TWI631625B - 具有抑制物之無電鍍銅沉積 - Google Patents

具有抑制物之無電鍍銅沉積 Download PDF

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TWI631625B
TWI631625B TW103121759A TW103121759A TWI631625B TW I631625 B TWI631625 B TW I631625B TW 103121759 A TW103121759 A TW 103121759A TW 103121759 A TW103121759 A TW 103121759A TW I631625 B TWI631625 B TW I631625B
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威廉Ｔ 李
小敏 賓
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蘭姆研究公司
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Abstract

本發明提供一種用於提供金屬填充特徵部於一層中的方法。一非保形金屬種子層係沉積於特徵部之頂部、側壁、及底部，其中沉積於特徵部之頂部和底部的種子層比沉積於特徵部側壁之種子層更多。在特徵部之頂部、側壁、及底部上之該金屬種子層係受到回蝕，其中一些金屬種子層殘留在特徵部的頂部和底部。在該等特徵部之頂部的種子層上之沉積係受抑制。提供一無電鍍「自下而上」的金屬之沉積以填充特徵部。

Description

具有抑制物之無電鍍銅沉積
本發明關於一種在半導體晶圓上形成半導體裝置的方法。更具體地，本發明涉及在低k介電層中形成金屬內連線。
在形成半導體裝置時，導電性金屬內連線係設置於低-k介電層中。大致地，特徵部係被蝕刻至一層中，然後以導體，例如銅填充。利用銅填充蝕刻特徵部的方法係描述在於2007年11月13日所公告、由Ding 等人之名為「用於改善突出部及側壁之金屬化種子層的濺鍍沉積和蝕刻」的美國專利第7294574號；於2010年2月9日所公告、由 Juliano 等人之名為「金屬種子層的選擇性再濺鍍」 的美國專利第7659197號；於2003年12月16日所公告、由Andryuschenko等人之名為「用於製備銅種子層之無電鍍銅沉積方法」的美國專利第6664122號；於2008年11月25日所公告、由Varadarajan 等人之名為「無電鍍銅填充處理」的美國專利第7456102號；於2009年3月10日公告、由Poole 等人之名為「無甲醛無電鍍銅組合物」的美國專利第7501014號；以及於2010年1月26日所公告、由Lubomirsky等人之名為「用於無電鍍銅沉積之處理」的美國專利第7651934號中，其係特別併入於此作為參考。
為了實現上述並根據本發明之目的，提供一種用於提供金屬填充特徵部於一層中的方法。一非保形金屬種子層係沉積於特徵部之頂部、側壁、及底部，其中沉積於特徵部之頂部和底部的種子層比沉積於特徵部側壁之種子層更多。回蝕於該等特徵部之頂部、側壁、及底部上之該金屬種子層，其中一些金屬種子層殘留在該等特徵部的頂部和底部上。在該等特徵部之頂部的種子層上之沉積係受抑制。提供一無電鍍「由下而上」的金屬之沉積以填充特徵部。
在本發明的另一種表現形式中，提供一種用於提供金屬填充特徵部於一層中的方法。一障壁層係沉積於特徵部之頂部、側壁、及底部。一非保形銅或銅合金種子層係沉積於特徵部之頂部、側壁、及底部上之障壁層上，其中沉積於特徵部之頂部及底部上的種子層比沉積於側壁的種子層更多。於該等特徵部之頂部、側壁、及底部上之該金屬種子層係被回蝕，其中一些金屬種子層殘留在該等特徵部的頂部和底部上。僅於該等特徵部之頂部上的該種子層上形成一聚合物鏈的抑制物層。提供無電鍍「由下而上」的銅或銅合金之沉積以填充特徵部。
本發明之這些及其它特徵部將於以下的本發明之詳細實施方式並結合下列圖式予以詳細描述。
本發明將參照如隨附圖式中所繪示之其若干較佳實施例進行詳細說明。在以下敘述中，提出許多具體細節以提供對本發明之深入了解。然而對熟習本技藝者將顯而易見，本發明可在缺少這些具體細節的部份或所有者的情況下實施。在其它情況下，已為人所熟知之程序步驟以及／或是結構將不再詳述，以不非必要地使本發明失焦。
在介電層中填充具有金屬線、介層窗、及接點之特徵部的各種方法可能會導致空隙產生。隨著特徵部尺寸減小，空隙出現的可能性及影響變大，從而使空隙之避免更加困難。本發明之一實施例減少在形成金屬線、介層窗、及接點於特徵部中時產生的空隙。
圖1為本發明之一實施例的高階流程圖。在此實施例中，提供複數特徵部於一層中（步驟104）。一障壁層係沉積於該層之表面上（步驟108）。一金屬種子層係沉積於該層之表面上（步驟112）。 較佳地，該金屬種子層係定向性且非保形地沉積，從而使沉積於特徵部之底部和頂部上的金屬種子層比沉積於特徵部之側壁上者更多。該金屬種子層被等向地回蝕（步驟116）。特徵部的頂部上之無電鍍沉積係受抑制（步驟124）。無電鍍沉積係用於沉積金屬，如鈷或銅或其它金屬或合金，以填充具有導電佈線或接點之特徵部（步驟128）。 在該介層窗之頂部上的抑制物層和金屬種子層係被移除（步驟132）。
在本發明之一較佳實施例中，特徵部係提供於一層中（步驟104）。圖2A為堆疊200的的示意性剖面圖，其具有基板204和具有特徵部220之層208。在此示例中，一或更多層216係設置於基板204和層208之間。 在此示例中，具有特徵部220之層208為一介電層。更佳地，層208為一低k介電層，具有小於4.0 的k值。 在此實施例中，該層為有機矽酸鹽玻璃（OSG）。
一障壁層係沉積於特徵部中（步驟108）。在此實施例中，障壁層包含Co、Ta、Ru、W、V、或有機層。在其它實施例中，障壁層可包含金屬氮化物層，如TiN、 RuN、VN、或TaN、或非晶碳層。圖2B為障壁層212被沉積後之堆疊200的示意性剖面圖。
一金屬種子層係被沉積，相對於特徵部之側壁，其沉積在特徵部之頂部及底部上的厚度更大（步驟112）。在此實施例中，該金屬種子層為銅或銅合金，其係由透過物理氣相沉積（PVD）提供之定向和非保形沉積所提供。圖2C為銅種子層相對於該特徵部的側壁，優先地沉積在特徵部之頂部和底部後的堆疊200之示意圖。 如圖所示，在特徵部之底部224上的沉積較多、在特徵部之頂部228上的沉積較多，且在側壁232上之沉積很少。 如圖所示，在特徵部之頂部228上係指在相鄰於特徵部220之層208的頂部上。 在此實施例中，亦形成靠近特徵部的頂部228之突出部236。 沉積之相對厚度係非按比例繪製，以能清楚地顯示不同的層。較佳地，在特徵部之底部224的銅沉積厚度與在特徵部側壁232的銅沉積厚度之比為至少3:1。 更佳地，在特徵部之底部224的銅沉積厚度與在特徵部側壁232的銅沉積厚度之比為至少5:1。 定向物理氣相沉積（PVD）可提供於特徵部側壁232上具有最少之沉積的非保形沉積。 此等定向PVD在本領域中係為已知。例如，定向PVD係教示於2012年8月28日所公告、由Su 等人之名為「用於改善側壁覆蓋率之原位銅種子層的形成」的美國專利第8252690號中，其係併入於此作為參考。
該金屬種子層係進行回蝕（步驟116）。較佳地，該蝕刻為一非定向蝕刻。此非定向蝕刻可為濕式蝕刻或乾式蝕刻。該蝕刻步驟應蝕刻種子層而非下方的障壁層。此非定向蝕刻會在特徵部的頂部、側壁和底部蝕刻約相等的金屬種子層。由於在側壁上的金屬種子層之沉積少很多，在側壁上之金屬種子層可在特徵部的頂部和底部之金屬種子層之前被完全移除。較佳地，在側壁上的金屬種子層係完全蝕刻掉，而在特徵部的頂部和底部上之金屬種子層仍然存在。 圖2D為金屬種子層被回蝕後之堆疊200之示意圖。在側壁上的金屬種子層被完全移除。在特徵部之頂部228上之金屬種子層及在特徵部之底部224上之金屬種子層係被蝕刻，但仍然存在。 突出部也已經被移除。在此蝕刻之示例中，金屬種子層係暴露至H2 O2 、NH3 、和環己二胺四乙酸（cyclohexanediaminetetraacetic acid ,CDTA）之溶液中。
於特徵部之頂部228上的無電鍍沉積受抑制（步驟124），而特徵部之底部224上的無電鍍沉積則未受抑制。在此實施例中，抑制物層係由太大而無法沉積至特徵部中之長聚合物鏈所形成。圖2E 為抑制物層240形成於在特徵部之頂部228的金屬種子層上方後之堆疊200之示意圖。在此實施例中，使用聚乙二醇（PEG）之抑制性分子形成一抑制物層。明確的PEG分子量將取決於該特徵部220之直徑或關鍵尺寸(critical dimension, CD)。在此實施例中，由於該PEG比特徵部的直徑大，因此所使用的PEG分子無法容納在特徵部220內。對於具有25nm的CD之特徵部而言，較佳的是該PEG分子具有至少6000的分子量。
堆疊200係接著進行無電鍍沉積（步驟128）。在此實施例中，無電鍍沉積形成銅或銅合金線、介層窗或接點於特徵部中。 圖2F為部分透過無電鍍沉積形成一部份銅接點244的堆疊200之示意圖。 吾人應注意接點係先形成於特徵部的底部。圖2G為完成無電鍍沉積後、完成之銅線、介層窗或接點248係形成於特徵部中的堆疊200之示意圖。在此實施例中，提供pH為6.0之浸洗槽，其具有濃度為0.05 M之硝酸銅 (Cu(NO3 )2 、濃度為0.15M之硝酸鈷(Co(NO3 )2 )、濃度為0.6M之乙二胺、濃度為0.875M之硝酸（HNO3 ）、濃度為3 mM之溴化鉀、以及濃度介於約0.000141 M和約0.000282 M之間的聚二硫二丙烷磺酸鈉（bis(sodium sulfopropyl) disulfide，SPS）。氬氣係用於將該溶液脫氧。 關於無電鍍銅沉積之額外的資訊可在於2007年11月20日公告、由Dordi等人之名為「用於銅之無電鍍沉積之鍍液」的美國專利第7297190號中找到，其係併入於此作為參考。 在其他實施例中，甲醛或其它有機還原劑可代替硝酸鈷使用。
可使用額外的處理以進一步形成特徵部。例如，回蝕或化學機械研磨（CMP）可用於移除抑制物層240、特徵部之頂部228上的部分種子層、部分的障壁層212、以及特徵部之頂部上的部分銅（步驟132）。 圖2H為已使用CMP將堆疊200平坦化後之堆疊200的示意圖。
在各種實施例中，較佳地特徵部深度與特徵部寬度之深寬比為至少3:1。更佳地，該深寬比為至少5:1。 最佳地，該深寬比為 3:1至5:1之間。 較佳地，該CD為小於50nm。更佳地，該CD為小於 30 nm。最佳地，該CD為小於 20nm。不同的實施例可用以填充為線、介層窗、或接點之特徵部。
使用ELD代替電鍍可移除側壁的金屬種子層。本發明之實施例利用該金屬種子層之物理氣相沉積係為非保形之優勢。本發明之實施例並未試圖使PVD處理更保形（此將隨著特徵部尺寸縮小而使缺陷增加），而使用固有的非保形沉積，以移除側壁種子層以提供改良的由下而上之填充沉積。 一實施例可在填充特徵部時提供抑制物層。
本發明雖根據若干較佳實施例加以描述，但仍有落於本發明之範圍內的替換、修改、及各種置換均等物。亦應注意有許多實施本發明之方法及裝置的替代性方式。因此欲使以下隨附請求項解釋為包含所有落於本發明之真正精神及範疇內的此替換、變更及各種置換均等物。
104‧‧‧步驟
108‧‧‧步驟
112‧‧‧步驟
116‧‧‧步驟
124‧‧‧步驟
128‧‧‧步驟
132‧‧‧步驟
200‧‧‧堆疊
204‧‧‧基板
208‧‧‧層
212‧‧‧障壁層
216‧‧‧層
220‧‧‧特徵部
224‧‧‧底部
228‧‧‧頂部
232‧‧‧側壁
236‧‧‧突出部
240‧‧‧抑制物層
244‧‧‧接點
248‧‧‧接點
本發明係藉由例示而非限制之方式顯示於隨附圖式中之圖形，且其中相似的元件符號表示相似的元件，且其中：
圖1為本發明之一實施例的流程圖。
圖2A-H為使用本發明之處理所形成之結構之示意圖。

Claims (19)

  1. 一種用於提供金屬填充之複數特徵部於一層中之方法，包含：沉積一障壁層於該等特徵部之頂部、側壁、及底部上；沉積一非保形銅或銅合金種子層於該等特徵部之頂部、側壁、及底部上之該障壁層上，其中沉積於該等特徵部之頂部和底部上的種子層比沉積於該等特徵部之側壁的種子層更多；回蝕於該等特徵部之頂部、側壁、及底部上之該種子層，其中一些種子層殘留在該等特徵部的頂部和底部上；僅於該等特徵部之頂部的該種子層上形成一聚合物鏈的抑制物層；及提供一無電鍍「由下而上」的銅或銅合金之沉積以填充該等特徵部。
  2. 一種用於提供金屬填充之複數特徵部於一層中之方法，包含：沉積一非保形金屬種子層於該等特徵部之頂部、側壁、及底部上，其中沉積於該等特徵部之頂部及底部上的種子層比沉積於側壁的種子層更多；回蝕於該等特徵部之頂部、側壁、及底部上之該種子層，其中一些種子層殘留在該等特徵部的頂部和底部上；抑制於該等特徵部之頂部上之種子層上的沉積；及提供一「由下而上」的無電鍍金屬之沉積以填充該等特徵部。
  3. 如申請專利範圍第2項之用於提供金屬填充之複數特徵部於一層中之方法，更包含在沉積該種子層前，沉積一障壁層於該等特徵部中。
  4. 如申請專利範圍第3項之用於提供金屬填充之複數特徵部於一層中之方法，其中該回蝕該種子層之步驟包含提供一濕式蝕刻。
  5. 如申請專利範圍第4項之用於提供金屬填充之複數特徵部於一層中之方法，其中該沉積該種子層之步驟，係以至少3：1之厚度比相對於該等特徵部之側壁沉積該種子層於該等特徵部之底部上。
  6. 如申請專利範圍第4項之用於提供金屬填充之複數特徵部於一層中之方法，其中該沉積該種子層之步驟，係以至少5：1之厚度比相對於該等特徵部之側壁沉積該種子層於該等特徵部之底部上。
  7. 如申請專利範圍第6項之用於提供金屬填充之複數特徵部於一層中之方法，其中該等特徵部其中至少一者具有至少3：1的深寬比。
  8. 如申請專利範圍第7項之用於提供金屬填充之複數特徵部於一層中之方法，其中該等特徵部具有小於30nm的關鍵尺寸(critical dimension,CD)。
  9. 如申請專利範圍第8項之用於提供金屬填充之複數特徵部於一層中之方法，其中該金屬的沉積為銅或銅合金之沉積。
  10. 如申請專利範圍第9項之用於提供金屬填充之複數特徵部於一層中之方法，其中該種子層係為銅或銅合金種子層。
  11. 如申請專利範圍第10項之用於提供金屬填充之複數特徵部於一層中之方法，其中該沉積該種子層之步驟包含提供物理氣相沉積。
  12. 如申請專利範圍第11項之用於提供金屬填充之複數特徵部於一層中之方法，其中該抑制於頂部上之該種子層之沉積的步驟包含：形成一抑制物層於該等特徵部之頂部上。
  13. 如申請專利範圍第12項之用於提供金屬填充之複數特徵部於一層中之方法，其中該抑制物層係由太大而無法沉積於該等特徵部中之複數聚合物鏈所形成。
  14. 如申請專利範圍第13項之用於提供金屬填充之複數特徵部於一層中之方法，其中該等聚合物鏈係透過將該種子層暴露至聚乙二醇而形成。
  15. 如申請專利範圍第2項之用於提供金屬填充之複數特徵部於一層中之方法，其中該沉積該種子層之步驟，係以至少3：1之厚度比相對於該等特徵部之側壁沉積該種子層於該等特徵部之底部上。
  16. 如申請專利範圍第2項之用於提供金屬填充之複數特徵部於一層中之方法，其中該等特徵部其中至少一者具有至少3：1的深寬比。
  17. 如申請專利範圍第2項之用於提供金屬填充之複數特徵部於一層中之方法，其中該抑制於頂部上之該種子層之沉積的步驟包含：形成一抑制物層於該等特徵部之頂部上。
  18. 如申請專利範圍第17項之用於提供金屬填充之複數特徵部於一層中之方法，其中該抑制物層係由太大而無法沉積於該等特徵部中之複數聚合物鏈所形成。
  19. 如申請專利範圍第18項之用於提供金屬填充之複數特徵部於一層中之方法，其中該等聚合物鏈係透過將該種子層暴露至聚乙二醇而形成。
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