW 201435083 A TW201435083 A TW 201435083A TW 102144061 A TW102144061 A TW 102144061A TW 102144061 A TW102144061 A TW 102144061A TW 201435083 A TW201435083 A TW 201435083A
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mass
cleaning
hydroxide
film
insulating film
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TW102144061A
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TWI582230B (zh
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Kenji Shimada
Fumiya Hamada
Toshiyuki OIE
Ryota Nakayama
Masaru Ohto
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Mitsubishi Gas Chemical Co
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Abstract

依本發明之理想態樣，藉由以含有過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水之清洗液進行清洗，能不腐蝕低介電率層間絕緣膜、銅或銅合金等配線材料、阻隔金屬及阻隔絕緣膜，而去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻。又，依本發明之理想態樣，即使於清洗液中添加了酸的情形仍能抑制銅配線之受損，即使於清洗液中添加鈦的情形仍不發生的過氧化氫的多量分解。

Description

半導體元件用清洗液及利用此清洗液之清洗方法
本發明係關於在半導體積體電路之製造步驟使用之清洗劑及使用此清洗劑之清洗方法。本發明特別關於清洗液及使用此清洗液之清洗方法，係對於在具有阻隔金屬、銅配線或銅合金配線、與低介電率層間絕緣膜之基板上，疊層了阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、及光阻後對該光阻施以選擇性曝光及顯影處理並形成光阻圖案，其次將此光阻圖案作為遮罩，對於前述有機矽氧烷系薄膜、硬遮罩、低介電率層間絕緣膜、阻隔絕緣膜施行乾蝕刻處理而得的半導體元件進行清洗，在抑制前述低介電率層間絕緣膜、銅配線、阻隔金屬、及阻隔絕緣膜之受損且同時能將前述有機矽氧烷系薄膜、硬遮罩、乾蝕刻殘渣及光阻除去。
高密集化的半導體元件之製造，通常係於矽晶圓等元件上形成成為導電用配線原材料的金屬膜等導電薄膜、或為了導電薄膜間之絕緣之層間絕緣膜後，於此表面均勻塗佈光阻而設置感光層，並對於其實施選擇性曝光及顯影處理，製成所望之抗蝕劑圖案。其次將此抗蝕劑圖案作為遮罩，對於層間絕緣膜實施乾蝕刻處理以於該薄膜形成理想的圖案。並且，一般會採行將抗蝕劑圖案及由於乾蝕刻處理所產生之殘渣物(以下稱為「乾蝕刻殘渣」)以氧電漿進行灰化或以清洗液等完全除去的一連串步驟。
近年來設計規則的微細化進展，信號傳送延遲成為主宰高速度演算處理的極限。所以，導電用配線原材料從鋁轉移成電阻更低的銅，隨之層間 絕緣膜也從矽氧化膜往低介電率層間絕緣膜(比介電率小於3之膜。以下稱為「低介電率層間絕緣膜」)轉移。又，為了防止銅向層間絕緣膜擴散，係將銅以鉭或氮化鉭等金屬(以下稱為「阻隔金屬」)與氮化矽、碳化矽等絕緣膜(以下稱為「阻隔絕緣膜」)覆蓋。再者，也開始使用具有填充在光阻與層間絕緣膜之間的基底元件的凸凹或溝等間隙而有平坦化之機能、吸收從元件反射的放射線的機能、及於乾蝕刻時維持層間絕緣膜之形狀並使精密微細加工容易之機能的膜。如此的膜例如有含有吸光化合物之有機矽氧烷薄膜(以下稱為「有機矽氧烷系薄膜」)。又，形成0.2μm以下的圖案時，利用膜厚1μm的抗蝕劑會使圖案的深寬比(抗蝕劑膜厚除以抗蝕劑線寬而得之比值)變得太大，發生圖案崩塌等問題。為解決此問題，有人採用：在實際欲形成之圖案膜與抗蝕劑膜之間插入Ti系或Si系的膜(以下稱為「硬遮罩」)，先以乾蝕刻將抗蝕劑圖案轉印到硬遮罩之後，將此硬遮罩作為蝕刻遮罩，以乾蝕刻將圖案轉印到實際欲形成之膜的硬遮罩法。此方法能夠更動蝕刻硬遮罩時之氣體與蝕刻實際欲形成之膜時之氣體，在蝕刻硬遮罩時能取得與抗蝕劑之選擇比，在蝕刻實際的膜時可選擇能取得與硬遮罩之選擇比的氣體，所以有能以薄的抗蝕劑形成圖案的好處。
但是以氧電漿去除硬遮罩或有機矽氧烷系薄膜、光阻時，存在於有機矽氧烷系薄膜下的低介電率層間絕緣膜會有暴露於氧電漿等而受損之虞。例如以通孔優先雙層鑲嵌製程(via first dual damascene process)形成圖案時，當以氧電漿去除填充於通孔部之有機矽氧烷系薄膜時，通孔部周邊的低介電率層間絕緣膜會受損，結果發生電特性顯著劣化的問題。另一方面，於硬遮罩或有機矽氧烷系薄膜之除去步驟，由於乾蝕刻殘渣附著在晶圓，故必須同時也去除乾蝕刻殘渣。因此尋求於使用低介電率層間絕緣膜之半導體元件製造時，能抑制低介電率層間絕緣膜、銅、阻隔金屬及阻隔絕緣膜之受損，並與氧電漿步驟同程度地去除硬遮罩或有機矽氧烷系薄膜、光阻且同時也去除乾蝕刻殘渣之方法。
近年，乾蝕刻一般使用氟碳系的氣體，所以於乾蝕刻殘渣中含氟。所以，在乾蝕刻殘渣之除去過程，清洗液中會混入氟。氟特別在pH呈酸性時 會對於低介電率層間絕緣膜與銅造成嚴重損害。但，即使是清洗液之pH非呈酸性，當使用已去除乾蝕刻殘渣後之清洗液清洗半導體元件時，仍會有觀察到低介電率層間絕緣膜與銅嚴重受損的情況。其受損原因尚不明瞭，但是推測當以氟碳系的氣體將含Si或O之低介電率層間絕緣膜進行乾蝕刻時，會與以HF溶解SiO2的情形同樣有部分乾蝕刻殘渣成為如H2SiF6之酸。據認為：由於乾蝕刻氣體的影響，造成半導體元件上也存在氟，所以在清洗液清洗的當中會局部性地形成氟酸，引起低介電率層間絕緣膜與銅之受損。而，尋求：即使乾蝕刻殘渣混入清洗液的情形，仍不會造成低介電率層間絕緣膜與銅受損而清洗半導體元件的方法。
有時，係使用鈦或氮化鈦作為硬遮罩。於此情形，若以清洗液除去硬遮罩，於清洗液中會混入鈦。為含有過氧化氧的清洗液的情形，若鈦混入，過氧化氫的分解會加速而使清洗液之保存安定性惡化，所以尋求抑制由於清洗液中混入鈦引起過氧化氫分解的方法。
專利文獻1提案：利用含有過氧化氫與胺基聚亞甲基膦酸類與氫氧化鉀及水之清洗液所為之半導體元件之清洗方法。
專利文獻2提案一種清洗液，其係含有過氧化氫、氫氧化4級銨及鎢之防蝕劑且pH為7以上10以下的配線基板處理液，其特徵為鎢之防蝕劑選自於由4級銨及其鹽、4級吡啶鎓及其鹽、4級聯吡啶鎓及其鹽、及4級咪唑鎓及其鹽構成之群組中之至少1種。
專利文獻3提案一種氮化鈦除去液，其含有10~40質量%之過氧化氫與四烷基氫氧化銨且於25℃之pH為6.0~8.2。
專利文獻4提供一種半導體裝置用清洗劑，含有氧化劑、金屬蝕刻劑、及界面活性劑，pH為10~14。
專利文獻5提供將鈦錯合化合物作為主要觸媒而製造之聚酯，並列舉 羥基多元羧酸及/或含氮多元羧酸作為該鈦錯合化合物之螯合劑。
【先前技術文獻】 【專利文獻】
【專利文獻1】WO2008/114616
【專利文獻2】日本特開2008-285508號公報
【專利文獻3】日本特開2010-10273號公報
【專利文獻4】日本特開2009-231354號公報
【專利文獻5】日本特開2007-211035號公報
但是專利文獻1~5有以下問題：未能充分去除硬遮罩、有機矽氧烷系薄膜、光阻、及乾蝕刻殘渣、或當清洗液中混入酸時，無法充分抑制對於銅之損害的問題。再者，會有鈦混入清洗液時之過氧化氫的分解多等問題(參照後述比較例1~5)。
本發明有鑑於上述以往的問題，課題為提供一種能抑制低介電率層間絕緣膜、銅配線、阻隔金屬、及阻隔絕緣膜之受損且同時能去除有機矽氧烷系薄膜、硬遮罩、乾蝕刻殘渣及光阻之清洗液及使用此清洗液之清洗方法。又，本發明之課題為提供即使於清洗液添加了酸的情形仍可抑制銅配線受損且即使於清洗液中添加了鈦的情形仍不會造成過氧化氫多量分解的清洗液，及使用此清洗液之清洗方法。
本發明包含以下態樣。
<1>一種清洗液，其清洗在具有阻隔金屬、銅配線或銅合金配線、與低介電率層間絕緣膜之基板上依序疊層阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、及光阻後對於該光阻施以選擇性曝光及顯影處理並形成光阻圖案，其次將此光阻圖案作為遮罩而對於該有機矽氧 烷系薄膜、硬遮罩、低介電率層間絕緣膜及阻隔絕緣膜施以乾蝕刻處理後的半導體元件，而去除該有機矽氧烷系薄膜、硬遮罩、乾蝕刻殘渣及光阻；該清洗液含有過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水。
<2>如<1>之清洗液，其中，該硬遮罩含有氮化鈦或鈦。
<3>如<1>或<2>之清洗液，其中，該4級銨氫氧化物係選自於由四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨及苄基三甲基氫氧化銨構成之群組中之至少1種以上。
<4>如<1>至<3>中任一項之清洗液，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)構成之群組中之至少1種以上。
<5>如<1>至<4>中任一項之清洗液，其中，鈉濃度為0.1ppm以下。
<6>一種半導體元件之清洗方法，其特徵為：將含有過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水之清洗液使用在半導體元件而去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻，該半導體元件係在具有阻隔金屬、銅配線或銅合金配線、與低介電率層間絕緣膜之基板上依序疊層阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、及光阻後對於該光阻施以選擇性曝光及顯影處理並形成光阻圖案，其次將此光阻圖案作為遮罩而對於該有機矽氧烷系薄膜、硬遮罩、低介電率層間絕緣膜及阻隔絕緣膜施以乾蝕刻處理而獲得。
<7>如<6>之半導體元件之清洗方法，其中，該硬遮罩含有氮化鈦或鈦。
<8>如<6>或<7>之半導體元件之清洗方法，其中，該4級銨氫氧化物係選自於由四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨及苄基三甲基氫氧化銨構成之群組中之至少1種以上。
<9>如<6>至<8>中任一項之半導體元件之清洗方法，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)構成之群組中之至少1種以上。
<10>如<6>至<9>中任一項之半導體元件之清洗方法，其中，鈉含量為0.1ppm以下。
依本發明之理想態樣，能提供抑制低介電率層間絕緣膜、銅配線、阻隔金屬、及阻隔絕緣膜之受損且同時去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻之清洗液，及使用此清洗液之清洗方法。又，依本發明之理想態樣，能提供於清洗液添加了酸的情形，仍抑制銅配線之受損，且於清洗液中添加了鈦的情形，仍不發生過氧化氫多量分解之清洗液，及使用此清洗液之清洗方法，能以良好產率製造高精度、高品質之半導體元件。
1‧‧‧阻隔金屬
2‧‧‧銅或銅合金配線
3‧‧‧阻隔絕緣膜
4‧‧‧低介電率層間絕緣膜
5‧‧‧硬遮罩
6‧‧‧有機矽氧烷系薄膜
7‧‧‧變質光阻
8‧‧‧乾蝕刻殘渣
圖1顯示包含阻隔金屬、銅配線或銅合金配線、阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻之半導體元件之概略剖面圖。
以下針對本發明顯示實施形態及例示物等詳細說明，但本發明不限於以下所示之實施形態及例示物等，可於不脫離本發明之要旨的範圍內任意變更並實施。
本發明之清洗液含有：過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水。以下針對各成分詳細說明。
本發明使用之過氧化氫之濃度範圍為10~30質量%，較佳為13~25質量%，尤佳為15~20質量%。若10~30質量%，能有效果地去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻。
本發明使用之4級銨氫氧化物之具體例，例如：四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、苄基三甲基氫氧化銨等。該等4級銨氫氧化物可單獨或組合摻合2種以上。
本發明使用之上述4級銨氫氧化物之濃度範圍為0.005~10質量%，較佳為0.01~8質量%，尤佳為0.05~5質量%。若為0.005~10質量%之範圍內，能抑制低介電率層間絕緣膜及銅配線之受損且同時有效去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻，即使於清洗液添加了酸的情形，仍抑制銅配線受損，且於清洗液中添加鈦的情形仍不發生過氧化氫之多量分解。
本發明使用之氫氧化鉀之濃度範圍為0.005~5質量%，較佳為0.01~3質量%，尤佳為0.02~1質量%。若為0.005~5質量%之範圍內，能抑制低介電率層間絕緣膜及銅配線之受損且有效去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻。
本發明使用之胺基聚亞甲基膦酸，例如：胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二乙三胺五(亞甲基膦酸)、1,2-丙二胺四(亞甲基膦酸)等。該等胺基聚亞甲基膦酸可單獨使用或組合摻合2種以上。
本發明使用之上述胺基聚亞甲基膦酸之濃度範圍為0.000005~0.005質量%，較佳為0.00001~0.003質量%，尤佳為0.0001~0.003質量%。若為0.000005~0.005質量%之範圍內，能抑制銅配線受損。
本發明之清洗液中，特別理想的組合係含有過氧化氫15~20質量%、4級銨氫氧化物0.01~8質量%、氫氧化鉀0.02~1質量%、胺基聚亞甲基膦酸0.00001~0.003質量%。
本發明之清洗液含有之作為雜質之鈉濃度，就質量而言為0.1ppm以下較佳，0.05ppm以下更佳，0.03ppm以下又更佳。又，鈉在上述氫氧化鉀中係不可避免的雜質，所以實際上在清洗用組成物中含量約0.001ppm。若含 有多於0.1ppm的鈉，製造之半導體之特性有下降之虞。
使用本發明之清洗液之硬遮罩，例如可使用氮化鈦或鈦。
本發明之清洗液中，可視需求在不損害本發明目的之範圍內摻合自以往使用於半導體用清洗液之添加劑。
例如：可以添加界面活性劑、消泡劑等作為添加劑。
使用本發明之清洗液之溫度為20~80℃，較佳為25~70℃之範圍，可依蝕刻條件或使用之半導體基體適當選擇。本發明之清洗方法視需要可以併用超音波。
使用本發明之清洗液之時間為0.3~20分鐘，較佳為0.5~10分鐘之範圍，可視蝕刻條件或使用之半導體基體適當選擇。
作為使用本發明之清洗液後之淋洗液，亦可使用如醇之有機溶劑，但僅以水淋洗即也已足夠。
本發明能適用之半導體元件及顯示元件，包含：矽、非晶質矽、多晶矽、玻璃等基板材料；氧化矽、氮化矽、碳化矽及該等之衍生物等絕緣材料；鉭、氮化鉭、釕、氧化釕等阻隔材料；銅、銅合金等配線材料；鎵-砷、鎵-磷、銦-磷、銦-鎵-砷、銦-鋁-砷等化合物半導體；鉻氧化物等氧化物半導體等。
作為低介電率層間絕緣膜一般而言係使用羥基倍半矽氧烷(HSQ)系或甲基倍半矽氧烷(MSQ)系之OCD(商品名、東京應化工業公司製)、碳摻雜氧化矽(SiOC)系之Black Diamond(商品名、應用材料公司製)、Aurora(商品名、ASM International公司製)、Coral(商品名、Novellus Systems公司製)、無機系之Orion(商品名、Trikon Tencnlogies公司製)。低介電率層間絕緣膜不限定於此等。
一般而言，作為阻隔金屬係使用鉭、氮化鉭、釕、錳、鎂、鈷及該等 之氧化物。阻隔金屬不限定於此等。
一般而言，作為阻隔絕緣膜係使用氮化矽、碳化矽、氮化碳化矽。阻隔絕緣膜不限定於此等。
【實施例】
其次利用實施例及比較例對於本發明更具體說明。惟，本發明不受限於該等實施例。
<材質之除去狀態與受損之評價方法及評價設備>
材質之除去狀態與受損之評價係以SEM觀察進行。SEM裝置使用日立先進科技(股)公司製、超高解析能力場效發射式的掃描電子顯微鏡SU9000。
<以添加了酸之清洗液之製備方法與添加了酸之清洗液清洗時之銅之受損之評價方法>
添加了酸的清洗液，係對於清洗液將10質量%氟酸水溶液以質量計為100：2的比例混合而製備。於既定溫度將具有銅配線之半導體元件浸漬於已添加氟酸的清洗液中既定時間，以SEM觀察銅之損害。
<已添加鈦之清洗液之過氧化氫之分解率>
將以質量計為100：0.005之比例混合清洗液與鈦粉末而得之組成物以60℃的恆溫水槽加熱4小時。以電位差滴定法(使用過錳酸鉀)測定加熱前後之過氧化氫濃度，並以下列計算式計算組成物的過氧化氫分解率。
過氧化氫分解率%=100-100×(加熱後清洗液重量×加熱後過氧化氫濃度)/(加熱前清洗液重量×加熱前過氧化氫濃度)
判定：
I.有機矽氧烷系薄膜6之除去狀態
A：有機矽氧烷系薄膜已完全除去。
B：有機矽氧烷系薄膜大部分被除去。
C：有機矽氧烷系薄膜未被除去。
A、B評為合格。
II.乾蝕刻殘渣8之除去狀態
A：乾蝕刻殘渣已完全除去。
B：乾蝕刻殘渣大部分被除去。
C：乾蝕刻殘渣未被除去。
A、B評為合格。
III.變質光阻7之除去狀態
A：光阻已完全除去。
B：光阻大部分被除去。
C：光阻未被除去。
A、B評為合格。
IV.鈦系硬遮罩5之除去狀態
A：硬遮罩已完全除去。
B：硬遮罩大部分被除去。
C：硬遮罩未被除去。
A、B評為合格。
V.銅2之受損
A：與清洗前相較，未觀察到銅變化。
B：銅表面觀察到些微粗糙。
C：觀察到銅有大洞。
A、B評為合格。
VI.低介電率層間絕緣膜4之受損
A：與清洗前相較，未觀察到低介電率層間絕緣膜變化。
B：低介電率層間絕緣膜有稍微凹陷。
C：低介電率層間絕緣膜有大幅凹陷。
A、B評為合格。
VII.以添加了酸的清洗液清洗時之銅2之受損
A：與清洗前相較，未觀察到銅變化。
B：銅表面觀察到些微粗糙。
C：觀察到銅有大洞。
A、B評為合格。
VIII.添加了鈦之清洗液之過氧化氫之安定性
A：過氧化氫分解率低於20%。
B：過氧化氫分解率為20~30%。
C：過氧化氫分解率大於30%。
-：加熱前不含過氧化氫，故未評價。
A、B評為合格。
(實施例1~22)
試驗使用具有如圖1所示之配線結構之剖面的半導體元件。為了去除TiN硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7，在表1記載的清洗液中以表2所示溫度、時間浸漬，之後實施以超純水淋洗，以乾燥氮氣噴射所為之乾燥。藉由以SEM觀察清洗後之半導體元件，判斷硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7之除去狀態，並判斷銅2、係阻隔金屬1之鉭(Ta)/氮化鉭(TaN)、係阻隔絕緣膜3之碳化矽、及係低介電率層間絕緣膜4之碳摻雜氧化矽之損傷。又，對於在表1記載之清洗液中添加了酸之清洗液，也以表2所示之溫度、時間浸漬，之後實施以超純水淋洗、以乾燥氮氣噴射乾燥，以SEM觀察清洗後的半導體元件，藉此觀察銅之受損。再者也檢查於清洗液中添加鈦時之過氧化氫之安定性。
可知：於使用表2所示之本發明之清洗液的實施例1~22中，能防止銅2及低介電率層間絕緣膜4之受損且同時將硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7完全除去。在所有的實施例中，未觀察到阻隔金屬1、及阻隔絕緣膜3之受損。又於使用添加了酸的清洗液時也未觀察到銅2受損。於清洗液中添加鈦的情形，過氧化氫之分解為30%以下。表1所示之清洗液之鈉濃度均為0.1ppm以下。
(比較例1)
使用專利文獻1記載之含有過氧化氫15質量%、氫氧化鉀0.02質量%、 1,2-丙二胺四(亞甲基膦酸)0.0005質量%、及水84.9795質量%之水溶液(表3之清洗液3A)，清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4及銅2受損。但是使用添加了酸之清洗液時，觀察到銅2受損，於清洗液中添加鈦的情形，過氧化化氫的分解多。
(比較例2)
使用專利文獻2記載之含有過氧化氫15質量%、苄基三甲基氫氧化銨0.45質量%、羥基氯苯胺0.01質量%、及水84.54質量%之水溶液(表3之清洗液3B)，清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5，但不能去除有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4及銅2受損。於使用添加了酸之清洗液時，也未觀察到銅2受損。於清洗液中添加鈦的情形，過氧化氫的分解仍少。
(比較例3)
使用專利文獻3記載之含有過氧化氫28.4質量%、四甲基氫氧化銨1.7質量%、乙二胺四乙酸1.4質量%、及水68.5質量%之水溶液(表3之清洗液3C)，清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。可去除硬遮罩5，但未能去除有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4受損，但觀察到銅2受損。再者，於使用添加了酸之清洗液時觀察到銅2受損，於清洗液中添加鈦的情形，過氧化化氫的分解多。
(比較例4)
使用專利文獻4記載之含有過氧化氫0.2質量%、四甲基氫氧化銨0.4質量%、氫氧化鉀0.1質量%、原過碘酸0.2質量%、二乙三胺0.02質量%、EMULGEN A-90 0.1質量%、鯨蠟基三甲基氯化銨0.01質量%、月桂基氯化吡啶鎓0.05質量%、三甲基氟化銨0.5質量%、及水98.42質量%之水溶液(表3之清洗液3D)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。未能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。 觀察到低介電率層間絕緣膜4與銅2受損。使用添加了酸之清洗液時，觀察到銅2受損。於清洗液中添加鈦的情形，過氧化氫的分解少。
(比較例5)
使用添加了將4級銨氫氧化物替換為專利文獻5記載之與鈦形成錯合化合物之螯合劑即羥基多元羧酸、過氧化氫、氫氧化鉀、胺基聚亞甲基膦酸及水而得的清洗液(表3之清洗液3E)，清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7大致已除去。未觀察到低介電率層間絕緣膜4之受損，但觀察到銅2受損。使用添加了酸之清洗液時，觀察到銅2受損。於清洗液中添加鈦的情形，過氧化氫的分解程度不是如此大。是以，在將羥基多元羧酸組合與過氧化氫、氫氧化鉀、胺基聚亞甲基膦酸及水之清洗液中添加酸的情形，仍會使銅配線受損。
可知專利文獻1~5記載之清洗液(比較例1~5)，作為抑制阻隔金屬、低介電率層間絕緣膜、及銅配線之受損且同時去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻之清洗液，清洗不充分、或使銅配線之受損、或清洗液之安定性差，而不能使用(表4)。
(比較例6)
使用含有過氧化氫17質量%、四甲基氫氧化銨0.5質量%、氫氧化鉀0.2質量%、及水82.3質量%之水溶液(表3之清洗液3F)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4及銅2受損。即使使用添加了酸之清洗液時，仍未觀察到銅2受損。但是於清洗液中添加鈦的情形，過氧化氫的分解多。
(比較例7)
使用含有過氧化氫17質量%、四甲基氫氧化銨0.5質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水82.4995質量%之水溶液(表3之清洗液 3G)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5，但無法去除有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。
(比較例8)
使用含有過氧化氫17質量%、氫氧化鉀0.2質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水82.7995質量%之水溶液(表3之清洗液3H)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4及銅2受損。但是於使用添加了酸之清洗液時觀察到銅2受損，於清洗液中添加鈦的情形，過氧化化氫的分解多。
(比較例9)
使用含有四甲基氫氧化銨0.5質量%、氫氧化鉀0.2質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水99.2995質量%之水溶液(表3之清洗液3I)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。未能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。觀察到低介電率層間絕緣膜4及銅2受損。
是以，3F、3G、3H、及3I之清洗液不能充分抑制低介電率層間絕緣膜、及銅配線之受損且同時去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻，或若添加酸則會使銅配線受損、或因鈦添加所致之過氧化氫之安定性不充分(表4)。
(比較例10)
使用含有過氧化氫17質量%、氫氧化鉀0.2質量%、1,3-丙烷二胺0.1質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水82.6995質量%之水溶液(表3之清洗液3J)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4受損，但觀察到銅2受損。於使用添加了酸之清洗液時觀察到銅2受損，於清洗液中添加鈦的情形，過氧化氫的分 解多。
(比較例11)
使用含有過氧化氫17質量%、氫氧化鉀0.2質量%、氨0.04質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水82.7595質量%之水溶液(表3之清洗液3K)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4受損，但觀察到銅2受損。使用添加了酸之清洗液時觀察到銅2受損，於清洗液中添加鈦的情形，過氧化化氫的分解多。
(比較例12)
使用含有過氧化氫17質量%、氫氧化鉀0.2質量%、2-(甲胺基)乙醇0.2質量%、二乙三胺五(亞甲基膦酸)0.0005質量%、及水82.5995質量%之水溶液(表3之清洗液3L)清洗圖1所示之半導體元件。表4顯示清洗條件與評價結果。能去除硬遮罩5、有機矽氧烷系薄膜6、乾蝕刻殘渣8及光阻7。未觀察到低介電率層間絕緣膜4受損但觀察到銅2受損。使用添加了酸之清洗液時觀察到銅2受損，於清洗液中添加鈦的情形，過氧化化氫的分解多。
TMAH：四甲基氫氧化銨
TEAH：四乙基氫氧化銨
TPAH：四丙基氫氧化銨
TBAH：四丁基氫氧化銨
BTMAH：苄基三甲基氫氧化銨
除去狀態I：有機矽氧烷系薄膜6之除去狀態
除去狀態II：乾蝕刻殘渣8之除去狀態
除去狀態III：變質光阻7之除去狀態
除去狀態IV：鈦系硬遮罩5之除去狀態
受損V：銅2之損傷
受損VI：低介電率層間絕緣膜4之損傷
受損VII：以添加了酸之清洗液清洗時之銅2之損傷
安定性VIII：添加了鈦時之過氧化氫之安定性
【表3】
除去狀態I：有機矽氧烷系薄膜6之除去狀態
除去狀態II：乾蝕刻殘渣8之除去狀態
除去狀態III：變質光阻7之除去狀態
除去狀態IV：鈦系硬遮罩5之除去狀態
受損V：銅2之損傷
受損VI：低介電率層間絕緣膜4之損傷
受損VII：以添加了酸之清洗液清洗時之銅2之損傷
安定性VIII：已添加鈦時之過氧化氫之安定性

Claims (10)

  1. 一種清洗液，其清洗在具有阻隔金屬、銅配線或銅合金配線、與低介電率層間絕緣膜之基板上依序疊層阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、及光阻後對於該光阻施以選擇性曝光及顯影處理並形成光阻圖案，其次將此光阻圖案作為遮罩而對於該有機矽氧烷系薄膜、硬遮罩、低介電率層間絕緣膜及阻隔絕緣膜施以乾蝕刻處理後得到的半導體元件，而去除該有機矽氧烷系薄膜、硬遮罩、乾蝕刻殘渣及光阻；該清洗液含有過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水。
  2. 如申請專利範圍第1項之清洗液，其中，該硬遮罩含有氮化鈦或鈦。
  3. 如申請專利範圍第1或2項之清洗液，其中，該4級銨氫氧化物係選自於由四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨及苄基三甲基氫氧化銨構成之群組中之至少1種以上。
  4. 如申請專利範圍第1或2項之清洗液，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)構成之群組中之至少1種以上。
  5. 如申請專利範圍第1或2項之清洗液，其中，鈉濃度為0.1ppm以下。
  6. 一種半導體元件之清洗方法，其特徵為：將含有過氧化氫10~30質量%、4級銨氫氧化物0.005~10質量%、氫氧化鉀0.005~5質量%、胺基聚亞甲基膦酸0.000005~0.005質量%及水之清洗液使用在半導體元件而去除硬遮罩、有機矽氧烷系薄膜、乾蝕刻殘渣及光阻，該半導體元件係在具有阻隔金屬、銅配線或銅合金配線、與低介電率層間絕緣膜之基板上依序疊層阻隔絕緣膜、低介電率層間絕緣膜、硬遮罩、有機矽氧烷系薄膜、及光阻後對於該光阻施以選擇性曝光及顯影處理並形成光阻圖案，其次將此光阻圖案作為遮罩而對於該有機矽氧烷系薄膜、硬 遮罩、低介電率層間絕緣膜及阻隔絕緣膜施以乾蝕刻處理而獲得。
  7. 如申請專利範圍第6項之半導體元件之清洗方法，其中，該硬遮罩含有氮化鈦或鈦。
  8. 如申請專利範圍第6或7項之半導體元件之清洗方法，其中，該4級銨氫氧化物係選自於由四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨及苄基三甲基氫氧化銨構成之群組中之至少1種以上。
  9. 如申請專利範圍第6或7項之半導體元件之清洗方法，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)構成之群組中之至少1種以上。
  10. 如申請專利範圍第6或7項之半導體元件之清洗方法，其中，鈉含量為0.1ppm以下。
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