TW521304B - Method and apparatus for treating low k dielectric layers to reduce diffusion - Google Patents

Method and apparatus for treating low k dielectric layers to reduce diffusion Download PDF

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Publication number
TW521304B
TW521304B TW090117266A TW90117266A TW521304B TW 521304 B TW521304 B TW 521304B TW 090117266 A TW090117266 A TW 090117266A TW 90117266 A TW90117266 A TW 90117266A TW 521304 B TW521304 B TW 521304B
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Taiwan
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layer
patent application
scope
item
plasma
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TW090117266A
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Kegang Huang
Judy L Huang
Ping Xu
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Applied Materials Inc
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    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • C23C16/56—After-treatment
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    • H01L21/76828—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. thermal treatment
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  • Chemical Vapour Deposition (AREA)

Description

521304 A7 B7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明（ 發明領域： 本發明所揭露者係關於一種在底材上積體電路的製 程及降低氧氣擴散進入介電層之方法。 發明背景： 過去十年間’眾所皆知的是積體電路的設計與製造 獲得持續且得預測的進展。能夠成功地獲得改善的其中 一個關键便是積體電路元件中能提供傳導途徑的多層内 連線技術。導體或半導體底材的微小尺寸特性，如水平 線及垂直接觸孔、介電孔（vias)或内連線（interc〇nnects)， 在大型積體電路及超大型積體電路技術中，已增加了改 善半導體元件電流密度的重要性。 為了再進一步改善積體電路中半導體元件的電流密 度，必須利用具低電阻率及低介電常數的材料（此處之定 義為在介電層中其介電常數約低於3 〇,在蝕刻中止層及 阻障層中約低於5.0)作為絕緣層來降低相鄰内連線^之 電容稱合。習知的介電材料在内連線間具相當的電容搞 合性，如此會導致串音（cross talk)現象且/或電阻_電容遲 延’亦即需要花費時間以消除降低半導體 積能量。 的系 然而’習知的低介電常數介電材料是能被 需要-阻障層來避免材料間之内層擴散至該低介 介電材料。習知阻障層材料的介電常數高於7兒吊數 如氮化矽。而當習知阻障層材料盥 ·以上， '、低介電常數材料相接 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐 ____________--------訂---------< (請先閱讀背面之注意事項再填寫本頁) 521304 A7 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（ 合時，該絕緣體堆疊會降低該低介兩〜 果，並通常會產生一介電常數無法、/ '數材料之改善效 在利用傳統的低介電常數介^低於,6』的堆疊。 另一個困難便是積體電路中鋼使用見枓當作絕緣層時， 阻率（1·7μΩ<ιη)及高傳導性使它2的增加。銅的低電 、 為内連線材料的選擇 冬一。不過，銅很容易地便會擴散 、 會改變鄰接層的電子元件特徵 十 且 ΑΑ你、# 例如形成一越過介電層 的傳導途徑，因而降低整個電路 一从^ ^ ^ 叩Τ信賴度並甚至造成 70件的故障°銅的這種㈣特性’特別是對於該新的且 低介電常數、易滲透及擴散的薄膜，增加了具抗擴散性 低介電常數阻障層的需要。 碳化碎層已被認為是作 > 彳#人 疋忭為低介電常數阻障材料的潛 在材料。尤其是如美國專利專利申請冑〇9/165,248，標 題為「作為阻障層及中止層之碳化石夕之況積」之申請案， 1 998年1〇 $ 1日中清，為本發明申請案之受讓人所擁 有並在此併入以兹參考，且本發明並無不一致之内容， 碳化石夕在該案中便被使用為一具低介電常數之阻障層。 然而，低介私$數之碳化矽層通常是可滲透且能讓 氧擴散入該介電層，特別是能擴散入謗介電層之表面。 氧能在該碳化矽介層中與矽材料反應形成氧化物，一般 相信該氧化物會增加導體材料（例如：鋼）擴散入碳化矽 的特性及降低該阻障層的整體效果。氧擴散入碳化矽層 的h況可發生於在沉積過程中碳化矽與氧的接觸或是當 該碳化矽層在處理室與核團工具（cluster t〇〇ls)的轉換之 第5頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1 ^1 ϋ -ϋ ϋ Βϋ i_i 1— ·ϋ * ϋ ^1 ^1 ϋ I ^1 —.1 I —·1 ϋ· 1§ ϋ 11 ϋ ϋ I #▲ (請先閱讀背面之注意事項再填寫本頁) A7
521304 五、發明說明（） 間接觸到氧化的環境。 此外，碳化矽層吸附氧之後將影響該碳化矽層與鄰 接材料之键結或附著性，特別是銅等傳導材料，炎jL會 ^成材料的層韌離。另外，在碳化矽層中所形成之氧化 物通常具有較相鄰的碳化矽材料為低的密度。形成於破 化矽層 < 表面及上層部分的低密度氧化物會導致該層變 (J如凸起或隆丘），在同形（conformally)填充高深寬 比物件時’特別不希望該變形行為發生，且這種形變會 在Ik後的材料沉積時形成空孔及其他沉積缺陷。 因此’便需要一能夠減少低介電常數介電層中氧擴 政之製％。在理想的情況中，該製程能夠減少阻障層中 氧的3里’例如在銅的金屬化製程中碳化矽層的使用。 發明概述： 本發明之各態樣係關於一種產生低介電常數介電層 (例如·蛟化矽）的方法，該介電層具有對氧的抗擴散性 及低氧含I，在銅的金屬化過程中可被利用作保護層及/ / 章層本發明其中之一怨樣為一種在處理室中處理 底材之方法，包括先於處理室中在一底材上沉積一低介 電常數介電層，輸入一處理氣體至該處理室中，產生該 處理氣體之電漿，並且將該低介電常數介電層曝露於該 處理氣體之中。 本發明之另一態樣為一種處理底材之方法，包括在 處理室中於該底材上沉積一碳化矽層，輸入一選自惰性 第6頁 本紙張反度適用中國國家標準（CNS)A4規格（210 x 297公釐） -----------^裝--------訂_| c請先閲讀背面之江意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521304 經濟部智慧財產局員工消費合作社印製 氣體、氮化氣體及其 處理室中，並將碳化 良該碳化矽層之表面 該惰性氣體可能包含 氣體可能包含氨、氮 意組合物。 本發明之另一態 數阻障層之方法，包 層，並在該低介電常 護層由一包含矽與氮 化物。 A7 發明說明（ 上述任意組合族群之處理氣體至該 矽層曝露於該處理氣體電槳中來改 以在該碳化梦層上形成—保護層。 氮、氣及其任意組合物，而該氮化 、氮與氫之混合物、氧化氮及其任 樣為—種在底材上形成一低介電常 括在甩材上沉積一低介電常數介電 數介電層上沉積一薄保護層。該保 的材料所構成，如氮化矽或矽氧氮 圖式簡單說明： 本發明之上述及其令3 、、 匕目的、特徵及優點可由下 細說明並配合圖示之說明 ^ J向更侍以彰顯，其中上述 述的本發明之特定描述可、 斤概 丁參考詳細說明中的特余眘 施例，這些特定實施例則以 貫 丨厂订 < 圖式配合說明。 不過在此當聲明的是， 订 < 圖不僅用以說明太筱 明之典型實施例，而並非用 本^ m ^ 艮疋本發明範圍，本菸明 之軌圍貫則包含其餘等效之實施例。 第1圖所示者為本發明所利 L 已商業使用的化學翕 相沉和（C V D )電漿處理室 、 主刹面圖； 第2圖所示者為一受惰性氣 * 私水處理的碳化矽層原子 /辰度尤X-ray光電子 ^ (X-ray Photoelectron 本紙張尺度_中關家標準(CNSM4規格
Hi n 1^1 ϋ fi · ϋ— K n ϋ .^1 ϋ i^i 一。, n I ϋ I ϋ n ϋ I 1— i (請先閱讀背面之注意事項再填寫本頁) 521304 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）
Spectroscopy, XPS)圖； 第3圖所示者為一受氮化氣體電漿處理的碳化矽層原子 濃度之X-ray光電子光譜圖； 第4圖所示者為一受電漿處理的碳化矽底材之剖面圖； 第5圖所示者為一具保護層之碳化矽層原子濃度之x_ray 光電子光譜圖； 第6圖所示者為受碳化矽層覆蓋的底材之剖面圖。 圖號對照說明： I n i·— emmmmm ammmm ϋ 1 · ϋ ·ϋ ϋ tmt ϋ ϋ ϋ ϋ- 1 ·_1 ϋ ·ϋ I #! (請先閱讀背面之注意事項再填寫本頁) 1 0化學氣相沉積處理室 11氣體分佈板 12晶座 13支撐柱 1 4抬升馬達 15處理室 16底材 17絕緣環 1 9氣體混合系統 24 管道 2 5 RF電源供應器 32真空幫浦系統 3 4系統控制器 3 6控制線 3 8記憶體 100金屬化堆疊 1 3 0咬底材 1 3 2氧化物層 1 3 4第一低介電常數碳化 矽阻障層 1 3 6抗擴散表面 1 3 8 銅層 1 4 0第二低介電常數碳化 矽阻障層 200金屬化堆疊 230矽底材 232氧化物層 第8頁 本紙張尺度綱巾關家標準（CNS)A4規格 521304 A7 ---- B7 — _ 一 五、發明說明（） 234 第一低介電常數碳化矽層 236氮化矽層 238銅層 240第二低介電常數碳化矽層 242氧化物層 發明詳細說明： 本發明係關於利用一製程設備’如位於加州聖塔克 拉拉的應用材料公司所生產的Centura®平台，來實行之 電漿處理及化學氣相沉積製程。該設備以包含一具有化 學氣相沉積處理室（CVD chamber)的整合平台為佳，如由 應用材料公司所生產的DxZTM化學氣相處理室或 ProduCerTM化學氣相處理室。以下對該處理室的描述僅 疋為了說明’而不應推斷或解釋為對本發明範圍之限制。 第1圖為可利用前述之製程產生並維持電漿的化學 氣相沉積處理室之剖面圖。處理室1 0包括一氣體分佈板 11，該氣體分佈板位於底材支撐板或晶座12之上並定義 了處理底材16的處理範圍。晶座12能間接受熱並位於 一支撐柱13上，如此晶座12便可以在一較低負荷或無 負荷的位置及一較高或接受處理的位置之間由抬升馬達 14來控制其移動。當該晶座12位於處理位置時，一絕 緣環1 7環繞該晶座i 2及其上之底材i 6的周圍。製種氣 體由氣體分佈板11上之入口輸入至該處理室1〇，並且 均勻地分佈於該處理區域及底材表面。該製程氣體利用 真空幫浦系統32由管道24排出。 第9頁 本紙張尺度適用中關家標準（CNS)A4規格（21G X 297公餐"^ ' -- (請先閱讀背面之注意事項再填寫本頁) 裝 訂· 經濟部智慧財產局員工消費合作社印製 521304 A7
五、發明說明（） 經濟部智慧財產局員工消費合作社印製 一熱加強製程或電漿加強製程可完成於處理室丨〇, 孩電漿加強製程以用來作為本發明後沉積層處理為佳。 在電漿處理的過程中，可在鄰近底材處形成一受控制的 電漿藉由RF電源供應器25及接地的晶座12向該氣體分 佈板11供應RF能量。一 RF電源供應器25能提供該氣 體分佈板1 1單一或混合頻率的RF來增強任何輸入至處 理罜1 5的反應物種的分解。一混合頻率之rf功率供應 一般提供約13.56MHz的高RF頻率（RF1)及約35〇kHz的 低RF頻率（RF2)。 典型的處理室内部，包括氣體分佈板丨丨、晶座12 及各種其他的處理室裝置皆是由鋁或電鍍鋁所製成。一 化學氣相沉積處理室典型的例子如美國專利案第 5,000，113號，標題「一熱CVD/PECVD處理室及二氧化 矽的熱CVD之利用及其多階平坦化製程」，由王等人獲 传專利’並轉濃給應用材料公司，在此併入以兹參考， 本發明並無不一致之内容。 邊抬升馬達1 4將晶座1 2在加工位置及一較低的底 材負荷位置間升起及下降。一系統控制器34由控制線36 控制該馬達、該氣體混合系統1 9及該RF電源供應器25。 該處理室包含由系統控制器3 4所控制的類比式配件，如 質流控制器（MFCs)及標準或脈衝式rf產生器，而該系 統控制器所執行的系統控制軟體儲存在記憶體3 8中，其 貫施例一硬式磁碟儲存裝置為佳。馬達及光學感應器皆 利用來移動及決定該可移動機械組件的位置，如真空幫 第10頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------II^_W ^--------訂-— (請先閱讀背面之注意事項再填寫本頁) 五、發明說明（） 浦32之節流閥與晶座12之定位馬達。 該系統控制器34控制該化學氣相沉積處理室之活動 並包括一硬式磁碟儲存裝置、一軟式磁碟儲存裝置及一 卡式架。該卡式架包含一單板計算機（single board eomputer，SBC)、類比式及數位式輸入/輸出板、介面板 及步進馬達控制器板。該系統控制器符合了定義電路板、 卡式房以及連接器尺寸及種類的Versa Modular Europeans(VME)標準。該標準亦規範了 16位元資料匯流 排與24位元定址匯流排之架構。儲存於該硬式磁碟儲存 裝置3 8中的電腦程式控制了系統控制器34之運轉。該 電腦程式係處理一特定製程之時點、氣體之混合、Rf功 率、晶座位置及其他參數。 該設備1 0之特定實施例在此描述本發明，但並不庶 推斷或解釋為對本發明範圍之限制。 典型製程 經濟部智慧財產局員工消費合作社印製 本發明之各態樣將在此描述以作為上述製程之較佳 參考。本發明各態樣與製造低介電常數介電層（例如· 0 化矽）之方法有關，該介電層能減少氧擴散及維持低氧本 量，在銅的金屬化過程當中並可被使用為保護層且/或阻 障層。該介電層可同步或不同步地與低氧含量形成，藉 著將該低介電常數介電層曝露於惰性氣體電装當中來辦 加該介電層之密度並形成一保護層表面，將低介電常數 介電層曝露於氮化電漿當中來形成一氮化物保護層表面 第11頁
經濟部智慧財產局員工消費合作社印製 於咸；丨電層上，或县获六士、 % ^ JS ΛΑ 一 θ邊低介電常數介電層上沉積一 薄保-層的方法來降低氧擴散入該層内。 本發明中一保護表面 ^ * 今、翁* 廣心地疋義為能減少水分擴 政、虱虱及其他有害狀況 ^ H 、例如·孩表面或該材料層曝露 於周k ^境或製程污染物 仅二祓@ 、 A T )义一材料或一材料層。該 保遠層那能減少導體金屬 I j Μ •銅）之擴散。在同一個 處理至中可同步完成二 ^ ^ ^ , Μ 4夕個製程或在同一製程系統 内不中斷真空狀態或不與 、狂T的5染物環境接觸。 、T施例巾/儿積一低介電常數介電層並利用本 土明I電漿製程於該低介電常數介電層上形成一保護表 面：，電漿製程能利用來處理一低介電常數介電層(例 士瓦化矽）以作為一低介電常數的保護層或阻障層。 由％ t矽構成的低介電常數介電層係由供應一流 動率約介於ΐθ至1000標準立方公分（standard centimeters，seem)之含矽碳源材料至一電漿處理室沉積 形成忒έ矽之奴源材料由一或多個有機矽燒前驅物所 構成，例如三甲基矽烷、二甲基矽烷、甲基矽烷及其紐 合物。此外’包含分離矽及包含碳之製程氣體（例如：石夕 燒及甲燒）亦分別地輸入該處理室來幫助碳化矽的沉積。 一惰性氣體（例如：氦、氬及其組合物）亦以約 5 0 seen 至5 000sccm間之流率輸入至該處理室中。維持該處理室 壓力於約100 milliTorr至15 Torr間。在沉積過程中， 維持該底材表面之溫度於約1〇〇°c至450°c間。該氣體分 佈板11放置於距底材約200 mils至600 mils。 第12頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521304 A7 --------B7 五、發明說明（） 供應該處理室10 一單頻13·56ΜΗζ之RF電源以產 生一功率獪度約介於〇 3 watts/cm2及3.2 watt/cm2間或 於200 mm底材上功率介於1〇〇 waUs至i〇〇〇 waUs之電 漿。提供該處理室以產生電漿以約介於〇 9 waUs/cm2至 2.3 Watts/Cm2間之功率密度或200mm底材上約介於 300watts至700watts之功率為佳。 一沉積碳化矽材料之典型製程方法包括以約sccm 至500 seem之流率輸入一含三甲基矽烷之製程氣體至一 處理室，以約1〇〇 “⑽至2000 sccm之流率輸入一氬之 惰性氣體至孩處理室，維持該處理室之氣壓於約3 至10 Torr間，保持一底材表面溫度於約2〇〇它至4⑻。c 間，並提供孩處理室約300watts至7〇〇waUs來產生該製 程氣體之電槳。該氣體分佈板n放置於距底材約3〇〇mUs 至 600 mils 〇 由上述之製程所沉積的低介電常數碳化矽層為氫化 之碳化石夕層，其介電常數約於5·5 ^下，並可作為阻障 層。此外，觀察上述製程參數進行沉積所獲得之低介電 常數碳化矽層，其中該層之組成為：石夕：碳之莫耳分率 約為1 : 1，且該層之氫原子濃度至少約為30%至45%之 馬1。在製造半導體元件時，該低介電常數碳切層可使 用作保護層、阻障層、餘刻中止層及反反應塗佈(anti_ reactive coatings) 〇 沉積低介電常數碳化梦層的製程已更完整地在美國 專利未定案，第09/165,248號，1 998年1〇月i日申請、 第13| 本紙張尺度適用中國國家標準(CNSM4規格（21G X 297公髮y ---------1 I —Awl --------訂---------* (請先閱讀背面之注意事項再填寫本頁) 521304
、發明說明（ 美國專利未定案，第09/21 9,945號，1 998年口 'i z 月 2 3 申請，以及美國專利未定案，第〇9/27〇,〇39 日 1 El L 死 ’ 1999 年 Γ4先閱讀背面之注意事項再填寫本頁) 月Μ日申請，在此併入以茲參考，本發明並無不— 又内容。本發明之實施例在此所描述的碳化矽芦^ 致 、，僅為描述本發明，該特定實施例不應限制本發明^〜 圍。本發明亦考慮了其他沉積碳化矽層之製程及材料^軏 惰性氣體電漿製程 本發明之一實施例，係將前述之沉積的低介電常數 碳化矽層曝露在一惰性氣體中，來增加該碳化矽層之密 度以形成一保護表面並降低擴散至該層之氧。將一底材 放入處理室中，並選擇氧、氬及其上述任意組合物族群 之惰性氣體，以約200至2000sccm之流率輸入至該處理 室中。在進行電漿處理製程時，維持處理室之壓力於約 1至12Torr，並維持底材的溫度於約1〇〇t：至45〇t：之間。 在進行電漿處理製程時，維持該底材溫度於約3 5 〇。〇為 較佳。 經濟部智慧財產局員工消費合作社印製 提供該處理室約0.08至6.4watts/cm2間之RF功率 密度，或提供200mm底材約25至2000watts的RF功率 來產生該惰性氣體的電漿。供應該處理室來產生電漿以 約0.3至3.2watts/cm2的功率密度，或2〇〇mm底材約100 至1 000watt的功率為佳。該電漿之處理時間為約3〇至120 秒鐘。以電漿來處理沉積層與沉積該低介電常數碳化矽 層可同步執行。 第u頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） 經濟部智慧財產局員工消費合作社印製 521304 A7 ---—---- —_B7__ 五、發明說明（） 一儿積碳化矽層之處理製程係以約400seem之流率 將氛輸入至含有2〇〇mm底材的處理室中。在該處理製程 中’將達到並維持約8τ〇ΓΓ的處理室氣壓及約35〇°c的底 材/皿度。亥處理室接受約1 · 2至1 · 6 watts/cm 2的RF功率 被度或約400至500 watts的RF功率以產生電漿，並處 理該碳化矽層約5 〇秒鐘。 沉積碳化梦層一較佳的處理製程係以約l3〇〇sccm的 流率將氦輸入含有200mm底材的處理室中，維持該處理 室壓力與底材溫度於約8.7Torr及35(TC，供應該處理室 約250watts以產生電漿，並維持該電漿約5〇秒。 该碳化石夕沉積處理室或相同整合系統之一不同處理 室可同步執行該電漿處理，亦即不需中斷製程間之真空 狀態。目别已觀祭到依本發明之惰性氣體電漿處理方法 所產生的碳化矽層，其氧含量約低於6%原子濃度。 第2圖所示者為根據本發明所揭露的惰性氣體電漿 製程所處理的5〇oA厚的碳化矽層之原子濃度（at〇mic concentration，atomic %)與濺擊時間之x_ray光電子光譜 (X-ray Photoelectron Spectropy，XPS)圖。該圖描述除氫 以外的碳化矽層元素，隨著該層深度不同之原子濃度。 該XPS之資料係以約20至25A的速率移除材料後，該 層每經濺擊一分鐘後所得之資料。第2圖的X轴，即藏 鍍時間’係该層不同深度之元素原子濃度讀數。第2圖 的Y軸係依據該層濺擊步驟時間的元素原子濃度，其中 碳表示為C’碎表示為Si，氧表示為〇，氮表示為n。 第15頁 本紙張尺度適財關家群（CNS)A4規格x 297公餐) "一 * 裝--------訂---------齊. (請先閱讀背面之注意事項再填寫本頁) 521304
經濟部智慧財產局員工消費合作社印製 五、發明說明（） 曰則巳覜祭到接受該 石夕層中氧的平均濃度為約4%至6%，較習知未經處理的 礙化層之氧之預期濃度約10%至15%為低。 一般相信該惰性電體之電漿物種藉由移除材料（例 如·薄膜上的妓與氫）、移除該材料的微孔與移除或降低 其空孔或其他缺陷來加強該層之表面密度。將一碳化矽 材料（、、勺90A至100A厚）與一碳化矽塊料下層之材料（約 〇A至420A厚）比較，前者表面密度約1·以至 1.59g/cm3，而後者之整體密度為約2 〇8至a」乜“Μ。 -般更認為增強表面之密度提供了一防止氧氣擴散 入Μ層之保護表面，與未經處理過的碳化矽層相比較， 該表面對氧氣擴散及材料氧化更具抵抗的效果，也加強 了孩層與連接層的黏著性。一 a 一 舨也相仏，在半導體製造 密度表面對其他材料⑽ 抵抗性。 辦狀文八 氮化氣體電漿製程 《月 < 另f施例’係將一低介電常數碳化 曝露於氮化氣體電漿中，以 产 在邊石反化矽層上形成一舍 氮的表面。該富含氮的碳切層表面包括氮化♦、: 亂化物、矽氧氮化物、或碳矽 反 甘&尸/ 乳鼠化物’在本發明Φ 1览化表面。該氮化氣體係選自氣、氮、 及其上述任意組合之族群。由於氨於乳化- 即高於25〇。(：後氨易解^ 、易解離性 風“離為電漿形態的特性，因此氨, 第16| --------I--裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 521304
經濟部智慧財產局員工消費合作社印制衣 五、發明說明（） 般便用來產生氮化表面。 本發明所描述的氮化表面能藉由以下的製程形成於 %化梦層上。在處理室中放置一底材並以約i 〇〇至 3OOsccm的流率輸入氮化氣體至該處理室中。維持該處 理室的壓力於約100 milliTorr至25 milliTorr間。維持 孩處理室的壓力於i Torr至12 T〇rr間為較佳，5 至 1 〇 Torr為更佳的狀態。在電漿處理的過程中，維持該底 材溫度於約1 〇 〇。〇至5 0 0。(：之間。 才疋供該處理室約〇·〇8至6.4 watts/cm2的RF功率密 度，或200mm底材約25至2000watts的RF功率來產生 私漿°提供約0.3至3.2 watts/cm2的RF功率密度或2〇〇mm 底材約100至l〇〇〇watts的功率為較佳。將該碳化矽層曝 露於該氮化電漿中約10至120秒鐘來產生一約5〇A至 400A厚的氮化表面。该碳化梦沉積之同一處理室或相同 整合系統之一不同處理室可同步執行該電漿處理。 一典型的沉積低介電常數介電層之氮化電漿處理製 程方法包括對含有200mm碳化矽底材的處理室以約2〇〇 至600sCCm的流率提供氨，於氮化過程中維持該處理室 壓力於約8至9Torr並維持該底材的溫度於約3〇〇£>c至4〇〇 °C，提供該處理室約1.2至1.6 watts/cm2之Rf功率密度 或約400至500watts的RF功率以產生電槳，並維持該 電漿約5至60秒鐘來修正該碳化矽表面以產生一氮化表 面。該電漿能在一個或多個處理循環中產生。而另一個 方法則是將碳化矽層曝露在該電漿製程中約2〇至6〇秒 第17頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------Φ·裝--------訂i (請先閱讀背面之注意事項再填寫本頁) 521304 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 鐘 孩氮化氣體更可由一惰性氣體所組成（例如：氬或 氦）’來f助處理該層之表面，亦可協助穩定該氣流及電 装反應。惰性氣體可以約低於2000seem的速率輸入至該 處理罜中來與氮化製程相接合。該氮化氣體亦可由一反 應氣體（例如：氫）所組成，來協助清除氮化製程中該層 的污染物。 该石反化砂沉積處理室或相同整合系統之一不同處理 i可同步執行該電漿處理，亦即不需中斷製程間之真空 狀態。目前已觀察到本發明揭露的氮化氣體電漿處理方 法可產生氧含量低於6%原子濃度的碳化矽層。 弟3圖所示者為一根據本發明所揭露的惰性氣體電 漿製程所處理的500A厚碳化矽層之原子濃度（at〇mic concentration，atomic %)與濺擊時間之x-ray光電子光譜 (X-ray Ph〇t〇electron Spectropy，xPS)圖。該碳化矽層經 過流率約40〇sccm氨的處理，處理室壓力維持在約， 提供200mm的底材約350wattsRF功率以產生電聚，並 維持該底材溫度於約35(rC。第3圖之Y軸顯示該碳化 層之平均氧濃度為4% ’低於未經處理過的碳化珍層之預 期10%至15%之氧濃度。 當氮氣電漿被使用於一電漿處理方法之實施例當 中，以在碳化矽層上形成一氮化表面時，今 T 邊虱化氣體覆 於該層上並且一不同的反應（例如：熱反應）會在該層及 該氮化氣體間促進該氮化反應。 第18頁 I ϋ I βϋ ϋ· 41— ϋ ·1 *1 ·1 ϋ ime 1§ · mmmtm n I— 1 If «^1 ϋ I (請先閲讀背面之注意事項再填寫本頁) 521304 A7 B7 五、 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 發明說明（ 本發明的另一實施例，係將該沉積低介電常數碳化 矽層曝露在該氮化氣體之中，並利用一熱加強製程方法 讓氧從該碳化碎層逸出並在該層上形成一氮化表面。一 熱製程至少包括以約1 00至3 OOOsccm的流率輸入該氮化 氣體至處理室中’維持該處理室壓力於約5至25 Torr間， 在處理過程中維持該底材溫度於約3 5 0 °C至5 0 0。(：間。此 外，亦可在該退火過程中維持該處理室壓力於約8Torr 至lOTorr °在該退火過程中維持該底材溫度於約45〇°C 為佳。 當氮被混入該碳化矽層之中，該氮化表面被認為能 在該碳化矽層上形成一由碳化矽、碳矽氮化物、矽氧氮 化物或碳矽氧氮化物所構成的薄氮化保護層表面。該氮 化表面與未經處理過的碳化矽層相較更具對氧擴散入碳 化矽層的阻抗能力。一般也認為該氮化保護層表面並不 會顯著地增加該碳化矽層的介電常數。更進一步來說， 對該層的表面進行氮化處理將使該非結晶的碳化矽層產 生氮的键結，因此當消除相鄰層間的缺陷時，便能增強 界面間的鍵結及黏著性。更進一步地說，目前已觀^到 孩氮化表面比起含有氧化矽的其他層，對其他材料（例 如：水或銅）的擴散具有更好的阻抗能力，因此在鋼的全 屬化製程當中增強了碳化矽層的阻障特性。 ▲ 弟4 B I員示在一利用本發明所揭冑的惰#氣體或氮 化氣體電漿方法所處理之銅的金屬化堆疊100中，將低 介電常數碳化矽層作為阻障層。該阻障層134係利用上 第19頁 本紙張尺度適財關家標準（CNS)A4規格⑵G x 297公^ --------I--裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 521304 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 述的低介電常數碳化矽沉積製葙 領I私所產生。該金屬化堆疊 1 〇 〇首先係在矽底材1 3 0上沉穑 ,,r 9 /儿積一約5〇〇〇A的氧化物層 132。約800A的第一低介電當 •私吊數石反化矽阻障層134隨後 沉積於該氧化物層132上。接戈 … 接著，利用本發明的惰性氣 體或氮化氣體電漿製程處理該第一低介電常數碳切阻 障層⑴以產生一抗擴散表面136。接下來，於該第一 低介電常數碳化梦阻障| 134的抗擴散表面136上沉積 一約测A厚的銅層138。在該铜層138上沉積_約8〇〇入 厚的第二低介電常數碳化矽阻障層14〇，並且在該第二 低介電常數碳化矽阻障I 14〇上沉積一約1〇〇〇入厚的氧 化物層 142。另一種方式盔 丄 禋万式為，亦可在該銅層之前沉積一 金屬氮化物阻障層（例如：氮化鈇（TiN)或氮化麵（TaN))來 進—步限制該銅層138對該碳化珍層134的層間擴散。 以上的金屬化堆疊100僅是為了供舉例說明，不應被分 析或解釋為限制本發明的範園。舉例來說，—雙镶嵌結 構製造過程之一特徵區中，該氮化矽層140可作為一蝕 刻阻障層或一反反應塗佈。 氮化矽保護層 本發明 < 另一實施例係以一由矽及氮構成之薄保護 層覆蓋於一低介電常數碳化矽層上，來降低進入該層之 氧的擴散。琢保護層由氮化矽、碳矽氮化物、矽氧氮化 物或碳矽氧氮化物所構成。 在一碳化碎層上沉積一保護層的方法包括以约至 第20頁 lx 297公釐） — — — — — — I — — if I ·1111111 一« — — — — — — I— ^^^^1 ri I I f.. (請先閱讀背面之注意事項再填寫本頁) 521304 經濟部智慧財產局員工消費合作社印製 A7 ______B7 _ 五、發明說明（） 100 0seem的流率輸入一含石夕的氣體以及以約50至 2000seem的流率輸入一含氮的氣體至處理室中。該含梦 的氣體係選自矽烷、甲基矽烷、三甲基矽烷、其替代衍 生物及其上述任意組合之族群。該含氮的氣體係選自氨、 氮、一氧化一氮、及其上述任組合之族群。該氮化氣體 含有氧（例如：一氧化二氮）來沉積一矽氧氮化物之保護 層。 維持該底材溫度於約100至5 50。(：。維持該處理室 壓力於約1至25Torr。一較佳的實施例係在沉積的過程 中，維持該處理室壓力於4至5Torr。提供約0.3至 3.2watts/cm2的RF功率密度或提供200mm底材約1〇〇至 lOOOwatts之RF功率至該處理室以產生該製程氣體之電 漿。 沉積該氮化矽層約25至500A厚。以沉積該保護層 約50至200人厚為較佳。該氮化矽層被預期能沉積任何 厚度，端視該製程對碳化矽層及保護層的應用。 該保護層沉積處理室或相同整合系統之一不同的處 理室可同步在碳化梦層上沉積一保護層’亦即不需中斷 製程間的真空狀態。該保護層之沉積與隨後的低介電碳 化矽層之沉積同步為佳，以避免該碳化矽層曝露在可能 產生污染及氧化作用的空氣之中。該氮化矽層及珍氧氮 化物層的碳含量低於5%原子濃度。當該氮化矽層及梦氧 氣化物層以上述的方法沉積後，其他能沉積由沙及氮組 成的保護層的方法及材料便能被預期得到。 第21頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521304 A7 B7 五、發明說明（） 第5圖顯示在一矽底材上所沉積並由如前段所述之 包含矽及氮的保護層所覆蓋的約500A厚的碳化矽層，其 原子濃度相對於濺擊時間的（X-ray Photoelectron Spectropy，XPS)圖。該保護層的沉積包括以約li5sccm 的速率輸入三甲基梦燒及以約1500sccm的速率輸入氨至 該處理室中，維持處理室壓力於約4至5Torr，提供約 3 50watts的RF功率至一 200mm底材，當三甲基矽烷與 氨反應時’維持該底材溫度於約3 5 〇。 Μ保護層沉積約400A厚。該保護層能沉積較400A 還薄的厚度以對一 SiN/SiC堆疊之介電常數k的全面衝 擊達到最小。第5圖的γ軸顯示出具有沉積保護層之該 層的平均氧濃度介於約2至4%之間，較未經處理的碳化 石夕層 < 預期的氧濃度約1 0至1 5 %為低。 如第5圖所示，經過濺擊過程約2〇分鐘後，該氮化 梦層皆已被濺擊’該氮化珍層的組成便能夠被測量出來。 依據孩層之成m ’量測料之氧濃度並未超過該平 =值約2至4%’此結果顯示該層現場沉積可減少該二氧 二广染程度。一般認為電漿增強該薄保護層的 ^:在該碳切層上形成—抵抗層’來形成—對氧具 性且不會影響該阻障層介電常數的整合阻 草層。更進一步地說，一般 刃、 化物對導Γ材料M 〜、、、因為虱化矽及矽氧氮 t導材枓（例如：銅）具更佳 氮仆功仅冷既 机彍散性，因此孩 :保濩層可改善該碳化矽阻障層的性質。 弟6圖所示者為一低介 一 吊數石反化矽阻障層，其被 第22頁
本紙張尺度適用^^_ m〇 X 2^iT
五、發明說明（ 揭露的氮切保護層所覆蓋。金屬化堆叠20l 23 2 夕底材230上沉積一約5000A厚的氧化 斤1。第一低介電常數碳切阻障層⑼隨後利用本S ::揭露的製程方法沉積在該氧化層232上約800A厚發 :製；氮化:保護層236藉由三…燒及氨之増強電 4。〇广積在該第一低介電常數碳…障層上約 00A。一約 50〇〇a 厚的 陸 ？ P現後、，儿積在該碳化矽阻 曰《虱石夕層236上。沒有顯示 化物阻障層（例如：氮化咎力a 金屬虱 鈦或氮化妲）也能較該銅層為先 永’儿知以限制銅擴散人# J门擴政入錢化矽層234。接著，沉積_ 約800A厚的第二低介♦登 弟低η私吊數碳化矽層240於該銅層23丨 ，最後是一約1000人厚的氧化物層242。 二般相信本發明所揭露的電漿處理製程改善了對掮 月阻抗性、強化了該低介電常數介電層（例如··碳化珍 =鄰的材料之間的内層鍵結及黏著…般亦編 私水處理製程亦降低了合凰 - “屬化組合層間的電阻或阻相 1，也藉由增加的沉積碳切層之介電常數該消除m 染物（例如：氧）。作A你 為保&層且/或阻障層，該低氧含^ 低介電常數之材料可降低銅之内層擴散與減少該保護
^或阻障層内連線《電容藕合。當關於處理低介電常I 夕層Ik後的描述，本發明亦考慮應用已知的製程3 其他半導體製造中能渗透層及其他習知的電常^ 電層。 込之說月僅為本發明中的較佳實施例，而非用， 第23頁 ---------·裝 f請先閱讀背面之注意事項再填寫本頁) _ n ϋ· 11 ϋ n «ϋ · i ϋ -I ϋ n 1 I 1 經濟部智慧財產局員工消費合作社印製 521304 A7 B7_ 五、發明說明（） 限定本發明之範圍，故利用這些實施例所進行的修改或 更動都不脫離在所附專利範圍所言明之範圍外，本發明 之範圍當以後述的專利申請範圍為基準。 -------------裝--------訂--------- 辞 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 第24頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 521304 A8 B8 C8 D8 六 經濟部智慧財產局員工消費合作社印製 申請專利範圍 1. 一種處理底材之方法，該方法至少包含： 在一處理室中沉積一低介電常數介電層在該底材 請 先 閱 讀 背 之 注 意 事 項 再 填 本 頁 上； 輸入一製程氣體至該處理室中； 在該處理室中產生該製程氣體之電漿；及 曝露該低介電常數介電層於該製程氣體電漿中。 2. 如申請專利範圍第1項所述之方法，其中上述之低介 電常數介電層具有原子濃度約為6%以下之氧含量。 3 ·如申請專利範圍第1項所述之方法，其中上述之低介 電常數介電層更包含碳化矽。 4 ·如申請專利範圍第1項所述之方法，其中上述之製程 氣體係選自氦、氬及其任意組合之族群。 5 ·如申請專利範圍第1項所述之方法，其中上述曝露該 低介電常數介電層於該電漿中之步驟係增加該低介電 常數介電層之表面密度。 6.如申請專利範圍第1項所述之方法，其中上述之製程 氣體係一選自氨、氮、氧化氮及其任意組合族群之氮 化氣體。 第25頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 521304 A8 B8 C8 D8 六 經濟部智慧財產局員工消費合作社印製 申請專利範圍 7.如申請專利範圍第6項所述之方法，其中上述之氮化 氣體於該低介電常數介電層上形成一氮化表面。 請 先 閱 讀 背 之 注 意 事 項 再 填 本 頁 8 ·如申請專利範圍第1項所述之方法，其中上述曝露該 低介電常數介電層於該電漿中之步騾更包含供應該處 理室約0.08至6.4watts/cm2電力的功率密度以產生該 電漿。 9 ·如申請專利範圍第8項所述之方法，其中上述之該低 介電常數介電層係曝露於該電漿當中約1 0至1 2 0秒 鐘。 I 0 ·如申請專利範圍第1項所述之方法，其中上述之處理 室壓力介於約lOOmilliTorr至25Torr。 II ·如申請專利範圍第1項所述之方法，其中上述處理該 底材之步驟更包括以約3000sccm或3000sccm以下的 流率輸入一含惰性氣體、氮化氣體或其任意組合之製 程氣體至該處理室中，並維持該處理室壓力於約1至 12Torr，供應該處理室約0.3至3.3watts/cm2功率密度 的電力以產生該電漿，並且維持該電漿約20至60秒 鐘。 1 2 ·如申請專利範圍第11項所述之方法，其中上述之低 第26頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 521304 A8 B8 C8 D8 六、申請專利範圍 介電常數介電層具有原子濃度約為6%以下之氧含量。 1 3 · —種處理底材的方法，該方法至少包含： 於處理室中沉積一碳化矽層在一底材上； 輸入一選自惰性氣體、氮化氣體及其上述任意組合 之族群之製程氣體至該處理室中； 在該處理室中產生該製程氣體之電漿；及 曝露該碳化矽層於該製程氣體電漿中以改良該碳化 矽層之表面，以產生一保護層表面於該碳化矽層上。 14_如申請專利範圍第13項所述之方法，其中上述之惰 性氣體係選自氦、氬及其任意組合之族群。 1 5 ·如申請專利範圍第1 3項所述之方法，其中上述之製 程氣體係一惰性氣體，且增強該碳化矽層之表面密度。 16. 如申請專利範圍第13項所述之方法，其中上述之氮 化氣體係選自氨、氮、氧化氮及其任意組合之族群。 17. 如申請專利範圍第13項所述之方法，其中上述之製 程氣體更包括一氮化氣體，並且在該低介電常數介電 層上形成一氮化表面。 18·如申請專利範圍第13項所述之方法，其中上述曝露 第27頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------‘---裝--- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521304 A8 B8 C8 D8 六、申請專利範圍 該低介電常數介電層於該電漿中之步驟更包含供應該 處理室約 0.3至 3.2watts/cm2功率密度的電力以產生 該電漿。 19·如申請專利範圍第18項所述之方法，其中上述之該 低介電常數介電層係曝露於該電漿當中約20至60秒 鐘。 20.如申請專利範圍第13項所述之方法，其中上述之處 理室壓力為約1至12Torr。 2 1 ·如申請專利範圍第1 3項所述之方法，其中上述處理 該底材之步驟更包括以約3 0 0 0 s c c m或3 0 0 0 s c c m以下 的流率輸入一含惰性氣體、氮化氣體或其任意組合之 製程氣體至該處理室中，並維持該處理室壓力於約5 至lOTorr，供應該處理室約1.2至1.6watts/cm2電力 的功率密度以產生該電漿，並且維持該電漿約20至60 秒鐘。 22.如申請專利範圍第13項所述之方法，其中上述之碳 化秒層係一阻障層、一领刻停止層、一保護層或一抗 反射塗佈層。 2 3 ·如申請專利範圍第1 3項所述之方法，其中上述之碳 第28頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------裝—— (請先閱讀背面之注意事項再填寫本頁) . 經濟部智慧財產局員工消費合作社印？衣 521304 A8 B8 C8 D8 六、申請專利範圍 化矽層具有原子濃度約為6%以下之氧含量。 24.—種在底材上形成一低介電常數阻障層之方法，該方 法至少包含： 在該底材上沉積一碳化矽層；及 在該碳化矽層上沉積一包含矽及氮的保護層。 2 5 ·如申請專利範圍第2 4項所述之方法，其中該保護層 係包含氮化矽或氮氧化矽。 26·如申請專利範圍第24項所述之方法，其中上述之沉 積該保護層包括： 輸入一含矽氣體及一含氮氣體至一内有該底材之處 理室中； 在該處理室中產生一電漿； 在該電漿當中讓該含矽氣體與該含氮氣體反應，以 沉積一含珍及氮之保護層。 27. 如申請專利範圍第26項所述之方法，其中上述之含 矽氣體係選自矽烷、甲基矽烷、三甲基矽烷、其替代 衍生物及其任意組合之族群。 28. 如申請專利範圍第26項所述之方法，其中上述之含 氮氣體係選自氨、氮、氧化氮及其任意組合之族群。 第29頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 · 521304 A8 B8 C8 D8 六、申請專利範圍 2 9 ·如申請專利範圍第2 6項所述之方法，其中上述之電 漿係由供應該處理室約0 · 3至3 · 2 watts/cm2功率密度 之電力所產生。 3 0 ·如申請專利範圍第2 6項所述之方法，其中上述之處 理室氣壓約為1至25Torr。 3 1.如申請專利範圍第24項所述之方法，其中上述包含 矽及氮之保護層係沉積約25至5 00A之厚度。 請 先 閱 讀 背 之 注 意 事 項 再 填 本 頁 經濟部智慧財產局員工消費合作社印刺衣 第30頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）
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US6794311B2 (en) 2004-09-21
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