TW201312656A - 於阻障表面上之鈷沉積 - Google Patents

於阻障表面上之鈷沉積 Download PDF

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TW201312656A
TW201312656A TW101146410A TW101146410A TW201312656A TW 201312656 A TW201312656 A TW 201312656A TW 101146410 A TW101146410 A TW 101146410A TW 101146410 A TW101146410 A TW 101146410A TW 201312656 A TW201312656 A TW 201312656A
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cobalt
layer
substrate
deposited
plasma
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TWI654684B (zh
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Jiang Lu
Hyoung-Chan Ha
Paul Ma
Seshadri Ganguli
Joseph F Aubuchon
Sang-Ho Yu
Murali Narasimhan
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Applied Materials Inc
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Abstract

本發明之實施例提供一種在一阻障層上沉積一鈷層並接著沉積一導電材料，如銅或一銅合金於其上的製程。在一實施例中，提供一沉積材料於一基材表面的方法，其包括以下步驟：在一基材上形成一阻障層，於氣相沉積製程(例如CVD或ALD)期間暴露此基材至二鈷六羰基丁基乙炔(CCTBA)及氫(H2)以在該阻障層上形成一鈷層，及沉積一導電材料於此鈷層之上。在某些範例中，此阻障層及/或此鈷層於如熱製程、原位電漿製程或遠距電漿製程之處理製程期間可暴露至一氣體或一試劑。

Description

於阻障表面上之鈷沉積
本發明之實施例大致有關用於製造電子及半導體元件的金屬化製程，更詳言之，本發明之實施例為有關在沉積一導電層或接觸材料於阻障層前沉積一鈷層於阻障層的方法。
銅為目前選用於多層金屬化製程的金屬，其對元件的製造為重要的。多層互連迫使製造製程要求高深寬比之孔的平坦化，該孔包括觸點、通孔、線及其他特徵。當特徵具有較高深寬比時，填充此特徵而不產生空隙或形變此特徵之幾何為更困難的。因製造者力求電路密度及品質，可靠地形成互連亦較困難。
因為銅相對低成本及製程性質，銅的使用已擴展至市場，故半導體製造商持續關注藉由減少銅擴散與抗濕潤性以改良在銅與介電材料間之邊界區的方法。因特徵尺寸已減小，已開發數種製程方法以製造銅互連。每一製程方法可增加誤差的可能性，如銅擴散越過邊界區、銅結晶結構變形及抗濕潤。物理氣相沉積(PVD)、化學氣相沉積(CVD)、原子層沉積(ALD)、電化學電鍍(ECP)、無電沉積、化學機械研磨(CMP)、電化學機械研磨(ECMP)及其他沉積與移除銅層的方法利用機械、電或化學方法以操作形 成互連的銅。可沉積阻障及覆蓋層以含有銅。
過去，使用一具有錫、鋁或鎂的鉭、氮化鉭或銅合金層提供在銅與其他材料間的阻障層或一黏合促進劑。此些選擇通常成本高且僅部份有效。因沿此邊界區的銅原子在多重步驟半導體處理期間遭受一般在温度、壓力、大氣條件或其他製程變數的改變，銅可能沿此邊界區移動並成為黏聚的銅。銅亦可能沿此邊界區較不均勻分散並成為抗濕潤的銅。在邊界區的此些改變包括銅原子之應力遷移及電遷移。銅穿越介電層或其他結構之應力遷移及電遷移的增加此生成結構的電阻且減少此生成元件的可靠度。
因此，存在一提升在阻障層上一導電層或接觸材料之安定性與黏合性之需求。亦然，存在改良含銅層之電遷移可靠度的需求，尤其是對於銅線的形成，同時防止銅擴散入鄰近的材料，如介電材料。
本發明之實施例為提供在沉積一導電層於阻障層前沉積一鈷層於阻障層的製程。在一實施例中，提供一沉積材料於基材表面的方法，其包括在基材上形成一阻障層，暴露此基材至二鈷六羰基丁基乙炔(dicobalt hexacarbonyl butylacetylene,CCTBA)及氫(H2)以於氣相沉積製程期間在該阻障層上形成一鈷層，及沉積一導電材料於此鈷層上。
在一範例中，基材可於熱CVD製程期間暴露於一含有CCTBA及氫的沉積氣體。在另一範例中，基材可接著於ALD製程期間暴露於CCTBA與氫。此基材在CVD或ALD製程期間亦可加熱至一自約100℃至約250℃範圍間的温度。此鈷層沉積少於約40Å的厚度。
在某些範例中，阻障層及/或鈷層在處理製程期間可暴露至一氣體或一試劑。此處理可為一熱製程、一原位電漿製程或一遠端電漿製程。此氣體或試劑可含有或為氮(N2)、氨(NH3)、氫(H2)、氨/氫混合物、矽烷、二矽烷、氦、氬、其之電漿、其之衍生物或其等之組合。此阻障層或此鈷層可暴露於此氣體、試劑或電漿約1秒至約30秒範圍內的一段時間。此基材在處理製程期間可加熱至約50℃至約400℃之温度範圍。
在某些範例中，此導電材料可含有銅或銅合金。此導電材料可含有一種晶層及塊體層(bulk layer)。或者，此導電材料可直接沉積於此鈷層上，如藉由電化學電鍍(ECP)製程。在一範例中，一含有銅的種晶層可藉由PVD製程或CVD製程沉積。在另一範例中，此塊體層含有銅且可藉由一ECP製程沉積。此阻障層可含有鉭、氮化鉭、鈦、氮化鈦、鎢、氮化鎢、其之合金、其之衍生物或其等之組合。在一範例中，此阻障層可為一配置在鉭層上的氮化鉭層。
在另一實施例中，提供一種用於在一基材表面上沉積材料的方法，其包括以下步驟：在一基材上形成一阻障層，在預處理製程期間暴露該阻障層至第一電漿，暴露該基材 至CCTBA及氫以於氣相沉積製程期間在該阻障層上形成一鈷層，於後處理製程期間暴露該鈷層至一第二電漿，及藉由一氣相沉積製程沉積一銅層於該鈷層上，如藉由一PVD製程或CVD製程。
在另一實施例中，提供一種用於在一基材表面上沉積材料的方法，其包括以下步驟：在一基材上形成一阻障層，在預處理製程期間暴露此阻障層至一電漿，暴露該基材至CCTBA及一還原氣體以於氣相沉積製程期間在該阻障層上形成一鈷層，於後處理製程期間暴露該鈷層至一氫電漿，及沉積一銅材料於該鈷層之上。在一範例中，此用於沉積該鈷層之氣相沉積製程及該後-處理製程為依序重複以形成一鈷材料。此鈷材料含有多鈷層，其中每一者在另一鈷層沉積前已暴露至一氫電漿。
本發明之實施例為提供在沉積一導電層於阻障層前沉積一鈷層於阻障層或層的方法。此鈷層及阻障層可各自可選擇地暴露至一處理製程，如電漿製程或一熱製程。此導電層可含有銅或一銅合金且藉由物理氣相沉積(PVD)製程、原子層沉積(ALD)製程、電化學電鍍(ECP)製程或一無電沉積製程沉積。此鈷層改良銅邊界區性質以促進黏合性、改良溝槽填充及電移動性能、減少擴散及黏聚並助長在製程期間基材表面的均勻的粗糙度與濕潤性。
第1圖圖示一說明本發明實施例之製程100的流程圖。製程100可用於在一基材上形成一互連或其他元件。在一實施例中，製程100之步驟110-150可在基材200上進行，如在第2A-2F圖中圖示。製程100包括在一基材上沉積或形成一阻障層(步驟110)，可選擇地暴露此阻障層至一預處理製程(步驟120)，沉積一鈷層於此阻障層上(步驟130)，可選擇地暴露此鈷層至一後處理製程(步驟140)，及沉積至少一個導電層於此鈷層上(步驟150)。
第2A圖圖示含有配置於下層202之上的介電層204之基材200。孔206形成於介電層204內且可為一通孔、鑲嵌、穿孔或其他形成於其內的通道。下層202可為一基材、基材表面、接觸層或視元件結構而定的另一層。介電層204可含有一介電材料，如一低k介電材料。在一範例中，介電層204含有一低k介電材料，如一碳氧化矽材料，或一碳摻雜之氧化矽材料，例如BLACK DIAMOND® II低k介電材料，其可得自位於美國加州聖克拉拉市之Applied Materials公司。用於介電層204之合宜材料的另一範例為碳化矽基膜，其係使用如述於共同讓渡之美國專利第6,537,733、6,790,788及6,890,850號的化學氣相沉積(CVD)或電漿輔助CVD(PE-CVD)製程形成，該些專利併入本案做為參考。
在一實施例中，在製程100之步驟110期間至少一個阻障層或材料可沉積或形成於一基材上。在一範例中，第2B圖圖示阻障層210配置於基材200上、在介電層204 之上，並共形地位於孔206內。阻障層210可為一層或多層。阻障層210可含有鈦、氮化鈦、鉭、氮化鉭、鎢、氮化鎢、其等之矽化物、其等之衍生物或其等之組合。在某些實施例中，阻障層210可含有鉭/氮化鉭，鈦/氮化鈦或鎢/氮化鎢之雙層。阻障層210可具有一在自約5Å至約50Å範圍間的厚度，較佳為自約10Å至約30Å，且可藉由PVD、ALD、電漿輔助ALD(PE-ALD)、CVD、PE-CVD、脈衝-CVD或其等之組合形成或沉積。
在一範例中，阻障層210含有藉由PVD製程沉積之金屬鉭的一下層及一藉由另一PVD製程沉積一配置在此氮化鉭下層之上的上層。在另一範例中，阻障層210含有藉由ALD製程沉積之金屬鉭的一下層及一藉由CVD製程沉積一配置於此氮化鉭下層之上的上層。在另一範例中，阻障層210含有藉由PVD製程沉積之金屬鉭的一下層及一藉由CVD製程沉積一配置此氮化鉭下層之上的上層。
例如，阻障層210可含有使用CVD製程或一ALD製程沉積的氮化鉭，其中含鉭化合物或鉭先驅物(例如，PDMAT)與氮先驅物(例如氨)反應。在一實施例中，鉭及/或氮化鉭藉由述於共同讓渡之於2002年10月25日申請之美國專利申請案第10/281,079號，且以US 2003-0121608公開之專利申請案中的ALD製程沉積為一阻障層210，該專利併入本案做為參考。在一範例中，Ta/TaN雙層可沉積為一阻障層210，如各自以ALD、CVD及/或PVD製程以任何順序沉積一層於另一層上之一金屬鉭層及一氮化鉭層。
在另一範例中，一Ti/TiN雙層可沉積為一阻障層210，如各自以ALD、CVD及/或PVD製程以任何順序沉積一層於另一層上之一金屬鈦層及一氮化鈦層。在另一範例中，一W/WN雙層可沉積為一阻障層210，如各自以ALD、CVD及/或PVD製程以任何順序沉積一層於另一層上之一金屬鎢層及一氮化鎢層。
在步驟120，阻障層210可選擇地暴露至一預處理製程，如一電漿製程或一熱製程。在電漿或熱預處理製程期間可暴露至基材200之製程氣體及/或試劑包括氫(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、氫與氨混合物(H2/NH3)、聯胺(N2H4)、矽烷(SiH4)、二矽烷(Si2H6)、氦、氬、其之衍生物、其之電漿或其等之組合。製程氣體可以在自約500 sccm至約10 slm範圍間之流速流入至此製程腔室或暴露至此基材，較佳為自約1 slm至約6 slm，例如約3 slm。
在一實施例中，在步驟120於此預處理製程期間，基材200及阻障層210可暴露至一電漿以除去阻障層210之污染物。基材200可置於一製程腔室內且曝於一製程氣體，該氣體可點燃以形成電漿。製程氣體可含有一種氣體化合物或多種氣體化合物。基材200可在室温(例如23℃)，但通常預熱至後續沉積製程的需求温度。基材200可加熱至自約100℃至約400℃範圍間之温度，較佳為自約125℃至約350℃，且更佳為約150℃至約300℃，如約200℃或約250℃。
此製程腔室可產生一原位電漿或裝設有一遠距電漿源(RPS)。在一實施例中，基材200可暴露至此電漿(例如，原位或遠距)自約0.5秒至約90秒之範圍間的一段時間，較佳為自約10秒至約60秒，且更佳為自約20秒至約40秒。此電漿在功率為自約100瓦特至約1,000瓦特範圍間產生，較佳為約200瓦特至約600瓦特，且更佳為約300瓦特至約500瓦特。此製程腔室通常具有一為約100托耳或更少之內部壓力，如在自約0.1托耳至約100托耳範圍間，較佳為自約0.5托耳至約50托耳，且更佳為自約1托耳至約10托耳。
在一範例中，基材200及阻障層210可暴露至由氫、氨、氮或其等之混合物產生的電漿。在另一範例中，基材200及阻障層210可暴露至由氫及氨產生的電漿。在另一範例中，基材200及阻障層210可暴露至由氫、氮、矽烷、二矽烷或其等之混合物產生的電漿。在另一範例中，基材200及阻障層210可暴露至由氫、氮、氬、氦或其等之混合物產生的電漿。
在另一實施例中，在步驟120，基材200及阻障層210於熱預處理製程期間可暴露至一製程氣體以除去阻障層210之污染物。此熱預處理製程可為一快速熱製程(RTP)或一快速熱退火(RTA)製程。基材200可置於一製程腔室內且曝於至少一製程氣體及/或試劑。此製程腔室可為一用於後續沉積製程之沉積腔室，如一PVD腔室、一CVD腔室或一ALD腔室。或者，此製程腔室可為一熱退火腔 室，如RADIANCE® RTA腔室，其可購自位於美國加州聖克拉拉市之Applied Materials公司。基材200可加熱至自約25℃至約800℃範圍間之温度，較佳為自約50℃至約400℃，且更佳為自約100℃至約300℃。基材200可加熱自約2分鐘至約20分鐘範圍間的一段時間，較佳為自約5分鐘至約15分鐘。例如，基材200在此製程腔室中可加熱至約400℃約12分鐘。
在一範例中，基材200及阻障層210當在此製程腔室中加熱時可曝於氫、氨、氮或其等之混合物。在另一範例中，基材200及阻障層210當在此製程腔室中加熱時可曝於氨/氫混合物。在另一範例中，基材200及阻障層210當在此製程腔室中加熱時可曝於氫、氮、矽烷、二矽烷或其等之混合物。在另一範例中，基材200及阻障層210當在此製程腔室中加熱時可曝於氫、氮、氬、氦或其等之混合物。
在另一實施例中，在製程100之步驟130期間，至少鈷材料或層可沉積或形成於此基材上。在一範例中，第2C圖說明鈷層220配置於基材200上，在阻障層210之上，且在孔206內共形。鈷層220通常為單一層，但可含有多層。鈷層220在遍及阻障層210上可為一連續或一不連續層。鈷層220可具有一約40Å或更少的厚度，如在自約2Å至約40Å之範圍間，較佳為約5Å至約30Å。鈷層220可藉由一氣相沉積製程，如CVD、PE-CVD、脈衝CVD、ALD、PE-ALD或PVD形成或沉積。此電漿輔助氣相沉積製程，亦即PE-CVD及PE-ALD，在此製程腔室內可為一原位電 漿製程，或可為一遠距電漿製程以致電漿可藉由一RPS點燃並直接進入此製程腔室。在許多範例中，鈷層220含有金屬鈷。或者，在其他範例中，鈷層220可含有一種或更多種鈷材料，如金屬鈷、矽化鈷、硼化鈷、磷化鈷、其之合金、其之衍生物或其等之組合。
在某些實施例中，鈷層220可在熱CVD製程、脈衝-CVD製程、PE-CVD製程或脈衝PE-CVD製程期間藉由同時導入一鈷先驅物與一試劑至製程腔室而形成或沉積。在其他實施例中，此鈷先驅物可在熱CVD製程、脈衝CVD製程、PE-CVD製程或脈衝PE-CVD製程期間於無一試劑下導入至此製程腔室。或者，在其他實施例中，鈷層220可在熱ALD製程或PE-ALD製程期間藉由依序導入一鈷先驅物與一試劑至製程腔室而形成或沉積。
在某些範例中，鈷層220可含有金屬鈷，但在其他範例中，可含有其他鈷材料。可藉由本文描述之CVD或ALD製程形成鈷材料(例如，金屬鈷或鈷合金)之合宜鈷驅物包括鈷羰基錯合物、鈷脒化合物、雙環戊二烯鈷化合物、鈷二烯基錯合物、鈷亞硝基錯合物、其之衍生物、其之錯合物、其之電漿或其等之組合。在某些實施例中，鈷材料可藉由更進一步描述於共同讓渡之美國專利第7,264,846及7,404,985號中的CVD與ALD製程沉積，該些專利併入本案做為參考。
在某些實施例中，可使用鈷羰基化合物或錯合物做為鈷先驅物。鈷羰基化合物或錯合物具有化學通式 (CO)xCoyLz，其中X可為1、2、3、4、5、6、7、8、9、10、11、或12，Y可為1、2、3、4或5，及Z可為1、2、3、4、5、6、7或8。此基團L為不存在、一配位體或多個配位體，其可為相同配位體或不同配位體，且包括環戊二烯基、烷基環戊二烯基(例如甲基環戊二烯基或五甲基環戊二烯基)、戊二烯基、烷基戊二烯基、環丁二烯基、丁二烯基、乙烯基、烯丙基(或丙烯基)、烯、二烯、炔、乙炔、丁基乙炔、亞硝基、氨、其之衍生物、其之錯合物、其之電漿或其等之組合。
在一實施例中，在沉積製程期間可使用二鈷六羰基乙醯基化合物以形成鈷材料(例如，鈷層220)。二鈷六羰基乙醯基化合物可具有化學通式(CO)6Co2(RC≡CR')，其中R及R'為獨立選自氫、甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、苯甲基、芳香族羥基、其之異構物、其之衍生物或其等之組合。在一範例中，二鈷六羰基丁基乙炔(CCTBA，(CO)6Co2(HC≡CtBu))為此鈷先驅物。二鈷六羰基乙醯基化合物之其他範例包括二鈷六羰基甲基丁基乙炔((CO)6Co2(MeC≡CtBu))、二鈷六羰基苯基乙炔((CO)6Co2(HC≡CPh))、二鈷六羰基甲基苯基乙炔((CO)6Co2(MeC≡CPh))、二鈷六羰基甲基乙炔((CO)6Co2(HC≡CMe))、二鈷羰基二甲基乙炔((CO)6Co2(MeC≡CMe))、其之衍生物、其之錯合物、其之電漿或其等之組合。其他範例之鈷羰基錯合物包括環戊二烯基鈷雙(羰基)(CpCo(CO)2)、三羰基烯丙基鈷 ((CO)3Co(CH2CH=CH2))、其之衍生物、其之錯合物、其之電漿或其等之組合。
在另一實施例中，可使用鈷脒酸鹽或鈷醯胺錯合物做為鈷先驅物。鈷醯胺錯合物具有化學通式(RR’N)xCo，其中X可為1、2或3，且R與R’獨立為氫、甲基、乙基、丙基、丁基、烷基、矽烷基、烷基矽烷基、其之衍生物或其等之組合。一些範例之鈷醯胺錯合物包括雙(二(丁基二甲基矽烷基)醯胺)鈷(((BuMe2Si)2N)2Co)、雙(二(乙基二甲基矽烷基)醯胺)鈷(((EtMe2Si)2N)2Co)、雙(二(丙基二甲基矽烷基)醯胺)鈷(((PrMe2Si)2N)2Co)、雙(二(三甲基矽烷基)醯胺)鈷(((Me3Si)2N)2Co)，三(二(三甲基矽烷基)醯胺)鈷(((Me3Si)2N)3Co)、其之衍生物、其之錯合物、其之電漿或其等之組合。
一些範例之鈷先驅物包括甲基環戊二烯基鈷雙(羰基)(MeCpCo(CO)2)、乙基環戊二烯基鈷雙(羰基)(EtCpCo(CO)2)、五甲基環戊二烯基鈷雙(羰基)(Me5CpCo(CO)2)、二鈷八(羰基)(Co2(CO)8)、亞硝基鈷三(羰基)((ON)Co(CO)3)、雙(環戊二烯基)鈷、(環戊二烯基)鈷(環己二烯基)、環戊二烯基鈷(1,3-己二烯基)、(環丁二烯基)鈷(環戊二烯基)、雙(甲基環戊二烯基)鈷、(環戊二烯基)鈷(5-甲基環戊二烯基)，雙(乙烯)鈷(五甲基環戊二烯基)、四羰基碘化鈷、鈷四羰基三氯矽烷、羰基氯三(三甲基膦)鈷、鈷三羰基-氫三丁基膦、乙炔二鈷六羰基、乙炔 二鈷五羰基三乙基膦、其之衍生物、其之錯合物、其之電漿或其等之組合。
在某些範例中，當藉由本文描述之製程形成鈷材料(例如，金屬鈷或鈷合金)時，可使用交替試劑與鈷先驅物反應，該試劑包括還原劑，其包括氫(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、聯胺(N2H4)、一氫與氨之混合物(H2/NH3)、硼烷(BH3)、二硼烷(B2H6)、三乙基硼烷(Et3B)、矽烷(SiH4)、二矽烷(Si2H6)、三矽烷(Si3H8)、四矽烷(Si4H10)、甲基矽烷(SiCH6)、二甲基矽烷(SiC2H8)、膦(PH3)、其之衍生物、其之電漿或其等之組合。
在一實施例中，含金屬鈷的鈷層220在熱CVD製程期間藉由同時將基材200暴露至一鈷先驅物氣體與一還原劑而沉積。在一可替代的實施例中，含金屬鈷的鈷層220在電漿輔助CVD製程期間藉由同時將基材200暴露至一鈷先驅物氣體與一還原劑而沉積。此電漿源可為在CVD腔室內的原位電漿源或裝設在CVD腔室外的RPS。此鈷先驅物氣體可藉由將一載體氣體(例如，氮或氬)通過一鈷先驅物(例如，CCTBA)安瓿而形成。此還原劑氣體可為單一化合物(例如，H2)，且因此不具有載體氣體。或者，此還原劑氣體可藉由將載體氣體通過一還原劑安瓿而形成。
此安瓿的加熱可依製程期間使用之鈷先驅物或還原劑而定。在一範例中，一含有鈷先驅物的安瓿，如二鈷六羰基乙醯基化合物或其他鈷羰基化合物(例如，(CO)xCoyLz)可加熱至一自約30℃至約500℃範圍間的温度。此鈷先 驅物氣體通常具有一自約100 sccm(每分鐘標準立方公分(standard cubic centimeters per minute))至約2,000 sccm範圍間之流速，較佳為自約200 sccm至約1,000 sccm，且更佳為自約300 sccm至約700 sccm，例如約500 sccm。此還原劑氣體通常具有一自約0.5 slm(每分鐘標準升(standard liters per minute))至約10 slm範圍間之流速，較佳為自約1 slm至約8 slm，且更佳為自約2 slm至約6 slm。在一範例中，還原劑氣體為氫且具有一自約2 slm至約6 slm範圍間之流速，如約4 slm。
此鈷先驅物氣體及此還原劑氣體於沉積製程期間可在進入製程腔室前、當時或之後組合以形成一沉積氣體以沉積鈷層220。基材200可置於一製程腔室內且可加熱至自約25℃至約800℃範圍間之温度，較佳為自約50℃至約400℃，且更佳為自約100℃至約250℃，如約150℃。一旦在預定温度，基材200可暴露至含有鈷先驅物氣體與還原劑氣體的沉積氣體自約0.1秒至約120秒範圍間的一段時間，較佳為自約1秒至約60秒，且更佳為自約5秒至約30秒。例如，基材200當於CVD製程期間形成鈷層220時，其在此製程腔室中可加熱至約150℃約10分鐘。
在步驟140，鈷層220可選擇地曝於一後處理製程，如一電漿製程或一熱製程。在電漿或熱後處理製程期間可曝於基材200及鈷層220的製程氣體及/或試劑包括氫(例如，H2或原子-H)、氮(例如，N2或原子-N)、氨(NH3)、一氫與氨之混合物(H2/NH3)、聯腔(N2H4)、矽烷(SiH4)、二 矽烷(Si2H6)、氦、氬、其之衍生物、其之電漿或其等之組合。此製程氣體可以自約500 sccm至約10 slm範圍間的流速流入此製程腔室或曝至基材，較佳為自約1 slm至約6 slm，例如約3 slm。
在一實施例中，在步驟140於此後處理製程期間，基材200及鈷層220可暴露至一電漿以除去鈷層220之污染物。基材200可置於一製程腔室內且曝於一製程氣體，該氣體可點燃以形成電漿。此製程氣體可含有一氣體化合物或多個氣體化合物。基材200可在室温(例如23℃)，但通常預熱至後續沉積製程的需求温度。基材200可加熱至自約100℃至約400℃範圍間之温度，較佳為自約125℃至約350℃，且更佳為自約150℃至約300℃，如約200℃或約250℃。
此製程腔室可產生一原位電漿或裝設有一RPS。在一實施例中，基材200可暴露至此電漿(例如，原位或遠距)自約0.5秒至約90秒之範圍間的一段時間，較佳為自約10秒至約60秒，且更佳為自約20秒至約40秒。此電漿在功率為自約100瓦特至約1,000瓦特範圍間產生，較佳為自約200瓦特至約600瓦特，且更佳為自約300瓦特至約500瓦特。此製程腔室通常具有一內部壓力為約100托耳或更少，如在自約0.1托耳至約100托耳範圍間，較佳為自約0.5托耳至約50托耳，且更佳為自約1托耳至約10托耳。
在一範例中，基材200及鈷層220可暴露至由氫、氨、氮或其等之混合物產生的電漿。在另一範例中，基材200及鈷層220可暴露至由氫及氨產生的電漿。在另一範例中，基材200及鈷層220可暴露至由氫、氮、矽烷、二矽烷或其等之混合物產生的電漿。在另一範例中，基材200及鈷層220可暴露至由氫、氮、氬、氦或其等之混合物產生的電漿。
在某些範例中，基材200及鈷層220可曝至由RPS點燃之氫氣產生的氫電漿。鈷層220可曝至具自約2 slm至約4 slm範圍間之流速的氫氣體。此製程腔室可具有一內部壓力自約1托耳至約10托耳範圍間，且此電漿係藉由具自約300瓦特至約500瓦特範圍間之功率的RPS點燃。在一實施例中，此電漿對於每一具有自約7Å至約10Å範圍間厚度的鈷材料沉積層係曝至鈷層220自約20秒至約40秒範圍間的一段時間。當形成鈷層220時，可在沉積鈷材料之多層後進行多重處理。
在另一實施例中，在步驟140於此後處理製程期間，基材200及鈷層220可暴露至一製程氣體以除去鈷層220之污染物。此熱後處理製程可為一RTP或RTA製程。基材200可置於一製程腔室內且曝於至少一種製程氣體及/或試劑。此製程腔室可為一在先前沉積製程使用或將在後續沉積製程使用之沉積腔室，如一PVD腔室、一CVD腔室或一ALD腔室。或者，此製程腔室可為一熱退火腔室，如RADIANCE® RTA腔室，其可購自位於美國加州聖克拉 拉市之Applied Materials公司。基材200可加熱至自約25℃至約800℃範圍間之温度，較佳為自約50℃至約400℃，且更佳為自約100℃至約300℃。基材200可加熱自約2分鐘至約20分鐘範圍間的一段時間，較佳為自約5分鐘至約15鐘。例如，基材200在此製程腔室中可加熱至約400℃約12分鐘。
在一範例中，基材200及鈷層220當在此製程腔室中加熱時可曝於氫、氨、氮或其等之混合物。在另一範例中，基材200及鈷層220當在此製程腔室中加熱時可曝於氨/氫混合物。在另一範例中，基材200及鈷層220當在此製程腔室中加熱時可曝於氫、氮、矽烷、二矽烷或其等之混合物。在另一範例中，基材200及鈷層220當在此製程腔室中加熱時可曝於氫、氮、氬、氦或其等之混合物。
第2C圖圖示在基材200上於介電層204內形成孔206。孔206含有共形配置於其內的阻障層210及鈷層220。在另一實施例中，在製程100之步驟150期間，一導電層可沉積或形成於鈷層220上。在一實施例中，此導電層為塊體層240，其可直接沉積於鈷層220上，如在第2D圖中所圖示。或者，在另一實施例中，此導電層為種晶層230及塊體層240。種晶層230可沉積遍及鈷層220且接著塊體層240可沉積遍及種晶層230，如在第2E-2F圖中說明。
種晶層230及塊體層240可在單一沉積製程或多重沉積製程期間沉積或形成。種晶層230可含有銅、鎢、鋁、釕、鈷、銀、鉑、鈀、其之合金、其之衍生物或其等之組合。 塊體層240可含有銅、鎢、鋁、其之合金、其之衍生物或其等之組合。通常，種晶層230及塊體層240可獨立含有銅、鎢、鋁、其之合金、其之衍生物或其等之組合。種晶層230及塊體層240可獨立地藉由使用一或一以上的沉積製程沉積，如一CVD製程、ALD製程、PVD製程、無電沉積製程、ECP製程、其之衍生物或其等之組合。
在一範例中，種晶層230及塊體層240之每一者含有銅或一銅合金。例如，含有銅之種晶層230可藉由PVD製程形成於鈷層220上，且接著含有銅之塊體層240可藉由ECP製程或無電沉積製程沉積以填充孔206。在另一範例中，含有銅之種晶層230可藉由ALD製程形成於鈷層220上，且接著含有銅之塊體層240可藉由ECP製程或無電沉積製程沉積以填充孔206。在另一範例中，含有銅之種晶層230可藉由CVD製程形成於鈷層220上，且接著含有銅之塊體層240可藉由ECP製程或無電沉積製程沉積以填充孔206。在另一範例中，含有銅之種晶層230可藉由無電製程形成於鈷層220上，且接著含有銅之塊體層240可藉由ECP製程或無電沉積製程沉積以填充孔206。在另一範例中，鈷層220做為一種晶層，則含有銅之塊體層240可藉由ECP製程或無電沉積製程直接沉積於其上以填充孔206。
在一範例中，種晶層230及塊體層240之每一者含有鎢或一鎢合金。例如，含有鎢之種晶層230可藉由PVD製程形成於鈷層220上，且接著含有鎢之塊體層240可藉由 CVD製程或脈衝CVD製程沉積以填充孔206。在另一範例中，含有鎢之種晶層230可藉由ALD製程形成於鈷層220上，且接著含有鎢之塊體層240可藉由CVD製程或脈衝CVD製程沉積以填充孔206。在另一範例中，含有鎢之種晶層230可藉由脈衝CVD製程形成於鈷層220上，且接著含有鎢之塊體層240可藉由CVD製程或脈衝CVD製程沉積以填充孔206。在另一範例中，含有鎢之種晶層230可藉由無電製程形成於鈷層220上，且接著含有鎢之塊體層240可藉由CVD製程或脈衝CVD製程沉積以填充孔206。在另一範例中，鈷層220做為一種晶層，則含有鎢之塊體層240可藉由CVD製程或脈衝CVD製程直接沉積於其上以填充孔206。
在本文實施例中使用的ALD製程腔室係可得自位於美國加州聖克拉拉市之Applied Materials公司。ALD製程腔室的詳細說明可見於共同讓渡的美國專利第6,916,398及6,878,206號，共同讓渡之於2002年10月25日申請之美國專利申請案第10/281,079號，且以US 2003-0121608早期公開之專利申請案，及共同讓渡之各別於2006年11月6日申請的美國專利申請號第11/556,745、11/556,752、11/556,756、11/556,758、11/556,763號且以美國專利公開號第2007-0119379、2007-0119371、2007-0128862、2007-0128863及2007-0128864號早期公開之申請案，該些專利併入本案做為參考。在另一實施例中，建構可用於ALD模式以及傳統CVD模式操作以沉積含鈷材料的腔室 係描述於共同讓渡之美國專利第7,204,886號，該專利併入本案做為參考。一用於形成含鈷材料的ALD製程之詳細描述更進一步揭露於共同讓渡美國專利第7,264,846及7,404,985號，該些專利併入本案做為參考。在其他實施例中，建構可用於ALD模式以及傳統CVD模式操作以沉積含鈷材料的腔室係TXZ®噴灑頭及CVD腔室，其可得自位於美國加州聖克拉拉市之Applied Materials公司。合宜之氣相沉積腔室的範例包括WXZTM CVD腔室，其可購自位於美國加州聖克拉拉市之Applied Materials公司。此氣相沉積腔室可適於藉由傳統CVD、脈衝CVD或PE-CVD技術以及藉由ALD與PE-ALD技術沉積材料。亦然，此氣相沉積腔室可用於處理製程，如一原位電漿製程、一遠距電漿製程或熱退火製程。
本文使用之「基材表面」或「基材」係指任何在一基材上形成的基材或材料表面，在其上可於一製造製程期間進行膜處理。例如，一可進行製程的基材表面包括材料如單晶、多晶或非晶矽、應變矽、在絕緣體上矽(SOI)、摻雜矽、矽化鍺、鍺、砷化鎵、玻璃、藍寶石、氧化矽、氮化矽、氮氧化矽及/或碳摻雜氧化矽，如SiOxCy，例如BLACK DIAMOND®低k介電材料，其可得自位於美國加州聖克拉拉市之Applied Materials公司。基材可具有不同尺寸，如100 mm、200 mm、300 mm或450 mm直徑晶圓，以及矩形或方形片。除非特別指明，本發明描述之實施例及範例通常在具有200 mm直徑或300 mm直徑的基材上進行， 更佳為300 mm直徑。本發明描述之製程可用於在許多基材及表面上沉積鈷材料(例如，金屬鈷)，尤其是阻障層及層。在本發明之實施例可使用的基材包括但未限制為半導體晶圓，如結晶矽(例如，Si<100>或Si<111>)、氧化矽、應變矽、矽化鍺、摻雜或未摻雜之多晶矽、摻雜或未摻雜之矽晶圓、及圖案化或未圖案化之晶圓。基材可暴露至預處理製程以研磨、蝕刻、還原、氧化、羥化、加熱、及/或退火此基材或基材表面。
雖然前述為有關本發明之實施例，但本發明之其他及進一步的實施例可未偏離本發明之技術之基本視野下完成，且本發明之範疇係由後文之申請專利範圍界定。
100‧‧‧說明製程的流程圖
110、120、130、140、150‧‧‧步驟
200‧‧‧基材
202‧‧‧下層
204‧‧‧介電層
206‧‧‧孔
210‧‧‧阻障層
220‧‧‧鈷層
230‧‧‧種晶層
240‧‧‧塊體層
在前文概述之本發明的更詳細描述可參考實施例，其之部份為說明於附圖中，以此方式，本發明於前文述及的特徵可更詳盡的瞭解。然而，需瞭解附圖僅為用以說明本發明之典型實施例，故因此不能被視為限制本發明的範疇，因為本發明容許其他等效的實施態樣。
第1圖圖示根據本文描述之一實施例說明一製程之流程圖；及第2A-2F圖圖示根據本文描述之一實施例在不同製程步驟中基材的示意圖。
200‧‧‧基材
202‧‧‧下層
204‧‧‧介電層
220‧‧‧鈷層
230‧‧‧種晶層
240‧‧‧塊體層

Claims (52)

  1. 一種用於在一基材上形成一含矽化鈷的材料的方法，包含以下步驟：暴露一基材至至少一個預清潔製程以暴露一含矽表面；在該含矽表面上沉積一矽化鈷材料；在該矽化鈷材料上沉積一金屬鈷材料；以及在該基材上沉積一金屬接觸材料，其中在一矽浸泡(soak)製程期間，該矽化鈷材料或該金屬鈷材料暴露至一含矽的還原氣體以及一電漿處理。
  2. 如請求項1所述之方法，其中該矽化鈷材料與該金屬鈷材料是在相同的處理腔室中沉積。
  3. 如請求項1所述之方法，其中透過在一化學氣相沉積製程或一原子層沉積製程期間將該基材暴露至一鈷先驅物與一矽先驅物，而沉積該矽化鈷材料。
  4. 如請求項3所述之方法，其中該矽化鈷材料包含一矽/鈷原子之比值，該比值大於0.5。
  5. 如請求項4所述之方法，其中該矽/鈷原子之比值在從約1至約2的範圍內。
  6. 如請求項1所述之方法，其中該金屬接觸材料包含一材料，該材料選自由鎢、銅、鋁、以及前述材料之組合所構成的群組。
  7. 如請求項6所述之方法，其中該金屬接觸材料的沉積包含以下步驟：形成一種晶層以及在該種晶層上形成一塊體層。
  8. 如請求項7所述之方法，其中該種晶層包含鎢且該塊體層包含鎢。
  9. 如請求項1所述之方法，其中一阻障材料沉積在該金屬鈷材料上，且該金屬接觸材料沉積在該阻障層上。
  10. 如請求項9所述之方法，其中該阻障材料包含一材料，該材料選自以下材料所構成之群組：鉭、氮化鉭、鈦、氮化鈦、鎢、氮化鎢、前述材料之合金以及前述材料之衍生物。
  11. 如請求項3所述之方法，其中該鈷先驅物包含一化合物，該化合物選自以下化合物所構成之群組：三羰基烯丙基鈷、環戊二烯基鈷雙(羰基)、甲基環戊二烯基鈷雙(羰基)、乙基環戊二烯基鈷雙(羰基)、五甲基環戊二烯基鈷雙(羰基)、二鈷八(羰基)、亞硝基鈷三(羰基)、 雙(環戊二烯基)鈷、(環戊二烯基)鈷(環己二烯基)、環戊二烯基鈷(1,3-己二烯基)、(環丁二烯基)鈷(環戊二烯基)、雙(甲基環戊二烯基)鈷、(環戊二烯基)鈷(5-甲基環戊二烯基)、雙(乙烯)鈷(五甲基環戊二烯基)、前述化合物的衍生物、前述化合物的錯合物、前述化合物的電漿、以及前述化合物的組合。
  12. 如請求項11所述之方法，其中該鈷先驅物包含一環戊二烯基鈷雙(羰基)。
  13. 如請求項3所述之方法，其中該鈷先驅物包含化學通式(CO)xCOyLz，其中：x是1、2、3、4、5、6、7、8、9、10、11、或12；y是1、2、3、4、或5；z是1、2、3、4、5、6、7、或8；以及L是一配位體，獨立地選自以下配位體所構成的群組：環戊二烯基、烷基環戊二烯基、甲基環戊二烯基、五甲基環戊二烯基、戊二烯基、烷基戊二烯基、環丁二烯基、丁二烯基、烯丙基、乙烯、丙烯、烯烴、二烯烴、炔、亞硝基、氨、前述配位體之衍生物、前述配位體之組合。
  14. 如請求項3所述之方法，其中該矽先驅物包含一化合物，該化合物選自由矽烷、二矽烷、前述化合物之衍生物、前述化合物之電漿、與前述化合物之組合所構 成的群組。
  15. 如請求項3所述之方法，其中該基材在該化學氣相沉積製程或該原子層沉積製程期間被加熱到至少100℃的溫度。
  16. 如請求項15所述之方法，其中該溫度是在約300℃至約400℃的範圍內。
  17. 如請求項1所述之方法，其中沉積該金屬鈷材料之前，將該矽化鈷材料暴露至一電漿。
  18. 如請求項17所述之方法，其中該電漿是透過一射頻由氫氣生成。
  19. 如請求項3所述之方法，其中該原子層沉積製程期間沉積該矽化鈷材料是透過以下步驟進行：進行一沉積循環以沉積一矽化鈷層；以及重複該沉積循環以形成複數個矽化鈷層，其中該沉積循環包含以下步驟：將該基材暴露到包含該矽先驅物的一還原氣體，同時依序將該基材暴露至該鈷先驅物以及一電漿。
  20. 如請求項19所述之方法，其中該電漿包含一氫電漿。
  21. 如請求項1所述之方法，其中在該矽浸泡製程期間，該矽化鈷材料暴露至該含矽的還原氣體以及該電漿處理。
  22. 如請求項1所述之方法，其中在該矽浸泡製程期間，該金屬鈷材料暴露至該含矽的還原氣體以及該電漿處理。
  23. 如請求項1所述之方法，其中於一脈衝式化學氣相沉積製程期間沉積該矽化鈷材料，此步驟是透過以下步驟進行：進行一沉積循環以沉積一矽化鈷層；以及重複該沉積循環以形成複數個矽化鈷層，其中該沉積循環包含以下步驟：將該基材暴露到一矽先驅物、一鈷先驅物、以及一電漿。
  24. 如請求項1所述之方法，其中該含矽表面包含多晶矽。
  25. 一種用於在一基材上形成一含矽化鈷的材料的方法，包含以下步驟：暴露一基材至至少一個預清潔製程以暴露一含矽表面；在該含矽表面上沉積一矽化鈷材料；將該基材暴露至一退火製程； 在該矽化鈷材料上沉積一阻障材料；以及在該阻障材料上沉積一金屬接觸材料，其中在一矽浸泡製程期間，該矽化鈷材料或該阻障材料暴露至一含矽的還原氣體以及一電漿處理。
  26. 如請求項25所述之方法，其中在該退火製程期間在一退火腔室內，該基材被加熱到至少約600℃的溫度。
  27. 如請求項25所述之方法，其中透過在一化學氣相沉積製程或一原子層沉積製程期間將該基材暴露至一鈷先驅物與一矽先驅物，而沉積該矽化鈷材料。
  28. 如請求項27所述之方法，其中該矽化鈷材料包含一矽/鈷原子之比值，該比值大於0.5。
  29. 如請求項28所述之方法，其中該矽/鈷原子之比值在從約1至約2的範圍內。
  30. 如請求項25所述之方法，其中該金屬接觸材料包含一材料，該材料選自由鎢、銅、鋁、以及前述材料之組合所構成的群組。
  31. 如請求項30所述之方法，其中該金屬接觸材料的沉積包含以下步驟：形成一種晶層以及在該種晶層上形成 一塊體層。
  32. 如請求項31所述之方法，其中該種晶層包含鎢且該塊體層包含鎢。
  33. 如請求項25所述之方法，其中該阻障材料包含一材料，該材料選自以下材料所構成之群組：鉭、氮化鉭、鈦、氮化鈦、鎢、氮化鎢、鈷、前述材料之合金以及前述材料之衍生物。
  34. 如請求項27所述之方法，其中該鈷先驅物包含一化合物，該化合物選自以下化合物所構成之群組：三羰基烯丙基鈷、環戊二烯基鈷雙(羰基)、甲基環戊二烯基鈷雙(羰基)、乙基環戊二烯基鈷雙(羰基)、五甲基環戊二烯基鈷雙(羰基)、二鈷八(羰基)、亞硝基鈷三(羰基)、雙(環戊二烯基)鈷、(環戊二烯基)鈷(環己二烯基)、環戊二烯基鈷(1,3-己二烯基)、(環丁二烯基)鈷(環戊二烯基)、雙(甲基環戊二烯基)鈷、(環戊二烯基)鈷(5-甲基環戊二烯基)、雙(乙烯)鈷(五甲基環戊二烯基)、前述化合物的衍生物、前述化合物的錯合物、前述化合物的電漿、以及前述化合物的組合。
  35. 如請求項34所述之方法，其中該鈷先驅物包含一環戊二烯基鈷雙(羰基)。
  36. 如請求項27所述之方法，其中該鈷先驅物包含化學通式(CO)xCOyLz，其中：x是1、2、3、4、5、6、7、8、9、10、11、或12；y是1、2、3、4、或5；z是1、2、3、4、5、6、7、或8；以及L是一配位體，獨立地選自以下配位體所構成的群組：環戊二烯基、烷基環戊二烯基、甲基環戊二烯基、五甲基環戊二烯暴、戊二烯基、烷基戊二烯基、環丁二烯基、丁二烯基、烯丙基、乙烯、丙烯、烯烴、二烯烴、炔、亞硝基、氨、前述配位體之衍生物、前述配位體之組合。
  37. 如請求項27所述之方法，其中該矽先驅物包含一化合物，該化合物選自由矽烷、二矽烷、前述化合物之衍生物、前述化合物之電漿、與前述化合物之組合所構成的群組。
  38. 如請求項27所述之方法，其中該基材在該化學氣相沉積製程或該原子層沉積製程期間被加熱到至少100℃的溫度。
  39. 如請求項38所述之方法，其中該溫度是在約300℃至約400℃的範圍內。
  40. 如請求項25所述之方法，其中沉積該阻障材料之前，將該矽化鈷材料暴露至一電漿。
  41. 如請求項40所述之方法，其中該電漿是透過一射頻由氫氣生成。
  42. 如請求項27所述之方法，其中該原子層沉積製程期間沉積該矽化鈷材料是透過以下步驟進行：進行一沉積循環以沉積一矽化鈷層；以及重複該沉積循環以形成複數個矽化鈷層，其中該沉積循環包含以下步驟：將該基材暴露到包含該矽先驅物的一還原氣體，同時依序將該基材暴露至該鈷先驅物以及一電漿。
  43. 如請求項42所述之方法，其中該電漿包含一氫電漿。
  44. 如請求項42所述之方法，其中在該矽浸泡製程期間，該阻障材料暴露至該含矽的還原氣體。
  45. 如請求項44所述之方法，進一步包含以下步驟：在該矽浸泡製程期間，將該阻障材料暴露至該電漿處理。
  46. 如請求項25所述之方法，其中於一脈衝式化學氣相沉積製程期間沉積該矽化鈷材料，此步驟是透過以下步 驟進行：進行一沉積循環以沉積一矽化鈷層；以及重複該沉積循環以形成複數個矽化鈷層，其中該沉積循環包含以下步驟：將該基材暴露到一矽先驅物、一鈷先驅物、以及一電漿。
  47. 如請求項25所述之方法，其中該含矽表面包含多晶矽。
  48. 一種用於在一基材上形成一含金屬矽化物的材料的方法，包含以下步驟：在一反應性預清潔製程期間將一基材暴露至一電漿以暴露一含矽表面，該電漿包含氫、氨、或前述電漿之組合；在該含矽表面上沉積一金屬矽化物材料；在一矽浸泡製程期間將該金屬矽化物材料暴露至一含矽的還原氣體與一電漿處理；在該金屬矽化物材料上沉積一阻障材料；以及沉積一鎢接觸材料覆於該阻障材料上，所述步驟進一步包含以下步驟：在一原子層沉積製程期間，在該阻障材料上沉積一鎢成核層；以及在一化學氣相沉積製程期間，沉積一鎢塊體層覆於該鎢成核層上。
  49. 如請求項48所述之方法，其中該金屬矽化物材料包含 至少一個材料，該材料選自由鎢、鎳、鉑、鈀、前述材料之組合、與前述材料之合金所構成的群組。
  50. 如請求項49所述之方法，其中在該矽浸泡製程期間，該阻障材料暴露至該含矽的還原氣體。
  51. 如請求項50所述之方法，進一步包含以下步驟：在該矽浸泡製程期間，將該阻障材料暴露至該電漿處理。
  52. 如請求項48所述之方法，其中該含矽表面包含多晶矽或氧化矽。
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