TW432486B - Method of improving surface morphology and reducing resistivity of chemical vapor deposition-metal films - Google Patents

Method of improving surface morphology and reducing resistivity of chemical vapor deposition-metal films Download PDF

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TW432486B
TW432486B TW087116727A TW87116727A TW432486B TW 432486 B TW432486 B TW 432486B TW 087116727 A TW087116727 A TW 087116727A TW 87116727 A TW87116727 A TW 87116727A TW 432486 B TW432486 B TW 432486B
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reaction chamber
film
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Chantal Arena
Ronald T Bertram
Emmanuel Guidotti
Joseph T Hillman
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Tokyo Electron Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Description

4324 86 - 苤號 87116727 五、發明說明（I) 發明範圍 本發明係關於在半導體基材上金屬薄膜之 (cvd)，特別是在基材表面上產生一具有相 ’及低; 阻率之金屬薄膜。 田千t及低電 發明背景 在積體電路（I◦的製造，包括金屬與似金 臈通常沉積於半導體基材表面，以提供路的_ 裝J間之導通與歐姆接點。例如，所需金= = 於半導體基材上的接點或導通孔之外露 、，’ 材之絕緣層的薄膜提供導通材料 =’此一穿越基 接之用。 刊竹之接頭u做為絕緣層間連 一已知的金屬沉積製程為化學，蒸氣沉積（cv :二利：-许多不同的沉積氣體或反應物氣體間之化與反應 常接近基材，而後L在:室；！引^ 種應副產物沉積於暴露的基材表面：j 面==氣=於的金屬薄膜具有平坦、似鏡 面型態會變得袓糙、霧；時，薄膜的表 流動電子所施Z的子會由於在高電流密度下的 的-端形成空洞型態1而2曰:5界移·，因此金屬線 空洞區域的電路故ϋ機率增加㈣冑壓型態’而使得在 钔'專臈'儿積時’除了為能獲得平坦的表面型態，對於半 O:\55\55253.ptc 2000.07.13. 005 案號.871167g_7 432486 月 曰 、發明說明（2) 導體基材之商業化生產而言 1.68//〇111115-(：111之電阻率，〜-电限平值砀现荆贫屬之電 阻率，電阻率高於約2 " ohms-cm的銅薄膜因其他具類似高 屬可取代銅而不且制:生Α Μ > # ϋ U …β 五 薄臈需且有接近整體電阻率 電阻.率值為純銅金屬之電 此 阻率，電阻率尚於洶Ζ " ohms-cm的銅薄膜因其他具類似高 電阻率之金屬可取代銅而不具製造技術之可行性。影經薄 膜電阻率的因素包括臈厚、密度、純度以及晶粒大小〔 因此，本發明提供製造塗布有具平坦表面型態與低電阻 率的金屬厚膜之基材的方法。 — 發明概述 :據本發明之原自，本發明的目的之一為提供基材表面 上有一具有相當平坦表面型態之金屬薄膜。 本發明之目的之二為提供美好本 之金屬薄膜。 心供基材表面上有-具有低電阻率 本發明的另一目的為提供基材表面上有一 表面型態及低電阻率之銅薄膜β 有相虽平坦 本發明尚有一目的為接供其^ ^ 約7 5 0埃且具有相當平 ’、土 一塗布厚度超過 oh一m之銅；臈：+…型癌以及電阻率小於約“ 是本發明針對於基材表面上沉 低電阻率之金屬薄獏的方*，本發Π:表面 材表面上沉積具有塗 月更疋針對於基 型態以及電阻率較約75。孕埃度以超下過： 方法。 埃以下之銅溽膜為佳的鋼薄膜之 根據本發明$ jg 暴露於電喂中舍止，本發明提供一方法，此方法為其从 电漿中。百先以化學菽乾乃忐為基材 '、轧積將金屬薄膜沉積於基
O:\55\55253.ptc 第6頁 200Γ) Ϊ9. 8.以修正 4324 Ββ 年 月 _ 案號 87116727 五、發明說明（3) 於電漿中，第二層金屬薄膜 已沉積薄膜層，接著又此基 沉積薄膜層的添加與電敷暴 較佳具體實施例中，電漿為 使用本發明之方法沉積的 電阻率且有相當平坦表面型 材表面，再將已塗布基材暴露 繼續沉積於基材表面上的先前 材暴露於電漿_，循環地進行 露，直到獲得所需的厚度。在 氫/氬電漿，而薄膜為銅薄膜 銅薄膜所具有接近純銅金屬之 態。 由於上述的優點，本發明提供可以化學蒸氣沉積於基材 表面上沉積具有相當平坦表面型態與低電阻率之金屬厚膜 的方法，本發明的其他目的與優點可經由後續的參考圖例 與說明而變為顯而易見。 圖例說明 圖1為承載器與基材之圖解。 圖2為銅CVD用反應室之剖面圖。
圖 號簡 要 說 明 20 代 表 承 載 器 22 代 表 半 導 體 基 材 24 代 表 原 生 氧 化 層 30 代 表 原 生 氧 化 層 34 代 表 矽 層 45 代 表 反 應 器 46 代 表 反 應 室 48 代 表 處 理 空 間 5 0 代 表 平 面 喷 頭 5 1 代 表 電 漿 生 產 裝置 O:\55\55253.ptc 第7頁 2000. 08. 25.007 乎; 4 3 24· 8 6案號87116727_年月日 L.，齡8❿補尤._ 五、發明說明（4) 5 2 代表射頻產生器 發明詳述 參照圖1，表示銅CVD時之半導體基材22使用之承載器 2 〇，典型的承载器2 0在其頂端2 6 a與侧邊2 6 b均有原生氧化 層2 4，基材2 2以承載器2 0支持著以進行處理，基材2 2之上 表面2 8有厚度為約1 0埃至約2 0埃的原生氧化層3 0，頂層3 0 位於厚度為約500埃之TiN層32的上方，而TiN層32塗布於 矽層3 4之上。 參照圖2，說明以化學蒸氣沉積將銅沉積於半導體基材 22的表面28之反應器45，反應器45包含包圍住處理空間48 之反應室46，如圖所示，反應室46之中，内部含有置於承 載器20上的基材22，CVD所需之反應氣體導入至處理空間
O:\55\55253.ptc 第7a頁 2000.08. 24. 008 4 324 8#l 87116727 年 月 a 89. 7:ΤΓΤ^ μ 五、發明4明（4) 4 8，氣體傳送系統如本發明所併入參考之美國專利第 5’ 628, 829號，'’化學蒸氣沉積（CVD)與電漿強化化學蒸氣 /儿積（PECVD)薄膜之低溫沉積的方法與裝置η的内容，該專 利提供製程所需之適當的氣流與分佈，通常氣體傳送系統 包含氣體分散元件，如反應室46内之平面喷頭50，喷頭50 分散入料反應氣體至反應室4 6之處理空間4 8，以確保均一 的分佈與氣體能接近承載器2 〇及基材2 2之氣流，均一的氣 體分佈與氣流對於均一且有效率的沉積，較密的電漿，及 均一的沉積薄膜乃是必需的。 對銅溥膜沉積而言，鋼先驅物—銅（一價）六氟乙醯酮三 乙石夕烧（(：111(1^&(：)(1；11^5))的兩個分子依下列不對稱反應 式發生反應，產生銅金屬： 2CuI(hfac)(tmvs) -> Cu° + Cun (hf ac)2 + 2 ( tmvs ) tmvs於先驅物蒸發時穩定先驅物，而hfac則在基材表面活 化先驅物達到較高的金屬化速率，反應室4 6的典型條件 為：基材為約1 7 0 t： ’反應壓力為約〇 5托至約2. 0托，先 驅物流速為約0. 2毫升/分鐘至約1, 〇毫升/分鐘之液體（相 當於約16-80 seem的蒸氣），以及稀釋液流速為約1〇〇 seem β 根據本發明之具體實施例之一，反應室4 6配置有用以先 將承载器20暴露於氫/氬電漿，再放置待處理基材22之電 滎生產裝置51。用以將承載器20暴露於氫/氬電漿之生產 裝置5 1 ’如本發明所併入參考之美國專利申請公告第 08/797,397號”氮化鈦基材表面上沉積鶴之化學蒸氣沉積
O:\55\55253.ptc 第8頁 2000.07. 13. 008 432486 五、發明說明（5) 方法"所述，裝置51較佳為包含連接於喷頭50之射頻（RF) 產生器52，可產生450 KHz。 在本發明之方法中，基材22以承載器20支持，於反應室 46内暴露於氫/氬電漿之中，反應室46的條件為：反應室 壓力為約1托；功率為約750 W ;頻率為約450 KHz ;氫氣 流速為約2 0 0 seem ;氬氣流速為約5 〇 sccm ;時間為約工0 秒；以及基材為約1 7 0 °C。 “Coppei^ChfacOCtmvs)以化學蒸氣沉積於基材22沉積一 薄層’以形成銅薄層，在較最佳具體實施例中，銅膜厚度 f近500埃，反應室46的條件為：基材溫度&17(rc ;反應 室壓力為約0,5-2.0托；先驅物流速為on 〇毫升/分 鐘’以及稀釋液流速為約1〇〇 sccm。 β接著將基材22暴露於與上述電漿暴露之相同條件下的氫 /二電生裝之V第，層鋼層再於與上述鋼沉積之相同反應 ^ ’’n下/儿積於第~層之上，較佳的第二層銅薄膜厚度 Γ:銅薄膜露與麵沉積之添加猶環可製作出所需厚 本發明以具體實施例的描述來說明 施例相當詳細，但不意味 的 承載器2。可先以金屬預d二疋顯而易見的’例如， 明所併人參考之中請專=除22的邊緣效應如本發 邊緣效應,，。 中之〉肖除金屬化學蒸氣沉積之 本發明以其廣泛的觀點 不受.特殊細節、代表性裝置及
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Claims (1)

  1. f。年ί -4^2-4-8^6&修正 案號 87116727 年 月 修正 ‘六…:-夺备春-士}範圍 1 · 一種以化學蒸氣沉積於半導體基材表面上沉積金屬薄 膜之方法，包括下列步驟： (a) 將基材暴露-於電漿中； (b) 沉積第一層金屬薄膜於基材之至少一個表面上； (c) 將已於其上沉積薄膜之基材暴露於電漿中；及 (d) 沉積第二層金屬薄膜於基材表面之第一層金屬薄 膜之上。 進一步包括重複步驟 其中暴露步驟（a )與 而沉積步驟（b)與（d)包 進一步包重複步驟（c) 沉積步驟係發生於壓 2 .如申請專利範圍第1項之方法 (c )與（d )以達到所要之膜厚。 3. 如申請專利範圍第1項之方法 (c)包括將基材暴露至氫/氬電類：， 括沉積銅薄膜。 4. 如申請專利範圍第3項之方法 與（d )以達到所要之膜厚。 5 .如申請專利範圍第3項之方法 力範圍為0 . 1 - 1 0托，且較佳範圍為0 . 5至2 . 0托下之反應室 内。. 6. 如申請專利範圍第3項之方法，沉積步驟係發生於先. 驅物流量範圍為0 . 0 1毫升/分鐘至5毫升/公分，且較佳為 0. 2毫升/分鐘至1 . 0毫升/分鐘之反應室内。 7. 如申請專利範圍第3項之方法，沉積步驟係發生於氫 氣流量範圍為10-1500 seem，且較佳為100 seem之反應室 内。 8 ·如申請專利範圍第3項之方法，沉積步驟係發生於承
    O:\55\55253.ptc 第1頁 2001.01. 16.013 432486 _案號 87116727_年月 曰. 修正_ 六、申請專利範圍 載器溫度範圍為1 2 0 - 2 8 0 °C ，且較佳為1 7 0 t：之反應室内。 9 .如申請專利範圍第3項之方法，暴露步驟係發生於壓 力為0 · 1 - 2 5托，較佳為1托下之反應室内。 1 0,如申請專利範圍第3項之方法，暴露步驟係發生於功 率範圍為50-1500 W，且較佳為750 W之反應室内。 1 1 .如申請專利範圍第3項之方法，曝露步驟係發生於頻 率範圍為250-500 KHz，且較佳為450 KHz之反應室内。 1 2.如申請專利範圍第3項之方法，暴露步驟係發生於氫 氣流量範圍為50-5000 seem，且較佳為200 seem之反應室 内。 1 3.如申請專利範圍第3項之方法，暴露步驟係發生於氬_( 氣流量範圍為10-1500 seem，且較佳為50 seem之反應室 内。 1 4.如申請專利範圍第3項之方法，暴露步驟係發生於承 載器溫度範圍為1 2 0 - 2 8 0 °C ，且較佳為1 7 0 °C之反應室内。 1 5 .如申請專利範圍第3項之方法，暴露步驟係發生於時 間範圍為2 - 2 4 0秒，且較佳為1 0秒之反應室内。 16. —種半導體基材上製造CVD-銅薄膜之方法，包括下 列步驟： (a) 將以承載器支持之基材暴露於氫/氬電漿； (b) 沉積第一層銅薄膜於基材之盖少一個表面上； (c) 將已於其上沉積薄膜之基材暴露於電漿；及 (d) 沉積厚度為300埃之第二層銅薄膜於基材表面的第 一層金屬薄膜之上。
    O:\55\55253.ptc 第2頁 2001.01. 16.014
    O:\55\55253.ptc 第3頁 2001. 01. 16.015
TW087116727A 1997-10-09 1998-10-12 Method of improving surface morphology and reducing resistivity of chemical vapor deposition-metal films TW432486B (en)

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