TW200907101A - Ti film depositing method, and storage medium - Google Patents

Ti film depositing method, and storage medium Download PDF

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Publication number
TW200907101A
TW200907101A TW097115409A TW97115409A TW200907101A TW 200907101 A TW200907101 A TW 200907101A TW 097115409 A TW097115409 A TW 097115409A TW 97115409 A TW97115409 A TW 97115409A TW 200907101 A TW200907101 A TW 200907101A
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Taiwan
Prior art keywords
substrate
chamber
film
gas
forming
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TW097115409A
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Chinese (zh)
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TWI425113B (en
Inventor
Kensaku Narushima
Satoshi Wakabayashi
Tetsu Zenko
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Tokyo Electron Co Ltd
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Publication of TWI425113B publication Critical patent/TWI425113B/en

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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
    • C23C16/06—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
    • C23C16/06—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
    • 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
    • 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
    • C23C16/44—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
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture 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
    • H01L21/18—Manufacture 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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition 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
    • H01L21/28518—Deposition 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 the conductive layers comprising silicides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture 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
    • H01L21/18—Manufacture 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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition 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
    • H01L21/28556—Deposition 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
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture 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
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying 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
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric

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

Abstract

To provide a Ti film depositing method capable of uniformly advancing cilicide formation in a plane of a substrate.A substrate having a Si portion is arranged on a loading stand. The substrate is heated and the pressure inside a chamber is set to be a predetermined value. A raw gas is converted into plasma by forming the high frequency electric field while introducing the raw gas containing a TiCl< SB> 4< /SB> gas and a reducing gas into the chamber. When depositing a Ti film on the Si portion of the substrate by generating the reaction by the TiCl< SB> 4< /SB> gas and the reducing gas on the surface of the substrate, the pressure in the chamber and the high frequency power to be applied are controlled so as to suppress the formation reaction of TiSi on the Si portion of the substrate.

Description

200907101 九、發明說明 【發明所屬之技術領域】 本發明是關於在腔室內供給含有Tic“氣體及還原氣 體之處理氣體，在被載置於腔室內之載置台上’含有Si 之部份的被處理基板之S i部份，形成T i膜。 【先前技術】 在半導體裝置之製造中，對應於最近之高密度化及高 積體化之要求，傾向將電路構成多層線構造，因此下層之 半導體裝置和上層之配線層之連接部的接觸孔，或上下配 線層彼此之連接部的通孔等之層間電性連接用之埋入技術 則爲重要。 如此接觸孔或通孔之埋入，一般使用A1(鋁）或W(鎢） 或是以該些爲主體之合金，但是爲了形成如此之金屬或合 金和下層之Si基板或poly-Si層之接觸，於該些埋入之前 ，藉由形成Ti膜，與基底之Si反應而在接觸孔之底之Si 擴散層上選擇生長TiSi2，取得良好之歐姆電阻（例如曰本 特開平5 -67 5 85號公報）。 於形成CVD-Ti膜之時，一般使用TiCl4氣體作爲原 料氣體，使用H2氣體作爲還原氣體，但是因該TiCl4氣體 之結合能量相當高，於單獨熱能量時若無1200 °C左右之高 溫則無法分解，故藉由倂用電漿能量之電漿CVD，通常以 製程溫度650°C左右執行成膜。再者，由促進反應之觀點 來看，採用比較高之壓力及高頻電力功率而形成電漿。 -5- 200907101 但是，近年來使用Ti膜以當作與閘極電極之聚砂上 之金屬接觸之接觸層，由於以往成膜溫度在6 5 0 °C附近’ 溫度過高，故硏究Ti膜之成膜在5 5 0°C附近之低溫。 但是，於在5 5 0°C附近執行成膜之時’即使使靨於被 處理基板之半導體晶圓之溫度均勻’在晶圓面內的矽化物 化產生偏差程度，造成面內之膜質均勻性惡化。再者’由 於電漿，對晶圓產生充電損傷或對腔室造成異常放電等之 電漿損傷。 另外，在現行之Ti膜成膜中，由電漿化之容易性之 觀點來看，先將Ar氣體及還原氣體之H2氣體導入至腔室 內而予以電漿化後再導入TiC 14氣體，但是由於之後導入 TiC 14氣體，使得放電狀態暫時性變化，在腔室內產生異 常放電，或產生對晶圓之電漿損傷。 【發明內容】 〔發明所欲解決之課題〕 本發明之目的是提供可以在被處理基板之面內均勻進 行矽化物化之Ti膜之成膜方法。 再者，本發明之其他目的是提供難以對被處理基板或 對腔室產生電漿損傷之Ti膜之成膜方法。 若藉由本發明之第1觀點，則提供一種鈦膜之成膜方 法’藉由成膜裝置，在具有Si部份之被處理基板之含有 Si部份形成Ti膜，該成膜裝置具有：收容被處理基板之 腔室；在腔室內載置被處理基板之載置台；加熱載置台上 -6- 200907101 之基板的加熱手段；供給含有TiCl4氣體及還原氣體之處 理氣體至腔室內之處理氣體供給手段；於上述載置台上之 被處理基板上方之空間形成高頻電場之高頻電場形成手段 ;和將上述腔室內予以排氣之排氣手段，包含··在上述載 置台配置具有S i部份之被處理基板之步驟；加熱被處理 基板之步驟；將腔室內設爲特定壓力之步驟；將含有 Ticu氣體及還原氣體之處理氣體導入至腔室內之步驟； 藉由上述高頻電場形成手段形成高頻電場，依此使上述處 理氣體電漿化之步驟；和在被處理基板之表面產生藉由上 述TiCl4氣體及還原氣體所引起之反應之步驟，藉由上述 反應’於被處理基板之Si部份形成Ti膜之時，以抑制在 被處理基板之Si部份的Ti Si之生成反應之方式，控制腔 室內壓力及所施加之高頻電力之功率。 此時’被處理基板之溫度在5 5 0 °C附近，以產生當作 前驅物之TiCl3成爲主體之成膜反應的方式，控制腔室內 壓力及所施加之高頻電力之功率爲佳。 若藉由本發明之第2觀點，則提供一種鈦膜之成膜方 法，藉由成膜裝置，在具有Si部份之被處理基板之Si部 份形成Ti膜，該成膜裝置具有：收容被處理基板之腔室 :在腔室內載置被處理基板之載置台；加熱載置台上之基 板的加熱手段；供給含有TiCl4氣體及還原氣體之處理氣 體至腔室內之處理氣體供給手段；於上述載置台上之被處 理基板上方之空間形成高頻電場之高頻電場形成手段；和 將上述腔室內予以排氣之排氣手段，包含：在上述載置台 200907101 配置具有Si部份之被處理基板之步驟；加熱 之步驟；將腔室內壓力予以抽真空之步驟；辦 氣體及還原氣體之處理氣體導入至腔室內之步 述高頻電場形成手段形成高頻電場，依此使上 電漿化之步驟；和在被處理基板之表面產 TiCl4氣體及還原氣體所引起之反應之步驟， 力爲266〜1 3 3 3Pa之範圍，高頻電力功率爲 之範圍內，將腔室內壓力設爲x(Pa)，將高頻 爲 y(W)之時，則滿足（y- 3 3 3 )&lt; 1 60400/(X-266) 若藉由本發明之第3觀點時，則提供一種 方法，藉由成膜裝置，在具有Si部份之被處 部份形成Ti膜，該成膜裝置具有··收容被處 室；在腔室內載置被處理基板之載置台；加熱 基板的加熱手段；供給含有TiC 14氣體及還原 氣體至腔室內之處理氣體供給手段；於上述載 處理基板上方之空間形成高頻電場之高頻電場 和將上述腔室內予以排氣之排氣手段，包含： 台配置具有s i部份之被處理基板之步驟；加 板之步驟；將腔室內壓力設成3 00〜800Pa之 ;將含有TiCl4氣體及還原氣體之處理氣體導 之步驟；將上述高頻電場形成手段之高頻電 300〜600W而形成高頻電場，依此使上述處理 之步驟；和在被處理基板之表面產生藉由上述 及還原氣體所引起之反應之步驟。 被處理基板 ί含有 TiCU 驟；藉由上 .述處理氣體 生藉由上述 在腔室內壓 200 〜1 000W 電力功率設 〇 :鈦膜之成膜 理基板之S i 理基板之腔 載置台上之 氣體之處理 置台上之被 形成手段； 在上述載置 熱被處理基 範圍之步驟 入至腔室內 力功率設爲 :氣體電漿化 TiCl4氣體 -8- 200907101 在上述第1至第3觀點中，可以將基板溫度設爲3 00 〜67(TC之範圍。尤其以基板溫度爲500t ±20°C之時爲佳 〇 若藉由本發明之第4觀點時，則提供一種鈦膜之成膜 方法，藉由成膜裝置，在具有Si部份之被處理基板之Si 部份形成Ti膜，該成膜裝置具有：收容被處理基板之腔 室；在腔室內載置被處理基板之載置台；加熱載置台上之 基板的加熱手段；供給含有TiCl4氣體及還原氣體之處理 氣體至腔室內之處理氣體供給手段；於上述載置台上之被 處理基板上方之空間形成高頻電場之高頻電場形成手段； 和將上述腔室內予以排氣之排氣手段，其特徵爲：包含： 在上述載置台配置具有含有Si部份之被處理基板之步驟 :加熱被處理基板之步驟；將腔室內設爲特定壓力之步驟 ;將含有TiCl4氣體及還原氣體及惰性氣體之處理氣體導 入至腔室內之步驟；藉由上述高頻電場形成手段形成高頻 電場，依此使上述處理氣體電漿化之步驟：和在被處理基 板之表面產生藉由上述TiCl4氣體及還原氣體所引起之反 應之步驟，將Tic 14氣體及還原氣體及惰性氣體導入至上 述腔室內之後，形成高頻電場而生成電漿之步驟。 在上述本發明之第4觀點中，藉由在被處理基板之Si 部份形成T i膜，使其界面砂化物化爲佳。 若藉由本發明之第5觀點時，則提供一種記憶媒體， 記憶有在電腦上動作，並控制成膜裝置之程式，上述控制 程式於實行時，以執行Ti膜之成膜方法的方式，使電腦 -9- 200907101 控制上述成膜裝置，該Ti膜之成膜方法是藉由成膜裝置 ，在具有Si部份之被處理基板之含有Si部份形成Ti膜， 該成膜裝置具有：收容被處理基板之腔室；在腔室內載置 被處理基板之載置台；加熱載置台上之基板的加熱手段； 供給含有Tic 14氣體及還原氣體之處理氣體至腔室內之處 理氣體供給手段；於上述載置台上之被處理基板上方之空 間形成高頻電場之高頻電場形成手段；和將上述腔室內予 以排氣之排氣手段，包含下述步驟：在上述載置台配置具 有s i部份之被處理基板；加熱被處理基板；將腔室內設 爲特定壓力；將含有Tic 14氣體及還原氣體之處理氣體導 入至腔室內；藉由上述高頻電場形成手段形成高頻電場， 依此使上述處理氣體電漿化；和在被處理基板之表面產生 藉由上述TiCl4氣體及還原氣體所引起之反應，藉由上述 反應，於被處理基板之S i部份形成Ti膜之時，以抑制在 被處理基板之S i部份的Ti S i之生成反應之方式，控制腔 室內壓力及所施加之高頻電力之功率。 在現行之Ti膜成膜中，自促進反應之觀點來看，雖 然將腔室內壓力設定成667Pa左右，將高頻電力設定成比 較高之8 00W左右而執行成膜處理，但是於以如此之條件 執行成膜之時，被處理基板之溫度在5 5 CTC附近，矽化物 產生偏差。本發明者調查其原因之結果，發現在該溫度附 近，於Si上藉由反應所生成之相從Ti轉移至TiSi，並矽 化物化容易產生偏差。然後，Ti Si之電阻高於在高溫下所 生成之T i S i 2或低溫下之S i，成膜特性也不同，故從T i -10- 200907101 轉移至Ti Si之轉移點附近，膜厚或膜質產生偏差。 在此，本發明者硏究即使在550°C附近也難以產生如 此之偏差之條件的結果，發現藉由控制腔室內壓力及所施 加之高頻電場之功率，可以難以生成TiSi，實質刪減Ti 和TiSi之轉移點，因此可以迴避上述般在55(rc附近產生 偏差。典型上，藉由降低腔室壓力及所施加之高頻電力之 功率’可以迴避在55(rc附近之膜厚或膜質之偏差，並且 可以隨著功率降低降低電漿損傷。 再者，藉由先將TiCl4氣體導入至腔室內後再形成高 頻電場，可以抑制異常放電之發生，並可以降低電漿損傷 。因此，除降低壓力及高頻電力功率之外，又於生成電漿 之前’導入TiCl4氣體，依此從低溫至高溫，不會產生電 漿損傷，可以實施安定性及均勻性高之Ti膜成膜。 【實施方式】 以下，參照附件圖面，針對本發明之實施形態具體予 以說明。 第1圖表示本發明之一實施形態所涉及之Ti膜之成 膜方法之實施所使用之Ti膜成膜裝置之一例的槪略剖面 圖。該Ti膜成膜裝置100是作爲藉由在平行平板電極形 成高電場，邊形成電漿，邊執行CVD成膜之電漿CVD成 膜裝置而構成。200907101 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a process for supplying a portion containing Si in a chamber containing a process gas containing a Tic "gas and a reducing gas and being placed in a chamber." The Si portion of the substrate is processed to form a Ti film. [Prior Art] In the manufacture of a semiconductor device, it is inclined to form a multi-layer line structure in accordance with the recent requirements for high density and high integration, and thus the lower layer It is important that the contact hole of the connection portion between the semiconductor device and the wiring layer of the upper layer or the via hole of the connection portion between the upper and lower wiring layers is electrically connected to each other. Thus, the contact hole or the via hole is buried. Generally, A1 (aluminum) or W (tungsten) or an alloy mainly composed of the same is used, but in order to form such a metal or alloy and the underlying Si substrate or the poly-Si layer, before the embedding, By forming a Ti film and reacting with the Si of the substrate to selectively grow TiSi2 on the Si diffusion layer at the bottom of the contact hole, a good ohmic resistance is obtained (for example, 曰本特平平 5-67 5 85). In the case of a -Ti film, TiCl4 gas is generally used as a material gas, and H2 gas is used as a reducing gas. However, since the TiCl4 gas has a relatively high binding energy, if it is not heated at a temperature of about 1200 °C, it cannot be decomposed. The film formation is usually carried out at a process temperature of about 650 ° C by plasma CVD using plasma energy. Further, from the viewpoint of promoting the reaction, plasma is formed by using relatively high pressure and high frequency power. -5- 200907101 However, in recent years, the Ti film has been used as a contact layer in contact with the metal on the sand of the gate electrode. Since the film formation temperature is too high at around 65 ° C, the Ti film is investigated. The film formation is at a low temperature around 550 ° C. However, when film formation is performed at around 550 ° C, 'even if the temperature of the semiconductor wafer on the substrate to be processed is uniform' in the wafer surface The degree of deviation of the bismuth compounding causes the film quality uniformity in the surface to deteriorate. Furthermore, the plasma damage caused by charging damage to the wafer or abnormal discharge to the chamber due to the plasma. In addition, the current Ti film formation Plasma From the viewpoint of easiness, the Ar gas and the reducing gas H2 gas are first introduced into the chamber and then plasma-formed and then introduced into the TiC 14 gas. However, since the TiC 14 gas is introduced later, the discharge state temporarily changes. An abnormal discharge occurs in the chamber, or a plasma damage to the wafer is generated. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a Ti film which can be uniformly mashed in the surface of a substrate to be processed. Further, another object of the present invention is to provide a method for forming a Ti film which is difficult to cause plasma damage to a substrate to be processed or to a chamber. According to a first aspect of the present invention, a titanium film is provided. a film forming method of forming a Ti film by a film forming apparatus in a Si-containing portion of a substrate having a Si portion, the film forming apparatus having: a chamber for accommodating a substrate to be processed; and a substrate to be processed placed in the chamber a mounting table; a heating means for heating the substrate on the mounting table -6-200907101; and a processing gas supply means for supplying the processing gas containing the TiCl4 gas and the reducing gas into the chamber; a high-frequency electric field forming means for forming a high-frequency electric field in a space above the substrate to be processed on the stage; and an exhaust means for exhausting the chamber, including: a portion having a portion S1 disposed on the mounting table a step of processing the substrate; a step of heating the substrate to be processed; a step of setting the chamber to a specific pressure; and a step of introducing a processing gas containing the Ticu gas and the reducing gas into the chamber; forming a high frequency by the high-frequency electric field forming means An electric field, a step of plasma-treating the processing gas; and a step of generating a reaction caused by the TiCl4 gas and the reducing gas on the surface of the substrate to be processed, and the Si portion of the substrate to be processed by the reaction At the time of forming the Ti film, the pressure in the chamber and the power of the applied high-frequency power are controlled so as to suppress the formation reaction of Ti Si in the Si portion of the substrate to be processed. At this time, the temperature of the substrate to be processed is in the vicinity of 550 ° C to generate a film forming reaction in which TiCl 3 as a precursor becomes a main body, and it is preferable to control the pressure in the chamber and the power of the applied high frequency power. According to a second aspect of the present invention, there is provided a method for forming a titanium film, wherein a film is formed on a Si portion of a substrate having a Si portion by a film forming apparatus, and the film forming apparatus has a housing a chamber for processing a substrate: a mounting table on which a substrate to be processed is placed in a chamber; a heating means for heating the substrate on the mounting table; and a processing gas supply means for supplying a processing gas containing TiCl4 gas and a reducing gas into the chamber; a high-frequency electric field forming means for forming a high-frequency electric field in a space above the substrate to be processed; and an exhausting means for exhausting the chamber, wherein the substrate to be processed having the Si portion is disposed on the mounting table 200907101 a step of heating; a step of evacuating the pressure in the chamber; and a step of introducing a high-frequency electric field forming means by the high-frequency electric field forming means for introducing the processing gas of the gas and the reducing gas into the chamber, thereby performing the step of plasma-up And the step of reacting with TiCl4 gas and reducing gas on the surface of the substrate to be processed, the force is in the range of 266~1 3 3 3Pa, high-frequency power Within the range, the pressure in the chamber is set to x (Pa), and when the high frequency is y (W), then (y - 3 3 3 ) &lt; 1 60400 / (X-266) is satisfied by the present invention. In the third aspect, there is provided a method of forming a Ti film on a portion having a Si portion by a film forming apparatus, the film forming apparatus having a housing chamber; and a substrate to be processed in the chamber a mounting table; a heating means for heating the substrate; a processing gas supply means for supplying the TiC 14 gas and the reducing gas into the chamber; forming a high-frequency electric field of the high-frequency electric field in the space above the substrate; and arranging the chamber The gas exhausting means comprises: a step of disposing a substrate having a si portion; a step of adding a plate; setting a pressure in the chamber to 300 to 800 Pa; and guiding the processing gas containing the TiCl 4 gas and the reducing gas a step of forming a high-frequency electric field by using a high-frequency electric current of 300 to 600 W in the high-frequency electric field forming means, thereby performing the above-described processing steps; and generating a reaction caused by the above-mentioned reducing gas on the surface of the substrate to be processed . The substrate to be processed ί contains a TiCU step; by the above-mentioned process gas, the above-mentioned chamber is placed on the chamber of the substrate of the substrate of the titanium film by pressing 200 to 1 000 W. a means for forming a gas on the processing stage; the step of placing the heat to be treated into the chamber; the force power is set to: gas-plasmaized TiCl4 gas-8-200907101, in the first to third aspects above, The substrate temperature can be set to 300 to 67 (the range of TC, especially when the substrate temperature is 500 t ± 20 ° C.) According to the fourth aspect of the present invention, a method for forming a titanium film is provided. Forming a Ti film on the Si portion of the substrate to be processed by the film forming apparatus, the film forming apparatus having: a chamber for accommodating the substrate to be processed; a mounting table on which the substrate to be processed is placed in the chamber; and heating a heating means for mounting a substrate on the stage; a processing gas supply means for supplying a processing gas containing TiCl4 gas and a reducing gas into the chamber; and a high-frequency electric field forming a high-frequency electric field in a space above the substrate to be processed on the mounting table And an exhausting means for exhausting the chamber, comprising: a step of disposing a substrate to be processed having a Si portion on the mounting table: a step of heating the substrate to be processed; and setting a chamber a step of a specific pressure; a step of introducing a processing gas containing a TiCl 4 gas and a reducing gas and an inert gas into the chamber; and forming a high-frequency electric field by the high-frequency electric field forming means, thereby pulverizing the processing gas And a step of generating a reaction between the TiCl 4 gas and the reducing gas on the surface of the substrate to be processed, and introducing a Tic 14 gas, a reducing gas, and an inert gas into the chamber to form a high-frequency electric field to generate a plasma. In the fourth aspect of the present invention, it is preferable to form a Ti film on the Si portion of the substrate to be processed, and it is preferable to form a memory. If the fifth aspect of the present invention is used, a memory is provided. The medium, the memory has a program that operates on the computer and controls the film forming device, and when the control program is executed, the method of performing the film formation of the Ti film is performed. Computer-9-200907101 The above-mentioned film forming apparatus is controlled by a film forming apparatus which forms a Ti film in a Si-containing portion of a substrate having a Si portion, and the film forming apparatus has a housing a chamber for processing a substrate; a mounting table on which the substrate to be processed is placed in the chamber; a heating means for heating the substrate on the mounting table; and a processing gas supply means for supplying the processing gas containing the Tic 14 gas and the reducing gas into the chamber; a high-frequency electric field forming means for forming a high-frequency electric field in a space above the substrate to be processed on the mounting table; and an exhausting means for exhausting the chamber, comprising the step of disposing the si portion on the mounting table a substrate to be processed; heating the substrate to be processed; setting a chamber to a specific pressure; introducing a processing gas containing a Tic 14 gas and a reducing gas into the chamber; and forming a high-frequency electric field by the high-frequency electric field forming means, thereby Treating gas plasma; and generating a reaction caused by the above TiCl4 gas and a reducing gas on the surface of the substrate to be processed, by the above reaction, Substrate processing part S i when the Ti film is formed, the reaction to inhibit the generation processing manner portion of the substrate S i S i of the Ti, the pressure in the chamber and controlling the power applied by the high frequency power. In the current Ti film formation, from the viewpoint of promoting the reaction, the pressure in the chamber is set to about 667 Pa, and the high-frequency power is set to a relatively high level of about 800 W to perform a film formation process. When the film formation is performed under conditions, the temperature of the substrate to be processed is around 5 5 CTC, and the telluride is deviated. As a result of investigating the cause, the inventors have found that the phase formed by the reaction on Si is transferred from Ti to TiSi in the vicinity of the temperature, and the crystallization is likely to vary. Then, the resistance of Ti Si is higher than that of T i S i 2 generated at a high temperature or S i at a low temperature, and the film formation characteristics are also different, so that the film is transferred from T i -10- 200907101 to the vicinity of the transfer point of Ti Si. Deviation in thickness or film quality. Here, the inventors of the present invention have found that it is difficult to generate TiSi by controlling the pressure in the chamber and the power of the applied high-frequency electric field even if the condition of such a deviation is hard to be generated at around 550 ° C, and substantial reduction is possible. The transfer point of Ti and TiSi, so it is possible to avoid the above-mentioned deviation in the vicinity of 255 (typically, by reducing the chamber pressure and the power of the applied high-frequency power), it is possible to avoid the film thickness near 55 (rc or The film quality is deviated, and the plasma damage can be reduced as the power is reduced. Furthermore, by introducing the TiCl4 gas into the chamber and then forming a high-frequency electric field, the occurrence of abnormal discharge can be suppressed, and the plasma damage can be reduced. In addition to lowering the pressure and high-frequency power, the TiCl4 gas is introduced before the plasma is generated, and from the low temperature to the high temperature, plasma damage is not generated, and the Ti film formation with high stability and uniformity can be performed. [Embodiment] Hereinafter, embodiments of the present invention will be specifically described with reference to the attached drawings. Fig. 1 is a view showing the formation of a Ti film according to an embodiment of the present invention. A schematic cross-sectional view of an example of a Ti film forming apparatus used for carrying out the method. The Ti film forming apparatus 100 is a method of performing CVD film formation by forming a high electric field on a parallel plate electrode while forming a plasma. A slurry CVD film forming apparatus is constructed.

該Ti膜成膜裝置100具有略圓筒狀之腔室1。在腔室 1內部，用以水平支撐屬於被處理基板之晶圓W的由A1N -11 - 200907101 所構成之承載器2，是在藉由被設置在其中央下部之圓筒 狀之支撐構件3支撐之狀態下被配置。在承載器2之外緣 部設置有用以導引晶圓W之引導環4。再者，於承載器埋 入有以鉬等之高熔點金屬所構成之加熱器5 ’該加熱器5 藉由自加熱器電源6供電’將屬於被處理基板之晶圓W 加熱至特定溫度。在承載器2表面附近’埋設有當作平行 平板電極之下部電極而發揮功能之電極8’該電極8被接 地。 在腔室1之天壁la隔著絕緣構件9設置有也當作平 行平板電極之上部電極發揮功能之噴淋頭1 〇。該噴淋頭 1〇是由上段塊體l〇a、中段塊體10b、下段塊體10c所構 成，構成略圓盤狀。上段塊體具有與中段塊體10b及 下段塊體1 〇c同時構成噴淋頭本體部之水平部1 〇d和連續 於該水平部1 〇d之外周上方之環狀支撐部1 〇e，形成凹狀 。然後，藉由該環狀支撐部支撐噴淋頭10全體。然 後，在下段塊體1 〇 e交互形成吐出氣體之吐出孔1 7和1 8 。在上段塊體l〇a之上面形成有第1氣體導入口 11和第2 氣體導入口 11。在上段塊體l〇a之中，多數氣體通路13 自第1氣體導入口 11分歧。於中段塊體l〇b形成有氣體 通路1 5，上述氣體通路1 3經水平延伸之連通路1 3 a而與 該些氣體通路15連通。並且，該氣體通路15與下段區塊 l〇c之吐出孔17連通。再者，在上段塊體l〇a中，多數氣 體通路14自第2氣體導入口 12分歧。於中段塊體10b形 成有氣體通路16，上述氣體通路14與氣體通路連通。並 -12- 200907101 且’該氣體通路16在中段塊體1 Ob連接於水平延伸之連 通路16a，該連通路16a連通於下段塊體10c之多數吐出 孔18。然後’上述第1及第2氣體導入口 n、12連接於 氣體供給機構2 0之氣體管。 氣體供給機構20具有供給屬於潔淨氣體之C1F3氣體 之CIF3氣體供給源21、供給屬於Ti化合物之TiCl4氣體 之氣體供給源22、供給Ar氣體之Ar氣體供給源 23、供給屬於還原氣體之H2氣體之&amp;氣體供給源24、供 給屬於氮化氣體之NH3氣體之nH3氣體供給源25、供給 N2氣體之N2氣體供給源26。然後，於ciF3氣體供給源 21連接有CIF3氣體供給管27及3〇b，於TiCl4氣體供給 源22連接有TiC U氣體供給管28，於Ar氣體供給源23 連接有Ar氣體供給管29 ’於h2氣體供給源24連接有H2 氣體供給管30，於NH3氣體供給源25連接有nh3氣體供 給管3 0 a ’於N 2氣體供給源2 6連接有N 2氣體供給管3 0 c 。然後’於各氣體管設置有質量流量控制器32及夾著質 量流量控制器之兩個閥3 1。 於上述第1氣體導入口 1 1連接有自T i C 14氣體供給源 22延伸之TiCU氣體供給線28，於該TiCl4氣體供給管28 連接有自c 1 F3氣體供給源2 1延伸之c 1 F 3氣體供給線2 7 及自Ar氣體供給源23延伸之Ar氣體供給管29。再者， 於上述第2氣體導入口 12連接有自H2氣體供給源24延 伸之I氣體供給管30 ’於該h2氣體供給管連接有自 NH3氣體供給源25延伸之NH3氣體供給管30a、自N2氣 -13- 200907101 體供給源26延伸之N2氣體供給管30c及自C1F3氣體供給 源21延伸之C1F3氣體供給管30b。因此，於製程時，來 自TiCU氣體供給源22之TiCl4氣體與來自Ar氣體供給 源23之Ar氣體同時經TiCl4氣體供給管28，自噴淋頭10 之第1氣體導入口 11到達至噴淋頭10內，經氣體通路13 、14而自吐出孔17吐出至腔室1內，另外來自H2氣體供 給源24之H2氣體經H2氣體供給管30而自噴淋頭10之 第2氣體導入口 12到達至噴淋頭10內，經氣體通路14、 16而自吐出孔18吐出至腔室1內。即是，噴淋頭1〇爲 TiCl4氣體和H2氣體完全獨立而被供給至腔室1內之事後 混合型，該些於吐出後混合產生反應。並且，在並不限於 此，即使在Ti C 14和H2混合之狀態下，將該些供給至腔室 1內之事先混合型亦可。 於噴淋頭1 0經整合器3 3連接有高頻電源3 4，成爲自 該闻頻電源34供給高頻電力至噴淋頭10。藉由自局頻電 源3 4供給高頻電力，使經噴淋頭1 0被供給至腔室1內之 氣體予以電漿化而執行成膜處理。 再者，於噴淋頭1 〇之上段塊體1 〇a之水平部1 0d，設 置有用以加熱噴淋頭1 〇之加熱器45。於該加熱器45連接 有加熱器電源46，藉由自加熱器電源供電至加熱器45， 使噴淋頭1 〇加熱至所欲之溫度。於上述塊體1 〇 a之凹部 設置有用以提升利用加熱器4 5所產生之加熱效率之隔熱 構件47。 在腔室1之底壁lb之中央部形成有圓形之孔35，在 -14- 200907101 底壁1B以覆蓋該孔25之方式設置有朝下方突出之排氣室 36。在排氣室36之側面連接有排氣管37，該排氣管37連 接有排氣裝置38。然後，藉由使排氣裝置38動作，可將 腔室1內減壓至特定真空度。 於承載器2，以可對承載器2之表面突出沉沒之方式 ’設置用以支撐晶圓W並使予以升降之3根（僅圖式兩根） 之晶圓支撐銷39，該些晶圓支撐銷39被固定於支撐版40 。然後’晶圓支撐銷3 9藉由汽缸等之驅動機構4 1經支撐 版4 0而升降。 在腔室1之側壁設置有在與腔室1鄰接設置之無圖式 之晶圓搬運室之間執行晶圓W之搬入搬出之搬入搬出口 42 ’和開關該搬入搬出口 42之閘閥43。 屬於Ti膜成膜裝置1 〇〇之構成部的加熱器電源6及 46、閥31、質量流量控制器32、整合器33、高頻電源34 等爲連接於由電腦所構成之控制部5 0而被控制之構成。 再者，控制部50連接有由工程管理者爲了管理Ti膜成膜 裝置100而執行指令輸入操作等之鍵盤，或將Ti膜成膜 裝置1 〇〇之運轉狀況予以可視化而顯示之顯示器等所構成 之使用者介面5 1。並且，於控制部50連接有記憶部52， 該記憶部52儲存有用以利用控制部50之控制實現在Ti 膜成膜裝置1 0 0所實行之各種處理之控制程式，或用以因 應處理條件使Ti膜成膜裝置1 00之各構成部實行處理之 程式即是處理程式。處理程式被記憶於記憶部5 2中之記 憶媒體。記憶媒體即使爲硬碟或半導體記憶體亦可，即使 -15 - 200907101 爲 CDROM、DVD等之可搬運性亦可。再者，即使由其他 裝置經例如專用迴路適當傳送處理程式亦可。然後，因應 所需藉由利用來自使用者介面5 1之指示等自記憶部52叫 出任意處理程式而使控制部50實行，依此在控制部50之 控制下，執行Ti膜成膜裝置1 00之所欲處理。 接著，針對上述搬之Ti膜成膜裝置100中之本實施 形態所涉及之Ti膜成膜處理方法予以說明。 在本實施形態中當作對象之晶圓W爲露出Si部份者 ，Si部份即使爲Si基板亦可，即使爲形成在其上方之聚 矽膜亦可，在其上方形成Ti膜。通常包含Si02膜（或是 Low-k膜）等之Si02以當作層間絕緣膜，在Si部份和Si〇2 部份之雙方形成Ti膜。 並且，在以下之說明中，氣體之流量之單位雖然使用 mL/mi，但是氣體由於溫度及氣壓使得體積極大變化，故 在本發明中，使用換算成標準狀態之値。並且，換算成標 準狀態之流量因通常以sccm(Standerd Cubic Centimeter p e r M i n u t e s )被標記’故同時記載s c c m。在此之標準狀態 爲溫度 〇°C(273.15K)’ 氣壓爲 latm( 1 0 1 3 2 5Pa)之狀態。 首先，在晶圓被搬入至腔室1內之狀態下，執行預塗 佈。在預塗佈中，藉由排氣裝置3 8使腔室1內成爲抽風 狀態，邊將Ar氣體和N2氣體導入至腔室1內，邊藉由加 熱器5使承載器2升溫’在承載器2之溫度安定於特定溫 度之時點，以特定流量導入T i C 14氣體，並且自高頻電源 34施加高頻電力，使被導入至腔室1內之Ar氣體、h2氣 -16- 200907101 體、T i C14氣體予以電獎化，依此於腔室1內壁、排氣室 36內壁、噴淋頭10及承載器2形成Ti膜，接著僅停止 TiCl4，流動當作氮化氣體之NH3氣體，並且對噴淋頭1〇 施加高頻電力，使該些氣體予以電漿化而使Ti膜氮化。 藉由多數次重複該些，形成預塗佈膜。 如此完成預塗佈之後，對晶圓W執行Ti膜之堆積。 在該Ti膜之堆積中，藉由加熱器5使承載器2上昇至特 定溫度之後，將腔室1內調整成與經閘閥4 3而連接之夕f 部氛圍相同，之後’打開閘閥4 3，自真空狀態之無圖式 之晶圓搬運室經搬入搬出口 42，將晶圓 W搬入至腔室i 內。接著，在預塗佈工程中，與在噴淋頭10等形成Ti膜 之程序相同，使導入至腔室1內之Ar氣體、H2氣體、 TiCl4氣體予以電漿化，而使該些反應，在晶圓W上堆積 特定厚度之Ti膜。 於堆積Ti膜之後，施予Ti膜之氮化處理。該氮化處 理是於上述Ti膜之成膜後’停止TiCl4氣體，設爲流動著 H2氣體及Ar氣體之狀態，將腔室1內（腔室壁或噴淋頭表 面等）加熱至適當溫度，並且流通當作氮化氣體之NH3氣 體，自高頻電源34對噴淋頭10施加高頻電力，而使處理 氣體電漿化，藉由電漿化之處理氣體將成膜於晶圓W之 Ti薄膜表面予以氮化，完成Ti膜成膜處理。 在此，在上述Ti膜之堆積中，以往雖然使用650 °C左 右比較高之成膜溫度，但是於當作與閘極電極之聚矽上之 金屬接觸之接觸層使用之時，要求更低溫的用途則是在 -17- 200907101 550°C左右取得成膜。 另外，以往由更促進矽化物化之觀點來看，採用將腔 室1內之壓力設爲667Pa左右，將高頻電力設爲800W左 右’比較局之壓力、商功率的條件。於在該條件下，在晶 圓W之含Si部份例如聚矽膜上形成Ti膜之時，可知矽化 物化在5 5 0°c附近產生偏差，膜質及膜厚也產生偏差。 針對其點詳細予以說明。 第2圖是將橫軸設爲晶圓溫度，將縱軸設爲電阻値 Rs之平均値（Ώ/口）及其偏差程度（1σ、％)，表示在Si上 和Si〇2上堆積Ti膜之時之各膜上之電阻値及其偏差之溫 度變化的圖式。再者，以各溫度表示在矽上生成之相。 再者，第3圖是將橫軸設爲晶圓溫度，將縱軸設爲膜 厚（nm)及該其偏差程度（1 σ、％)，表示在Si上和Si02上 堆積Ti膜之時之各膜上之膜厚及其偏差之溫度變化的圖 式。 並且，第2圖、第3圖之成膜條件是將腔室內之壓力 設爲667Pa，Ti膜堆積是將氣體流量設爲TiCl4/Ar/H2: 12/1600/4000(m L/min(sccm))，將高頻電力功率設爲 8 00W，將時間設爲3 0 0 sec，氮化處理是將氣體流量設爲 NH3/Ar/H2: 1 5 00/ 1 6 00/2000(mL/min(sccm))，將高頻電力 功率設爲800W，將時間設爲30sec。 如第2圖所示般，矽氧化膜上之膜隨著晶圓溫度上昇 ，雖然膜之電阻値有單調減少之傾向，但是聚矽上之膜在 5 5 0 °C附近可見電阻値急遽上昇。再者，在5 90°C附近可見 -18- 200907101 電阻値之曲折點。該是由於在矽上形成Ti膜之時藉由溫 度所生成之相不同，在低溫生成Ti，在中溫生成矽化鈦 (TiSi) ’在高溫生成二矽化鈦（TiSi2)，於 5 5 0 °c具有 Ti/TiSi轉移點，在5 90 °C附近具有TiSi/TiSi2轉移點之故 。可知電阻値之標靶對應於該些轉移點也變大。尤其，在 成爲Ti成膜溫度之標靶的55 0°C，如圖示般，可見較大之 電阻値偏差。 再者，如第3圖所示般，矽氧化膜上之成膜速度隨著 溫度上昇，單調增加，對此聚矽膜上之成膜速度在移轉至 TiSi之550 °C附近下降，並在屬於TiSi生成溫度之550〜 59(TC附近，成膜速度低於矽氧化膜上之膜厚的成膜速度 。即是，在該溫度範圍，在聚矽上之成膜速度對於在矽氧 化膜上之成膜速度所表示之選擇比小於1。在Ti生成區域 中由於選擇比大約爲1，故在轉移點之5 50 °c附近選擇比 偏差。 即是，在以往之條件中，當晶圓溫度爲55 0°C在Si及 Si 〇2上執行Ti成膜時，矽化物化產生偏差，膜質及膜厚 也產生偏差。 如此產生偏差應是在5 5 0 °C中之矽化物化之結構成爲 下述般之故。 首先，屬於成膜原料之TiCl4在電漿中隨著（1)式之反 應而活性化。接著，被活性化之TiCl〆隨著（2)式之反應 而被還原，形成TiCl3，成爲有助於反應之類型。再者， Ti Cl3*彼此隨著（3)式反應而形成TiCl2，該也成爲有注於 -19- 200907101 反應之前驅物。This Ti film forming apparatus 100 has a chamber 1 having a substantially cylindrical shape. Inside the chamber 1, a carrier 2 composed of A1N -11 - 200907101 for horizontally supporting a wafer W belonging to a substrate to be processed is a cylindrical support member 3 provided at a lower central portion thereof. It is configured in the state of support. A guide ring 4 for guiding the wafer W is provided at the outer edge of the carrier 2. Further, a heater 5' composed of a high melting point metal such as molybdenum is embedded in the carrier. The heater 5 is heated by the heater power source 6 to heat the wafer W belonging to the substrate to be processed to a specific temperature. An electrode 8' functioning as a lower electrode of the parallel plate electrode is embedded in the vicinity of the surface of the carrier 2, and the electrode 8 is grounded. A shower head 1 that functions as an upper electrode of the parallel plate electrode is provided in the ceiling wall la of the chamber 1 via the insulating member 9. The shower head 1 is composed of an upper block l〇a, a middle block 10b, and a lower block 10c, and is formed in a substantially disk shape. The upper block has a horizontal portion 1 〇d of the shower head body portion and an annular support portion 1 〇e continuous with the outer periphery of the horizontal portion 1 〇d at the same time as the middle block body 10b and the lower block body 1 〇c. Formed in a concave shape. Then, the entire shower head 10 is supported by the annular support portion. Then, the lower block 1 〇 e alternately forms the discharge holes 17 and 18 of the discharge gas. The first gas introduction port 11 and the second gas introduction port 11 are formed on the upper block l〇a. Among the upper block l〇a, most of the gas passages 13 are diverged from the first gas introduction port 11. A gas passage 15 is formed in the middle block l〇b, and the gas passage 13 communicates with the gas passages 15 via the horizontally extending communication passage 13a. Further, the gas passage 15 communicates with the discharge port 17 of the lower block l〇c. Further, in the upper block l〇a, most of the gas passages 14 are diverged from the second gas introduction port 12. A gas passage 16 is formed in the middle block 10b, and the gas passage 14 communicates with the gas passage. Further, -12-200907101 and the gas passage 16 are connected to the horizontally extending connecting passage 16a at the intermediate block 1 Ob, and the communication passage 16a communicates with the plurality of discharge holes 18 of the lower block 10c. Then, the first and second gas introduction ports n and 12 are connected to the gas pipe of the gas supply mechanism 20. The gas supply mechanism 20 has a CIF3 gas supply source 21 that supplies C1F3 gas belonging to a clean gas, a gas supply source 22 that supplies TiCl4 gas belonging to a Ti compound, an Ar gas supply source 23 that supplies an Ar gas, and an H2 gas that supplies a reducing gas. The gas supply source 24 supplies an nH3 gas supply source 25 which is an NH3 gas belonging to a nitriding gas, and an N2 gas supply source 26 which supplies N2 gas. Then, the CIF3 gas supply pipes 27 and 3〇b are connected to the ciF3 gas supply source 21, the TiC U gas supply pipe 28 is connected to the TiCl4 gas supply source 22, and the Ar gas supply pipe 29' is connected to the Ar gas supply source 23. The H2 gas supply source 24 is connected to the H2 gas supply pipe 30, and the NH3 gas supply source 25 is connected to the nh3 gas supply pipe 3 0 a '. The N 2 gas supply source 2 6 is connected to the N 2 gas supply pipe 3 0 c . Then, a mass flow controller 32 and two valves 31 sandwiching the mass flow controller are disposed in each gas pipe. A TiCU gas supply line 28 extending from the Ti C 14 gas supply source 22 is connected to the first gas introduction port 1 1 , and a c 1 extending from the c 1 F 3 gas supply source 2 1 is connected to the TiCl 4 gas supply pipe 28 . The F 3 gas supply line 27 and the Ar gas supply pipe 29 extending from the Ar gas supply source 23 are provided. Further, an I gas supply pipe 30' extending from the H2 gas supply source 24 is connected to the second gas introduction port 12, and the NH3 gas supply pipe 30a extending from the NH3 gas supply source 25 is connected to the h2 gas supply pipe. N2 gas-13-200907101 The N2 gas supply pipe 30c extended by the body supply source 26 and the C1F3 gas supply pipe 30b extended from the C1F3 gas supply source 21. Therefore, at the time of the process, the TiCl4 gas from the TiCU gas supply source 22 and the Ar gas from the Ar gas supply source 23 pass through the TiCl4 gas supply pipe 28 simultaneously from the first gas introduction port 11 of the shower head 10 to the shower head. In the case of 10, the gas passages 13 and 14 are discharged from the discharge port 17 into the chamber 1, and the H2 gas from the H2 gas supply source 24 passes through the H2 gas supply pipe 30 from the second gas introduction port 12 of the shower head 10. It reaches the shower head 10 and is discharged into the chamber 1 through the gas passages 14, 16 from the discharge port 18. That is, the shower head 1 is a post-mixing type in which the TiCl4 gas and the H2 gas are completely independent and supplied into the chamber 1, and these are mixed and reacted after the discharge. Further, the present invention is not limited thereto, and the premix type may be supplied to the chamber 1 even in a state where Ti C 14 and H2 are mixed. The high-frequency power source 34 is connected to the shower head 10 via the integrator 3 3, and the high-frequency power is supplied from the frequency power source 34 to the shower head 10. The high-frequency power is supplied from the local power source 34, and the gas supplied into the chamber 1 through the shower head 10 is plasma-formed to perform a film forming process. Further, a heater 45 for heating the shower head 1 is provided in the horizontal portion 10d of the upper block 1 〇a of the upper shower head 1 。. A heater power source 46 is connected to the heater 45, and the shower head 1 is heated to a desired temperature by supplying power from the heater power source to the heater 45. A heat insulating member 47 for improving the heating efficiency by the heater 45 is provided in the recess of the block 1 〇 a. A circular hole 35 is formed in a central portion of the bottom wall lb of the chamber 1, and a bottom chamber 1B is provided at -14-200907101 to cover the hole 25 so as to protrude downward. An exhaust pipe 37 is connected to the side of the exhaust chamber 36, and an exhaust device 38 is connected to the exhaust pipe 37. Then, by operating the exhaust device 38, the inside of the chamber 1 can be decompressed to a specific degree of vacuum. The carrier 2 is provided with three wafer support pins 39 for supporting and lifting the wafer W in a manner that can sink and sink the surface of the carrier 2, the wafers The support pin 39 is fixed to the support plate 40. Then, the wafer support pin 39 is lifted and lowered by the drive mechanism 4 1 of the cylinder or the like via the support plate 40. On the side wall of the chamber 1, a loading/unloading port 42' for performing loading and unloading of the wafer W between the wafer transfer chambers (not shown) disposed adjacent to the chamber 1 and a gate valve 43 for opening and closing the transfer port 42 are provided. The heater power sources 6 and 46, the valve 31, the mass flow controller 32, the integrator 33, the high-frequency power source 34, and the like belonging to the components of the Ti film forming apparatus 1 are connected to a control unit 50 composed of a computer. It is composed of control. Further, the control unit 50 is connected to a keyboard that performs an instruction input operation or the like by the engineering manager to manage the Ti film forming apparatus 100, or a display that displays the operation state of the Ti film forming apparatus 1 and visualizes it. The user interface 5 1 is constructed. Further, a control unit 50 is connected to the memory unit 52, and the memory unit 52 stores a control program for realizing various processes performed by the Ti film forming apparatus 100 by the control of the control unit 50, or for responding to processing conditions. The program for executing the processing of each component of the Ti film forming apparatus 100 is a processing program. The processing program is memorized in the memory medium in the memory unit 52. Even if the memory medium is a hard disk or a semiconductor memory, even -15 - 200907101 can be handled as a CDROM or a DVD. Furthermore, even if the processing program is appropriately transmitted by another device via, for example, a dedicated loop. Then, the control unit 50 is executed by calling the arbitrary processing program from the memory unit 52 by the instruction from the user interface 51, and the Ti film forming apparatus 1 is executed under the control of the control unit 50. 00 wants to deal with. Next, a Ti film formation processing method according to the present embodiment in the above-described Ti film forming apparatus 100 will be described. In the present embodiment, the wafer W to be used is a portion in which Si is exposed, and the Si portion may be a Si substrate, and a Ti film may be formed thereon even if it is formed on the polysilicon film formed thereon. Usually, SiO 2 such as a SiO 2 film (or a Low-k film) is used as an interlayer insulating film, and a Ti film is formed on both the Si portion and the Si 〇 2 portion. Further, in the following description, although the unit of the flow rate of the gas is used in the range of mL/mi, the gas greatly changes in volume due to the temperature and the gas pressure. Therefore, in the present invention, the conversion to the standard state is used. Further, the flow rate converted into the standard state is usually marked with sccm (Standerd Cubic Centimeter p e r M i n u t e s ), so s c c m is also described. The standard state here is the state of temperature 〇 ° C (273.15 K)' and the pressure is latm (1 0 1 3 2 5 Pa). First, a pre-coating is performed in a state where the wafer is carried into the chamber 1. In the precoating, the inside of the chamber 1 is brought to the exhaust state by the exhaust device 38, and the Ar gas and the N2 gas are introduced into the chamber 1 while the carrier 2 is heated by the heater 5 'on the load. When the temperature of the device 2 is stabilized at a specific temperature, the T i C 14 gas is introduced at a specific flow rate, and high-frequency power is applied from the high-frequency power source 34 to introduce the Ar gas and the h 2 gas into the chamber 1 - 200907101 The body and the T i C14 gas are electrically prized, thereby forming a Ti film on the inner wall of the chamber 1, the inner wall of the exhaust chamber 36, the shower head 10 and the carrier 2, and then only stopping TiCl4, and flowing as a nitriding gas The NH3 gas is applied with high frequency power to the shower head 1 ,, and the gases are plasmad to nitride the Ti film. The precoat film is formed by repeating this a plurality of times. After the precoating is completed in this manner, the deposition of the Ti film is performed on the wafer W. In the stacking of the Ti film, after the carrier 2 is raised to a specific temperature by the heater 5, the inside of the chamber 1 is adjusted to be the same as the atmosphere of the evening f portion connected via the gate valve 43, and then the gate valve 4 is opened. The wafer transfer chamber from the vacuum state of the wafer transfer chamber is carried into the transfer port 42 to carry the wafer W into the chamber i. Then, in the precoating process, the Ar gas, the H 2 gas, and the TiCl 4 gas introduced into the chamber 1 are plasmad in the same manner as the procedure for forming the Ti film in the shower head 10 or the like, and the reactions are caused. A Ti film of a specific thickness is deposited on the wafer W. After the Ti film is deposited, the nitridation treatment of the Ti film is performed. This nitriding treatment is to stop the TiCl 4 gas after the film formation of the Ti film, and to heat the chamber 1 (the chamber wall or the shower head surface, etc.) to a proper temperature in a state in which the H 2 gas and the Ar gas flow. And flowing NH3 gas as a nitriding gas, applying high-frequency power to the shower head 10 from the high-frequency power source 34, and plasma-treating the processing gas, and forming a film on the wafer W by the plasma processing gas The surface of the Ti film is nitrided to complete the Ti film formation process. Here, in the deposition of the Ti film, a relatively high film formation temperature of about 650 ° C is conventionally used, but when it is used as a contact layer in contact with a metal on a gate electrode of a gate electrode, a lower temperature is required. The use is to form a film at around 550-200907101 550 °C. In addition, in the past, from the viewpoint of promoting the bismuth compounding, the pressure in the chamber 1 is set to about 667 Pa, and the high-frequency power is set to about 800 W. Under the above conditions, when a Ti film is formed on a Si-containing portion of the wafer W, for example, a polyfluorene film, it is understood that the crystallization of the bismuth is in the vicinity of 550 ° C, and the film quality and film thickness are also deviated. The details will be described in detail. Fig. 2 is a graph showing the horizontal axis as the wafer temperature and the vertical axis as the average 値(Ώ/口) of the resistor 値Rs and the degree of deviation (1σ, %), indicating that Ti is deposited on Si and Si〇2. A pattern of the temperature change of the resistance 各 and its deviation on each film at the time of the film. Furthermore, the phase generated on the crucible is represented by each temperature. In addition, in the third drawing, the horizontal axis is the wafer temperature, and the vertical axis is the film thickness (nm) and the degree of variation (1 σ, %), which indicates when the Ti film is deposited on Si and SiO 2 . A pattern of the film thickness on each film and the temperature change of its deviation. Further, the film formation conditions in Figs. 2 and 3 are such that the pressure in the chamber is 667 Pa, and the Ti film deposition is such that the gas flow rate is TiCl4/Ar/H2: 12/1600/4000 (m L/min (sccm). )), the high-frequency power is set to 800 W, the time is set to 300 sec, and the nitriding process is to set the gas flow rate to NH3/Ar/H2: 1 5 00/ 1 6 00/2000 (mL/min) (sccm)), the high-frequency power was set to 800 W, and the time was set to 30 sec. As shown in Fig. 2, the film on the tantalum oxide film increases with the wafer temperature, although the resistance of the film tends to decrease monotonously, but the film on the polythene sees a sharp rise in resistance around 550 °C. . Furthermore, the tortuosity of the resistor -18-200907101 is visible near 5 90 °C. This is due to the difference in the phase formed by the temperature at the time of forming the Ti film on the crucible, the formation of Ti at a low temperature, and the formation of titanium telluride (TiSi) at a medium temperature to form titanium dioxide (TiSi2) at a high temperature, at 50 ° ° c has a Ti/TiSi transfer point and has a TiSi/TiSi2 transfer point around 5 90 °C. It can be seen that the target of the resistor 値 also becomes larger corresponding to the transition points. In particular, at 55 °C which is the target of the Ti film formation temperature, as shown in the figure, a large resistance 値 deviation can be seen. Furthermore, as shown in Fig. 3, the film formation rate on the tantalum oxide film monotonously increases as the temperature rises, and the film formation speed on the polysilicon film decreases toward 550 °C of TiSi, and Between 550 and 59 (the vicinity of TC, the film formation rate is lower than the film thickness of the film thickness on the tantalum oxide film. That is, in this temperature range, the film formation rate on the polyfluorene is oxidized in the ruthenium. The film formation rate on the film indicates a selection ratio of less than 1. Since the selection ratio is about 1 in the Ti generation region, the ratio deviation is selected in the vicinity of 5 50 °c of the transfer point. That is, in the conventional conditions, when When the wafer temperature is 55 ° ° C and Ti is formed on Si and Si 〇 2, the bismuth crystallization is deviated, and the film quality and film thickness are also deviated. The deviation should be 矽化化 at 550 °C. The structure is as follows. First, TiCl4, which is a film-forming raw material, is activated in the plasma by the reaction of the formula (1). Then, the activated TiCl is reacted with the reaction of the formula (2). Reduction, formation of TiCl3, which becomes a type that contributes to the reaction. Furthermore, Ti Cl3* follows each other (3) The reaction forms TiCl2, which also becomes a precursor before the reaction of -19-200907101.

TiCl4 + Ar— TiCl4* +Ar (1)TiCl4 + Ar- TiCl4* +Ar (1)

TiCl4* +H + — TiCl2 + HCl (2)TiCl4* +H + — TiCl2 + HCl (2)

TiCl3* + T1CI3* ^ TiCl2 + TiCl4 (3) 即是，有助於反應之前驅物存在TiCl3和TiCh兩 類。該些TiCl3和TiCl2是矽化物化之機構不同。 將前驅物爲TiCl3之時之推定機構表示於第4圖A 第4圖C。於成膜初期如第4圖A所示般，在Si基板 吸附TiCl3，並且藉由H2被還原，在Si基板上形成Ti ，藉由熱被矽化物化。再者，於成膜後期，如第4圖B 示般’在矽化物上吸附TiC 13 ’藉由H2還原而在矽化物 形成Ti膜，藉由熱被矽化物化。即是，無論於成膜初 或成膜後期，機構基本上不變化，如第4圖C所示般， 厚對於時間直線性變化。即是，成膜速度爲一定。並且 如此之機構相當於上述Ti生成區域。 接著，於第5圖A至第5圖C表示前驅物爲TiC 12 時之推定機構。首先，於成膜初期如第5圖A所示般， Si基板上吸附TiCl2，在Si基板上直接與Si反應而成 矽化物（Si還原），Si被蝕刻（成爲SiCl2而揮發）。然後 矽化物中之Ti擴散至S i基板中。再者，於成膜後期， 第5圖B所示般，在矽化物上吸附S i C12，矽化物中之 擴散至矽化物之Si基板中，並且SiCl2直接與基版中之 種 至 上 膜 所 上 期 膜 ， 之 在 爲 如 Ti Si -20- 200907101 反應而成爲矽化物（Si還原），Si被蝕刻（成爲SiCl2而揮發 )。TiCl2不被H2還原是Ti-Si-Cl結合大於HC1結合之故 。如此一來於Ti擴散有助於矽化物之時，成膜後期因Ti 之擴散速度下降，故如第5圖C所示般，於成膜後期有成 膜速度下降之傾向。並且，如此之機構相當於上述TiSi 生成區域。 於在550 °c成膜之時，如此一來雖然藉由兩種類之前 驅物之反應成膜，但是Ti Cl4因通過電漿中之分解一面前 進一面排氣，故Ti Cl4在晶圓之邊緣部持續分解，生成更 多之Ti Cl2。因此，在晶圓邊緣部，以Ti Cl2爲前驅物之 上述第5圖A〜第5圖C之機構之成膜過程成爲支配性。 另外，在晶圓中心部，Ti Cl4之分解無法充分進行，前驅 物成爲Ti Cl3停止，上述第4圖A至第4圖C之機構之 成膜過程成爲支配性。 如此一來，於將溫度以外之條件如以往般在5 5 0 °C執 行成膜之時，在晶圓面內產生矽化物偏差，膜質或膜厚偏 差。爲了解除如此之偏差，至少執行降低高頻電力功率， 及降低腔室1內之壓力則爲有效。 即是，藉由降低高頻電力之功率，减弱TiCl4之分解 ，在晶圓中心部和邊緣部任一者皆執行第4圖A至第4圖 C之機構所產生之成膜，可以抑制矽化物之偏差，抑制膜 質及膜厚之偏差。再者，藉由降低壓力，腔室內之排氣流 速變快，爲了於分解進行之前，使TiCl4從電漿逃脫，抑 制分解，成爲邊緣部之前驅物以TiCl3爲主體者，同樣在 -21 - 200907101 晶圓中心部和邊緣部任一者皆執行第4圖至第4圖C之機 構所產生之成膜，可以抑制矽化物化之偏差，抑制膜質及 膜厚之偏差。 當圖式該偏差改善之機構之圖像時，則如第6圖所示 般。第6圖是在以橫軸爲腔室內壓力，以縱軸爲高頻電力 功率之座標中，表示將5 0 0 °C中以T i C13當作前驅物之反 應爲主體之區域，和以TiC 12當作前驅物之反應爲主體之 區域的境界。在晶圓之邊緣部，如上述般，因容易產生 TiC 12，故境界線移動。以往之條件是被畫在中心部之境界 線和邊緣部之境界線之間。由該圖可知，藉由降低高頻電 力功率及壓力之至少一方，中心部及邊緣部中之任一者皆 可以TiC 13當作前驅物之反應爲主體。 即使爲3 0 Omni晶圓般之大型晶圓，爲了實現邊緣也 安定而以TiC 13當作前驅物之反應爲主體之成膜處理，將 腔室內壓力設爲x(Pa)，將高頻電力設爲y(W0之時，則以 滿足以下之（4 )式爲佳。 (y- 3 3 3 )&lt; 1 60400/(x-2 66)…（4) 但是，將其他條件設爲TiCU: 3〜20mL/min(sccm)， Ar 流量：100 〜2000mL/min(sccm) ’ H2 流量：1000 〜 5 00 0mL/min(sccm)，晶圓溫度：5 00〜600 °C之範圍內。 接著，以根據如此之點降低高頻電力功率及腔室內壓 力之條件，針對形成Ti膜之結果予以說明。 -22- 200907101 第7圖爲表示較以往降低高頻電力功率及腔室內壓力 之時，在Si上和Si02上堆積Ti膜之際的各膜上之電阻値 及其偏差之溫度變化之圖式。並且，在第7圖一倂表示各 溫度中在矽上昇成之相。 再者，第8圖爲表示較以往降低高頻電力功率及腔室 內壓力之時，在Si上和Si02上堆積Ti膜之際的各膜上之 膜厚及其偏差之溫度變化之圖式。 並且，第7圖、第8圖時之成膜條件是將腔室內之壓 力設爲5 00Pa，Ti膜堆積是將氣體流量設爲TiCl4/Ar/H2: 12/1600/4000(m L/min(sccm))，將高頻電力功率設爲 500W，將時間設爲29sec，氮化處理是將氣體流量設爲 NH3/Ar/H2 : 1 5 00/ 1 600/2000(m L/min(sccm))，高頻電力功 率：800W，時間：29 sec ° 如第7圖所示般，於降以往降低高頻電力功率及腔室 內壓力之時，生成Ti Si之區域消失，在550 °C附近不見電 阻値急遽上昇。再者，如第8圖所示般，於較以往降低高 頻電力功率及腔室內壓力之時，在500〜590 °C附近不見選 擇比之逆轉，表示安定之膜厚。由以上之結果，確認出降 低高頻電力功率，及降低腔室內之壓力則爲有效。 接著，針對將晶圓溫度設爲550 °C，使腔室內壓力及 高頻電力功率變化而予以成膜之時之特性變化進行調查之 結果予以說明。並且，在此作爲其他條件，Ti膜堆積是將 氣體流量設爲 TiCl4/Ar/H2: 1 2/ 1 600/4000(m L/min(sccm)) ，將時間設爲 30sec，氮化處理是將氣體流量設爲 -23- 200907101 NH3/Ar/H2: 1 5 0 0/ 1 600/20000 L/min(sccm))’ 高頻電力功 率：8 0 0 W，時間 3 0 s e c。 第9圖至第12圖是表示將橫軸設爲腔室內壓力，將 縱軸設爲高頻電力功率之晶圓溫度5 5 0°C的座標’第9圖 爲表示膜厚之選擇比（Si上之膜厚/ Si〇2上之膜厚）之等高 線之圖式，第10圖爲表示平均膜厚之等高線之圖式’第 11圖爲表不偏差之等尚線之圖式’弟12 Θ爲表不電阻値 之平均値之等高線之圖式。 從該些圖式，確認出藉由使腔式內壓力及/或高頻電 力功率較以往（667Pa、800 W)降低，則可以確保膜厚之選 擇比爲1以上，膜厚本身也變厚’並且電阻値Rs較以往 滴且電阻値之偏差也較小。 由該些圖可知滿足上述（4)式，並且以腔室內壓力在 266〜1333W之範圍，高頻電力功率在200〜1000W之範 圍爲佳。尤其，若再以難產生電將對晶圓W或腔室1造 成損傷之觀點，來看可知腔室內壓力以3 00〜8 00Pa之範 圍，高頻電力功率爲300〜600W之範圍爲佳。 針對晶圚溫度，上述條件在5 5 0 °C，更具體而言爲 550±20°C之時尤其有效，相對於300〜670 °C可適用，藉由 採用上述條件，可以在晶圓溫度爲3 0 0〜6 7 0 °C之寬廣範圍 執行安定之矽化物化。 接著，針對堆積Ti膜之時之電漿形成時序予以說明 〇 以往，由電漿化之容易性之觀點來看，先將Ar氣體 -24- 200907101 及屬於還原氣體之H2氣體導入至腔室內而予以電漿化之 後，導入TiCl4氣體（預電漿）’由於之後導入TiCl4氣體， 放電狀態暫時性變化，溫度高達64(TC，並且高頻電力功 率也成爲較高之8 00W，故與該事態相輔而產生如在腔室 內產生異常放電，或電漿對晶圓造成損傷之不當情形。 爲了防止該事態，如第13圖A所示般，以於電漿之 生成前先導入TiCl4(預TiCl4)爲佳。具體而言，如第13圖 B所示般，於導入Ar氣體+H2氣體之後，導入TiCl4，之 後使電漿點燃爲佳。 該是因於形成電漿之後供給TiCl4氣體而所產生之電 漿散亂大於導入TiCl4氣體之後點燃電漿之時的散亂之故 。再者，如此藉由於電漿點燃之前先供給TiCl4氣體， 可以使膜之電阻更縮小。TiCl4氣體是於電漿點燃前2秒 以上供給爲佳。 採用如此比電漿先導入TiCl4氣體之順序，並且以上 述般之高頻電力功率及/或腔室內壓力爲低之條件執行Ti 成膜，依此可以使電獎所產生之放電更佳安定化，並可以 更有效果抑制異常放電或對晶圓所造成之損傷。即使針對 比電漿先導入該Tie 14氣體之順序，亦可在晶圓溫度爲 300〜670 °C之寬廣範圍適用。 再者，於採用比電漿先導入TiCl4氣體之順序之時’ 則在成膜溫度爲6 2 0〜6 5 0 °C附近，因溫度而產生之膜厚選 擇比的變化，比採用使電漿點燃之順序之時較大之傾向， 但是於採用比電漿先導入TiC 14氣體之順序，並且在高頻 -25- 200907101 電力功率及/或腔室內壓力低之條件下，執行Ti成膜，依 此可以縮小選擇比之變化。將此表示於第14圖。該圖爲 表示將橫軸設爲晶圓溫度，將縱軸設爲膜厚之選擇比，以 以往之8 00W、667Pa之條件執行預電漿之時，以相同條 件執行預TiCl4之時，藉由在5 00W、5 0 0Pa之條件下執行 預TiC 14時之溫度，選擇比產生變化之圖式。如該圖所示 般，確認出於以以往之800W、667Pa之條件執行預TiCl4 之時，雖然在成膜溫度爲620〜65 0 t附近選擇比之變化大 ，但是於在5 00W、5 00Pa之條件執行TiCl4之時，則與預 電漿相同，選擇比幾乎不變化。 並且，堆積Ti膜之時之其他條件之最佳範圍則如同 下述。 i) 來自高頻電源34之高頻電力之頻率：3〇OkHz〜 27MHz ii) TiCl4 氣體流量：3〜20mL/min(sccm) iii) Ar 氣體流量·· 1000 〜2000mL/min(sccm) iv) H2 氣體流量：1000〜5000mL/min(sccm) 再者，氮化處理之時之最佳條件則如同下述。TiCl3* + T1CI3* ^ TiCl2 + TiCl4 (3) is that it contributes to the presence of TiCl3 and TiCh in the precursor before the reaction. These TiCl3 and TiCl2 are different in the mechanism of mashification. The estimation mechanism when the precursor is TiCl3 is shown in Fig. 4A, Fig. 4C. In the initial stage of film formation, as shown in Fig. 4A, TiCl3 was adsorbed on the Si substrate, and was reduced by H2, and Ti was formed on the Si substrate, and was deuterated by heat. Further, in the late stage of film formation, as shown in Fig. 4B, the adsorption of TiC 13 ' on the telluride is reduced by H 2 to form a Ti film on the telluride, which is deuterated by heat. That is, the mechanism does not substantially change at the beginning of film formation or at the later stage of film formation, and as shown in Fig. 4C, the thickness changes linearly with respect to time. That is, the film formation speed is constant. And such a mechanism corresponds to the above Ti generation region. Next, in Fig. 5 to Fig. 5C, the estimation mechanism when the precursor is TiC 12 is shown. First, as shown in Fig. 5A, the TiCl2 is adsorbed on the Si substrate, and the Si substrate is directly reacted with Si to form a telluride (Si reduction), and Si is etched (to become volatilized by SiCl2). The Ti in the telluride is then diffused into the Si substrate. Further, in the later stage of film formation, as shown in FIG. 5B, S i C12 is adsorbed on the telluride, and the silicide is diffused into the Si substrate of the telluride, and the SiCl 2 is directly bonded to the substrate in the base plate. The upper film is a telluride (Si reduction) in the reaction of Ti Si -20-200907101, and Si is etched (to become volatilized by SiCl2). The reduction of TiCl2 by H2 is due to the fact that Ti-Si-Cl bonding is greater than HC1 binding. As described above, when Ti diffusion contributes to the telluride, the diffusion rate of Ti decreases in the late stage of film formation. Therefore, as shown in Fig. 5C, the film formation rate tends to decrease at the later stage of film formation. Further, such a mechanism corresponds to the above-described TiSi generation region. At the time of film formation at 550 °c, although the film is formed by the reaction of two kinds of precursors, TiCl4 is exhausted while advancing through the decomposition in the plasma, so TiCl4 is on the edge of the wafer. The part continues to decompose and generate more Ti Cl2. Therefore, at the edge portion of the wafer, the film formation process of the above-described fifth to fifth panels A to 5, which uses TiCl2 as a precursor, becomes dominant. Further, in the center portion of the wafer, the decomposition of TiCl4 is not sufficiently performed, and the precursor stops TiCl3, and the film formation process of the mechanism of Figs. 4A to 4C becomes dominant. As a result, when the film is formed at a temperature of 550 ° C as in the conventional conditions, a teller deviation occurs in the wafer surface, and the film quality or film thickness is deviated. In order to cancel such deviation, it is effective to perform at least the reduction of the high-frequency power and the pressure in the chamber 1. That is, by reducing the power of the high-frequency power, the decomposition of TiCl4 is weakened, and film formation by the mechanism of Figs. 4A to 4C is performed at either the center portion and the edge portion of the wafer, thereby suppressing the deuteration. The deviation of the substance suppresses the deviation of the film quality and the film thickness. Furthermore, by lowering the pressure, the flow velocity of the exhaust gas in the chamber becomes faster. In order to prevent the decomposition of TiCl4 from the plasma before the decomposition, the decomposition of the TiCl4 is suppressed, and the precursor of the edge portion is TiCl3 as the main body, also in the case of -21 200907101 Any one of the center part and the edge part of the wafer performs the film formation by the mechanism of FIG. 4 to FIG. 4C, and can suppress the deviation of the bismuth formation and suppress the variation of the film quality and the film thickness. When the image of the mechanism for improving the deviation is plotted, it is as shown in Fig. 6. Fig. 6 is a view showing a region in which the horizontal axis is the pressure in the chamber and the vertical axis is the power of the high-frequency electric power, and the region in which the reaction of TiC13 as a precursor is taken as the main body at 500 °C, and The reaction of TiC 12 as a precursor is the realm of the region of the main body. At the edge portion of the wafer, as described above, since the TiC 12 is easily generated, the boundary line moves. In the past, the condition was drawn between the boundary between the boundary line and the edge of the center. As can be seen from the figure, by reducing at least one of the high-frequency power and the pressure, either the center portion or the edge portion can be made mainly by the reaction of TiC 13 as a precursor. Even for large wafers like the 3 0 Omni wafer, in order to achieve the edge stability, the film formation process using TiC 13 as the precursor is the main process, and the chamber pressure is set to x (Pa), and the high frequency power is used. When it is set to y (W0, it is preferable to satisfy the following formula (4). (y- 3 3 3 ) &lt; 1 60400/(x-2 66) (4) However, other conditions are set to TiCU : 3 to 20 mL/min (sccm), Ar flow rate: 100 to 2000 mL/min (sccm) 'H2 flow rate: 1000 to 5 00 0 mL/min (sccm), wafer temperature: 5 00 to 600 °C. Next, the result of forming the Ti film according to the conditions of lowering the high-frequency power and the pressure in the chamber according to such a point will be described. -22- 200907101 Figure 7 shows the time when the high-frequency power and the pressure in the chamber are lowered. A graph of the temperature change of the resistance 値 and its deviation on each film when Si is deposited on Si and SiO 2 , and the phase of the enthalpy rise at each temperature is shown in Fig. 7 . Figure 8 is a graph showing the film thickness on each film when Si is deposited on Si and SiO 2 when the high-frequency power and the pressure in the chamber are lowered. The pattern of the temperature change of the deviation is also shown in Fig. 7 and Fig. 8 is that the pressure in the chamber is set to 500 Pa, and the Ti film deposition is set to TiCl4/Ar/H2: 12 /1600/4000 (m L/min (sccm)), the high-frequency power is set to 500 W, the time is set to 29 sec, and the nitriding treatment is to set the gas flow rate to NH3/Ar/H2: 1 5 00 / 1 600 /2000(m L/min(sccm)), high-frequency power: 800W, time: 29 sec ° As shown in Fig. 7, when lowering the high-frequency power and the pressure in the chamber, Ti Si is generated. The area disappeared, and no resistance was observed in the vicinity of 550 °C. In addition, as shown in Fig. 8, when the high-frequency power and the pressure in the chamber were lowered, the selection was not found near 500 to 590 °C. It is effective to reduce the high-frequency power and lower the pressure in the chamber by the above results. Next, the pressure in the chamber is set to 550 °C. And the results of investigating changes in characteristics at the time of film formation at the time of high-frequency power change, and As another condition, the Ti film deposition is such that the gas flow rate is TiCl4/Ar/H2: 1 2/ 1 600/4000 (m L/min (sccm)), the time is set to 30 sec, and the nitriding treatment is the gas flow rate. Set to -23- 200907101 NH3/Ar/H2: 1 5 0 0/ 1 600/20000 L/min(sccm))' High-frequency power: 800 W, time 30 sec. Fig. 9 to Fig. 12 are diagrams showing the coordinates of the wafer temperature of the high temperature electric power at a wafer temperature of 550 ° C with the horizontal axis as the pressure in the chamber, and Fig. 9 is a graph showing the selection ratio of the film thickness ( The pattern of the contour line of the film thickness on Si/the film thickness on Si〇2, and the figure 10 shows the pattern of the contour line of the average film thickness. The eleventh figure shows the figure of the line that does not deviate. 12 Θ is a graph of the contour of the average 値 of the resistance 値. From these patterns, it has been confirmed that by lowering the intracavity pressure and/or the high-frequency electric power compared to the conventional (667 Pa, 800 W), it is possible to ensure that the film thickness selection ratio is 1 or more, and the film thickness itself is also thick. 'And the resistance 値Rs is smaller than the previous drop and the resistance 値 is also small. It is understood from the above figures that the above formula (4) is satisfied, and the pressure in the chamber is in the range of 266 to 1333 W, and the high-frequency electric power is preferably in the range of 200 to 1000 W. In particular, in view of the fact that it is difficult to generate electricity to damage the wafer W or the chamber 1, it is preferable that the pressure in the chamber is in the range of 300 to 800 Pa, and the high-frequency electric power is preferably in the range of 300 to 600 W. For the wafer temperature, the above conditions are particularly effective at 550 ° C, more specifically 550 ± 20 ° C, and are applicable with respect to 300 to 670 ° C. By using the above conditions, the wafer temperature can be used. For a wide range of 3 0 0 to 6 70 ° C, the stability of the deuteration is carried out. Next, the plasma formation timing at the time of depositing the Ti film will be described. Conventionally, from the viewpoint of easiness of plasma formation, Ar gas-24-200907101 and H2 gas belonging to a reducing gas are introduced into the chamber. After being pulverized, TiCl4 gas (pre-plasma) is introduced. Since the TiCl4 gas is introduced later, the discharge state temporarily changes, the temperature is as high as 64 (TC, and the high-frequency power is also higher at 800 W, so the situation Complementing the improper situation of generating an abnormal discharge in the chamber or causing damage to the wafer by the plasma. To prevent this, as shown in Fig. 13A, the TiCl4 is introduced before the plasma is generated. TiCl4) is preferable. Specifically, as shown in Fig. 13B, after introducing Ar gas + H2 gas, TiCl4 is introduced, and then plasma is preferably ignited. This is because TiCl4 gas is supplied after plasma formation. The generated plasma dispersion is greater than the scattering of the plasma after the introduction of the TiCl4 gas. Further, the resistance of the film can be further reduced by supplying the TiCl4 gas before the plasma is ignited. The TiCl4 gas is It is preferable to supply the slurry more than 2 seconds before the ignition. In this order, the TiCl4 gas is introduced first, and the Ti film formation is performed under the conditions of the above-mentioned high-frequency power and/or the chamber pressure, thereby making it possible to The electric discharge generated by the electric prize is better stabilized, and it can be more effective in suppressing abnormal discharge or damage to the wafer. Even in the order of introducing the Tie 14 gas first than the plasma, the wafer temperature can be 300. It is suitable for a wide range of ~670 °C. In addition, when the order of introduction of TiCl4 gas is first introduced, the film thickness is caused by temperature at a film formation temperature of 6 2 0 to 65 ° C. The change in the selection ratio is greater than the tendency to ignite the plasma, but in the order in which the TiC 14 gas is introduced first than the plasma, and in the high frequency -25-200907101 power and/or chamber pressure Under low conditions, Ti film formation is performed, and the change in the selection ratio can be reduced. This is shown in Fig. 14. This figure shows the selection ratio of the horizontal axis as the wafer temperature and the vertical axis as the film thickness. , in the past 8 00W, 667Pa conditions When pre-plasma is performed, when the pre-TiCl4 is performed under the same conditions, the temperature of the pre-TiC 14 is performed under the conditions of 500 W and 500 Pa, and the pattern of the change is selected as shown in the figure. When it is confirmed that the pre-TiCl4 is performed under the conditions of the conventional 800 W and 667 Pa, the change is larger than the change in the film formation temperature of 620 to 65 0 t, but when the TiCl 4 is performed under the conditions of 500 W and 500 Pa The same as the pre-plasma, the selection ratio hardly changes. And the optimum range of other conditions at the time of depositing the Ti film is as follows. i) Frequency of high-frequency power from high-frequency power source 34: 3〇OkHz~ 27MHz ii) TiCl4 gas flow rate: 3~20mL/min(sccm) iii) Ar gas flow rate·· 1000~2000mL/min(sccm) iv) H2 gas flow rate: 1000 to 5000 mL/min (sccm) Further, the optimum conditions at the time of nitriding treatment are as follows.

i) 來自高頻電源34之高頻電力 頻率：3 00kHz 〜27MHz 功率：500〜1500Wi) High frequency power from high frequency power supply 34 Frequency: 3 00 kHz ~ 27 MHz Power: 500~1500W

ii) 藉由加熱器5所產生之承載器2之溫度：300〜670 °C iii) Ar 氣體流量· 800 〜2000mL/min(sccm) -26- 200907101 iv) H2 氣體流量：1 500 〜4500mL/min(sccm) v) NH3 氣體流量·· 500 〜2000mL/min(sccm) iv)腔室內壓力：133 〜1 3 3 3 Pa(l 〜lOTorr) 並且，氮化處理並非必要，但以防止Ti膜之氧化等 之觀點來看以實施爲佳。 對特定片之晶圓執行如此T i膜之堆積處理及氮化處 理之後，實施腔室1內之洗淨。洗淨處理在腔室1內不存 在晶圓之狀態下，將C1F3氣體導入至腔室1內，執行乾 洗。乾洗是藉由加熱器5 —面加熱承載器2，一面執行， 但是此時之溫度以設爲170〜25 0°C爲佳。 並且’本發明並不限定於上述實施形態，可作各種變 形。例如’在上述實施形態中，藉由對噴淋頭施加高頻電 力’形成闻頻電場，但是並不限定於此，若藉由高頻電場 可形成本發明即可。再者，作爲被處理基板，並不限定於 半導體晶圓，例如即使爲液晶顯示裝置（L C D)用基板等之 其他基板亦可。 【圖式簡單說明】 第1圖爲表示使用於本發明之一實施形態所涉及之τi 膜之成膜方法之實施的Ti膜成膜裝置之一例的槪略剖面 圖。 弟2圖爲表不在局頻電力功率8〇〇w，腔室內壓力 667Pa’在Si上和SiCh上堆積Ti膜之時，在各膜上之電 -27- 200907101 阻値及其偏差之溫度變化及以各溫度在矽上生成之相的圖 式。 第3圖爲表示再高頻電力功率 800W，腔室內壓力 667Pa，在Si上和Si02上堆積Ti膜之時，在各膜上之膜 厚及其偏差之溫度變化的圖式。 第4圖A爲模式性表示前驅物爲TiCl3之時之成膜初 期之矽化物化之推定機構之圖式。 第4圖B爲模式性表示前驅物爲T i C 13之時之成膜後 期之矽化物化之推定機構之圖式。 第4圖C爲模式性表示前驅物爲TiC 13之時之成膜時 間和膜厚之關係圖。 第5圖A爲模式性表示前驅物爲TiCI2之時之成膜初 期之矽化物化之推定機構之圖式。 第5圖B爲模式性表示前驅物爲TiCl2之時之成膜後 期之矽化物化之推定機構之圖式。 第5圖C爲模式性表示前驅物爲TiC 12之時之成膜時 間和膜厚之關係圖。 第6圖爲表示以橫軸設爲腔室內壓力，以縱軸設爲高 頻電力功率之座標中，在5 5 0°C中將以TiCl3設爲前軀體 之反應作爲主體之區域和將以TiCl2設爲前軀體之反應作 爲主體之區域之境界的圖式。 第 7圖爲表示在高頻電力功率5 00W，腔室內壓力 500Pa，在Si上和Si〇2上堆積Ti膜之時，在各膜上之電 阻値及其偏差之溫度變化及以各溫度在矽上生成之相的圖 -28- 200907101 式。 第8圖爲表示在高頻電力功率500W，腔室內壓力 5 00Pa，在Si上和Si02上堆積Ti膜之時，在各膜上之膜 厚及其偏差之溫度變化的圖式。 第9圖爲表示以橫軸設爲腔室內壓力，以縱軸設爲高 頻電力功率之晶圓溫度5 5 0°C之座標中，膜厚之選擇比（Si 上之膜厚/ Si〇2上之吴厚）之等闻線之圖式。 第1 0圖爲表示以橫軸設爲腔室內壓力，以縱軸設爲 高頻電力功率之晶圓溫度550 °c之座標中，平均膜厚之等 高線之圖式。 第1 1圖爲表示以橫軸設爲腔室內壓力，以縱軸設爲 高頻電力功率之晶圓溫度5 5 0 °C之座標中，電阻値偏差程 度之等高線之圖式。 第1 2圖爲表示以橫軸設爲腔室內壓力’以縱軸設爲 高頻電力功率之晶圓溫度5 5 0。(：之座標中，電阻値之平均 値之等商線之圖式。 第13圖A爲表示堆積Ti膜之時之電漿形成時序之最 佳例之圖式。 第13圖B爲表示堆積Ti膜之時之電漿形成時序之最 佳例之圖式。 第14圖爲表示以往之800W、667Pa之條件下執行電 漿之時’以相同條件執行預TiCl4之時，以500W、5 00Pa 之條件執行預T i C 14之時，藉由溫度選擇比產生變化之圖 式。 -29- 200907101 【主要元件符號說明】 100 : Ti膜成膜裝置 1 :腔室 2 :承載器 3 :支撐構件 4 ·’引導環 5 :加熱器 6 :加熱器電源 8 :電極 1 a :天壁 9 :絕緣構件 1 0 :噴淋頭 l〇a :上段塊體 10b :中段區塊體 l〇c :下段區塊體 1 0 d :水平部 l〇e :環狀支撐部 1 1 :第1氣體導入口 12:第2氣體導入口 1 3 :氣體通路 1 4 :氣體通路 1 5 :氣體通路 1 6 :氣體通路 1 7 :吐出孔 -30 200907101 1 8 :吐出孔 20 :氣體供給機構 21 : C1F3氣體供給源 22 : TiCl4氣體供給源 23 ·’ Ar氣體供給源 24 : H2氣體供給源 25 : NH3氣體供給源 26 : N2氣體供給源 27 : C1F3氣體供給管 28 : TiCl4氣體供給管 29 : Ar氣體供給管 3 0 : H2氣體供給管 30a : NH3氣體供給管 3〇c : N2氣體供給管 3 1 :閥 3 2 :質量流量控制器 33 :整合器 3 4 :高頻電源 3 5 ··孔 3 6 :排氣室 3 7 :排氣管 3 8 :排氣裝置 3 9 =晶圓支撐銷 4 0 :支撐板 -31 200907101 4 1 :驅動機構 42 :搬入搬出口 4 3 :聞閥 4 5 :加熱器 4 6 :加熱器電源 47 :隔熱構件 5 0 :控制部 5 1 :使用者介面 5 2 :記憶部 -32-Ii) Temperature of the carrier 2 generated by the heater 5: 300 to 670 ° C iii) Ar gas flow rate · 800 to 2000 mL/min (sccm) -26- 200907101 iv) H2 gas flow rate: 1 500 to 4500 mL / Min(sccm) v) NH3 gas flow rate · 500 ~ 2000mL / min (sccm) iv) Chamber pressure: 133 ~ 1 3 3 3 Pa (l ~ lOTorr) And, nitriding treatment is not necessary, but to prevent Ti film From the viewpoint of oxidation, etc., it is preferable to carry out the implementation. After the deposition processing and the nitridation treatment of the Ti film are performed on the wafer of the specific wafer, the cleaning in the chamber 1 is performed. In the cleaning process, the C1F3 gas is introduced into the chamber 1 in a state where the wafer is not present in the chamber 1, and dry washing is performed. The dry cleaning is performed by heating the carrier 2 on the side of the heater 5, but the temperature is preferably set to 170 to 25 °C. Further, the present invention is not limited to the above embodiment, and various modifications are possible. For example, in the above embodiment, the frequency electric field is formed by applying high frequency electric power to the shower head. However, the present invention is not limited thereto, and the present invention may be formed by a high frequency electric field. In addition, the substrate to be processed is not limited to the semiconductor wafer, and may be, for example, another substrate such as a substrate for a liquid crystal display device (L C D). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a Ti film forming apparatus used for a film forming method of a τi film according to an embodiment of the present invention. Brother 2 shows that the temperature of the electrical current -27-200907101 on the various membranes is not in the local frequency power of 8〇〇w, and the chamber pressure is 667Pa' on the Si and the Ti film is deposited on the SiCh. And a pattern of phases generated at each temperature on the crucible. Fig. 3 is a view showing the temperature change of the film thickness and the variation on each film when the re-high-frequency power is 800 W and the pressure in the chamber is 667 Pa, when the Ti film is deposited on Si and SiO 2 . Fig. 4A is a view schematically showing a mechanism for estimating the mashification at the initial stage of film formation when the precursor is TiCl3. Fig. 4B is a view schematically showing an estimation mechanism for deuteration in the post-film formation period when the precursor is T i C 13 . Fig. 4C is a view schematically showing the relationship between the film formation time and the film thickness when the precursor is TiC 13. Fig. 5A is a view schematically showing a mechanism for estimating the crystallization of the initial film formation when the precursor is TiCI2. Fig. 5B is a view schematically showing an estimation mechanism for deuteration in the post-film formation period when the precursor is TiCl2. Fig. 5C is a view schematically showing the relationship between the film formation time and the film thickness when the precursor is TiC12. Fig. 6 is a view showing a region in which the horizontal axis is the pressure in the chamber, and the vertical axis is the coordinate of the high-frequency electric power, and the reaction in which the reaction of TiCl3 is used as the precursor is performed at 550 ° C. TiCl2 is set as a pattern of the reaction of the precursor as the boundary of the region of the main body. Fig. 7 is a diagram showing the temperature change of the resistance 値 and its deviation on each film at a high-frequency power of 500 00 W, a chamber pressure of 500 Pa, and a Ti film deposited on Si and Si〇2, and at each temperature. Figure -28- 200907101 of the phase generated on the raft. Fig. 8 is a view showing the temperature change of the film thickness and the variation on each film when the Ti film is deposited on Si and SiO 2 at a high-frequency power of 500 W and a pressure of 5 00 Pa in the chamber. Fig. 9 is a graph showing the selection ratio of the film thickness (the film thickness on Si / Si 以 in the coordinates of the wafer temperature of 550 ° C with the horizontal axis as the pressure in the chamber and the vertical axis as the high-frequency power). 2 on the Wu Hou) and the pattern of the line. Fig. 10 is a diagram showing the contour of the average film thickness in the coordinates of the wafer temperature of 550 °C in which the horizontal axis is the chamber pressure and the vertical axis is the high-frequency power. Fig. 1 is a view showing a contour line in which the horizontal axis is the pressure in the chamber, and the vertical axis is the wafer temperature of the high-frequency power of 550 ° C, and the resistance 値 deviation degree is plotted. Fig. 1 is a graph showing the wafer temperature 550 at which the vertical axis is the pressure in the chamber and the vertical axis is the high-frequency power. (In the coordinates of the coordinates of the average 値 of the resistance 値, Fig. 13A is a diagram showing a preferred example of the plasma formation timing when the Ti film is deposited. Fig. 13B shows the accumulation Fig. 14 is a view showing a preferred example of the plasma formation timing at the time of the Ti film. Fig. 14 is a view showing the case where the pre-TiCl4 is performed under the same conditions when the plasma is executed under the conditions of 800 W and 667 Pa in the past, at 500 W, 500 Pa The condition is changed by the temperature selection ratio when the pre-T i C 14 is executed. -29- 200907101 [Description of main component symbols] 100 : Ti film forming apparatus 1: chamber 2: carrier 3: support Member 4 · 'Guide ring 5 : Heater 6 : Heater power supply 8 : Electrode 1 a : Sky wall 9 : Insulating member 1 0 : Shower head l〇a : Upper block 10b : Middle block block l〇c : Lower block block 10 d: horizontal portion l〇e: annular support portion 1 1 : first gas introduction port 12: second gas introduction port 13: gas passage 1 4 : gas passage 1 5 : gas passage 1 6 : gas passage 1 7 : discharge hole -30 200907101 1 8 : discharge hole 20 : gas supply mechanism 21 : C1F3 gas supply source 22 : TiCl 4 gas supply source 23 · ' Ar gas supply source 24: H2 gas supply source 25: NH3 gas supply source 26: N2 gas supply source 27: C1F3 gas supply pipe 28: TiCl4 gas supply pipe 29: Ar gas supply pipe 3 0: H2 gas supply pipe 30a: NH3 Gas supply pipe 3〇c : N2 gas supply pipe 3 1 : Valve 3 2 : Mass flow controller 33 : Integrator 3 4 : High-frequency power supply 3 5 · Hole 3 6 : Exhaust chamber 3 7 : Exhaust pipe 3 8: Exhaust device 3 9 = Wafer support pin 4 0 : Support plate - 31 200907101 4 1 : Drive mechanism 42 : Carry in and out port 4 3 : Smell valve 4 5 : Heater 4 6 : Heater power supply 47 : Heat insulation Member 50: Control unit 5 1 : User interface 5 2 : Memory unit - 32-

Claims (1)

200907101 十、申請專利範圍 1. 一種鈦膜之成膜方法，藉由成膜裝置，在具有Si部 份之被處理基板之含有Si部份形成Ti膜，該成膜裝置具 有：收容被處理基板之腔室；在腔室內載置被處理基板之 載置台；加熱載置台上之基板的加熱手段；供給含有 TiC〗4氣體及還原氣體之處理氣體至腔室內之處理氣體供 給手段；於上述載置台上之被處理基板上方之空間形成高 頻電場之尚頻電場形成手段；和將上述腔室內予以排氣之 排氣手段，其特徵爲··包含 在上述載置台配置具有Si部份之被處理基板之步驟 加熱被處理基板之步驟； 將腔室內設爲特定壓力之步驟； 將含有TiCl4氣體及還原氣體之處理氣體導入至腔室 內之步驟； 藉由上述高頻電場形成手段形成高頻電場，依此使上 述處理氣體電漿化之步驟；和 在被處理基板之表面產生藉由上述TiCl4氣體及還原 氣體所引起之反應之步驟， 藉由上述反應，於被處理基板之S i部份形成Ti膜之 時，以抑制在被處理基板之Si部份的TiSi之生成反應之 方式，控制腔室內壓力及所施加之高頻電力之功率。 2. 如申請專利範圍第〗項所記載之鈦膜之成膜方法， 其中，被處理基板之溫度在5 50°C附近，以產生當作前驅 -33- 200907101 物之TiCh成爲主體之成膜反應的方式，控制腔室內壓力 及所施加之高頻電力之功率。 3 ·如申請專利範圍第1項所記載之鈦膜之成膜方法， 其中，基板溫度爲3 00〜670T：。 4 ·如申請專利範圍第3項所記載之鈦膜之成膜方法， 其中，基板溫度爲5 00°C±20°C。 5 ·如申請專利範圍第1項所記載之鈦膜之成膜方法， 其中，被處理基板除Si部份之外還具有Si02部份，在Si 部份和Si02部份之雙方形成Ti膜。 6 _如申請專利範圍第1項所記載之鈦膜之成膜方法， 其中，藉由在被處理基板之Si部份形成Ti膜，使其界面 矽化物化。 7.—種鈦膜之成膜方法，藉由成膜裝置，在具有Si部 份之被處理基板之Si部份形成Ti膜，該成膜裝置具有： 收容被處理基板之腔室；在腔室內載置被處理基板之載置 台：加熱載置台上之基板的加熱手段；供給含有TiCl4氣 體及還原氣體之處理氣體至腔室內之處理氣體供給手段； 於上述載置台上之被處理基板上方之空間形成高頻電場之 高頻電場形成手段；和將上述腔室內予以排氣之排氣手段 ，其特徵爲：包含 在上述載置台配置具有Si部份之被處理基板之步驟 t 加熱被處理基板之步驟： 將腔室內壓力予以抽真空之步驟； -34- 200907101 將含有Tic 14氣體及還原氣體之處理氣體導入至腔室 內之步驟； 藉由上述高頻電場形成手段形成高頻電場，使上述處 理氣體電漿化之步驟；和 在被處理基板之表面產生藉由上述TiCl4氣體及還原 氣體所引起之反應之步驟， 在腔室內壓力爲266〜1333Pa之範圍，高頻電力功率 爲200〜1 00 0W之範圍內，將腔室內壓力設爲x(pa),將 高頻電力功率設爲y(W)之時，則滿足 (y- 3 3 3 ) &lt; 1 60400/(x-266)。 8 .如申請專利範圍第7項所記載之鈦膜之成膜方法， 其中，基板溫度爲300〜670°C。 9 .如申請專利範圍第8項所記載之鈦膜之成膜方法， 其中，基板溫度爲500°C±20°C。 10.如申請專利範圍第7項所記載之鈦膜之成膜方法 ，其中，被處理基板除Si部份之外還具有Si02部份，在 Si部份和Si02部份之雙方形成Ti膜。 1 1 ·如申請專利範圍第7項所記載之鈦膜之成膜方法 ，其中’藉由在被處理基板之Si部份形成Ti膜，使其界 面矽化物化。 12.—種鈦膜之成膜方法，藉由成膜裝置，在具有Si 部份之被處理基板之Si部份形成Ti膜，該成膜裝置具有 :收容被處理基板之腔室；在腔室內載置被處理基板之載 置台；加熱載置台上之基板的加熱手段；供給含有TiCl4 -35- 200907101 氣體及還原氣體之處理氣體至腔室內之處理氣體供給手段 ;於上述載置台上之被處理基板上方之空間形成高頻電場 之局頻電場形成手段；和將上述腔室內予以排氣之排氣手 段，其特徵爲：包含 在上述載置台配置具有含有Si部份之被處理基板之 步驟； 加熱被處理基板之步驟； 將腔室內壓力設成300〜800Pa之範圍之步驟； 將含有TiC丨4氣體及還原氣體之處理氣體導入至腔室 內之步驟； 將上述高頻電場形成手段之高頻電力功率設爲3 00〜 600W而形成高頻電場，依此使上述處理氣體電漿化之步 驟；和 在被處理基板之表面產生藉由上述TiCl4氣體及還原 氣體所引起之反應之步驟。 1 3 .如申請專利範圍第1 2項所記載之鈦膜之成膜方法 ，其中，基板溫度爲300〜670 °C。 1 4 .如申請專利範圍第1 3項所記載之鈦膜之成膜方法 ，其中，基板溫度爲5 00 °C±20°C。 1 5 ·如申請專利範圍第1 2項所記載之鈦膜之成膜方法 ，其中，被處理基板除Si部份之外還具有Si 02部份，在 Si部份和Si02部份之雙方形成Ti膜。 1 6 .如申請專利範圍第1 2項所記載之鈦膜之成膜方法 ，其中，藉由在被處理基板之Si部份形成Ti膜，使其界 -36- 200907101 面矽化物化。 17.—種鈦膜之成膜方法’藉由成膜裝置，在具有Si 部份之被處理基板之S i部份形成T i膜，該成膜裝置旦有· :收容被處理基板之腔室；在腔室內載置被處理基板之載 置台；加熱載置台上之基板的加熱手段；供給含有Tic!4 氣體及還原氣體之處理氣體至腔室內之處理氣體供給手段 ;於上述載置台上之被處理基板上方之空間形成高頻電場 之高頻電場形成手段；和將上述腔室內予以排氣之排氣手 段，其特徵爲：包含 在上述載置台配置具有Si部份之被處理基板之步驟 » 加熱被處理基板之步驟； 將腔室內設爲特定壓力之步驟； 將含有TiCl4氣體及還原氣體及惰性氣體之處理氣體 導入至腔室內之步驟； 藉由上述局頻電場形成手段形成局頻電場，依此使上 述處理氣體電漿化之步驟；和 在被處理基板之表面產生藉由上述Tici4氣體及還原 氣體所引起之反應之步驟， 將TiCl4氣體及還原氣體及惰性氣體導入至上述腔室 內之後，形成高頻電場而生成電漿。 1 8 .如申請專利範圍第1 7項所記載之鈦膜之成膜方法 ，其中，在腔室內壓力爲266〜1333Pa之範圍’高頻電力 功率爲200〜1000W之範圍內，將腔室內壓力設爲x(Pa) -37- 200907101 ，將高頻電力功率設爲y(w)之時，則滿足 (y-3 3 3 ) &lt; 1 60400/(x-266)。 1 9.如申請專利範圍第1 7項所記載之鈦膜之成膜方法 ，其中，腔室內壓力爲3 00〜8 OOPa之範圍，高頻電力功 率爲300〜600W之範圍。 2 〇 ·如申請專利範圍第1 7項所記載之鈦膜之成膜方法 ，其中，基板溫度爲300〜670 °C。 2 1 .如申請專利範圍第2 0項所記載之鈦膜之成膜方法 ，其中，基板溫度爲620〜650 °C。 22 ·如申請專利範圍第1 7項所記載之鈦膜之成膜方法 ’其中’被處理基板除Si部份之外還具有Si〇2部份，在 Si部份和Si02部份之雙方形成Ti膜。 23·如申請專利範圍第17項所記載之鈦膜之成膜方法 ’其中’藉由在被處理基板之Si部份形成Ti膜，使其界 面矽化物化。 2 4. —種記憶媒體’記憶有在電腦上動作，並控制成 膜裝置之程式，其特徵爲： 上述控制程式於實行時’以執行Ti膜之成膜方法的 方式’使電腦控制上述成膜裝置，該Ti膜之成膜方法是 藉由成膜裝置在具有Si部份之被處理基板之含有Si部份 形成Ti膜’該成膜裝置具有：收容被處理基板之腔室； 在腔室內載置被處理基板之載置台；加熱載置台上之基板 的加熱手段；供給含有Tic 14氣體及還原氣體之處理氣體 至腔室內之處理氣體供給手段；於上述載置台上之被處理 -38- 200907101 基板上方之空間形成高頻電場之高頻電場形成手段；和將 上述腔室內予以排氣之排氣手段，包含 在上述載置台配置具有Si部份之被處理基板之步驟 &gt; 加熱被處理基板之步驟； 將腔室設爲特定壓力之步驟； 將含有TiCl4氣體及還原氣體之處理氣體導入至腔室 內之步驟； 藉由上述高頻電場形成手段形成高頻電場，依此使上 述處理氣體電漿化之步驟；和 在被處理基板之表面產生藉由上述TiCl4氣體及還原 氣體所引起之反應之步驟， 藉由上述反應，於被處理基板之Si部份形成Ti膜之 時，以抑制在被處理基板之Si部份的Ti Si之生成反應之 方式，控制腔室內壓力及所施加之高頻電力之功率。 -39-200907101 X. Patent Application Range 1. A film forming method for a titanium film, comprising a Si film formed on a Si-containing portion of a substrate having a Si portion by a film forming apparatus, the film forming apparatus having: a substrate to be processed a chamber; a mounting table on which the substrate to be processed is placed in the chamber; a heating means for heating the substrate on the mounting table; and a processing gas supply means for supplying a processing gas containing TiC 4 gas and a reducing gas into the chamber; a frequency-increasing electric field forming means for forming a high-frequency electric field in a space above the substrate to be processed; and an exhausting means for exhausting the chamber, wherein the mounting means includes a Si portion a step of processing the substrate to heat the substrate to be processed; a step of setting the chamber to a specific pressure; a step of introducing a processing gas containing TiCl 4 gas and a reducing gas into the chamber; forming a high-frequency electric field by the high-frequency electric field forming means And the step of plasma-treating the processing gas; and generating the TiCl4 gas and the reducing gas on the surface of the substrate to be processed In the step of causing the reaction, when the Ti film is formed on the Si portion of the substrate to be processed by the above reaction, the pressure in the chamber is controlled in such a manner as to suppress the formation reaction of TiSi in the Si portion of the substrate to be processed. The power of the applied high frequency power. 2. The method for forming a titanium film according to the scope of the patent application, wherein the temperature of the substrate to be processed is around 50 ° C to produce a film as a precursor of TiCh as a precursor-33-200907101. The manner of reaction controls the pressure in the chamber and the power of the applied high frequency power. 3. The method of forming a titanium film according to the first aspect of the invention, wherein the substrate temperature is 300 to 670 T:. 4. The method of forming a titanium film according to the third aspect of the invention, wherein the substrate temperature is 500 ° C ± 20 ° C. 5. The method for forming a titanium film according to the first aspect of the invention, wherein the substrate to be processed further has a SiO 2 portion in addition to the Si portion, and a Ti film is formed on both the Si portion and the SiO 2 portion. The method of forming a titanium film according to the first aspect of the invention, wherein a Ti film is formed on the Si portion of the substrate to be processed, and the interface is mashed. 7. A method for forming a titanium film, comprising: forming a Ti film on a Si portion of a substrate having a Si portion by a film forming apparatus, the film forming apparatus having: a chamber for accommodating the substrate to be processed; a mounting table on which a substrate to be processed is placed in the room: a heating means for heating the substrate on the mounting table; a processing gas supply means for supplying a processing gas containing TiCl4 gas and a reducing gas into the chamber; and a substrate above the substrate to be processed on the mounting table a high-frequency electric field forming means for forming a high-frequency electric field in space; and an exhausting means for exhausting the chamber, wherein the step of heating the substrate to be processed is performed by including a substrate to be processed having a Si portion on the mounting table Step: a step of evacuating the pressure in the chamber; -34- 200907101 a step of introducing a processing gas containing Tic 14 gas and a reducing gas into the chamber; forming a high-frequency electric field by the high-frequency electric field forming means a step of treating gas plasma; and a step of generating a reaction caused by the above TiCl 4 gas and a reducing gas on the surface of the substrate to be processed When the pressure in the chamber is in the range of 266 to 1333 Pa and the high-frequency power is 200 to 100 W, the pressure in the chamber is x (pa), and when the high-frequency power is y (W), Then (y - 3 3 3 ) &lt; 1 60400 / (x-266) is satisfied. 8. The method for forming a titanium film according to claim 7, wherein the substrate temperature is 300 to 670 °C. 9. The method of forming a titanium film according to claim 8, wherein the substrate temperature is 500 ° C ± 20 ° C. 10. The method for forming a titanium film according to claim 7, wherein the substrate to be processed further has a SiO 2 portion in addition to the Si portion, and a Ti film is formed on both the Si portion and the SiO 2 portion. The film forming method of the titanium film according to the seventh aspect of the invention, wherein the interface is formed by a Ti film formed on the Si portion of the substrate to be processed. 12. A method for forming a titanium film, comprising: forming a Ti film on a Si portion of a substrate having a Si portion by a film forming apparatus, the film forming apparatus having: a chamber for accommodating the substrate to be processed; a mounting table on which the substrate to be processed is placed in the room; a heating means for heating the substrate on the mounting table; a processing gas supply means for supplying a processing gas containing a gas of TiCl4 - 35 - 200907101 and a reducing gas into the chamber; and a means for supplying the substrate on the mounting table a local frequency electric field forming means for forming a high-frequency electric field in a space above the substrate; and an exhausting means for exhausting the chamber, wherein the step of disposing the substrate to be processed having the Si portion is included in the mounting table a step of heating the substrate to be processed; a step of setting the pressure in the chamber to a range of 300 to 800 Pa; a step of introducing a processing gas containing TiC丨4 gas and a reducing gas into the chamber; and forming the high-frequency electric field forming means The frequency power is set to be 300 to 600 W to form a high-frequency electric field, thereby the step of plasma-treating the processing gas; and generating on the surface of the substrate to be processed The step of reacting the above TiCl4 gas and the reducing gas. The method of forming a titanium film according to the first aspect of the invention, wherein the substrate temperature is 300 to 670 °C. The method of forming a titanium film according to the first aspect of the invention, wherein the substrate temperature is 500 ° C ± 20 ° C. The film forming method of the titanium film as described in claim 12, wherein the substrate to be processed has a Si 02 portion in addition to the Si portion, and is formed on both the Si portion and the Si02 portion. Ti film. The method for forming a titanium film according to the first aspect of the invention, wherein the Ti film is formed on the Si portion of the substrate to be processed, and the boundary is 矽-36-200907101. 17. A method for forming a titanium film by forming a T i film on a portion of a portion of a substrate having a Si portion by a film forming apparatus, the film forming apparatus having: a chamber for accommodating the substrate to be processed a chamber; a mounting table on which the substrate to be processed is placed in the chamber; a heating means for heating the substrate on the mounting table; and a processing gas supply means for supplying the processing gas containing the Tic! 4 gas and the reducing gas into the chamber; on the mounting table a high-frequency electric field forming means for forming a high-frequency electric field in a space above the substrate to be processed; and an exhaust means for exhausting the chamber, wherein the substrate is provided with a substrate having a Si portion disposed on the mounting table. Step » a step of heating the substrate to be processed; a step of setting the chamber to a specific pressure; a step of introducing a processing gas containing TiCl 4 gas and a reducing gas and an inert gas into the chamber; forming a local frequency by the above-described local frequency electric field forming means An electric field, a step of plasma-treating the above-mentioned processing gas; and a step of generating a reaction caused by the above-mentioned Tici4 gas and a reducing gas on the surface of the substrate to be processed After the TiCl4 gas, the reducing gas, and the inert gas are introduced into the chamber, a high-frequency electric field is formed to generate a plasma. 1 . The method for forming a titanium film according to claim 17, wherein the pressure in the chamber is within a range of a range of 266 to 1333 Pa in the chamber and a high-frequency electric power of 200 to 1000 W. When x (Pa) -37 - 200907101 is set, when the high-frequency power is y (w), (y-3 3 3 ) &lt; 1 60400 / (x - 266) is satisfied. The film forming method of the titanium film according to the seventh aspect of the invention, wherein the chamber pressure is in the range of 300 to 800 Pa, and the high frequency power is in the range of 300 to 600 W. 2. The method of forming a titanium film according to claim 17, wherein the substrate temperature is 300 to 670 °C. The film forming method of the titanium film as described in claim 20, wherein the substrate temperature is 620 to 650 °C. 22. The method for forming a titanium film as described in claim 17 of the patent application, wherein the substrate to be processed has a Si〇2 portion in addition to the Si portion, and is formed on both the Si portion and the Si02 portion. Ti film. A film forming method for a titanium film according to the seventeenth aspect of the invention, wherein the interface is formed by forming a Ti film on the Si portion of the substrate to be processed. 2 4. A kind of memory medium 'memorizes a program that operates on a computer and controls a film forming apparatus, and is characterized in that: when the control program is executed, 'the method of performing the film formation method of the Ti film' is caused by the computer to control the above-mentioned a film device, the film forming method of the Ti film is: forming a Ti film by a film forming device in a Si-containing portion of the substrate having a Si portion; the film forming device having: a chamber for accommodating the substrate to be processed; a mounting table on which a substrate to be processed is placed in the room; a heating means for heating the substrate on the mounting table; a processing gas supply means for supplying a processing gas containing Tic 14 gas and a reducing gas into the chamber; and being processed on the mounting table - 38 - 200907101 A high-frequency electric field forming means for forming a high-frequency electric field in a space above the substrate; and a step of exhausting the inside of the chamber to include a substrate to be processed having a Si portion on the mounting table> Heating a step of processing the substrate; a step of setting the chamber to a specific pressure; a step of introducing a processing gas containing TiCl 4 gas and a reducing gas into the chamber; The high-frequency electric field forming means forms a high-frequency electric field, thereby the step of plasma-treating the processing gas; and the step of generating a reaction caused by the TiCl4 gas and the reducing gas on the surface of the substrate to be processed, by the above reaction When the Ti film is formed on the Si portion of the substrate to be processed, the pressure in the chamber and the power of the applied high-frequency power are controlled so as to suppress the formation reaction of Ti Si in the Si portion of the substrate to be processed. -39-
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