TWI424286B - 金屬基材的半水性剝除及清潔配方及其使用方法 - Google Patents
金屬基材的半水性剝除及清潔配方及其使用方法 Download PDFInfo
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- TWI424286B TWI424286B TW099125498A TW99125498A TWI424286B TW I424286 B TWI424286 B TW I424286B TW 099125498 A TW099125498 A TW 099125498A TW 99125498 A TW99125498 A TW 99125498A TW I424286 B TWI424286 B TW I424286B
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- Prior art keywords
- formulation
- weight
- semi
- ether
- aqueous stripping
- Prior art date
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- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- C11D7/3218—Alkanolamines or alkanolimines
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- C11D7/50—Solvents
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Description
本專利申請案請求08/05/2009申請的美國臨時專利申請案序號第61/231,393號的益處。
本發明係關於一種半水性配方及使用該半水性配方移除巨大光阻劑、蝕刻後及灰化後殘餘物以及污染物的方法。
在製造半導體和半導體微電路時，經常必須以聚合性有機物質塗佈基材材料。一些基材材料的實例包括，鋁、鈦、銅及塗佈二氧化矽的矽晶圓(其任意具有鋁、鈦或銅的金屬元素)等。通常，該聚合性有機物質為光阻劑材料。這是一種能在光微影術的曝光之後藉由顯影形成蝕刻遮罩的材料。在有些案例中，該光阻劑層需要再加工。在後繼處理步驟中從該基材的表面移除至少一部分光阻劑。有一種從基材移除光阻劑的常用方法為溼式化學法。經調配用以自該基材移除該光阻劑的溼式化學藥品組成物應該能做到這樣而不需要腐蝕、溶解及/或弄鈍任何金屬迴路的表面；以化學方式改變該無機基材；及/或攻擊該基材本身。另一種移除移除光阻劑的方法為經由乾式灰化法，其中藉由利用氧或形成氣，例如氫，的電漿灰化法移除該光阻劑。該等殘餘物或副產物可為該光阻劑本身或該光阻劑、底下的基材及/或蝕刻氣體的組合。這些殘餘物或副產物經常被稱為側壁聚合物、罩或圍籬。
逐漸地，反射性離子蝕刻(RIE)，為導孔、金屬線和溝槽形成的期間為了圖案轉移所選擇的方法。例如，複雜的半導體元件，例如先進的DRAMS和微處理器，其需要多層的後段製程互連件配線，利用RIE以製造導孔、金屬線和溝槽結構。使用導孔，穿過該中間層介電質，以提供矽、矽化物或金屬配線與下一個配線層之間的接觸。
金屬線為用作元件互連件的導電結構。形成金屬線結構時使用溝槽結構。導孔、金屬線及溝槽結構經常露暴出金屬和合金，例如Al、Al和Cu合金、Cu、Ti、TiN、Ta、TaN、W、TiW、矽或矽化物，例如鎢、鈦或鈷的矽化物。該RIE方法經常留下殘餘物或複雜的混合物，其可能包括再濺射的氧化物材料、來自光阻劑的有機材料及/或用以微影方式界定該等導孔、金屬線及/或溝槽結構的抗反射塗佈杪料。
吾人所欲為提供能移除那些不想要的材料而不會腐蝕、溶解或鈍化該基材的暴露表面的清潔配方及方法。在一些例子中，該等不想要的材料為被稱為光阻劑的聚合物組成物。在其他例子中，待移除的不想要的材料為蝕刻或灰化過程的殘餘物或單純地污染物。
在此技術領域中的專利包括US 6,627,587、US 6,723,691、准予Naghshineh等人的US 6,851,432及公告的專利申請案US2006/0016785。
本計畫的總括性目標在於開發一種用於金屬基材，例如鋁及銅基材，的非羥基胺的剝除及清潔配方。這樣的一種剝除劑將具有比羥基胺剝除劑更低的擁有成本(COO)。
因此，本發明之一觀點為一種用於移除巨大光阻劑以及蝕刻後及灰化後殘餘物的配方。該配方包含：烷醇胺、水可混溶性有機共溶劑、季銨化合物、不含游離酸官能基的腐蝕抑制劑及剩餘部分的水。其pH大於9。對於本發明而言，“可混溶性”包括可溶性。
根據本發明的另一觀點，從一基材移除巨大光阻劑以及蝕刻後及灰化後殘餘物的方法包含：將上述列舉的配方法施塗於基材以從該基材移除該光阻劑、蝕刻後和灰化後殘餘物以及污染物。
本發明說明主要設計用於從金屬基材移除光阻劑、蝕刻後和灰化後殘餘物以及污染物的配方。該配方包含烷醇胺、水可混溶性有機共溶劑、季銨化合物、腐蝕抑制劑及剩餘部分的水。其pH大於9。對於本發明而言，“可混溶性”包括可溶性。
在某些具體實施例中，烷醇胺包括但不限於：單乙醇胺、N-甲基乙醇胺、三乙醇胺、異丙醇胺、二乙基羥基胺及其混合物。
在某些具體實施例中，該水可混溶性有機共溶劑可為甘醇醚或呋喃甲醇。該等甘醇醚可包括甘醇單(C1
-C6
)烷基醚類及甘醇二(C1
-C6
)烷基醚類，例如但不限於(C1
-C6
)烷二醇類、(C1
-C6
)烷基醚類及(C1
-C20
)烷二醇類二(C1
-C6
)烷基醚類。甘醇醚類的實例為二丙二醇甲基醚、三丙二醇甲基醚、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、二乙二醇單異丁基醚、二乙二醇單苯甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、三乙二醇單甲基醚、三乙二醇二甲基醚、聚乙二醇單甲基醚、二乙二醇甲基乙基醚、三乙二醇乙二醇單甲基醚醋酸酯、乙二醇單乙基醚醋酸酯、丙二醇單甲基醚、丙二醇二甲基醚、丙二醇單丁基醚、丙二醇單丙基醚、二丙二醇單甲基醚、二丙二醇單丙基醚、二丙二醇單異丙基醚、二丙二醇單丁基醚、二丙二醇二異丙基醚、三丙二醇單甲基醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇及其混合物。甘醇醚更常的實例為丙二醇單甲基醚、丙二醇單丙基醚、叁(丙二醇)單甲基醚及2-(2-丁氧基乙氧基)乙醇。呋喃甲醇的實例為四氫呋喃甲醇(THFA)。
全部有機溶劑(烷醇胺及水可混溶性有機共溶劑)係在1重量%至50重量%的範圍，而較佳範圍為5重量%至40重量%。去離子(DI)水為40重量%至95重量%，而較佳範圍為50重量%至80重量%。
在某些具體實施例中，該季銨化合物包括但不限於：氫氧化季銨，例如氫氧化四甲基銨(TMAH)、氫氧化四乙基銨、氫氧化四丁基銨(TBAH)、氫氧化四丙基銨、氫氧化三甲基乙基銨、氫氧化(2-羥乙基)三甲基銨、氫氧化(2-羥乙基)三乙基銨、氫氧化(2-羥乙基)三丙基銨、氫氧化(1-羥丙基)三甲基銨、氫氧化乙基三甲基銨、氫氧化二乙基二甲基銨及氫氧化苯甲基三甲基銨及其混合物。該等季銨化合物以介於0.5重量%至10重量%或5重量%至10重量%的量存在。
在某些具體實施例中，該組成物可包括0.5重量%至15重量%的一或更多腐蝕抑制劑。任何此技藝中用於類似應用的習知腐蝕抑制劑均可使用。可使用的腐蝕抑制劑的實例包括：苯磷二酚、第三丁基苯磷二酚、焦性沒食子酸、苯并***(BZT)、間苯二酚、沒食子酸酯及其混合物。這些為不含游離酸官能基的腐蝕抑制劑，其避免金屬的腐蝕。
不含游離酸官能基並且已經於下列實施例中顯示出不會不當地使金屬遭受腐蝕的特定腐蝕抑制劑的實例包括：胺茴酸、沒食子酸、辛酸、硬脂酸、苯甲酸、鄰苯二甲酸、順丁烯二酸、反丁烯二酸、D,L-蘋果酸、丙二酸、對苯二甲酸、順丁烯二酸酐、對苯二甲酸酐、羧基苯并***、乳酸、檸檬酸等及其混合物或附帶前述列舉的腐蝕抑制劑。
儘管本發明已經關聯清潔半導體基材作主要說明，但是本發明的清潔配方可用以清潔任何包括有機及無機殘餘物的基材或半導體元件。
提供下列實施例以達到進一步舉例說明本發明的目的，但是完全沒有限制彼的意圖。
底下提供本發明中的配方之實例。把該等配方中所用的縮寫列在下面。
THFA=四氫呋喃甲醇
TMAH=氫氧化四甲基銨
DPM=二丙二醇甲基醚
TBAH=氫氧化四丁基銨
MEA=單乙醇胺
NMEA=N-甲基乙醇胺
p-TSA=p-甲苯磺酸
t-PGME=三丙二醇甲基醚
PG=丙二醇
DEHA=二乙基羥基胺
在下列實施例中，全部量均以重量百分比提供並且加起來至多100重量百分比。文中所揭示的組成物係於室溫在一容器中將組成分混在一起直到所有固體均溶解而製備。表I中陳述文中所揭示的某些組成物的實施例。
複雜的半導體元件，例如DRAMS和微處理器，其需要多層的後段製程(BEOL)互連件配線，利用反應性離子蝕刻(RIE)以製造導孔、金屬線和墊片。該等導孔，在清潔實驗中使用，係穿過該中間層介電質至蝕刻阻擋層，例如；TiN、SiN等等，而該等金屬線為用作元件互連件的傳導結構。
該等基材(金屬1至3)有些被灰化，而其他的沒被灰化。當該等基材被灰化時，被清潔的主要殘餘物為蝕刻劑殘餘物。若該等基材沒被灰化時，則被清潔或剝除的主要殘餘物為蝕刻殘餘物和光阻劑二者。金屬1至3為不同的迴路結構，其各自由鋁金屬裝配。
清潔試驗用305 M1的清潔組成物在具有設於600 rpm的”圓形鐵氟龍攪拌棒的400mL燒杯中進行。必要的話，在加熱板上把該等清潔組成物加熱至預期的溫度，指示於下文。在下列條件組合之下把尺寸大約1” x 1”的晶圓片斷浸在該等組成物中：處理時間介於1分鐘至30分鐘，於介於25℃至75℃的處理溫度。
表II中總結清潔結果。
在所用的不同腐蝕抑制劑當中，與常用的腐蝕抑制劑：沒食子酸(實施例A至N)、辛酸(實施例S至T)、硬脂酸(實施例U)、第三丁基苯甲酸(實施例Y)、苯磷二酚(實施例O、Q)或苯磷二酚和沒食子酸的組合(實施例N、P、R)相比，具有焦性沒食子酸及第三丁基苯磷二酚的配方進行的好非常多(實施例V、W至X、Z、A1至A8)。表II中的數據指示使用25%稀釋的TMAH及沒有不具有游離酸官能基(羧酸或磺酸)(“不含游離酸官能基”)的腐蝕抑制劑之配方在移除光阻劑及避免金屬腐蝕方面表現得比較好。
前述實施例及較佳具體實施例的說明應該被當作舉例說明，而非限制本發明，其係如申請專利範圍所界定。咸能輕易明白，上述特徵的許多變化及組合均可被利用而不會悖離本發明，如申請專利範圍中所明示。這樣的變化不得被視為悖離本發明的精神和範圍，而且意欲將所有這樣的變化涵括於下列申請專利範圍的範疇之內。
Claims (6)
- 一種半水性剝除及清潔配方，其包含：a. 19-22重量%的單乙醇胺；b. 二丙二醇甲基醚(DPM)；c. 2.3-3.5重量%的氫氧化四甲基銨(TMAH)；d. 第三丁基苯磷二酚；及e. 剩餘部分的水；其中該配方的pH大於9，其中該二丙二醇甲基醚及氫氧化四甲基銨以前者對後者的重量比從13.7：1至27.2：1存在於該配方中，該二丙二醇甲基醚及單乙醇胺以前者對後者的重量比從0.5：1至1.2：1存在於該配方中，且氫氧化四甲基銨及第三丁基苯磷二酚以前者對後者的重量比從0.3：1至0.4：1存在於該配方中。
- 如申請專利範圍第1項之半水性剝除及清潔配方，其中該氫氧化四甲基銨為25%濃度在水中。
- 一種半水性剝除及清潔配方，其包含：a. 19至22重量%的單乙醇胺；b. 12重量%的二丙二醇甲基醚(DPM)；c. 2.3至3.5重量%的氫氧化四甲基銨(TMAH)；d. 2.3重量%的第三丁基苯磷二酚；及e. 剩餘部分的水； 其中該配方的pH大於9。
- 如申請專利範圍第3項之半水性剝除及清潔配方，其中該氫氧化四甲基銨為25%濃度在水中。
- 一種從半導體基材移除光阻劑、蝕刻或灰化殘餘物及污染物之方法，其包含：使該半導體基材與如申請專利範圍第1項的配方接觸。
- 一種從半導體基材移除光阻劑、蝕刻或灰化殘餘物及污染物之方法，其包含：使該半導體基材與如申請專利範圍第3項的配方接觸。
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| SG168509A1 (en) | 2011-02-28 |
| KR101230319B1 (ko) | 2013-02-06 |
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| EP2281867B1 (en) | 2017-03-22 |
| US20110034362A1 (en) | 2011-02-10 |
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| JP5584044B2 (ja) | 2014-09-03 |
| CN101993797A (zh) | 2011-03-30 |
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| EP2281867A1 (en) | 2011-02-09 |
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