TW201124554A - Film forming method and storage medium - Google Patents

Film forming method and storage medium Download PDF

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Publication number
TW201124554A
TW201124554A TW099131351A TW99131351A TW201124554A TW 201124554 A TW201124554 A TW 201124554A TW 099131351 A TW099131351 A TW 099131351A TW 99131351 A TW99131351 A TW 99131351A TW 201124554 A TW201124554 A TW 201124554A
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TW
Taiwan
Prior art keywords
film
film forming
substrate
reducing agent
forming method
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Application number
TW099131351A
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English (en)
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TWI404822B (zh
Inventor
Yasuhiko Kojima
Shuji Azumo
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Tokyo Electron Ltd
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Publication of TW201124554A publication Critical patent/TW201124554A/zh
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Publication of TWI404822B publication Critical patent/TWI404822B/zh

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    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical 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
    • C23C16/18Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
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    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/52Controlling or regulating the coating process
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    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56After-treatment
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    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
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    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1653Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/1658Process features with two steps starting with metal deposition followed by addition of reducing agent
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/166Process features with two steps starting with addition of reducing agent followed by metal deposition
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1675Process conditions
    • C23C18/1678Heating of the substrate
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1689After-treatment
    • C23C18/1692Heat-treatment
    • C23C18/1696Control of atmosphere
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    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/0262Reduction or decomposition of gaseous compounds, e.g. CVD
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562Selective deposition
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    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841Barrier, adhesion or liner layers
    • H01L21/76843Barrier, adhesion or liner layers formed in openings in a dielectric

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Chemical Vapour Deposition (AREA)

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201124554 六、發明說明: 【發明所屬之技術領域】
Co膜等之成膜 本發明關於一種藉由CVD法來形成 方法及記憶媒體。 【先前技術】 近年來’隨著半導體元件的高速化、導線圖案的微 細化等,導電性較A1高且抗電子遷移性等亦良好之Cu 作為-種導線便受到矚目。關於使用電解電艘於Cu導 線且藉由電解電鍍所形成之Cu導線的種晶層,從提高 埋入性之觀點來看,便評估從習知的CU轉變為Co。 另一方面,針對M0S型半導體之源極、汲極電極、 閘極電極之與Si之間的接觸,—直以來係、於形成c〇膜 或Nl膜後使用矽化後的CoSix或NiSix。 、雖然c〇膜或Ni膜的成膜方法多半係使用濺鍍法中 代表性的物理紐(PVD)法,但隨著半導體元件的微細 =,階梯覆蓋率(step c〇verage)不良之缺點亦愈來愈顯 者0 因此,Co膜或Ni膜的成膜方法便使用含有c〇或 二1之原料氣制触解反應,抑或藉由制料氣體的 退原性氣體所進行之還原反應而於基板上形成C 〇膜或 Ni膜之化學蒸鑛(CVD)法。藉由這類cvd法所成媒《 膜或Ni膜的階梯覆盍率(段差被覆性)良好,且對細 長且深之圖案内的成膜性優異。因此,藉由CVD法所 201124554 成膜之Co膜或]STi膜對微細圖案的追隨性高,且適合作 為Cu電鐘的種晶層或接觸層。 關於藉由CVD法所成膜之c〇膜,學術論文(例如 nature materials/Vol.2 November 2003 pp749〜754)中發 表了一種方法’其係使用銘跡(Cobalt amidinate)來作為 成膜原料(前驅物)’且使用H2或NH3來作為還原劑。 然而’使用鈷脒與H2之CVD法的反應性很低,且 膜中容易殘留有不純物’而使得膜的品質不佳。又,為 了解決反應性低之問題而在高溫下進行成膜時,卻會有 因Co的凝集而使得表面性狀惡化之問題。又,使用始 脒與NH3之CVD法由於會形成有c〇的氮化物,故會 有膜的阻值變高之問題。 針對Ni膜雖亦考慮使用鎳脒(Nickel amidinate),且 使用Hz或NH3來作為還原劑,並藉由CVD法來進行成 膜,但仍會發生同樣的問題。 【發明内容】 因此,本發明之目的在於提供一種可使用鈷脒來作 為成膜原料’並在低溫_下形成表面狀態及膜質良好的 Co膜之成膜方法。 本發明另一目的在於提供一種使用鎳脒來作為成 膜原料’並在低溫下形成表面狀態及膜質良好的Ni膜 之成膜方法。 本發明另一其他目的在於提供一種記憶有用以實 6 201124554 施》亥等成膜方法的程式之記憶媒體。 本發明者等為了達成上述目的再三 現在使用銘脒或鎳辟來作為成膜原 i心,务 :作為還原劑,便能夠以低溫且可適用“以幾: 成膜逮度來形成Co膜、Ni^ , 體裂私的 質亦良好’進而完成本發明。、、,貝與狀態或膜 包含=發=;觀點係提供-種成媒方法,其 將含有姑滕之成膜原料與含有二::相狀態下 處理容器内,而於基板上形成還原劍導入至該 •^明另-觀點提供—種成膜方法 驟.將基板搬人處理容器内; 3义下乂 之成膜原料與含有叛酸之還原劑入 字含有錄月米 内,而於基板上形成^導人至錢理容器 上動種記憶媒體,係於電腦 式係於執行成縣置的程式;其中該程 置執行包含有以下成縣置’以使該成膜裝 器内;在氣相狀離 < 、膜方法:將基板搬入處理容 之還原劑導人至^ : 3有銘辟之成膜原料與含有緩酸 本發明另;=二’而於基板上形成C。膜。 上動作,並記射憶制,係於電腦 式係於執行時,使電腦控制該成=程式;其中該程 有以下步驟之成膜方法:將基板搬入處理容 201124554 器内;在氣相狀態下將含有鎳脒之成膜原料與含有缓酸 之還原劑導人至該處理容器内,而於基板上形成奶膜。 【實施方式】 以下,參照添附圖式加以說明本發明之實施型態。 〈用以實施科明成膜方法之成膜裝置之—例〉 圖1係顯示用以實施本發明成膜方法之成膜裝置 的一例之概略剖面圖。 、义 此成膜裝置100具有氣密地構成為大致呈圓筒狀 之處理室1,並且於其中配置有用以水平地支撐被處理 基板(半導體晶圓W)之载置台2,該载置台2係以設置 於其中央下部的圓筒狀支撐構件3而被加以支撐。^載 置台2係^ A1Ν等之陶I所構成。又,載置台2埋二有 加熱器5,而該加熱器5則連接有加熱器電源6。另— 方面,載置台2的上表面附近設置有熱電偶7,熱電偶 7的訊號係被傳送至加熱器控制器8。然後,加^器控 制器8會根據熱電偶7的§孔號來將指令傳送至加熱琴電 源6’以控制加熱器5的加熱而將晶圓w控制在特定溫 度。此外,載置台2係設置有可相對於載置台2的表面 而呈突出或凹陷之3根晶圓昇降銷(未圖示),並在搬送 晶圓W時’成為從載置台2的表面突出之狀雜。. ' 處理室1的頂壁la處形成有圓形孔化,並嵌入有 從該處向處理室1内突出之喷淋頭1〇。噴淋頭1〇係用 以將後述氣體供應機構30所供應之成膜用氣體喷出至 8 201124554 處理室1内,且於其上部處具有用以導入成膜原料氣體 之第1導入通道11,與用以將還原劑導入至處理室1 内之第2導入通道12。該等第1導入通道11與第2導 入通道12係個別地設置於喷淋頭10内,而成膜原料氣 體與還原劑會在噴出後混合。 喷淋頭10内部係上下2段地設置有空間13、14。 上側的空間13連接有第1導入通道11,而第1氣體喷 出通道15係從該空間13延伸至喷淋頭10的底面。而 下側的空間14則連接有第2導入通道12,第2氣體噴 出通道16係從該空間14延伸至噴淋頭10的底面。亦 即,喷淋頭10係將成膜原料氣體與作為還原劑之羧酸 氣體各自獨立地從喷出通道15及16喷出。 處理室1的底壁處設置有朝下方突出之排氣室 21。排氣室21的側面連接有排氣管22,而該排氣管22 則連接有具有真空幫浦或壓力控制閥等之排氣裝置 23。然後,藉由使該排氣裝置23作動,便能夠將處理 室1内減壓至特定的真空度。 處理室1的側壁處,設置有用以在與晶圓搬送室(未 圖示)之間進行晶圓W的搬出入之搬出入口 24,與用以 開閉該搬出入口 24之閘閥G。又,處理室1的壁部處 設置有加熱器26,而能夠在成膜處理時控制處理室1 内壁的溫度。 氣體供應機構3 0具有用以儲存成膜原料S之成膜 原料槽31。成膜原料S在形成Co膜時係使用鈷脒,而 201124554 在形成Νι膜時則使用鎳脒《姑脒可使用例如雙(N_特丁 基-Ν’-乙基-丙醯脒)始⑼(Co(tBu_Et_Et amd)2)。又,鎳 脒可使用例如雙(Ν,Ν,-二-特丁基-乙醯脒)鎳 (II)(Ni(tBu-amd)2)。 由於該等成膜原料S通常在常溫下為固體,故成膜 原料槽31的周圍設置有加熱器32,藉以加熱成膜原料 並使其液化。又,自成膜原料槽31的底部係插入有用 以供應作為载送氣體,例如Ar氣體之載送氣體配管 33。載送氣體配管33係設置有流量控制器34及將流量 控制器34挾置其中之2個閥門35。又,成膜原料槽31 係從上方插入有成膜原料供應配管36,而成膜原料供 應配管%的另一端則連接於第1導入通道u。然後, 因加熱器32之加熱而變成液體之成膜原料會因載送氣 體配所供應的載送氣體而起泡並成為氣體狀,且 經由成膜原料配管36及第1導人通道11被供應至喷淋 頭1〇 i成膜簡供應配管36的周圍係設置有使氣體狀 的,腰原料;F會液化之加熱器37。又,成膜原料供應 配匕36 5又置有流量調整閥38、其下游侧的開閉閥 及第1導人通道11附近關閉閥40。 喷淋頭10的第2導入通道12係連接有用以供應還 = 體還原劑供應配管44。該還原劑供應配 ^ 係連接有用以供應還原劑(叛酸氣體)之叛酸供應 源46 °又’違還原劑供應配管44的第2導入通道12 附近” 5又有閥門45。再者,該還原劑供應配管44係設 10 2〇Π24554 置有流量控制器47及將流量控制器47挾置其中之2個 閥門48。還原劑供應配管44的流量控制器47上游側 係分岔有载送氣體供應配管44a,而該載送氣體配管4如 則連接有載送氣體供應源4〗。然後,用以將成膜原料(鈷 脒或鎳脒)還原之還原劑(羧酸氣體)會從羧酸供應源4 6 通過還原劑供應配管44及喷淋頭10被供應至處理室j 内又’载送氣體(例如Ar氣體)會從載送氣體供應源 41通過載送氣體供應配管44a、還原氣體供應配管^4 及噴淋頭10被供應至處理室丨内。還原劑之綾酸較佳 地可使用曱酸(HC〇〇H)、乙酸(CH3C〇〇H)。 成膜褒置100具有控制部5〇,而藉由該控制部刈 $進行各構成部(例如加熱器電源6、排氣裝置23、流 量控制器34、47、流量調整閱38、間門35、39、4〇 : 45、48等)之控制,或透過加熱器控制器8來進行載置 台2的溫度控制等。該控制部5〇具有具備微處理器(電 腦)之程序控制器51、使用者介面52及記憶部Μ。程 序控制器係縣為料接有賴数⑽的各構成 部並加以控制。使用者介面52連接於程序控制器5卜 係由作業員為了管理成膜裝t刚的各構成部而進行 才"的輪人操作等之鍵盤,或可視化地顯示成膜裂置 100之各構成部的稼働狀況之顯示器等所構成。記憶邹 «亦連接於程序控制器,該記憶部μ係收納有為了 利用製程控制器51的控制來實現成膜裝置t⑻所執行 的各種處理之㈣料’或配合處理條件綠成膜裝置 201124554 配方=執行特定處理之控制程式(即處理製程 部ί3中;訊等)°處理製程配方係記憶在記憶 辟料:媒體(未圖示)。記憶媒體可固定地設置於 動亦:為CDR〇M、DVD、快閃記憶體等可移 當二I可方從其他裝置,例域 示等然ί將=,藉由利用來自使用者介面52的指 丁寻轉特定處理製程配方從記憶 程序控制器51執行,以在程序控制器51二= 膜裝置_奸所欲處理。 批制下於成 形態^本㈣之成翁法應祕CG _賴之實施 行之2 針對將利用上述方式構成的成膜裝置而進 加以t 法,應用於c°骐的成膜之實施形態 ,形成Co膜時,首先,打開閘間G,並藉由未圖 二置來將晶圓w導入至處理室1内,而载置 :=roxc™^ 用:=又,_蜀層來使用時,晶圓w係使 -成極'基板面,或表 接著’藉由排氣裝置23來將處理室1内排氣,以 12 201124554 使處理室1内的壓力為1.33〜1333Pa(10mTorr〜lOTorr), 並藉由加熱器5來加熱載置台2,以使載置台2的溫度 (晶圓溫度)為300°C以下,較佳為120〜250°C,且透過載 送氣體供應源41、載送氣體供應配管44a、還原劑供應 配管44、喷淋頭10,來以100〜1500mL/min(sccm)的流 量將載送氣體供應至處理室1内,以進行穩定化。 在進行特定時間的穩定化而條件穩定後的時間點 下,藉由加熱器32並以100〜1500mL/min(sccm)的流 量,來將載送氣體從配管33供應至被加熱到例如 60〜120°C之成膜原料槽31,並藉由起泡來將作為成膜 原料之鈷脒(例如雙(N-特丁基-NL乙基-丙醯脒)鈷 (II)(Co(tBu-Et-Et-amd)2))的蒸氣從成膜原料供應配管 36透過噴淋頭10而導入至處理室1内,更進一步地從 羧酸供應源46來將作為還原劑之氣體狀羧酸透過還原 劑供應配管44及喷淋頭10而導入至處理室1内,以開 始Co膜的成膜。 鈷胨具有下式(1)般的結構式,通常在常溫下為液 體。如式(1)所示,鈷脒的Co原子係鍵結於4個N原子, 藉由利用還原劑(幾_酸)來將該鍵結切斷,以獲得Co膜。 [化學式1] 13 201124554
Rl、R2、R3、R4、R5、Κ·6表不石炭化氮系官能基。 為鈷脒的具體範例之Co(tBu-Et-Et-amd)2,其液體 蒸氣壓在 110 °C下為 3990Pa(30Torr)以下。將 Co(tBu-Et-Et-amd)2的結構式顯示於下式(2)。 [化學式2]
作為還原劑使用之羧酸,如上所述,較佳地可使用 曱酸(HCOOH)及乙酸(CH3COOH)。羧酸當中,該等的 14 201124554 還原性特別高。該等當中又以甲酸為更佳。 當使用Co(tBu-Et-Et-amd)2時,在上述載送氣體流 量(100〜1500mL/min(sccm))之範圍下’於原料容器= 為80C、容器内壓力為1()TQrr之條件下等的成膜處理 中之鈷脒流量為2〜30mL/min(Sccm)左右。又,還原劑(羧 酸)流量為1〜2000mL/min(sccm)左右。 如圖2所示,成膜序列可舉例通常的Cvd,其係 同時供應成膜原料(此情況下為鈷脒)與還原劑(羧酸' 又,如圖3所示,亦可利用所謂的ALD方法,其係夾 雜著吹淨而交互地進行成膜原料(鈷脒)與還原劑^缓"酸) 的供應。吹淨可藉由供應載送氣體來進行。藉由該ALD 方法,便可更加降低成膜溫度。 ,然後,依上述方式形成Co膜後,進行吹淨步驟。 吹淨步驟中,係在停止對成膜原料槽31之載送氣體的 供應且停止鈷脒的供應後,使排氣裝置23的真空幫浦 為切斷狀態’並以載送氣體作為吹淨氣體而從載送氣體 i、應源41流入至處理室丨内,來將處理室丨内吹淨。 此時,從盡可能迅速地將處理室〗内吹淨之觀點來看, 斷斷續續地進行載送氣體之供應為佳。 一。人淨步驟結束後,打開閘閥G,並藉由搬送裝置(未 圖不)而經由搬出入口 24來將晶圓W搬出。藉此,便 元成1片晶圓W的一連串步驟。 、如上所述地,針對成膜原料之鈷脒,而使用羧酸作 為還原劑來進行CVD成膜時,由於羧酸對鈷脒的還原 201124554 能力很高’故可在120〜300〇C的低溫下,以實用 速度來形成Co月莫。缓酸當中,又以使用^ ^月萬 或乙酸(CHsCOOH)的情況可獲得特別高的還原处ϋίί) 能夠以12〇〜250。〇的低溫且實用的成膜率來开=尤並 物少且膜質良好的Co膜。又,如上所述地於了純 低溫下且以實用的成膜率來形成c〇膜,故不容易I在 Co的凝集’從而獲得表面性質與狀態良好的二膜I生 依上述方式形成的C。膜適合作為利用電解電。 形成之Cu導線的種晶層n亦可作為cvd/所 的基底膜來純使用。再者,t作為躺層使用時^鱗 石夕基板表面絲賴表面依上述方式形成c。膜後,’於 在惰性氣體氛圍或還原氣體氛圍下進行用以夕= 處理。此時的熱處理溫度較佳為450〜800〇c。 …' 形^將本發明之成膜方法躺於Ni朗成膜之實施 、接下來,針對將彻上述成難置而進行之本發明 成膜方法,應用於Ni朗成膜之實施形態加以說明X。 一在形成Nl膜時,首先,打開閘閥G,並藉由未圖 示之搬送裝置來將晶圓w導人至處理室i内,而載置 於載置台2上。將恥膜作為接觸層來使用時,晶圓w W吏用表面露出有成為源極、沒極電極之石夕基板面, 或表面形成有聚矽膜者。 接著,藉由排氣裝置23來將處理室1内排氣,以 使處理室1内的壓力為133〜1333p歧1〇mT〇rr〜i〇T〇r〇, 16 201124554 並藉由加熱器5來加熱載置台2,以使載置台2的溫度 (晶圓溫度)為300°C以下,較佳為120〜250°C,且透過載 送氣體供應源41、載送氣體供應配管44a、還原劑供應 配管44、喷淋頭10,並以100〜1500mL/min(sccm)的流 量來供應載送氣體,以進行穩定化。 在進行特定時間的穩定化而條件穩定後的時間點 下,藉由加熱器32並以100〜1500mL/min(sccm)的流 量,來將載送氣體從配管33供應至被加熱至例如 60〜120°C之成膜原料槽31,並藉由起泡來將作為成膜 原料之鎳脒(例如雙(N,N'-二-特丁基-乙醯脒)鎳 (II)(Ni(tBu-amd)2))的蒸氣從成膜原料供應配管36透過 喷淋頭10而導入至處理室1内,更進一步地從羧酸供 應源46來將作為還原劑之氣體狀羧酸透過還原劑供應 配管44及喷淋頭10而導入至處理室1内,以開始Ni 膜的成膜。 鎳脒具有下式(3)般的結構式,通常在常溫下為固 體,熔點為85〜90°C。如式(3)所示,鎳脒的Ni原子係 鍵結於4個N原子,藉由利用還原劑(羧酸)來將該鍵結 切斷,以獲得Ni膜。 [化學式3] 17 201124554
R/7、Rs、尺3、RlO、Rll、Rl2表不碳化氮糸官能基。 鎳脒的具體範例之Ni(tBu-amd)2的熔點為87°C,液 體蒸氣壓在90 °C下為26.6Pa(200Torr)以下。將 Ni(tBu-amd)2的結構式顯示於下式(4)。 [化學式4] ch3 ch3
I I h3c - c - ch3 h3c - c - ch3 I / ^ Nx J、 h3c - c '[n( λ> c - ch3 (4)
N N
/ I
H3C — C ~ CH3 H3C — C — CH3 i I ch3 ch3 作為還原劑使用之魏酸,如上所述,較佳地可使用 曱酸(HCOOH)及乙酸(CH3COOH)。羧酸當中,該等的 還原性特別高。該等當中又以曱酸為更佳。 18 201124554 當使用Ni(tBu-amd)2時,在上述載诸乌 (100〜1500mL/min(sccm))之範圍下,於原料容器、取:里 9〇=、容器内壓力為·Γ之條件下等的成 之鎳脒流量為2〜30mL/min(sccm)左右。又,還 笮 酸)流量為 1〇〜2〇〇〇mL/min(sccm;)左右。 (幾 如圖2所示,成臈序列可舉例通常的Cvd,爱么 同時供應&膜原料(此情況下為鎳脑)與還原劑後酸、係 又二如圖3所示,亦可利用所謂的ALD方法,;二二 雜著吹淨而交魏騎賴 (_)與_劑二夹 的供應。吹淨可藉由供應載送氣體來進行。藉由該:二) 方法’便可更加降低成膜溫度。 / 然後,依上述方式形成Ni膜後,進行吹淨 吹淨步驟中,係在停止對成膜原料槽31之載送氣% 供應且停止錄脒的供應後,使排氣裝置23的真空^ 為切斷狀態’並以載送氣體作為吹淨氣體而從載送氣妒 七、,源41流入至處理室1内,來將處理室1内吹淨 此恰,從盡可能迅速地將處理室丨内吹淨之觀點 斷斷續續地進行錢氣叙供絲佳。 ’ 一吹淨步驟結束後,打開閘閥G,並藉由搬送裝置(未 ,不)而經由搬出入口 24來將晶圓w搬出。藉此,便 完成1片晶圓W的一連串步驟。 如上所述地,針對成膜原料之鎳脒,而利用羧酸作 ,原巧來進行CVD成膜時,由於羧酸對鎳脒的還原 月匕力很向,故可在12〇〜3〇〇〇c的低溫下,以實用的成膜 19 201124554 速度來形成Νι膜。羧酸當中,又以使用曱酸 ,乙酸(CH3CO〇H)的情況可獲得特別高的還原能力並 能夠以12G〜250。(:的低溫且實用的成膜率來形成不絶 物少且膜質良好的Ni膜^又,如上所述地,由於可在 低溫下且以實用的成膜率來形成Ni膜,故不容易發生 Νι的凝集’從而獲得表面性質與狀態良好的见膜。 依上述方式形成的Ni膜適合作為接觸層。當作為 接觸層使㈣,卿基絲面或聚賴表面依上述方式 形成见膜後,係在惰性氣體氛圍或還原氣體氛圍下進 行用以矽化之熱處理。此時的熱處理溫度較 300〜700oC。 场 如以上所述,雖係針對成膜原料(鈷脒或鎳脒),而 使用羧酸來作為還原劑,但由於羧酸對鈷肺及鎳脒的還 原能力很高,故可藉由CVD法而在低溫下且實用的成 膜率來形成不純物少且膜f良好的c。膜或州膜。又, 由於如上所述地可在低溫下且以實用的成膜率來成 膜’故不容易發生CG或Ni的凝集,從而獲得表面性質 與狀態良好的Co膜及Ni膜。 <本發明之其他應用> 此外,本發明不限於上述實施形態,而可做各種變 化。例如上述實施形態中,構成成膜原料之鈷脒雖例示 了 Co(tBu-Et-Et-amd)2’ 而鎳脒雖例示了 Ni(tBu_amd)2, 但並未限於於此。又,構成還原劑之羧酸亦不限於曱酸 及乙酸,而可使用丙酸、丁酸、戊酸等其他的羧酸。 201124554 又,關於成膜原料之鈷脒、鎳脒的供應方法, 需限定於上述實施形態的方法,而可應用各種方法 者,關於成職置亦不限於上述實施形態 =裝進置成膜原料氣歸解所設置之電 板之體晶圓來作為被處理基 卿)基板等之其他2限於此,*亦可為平面顯示器 【圖式簡單說明】 的—實财發明㈣枝之成膜裝置 圖2係顯示成膜序列的-例之時序圖。 圖3係顯示成膜序列的其他範例之時序圖。 r7L件符號說明】 G 閘閥 S 成膜原料 W 晶圓 1 處理室 la 頂壁 lb 圓形孔 2 載置台 3 支撐構件 21 201124554 5 加熱器 6 加熱器電源 7 熱電偶 8 加熱器控制器 10 喷淋頭 11 第1導入通道 12 第2導入通道 13、 14 空間 15 第1氣體喷出通道 16 第2氣體喷出通道 21 排氣室 22 排氣管 23 排氣裝置 24 搬出入口 26 加熱器 30 氣體供應機構 31 成膜原料槽 32 加熱器 33 載送氣體配管 34 流量控制器 35 ' 39、40、45、48 36 成膜原料供應配管 37 加熱器 38 流量調整閥 22 201124554 41 載送氣體供應源 44 還原劑供應配管 44a 載送氣體供應配管 46 羧酸供應源 47 流量控制器 50 控制部 51 程序控制器 52 使用者介面 53 記憶部 100 成膜裝置 23

Claims (1)

  1. 201124554 七、申請專利範圍: 1. 一種成膜方法,係包含以下步驟: 將基板搬入處理容器内; 於氣相狀態下將含有鈷脒之成膜原料與含有 羧酸之還原劑導入至該處理容器内,而於基板上形 成Co膜。 2. 如申請專利範圍第1項之成膜方法,其中構成該成 膜原料之鈷脒為雙(N -特丁基-N'-乙基-丙酸脒)鈷 (II” 3. 如申請專利範圍第1項之成膜方法,其中於基板上 形成Co膜後,係藉由電解電鍍來沈積Cu。 4. 如申請專利範圍第1項之成膜方法,其中於基板上 形成Co膜後,係藉由CVD來沈積Cu。 5. 如申請專利範圍第1項之成膜方法,其中該Co膜 係形成於矽上,並於成膜後,在惰性氣體氛圍或還 原氣體氛圍下進行用以矽化之熱處理。 6. 如申請專利範圍第1項之成膜方法,其中成膜時的 基板溫度為300°C以下。 7. 如申請專利範圍第1項之成膜方法,其中構成該還 原劑之羧酸為曱酸。 8. 如申請專利範圍第1項之成膜方法,其中構成該還 原劑之羧酸為乙酸。 9. 如申請專利範圍第1項之成膜方法,其中係將該成 膜原料與該還原劑同時供應至該處理容器内。 24 201124554 i〇.=申請專利範圍第i項之成膜方法,其中係將 與該還原劑夾雜著吹淨氣體的供應而‘互 地供應至該處理容器内。 ,又互 11. 一種成膜方法,係包含以下步驟: 將基板搬入處理容器内; 、於f相狀態下將含有鎳脒之成膜原料與含有 幾酸之逛原劑導入至兮虚採六& 成Ni膜。 ㈣内,而於基板上形 12. 13. 14. ,申請專利範圍第n項之成財法,其巾該奶膜 係形成於#上,並於成難,在雜氣體氛圍或還 原氣體氛圍下進行用以矽化之熱處理。 如申請專利範圍第n項之成膜方法,其中成膜時 的基板溫度為300oC以下。 15. 16. 如申請專利範圍第11項之成膜方法 還原劑之羧酸為甲酸。如申請專利範圍第11項之成膜方法 還原劑之羧酸為乙酸。 其中構成該 其中構成該 17. 如申請專利範圍第11項之成膜方法,其中係將該 成膜原料與該還原劑同時供應至該處理容器内。 18. 如申請專利範圍第η項之成膜方法,其中係將該 成膜原料與該還原劑夾雜著吹淨氣體的供應而交 25 201124554 互地供應至該處理容器内。 19. 一種記憶媒體,係於電腦上動作,並記憶有用以控 制成膜裝置的程式; 其中該程式係於執行時,使電腦控制該成膜裝 置,以使該成膜裝置執行包含有以下步驟之成膜方 法:將基板搬入處理容器内;在氣相狀態下將含有 鈷胨之成膜原料與含有羧酸之還原劑導入至該處 理容器内,而於基板上形成Co膜。 20. —種記憶媒體,係於電腦上動作,並記憶有用以控 制成膜裝置的程式; 其中該程式係於執行時,使電腦控制該成膜裝 置,以使該成膜裝置執行包含有以下步驟之成膜方 法:將基板搬入處理容器内;在氣相狀態下將含有 鎳脒之成膜原料與含有羧酸之還原劑導入至該處 理容器内,而於基板上形成Ni膜。 26
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