TWI684676B - 微影蝕刻用洗淨液、及基板之洗淨方法 - Google Patents
微影蝕刻用洗淨液、及基板之洗淨方法 Download PDFInfo
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- TWI684676B TWI684676B TW104135440A TW104135440A TWI684676B TW I684676 B TWI684676 B TW I684676B TW 104135440 A TW104135440 A TW 104135440A TW 104135440 A TW104135440 A TW 104135440A TW I684676 B TWI684676 B TW I684676B
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Abstract
本發明課題在於提供一種不僅蝕刻處理後所殘留之殘渣物的去除性能優異，對選自由鈷及其合金所成之群中的至少1種金屬的腐蝕抑制機能亦優良的微影蝕刻用洗淨液、及使用該洗淨液的基板之洗淨方法。
解決手段為，本發明之微影蝕刻用洗淨液係含有羥胺、由羥胺以外之胺化合物及四級銨氫氧化物所成之群中選出的至少1種鹼性化合物、及水，且pH為8以上。上述洗淨液較佳使用於包含選自由鈷及其合金所成之群中的至少1種金屬的基板之洗淨。又，上述洗淨液中，較佳的是羥胺的含量為6質量%以上、及/或、pH為11以上。或者，上述洗淨液較佳進一步含有有機酸。
Description
本發明係有關於一種微影蝕刻用洗淨液(以下，單稱「洗淨液」)、及使用該洗淨液的基板之洗淨方法。
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，此種半導體裝置係藉由以阻劑圖型為遮罩實施蝕刻處理的微影蝕刻法，對上述各層進行加工而製成。
源自上述微影蝕刻法中所使用的阻劑膜、暫時性層合膜(亦稱犧牲膜)，甚而在蝕刻步驟中生成之源自金屬配線層或低介電體層的殘渣物，係使用洗淨液加以去除，以防其成為半導體裝置之故障源，並防止其成為次一步驟之阻障。
以往，作為在此種半導體裝置製造步驟中使用的微影蝕刻用洗淨液，有人提出以四級銨氫氧化物為主成分的洗淨液(例如參照專利文獻1及2)。此種以四級銨化合物為主成分的洗淨液，比起其之前的洗淨液，對各
種殘渣物的去除性能大幅改善，且對易腐蝕性材料的腐蝕抑制機能亦優良。
[專利文獻1]日本特開2002-357908號公報
[專利文獻2]日本特開2004-103771號公報
近年來，隨著半導體裝置的高密度化、高積體化，而採用使用鑲嵌法的配線形成方法。在此種配線形成方法中，作為構成半導體裝置之金屬配線層的金屬配線材料係採用易生腐蝕的銅，更且，對於構成低介電體層的低介電體材料(又稱低介電常數材料，Low-k材料)，也朝向低介電率化發展，而逐漸採用易生腐蝕的低介電常數材料。又，鎢及鈷常以單質或合金的形態，經採用為半導體裝置中的金屬配線之覆蓋材料。
然而，習知洗淨液，其對銅、低介電常數材料、及鎢的腐蝕抑制機能雖優良，但對鈷及其合金的腐蝕抑制機能不足。因此，如欲藉由洗淨液去除形成有表面覆蓋有鈷或其合金之金屬配線層的基板在蝕刻處理後所殘留的殘渣物時，有所謂鈷或其合金容易腐蝕的問題。因此，便要求一種不僅蝕刻處理後所殘留之殘渣物的去除性能優
異，且對鈷及其合金的腐蝕抑制機能亦優良的微影蝕刻用洗淨液。
本發明係有鑑於此種以往之實情而完成者，係以提供一種不僅蝕刻處理後所殘留之殘渣物的去除性能優異，對選自由鈷及其合金所成之群中的至少1種金屬的腐蝕抑制機能亦優良的微影蝕刻用洗淨液、及使用該洗淨液的基板之洗淨方法為目的。
本案發明人等為解決上述課題而致力重複研究。其結果發現，藉由對微影蝕刻用洗淨液添加羥胺，並且將微影蝕刻用洗淨液的pH設定為8以上則可解決上述課題，終至完成本發明。具體而言，本發明係提供以下者：
本發明之第一形態為一種微影蝕刻用洗淨液，其係含有羥胺、由羥胺以外之胺化合物及四級銨氫氧化物所成之群中選出的至少1種鹼性化合物、及水，且pH為8以上。
本發明之第二形態為一種基板之洗淨方法，其係包含對具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，使用上述洗淨液進行洗淨的洗淨步驟。
本發明之第三形態為一種基板之洗淨方法，其係包含：在具備在表面的至少一部分具有由選自由鈷及
其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由上述蝕刻遮罩層露出的上述基板進行蝕刻的蝕刻步驟；及使用上述洗淨液，對經蝕刻之上述基板進行洗淨的洗淨步驟，在上述洗淨步驟中，上述金屬層的至少一部分係朝上述基板的表面露出。
本發明之第四形態為一種基板之蝕刻加工方法，其係包含：在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由上述蝕刻遮罩層露出的上述基板進行蝕刻的蝕刻步驟；及使用上述洗淨液，對經蝕刻之上述基板進行洗淨的洗淨步驟，在上述洗淨步驟中，上述金屬層的至少一部分係朝上述基板的表面露出。
根據本發明，可提供一種不僅蝕刻處理後所殘留之殘渣物的去除性能優異，對選自由鈷及其合金所成之群中的至少1種金屬的腐蝕抑制機能亦優良的微影蝕刻用洗淨液、及使用該洗淨液的基板之洗淨方法。
1‧‧‧金屬層
2a、2b‧‧‧絕緣層
10‧‧‧基板
11‧‧‧金屬區域
12‧‧‧蝕刻遮罩層
13‧‧‧凹部
14‧‧‧本發明之微影蝕刻用洗淨液
第1圖為表示本發明一實施形態之基板之洗淨方法的
縱剖面圖。
本發明之微影蝕刻用洗淨液係含有羥胺、由羥胺以外之胺化合物及四級銨氫氧化物所成之群中選出的至少1種鹼性化合物、及水，且pH為8以上。本發明之洗淨液係使用於例如包含選自由鈷及其合金所成之群中的至少1種金屬的基板之洗淨，作為其一例，可使用於具備在表面的至少一部分具有由上述金屬所構成之金屬層的金屬區域(例如以由上述金屬所構成之金屬層覆蓋表面的至少一部分的金屬區域)之基板之洗淨，上述金屬層的至少一部分可朝上述基板的表面露出。作為上述金屬層，可舉出金屬配線的覆蓋層等。作為上述基板，可舉出在矽晶圓等的基板上層合金屬配線層、低介電體層、絕緣層等而形成有半導體裝置的基板。又，作為構成上述金屬區域的材料，可舉出例如銅。本發明之洗淨液，其對選自由鈷及其合金所成之群中的至少1種金屬的腐蝕抑制機能優良。因此，於上述基板之洗淨時，縱使本發明之洗淨液接觸到上述金屬層，上述金屬層的腐蝕仍可良好地獲抑制。
作為上述金屬區域，可舉出例如形成有半導體裝置之基板上的金屬配線層、插塞、其他的金屬構造物。此外，作為鈷的合金，可舉出鈷與其他的過渡元素及
主族元素(例如磷、硼、矽等)之至少1種的合金，具體而言，可例示CoWPB等含有磷及/或硼之合金、或CoSi等的矽化物。
本發明之洗淨液的pH為8以上，較佳為11以上，更佳為11~13.5。上述pH若為8以上，可抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕，同時容易提高對蝕刻處理後所殘留之殘渣物的去除性能。又，上述pH若為11以上，則可更有效地抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕，同時容易提高對蝕刻處理後所殘留之殘渣物的去除性能。此外，諸如後述，當本發明之洗淨液含有有機酸時，上述pH較佳為8以上且未達11，更佳為8~10。
以下，就本發明之洗淨液的各成分詳細加以說明，惟，若非合先敘明，否則作為上述成分可使用市售品。
本發明之洗淨液係透過含有羥胺，而對蝕刻處理後所殘留之殘渣物的去除性能優良。羥胺的含量，相對於洗淨液總量，較佳為6質量%以上，更佳為6~15質量%，再更佳為6~10質量%。透過採用此種含量，可提高對蝕刻處理後所殘留之殘渣物的去除性能。其中，當本發明之洗淨液的pH為11以上時，羥胺的含量若處於上述之範圍內，則特別容易提升對蝕刻處理後所殘留之殘渣物的去除性能。
鹼性化合物只要是由羥胺以外之胺化合物及四級銨氫氧化物所成之群中選出的至少1種，則不特別限定。在本發明之洗淨液中，上述鹼性化合物係使用於調整上述洗淨液的pH，可特別有用地使用於將上述pH保持於11以上。上述胺化合物及四級銨氫氧化物之各者可單獨使用，亦可組合2種以上使用。
作為羥胺以外之胺化合物，以可確保對蝕刻處理後所殘留之殘渣物的去除性能，同時可更有效地抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕而言，較佳為具有環狀結構的胺化合物。在具有環狀結構的胺化合物中，胺基可僅存在於上述環狀結構中及上述環狀結構外的其中一者，亦可存在於兩者。作為具有環狀結構的胺化合物，可舉出例如四氫糠基胺、N-(2-胺基乙基)哌嗪、1,8-二氮雜雙環〔5.4.0〕十一烯-7、1,4-二氮雜雙環〔2.2.2〕辛烷、羥乙基哌嗪、哌嗪、2-甲基哌嗪、反-2,5-二甲基哌嗪、順-2,6-二甲基哌嗪、2-哌嗪甲醇、環己胺、1,5-二氮雜雙環〔4,3,0〕壬烯-5等。
作為四級銨氫氧化物，可舉出例如下述通式(a1)所示之化合物：
上述通式(a1)中，Ra1~Ra4分別獨立地表示碳數1~16之烷基、碳數6~16之芳基、碳數7~16之芳烷基、或碳數1~16之羥烷基。Ra1~Ra4的至少2個可相互鍵結而形成環狀結構，尤其是，Ra1與Ra2之組合及Ra3與Ra4之組合的至少一者可相互鍵結而形成環狀結構。
上述通式(a1)所示之化合物當中，基於容易取得觀點較佳為由四甲基銨氫氧化物、四乙基銨氫氧化物、四丙基銨氫氧化物、四丁基銨氫氧化物、甲基三丙基銨氫氧化物、甲基三丁基銨氫氧化物、乙基三甲基銨氫氧化物、二甲基二乙基銨氫氧化物、苯甲基三甲基銨氫氧化物、十六基三甲基銨氫氧化物、(2-羥乙基)三甲基銨氫氧化物、及螺-(1,1’)-聯吡咯烷鎓氫氧化物所成之群中選出的至少1種。又，更佳為四甲基銨氫氧化物、四丁基銨氫氧化物、及苯甲基三甲基銨氫氧化物。
鹼性化合物的含量，相對於洗淨液總量，以羥胺以外之胺化合物而言較佳為0.1~50質量%，更佳為1~45質量%；以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%。透過採用此種含量，可將上述洗淨液的pH保持於8以上之所期望的範圍，尤為11以上，可抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕，同時可提高對蝕刻處理後所殘留之殘渣物的去除性能。此外，當上述洗淨液含有有機酸時，藉由併用鹼性化合物與有機酸，並使鹼性化合物的含量成為上述之範圍內，可將上述pH保持於8以上之所期望的範圍，尤為
8以上且未達11，可抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕，同時可提高對蝕刻處理後所殘留之殘渣物的去除性能。
水的含量，相對於洗淨液總量，較佳為10~80質量%，更佳為20~75質量%，再更佳為25~70質量%。水的含量若處於上述範圍內，則水可作為溶劑，特別穩定且均勻地溶解其他的成分。
本發明之洗淨液亦可進一步含有有機酸。在本發明之洗淨液中，有機酸係使用於調整上述洗淨液的pH，特別有用地使用於將上述pH保持於8以上且未達11，較佳為8~10。有機酸可單獨使用，亦可組合2種以上使用。
作為有機酸，可舉出例如羧酸、有機磺酸、有機硫代羧酸、有機二硫代羧酸等。就羧酸而言，只要是具有羧基的化合物，則不特別限定，亦包含羥基羧酸(即鍵結於羰基碳原子以外之碳原子的至少1個氫原子經羥基取代的羧酸)、巰基羧酸(即鍵結於羰基碳原子以外之碳原子的至少1個氫原子經巰基取代的羧酸)等。作為羧酸的具體例，可舉出檸檬酸、硫代乙醇酸、沒食子酸、乳酸、蟻酸、草酸、乙酸、丙酸、丙二酸、琥珀酸、戊二酸、馬來酸、富馬酸、鄰苯二甲酸、乙醇酸、水楊酸、酒
石酸、蘋果酸、戊酸、異戊酸、1,2,3-苯三羧酸、葡萄糖酸、二乙醇酸、苯甲酸、二羥基苯甲酸等。作為有機磺酸，可舉出例如甲磺酸、苯磺酸等。作為有機硫代羧酸，可舉出例如硫代乙酸、硫代苯甲酸等。作為有機二硫代羧酸，可舉出例如二硫代乙酸、二硫代苯甲酸等。其中，較佳為羧酸，更佳為羥基羧酸及巰基羧酸，再更佳為檸檬酸、硫代乙醇酸、及沒食子酸。
有機酸的含量只要是使上述洗淨液的pH成為8以上的量，則不特別限定，可根據有機酸的種類適當選擇，例如，相對於洗淨液總量，較佳為0.1~8質量%，更佳為0.5~4.5質量%。透過採用此種含量，可將上述洗淨液的pH保持於8以上之所期望的範圍，尤為8以上且未達11，可抑制選自由鈷及其合金所成之群中的至少1種金屬的腐蝕，同時可提高對蝕刻處理後所殘留之殘渣物的去除性能。
本發明之洗淨液亦可進一步含有水溶性有機溶劑。作為水溶性有機溶劑，可使用該領域中所慣用的化合物。水溶性有機溶劑可單獨使用，亦可組合2種以上使用。
作為水溶性有機溶劑，可舉出例如二甲基亞碸等的亞碸類；二甲碸、二乙碸、雙(2-羥乙基)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-羥甲基-2-吡咯啶酮、N-羥乙基-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；乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、乙二醇單烯丙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-3-甲基-1-丁醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單丁醚、二乙二醇單苯甲醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單丙醚、二丙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丙醚、三乙二醇單丁醚、三丙二醇單丁醚、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚等的二醇醚系溶劑；乙二醇單乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單酸酯等的二醇酯系溶劑。
其中作為較佳之水溶性有機溶劑而選出者，係由3-甲氧基-3-甲基-1-丁醇、二甲基亞碸、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、二乙二醇單乙醚、及二乙二醇單丁醚所成之群中選出的至少1種。
當本發明之洗淨液含有水溶性有機溶劑時，
水溶性有機溶劑的含量，相對於洗淨液總量，較佳為1~60質量%，更佳為10~50質量%，再更佳為15~45質量%。水溶性有機溶劑的含量若處於上述範圍內，則水溶性有機溶劑可與水共同作為溶劑，特別穩定且均勻地溶解其他的成分。
本發明之洗淨液中亦可添加有防蝕劑、界面活性劑等其他的成分。作為防蝕劑，不特別限定，可舉出例如咪唑系化合物、苯并三唑系化合物、含有巰基之化合物等。作為界面活性劑，不特別限定，可舉出例如非離子系界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑、兩性界面活性劑等。
本發明之第一基板之洗淨方法係包含對具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，使用本發明之洗淨液進行洗淨的洗淨步驟。
本發明之第二基板之洗淨方法係包含：在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由上述蝕刻遮罩層露出的上述基板進行蝕刻的蝕刻
步驟；及使用本發明之洗淨液，對經蝕刻之上述基板進行洗淨的洗淨步驟，在上述洗淨步驟中，上述金屬層的至少一部分係露出。
以下，參照第1圖，就本發明一實施形態之第二基板之洗淨方法加以說明。
在蝕刻遮罩層形成步驟中，係如第1圖(a)及第1圖(b)所示，在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層1的金屬區域11之基板10的表面，形成既定之圖型的蝕刻遮罩層12。作為金屬層1，可舉出金屬配線的覆蓋層等，在第1圖中，特別示出金屬層1為金屬配線的覆蓋層的情形。此外，金屬層1及金屬區域11係埋入於絕緣層2a及2b中。蝕刻遮罩層12的材料不特別限定。作為蝕刻遮罩層12的較佳之材料，可舉出例如各種的阻劑材料、SiO2或SiN等的無機矽化合物。當蝕刻遮罩層12由阻劑材料構成時，蝕刻遮罩層12係藉由向來周知的光微影蝕刻法形成。當蝕刻遮罩層12為無機矽化合物時，蝕刻遮罩層12可藉由在基板10的表面形成無機矽化合物的薄膜後，在無機矽化合物的薄膜上，在相當於蝕刻遮罩層12之開口部的部位形成具有開口的阻劑圖型，並藉由蝕刻剝離由阻劑圖型之開口部露出的無機矽化合物的薄膜，接著去除阻劑圖型而形成。又，蝕刻遮罩層12，藉由在相當於蝕
刻遮罩層12的部位形成具有開口的阻劑圖型後，採用CVD法使無機矽化合物堆積於阻劑圖型的開口部，接著去除阻劑圖型的方法亦可形成。
在蝕刻步驟中，係如第1圖(b)及第1圖(c)所示，對由蝕刻遮罩層12露出的基板10進行蝕刻而形成凹部13。藉由凹部13的形成，金屬層1的至少一部分即朝基板10的表面露出。在蝕刻步驟中，作為對由蝕刻遮罩層12露出的基板10進行蝕刻的方法，不特別限定，可舉出例如藉由電漿(氧、氬等)、電暈放電等的乾蝕刻。
在洗淨步驟中，係如第1圖(d)所示，使用本發明之微影蝕刻用洗淨液14，對經蝕刻之基板10進行洗淨。此時，金屬層1的至少一部分係朝基板10的表面露出，與洗淨液14接觸。洗淨液14，其對選自由鈷及其合金所成之群中的至少1種金屬的腐蝕抑制機能優良。因此，縱使洗淨液14接觸到金屬層1，對金屬層1的腐蝕仍可良好地抑制。從而，藉由經過洗淨步驟，可抑制金屬層1的腐蝕，同時可有效地去除蝕刻處理後所殘留的殘渣物。
以下示出本發明之實施例，對本發明更詳細
地加以說明，惟本發明不受下述實施例所限定。
胺化合物1：四氫糠基胺
胺化合物2：N-(2-胺基乙基)哌嗪
胺化合物3：1,8-二氮雜雙環〔5.4.0〕十一烯-7
胺化合物4：1,4-二氮雜雙環〔2.2.2〕辛烷
TMAH：四甲基銨氫氧化物
TBAH：四丁基銨氫氧化物
BeTMAH：苯甲基三甲基銨氫氧化物
有機酸1：檸檬酸
有機酸2：硫代乙醇酸
有機酸3：沒食子酸
溶劑1：3-甲氧基-3-甲基-1-丁醇
此外，胺化合物1~4係分別以下述式(a2)~(a5)表示。
以表1或2所示量(單位：質量%)混合表1或2所
示之材料，調製成微影蝕刻用洗淨液。此外，就各試劑而言，對於無特別記載者，係使用一般市售的試劑。
對表面具有30nm之Ti層的矽基板上滴下碳系硬遮罩(下稱「C-HM」)形成用樹脂組成物(東京應化工業(股)製，TBLM-800 EM)，將該基板以2000rpm旋轉，使組成物均分於上述基板整面，而形成均勻的膜。其後，在220℃下進行以乾燥與樹脂的交聯為目的之熱處理90秒，得到膜厚1400Å的C-HM。
其次，依以下條件，對上述C-HM進行乾蝕刻，得到C-HM的蝕刻殘渣物(即殘留於矽基板上之薄膜狀的C-HM)。乾蝕刻後的膜厚為約400Å。
裝置：TCA-3822(東京應化工業(股)製)
功率：800W
壓力：40Pa
載臺溫度：40℃
氣體：CF4、300ml/分
時間：3分鐘
使乾蝕刻後的上述基板浸漬於加熱至55℃的上述洗淨液中5分鐘。浸漬結束後，以純水沖洗上述基板，與上述基板的主平面呈垂直地將上述基板切斷。以SEM觀察剖面，確認蝕刻殘渣物是否被去除。當蝕刻殘渣物完全被去除時，評為「殘渣去除性良好」。又，當蝕刻
殘渣物部分被去除時，評為「殘渣去除性大致良好」。另一方面，當蝕刻殘渣物全面性地殘留時，則評為「殘渣去除性不良」。將結果示於表1。
將鈷或鎢成膜於表面具有30nm之Ti層的矽基板上，得到具備100nm之鈷層或鎢層的基板。將該基板浸漬於加熱至55℃的上述洗淨液中60分鐘。浸漬結束後，以純水沖洗上述基板，測定鈷層或鎢層的膜厚，由浸漬前後之膜厚的差求出鈷層或鎢層的蝕刻速度。將結果示於表1或2。
此外，當蝕刻速度為1.0nm/分以下時，評為「對鈷的腐蝕抑制機能優良」；當蝕刻速度為0.100nm/分以下時，評為「對鈷的腐蝕抑制機能特別優良」。又，當蝕刻速度為0.20nm/分以下時，則評為「對鎢的腐蝕抑制機能優良」。
由表1可知，pH為11以上的實施例1~15之洗淨液，可看出其不僅對蝕刻處理後所殘留之殘渣物的去除性能優異，對鈷的腐蝕抑制機能亦優良。其中，含有6質量%以上的羥胺，且pH為11以上的實施例1~13之洗淨液，可看出其對蝕刻處理後所殘留之殘渣物的去除性能特別優異。
由表2可知，pH為8以上的實施例16~24之微影蝕刻用洗淨液，可看出其不僅對鎢的腐蝕抑制機能優異，對鈷的腐蝕抑制機能亦優良。另一方面，pH未達8
的比較例1~4之微影蝕刻用洗淨液，可看出其對鎢的腐蝕抑制機能雖優異，但對鈷的腐蝕抑制機能不佳。
1‧‧‧金屬層
2a、2b‧‧‧絕緣層
10‧‧‧基板
11‧‧‧金屬區域
12‧‧‧蝕刻遮罩層
13‧‧‧凹部
14‧‧‧本發明之微影蝕刻用洗淨液
Claims (14)
- 一種微影蝕刻用洗淨液，其係含有羥胺6質量%以上、具有環狀結構的胺化合物0.1~50質量%、及水10~80質量%，且pH為8以上，前述具有環狀結構的胺化合物係選自由四氫糠基胺、N-(2-胺基乙基)哌嗪、1,8-二氮雜雙環〔5.4.0〕十一烯-7、1,4-二氮雜雙環〔2.2.2〕辛烷、羥乙基哌嗪、哌嗪、2-甲基哌嗪、反-2,5-二甲基哌嗪、順-2,6-二甲基哌嗪、2-哌嗪甲醇及1,5-二氮雜雙環〔4,3,0〕壬烯-5所成之群中的至少1種。
- 如請求項1之洗淨液，其係進一步含有四級銨氫氧化物0.05~10質量%。
- 如請求項1之洗淨液，其中pH為11以上。
- 一種微影蝕刻用洗淨液，其係含有羥胺6質量%以上、由羥胺以外之胺化合物0.1~50質量%及四級銨氫氧化物0.05~10質量%所成之群中選出的至少1種鹼性化合物、及水10~80質量%，且pH為11以上。
- 如請求項4之洗淨液，其中前述胺化合物為具有環狀結構的胺化合物。
- 如請求項1或4之洗淨液，其係使用於包含選自由鈷及其合金所成之群中的至少1種金屬的基板之洗淨。
- 如請求項1或4之洗淨液，其係進一步含有有機酸0.1~8質量%。
- 如請求項1或4之洗淨液，其係進一步含有水溶性 有機溶劑1~60質量%。
- 一種基板之洗淨方法，其係包含對具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，使用如請求項1至8中任一項之洗淨液進行洗淨的洗淨步驟。
- 一種基板之洗淨方法，其係包含：在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由前述蝕刻遮罩層露出的前述基板進行蝕刻的蝕刻步驟；及使用如請求項1至8中任一項之洗淨液，對經蝕刻之前述基板進行洗淨的洗淨步驟，在前述洗淨步驟中，前述金屬層的至少一部分係朝前述基板的表面露出。
- 一種基板之蝕刻加工方法，其係包含：在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由前述蝕刻遮罩層露出的前述基板進行蝕刻的蝕刻步驟；及使用如請求項1至8中任一項之洗淨液，對經蝕刻之前述基板進行洗淨的洗淨步驟，在前述洗淨步驟中，前述金屬層的至少一部分係朝前 述基板的表面露出。
- 一種基板之洗淨方法，其係包含對具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，使用微影蝕刻用洗淨液進行洗淨的洗淨步驟，前述洗淨液含有羥胺6質量%以上、由羥胺以外之胺化合物0.1~50質量%及四級銨氫氧化物0.05~10質量%所成之群中選出的至少1種鹼性化合物、及水10~80質量%，且pH為8以上。
- 一種基板之洗淨方法，其係包含：在具備在表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由前述蝕刻遮罩層露出的前述基板進行蝕刻的蝕刻步驟；及使用微影蝕刻用洗淨液，對經蝕刻之前述基板進行洗淨的洗淨步驟，在前述洗淨步驟中，前述金屬層的至少一部分係朝前述基板的表面露出，前述洗淨液含有羥胺6質量%以上、由羥胺以外之胺化合物0.1~50質量%及四級銨氫氧化物0.05~10質量%所成之群中選出的至少1種鹼性化合物、及水10~80質量%，且pH為8以上。
- 一種基板之蝕刻加工方法，其係包含：在具備在 表面的至少一部分具有由選自由鈷及其合金所成之群中的至少1種金屬所構成之金屬層的金屬區域之基板的表面，形成既定之圖型的蝕刻遮罩層的蝕刻遮罩層形成步驟；對由前述蝕刻遮罩層露出的前述基板進行蝕刻的蝕刻步驟；及使用微影蝕刻用洗淨液，對經蝕刻之前述基板進行洗淨的洗淨步驟，在前述洗淨步驟中，前述金屬層的至少一部分係朝前述基板的表面露出，前述洗淨液含有羥胺6質量%以上、由羥胺以外之胺化合物0.1~50質量%及四級銨氫氧化物0.05~10質量%所成之群中選出的至少1種鹼性化合物、及水10~80質量%，且pH為8以上。
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