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TW201234480A - Method of modifying insulating film - Google Patents

Method of modifying insulating film Download PDF

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Publication number
TW201234480A
TW201234480A TW100135001A TW100135001A TW201234480A TW 201234480 A TW201234480 A TW 201234480A TW 100135001 A TW100135001 A TW 100135001A TW 100135001 A TW100135001 A TW 100135001A TW 201234480 A TW201234480 A TW 201234480A
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TW
Taiwan
Prior art keywords
plasma
treatment
modifying
insulating film
processing
Prior art date
Application number
TW100135001A
Other languages
Chinese (zh)
Inventor
Yoshinori Osaki
Tetsuro Takahashi
Koji Maekawa
Original Assignee
Tokyo Electron Ltd
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Publication of TW201234480A publication Critical patent/TW201234480A/en

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    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
    • H01L21/02329—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen
    • H01L21/02332—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen into an oxide layer, e.g. changing SiO to SiON
    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
    • 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
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

A method of modifying an insulating film is provided to control the small reduction of nitrogen concentration in a silicon oxide nitride film since a reforming process starts while a vacuum atmosphere is maintained after plasma nitriding process. A wafer of a processing object is carried into a plasma processing apparatus(S1). A plasma nitriding process is performed for a silicon oxide film on a wafer surface and a silicon oxide nitride film is formed(S2). A surface of the silicon oxide nitride film is oxidized by plasma by using the plasma processing apparatus(S3). The wafer is carried out from the plasma processing apparatus(S4).

Description

201234480 六、發明說明： 【發明所屬之技術領域】 本發明係關於可以利用於例如MOS構造的裝置的製 造之絕緣膜之改質方法。 【先前技術】 以MOSFET爲代表的半導體裝置，爲了防止所謂硼的 穿透現象，作爲閘極絕緣膜使用氧化氮化矽（SiON )膜。 此外，伴隨著近年來的半導體裝置的細微化/高性能化的 要求，閘極絕緣膜的薄膜化逐漸接近極限。把氧化矽（ Si02 )膜薄膜化的場合，由於直接穿隧效應使得洩漏電流 成指數增加，使得耗電量大增。對此，在減低洩漏電流的 目的下，作爲閘極絕緣膜也使用氧化氮化矽膜。 氧化氮化矽膜，例如可以對以熱氧化等方法形成的 Si02膜，使氮氣體之電漿作用而形成。接著，對如此藉由 電漿氮化處理形成的氧化氮化矽膜，爲了防止膜質的劣化 ，被提議了進而進行熱退火等改質處理（專利文獻1〜3) 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開2004-25377號公報 〔專利文獻2〕日本特開2006-156995號公報 〔專利文獻3〕國際公開W02008/081724號公報 -5- 201234480 【發明內容】 〔發明所欲解決之課題〕 將Si〇2膜電漿氮化處理而形成的氧化氮化矽膜，伴 隨著氮化處理後時間的經過，氮原子會由膜中往外部放出 (所謂「氮脫離現象」）。發生氮脫離現象時’即使以相 同條件進行電漿氮化處理，也會隨著直到次一步驟爲止的 等待時間的不同，而使得半導體晶圓間/批次間於氧化氮 化矽膜的氮濃度產生有差異的結果’使得最終製品的品質 管理變得困難。例如，將氧化氮化矽膜作爲MOSFET等電 晶體之閘極絕緣膜利用的場合，隨著氮濃度的差異，抑制 硼的穿透現象或洩漏電流的效果會改變，而有引起裝置的 可信賴性降低或生產率下降之虞。 亦即，本發明，目的在於抑制藉由電漿氮化處理而形 成的氧化氮化矽膜所構成的氮脫離導致之膜中氮濃度的降 低，使被處理體之間/批次之間的氮濃度的差異抑制於最 小限度，提供使膜中的氮濃度保持一定使其安定化之氧化 氮化矽膜。 〔供解決課題之手段〕 本發明之絕緣膜之改質方法，其特徵爲具備：電漿氮 化處理露出於被處理體的表面之氧化矽膜，形成氧化氮化 矽膜之氮化處理步驟，及氧化處理前述氧化氮化矽膜之改 質步驟；前述淡化處理步驟結束後，在維持真空氛圍的狀 -6- 201234480 態下，接著開始前述改質步驟。 本發明之絕緣膜之改質方法，在氮化處理步驟之後的 氧化氮化矽膜之膜中氮濃度爲Nco，前述改質步驟後的氧 化氮化矽膜之膜中氮濃度的目標値爲NCT時，以成爲Nco > NCT的方式進行前述電漿氮化處理爲佳。 於本發明之絕緣膜之改質方法，前述改質步驟，包含 根據藉由具有複數孔之平面天線對處理容器內導入微波而 產生處理氣體的電漿之電漿處理裝置所進行的電漿氧化處 理爲較佳。在此場合’以對一個被處理體，使前述電漿氮 化處理及前述電漿氧化處理，在前述電漿處理裝置之同一 處理容器內連續地進行爲較佳。在此場合，前述電漿氮化 處理之後，前述電漿氧化處理之前，以抽真空或者掃氣（ purge )處理除去殘留於前述處理容器內的氮氣爲較佳。 此外，前述電漿氧化處理之後，作爲前述改質步驟之一部 分，進而包含在氧化氛圍下使被處理體在8 00°C以上11〇〇 °〇以下的範圍內之溫度進行退火處理的步驟爲較佳。 此外，本發明之絕緣膜之改質方法，前述電漿氧化處 理的處理壓力以6 7Pa以上1333Pa以下的範圍內爲較佳。 此外，於本發明之絕緣膜之改質方法，前述電漿氧化 處理，係使氧氣體對全部處理氣體之體積流量比率在 0.1 %以上2 0 %以下的範圍內進行的爲較佳。 此外，本發明之絕緣膜之改質方法，前述電漿氧化處 理的處理溫度，以200 °C以上600 °C以下之範圍內爲較佳 201234480 此外，本發明之絕緣膜之改質方法，前述電漿氧化處 理的處理時間，以1秒以上90秒以下之範圍內爲較佳。 此外，本發明之絕緣膜之改質方法，最好是藉由具有 複數孔的平面天線對處理容器內導入微波而產生處理氣體 的電漿之電漿處理裝置來進行前述氮化處理步驟，藉由在 氧化氛圍使被處理體在800°C以上ll〇〇°C以下的範圍內之 溫度進行退火處理的退火裝置來進行前述改質步驟。在此 場合，前述退火處理的處理時間，以在1 〇秒以上5 0秒以 下的範圍內爲較佳。此外，被處理體由前述電漿處理裝置 往前述退火裝置之移送以在真空狀態下進行的爲較佳。 此外，本發明之絕緣膜之改質方法，前述氧化氮化矽 膜爲MOS構造裝置之閘極絕緣膜者爲較佳。 〔發明之效果〕 根據本發明，可以藉由在電漿氮化處理後維持真空氛 圍，同時接著開始改質步驟，而改善氧化氮化矽膜的膜質 ，抑制氧化氮化矽膜之經時的氮濃度減少（氮脫離）。亦 即，藉由把本發明之絕緣膜之改質方法，利用於例如 MOSFET等之MOS構造裝置的閘極絕緣膜的改質，可以 有效果地抑制洩漏電流的增加或硼的穿透，同時可抑制晶 圓之間/批次之間的閘極絕緣膜的氮濃度的差異，改善半 導體裝置之可信賴性與生產率。 【實施方式】 -8 - 201234480 〔第1實施型態〕 以下，參照圖面詳細說明本發明之實施型態。本實施 型態之絕緣膜之改質方法，可以包含對氮化矽膜，進行電 漿氮化處理，形成氧化氮化矽膜的步驟，及對此氧化氮化 矽膜進行電漿氧化處理的改質步驟。 圖1係模式顯示使用於相關於第1實施型態的絕緣膜 之改質方法的電漿處理裝置100的槪略構成之剖面圖。圖 2係顯示圖1之電漿處理裝置100的平面天線之平面圖。 圖3係顯示控制圖1的電漿處理裝置1 00的控制部的構成 例之圖。 電漿處理裝置100，被構成爲以複數之具有縫隙狀之 孔的平面天線，特別是RLSA( Radial Line Slot Antenna :徑向線縫隙天線）對處理容器內導入微波，使發生而得 到高密度且低電子溫度的微波激發電漿之RLSA微波電漿 處理裝置。在電漿處理裝置100，可根據lxlOIG〜5xl012 / cm3之電漿密度，且具有〇·7〜2eV之低電子溫度的電漿 來進行處理。亦即，電漿處理裝置100，於各種半導體裝 置之製造過程’可以在進行電漿氮化處理、電漿氧化處理 之目的上適切地利用。 電漿處理裝置100’主要的構成，爲具備：被構成爲 氣密的處理容器1、對處理容器1內供給氣體的氣體供給 裝置18、減壓排氣處理容器1內之用的具備真空泵24的 排氣裝置’設於處理容器1的上部，對處理容器1內導入 微波的微波導入機構27，以及控制這些電漿處理裝置10〇 -9- 201234480 之各構成部的控制部50。 處理容器1，係由被接地的約略圓筒狀的容器所形成 。又，處理容器1由角筒形狀的容器來形成亦可。處理容 器1，具有鋁等金屬或其合金所構成的底壁la與側壁lb 〇 於處理容器1的內部，設有供水平地支撐被處理體芝 半導體晶圓（以下簡稱爲「晶圓」）w之用的載置台2。 載置台2，係由熱傳導性高的材質，例如A1N等陶瓷所構 成的。此載置台2，藉由從排氣室11的底部.中央往上方延 伸的圓筒狀之支撐構件3所支撐。支撐構件3，例如由 A1N等陶瓷所構成。 此外，於載置台2，設有覆蓋其外緣部，導引晶圓W 之用的覆蓋環 4。此覆蓋環 4，例如係以石英、A1N、 Al2〇3、SiN等材質構成的環狀構件。覆蓋環4，以覆蓋載 置台2的表面與側面爲較佳。藉此，可以防止金屬汙染。 此外，於載置台2，被埋入作爲溫度調節機構之電阻 加熱型的加熱器5。此加熱器5，藉由從加熱器電源5 a供 電而加熱載置台2，以該熱均勻地加熱被處理基板之晶圓 W。 此外，於載置台2，被配備有熱電偶（TC ) 6。藉此 熱電偶6進行載置台2的溫度測量，可以控制晶圓W的 加熱溫度在例如室溫置900°C爲止之範圍。 此外，於載置台2，設有支撐晶圓W而使其升降之用 的晶圓支撐栓（未圖示）。各晶圓支撐栓，係可對載置台 -10- 201234480 2的表面突起隱沒的方式設置的。 於處理容器1的內周，設有由石英所構成的圓筒狀的 襯墊7。此外，於載置台2的外周側’爲了使處理容器1 內均勻地排氣，環狀地設置具有多數排氣孔8a的石英製 的擋板片（baffle plate) 8。此擋板片8藉由複數支柱9 支撐。 於處理容器1的底壁la的約略中央部，被形成圓形 的開口部10。於底壁la與此開口部1〇連通，設有往下方 突出的排氣室11。於此排氣室11，被連接排氣管12，透 過此排氣管12連接至真空泵24。 於處理容器1的上部，被配備著中央部開口的環狀蓋 .構件1 3。開口的內周，往內側（處理容器內空間）突出， 形成環狀的支撐部13a。 處理容器1的側壁lb，設有成爲環狀的氣體導入部 15。此氣體導入部15，被連接供給含氮氣體、含氧氣體或 電漿激發用氣體之氣體供給裝置18。又，氣體導入部15 設爲噴嘴狀或者蓮蓬頭狀亦可。 此外，於處理容器1的側壁lb，在電漿處理裝置100 、及與此鄰接的真空側搬送室1 03之間，設有供進行晶圓 W的搬出搬入之搬出入口 16，及開閉此搬出入口 16的閘 閥G1 〇 氣體供給裝置1 8，具有氣體供給源（例如，惰性氣體 供給源19a、含氮氣體供給源19b、含氧氣體供給源19c) ’與配管（例如氣體管線20a、20b、20c )，流量控制裝 -11 - 201234480 置（例如，質量流量計2 1 a、2 1 b、2 1 c ) ’與閥（例如， 開閉閥22a、22b、22c)。又’氣體供給裝置18，作爲前 述以外之未圖示的氣體供給源’例如亦可具有使用於置換 處理容器1內的氛圔時使用的洗滌氣體供給源等。 作爲惰性氣體’例如可以使用氮氣或稀有氣體等。作 爲稀有氣體，例如可以使用氬氣、氪氣、氙氣、氮氣等。 其中，由經濟性優異的觀點來看已使用氬氣特佳。作爲使 用於電漿氮化處理的含氮氣體’例如可以使用氮氣、一氧 化氮、二氧化氮、氨氣等。此外，作爲使用於電漿氧化處 理的含氧氣體，例如可以使用氧氣（02 )、水蒸氣（H20 )、一氧化氮（NO)、一氧化二氮（N2〇)等。 惰性氣體、含氮氣體及含氧氣體，由氣體供給裝置1 8 之惰性氣體供給源19a、含氮氣體供給源19b及含氧氣體 供給源19c，分別透過氣體管線20a、20b、20c到達氣體 導入部15，由氣體導入部15被導入處理容器1內。於連 接於各氣體供給源的各個氣體管線20a、20b、20c，設有 質量流量計2 1 a、2 1 b、2 1 c及其前後之1組開閉閥22 a ' 2 2b、22c。藉由這樣的氣體供給裝置18的構成，可以控 制供給的氣體的切換或流量等。 排氣裝置，具備真空泵24。真空泵24’係由例如渦 輪分子泵等高速真空泵等所構成。真空泵24’透過排氣管 12被連接於處理容器丨的排氣室11。處理容器1內的氣 體，往排氣室1 1的空間1 1 a內均勻流入，進而藉由從空 間1 1 a使真空栗24動作，透過排氣管1 2往外部排氣。藉 -12- 201234480 此，可以使處理容器1內的特定真空度，高速地減壓至例 如 0 · 1 3 3 P a ° 其次，說明微波導入機構27的構成。微波導入機構 27，主要的構成包括：透過板28、平面天線31、遲波材 33、覆蓋構件34、導波管37、匹配電路38以及微波產生 裝置39。 使微波透過的透過板28,於蓋構件13被配備於在內 周側伸出之支撐部1 3 a上。透過板2 8，係由介電質，例如 石英或氧化鋁、氧化氮等陶瓷所構成。此透過板28與支 撐部13a之間，透過密封構件29氣密地密封住。亦即， 處理容器1內被保持爲氣密。 平面天線31，於透過板28的上方，以與載置台2對 向的方式設置。平面天線31成圓板狀。又，平面天線3 1 的形狀不限於圓板狀，例如亦可爲四角板狀。此平面天線 31，被卡止於蓋構件13的上端。 平面天線3 1，例如由表面被鍍金或鍍銀的銅板或鋁板 所構成。平面天線31，具有放射微波的多數狹縫狀之微波 放射孔3 2。微波放射孔3 2，以特定的圖案貫通形成平面 天線3 1。 各個微波放射孔3 2，例如如圖2所示，成細長的長方 形狀（狹縫狀）。接著，典型的安排是鄰接的微波放射孔 32被配置爲「T」字形。此外，如此般被組合配置爲特定 的形狀（例如T字形）的微波放射孔32，進而全體被配 置爲同心圓狀。 -13- 201234480 微波放射孔3 2的長度或排列間隔，因應於微波的 長（λ g )而決定。例如，微波放射孔3 2的間隔，以成 Ag/4〜Ag的方式配置。又，於圖2，被形成爲同心 狀的鄰接的微波放射孔32彼此的間隔以Ar表示。又， 波放射孔3 2的形狀，亦可爲圓形狀、圓弧狀等其他形 。進而，微波放射孔3 2的配置型態沒有特別限定，除 同心圓狀以外，例如可以配置爲螺旋狀、放射狀等。 於平面天線31的上面，設有具有比真空更大的介 率之遲波材33。此遲波材33，是因爲在真空中微波的 長會變長，而具有使微波的波長縮短而調整電漿的機能 作爲遲波材33的材質，例如可以使用石英、聚四氟乙 樹脂、聚醯亞胺樹脂等。 又，平面天線31與透過板2 8之間，或者遲波材 與平面天線3 1之間分別使其接觸或者離開皆可，以使 接觸爲較佳。 於處理容器1的上部，以覆蓋這些平面天線31及 波材33的方式設有覆蓋構件34。覆蓋構件34例如由鋁 不鏽鋼等金屬材料所形成。以此覆蓋構件34與平面天 31形成偏平導波路。蓋構件13的上端與覆蓋構件34’ 藉由密封構件35密封的。此外，於覆蓋構件34的內部 被形成冷卻水流路34a。藉由使冷卻水流通於此冷卻水 路34a，可以冷卻覆蓋構件34、遲波材33、平面天線 以及透過板2 8。又，覆蓋構件3 4被接地。 覆蓋構件34之上壁（頂部）中央被形成開口部36 波 爲 圓 微 狀 了 電 波 〇 烯 33 其 遲 或 線 是 ， 流 3 1 -14- 201234480 於此開口部36被連接著導波管37。於導波管37的另一端 側’透過匹配電路38被連接著產生微波的微波產生裝置 39 〇 導波管37，具有由前述覆蓋構件34的開口部36往上 方延伸出去的剖面爲圓形的同軸導波管37a、及於此同軸 導波管37a的上端部透過模式變換器40連接的延伸於水 平方向的矩形導波管3 7b。模式變換器40，具有把在矩形 導波管3 7b內以TE模式傳播的微波變換爲TEM模式的功 能。 同軸導波管37a的中心有內導體41延伸。此內導體 41，於其下端部被連接固定於平面天線31的中心。藉由 這樣的構造，微波透過同軸導波管37a的內導體41往覆 蓋構件3 4與平面天線31形成的偏平導波路成放射狀地效 率佳地均勻傳播，由平面天線3 1的微波放射孔（狹縫） 32導入處理容器內，產生電漿。 藉由如以上構成的微波導入機構27，在微波產生裝置 39產生的微波透過導波管37往平面天線31傳播，進而介 由透過板28被導入處理容器1內。又，作爲微波的頻率 ，例如以2.45GHz爲佳，其他可以使用8.35GHz、1.98GHz 等。 電漿處理裝置1〇〇之各構成部，成爲被連接於控制部 50而被控制的構成。控制部50，具有電腦，例如圖3所 示，具備：具有CPU的處理控制器51、被連接於此處理 控制器5 1的使用者界面52以及記憶部53。處理控制器 -15- 201234480 51，於電漿處理裝置100,是統括相關於例如溫度、壓力 、氣體流量、微波輸出等處理條件之各構成部（例如，加 熱器電源5a、氣體供給裝置18、真空泵24、微波產生裝 置3 9等）而進行控制的手段。 使用者界面52,具有工程管理者爲了管理電漿處理裝 置100而進行指令的輸入操作等之鍵盤，或者使電漿處理 裝置100的工作狀況可視化而進行顯示的顯示器等。此外 ，於記憶部53,保存著被記錄著在電漿處理裝置100執行 的各種處理以處理控制器51的控制而實現之用的控制程 式（軟體）或者被記錄著處理條件資料等的配方。 接著，因應必要，以來自使用者界面52的指示等由 記憶部5 3叫出任意的配方在處理控制器5 1執行，而在處 理控制器51的控制下，在電漿處理裝置100的處理容器1 內進行所要的處理。此外，前述控制程式或處理條件資料 等配方，可以利用被容納於電腦可讀取的記憶媒體，例如 CD-ROM、硬碟、磁碟片、快閃記憶體、DVD、藍光碟片 等的狀態者，或者是由其他裝置，例如透過專線而隨時線 上利用。 在如此構成的電漿處理裝置100，可以在60(TC以下 的低溫下不對下底層等造成損傷地進行電漿處理。此外， 電漿處理裝置1 00，因爲電漿的均勻性優異，所以例如對 於直徑3 00mm以上的大型晶圓W也可以在晶圓W的面內 實現處理的均勻性。 其次，參照圖4〜圖7說明於電漿處理裝置1 00進行 -16- 201234480 的絕緣模之改質方法。圖4係顯示作爲絕緣膜之 的改質步驟的流程之流程圖，圖4〜圖7係說明 驟之流程圖。 本實施型態之絕緣膜的改質方法，例如藉由| 之步驟S1至步驟S4的順序來實施。首先，在圖 S1，把處理對象之晶圓W搬入電漿處理裝置1〇〇 此處，在晶圓W表面附近，被形成矽層301 上之氧化矽（Si02)膜303。接著，在步驟S2， 示，使用電漿處理裝置1〇〇對晶圓W的氧化矽丨 行電漿氮化處理。藉由電漿氮化處理，氧化矽膜 化而被改質爲氧化氮化矽（SiON)膜305。在此 處理，預估在之後的電漿氧化處理步驟（步驟 濃度的減少，以成爲比最終的目標氮濃度NCT更 〜3 %程度的氮濃度Nco的方式進行氮化處理。步 電漿氮化處理的條件，只要可以實現氮濃度Nco 特別限定，能夠以任意的條件來進行。 其次，在步驟S3，如圖6所示，使用電漿 1 〇 0，電漿氧化處理氧化氮化矽膜3 0 5的表面。歩 電漿氧化處理，由抑制氧化氮化矽膜3 05的氧化 的觀點來看，最好是在步驟S2之電漿氮化處理 接著在處理容器1內維持氛圍爲真空的狀態’在 處理結束起1 8 0秒以內，較佳者爲6 0秒以內實 步驟，在氧化氮化矽膜305的表層之例如深度方 氧化0.5〜l.Onm程度之範圍，改質爲氧濃度高 氧化砂膜 其主要步 圖4所示 4的步驟 〇 ，及於其 如圖5所 漠3 03進 3 〇3被氮 電漿氮化 S3 )之氮 高例如1 驟S 2的 即可沒有 處理裝置 5驟S 3的 與氮脫離 結束後， 電漿氮化 施。在此 向上電漿 的氧化氮 -17- 201234480 化矽膜3 05B。藉此，如圖7所示，於矽層301上，作爲 氧化氮化砂膜305，形成氧化氮化砂膜305A，及於其上被 改質的富含氧之氧化氮化矽膜3 05 B。 〔電漿氧化處理的順序〕 步驟S 3之電漿氧化處理的順序與條件如下。首先， 減壓排氣電漿處理裝置100之處理容器1內，同時由氣體 供給裝置1 8之惰性氣體供給源1 9a、含氧氣體供給源1 9c ，把例如Ar氣體、02氣體以特定的流量分別透過氣體導 入部15導入處理容器1內。如此進行，把處理容器1內 調節爲特定的壓力。 其次，以微波產生裝置39產生的特定頻率例如2.45 GHz的微波透過匹配電路38導往導波管37。被導到導波 管37的微波，依序通過矩形導波管37b及同軸導波管37a ，透過內導體41被供給至平面天線。總之，微波，在矩 形導波管3 7b內以TE模式傳送，此TE模式的微波以模 式變換器40變換爲TEM模式，透過同軸導波管37a被傳 送往藉由覆蓋構件3 4與平面天線3 1構成的偏平導波路。 接著，微波由在平面天線31被貫通形成的狹縫狀的微波 放射孔32介由透過板28放射往處理容器1內之晶圓W 的上方空間。此時的微波輸出，例如在處理200mm直徑 以上的晶圓W的場合，可以在1 000W以上5000W以下的 範圍內因應目的而選擇。 藉由從平面天線3 1經過透過板28對處理容器1放射 -18- 201234480 的微波，在處理容器1內形成電磁場，ΑΓ氣體及〇2氣體 分別進行電漿化。此被激發的電漿，藉由微波由平面天線 3 1的多數之微波放射孔32放射出，而爲約略1χ101()〜5χ 1012/ cm3之高密度，且在晶圓W附近，具有約略1.2eV 以下的低電子溫度。如此進行形成的電漿，對於下底膜之 離子等導致的電漿損傷很少。接著，藉由電漿中的活性種 〇2 +離子或0 ( )自由基的作用對晶圓W進行電漿氧化 處理。亦即，藉由使晶圓W的氧化氮化矽膜305的表面 極薄地氧化，替代膜的最表面之不安定狀態的Si-N結合 或游離的N，而被形成Si-Ο結合形成富含氧的氧化氮化 矽膜305B。藉此，氧化氮化矽膜中的氮成爲不脫離而被 保持住的狀態，可以使氮濃度維持一定且爲安定的狀態。 〔電漿氧化處理條件〕 作爲電漿氧化處理之處理氣體，最好使用包含稀有氣 體與含氧氣體之氣體。作爲稀有氣體最好使用Ar氣體， 作爲含氧氣體最好使用〇2氣體。此時，〇2氣體對全部處 理氣體之體積流量比率（02氣體流量/全部處理氣體流量 之百分率），由抑制氧化氮化矽膜305中的氮濃度之隨時 間減少的效果之觀點來看，以0.1 %以上20%以下之範圍內 爲佳，以1%以上15%以下之範圍內更佳，以10%以上 1 5 %以下之範圍內又更佳。在電漿氧化處理，例如Ar氣體 的流量爲 500mL/min( seem)以上 5000mL /min (seem )以下的範圍內，〇2氣體之流量爲5mL/min(sccm)以 -19- 201234480 上lOOOmL / min (seem)以下之範圍內以成爲前述流量比 的方式設定爲佳。 此外，處理壓力，由有效果地抑制氧化氮化矽膜305 中的氮濃度的隨時間之減少的觀點來看，例如以67Pa以 上1 3 3 3Pa以下之範圍內爲較佳，以133.3Pa以上1 33 3Pa 以下之範圍爲更佳，以3 33Pa以上1 3 3 3Pa以下之範圍又 更佳。電漿氧化處理之處理壓力未滿67Pa的話，作爲電 漿中的氧化活性種以離子成分具支配性地位，所以氧化速 率變高，把氧化矽膜303氮化而得的氧化氮化矽膜3 05的 表面的氮濃度會降低。 此外，微波的功率密度，由在電漿中有效率地產生活 性種〇2 +離子或0(^2)自由基之的觀點來看，以0.51W /cm2以上2.56W/ cm2以下之範圍內爲較佳，要使氧化 氮化矽膜3 05的表面以極薄的厚度氧化以電漿能量較小者 爲佳，所以在〇.51W/cm2以上1.54W/cm2的範圍內爲更 佳。又，微波的功率密度，意味著對透過板28之每lem2 面積供給的微波功率（以下也相同）。例如，在處理200 mm直徑以上的晶圓W的場合，以使微波功率在1000W以 上5 000W以下的範圍爲較佳。 此外，晶圓W的加熱溫度，作爲載置台2的溫度， 例如以設定爲200°C以上600 °C以下的範圍內爲較佳，設 定爲400t以上60(TC以下的範圍內爲更佳。 此外，電漿氧化處理的處理時間，由僅使氧化氮化矽 膜3 05中的表層氧化的觀點來看，例如以1秒以上90秒 -20- 201234480 以下的範圍內爲較佳，設定爲1秒以上60秒以下的 內爲更佳。如此，藉由在短時間進行電獎處理可以使 氮化砂膜305的表面氧化極薄的厚度。此外，使電號 處理在與電漿氮化處理相同的處理容器1內進行的場 使氧化矽膜電漿氮化處理後，使處理容器1內的殘留 抽真空而排氣，或者抽真空後供給Ar氣等而迅速地 排氣爲較佳。 以上的條件，作爲配方被保持於控制部5 0的記 53。接著，藉由處理控制器51讀出該配方而往電漿 裝置100的各構成部例如氣體供給裝置18、真空泵 微波產生裝置39、加熱器電源5a等送出控制訊號， 要的條件進行電漿氧化處理。 如以上所述改質氧化氮化矽膜3 05後，在步驟 藉由把晶圓W由電漿處理裝置1〇〇搬出，結束對1 圓W之處理。 於本實施型態，在被改質的氧化氮化矽膜3 0 5 B 由電漿氧化，使氧化氮化矽膜3 05中的不安定的氮原 置換爲氧原子，往膜外放出。因此，氧化氮化矽膜 中的氮濃度NC1，比電漿氮化處理之後的氧化氮化 3〇5的氮濃度Nco更低（NC0> NC1 )。此外，未藉由 氧化處理而改質的深部的氧化氮化矽膜305A的氮 NC2 ’幾乎等於電漿氮化處理之後的氮濃度Nc0之値 即’以最終形成的氧化氮化砍膜3 0 5 A的氮濃度N c 2 化氮化矽膜3 05B之氮濃度NC1的平均，接近於目標 範圍 氧化 氧化 合， 氮氣 進行 憶部 處理 24 ' 以所 S4， 枚晶 ，藉 子被 3 0 5 B 矽膜 電漿 濃度 。亦 與氧 氮濃 -21 - 201234480 度NCT的方式，來進行步驟S2的電漿氮化處理及步丨 的電漿氧化處理爲較佳。 在本實施型態，可以使步驟S2的電漿氮化處理 步驟S3的電漿氧化處理，在電漿處理裝置1〇〇之同 理容器內連續地進行。亦即，電漿氮化處理後，在氧 化矽膜3 05中還未產生氮濃度的經時變化（自然減少 ，可以進行電漿氧化處理而謀求氧化氮化矽膜3 05中 濃度的安定化。又，在本實施型態，使用與後述之基 理系統200 (圖9)同樣的多真空室構造之叢集工具 不同的處理容器內進行步驟S2的電漿氮化處理，與 S3的電漿氧化處理亦可。 〔第2實施型態〕 其次，參照圖8至圖13，同時說明相關於本發明 2實施型態之絕緣膜之改質方法。本實施型態之絕緣 改質方法，可以包含對氮化矽膜，進行電漿氮化處理 成氧化氮化矽膜的步驟，及對此氧化氮化矽膜進行氧 火處理的改質步驟。此處，本實施型態之電漿氮化處 也可以使用與在第1實施型態使用的同樣的電漿處理 100(圖1〜圖3)來實施。 氧化退火處理，例如可以使用圖8所示之退火處 置1 0 1來進行。此退火處理裝置1 0 1，係控制性佳可 時間加熱的裝置，例如可以作爲把形成於晶圓W的 等，在氧化性氣體氛圍下在800〜1100 °c程度的高溫 聚S3 ，與 一處 化氮 )時 的氮 板處 ，在 步驟 之第 膜之 ，形 化退 理， 裝置 理裝 以短 薄膜 區域 -22- 201234480 ，在短時間內可以氧化退火處理之RTP ( Rapid Thermal Process)裝置來使用。 於圖8，符號71爲圓筒狀的處理容器’於此處理容器 71的下方可裝拆地設有下部發熱單元72 ’此外’於處理 容器71的上方，以與下部發熱單元72對向的方式可裝拆 地設有上部發熱單元74。下部發熱單元72’具有作爲複 數被排列於水冷套管73的上面之加熱手段的鎢絲燈76。 同樣地，上部發熱單元74，具有水冷套管75’與作爲複 數被排列於其下面之加熱手段的鎢絲燈7 6。又，作爲燈， 不限於鎢絲燈，例如亦可使用鹵素燈、氙氣燈、水銀燈、 閃光燈等。如此，於處理容器71內相互對向而配備的各 鎢絲燈76，被連接於未圖示的電源，藉由控制部50調節 來自該處的電力供給量，可以控制發熱量。又’控制部50 的構成，與第1實施型態同樣（參照圖3 )。 在下部發熱單元72與上部發熱單元74之間’設有供 支撐晶圓W之用的支撐部77。此支撐部77 ’具有供在把 晶圓W保持於處理容器71內的處理空間的狀態下進行支 撐之用的晶圓支撐栓77a、及支撐供於處理中測量晶圓W 的溫度之用的熱襯墊78的襯墊設置部77b。此外’支撐部 77，與未圖示的旋轉機構連結，使支撐部77可作爲全體 繞著鉛直軸的周圍旋轉。藉此，處理中晶圓W以特定速 度旋轉，謀求熱處理的均勻化。 處理容器71的下方，被配置熱電溫度計81’於熱處 理中使來自熱襯墊78的熱線，透過埠81a以及光纖81b， -23- 201234480 以熱電溫度計81測量，而可以間接把握到晶圓W的溫度 。又，直接測量晶圓W的溫度亦可。 此外，於熱襯墊78的下方，在與下部發熱單元72之 鎢絲燈76之間中介配備著石英構件79，如圖所示前述埠 8 1 a，設於此石英構件79 »又，配備複數埠8 1 a亦爲可能 。進而，於晶圓W的上方，也在與上部發熱單元74的鎢 絲燈76之間，中介配備著石英構件80a。此外，以爲繞晶 圓W的方式，於處理容器71的內周面也被配設石英構件 80b。又，供支撐晶圓W而升降之抬起栓（未圖示），係 貫通熱襯墊78而設，使用於晶圓W的搬出搬入。 下部發熱單元72與處理容器71之間，及上部發熱單 元74與處理容器71之間，分別中介著密封構件（未圖示 )，使處理容器71內成爲氣密狀態。此外，於處理容器 71的側部，被配備連接於氣體導入管82的氣體供給裝置 83，藉由未圖示的流量控制裝置，可以對處理容器71的 處理空間內，導入例如〇2氣體、NO、N20、H20 (由02 與H2以水蒸汽產生器產生）等之氧化性氣體，或者因應 必要進而包括稀有氣體等惰性氣體等。此外，於處理容器 71的下部，設有排氣管84，藉由未圖示的真空泵等排氣 裝置，以可以減壓處理容器71內的方式構成。 退火處理裝置101之各構成部，與電漿處理裝置1〇〇 同樣，成爲被連接於控制部5 0而被控制的構成。接著’ 以來自使用者界面5 2的指示等由記憶部5 3叫出任意的配 方在處理控制器51執行，而在處理控制器5 1的控制下， -24- 201234480 進行在退火處理裝置101之氧化退火處理。例如， 理控制器5 1控制往設於下部發熱單元72與上部發 7 4的各鎢絲燈7 6之電力供給量，而可以調節晶圓 熱速度或加熱溫度。此外，可以調節由氣體供給藥 往處理容器71內供給的氧化性氣體的流量或比率。 圖9係對於晶圓W，在真空條件下連續進行例 氮化處理及氧化退火處理的方式構成的基板處理系 之槪略構成圖。此基板處理系統200，被構成爲多 構造之叢集工具。 基板處理系統200，作爲主要的構成，具備對^ 進行各種處理的4個處理模組l〇〇a，l〇〇b，101a， 及對於這些處理模組l〇〇a，100b，101a，101b透 G 1連接的真空側搬送室1 03、及透過閘閥G2被連 真空搬送室103的2個加載互鎖真空室l〇5a，105b 此2個加載互鎖真空室105a，105b透過閘閥G3連 載單元107。 4個處理模組100a，100b，101a，101b，亦可 W進行相同內容的處理，或者亦可分別進行不同內 理。在本實施型態，係以在處理模組l〇〇a，10 Ob， W之矽被電漿氮化處理形成氧化氮化矽膜，在處 1 0 1 a，1 0 1 b，可以把藉由電漿氮化處理形成的氧化 膜，進而進行氧化退火處理的方式構成。 於構成爲可抽真空的真空側搬送室1 03，設有 理模組 l〇〇a，100b，101a，101b或者加載互鎖 藉由處 熱單元 W的加 !置 83 如電漿 統 2 00 真空室 i圓W 101b， 過閘閥 接於此 ，及對 接的裝 對晶圓 容的處 使晶圓 理模組 氮化矽 對於處 真空室 -25- 201234480 105a，105b進行晶圓W的收授的第1基板搬送裝置之搬 送裝置109。此搬送裝置109，具有以相互對向的方式配 置的一對搬送臂部llla，lllb。各搬送臂部llla，lllb 以同一旋轉軸爲中心，構成爲可以屈曲及旋轉。此外，於 各搬送臂部lUa，111b的先端，設有分別載置晶圓W進 行保持之用的叉部113a、113b。搬送裝置109，於這些叉 部1 13a，1 13b上載置晶圓W的狀態下，在處理模組1〇〇a ，100b，101a，101b 之間，或者處理模組 l〇〇a，l〇〇b， 101a，101b與加載互鎖真空室105a，105b之間進行晶圓 W的搬送。 於加載互鎖真空室l〇5a，105b內，設有分別載置晶 圓W之載置台106a、106b。加載互鎖真空室l〇5a，105b ，係以切換真空狀態與大氣開放狀態的方式被構成。透過 此加載互鎖真空室l〇5a，105b的載置台l〇6a，106b，在 真空側搬送室1 03與大氣側搬送室1 1 9 (後述）之間進行 晶圓W的收授。 裝載單元107，具有被設置作爲進行晶圓w的搬送之 第2基板搬送裝置的搬送裝置117之大氣側搬送室119, 與鄰接配備於此大氣側搬送室1 1 9的3個奘載埠LP，及 鄰接配備於大氣側搬送室1 1 9的其他側面，作爲進行晶圓 W的位置測定的位置測定裝置之位置測定器1 2 1。 大氣側搬送室1 1 9，具備例如使氮氣或清淨空氣往下 流動的循環設備（省略圖示），維持清潔的環境。大氣側 搬送室119，成平面俯視矩形形狀，沿著其長邊方向設有 -26- 201234480 導軌123。搬送裝置117以可在此導軌123上滑動移動的 方式被支撐。總之，搬送裝置117藉由未圖示的驅動機構 ，以可沿著導軌123往X方向搬送的方式被構成。此搬送 裝置117，具有被配置爲上下2段的一對搬送臂部125a， 125b。各搬送臂部125a，125b構成爲可以屈曲及旋轉。 於各搬送臂部125a，125b的先端，設有作爲分別載置晶 圓W進行保持的保持構件的叉部127a、127b。搬送裝置 1 17，於這些叉部127a，127b上載置晶圓W的狀態下，在 裝載埠LP的晶圓匣CR，與加載互鎖真空室105a，105b ，與位置測定器1 2 1之間進行晶圓W的搬送。 裝載埠LP，可以載置晶圓匣CR。晶圓匣CR，係以 可以相同間隔多段地載置收容複數枚晶圓W的方式構成 〇 位置測定器121，具備藉由未圖示的驅動馬達而被旋 轉的旋轉板133、及被設於此旋轉板133的外周位置，供 檢測晶圓W的周緣部的光學感測器1 3 5。 〔晶圓處理的步驟〕 於基板處理系統200，以下列步驟進行對晶圓w的電 漿氮化處理’及氧化退火處理。首先，使用大氣側搬送室 119之搬送裝置117之叉部12 7a、127b之任一，由裝載埠 LP之晶圓厘CR取出1枚晶圓W，在位置測定器121對準 位置之後，被搬入加載互鎖真空室l〇5a (或l〇5b)。在 晶圓W被載置於載置台l〇6a (或l〇6b)的狀態之加載互 -27- 201234480 鎖真空室l〇5a (或105b)，閘閥G3被關閉，內部被減壓 排氣爲真空狀態。其後，閘閥G2被開放，藉由真空側搬 送室103內的搬送裝置109之叉部113a、113b使晶圓W 由加載互鎖真空室105a (或105b)運出。 藉由搬送裝置109由加載互鎖真空室105a (或105b )運出的晶圓 W，首先被搬入處理模組100a、100b之任 一，在關閉閘閥G1後對晶圓W進行電漿氮化處理》 接著，開放前述閘閥G1，使被形成氧化氮化矽膜305 的晶圓W藉由搬送裝置109由處理模組100a (或100b) 在維持真空狀態的情況下被搬入處理模組l〇la、101b之 任一方。接著，在關閉閘閥G1後對晶圓W進行氧化退火 處理。 接著，開放前述閘閥G 1，使被形成改質了的氧化氮 化矽膜305的晶圓W藉由搬送裝置109由處理模組101a (或1 〇 1 b )在維持真空狀態的情況下被搬出，而被搬入加 載互鎖真空室l〇5a (或者l〇5b)。接著，以與前述相反 的步驟，在裝載埠LP之晶圓匣CR收容處理完畢的晶圓 W，結束基板處理系統200之對1枚晶圓W之處理。又， 基板處理系統2 00之各處理裝置的配置，只要是可以有效 率地進行處理的配置，無論任何配置構成皆可。進而，基 板處理系統200之處理模組的數目不限於4個，亦可爲5 個以上。 圖1 0係顯示作爲絕緣膜之氧化矽膜的改質步驟的流 程之流程圖，圖1 1〜圖1 3係說明其主要步驟之流程圖。 -28- 201234480 本實施型態之絕緣膜的改質方法，例如藉由圖1 〇所 示之步驟S11至步驟S15的順序來實施◊此處，步驟S11 、S12爲止的步驟，可以與第1實施型態之步驟S1、S2 同樣地實施。首先，在圖10的步驟S11，藉由真空側搬 送室103內的搬送裝置109，把處理對象之晶圓W搬入電 漿處理裝置1 〇 〇 (處理模組1 〇 〇 a或1 0 0 b )。此處，在晶 圓W表面附近，被形成矽層301，及於其上之氧化矽（ Si〇2)膜303。接著，在步驟S12，如圖11所示，對晶圓 W的氧化矽膜303進行電漿氮化處理。藉由電漿氮化處理 ，氧化矽膜3 03被氮化而形成氧化氮化矽（SiON)膜305 。在此電漿氮化處理，預估在之後的氧化退火處理步驟（ 步驟S 1 4 )之氮濃度的減少，以成爲比最終的目標氮濃度 NCT更高例如1〜3%程度的氮濃度Nco的方式進行氮化處 理。步驟S12的電漿氮化處理的條件，只要可以實現氮濃 度NC0即可沒有特別限定，能夠以任意的條件來進行。 其次，在步驟S13，把晶圓W由電漿處理裝置100( 處理模組100a或100b)移送至退火處理裝置101 (處理 模組l〇la或l〇lb)。此移送，是藉由真空側搬送室103 內的搬送裝置1 09在維持真空狀態下實施的。 其次，在步驟S14，如圖12所示，使用退火處理裝 置1 〇1，氧化退火處理氧化氮化矽膜3 05的表面。氧化退 火處理’由抑制氧化氮化矽膜3 05的表氧化與氮脫離的觀 點來看’最好是在步驟S12之電漿氮化處理結束後，維持 真空的狀態將晶圓W搬入退火處理裝置101，在電漿氮化 -29- 201234480 處理結束起1 80秒以內，較佳者爲60秒以內實施。在此 步驟，在氧化氮化矽膜3 03的表層之例如深度方向氧化 0.5〜l.Onm程度之範圍，改質爲氧濃度高的氧化氮化矽膜 3 0 5 B。藉此，如圖1 3所示，於矽層3 0 1上，作爲氧化氮 化矽膜3 0 5，形成氧化氮化矽膜3 05 A，及於其上被改質的 富含氧之氧化氮化矽膜3 05 B。 〔氧化退火處理之步驟〕 首先，於退火處理裝置101，於處理容器71內之支撐 部77設置晶圓W後，形成氣密的空間。接著，在處理控 制器51的控制之下，由未圖示的電源把特定的電力供給 至下部發熱單元72及上部發熱單元74之各鎢絲燈76的 發熱體（省略圖示）而開啓開關（ON)時，各發熱體發 熱，產生的熱能通過石英構件79以及石英構件80a到達 晶圓W，以根據配方的條件（升溫速率、加熱溫度、氣體 流量等）使晶圓W由上下急速加熱。藉由加熱晶圓w同 時由氣體供給裝置83以特定的流量導入〇2氣體等含氧氣 體’同時使未圖示的排氣裝置動作由排氣管8 4進行排氣 ’使處理容器71內爲減壓狀態之氧化氛圍。 氧化退火處理時，藉由未圖示的旋轉機構使支撐部77 全體繞鉛直軸旋轉，亦即在水平方向例如以8 0 r p m的旋 轉速度旋轉’而使晶圓W旋轉。結果，確保往晶圓W之 供給熱量的均勻性。此外，於熱處理中藉由熱電溫度計8 i 測量熱襯塾7 8的溫度可以間接測定晶圓w的溫度。藉由 -30- 201234480 熱電溫度計81測量的溫度資料，被反饋至處理控制器5 1 ，在與配方之設定溫度之間有差異的場合，調節往鎢絲燈 76供給的電力》 結束熱處理後，關閉（斷電）下部發熱單元72及上 部發熱單元74之鎢絲燈76，同時對處理容器71內，由未 圖示的洗滌埠流入氮氣等洗滌氣體同時由排氣管84排氣 冷卻晶圓W後，進行搬出。 此外，氧化退火處理，如以下所例示的把升溫步驟分 爲數個階段（例如3階段）來實施爲較佳。 首先，在第1升溫階段，升溫晶圓W直到晶圓W的 放射率成爲最大的第1溫度。此處，晶圓W的放射率是 因應於形成在晶圓W的氧化氮化矽膜而設定的。 其次，在第2升溫階段，由晶圓W的放射率成爲最 大的溫度（第1溫度），升溫晶圓W直到到達比處理溫 度更低的第2溫度。此處，第2溫度X是以滿足下列關係 式3$ (Τ-Χ)/Υ$7〔其中，T:處理温度、Y:第3升 溫速率之每1秒的升温温度幅度〕的方式規定的溫度。 於前述關係式，（T-X)/Y未滿3的場合，第3升 溫階段與其升溫速率之關係太短，容易產生過度加熱，提 高晶圓W發生翹曲或滑移的可能性所以不佳。相反地， 於前述關係式’ （T-X ) / Υ超過7的場合，第3升溫階 段與其升溫速率的關係會變得太長，導至處理的產出率降 低所以不佳。第2溫度X例如以處理溫度Τ的8 5 %〜9 5 % 的溫度爲較佳。 -31 - 201234480 在第3升溫階段，由第2溫度升溫被處理基板直到到 達處理溫度爲止。接著’於處理溫度（例如800 °C〜1 100 t)，實施在定溫下之氧化退火處理，結束特定時間的處 理之後，藉由以特定的降溫速率降低晶圓W的溫度，結 束熱處理。 從第1升溫階段直到第3升溫階段的過程中，第2升 溫階段的升溫速率比第3升溫階段的升溫速率更高。這是 因爲在第2升溫階段，主要由提高產出率的觀點來看，以 盡可能提高升溫速率爲較佳。但是，以很高的升溫速率升 溫至處理溫對，會有發生過度加熱或者由於劇烈的溫度變 化而在被處理基板之面內產生加熱速度不均勻，對被處理 基板施加熱應力（應變），而發生翹曲或者結晶缺陷之滑 移。因此，藉由在第2升溫階段之後，設比此階段升溫速 率低的第3升溫階段，防止過度加熱或者使被處理基板在 面內的加熱速度均勻化，防止被處理基板的翹曲或滑移的 發生。 此外，第3升溫階段的升溫速率，最好比第1升溫階 段的升溫速率更高。在第1升溫階段，升溫晶圓W直到 晶圓W的放射率成爲最大的溫度（第1溫度），但在到 達此第1溫度爲止時容易在被處理基板產生翹曲。亦即， 在第1升溫階段的升溫速率太高的話，會使得在被處理基 板的面內的加熱速度變得不均勻而在被處理基板產生翹曲 ’或者滑移等。亦即，在第1升溫階段的升溫速率，最好 是在第3升溫階段的升溫速率之下，在3步驟之升溫階段 -32- 201234480 中，設定爲最低是較佳的。 藉由氧化退火處理’藉由使晶圓w的氧化氮化矽膜 305的表面極薄地氧化’替代膜的最表面之不安定狀態的 Si-N結合或游離的Ν’而被形成Si_〇結合形成富含氧的 氧化氮化矽膜305 B。藉此，氧化氮化矽膜中的氮成爲不 脫離而被保持住的狀態’可以使氮濃度維持一定且爲安定 的狀態。 〔氧化退火處理之條件〕 作爲氧化退火處理的含氧氣體，只要是在處理容器71 內可以形成氧化氛圍的氣體即可沒有特別限定，例如以 〇2氣體、NO氣體、N20氣體、H20(水蒸氣）爲較佳， 於這些成分混入作爲惰性氣體之Ar等稀有氣體或N2等亦 可。使用〇2氣體與N2氣體的混合氣體的場合，爲了要提 高改質效果，以使02氣體流量：N2氣體流量之體積比率 成爲例如10: 1〜1: 2的範圍內的方式進行混合爲較佳。 在本發明方法，由有效果地抑制氧化氮化矽膜中的氮濃度 之隨時間減少的觀點來看，特別以使用02氣體之氧化退 火處理爲較佳。此時，含氧氣體的流量可以設定在〇.5mL / min ( seem )以上 2000mL/ min ( seem )以下之範圍內 ο 此外’處理壓力，由有效果地抑制氧化氮化矽膜中的 氮濃度的隨時間之減少的觀點來看，例如以1 〇Pa以上 1 5 000Pa以下之範圍內爲較佳，以133Pa以上i〇〇〇〇pa以 -33- 201234480 下之範圍爲更佳。 此外，晶圓w的加熱溫度，作爲熱電溫度計81的 量溫度，例如以在800°C以上1 100°C以下的範圍內爲較 ，設定爲900°C以上110CTC以下的範圍內爲更佳。 此外，氧化退火處理的處理時間，由僅使氧化氮化 膜3 0 5中的表層氧化的觀點來看，例如以1 〇秒以上5 0 以下的範圍內爲較佳，設定爲10秒以上30秒以下的範 內爲更佳。如此，藉由在短時間進行氧化退火可以使氧 氮化矽膜3 05的表面氧化極薄的厚度。此外可以抑制氧 氮化矽膜305的增膜（電氣膜厚（EOT)的增大）。 以上的條件，作爲配方被保持於控制部5 0的記憶 53。接著，藉由處理控制器51讀出該配方而往退火處 裝置1 0 1的各構成部例如氣體供給裝置8 3、排氣裝置（ 圖示）、下部發熱單元72及上部發熱單元74 (鎢絲燈 )等送出控制訊號，以所要的條件進行氧化退火處理。 如以上所述進行改質氧化氮化矽膜3 05後，在步 S15，藉由真空搬送室103內的搬送裝置109把處理完 的晶圓W由退火處理裝置1 0 1 (處理模組1 0 1 a或1 0 1 b 搬出，以前述順序收容於裝載埠LP之晶圓卡匣CR。 於本實施型態，在被改質的氧化氮化矽膜3 0 5 B， 由氧化退火處理，使氧化氮化矽膜305中的不安定的氮 子被置換爲氧原子，往膜外放出。因此，氧化氮化矽 305B中的氮濃度NC1，比電漿氮化處理之後的氧化氮化 膜3 05的氮濃度Nco更低（NC0>NC1)。此外，未藉由 測 佳 矽 秒 圍 化 化 部 理 未 76 驟 畢 ) 藉 原 膜 矽 氧 -34- 201234480 化退火處理而改質的深部的氧化氮化矽膜3 0 5A的氮濃度 NC2，幾乎等於電漿氮化處理之後的氮濃度Nco之値。亦 即，以最終形成的氧化氮化矽膜3 0 5A的氮濃度NC2與氧 化氮化矽膜3 05 B之氮濃度NC1的平均，接近於目標氮濃 度NCT的方式，來進行步驟S12的電漿氮化處理及步驟 S14的氧化退火處理爲較佳。 在本實施型態，可以使步驟S12的電漿氮化處理，與 步驟S14的氧化退火處理，於基板處理系統200在維持真 空條件的狀態下連續地進行。亦即，電漿氮化處理後，在 氧化氮化矽膜3 05中還未產生氮濃度的經時變化（自然減 少）時，可以進行電漿氧化處理而謀求氧化氮化矽膜3 0 5 中的氮濃度的安定化。 本實施型態之其他構成及效果，與第1實施型態相同 〔第3實施型態〕 其次，參照圖14至圖18，同時說明相關於本發明之 第3實施型態之絕緣膜之改質方法。本實施型態之絕緣膜 之改質方法，可以包含對氮化矽膜，進行電漿氮化處理， 形成氧化氮化矽膜的步驟，及對此氧化氮化矽膜進行電漿 氮化處理的第1改質步驟，與進而對氧化氮化矽膜進行氧 化退火處理的第2改質步驟。此處，本實施型態之電漿氮 化處理及電漿氧化處理，也可以使用與在第1實施型態使 用的同樣的電漿處理裝置100 (圖1〜圖3)來實施。氧化 -35- 201234480 退火處理，例如可以使用圖8所示之退火處理裝置ιοί來 進行。此外，以上的處理’可以於與圖9所示的基板處理 系統200同樣構成的多真空室構造之叢集工具來進行。 圖14係顯示作爲絕緣膜之氧化矽膜的改質步驟的流 程之流程圖’圖15〜圖18係說明其主要步驟之流程圖。 本實施型態之絕緣膜的改質方法，例如藉由圖1 4所 示之步驟S21至步驟S26的順序來實施。此處，步驟S21 〜S23爲止的步驟’可以與第1實施型態之步驟si〜S3 同樣地實施。首先’在圖14的步驟S21，藉由真空側搬 送室103內的搬送裝置109，把處理對象之晶圓w搬入電 漿處理裝置1〇〇(處理模組l〇〇a或l〇〇b)。此處，在晶 圓W表面附近，被形成矽層301，及於其上之氧化矽（ Si02)膜303。接著，在步驟S22，如圖15所示，對晶圓 W的氧化矽膜303進行電漿氮化處理。藉由電漿氮化處理 ，氧化矽膜3 03被氮化而形成氧化氮化矽（SiON )膜305 。在此電漿氮化處理，預估在之後的電漿氧化處理步驟（ 步驟S23)及氧化退火處理（步驟S25)之氮濃度的減少 ，以成爲比最終的目標氮濃度nct更高例如1〜3 %程度的 氮濃度Nco的方式進行氮化處理。步驟S22的電漿氮化處 理的條件，只要可以實現氮濃度Nco即可沒有特別限定， 能夠以任意的條件來進行。 其次，在步驟S23，如圖16所示，使用電漿處理裝 置100，電漿氧化處理氧化氮化矽膜3 05的表面。電漿氧 化處理，由抑制氧化氮化矽膜3 05的氧化與氮脫離的觀點 -36- 201234480 來看，最好是在步驟S22之電漿氮化處理結束後，接著在 處理容器1內維持氛圍爲真空的狀態，在電漿氮化處理結 束起1 80秒以內，較佳者爲60秒以內實施。在此步驟， 在氧化氮化矽膜305的表層之例如深度方向上電漿氧化 0.5〜l.Onm程度之範圍，改質爲氧濃度高的氧化氮化矽膜 305B。藉此，如圖17所示，於砂層301上，被形成氧化 氮化矽膜3 05A，及於其上被改質的富含氧之氧化氮化矽 膜3 05 B。電漿氧化處理的條件，與第1實施型態的步驟 S 1 3同樣。 其次，在步驟S24，把晶圓W由電漿處理裝置100 ( 處理模組l〇〇a或100b)移送至退火處理裝置101 (處理 模組l〇la或101b)。此移送，是藉由真空側搬送室103 內的搬送裝置1〇9在維持真空狀態下實施的。 其次，在步驟S25，如圖17所示，使用退火處理裝 置101，氧化退火處理氧化氮化矽膜3 05的表面。在此步 驟，在氧化氮化矽膜3 0 5的表層之例如深度方向氧化0.5 〜l.Onm程度之範圍，改質爲氧濃度高的氧化氮化矽膜 305B。藉此，如圖18所示，於砂層301上，作爲氧化氮 化矽膜3 05，形成氧化氮化矽膜305 A，及於其上被改質的 富含氧之氧化氮化矽膜3 05B。氧化退火處理的條件，與 第2實施型態的步驟S14同樣。 如以上所述進行改質氧化氮化矽膜305後，在步驟 S26，藉由真空搬送室103內的搬送裝置109把處理完畢 的晶圓W由退火處理裝置101 (處理模組l〇la或101b) -37- 201234480 搬出，以前述順序收容於裝載埠LP之晶圓卡匣CR。 在本實施型態，藉由電漿氧化處理與氧化退火處理之 組合，使晶圓W的氧化氮化矽膜3 05的表面極薄地氧化 ，替代膜的最表面之不安定狀態的Si-N結合或游離的N ，而被形成Si-Ο結合形成富含氧的氧化氮化矽膜3 05B。 藉此，氧化氮化矽膜中的氮成爲不脫離而被保持住的狀態 ，可以使氮濃度維持一定且爲安定的狀態。 於本實施型態，在被改質的氧化氮化矽膜3 05 B，藉 由電漿氧化處理與氧化退火處理之組合，使氧化氮化矽膜 305中的不安定的氮原子被置換爲氧原子，往膜外放出。 因此，氧化氮化矽膜3 05 B中的氮濃度NC1，比電漿氮化 處理之後的氧化氮化矽膜3 05的氮濃度Nco更低（Nco> Nci )。此外，未藉由電漿氧化處理及氧化退火處理而改 質的深部的氧化氮化矽膜3 05 A的氮濃度NC2，幾乎等於 電漿氮化處理之後的氮濃度Nco之値。亦即，以最終形成 的氧化氮化矽膜3 0 5A的氮濃度NC2與氧化氮化矽膜305B 之氮濃度NC1的平均，接近於目標氮濃度NCT的方式，來 進行步驟S22的電漿氮化處理，以及步驟S23的電漿氧化 處理及步驟S25的氧化退火處理爲較佳。 在本實施型態，可以使步驟S22的電漿氮化處理，與 步驟S23的電漿氧化處理及步驟S25的氧化退火處理，於 基板處理系統200在維持真空條件的狀態下連續地進行。 亦即，電漿氮化處理後，在氧化氮化矽膜3 05中還未產生 氮濃度的經時變化（自然減少）時，可以進行電漿氧化處 -38- 201234480 理及氧化退火處理而謀求氧化氮化矽膜305 安定化。 又，在本實施型態，如圖14所示，於; 漿氮化處理之後，進行步驟S23的電漿氧化 進行步驟S25的氧化退火處理，但是在步驟 化處理之後，先進行氧化退火處理，接著進 理亦可。此外，步驟S22的電漿氮化處理， 電漿氧化處理，可以改變處理容器而進行 S22的電漿氮化處理，在處理模組100a進 的電漿氧化處理在處理模組1 〇〇b進行亦可。 本實施型態之其他構成及效果，與第1 態相同。 〔作用〕 在把氧化矽膜進行電漿氮化處理之後的 中，包含不安定狀態之Si-N結合或氮原子 ，隨著時間的經過徐徐由氧化氮化矽膜往外 離現象）。本案發明人，認爲在電漿氮化處 經時性的氧化氮化矽膜中的氮濃度降低的氮 因爲Si-N結合容易被切斷，替代地取入氛 至膜中，置換爲Si-Ο結合的緣故。在此， ，在電漿氮化處理之後（例如1 80秒以內） 氛圍的狀態下，對氧化氮化矽膜的表層施以 電漿氧化處理及/或氧化退火處理的改質處 中的氮濃度的 步驟S 2 2的電 處理，其後， S22的電漿氮 行電漿氧化處 與步驟S23的 。例如，步驟 行，步驟 S23 及第2實施型 氧化氮化矽膜 。這些氮原子 部放出（氮脫 理後，會產生 脫離現象，是 圍中的氧原子 將此想法逆轉 ，在維持真空 短時間的包括 理，使該表層 -39- 201234480 部分的Si-N結合強制轉換爲Si-Ο結合，同時促進游離狀 態的氮原子往膜外放出。藉由改質處理，在氧化氮化矽膜 的表層附近，形成薄的富含氧（Si-Ο結合爲緻密的）改質 層。此改質層，發揮一種障壁功能，發會抑制氮原子由氧 化氮化矽膜中的改質層更深部之放出。亦即，藉由改質處 理，可以防止長時間持續性的氮濃度的降低（氮脫離現象 )。此外，改質處理，伴隨著氧化氮化矽膜表面附近之某 個程度的氮濃度的減少，但可以藉由預先估計減少幅度而 於電漿氮化處理步驟預先摻入較多的氮，把改質步驟後之 氧化氮化矽膜控制在目標氮濃度。 其次，說明成爲本發明的基礎之實驗資料。 試驗例1 : 藉由對於藉由乾式氧化法形成的厚度3.2nm的Si02 膜，使用與圖1所示的電漿處理裝置100同樣構成的電漿 處理裝置，以下列條件進行電漿氮化處理，形成4階段不 同氮濃度（氮濃度：高、中-高' 中-低、低）的Si ON膜 〔電漿氮化處理條件〕 氫氣流量· 500 或 1000mL/min(sccm) N2 氣體流量：20〇mL/min ( seem) 處理壓力：35Pa ( 260mTorr )201234480 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of modifying an insulating film which can be used in the manufacture of a device such as a MOS structure. [Prior Art] In order to prevent the so-called boron penetration phenomenon, a semiconductor device represented by a MOSFET is used as a gate insulating film using a yttrium niobium oxide (SiON) film. In addition, with the demand for miniaturization and high performance of semiconductor devices in recent years, the thin film of the gate insulating film has gradually approached the limit. When the yttrium oxide (SiO 2 ) film is thinned, the leakage current increases exponentially due to the direct tunneling effect, so that the power consumption is greatly increased. On the other hand, a zirconia film is also used as the gate insulating film for the purpose of reducing the leakage current. The ruthenium oxynitride film can be formed, for example, by a plasma action of a nitrous oxide film formed by a method such as thermal oxidation. Then, in order to prevent deterioration of the film quality, the ruthenium oxynitride film formed by the plasma nitriding treatment is proposed to be subjected to modification treatment such as thermal annealing (Patent Documents 1 to 3) [Prior Art Document] [Patent [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-25377 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2006-156995 (Patent Document 3) International Publication No. WO2008/081724A-5-201234480 Problem to be Solved] The yttrium oxynitride film formed by nitriding the Si〇2 film plasma is released from the film to the outside with the passage of time after the nitriding treatment (so-called "nitrogen detachment phenomenon" "). When nitrogen detachment occurs, 'even if the plasma nitriding treatment is performed under the same conditions, the nitrogen between the semiconductor wafers/batch is between the wafers and the batches. The difference in concentration produces a result that makes quality management of the final product difficult. For example, when a hafnium oxynitride film is used as a gate insulating film of a transistor such as a MOSFET, the effect of suppressing the penetration of boron or the leakage current changes depending on the difference in nitrogen concentration, and the device is trusted. Reduced sex or reduced productivity. That is, the present invention has an object of suppressing a decrease in the concentration of nitrogen in the film caused by nitrogen detachment of the yttrium niobium oxide film formed by the plasma nitriding treatment, so that between the treated bodies/between the batches The difference in nitrogen concentration is suppressed to a minimum, and a ruthenium oxynitride film which maintains a constant nitrogen concentration in the film to stabilize it is provided. [Means for Solving the Problem] The method for modifying an insulating film according to the present invention includes a nitriding treatment step of forming a yttrium oxide film exposed on the surface of the object to be processed by plasma nitriding to form a yttrium niobium oxide film. And a modification step of oxidizing the ruthenium oxynitride film; after the fading treatment step is completed, the tempering step is started in a state of maintaining a vacuum atmosphere - 6 - 201234480. In the method for modifying the insulating film of the present invention, the nitrogen concentration in the film of the yttria-nitride film after the nitriding treatment step is Nco, and the target concentration of the nitrogen concentration in the film of the yttria-nitride film after the modifying step is In the case of NCT, it is preferred to carry out the above plasma nitriding treatment so as to be Nco > NCT. In the method for modifying the insulating film of the present invention, the modifying step includes plasma oxidation according to a plasma processing apparatus for generating a plasma of a processing gas by introducing microwaves into the processing container by a planar antenna having a plurality of holes. Processing is preferred. In this case, it is preferred that the plasma nitriding treatment and the plasma oxidizing treatment are continuously performed in the same processing vessel of the plasma processing apparatus for one object to be processed. In this case, after the plasma nitriding treatment, it is preferred to remove the nitrogen remaining in the processing vessel by evacuation or purge before the plasma oxidation treatment. Further, after the plasma oxidation treatment, as a part of the reforming step, the step of annealing the temperature of the object to be treated in a range of from 800 ° C to 11 ° C in an oxidizing atmosphere is Preferably. Further, in the method of modifying the insulating film of the present invention, the treatment pressure of the plasma oxidation treatment is preferably in the range of from 6 7 Pa to 1333 Pa. Further, in the method for modifying the insulating film of the present invention, the plasma oxidation treatment is such that the volume flow ratio of the oxygen gas to the entire processing gas is at 0. It is preferable to carry out in the range of 1% or more and 20% or less. Further, in the method for modifying the insulating film of the present invention, the processing temperature of the plasma oxidation treatment is preferably in the range of 200 ° C. or higher and 600 ° C or lower. Further, the method for modifying the insulating film of the present invention is as described above. The treatment time of the plasma oxidation treatment is preferably in the range of from 1 second to 90 seconds. Further, in the method for modifying the insulating film of the present invention, it is preferable that the nitriding treatment step is performed by a plasma processing apparatus which generates a plasma of a processing gas by introducing a microwave into a processing container by a planar antenna having a plurality of holes. The above-described modification step is carried out by an annealing apparatus which performs annealing treatment at a temperature in a range of 800 ° C or more and 11 ° C or less in an oxidizing atmosphere. In this case, the treatment time of the annealing treatment is preferably in the range of 1 sec. or more and 50 sec or less. Further, it is preferred that the object to be processed is transferred from the plasma processing apparatus to the annealing apparatus to be carried out under vacuum. Further, in the method of modifying the insulating film of the present invention, the yttrium oxynitride film is preferably a gate insulating film of a MOS structure device. [Effects of the Invention] According to the present invention, it is possible to improve the film quality of the yttrium niobium oxide film by maintaining the vacuum atmosphere after the plasma nitriding treatment, and then to start the reforming step, thereby suppressing the aging of the yttrium oxynitride film. Nitrogen concentration is reduced (nitrogen detachment). In other words, by modifying the insulating film of the present invention, it is possible to effectively suppress the increase of the leakage current or the penetration of boron by utilizing the modification of the gate insulating film of the MOS structure device such as a MOSFET. The difference in nitrogen concentration of the gate insulating film between wafers/batch can be suppressed, and the reliability and productivity of the semiconductor device can be improved. [Embodiment] -8 - 201234480 [First Embodiment] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. The modification method of the insulating film of this embodiment may include a step of performing plasma nitridation treatment on the tantalum nitride film to form a tantalum oxide film, and plasma-oxidizing the tantalum nitride film. Modification steps. Fig. 1 is a cross-sectional view showing a schematic configuration of a plasma processing apparatus 100 for use in a modification method of an insulating film according to the first embodiment. 2 is a plan view showing a planar antenna of the plasma processing apparatus 100 of FIG. 1. Fig. 3 is a view showing an example of a configuration of a control unit for controlling the plasma processing apparatus 100 of Fig. 1; The plasma processing apparatus 100 is configured to include a plurality of planar antennas having slit-shaped holes, and in particular, RLSA (radiial line Slot Antenna) introduces microwaves into the processing container to generate high density. RLSA microwave plasma processing apparatus for microwave-excited plasma with low electron temperature. The plasma processing apparatus 100 can be processed according to a plasma density of lxlOIG to 5xl012 / cm3 and a plasma having a low electron temperature of 〜7 to 2eV. That is, the plasma processing apparatus 100 can be suitably used for the purpose of performing plasma nitriding treatment or plasma oxidation treatment in the manufacturing process of various semiconductor devices. The plasma processing apparatus 100' is mainly configured to include a processing container 1 that is airtight, a gas supply device 18 that supplies gas into the processing container 1, and a vacuum pump 24 that is used in the reduced pressure exhaust processing container 1. The exhaust device 'is provided in the upper portion of the processing container 1, the microwave introducing mechanism 27 that introduces microwaves into the processing container 1, and the control unit 50 that controls the respective components of the plasma processing apparatuses 10〇-9- 201234480. The processing container 1 is formed of a substantially cylindrical container that is grounded. Further, the processing container 1 may be formed of a container having a rectangular tube shape. The processing container 1 has a bottom wall 1a and a side wall 1b which are made of a metal such as aluminum or an alloy thereof, and is disposed inside the processing container 1, and is provided to horizontally support the semiconductor wafer to be processed (hereinafter referred to as "wafer"). The mounting table 2 for use. The mounting table 2 is made of a material having high thermal conductivity, such as ceramics such as A1N. This mounting table 2 is provided from the bottom of the exhaust chamber 11. The central support member 3 extending upward is supported by the center. The support member 3 is made of, for example, a ceramic such as A1N. Further, the mounting table 2 is provided with a cover ring 4 for covering the outer edge portion and guiding the wafer W. The cover ring 4 is, for example, a ring member made of a material such as quartz, A1N, Al2〇3, or SiN. It is preferable to cover the ring 4 to cover the surface and the side of the mounting table 2. Thereby, metal contamination can be prevented. Further, on the mounting table 2, a resistance heating type heater 5 as a temperature adjustment mechanism is buried. The heater 5 heats the stage 2 by supplying power from the heater power source 5a, and uniformly heats the wafer W of the substrate to be processed by the heat. Further, the mounting table 2 is equipped with a thermocouple (TC) 6. Thereby, the temperature measurement of the mounting table 2 is performed by the thermocouple 6, and the heating temperature of the wafer W can be controlled to a range of, for example, 900 ° C at room temperature. Further, on the mounting table 2, a wafer support plug (not shown) for supporting and lifting the wafer W is provided. Each wafer support pin can be set in such a manner that the surface protrusion of the mounting table -10- 201234480 2 is hidden. On the inner circumference of the processing container 1, a cylindrical spacer 7 made of quartz is provided. Further, in order to uniformly exhaust the inside of the processing container 1 on the outer peripheral side of the mounting table 2, a quartz baffle plate 8 having a plurality of exhaust holes 8a is annularly provided. This baffle piece 8 is supported by a plurality of struts 9. At a substantially central portion of the bottom wall 1a of the processing container 1, a circular opening portion 10 is formed. The bottom wall 1a communicates with the opening portion 1 and is provided with an exhaust chamber 11 that protrudes downward. The exhaust chamber 11 is connected to the exhaust pipe 12, and is connected to the vacuum pump 24 through the exhaust pipe 12. In the upper part of the processing container 1, an annular cover having a central opening is provided. Member 1 3. The inner circumference of the opening protrudes toward the inner side (the space inside the processing container) to form an annular support portion 13a. The side wall 1b of the processing container 1 is provided with a gas introduction portion 15 that is annular. The gas introduction unit 15 is connected to a gas supply device 18 that supplies a nitrogen-containing gas, an oxygen-containing gas, or a plasma excitation gas. Further, the gas introduction portion 15 may be in the form of a nozzle or a showerhead. Further, in the side wall 1b of the processing container 1, between the plasma processing apparatus 100 and the vacuum side transfer chamber 103 adjacent thereto, a carry-out port 16 for carrying out the loading and unloading of the wafer W, and opening and closing the carry-out are provided. The gate valve G1 of the inlet 16 and the gas supply device 1 8 have a gas supply source (for example, an inert gas supply source 19a, a nitrogen-containing gas supply source 19b, and an oxygen-containing gas supply source 19c)' and a pipe (for example, gas lines 20a and 20b, 20c), flow control device-11 - 201234480 (for example, mass flow meter 2 1 a, 2 1 b, 2 1 c ) 'and valve (for example, on-off valves 22a, 22b, 22c). Further, the gas supply device 18 may be a gas supply source (not shown), for example, and may have a washing gas supply source or the like used when the atmosphere in the replacement processing container 1 is used. As the inert gas, for example, nitrogen gas or a rare gas or the like can be used. As the rare gas, for example, argon gas, helium gas, neon gas, nitrogen gas or the like can be used. Among them, argon gas has been particularly excellent from the viewpoint of economical superiority. As the nitrogen-containing gas used for the plasma nitriding treatment, for example, nitrogen gas, nitrogen monoxide, nitrogen dioxide, ammonia gas or the like can be used. Further, as the oxygen-containing gas used for the plasma oxidation treatment, for example, oxygen (02), water vapor (H20), nitrogen monoxide (NO), nitrous oxide (N2) or the like can be used. The inert gas, the nitrogen-containing gas, and the oxygen-containing gas are supplied from the inert gas supply source 19a of the gas supply device 18, the nitrogen-containing gas supply source 19b, and the oxygen-containing gas supply source 19c, respectively, through the gas lines 20a, 20b, and 20c to the gas introduction. The portion 15 is introduced into the processing container 1 by the gas introduction portion 15. Each of the gas lines 20a, 20b, and 20c connected to each of the gas supply sources is provided with mass flow meters 2 1 a, 2 1 b, and 2 1 c and a group of on-off valves 22 a ' 2 2b and 22 c before and after. With such a configuration of the gas supply device 18, switching of the supplied gas, flow rate, and the like can be controlled. The exhaust device is provided with a vacuum pump 24. The vacuum pump 24' is constituted by a high-speed vacuum pump such as a turbo molecular pump. The vacuum pump 24' is connected to the exhaust chamber 11 of the processing vessel 透过 through the exhaust pipe 12. The gas in the processing chamber 1 is uniformly flowed into the space 11a of the exhaust chamber 1 1 , and the vacuum pump 24 is operated from the space 1 1 a to be exhausted to the outside through the exhaust pipe 12 . By the means of -12-201234480, the specific degree of vacuum in the processing container 1 can be reduced at a high speed to, for example, 0 · 1 3 3 P a °. Next, the configuration of the microwave introducing mechanism 27 will be described. The microwave introducing mechanism 27 mainly includes a transmitting plate 28, a planar antenna 31, a late wave material 33, a covering member 34, a waveguide 37, a matching circuit 38, and a microwave generating device 39. The transmissive plate 28 through which the microwaves are transmitted is provided on the support portion 13a projecting from the inner peripheral side of the cover member 13. The transmission plate 28 is made of a dielectric material such as quartz or alumina or nitrogen oxide. The transmission plate 28 and the support portion 13a are hermetically sealed by the sealing member 29. That is, the inside of the processing container 1 is kept airtight. The planar antenna 31 is disposed above the transmissive plate 28 so as to face the mounting table 2. The planar antenna 31 has a circular plate shape. Further, the shape of the planar antenna 3 1 is not limited to a disk shape, and may be, for example, a square plate shape. This planar antenna 31 is locked to the upper end of the cover member 13. The planar antenna 3 1, for example, is composed of a copper plate or an aluminum plate whose surface is gold plated or silver plated. The planar antenna 31 has a plurality of slit-shaped microwave radiation holes 32 that radiate microwaves. The microwave radiation holes 32 are formed to penetrate the planar antenna 31 in a specific pattern. Each of the microwave radiation holes 32 has an elongated rectangular shape (slit shape) as shown, for example, in Fig. 2 . Next, a typical arrangement is that the adjacent microwave radiation holes 32 are arranged in a "T" shape. Further, the microwave radiation holes 32 which are collectively arranged in a specific shape (e.g., T-shape) are arranged in a concentric shape as a whole. -13- 201234480 The length or arrangement interval of the microwave radiation holes 32 is determined by the length (λ g ) of the microwave. For example, the interval between the microwave radiation holes 32 is arranged so as to be Ag/4 to Ag. Further, in Fig. 2, the interval between the adjacent microwave radiation holes 32 formed in a concentric shape is represented by Ar. Further, the shape of the wave radiation hole 32 may be other shapes such as a circular shape or an arc shape. Further, the arrangement type of the microwave radiation holes 32 is not particularly limited, and may be, for example, a spiral shape or a radial shape, in addition to the concentric shape. On the upper surface of the planar antenna 31, a late wave material 33 having a dielectric ratio larger than a vacuum is provided. In the case of the late wave material 33, the length of the microwave is increased in the vacuum, and the function of adjusting the plasma by shortening the wavelength of the microwave is used as the material of the late wave material 33. For example, quartz or polytetrafluoroethylene resin can be used. Polyimine resin and the like. Further, between the planar antenna 31 and the transmissive plate 28, or between the late wave material and the planar antenna 31, respectively, it is possible to make contact or leave, so that contact is preferable. A cover member 34 is provided on the upper portion of the processing container 1 so as to cover the planar antenna 31 and the wave member 33. The covering member 34 is formed of, for example, a metal material such as aluminum stainless steel. Thereby, the covering member 34 forms a flat guiding wave path with the flat surface 31. The upper end of the cover member 13 and the covering member 34' are sealed by the sealing member 35. Further, a cooling water flow path 34a is formed inside the covering member 34. The cover member 34, the late wave material 33, the planar antenna, and the transmission plate 28 can be cooled by circulating cooling water through the cooling water passage 34a. Further, the covering member 34 is grounded. The center of the upper wall (top) of the covering member 34 is formed with an opening portion 36. The wave is rounded. The electric wave terpene 33 is delayed or lined. The flow is 3 1 -14 - 201234480. The opening portion 36 is connected to the waveguide 37. . The microwave generating device 39 that generates the microwave is connected to the other end side of the waveguide 37 through the matching circuit 38, and the waveguide 37 has a circular cross section extending upward from the opening 36 of the covering member 34. The coaxial waveguide 37a and the upper end portion of the coaxial waveguide 37a are transmitted through the mode converter 40 and extend in the horizontal direction of the rectangular waveguide 37b. The mode converter 40 has a function of converting the microwave propagating in the TE mode in the rectangular waveguide tube 7 7b into the TEM mode. The center of the coaxial waveguide 37a has an inner conductor 41 extending. The inner conductor 41 is connected and fixed to the center of the planar antenna 31 at its lower end. With such a configuration, the microwaves are transmitted through the inner conductor 41 of the coaxial waveguide 37a to the flat waveguide formed by the covering member 34 and the planar antenna 31, and are uniformly radiated efficiently, and the microwave radiating holes of the planar antenna 31 are radiated. (Slit) 32 is introduced into the processing container to generate plasma. According to the microwave introducing mechanism 27 configured as described above, the microwave generated by the microwave generating device 39 is transmitted through the waveguide 37 to the planar antenna 31, and is introduced into the processing container 1 through the transmissive plate 28. Also, as the frequency of the microwave, for example, 2. 45GHz is better, others can use 8. 35GHz, 1. 98GHz and so on. Each component of the plasma processing apparatus 1 is configured to be connected to the control unit 50 and controlled. The control unit 50 has a computer, for example, as shown in Fig. 3, and includes a processing controller 51 having a CPU, a user interface 52 connected to the processing controller 51, and a storage unit 53. The processing controller -15-201234480 51 is a constituent unit (for example, a heater power source 5a, a gas supply device 18, and the like) that is integrated with processing conditions such as temperature, pressure, gas flow rate, and microwave output. The vacuum pump 24, the microwave generating device 39, and the like are controlled. The user interface 52 includes a keyboard for inputting an instruction by the engineering manager to manage the plasma processing apparatus 100, or a display for visualizing the operation state of the plasma processing apparatus 100. Further, in the storage unit 53, a control program (software) for realizing various processes executed by the plasma processing apparatus 100 to process the control of the controller 51, or a recipe in which processing condition data or the like is recorded is stored. Then, if necessary, an arbitrary recipe called by the memory unit 53 is executed by the processing controller 51 in response to an instruction from the user interface 52, and processing by the plasma processing apparatus 100 under the control of the processing controller 51. The desired treatment is carried out in the container 1. In addition, the recipes such as the control program or the processing condition data may be in a state of being stored in a computer-readable memory medium such as a CD-ROM, a hard disk, a floppy disk, a flash memory, a DVD, a Blu-ray disk, or the like. Or, by other devices, for example, through the dedicated line and online at any time. In the plasma processing apparatus 100 configured as described above, it is possible to perform plasma treatment without causing damage to the lower substrate or the like at a low temperature of 60 or less. Further, the plasma processing apparatus 100 has excellent uniformity of plasma, for example, For a large wafer W having a diameter of 300 mm or more, the uniformity of processing can be realized in the plane of the wafer W. Next, an insulating mold of -16-201234480 in the plasma processing apparatus 100 will be described with reference to FIGS. 4 to 7. Fig. 4 is a flow chart showing the flow of a reforming step as an insulating film, and Fig. 4 to Fig. 7 are flow charts for explaining the steps of the insulating film of the present embodiment, for example, by | Steps S1 to S4 are performed in the order of the steps S1 to S4. First, in FIG. S1, the wafer W to be processed is carried into the plasma processing apparatus 1 where oxidation of the germanium layer 301 is formed in the vicinity of the surface of the wafer W.矽(SiO 2 ) film 303. Next, in step S2, plasma nitridation treatment of the cerium oxide of the wafer W is performed using the plasma processing apparatus 1 。. It was modified to a yttrium niobium oxide (SiON) film 305. Here The treatment is estimated to be followed by a plasma oxidation treatment step (the step concentration is reduced to be nitriding in a manner that is more than 3% of the final target nitrogen concentration NCT of the nitrogen concentration Nco. Step by step plasma nitriding treatment The condition is not particularly limited as long as the nitrogen concentration Nco can be achieved, and can be carried out under any conditions. Next, in step S3, as shown in Fig. 6, the plasma yttrium oxide film is treated by plasma 〇0, plasma oxidation. The surface of the ruthenium plasma oxidation treatment is preferably a state in which the plasma nitridation treatment in the step S2 is followed by maintaining the atmosphere in a vacuum in the processing container 1 from the viewpoint of suppressing oxidation of the ruthenium oxynitride film 305. In the case of less than 180 seconds from the end of the process, preferably within 60 seconds, the surface layer of the tantalum oxide film 305 is oxidized, for example, by a depth of 0. 5~l. The range of Onm degree is changed to the oxygen concentration high oxidized sand film. The main step is the step 4 shown in Fig. 4, and the nitrogen in the sample is as shown in Fig. 5, 3 03 into 3 〇 3 by nitrogen plasma nitriding S3) For example, if the step S 2 is high, the treatment device 5 is not subjected to the detachment of nitrogen from the step S 3 , and the plasma is nitrided. Here, the plasma is oxidized with nitrogen oxide -17- 201234480. Thereby, as shown in FIG. 7, on the tantalum layer 301, as the oxidized nitriding sand film 305, a oxidized nitriding sand film 305A, and an oxygen-rich yttria-yttria film 3 05 modified thereon are formed. B. [Sequence of Plasma Oxidation Treatment] The order and conditions of the plasma oxidation treatment of the step S3 are as follows. First, in the processing container 1 of the reduced-pressure exhaust plasma processing apparatus 100, the inert gas supply source 19a of the gas supply device 18, the oxygen-containing gas supply source 19c, and, for example, the Ar gas and the 02 gas are specified. The flow rate is introduced into the processing container 1 through the gas introduction unit 15 . In this manner, the inside of the processing container 1 is adjusted to a specific pressure. Next, the specific frequency generated by the microwave generating device 39 is, for example, 2. The 45 GHz microwave is conducted through the matching circuit 38 to the waveguide 37. The microwave guided to the waveguide 37 is sequentially supplied to the planar antenna through the inner conductor 41 through the rectangular waveguide 37b and the coaxial waveguide 37a. In short, the microwave is transmitted in the TE mode in the rectangular waveguide 37b, and the TE mode microwave is converted into the TEM mode by the mode converter 40, and transmitted through the coaxial waveguide 37a to the planar member through the cover member 34 and the planar antenna. 3 1 constitutes a flat guide wave path. Then, the microwaves are radiated from the slit-shaped microwave radiation holes 32 formed by the planar antenna 31 through the transmission plate 28 to the space above the wafer W in the processing container 1. The microwave output at this time can be selected in the range of 1 000 W or more and 5000 W or less, for example, in the case of processing the wafer W having a diameter of 200 mm or more. By radiating the microwave of -18-201234480 from the planar antenna 31 through the transmission plate 28 to the processing container 1, an electromagnetic field is formed in the processing container 1, and the helium gas and the helium gas are respectively plasmad. The excited plasma is radiated by a plurality of microwave radiation holes 32 of the planar antenna 31 by microwaves, and has a high density of about 1 χ 101 () 〜 5 χ 1012 / cm 3 and has approximately 1 in the vicinity of the wafer W. . Low electron temperature below 2eV. The plasma thus formed has little damage to the plasma caused by ions or the like of the underlying film. Next, the wafer W is subjected to plasma oxidation treatment by the action of the active species 〇2 + ions or 0 ( ) radicals in the plasma. That is, by extremely thinly oxidizing the surface of the yttria-ruthenium oxide film 305 of the wafer W, instead of the Si-N bond or the free N in the unstable state on the outermost surface of the film, Si-Ο is formed to form a rich Oxygen oxynitride ruthenium oxide film 305B. Thereby, the nitrogen in the yttrium niobium oxide film is maintained without being detached, and the nitrogen concentration can be maintained constant and in a stable state. [Magnetic Oxidation Treatment Condition] As the treatment gas for the plasma oxidation treatment, it is preferable to use a gas containing a rare gas and an oxygen-containing gas. As the rare gas, Ar gas is preferably used, and as the oxygen-containing gas, 〇2 gas is preferably used. At this time, the volume flow ratio of the 〇2 gas to the entire process gas (the percentage of the 02 gas flow rate/the total process gas flow rate) is determined by the effect of suppressing the decrease in the nitrogen concentration in the yttria-nitride film 305 over time. With 0. It is preferably in the range of 1% or more and 20% or less, more preferably in the range of 1% or more and 15% or less, and more preferably in the range of 10% or more and 15% or less. In the plasma oxidation treatment, for example, the flow rate of the Ar gas is 500 mL/min or more and 5000 mL /min (seem) or less, the flow rate of the helium gas is 5 mL/min (sccm) to 10000-201234480 on 1000 mL / In the range below min (seem), it is preferable to set the flow rate ratio as follows. Further, the treatment pressure is preferably in the range of 67 Pa or more and 1 3 3 3 Pa or less, from the viewpoint of effectively suppressing the decrease of the nitrogen concentration in the hafnium oxynitride film 305 with time, 133. The range of 3 Pa or more and 1 33 3 Pa or less is more preferable, and the range of 3 33 Pa or more and 1 3 3 3 Pa or less is more preferable. When the treatment pressure of the plasma oxidation treatment is less than 67 Pa, the oxidation active species in the plasma is dominant in the ion component, so that the oxidation rate becomes high, and the tantalum oxide film 3 is obtained by nitriding the tantalum oxide film 303. The nitrogen concentration of the surface of 05 will decrease. In addition, the power density of the microwave is determined by the efficiency of the real-life species in the plasma, 2 + ions or 0 (^ 2) radicals. 51W / cm2 or more 2. It is preferable to be in the range of 56 W/cm 2 or less, and it is preferable to oxidize the surface of the yttrium niobium oxide film 305 with an extremely thin thickness to have a smaller plasma energy. 51W/cm2 or more 1. A range of 54 W/cm 2 is more preferable. Further, the power density of the microwave means the microwave power supplied to each lem2 area of the transmission plate 28 (the same applies hereinafter). For example, when processing a wafer W having a diameter of 200 mm or more, it is preferable to have a microwave power of 1000 W or more and 5 000 W or less. In addition, the heating temperature of the wafer W is preferably set to be in the range of 200 ° C or more and 600 ° C or less, and is preferably set to 400 t or more (60 or less in the range of TC or less). Further, the treatment time of the plasma oxidation treatment is preferably in the range of 1 second or more and 90 seconds -20 to 201234480 or less, from the viewpoint of oxidizing only the surface layer of the yttria-nitride film 305. The inside of 1 second or more and 60 seconds or less is more preferable. Thus, the surface of the nitrided film 305 can be oxidized to a very thin thickness by performing the electric prize treatment in a short time. Further, the electric number is treated in the plasma nitriding with the plasma. After the oxidized ruthenium film plasma nitriding treatment is performed in the same processing chamber 1 , the residual in the processing chamber 1 is evacuated and exhausted, or the Ar gas is supplied after evacuation, and the gas is quickly exhausted. The above conditions are held as a recipe 53 in the control unit 50. Then, the processing controller 51 reads the recipe and supplies the components to the plasma device 100 such as the gas supply device 18 and the vacuum pump microwave generating device. 39, heater power supply 5a, etc. The signal is subjected to the plasma oxidation treatment. After the ruthenium oxide film 305 is modified as described above, the wafer W is carried out by the plasma processing apparatus 1 at the end, and the end of the circle W is completed. In this embodiment, the modified yttrium oxynitride film 3 0 5 B is oxidized by the plasma to replace the unstable nitrogen atom in the yttrium oxynitride film 305 with an oxygen atom, to the film. Therefore, the nitrogen concentration NC1 in the hafnium oxynitride film is lower than the nitrogen concentration Nco of the niobium oxide oxide 3〇5 after the plasma nitriding treatment (NC0> NC1). Further, it is not treated by oxidation. The modified nitrogen ruthenium nitride film 305A has a nitrogen NC2' which is almost equal to the nitrogen concentration Nc0 after the plasma nitriding treatment, ie, the nitrogen concentration N c 2 of the finally formed oxynitride cleavage film 3 0 5 A. The average nitrogen concentration of the niobium nitride film 3 05B is close to the target range of oxidative oxidation, and the nitrogen is subjected to the meso-treatment of the 24' to the S4, the crystal, and the borrower is the plasma concentration of the 3 5 5 B. With the method of oxygen-nitrogen concentration-21 - 201234480 degree NCT, the plasma nitriding treatment and step of step S2 are performed. The plasma oxidation treatment of ruthenium is preferred. In this embodiment, the plasma oxidation treatment of the plasma nitriding treatment step S3 of step S2 can be continuously performed in the same container of the plasma processing apparatus 1 That is, after the plasma nitriding treatment, there is no change in the nitrogen concentration over time in the yttrium oxide film 305 (naturally reduced, plasma oxidation treatment can be performed to achieve the stability of the yttrium oxide yttrium oxide film 305). Further, in the present embodiment, the plasma nitriding treatment of the step S2 is performed in a processing container different from the cluster tool having the multi-vacuum chamber structure similar to the nucleus system 200 (Fig. 9) to be described later, and the electric power of the S3 is performed. Slurry oxidation treatment is also possible. [Second Embodiment] Next, a modification method of the insulating film according to the second embodiment of the present invention will be described with reference to Figs. 8 to 13 . The insulating modification method of this embodiment may include a step of plasma nitriding the tantalum nitride film into a hafnium oxynitride film, and a modification step of oxidizing the niobium oxide film. Here, the plasma nitriding portion of the present embodiment can also be implemented by using the same plasma treatment 100 (Figs. 1 to 3) as used in the first embodiment. The oxidation annealing treatment can be carried out, for example, by using the annealing treatment shown in Fig. 8 . The annealing treatment apparatus 101 is a device which is controlled to be heated for a long time, and can be used, for example, as a high temperature S3 at a temperature of 800 to 1100 ° C in an oxidizing gas atmosphere. At the nitrogen plate at the time of nitrogenation, in the film of the step, the shape is retreated, and the device is equipped with a short film region-22-201234480, which can be oxidized and annealed in a short time. To use. In Fig. 8, reference numeral 71 denotes a cylindrical processing container. A lower heat generating unit 72' is disposed detachably from below the processing container 71, and is disposed above the processing container 71 so as to oppose the lower heat generating unit 72. The upper heat generating unit 74 is detachably provided. The lower heat generating unit 72' has a tungsten lamp 76 as a heating means that is arranged in plural on the upper surface of the water-cooling jacket 73. Similarly, the upper heat generating unit 74 has a water-cooling jacket 75' and a tungsten lamp 74 as a heating means arranged plurally below it. Further, the lamp is not limited to a tungsten lamp, and for example, a halogen lamp, a xenon lamp, a mercury lamp, a flash lamp or the like can be used. In this way, each of the tungsten lamps 76 provided in the processing container 71 facing each other is connected to a power source (not shown), and the control unit 50 adjusts the amount of electric power supplied therefrom to control the amount of heat generation. Further, the configuration of the control unit 50 is the same as that of the first embodiment (see Fig. 3). A support portion 77 for supporting the wafer W is provided between the lower heat generating unit 72 and the upper heat generating unit 74. The support portion 77' has a wafer support plug 77a for supporting the wafer W in a processing space in the processing container 71, and a wafer supporting plug for supporting the temperature of the wafer W during processing. The pad setting portion 77b of the thermal pad 78. Further, the support portion 77 is coupled to a rotation mechanism (not shown) so that the support portion 77 can rotate around the entire vertical axis. Thereby, the wafer W is rotated at a specific speed during processing, and the heat treatment is uniformized. Below the processing container 71, the thermoelectric thermometer 81' is placed in the heat treatment to pass the hot wire from the thermal pad 78 through the crucible 81a and the optical fiber 81b, -23-201234480 by the thermoelectric thermometer 81, and the wafer W can be indirectly grasped. temperature. Moreover, the temperature of the wafer W can be directly measured. Further, under the thermal pad 78, a quartz member 79 is interposed between the tungsten lamp 76 and the tungsten lamp 76 of the lower heat generating unit 72, as shown in the above-mentioned 埠8 1 a, which is provided in the quartz member 79 » It is also possible to have a 埠8 1 a. Further, above the wafer W, a quartz member 80a is interposed between the tungsten lamp 76 of the upper heat generating unit 74. Further, the quartz member 80b is also disposed on the inner peripheral surface of the processing container 71 so as to surround the wafer W. Further, a lifting plug (not shown) for supporting the wafer W to be lifted and lowered is provided through the thermal pad 78, and is used for loading and unloading the wafer W. A sealing member (not shown) is interposed between the lower heat generating unit 72 and the processing container 71, and between the upper heat generating unit 74 and the processing container 71, and the inside of the processing container 71 is made airtight. Further, a gas supply device 83 connected to the gas introduction pipe 82 is provided at a side portion of the processing container 71, and a flow rate control device (not shown) can introduce, for example, 〇2 gas into the processing space of the processing container 71. An oxidizing gas such as NO, N20, or H20 (produced by a steam generator from 02 and H2), or an inert gas such as a rare gas, if necessary. Further, in the lower portion of the processing container 71, an exhaust pipe 84 is provided, and the inside of the container 71 can be reduced in pressure by an exhaust device such as a vacuum pump (not shown). Each component of the annealing treatment apparatus 101 is configured to be connected to the control unit 50 in the same manner as the plasma processing apparatus 1A. Then, the recipe is called by the processing unit 51 by an instruction from the user interface 52, etc., and is executed by the processing controller 51 under the control of the processing controller 51, and the annealing processing apparatus 101 is performed at -24-201234480. Oxidation annealing treatment. For example, the controller 51 controls the amount of power supplied to each of the tungsten lamps 7 provided in the lower heat generating unit 72 and the upper portion 74, and the wafer thermal speed or heating temperature can be adjusted. Further, the flow rate or ratio of the oxidizing gas supplied from the gas supply medicine into the processing container 71 can be adjusted. Fig. 9 is a schematic structural view showing a substrate processing system in which a wafer argon is continuously subjected to an example of nitriding treatment and oxidation annealing treatment under vacuum conditions. This substrate processing system 200 is constructed as a multi-construction cluster tool. The substrate processing system 200 has, as a main configuration, four processing modules 10a, 10b, 101a for performing various processing, and for these processing modules 10a, 100b, 101a, 101b. The vacuum side transfer chamber 103 connected through G1 and the two load lock vacuum chambers l5, 105b connected to the vacuum transfer chamber 103 through the gate valve G2 are serially connected via the gate valve G3. Unit 107. The four processing modules 100a, 100b, 101a, 101b may also perform the same content processing, or may perform different processing separately. In this embodiment, the yttrium oxynitride film is formed by plasma nitriding treatment after the processing module 10a, 10 Ob, W, at 1 0 1 a, 1 0 1 b, The oxide film formed by the plasma nitridation treatment is further configured to perform an oxidation annealing treatment. The vacuum side transfer chamber 103, which is configured to be evacuated, is provided with a rational module l〇〇a, 100b, 101a, 101b or a load interlock by a heating unit W. 83 such as a plasma system 2 00 vacuum Room i circle W 101b, the gate valve is connected thereto, and the docking wafer is placed on the wafer, and the wafer module is nitrided. The wafer W is accepted for the vacuum chamber-25-201234480 105a, 105b. The transport device 109 of the first substrate transfer device. This conveying device 109 has a pair of conveying arm portions 111a and 111b that are disposed to face each other. Each of the transfer arm portions 111a and 11b is configured to be flexible and rotatable about the same rotation axis. Further, at the tip end of each of the transfer arm portions 1Ua, 111b, fork portions 113a and 113b for holding the wafer W for holding are provided. The transport device 109 is disposed between the processing modules 1a, 100b, 101a, and 101b or the processing module 10a, l in a state where the wafers W are placed on the forks 1 13a and 1 13b. The wafer W is transferred between the 〇b, 101a, 101b and the load lock chambers 105a, 105b. Inside the load lock chambers 5a, 105b, mounting stages 106a, 106b on which the wafers W are placed, respectively, are provided. The interlocking vacuum chambers 10a, 105b are configured to switch between a vacuum state and an open state of the atmosphere. The wafers W are transferred between the vacuum side transfer chamber 103 and the atmosphere side transfer chamber 1 1 9 (described later) through the mounts 16a, 106b of the load lock chambers 105a, 105b. The loading unit 107 has an atmosphere-side transfer chamber 119 that is provided as a transport device 117 that is a second substrate transport device that transports the wafer w, and three load ports that are adjacent to the air-side transfer chamber 1 19 And the other side surface provided in the atmospheric side transfer chamber 1 19 as the position measuring device 1 2 1 of the position measuring device for measuring the position of the wafer W. The atmosphere-side transfer chamber 119 has, for example, a circulation device (not shown) that allows nitrogen or clean air to flow downward, and maintains a clean environment. The atmosphere side transfer chamber 119 has a rectangular shape in plan view and a -26-201234480 guide rail 123 along the longitudinal direction thereof. The conveying device 117 is supported so as to be slidable on the guide rail 123. In short, the transport device 117 is configured to be transportable along the guide rail 123 in the X direction by a drive mechanism (not shown). This transfer device 117 has a pair of transfer arm portions 125a and 125b arranged in two stages. Each of the transfer arm portions 125a and 125b is configured to be bendable and rotatable. At the tip end of each of the transfer arm portions 125a and 125b, fork portions 127a and 127b as holding members for holding the wafer W and holding them are provided. In the state where the wafer W is placed on the fork portions 127a and 127b, the transfer device 1 is placed between the wafer cassette CR loaded with the LP, the load lock chambers 105a and 105b, and the position measuring device 1 2 1 . The wafer W is transferred. The wafer 匣CR can be placed by loading the 埠LP. The wafer cassette CR is configured such that the plurality of wafers W are placed in a plurality of stages at the same interval, and the rotary position plate 133 is rotated by a drive motor (not shown) and is provided. The outer peripheral position of the rotating plate 133 is an optical sensor 135 for detecting the peripheral portion of the wafer W. [Step of Wafer Processing] In the substrate processing system 200, the plasma nitridation treatment and the oxidation annealing treatment of the wafer w are performed in the following steps. First, one of the fork portions 12 7a and 127b of the transport device 117 of the atmospheric-side transfer chamber 119 is used to take out one wafer W from the wafer CR loaded in the LP, and after the position measuring device 121 is aligned, Move into the load lock chamber l〇5a (or l〇5b). In the state where the wafer W is placed on the stage l〇6a (or l〇6b), the lock chamber -27-201234480 locks the vacuum chamber l〇5a (or 105b), the gate valve G3 is closed, and the inside is decompressed and exhausted. It is in a vacuum state. Thereafter, the gate valve G2 is opened, and the wafer W is carried out by the load lock chamber 105a (or 105b) by the fork portions 113a, 113b of the transfer device 109 in the vacuum side transfer chamber 103. The wafer W transported by the loading interlocking vacuum chamber 105a (or 105b) by the transport device 109 is first carried into any one of the processing modules 100a and 100b, and the wafer W is plasma nitrided after the gate valve G1 is closed. Processing Next, the gate valve G1 is opened, and the wafer W on which the tantalum nitride film 305 is formed is carried into the processing module by the processing module 100a (or 100b) while maintaining the vacuum state by the transfer device 109. One of la, 101b. Next, the wafer W is subjected to an oxidation annealing treatment after the gate valve G1 is closed. Next, the gate valve G1 is opened, so that the wafer W on which the modified hafnium oxynitride film 305 is formed is transported by the processing module 101a (or 1 〇1 b ) by the transfer device 109 while maintaining the vacuum state. Move out and move into the load lock chamber l〇5a (or l〇5b). Next, in the opposite step to the above, the processed wafer W is loaded on the wafer 匣CR loaded with 埠LP, and the processing of one wafer W of the substrate processing system 200 is completed. Further, the arrangement of each processing device of the substrate processing system 200 may be any configuration as long as it can be processed efficiently. Further, the number of processing modules of the substrate processing system 200 is not limited to four, and may be five or more. Fig. 10 is a flow chart showing the flow of a modification step of a ruthenium oxide film as an insulating film, and Fig. 11 to Fig. 13 are flowcharts showing main steps thereof. -28-201234480 The method for modifying the insulating film of the present embodiment is carried out, for example, by the sequence of steps S11 to S15 shown in FIG. 1A, and the steps up to steps S11 and S12 can be performed with the first step. The steps S1 and S2 of the embodiment are implemented in the same manner. First, in step S11 of FIG. 10, the wafer W to be processed is carried into the plasma processing apparatus 1 by the transport device 109 in the vacuum side transfer chamber 103 (processing module 1 〇〇a or 1 0 0 b) ). Here, in the vicinity of the surface of the wafer W, a tantalum layer 301 and a yttrium oxide (Si 2 ) film 303 thereon are formed. Next, in step S12, as shown in Fig. 11, the yttrium oxide film 303 of the wafer W is subjected to plasma nitriding treatment. The yttrium oxide film 303 is nitrided by plasma nitridation to form a yttrium niobium oxide (SiON) film 305. In this plasma nitriding treatment, the decrease in the nitrogen concentration in the subsequent oxidation annealing treatment step (step S14) is estimated to be higher than the final target nitrogen concentration NCT, for example, a nitrogen concentration of 1 to 3%. The way to perform nitriding treatment. The conditions of the plasma nitriding treatment in the step S12 are not particularly limited as long as the nitrogen concentration NC0 can be achieved, and can be carried out under arbitrary conditions. Next, in step S13, the wafer W is transferred from the plasma processing apparatus 100 (processing module 100a or 100b) to the annealing processing apparatus 101 (processing module 10a or l). This transfer is carried out by the transfer device 109 in the vacuum side transfer chamber 103 while maintaining the vacuum state. Next, in step S14, as shown in Fig. 12, the surface of the tantalum oxide film 305 is oxidatively annealed using the annealing treatment apparatus 1 〇1. Oxidation annealing treatment 'From the viewpoint of suppressing the surface oxidation and nitrogen detachment of the yttrium oxynitride film 305, it is preferable to carry out the annealing process after the plasma nitridation treatment in step S12 is completed and the vacuum is maintained. The device 101 is implemented within 180 seconds from the end of the plasma nitridation -29-201234480 process, preferably within 60 seconds. In this step, for example, the surface layer of the tantalum oxide film 303 is oxidized in the depth direction. 5~l. The range of the Onm range is changed to a cerium oxide film of high oxygen concentration of 3 0 5 B. Thereby, as shown in FIG. 13, on the tantalum layer 310, as the tantalum oxide film 305, a tantalum oxide film 305A is formed, and the oxygen-enriched material is modified thereon. Bismuth oxide film 3 05 B. [Step of Oxidation Annealing Treatment] First, in the annealing treatment apparatus 101, after the wafer W is placed on the support portion 77 in the processing chamber 71, an airtight space is formed. Next, under the control of the processing controller 51, specific power is supplied to a heating element (not shown) of each of the tungsten lamps 76 of the lower heat generating unit 72 and the upper heat generating unit 74 by a power source (not shown), and the switch is turned on. (ON), each of the heat generating elements generates heat, and the generated heat energy reaches the wafer W through the quartz member 79 and the quartz member 80a, and the wafer W is rapidly heated from the upper and lower sides according to the conditions of the formulation (heating rate, heating temperature, gas flow rate, etc.). . By heating the wafer w and introducing an oxygen-containing gas such as helium gas at a specific flow rate by the gas supply device 83, the exhaust device (not shown) is operated to be exhausted by the exhaust pipe 84 to make the inside of the processing container 71 It is an oxidizing atmosphere in a reduced pressure state. In the oxidation annealing treatment, the entire support portion 77 is rotated about the vertical axis by a rotating mechanism (not shown), that is, rotated in the horizontal direction at a rotation speed of, for example, 80 μm, to rotate the wafer W. As a result, uniformity of heat supply to the wafer W is ensured. Further, the temperature of the wafer w can be indirectly measured by measuring the temperature of the thermal lining 78 by the thermoelectric thermometer 8 i during the heat treatment. The temperature data measured by the thermoelectric thermometer 81 of -30-201234480 is fed back to the processing controller 51, and the electric power supplied to the tungsten lamp 76 is adjusted when there is a difference from the set temperature of the recipe. The tungsten lamp 76 of the lower heat generating unit 72 and the upper heat generating unit 74 is turned off (powered off), and in the processing container 71, a washing gas such as nitrogen gas is supplied from a washing bowl (not shown), and the wafer is exhausted by the exhaust pipe 84 to cool the wafer. After W, move out. Further, the oxidation annealing treatment is preferably carried out by dividing the temperature rising step into several stages (e.g., three stages) as exemplified below. First, in the first temperature rising phase, the wafer W is heated up to the first temperature at which the emissivity of the wafer W becomes maximum. Here, the emissivity of the wafer W is set in response to the hafnium oxynitride film formed on the wafer W. Then, in the second temperature rising phase, the radiation rate of the wafer W becomes the maximum temperature (first temperature), and the wafer W is heated up to reach a second temperature lower than the processing temperature. Here, the second temperature X is defined in such a manner as to satisfy the following relationship: 3$(Τ-Χ)/Υ$7 (where T: the treatment temperature and Y: the third temperature increase rate per 1 second of the temperature rise temperature range) temperature. In the above relational expression, when (T-X)/Y is less than 3, the relationship between the third temperature rising stage and the temperature rising rate is too short, and overheating is likely to occur, which may increase the possibility of warpage or slippage of the wafer W, which is not preferable. On the other hand, when the above relational expression '(T-X) / Υ exceeds 7, the relationship between the third temperature rising stage and the temperature rising rate becomes too long, and the yield to the processing is lowered, so that it is not preferable. The second temperature X is preferably, for example, a temperature of 85 to 5% of the treatment temperature Τ. -31 - 201234480 In the third temperature rising phase, the substrate to be processed is heated by the second temperature until the processing temperature is reached. Then, at the processing temperature (e.g., 800 ° C to 1 100 t), an oxidation annealing treatment at a constant temperature is performed, and after the treatment for a specific period of time is completed, the temperature of the wafer W is lowered at a specific temperature decreasing rate to terminate the heat treatment. During the first temperature rising phase to the third temperature rising phase, the temperature rising rate in the second temperature rising stage is higher than the temperature rising rate in the third temperature increasing stage. This is because it is preferable to increase the rate of temperature increase as much as possible in the second temperature rising stage from the viewpoint of increasing the yield. However, when the temperature is raised to a treatment temperature at a high temperature increase rate, excessive heating may occur or a heating rate may be uneven in the surface of the substrate to be processed due to a severe temperature change, and thermal stress (strain) may be applied to the substrate to be processed. The occurrence of warpage or slippage of crystal defects occurs. Therefore, by the third temperature rising stage which is lower than the temperature increase rate in this stage after the second temperature rising stage, excessive heating or uniform heating rate in the surface of the substrate to be processed is prevented, and warpage or slippage of the substrate to be processed is prevented. The occurrence of the move. Further, it is preferable that the temperature increase rate in the third temperature rising stage is higher than the temperature increase rate in the first temperature rising stage. In the first temperature rising step, the wafer W is heated until the emissivity of the wafer W becomes the maximum temperature (first temperature), but warpage is likely to occur on the substrate to be processed when the first temperature is reached. In other words, when the rate of temperature rise in the first temperature rising step is too high, the heating rate in the plane of the substrate to be processed becomes uneven, and warpage or slippage occurs in the substrate to be processed. That is, it is preferable that the temperature increase rate in the first temperature rising stage is lower than the temperature increase rate in the third temperature rising stage, and it is preferable to set the temperature to the lowest in the three-step temperature rising stage -32 to 201234480. By the oxidative annealing treatment, 'Si_N bond or free Ν' of the unstable surface of the outermost surface of the film is formed by oxidizing the surface of the yttria 305 film 504 of the wafer w. The formation of an oxygen-rich hafnium oxynitride film 305 B is combined. As a result, the nitrogen in the niobium oxynitride film is held in a state where it is held without being detached, and the nitrogen concentration can be maintained constant and in a stable state. [Conditions of Oxidation Annealing Treatment] The oxygen-containing gas to be subjected to the oxidation annealing treatment is not particularly limited as long as it can form an oxidizing atmosphere in the processing container 71, and for example, 〇2 gas, NO gas, N20 gas, H20 (water) Vapor is preferable, and a rare gas such as Ar or an N 2 gas which is an inert gas may be mixed in these components. When a mixed gas of 〇2 gas and N2 gas is used, in order to improve the reforming effect, the volume ratio of the 02 gas flow rate: N2 gas flow rate is, for example, in the range of 10:1 to 1:2. good. In the method of the present invention, it is preferable to use an oxidation annealing treatment using 02 gas from the viewpoint of effectively suppressing the decrease in the nitrogen concentration in the hafnium oxynitride film over time. At this time, the flow rate of the oxygen-containing gas can be set at 〇. 5 mL / min ( seem ) or more in the range of 2000 mL / min ( seem ) or less ο In addition, the 'treatment pressure is from the viewpoint of effectively suppressing the decrease of the nitrogen concentration in the yttrium niobium oxide film with time, for example, 1 It is preferable that the range of 〇Pa or more is less than 15,000 Pa, and the range of 133 Pa or more i〇〇〇〇pa is preferably -33-201234480. In addition, the heating temperature of the wafer w is preferably in the range of 800 ° C or more and 1 100 ° C or less, and is preferably in the range of 900 ° C or more and 110 CTC or less. In addition, the treatment time of the oxidative annealing treatment is preferably in the range of from 1 sec to 5 Torr, from the viewpoint of oxidizing only the surface layer of the oxynitride film 305, and is set to 10 seconds or more. The range below seconds is better. Thus, the surface of the yttrium oxynitride film 305 can be extremely thinned by oxidation annealing in a short time. Further, it is possible to suppress the film formation (increased electric film thickness (EOT)) of the hafnium oxynitride film 305. The above conditions are held in the memory 53 of the control unit 50 as a recipe. Next, the processing controller 51 reads out the recipe and supplies the components of the annealing unit 10 1 such as the gas supply device 83, the exhaust device (illustration), the lower heat generating unit 72, and the upper heat generating unit 74 (tungsten). The lamp signal is sent out of the control signal, and the oxidation annealing treatment is performed under the required conditions. After the modified yttrium niobium oxide film 305 is performed as described above, the processed wafer W is processed by the annealing device 109 in the vacuum transfer chamber 103 in step S15 (processing module 1) 0 1 a or 1 0 1 b is carried out and stored in the wafer cassette CR of the loading cassette LP in the above-described order. In the present embodiment, the modified yttria yttria film 3 0 5 B is treated by oxidation annealing. The unstable nitrogen in the hafnium oxynitride film 305 is replaced by an oxygen atom and is released outside the film. Therefore, the nitrogen concentration NC1 in the niobium oxynitride 305B is higher than that of the nitriding after the plasma nitriding treatment. The nitrogen concentration Nco of the membrane 305 is lower (NC0> NC1). In addition, it has not been modified by the original membrane enthalpy-oxygen-34-201234480 annealing treatment. The nitrogen concentration NC2 of the deep lanthanum oxynitride film 3 0 5A is almost equal to the nitrogen concentration Nco after the plasma nitriding treatment. That is, the electric power of step S12 is performed so that the average nitrogen concentration NC2 of the finally formed niobium oxynitride film 305A and the nitrogen concentration NC1 of the lanthanum oxynitride film 305B are close to the target nitrogen concentration NCT. The slurry nitriding treatment and the oxidation annealing treatment in the step S14 are preferred. In the present embodiment, the plasma nitriding treatment in step S12 and the oxidation annealing treatment in step S14 can be continuously performed in the state in which the substrate processing system 200 maintains the vacuum condition. That is, after the plasma nitriding treatment, when the zirconium oxynitride film 305 has not produced a change in the nitrogen concentration over time (naturally reduced), the plasma oxidation treatment may be performed to obtain the yttria yttrium oxide film 3 0 5 The stability of the nitrogen concentration in the medium. Other configurations and effects of the present embodiment are the same as those of the first embodiment. [Third embodiment] Next, with reference to Figs. 14 to 18, the modification of the insulating film according to the third embodiment of the present invention will be described. Quality method. The method for modifying the insulating film of the present embodiment may include a step of plasma nitriding the tantalum nitride film to form a tantalum oxide film, and plasma nitriding the tantalum nitride film. The first modification step is followed by a second modification step of performing an oxidation annealing treatment on the hafnium oxynitride film. Here, the plasma nitriding treatment and the plasma oxidation treatment of the present embodiment can also be carried out using the same plasma processing apparatus 100 (Figs. 1 to 3) as used in the first embodiment. Oxidation -35 - 201234480 Annealing treatment can be carried out, for example, using the annealing treatment apparatus ιοί shown in Fig. 8. Further, the above processing ' can be performed in a cluster tool of a multi-vacuum chamber structure configured similarly to the substrate processing system 200 shown in Fig. 9 . Fig. 14 is a flow chart showing the flow of the reforming step of the ruthenium oxide film as the insulating film. Fig. 15 to Fig. 18 are flowcharts showing the main steps thereof. The method of modifying the insulating film of the present embodiment is carried out, for example, by the sequence of steps S21 to S26 shown in Fig. 14. Here, the steps 'steps from step S21 to step S23' can be carried out in the same manner as steps si to S3 of the first embodiment. First, in step S21 of Fig. 14, the wafer w to be processed is carried into the plasma processing apparatus 1 by the transport device 109 in the vacuum side transfer chamber 103 (processing module l〇〇a or l〇〇b) ). Here, in the vicinity of the surface of the wafer W, a tantalum layer 301 and a yttrium oxide (SiO 2 ) film 303 thereon are formed. Next, in step S22, as shown in Fig. 15, the yttrium oxide film 303 of the wafer W is subjected to plasma nitriding treatment. The yttrium oxide film 303 is nitrided by plasma nitridation to form a yttrium niobium oxide (SiON) film 305. In this plasma nitriding treatment, the decrease in the nitrogen concentration in the subsequent plasma oxidation treatment step (step S23) and the oxidation annealing treatment (step S25) is estimated to be higher than the final target nitrogen concentration nct, for example, 1~ The nitriding treatment is carried out in a manner of a nitrogen concentration of 3%. The conditions of the plasma nitridation treatment in the step S22 are not particularly limited as long as the nitrogen concentration Nco can be achieved, and can be carried out under arbitrary conditions. Next, in step S23, as shown in Fig. 16, the plasma treatment apparatus 100 is used to plasma-treat the surface of the tantalum oxide film 305. The plasma oxidation treatment is controlled from the viewpoint of suppressing oxidation and nitrogen detachment of the ruthenium oxynitride film 305 - 36-201234480, preferably after the plasma nitridation treatment in step S22 is completed, and then maintained in the processing vessel 1. The atmosphere is in a vacuum state, and is performed within 180 seconds from the end of the plasma nitriding treatment, preferably within 60 seconds. In this step, plasma is oxidized in the depth direction of the surface layer of the tantalum oxide film 305, for example. 5~l. The range of the Onm degree is modified to a yttrium oxynitride film 305B having a high oxygen concentration. Thereby, as shown in Fig. 17, on the sand layer 301, a tantalum nitride film 305A, and an oxygen-rich yttria film 305B modified thereon are formed. The conditions of the plasma oxidation treatment are the same as those of the step S1 3 of the first embodiment. Next, in step S24, the wafer W is transferred from the plasma processing apparatus 100 (processing module 10a or 100b) to the annealing processing apparatus 101 (processing module 10a or 101b). This transfer is performed by the transfer device 1〇9 in the vacuum side transfer chamber 103 while maintaining the vacuum state. Next, in step S25, as shown in Fig. 17, the surface of the tantalum oxide film 305 is oxidatively annealed using the annealing treatment apparatus 101. In this step, for example, the surface layer of the yttrium niobium oxide film 305 is oxidized by 0. 5 ~ l. The range of the Onm degree is modified to a yttrium oxynitride film 305B having a high oxygen concentration. Thereby, as shown in FIG. 18, on the sand layer 301, a hafnium oxynitride film 305 A is formed as a tantalum oxide film 305, and an oxygen-rich hafnium oxynitride film 3 which is modified thereon is formed. 05B. The conditions of the oxidation annealing treatment are the same as those in the second embodiment. After the modified yttrium niobium oxide film 305 is performed as described above, the processed wafer W is processed by the annealing device 101 (the processing module l〇la or the transfer device 109 in the vacuum transfer chamber 103) in step S26. 101b) -37- 201234480 Move out and store in the above-mentioned order on the wafer cassette CR loaded in the LP. In this embodiment, the surface of the yttria film 305 of the wafer W is extremely thinly oxidized by a combination of a plasma oxidation treatment and an oxidative annealing treatment, instead of the Si-N in the unstable state on the outermost surface of the film. The combined or free N is formed by Si-germanium to form an oxygen-rich cerium oxide oxide film 305B. Thereby, the nitrogen in the niobium oxynitride film is held without being separated, and the nitrogen concentration can be maintained constant and in a stable state. In the present embodiment, in the modified yttrium oxynitride film 305B, the combination of the plasma oxidation treatment and the oxidative annealing treatment causes the unstable nitrogen atom in the yttrium oxynitride film 305 to be replaced with Oxygen atoms are released out of the membrane. Therefore, the nitrogen concentration NC1 in the hafnium oxynitride film 305B is lower than the nitrogen concentration Nco of the hafnium oxynitride film 305 after the plasma nitriding treatment (Nco> Nci). Further, the nitrogen concentration NC2 of the deep niobium oxynitride film 305A which is not modified by the plasma oxidation treatment and the oxidation annealing treatment is almost equal to the nitrogen concentration Nco after the plasma nitriding treatment. That is, the plasma nitrogen of step S22 is performed so that the average nitrogen concentration NC2 of the finally formed niobium oxynitride film 3 0 5A and the nitrogen concentration NC1 of the hafnium oxynitride film 305B are close to the target nitrogen concentration NCT. The treatment, the plasma oxidation treatment in step S23, and the oxidation annealing treatment in step S25 are preferred. In the present embodiment, the plasma nitriding treatment in the step S22, the plasma oxidation treatment in the step S23, and the oxidation annealing treatment in the step S25 can be continuously performed in the state in which the substrate processing system 200 maintains the vacuum condition. That is, after the plasma nitriding treatment, when the zirconium oxynitride film 305 has not produced a change in the nitrogen concentration over time (naturally reduced), the plasma oxidation can be performed at -38-201234480 and the oxidation annealing treatment is performed. The niobium oxynitride film 305 is stabilized. Further, in the present embodiment, as shown in FIG. 14, after the plasma nitriding treatment, the plasma oxidation in the step S23 is performed to perform the oxidation annealing treatment in the step S25, but after the step processing, the oxidation annealing treatment is performed first. Then it can be done. In addition, in the plasma nitriding treatment in step S22, the plasma oxidation treatment, the processing vessel can be changed to perform the plasma nitriding treatment of S22, and the plasma oxidation treatment in the processing module 100a is performed in the processing module 1 〇〇b. Also. The other configurations and effects of this embodiment are the same as those of the first embodiment. [Operation] After the yttrium oxide film is subjected to plasma nitriding treatment, Si-N bond or nitrogen atom in an unstable state is contained, and the film is gradually removed from the ruthenium oxynitride film over time. The inventors of the present invention thought that nitrogen having a reduced nitrogen concentration in the ruthenium oxynitride film at the time of plasma nitridation is easily cut off due to Si-N bonding, and is instead taken into the film and replaced with Si. - The reason for the combination of Ο. Here, in the state after the plasma nitriding treatment (for example, within 180 seconds), the surface layer of the yttrium niobium oxide film is subjected to plasma oxidation treatment and/or oxidation annealing treatment. The concentration of the step S 2 2 is electrically treated, after which the plasma nitrogen of S22 is plasma-oxidized at step S23. For example, the step is performed, step S23 and the second embodiment of the hafnium oxynitride film. These nitrogen atoms are released (after nitrogen decontamination, there will be a detachment phenomenon, which is the reverse of the idea of oxygen atoms in the circumference, and the Si-N combination of the surface layer-39-201234480 is forced to be maintained in the short-term maintenance of the vacuum. Conversion to Si-Ο bonding, while promoting the release of nitrogen atoms in the free state out of the film. By reforming, a thin oxygen-rich (Si-Ο bonded to dense) is formed near the surface layer of the yttria-nitride film. Modification layer, which functions as a barrier function, inhibits the release of nitrogen atoms from the deeper layer of the modified layer in the yttrium niobium oxide film. That is, it can prevent long-term persistence by modifying the treatment. The decrease in nitrogen concentration (nitrogen detachment phenomenon). In addition, the modification treatment is accompanied by a decrease in the nitrogen concentration near the surface of the ruthenium oxynitride film, but it can be nitrided by plasma in advance by estimating the reduction range. The treatment step is pre-mixed with a large amount of nitrogen, and the ruthenium oxynitride film after the reforming step is controlled to the target nitrogen concentration. Next, the experimental data which is the basis of the present invention will be described. Test Example 1: By using dry type Method 3 is formed of a thickness. A 2 nm SiO 2 film was subjected to plasma nitriding treatment using the plasma processing apparatus having the same configuration as that of the plasma processing apparatus 100 shown in Fig. 1 to form four stages of different nitrogen concentrations (nitrogen concentration: high, medium-high). 'Medium-low, low' Si ON film [plasma nitriding treatment conditions] Hydrogen flow rate · 500 or 1000 mL/min (sccm) N2 Gas flow rate: 20 〇 mL/min (see) Processing pressure: 35 Pa (260 mTorr)

載置台溫度：400°C -40- 201234480Mounting table temperature: 400 ° C -40 - 201234480

微波功率：1 900W 處理時間：5秒、3 0秒、1 1 5秒或3 0 0呑 將各SiON膜放置於27°C氛圍，測定經 濃度。結果顯不於圖19。圖19之縱軸顯示 氮濃度，橫軸顯示經過時間。由此結果，顯 的減少傾向，在初期氮濃度越低時越小，越 情形，應該是在SiON膜表面Si-N結合多的 由外部氧而氧化，Si-N結合變化爲Si-Ο結 往膜外放出的結果。 其次，對圖19中的氮濃度爲「中-高」 使用與圖1所示的電漿處理裝置100同樣構 裝置，以下列2種條件實施電漿氧化處理， 電漿氮化處理之後的初期之氮濃度的經時性 ，電漿氧化處理，接著電漿氮化處理在180 處理容器內實施。結果顯示於圖20。圖20 由電漿氮化處理結束起之氮濃度的減少率（ 由電漿氮化處理步驟結束起經過1小時後的 。此外，圖21依不同處理條件顯示電漿氮 16小時後之SiON膜的氮濃度、經過1小時 的氮濃度的差分（縱軸）°又’圖20及圖2 」，意味著不進行電漿氧化處理而保持電漿 態。 〔條件1 :高氧化速率〕 時性之膜中氮 SiON膜中的 示膜中氮濃度 高時越大。此 場合，容易藉 合，而游離氮 之SiON膜， 成的電漿處理 評估氮濃度對 減少率。此處 秒以內於同一 之縱軸，顯示 %)，橫軸爲 氮濃度（％) 化處理後經過 後之SiON膜 :1中的「標準 氮化處理的狀 -41 - 201234480Microwave power: 1 900 W Treatment time: 5 seconds, 30 seconds, 1 15 seconds, or 300 Å Each SiON film was placed in an atmosphere at 27 ° C, and the concentration was measured. The results are not as shown in Figure 19. The vertical axis of Fig. 19 shows the nitrogen concentration, and the horizontal axis shows the elapsed time. As a result, the tendency to decrease is small, and the smaller the initial nitrogen concentration is, the smaller the situation is. The Si-N bond on the surface of the SiON film is oxidized by external oxygen, and the Si-N bond is changed to Si-Ο junction. The result of release to the outside of the membrane. Next, the nitrogen concentration in Fig. 19 is "medium-high". The apparatus is configured in the same manner as the plasma processing apparatus 100 shown in Fig. 1, and the plasma oxidation treatment is carried out under the following two conditions, and the initial stage after the plasma nitriding treatment is performed. The temporality of the nitrogen concentration, the plasma oxidation treatment, and the plasma nitridation treatment were carried out in a 180 treatment vessel. The results are shown in Figure 20. Fig. 20 Reduction rate of nitrogen concentration from the end of the plasma nitriding treatment (after 1 hour from the end of the plasma nitriding treatment step. Further, Fig. 21 shows the SiON film after 16 hours of plasmonic nitrogen according to different treatment conditions. The difference between the nitrogen concentration and the nitrogen concentration over one hour (vertical axis) and 'Fig. 20 and Fig. 2' means that the plasma state is maintained without plasma oxidation treatment. [Condition 1: High oxidation rate] In the film, the nitrogen concentration in the film of nitrogen in the SiON film is higher. In this case, it is easy to borrow, and the plasma of the free nitrogen SiON film is used to evaluate the nitrogen concentration to reduce the rate. The vertical axis shows %), and the horizontal axis is the nitrogen concentration (%). After the treatment, the SiON film: 1 in the standard nitriding treatment -41 - 201234480

Ar 氣體流量：2000mL / min ( seem) 〇2 氣體流量：20mL / min ( seem) 流量百分率（02/Ar+02):約1% 處理壓力：127Pa( 95 0mTorr)Ar gas flow rate: 2000mL / min (see) 〇2 gas flow rate: 20mL / min (see) Flow percentage (02/Ar+02): about 1% Processing pressure: 127Pa (95 0mTorr)

載置台溫度：400°C 微波功率：2750W 微波功率密度：0.97W/cm2 (透過板之面積每lem2) 處理時間：3秒 〔條件2 :低氧化速率〕Stage temperature: 400°C Microwave power: 2750W Microwave power density: 0.97W/cm2 (area per lem2 through the plate) Processing time: 3 seconds [Condition 2: Low oxidation rate]

Ar 氣體流量：2000mL/min(sccm) 〇2 氣體流量：300mL/min(sccm) 流量百分率（02/Ar+02):約13% 處理壓力：3 3 3 Pa( 2500mTorr)Ar gas flow rate: 2000 mL/min (sccm) 〇2 gas flow rate: 300 mL/min (sccm) Flow percentage (02/Ar+02): about 13% Treatment pressure: 3 3 3 Pa (2500 mTorr)

載置台溫度：400°C 微波功率：2750W 微波功率密度：〇.97W/cm2 (透過板之面積每lem2) 處理時間：3秒 由圖2〇及圖21，確認了對SiON膜，不論進行高氧 化速率之條件1及低氧化速率之條件2之任一方的電漿氧 化的場合，都比不進行電漿氧化處理的場合，更能抑制氮 濃度的減少。總之，藉由對SiON膜進行電漿氧化處理， 抑制了氮濃度之經時性減少。特別是在處理壓力爲3 33 Pa 、氧氣體之體積流量比率爲1 3 %的條件2，即使同樣的經 -42- 201234480 過時間也可見到圖點的位置於圖20中的上方大幅改變。 亦即，確認了在供改質處理SiON膜之電漿氧化處理，處 理壓力以127Pa以上爲較佳，3 3 3 Pa以上更佳，所有處理 氣體中的氧流量比，以1 %以上爲佳’ 1 3 %以上爲更佳。 此外，圖22顯示電漿氧化處理前後之SiON膜中的 XPS (X線光電子分光）分析的結果。圖22之縱軸顯示膜 中的氮濃度及氧濃度有相關之強度，橫軸顯示膜中的深度 。由此圖22，可知藉由電漿氧化處理，在膜表面起極淺層 的0.5nm以下的深度處氧濃度增加，相反的氮濃度則減少 試驗例2 對藉由乾式氧化法形成的厚度6nm的Si02膜，使用 與圖1所示的電漿處理裝置1〇〇同樣構成的電漿處理裝置 ，以下列條件進行電漿氮化處理，形成SiON膜。 〔電漿氮化處理條件〕 空氣流量：l〇〇〇mL/min(sccm) 氮氣流量：2 0 0 m L / m i n ( s c c m ) 處理壓力：35Pa( 260mTorr) 載置台溫度：400°C 微波功率：1 900W 處理時間：1 1 5秒 對此SiON膜，以如下所示之條件進行了退火處理。 -43- 201234480 此處，退火處理，接在電漿氮化處理後，在維持於真空的 情況下往與圖8所示的退火處理裝置101同樣構成的裝置 搬入被形成SiON膜的晶圓W，在180秒以內完成搬送。 〔退火條件1 : 〇2退火〕 〇2 氣體流量：2L/min ( slm) 〔退火條件2 : 02 · N2退火〕 〇2氣體流量：N2氣體流量比=1 : 1 〇2 氣體流量：lL/min(slm) N2 氣體流量：lmL/min(sccm) 〔退火條件3 : N2退火〕 N2 氣體流量：2mL/min ( seem) 〔共通條件〕 處理壓力：1 33Pa ( ITorr ) 、667Pa ( 5Torr )或 9998Pa ( 75Torr) 處理溫度：900°C、1050°C、或 ll〇〇°C 處理時間：1 5秒 圖23係顯示電漿氮化處理後經過1 00小時後的氮濃 度對處理之後的SiON膜的氮濃度之減少率（縱軸）與退 火處理的條件之關係。此外，圖23中的「標準」，意味 著不進行退火處理而保持在電漿氮化處理後的狀態的場合 -44 - 201234480 。可知爲了要把氮氣濃度的減少率抑制在目標値之1 %以 下，與其採退火條件3之N2退火，不如退火條件1之02 退火或者退火條件2之02·Ν2退火爲較佳。此外，在退 火條件1之〇2退火之中，確認了處理壓力及處理溫度越 高，抑制氮濃度的減少的效果越大。 如以上所述，對於電漿氮化處理後的SiON膜，確認 了藉由進行電漿氧化處理或氧化退火處理，可以改善氧化 氮化矽膜的膜質，抑制氮脫離。此外，由前述結果可以理 解對於電漿氮化處理後的SiON膜，進行電漿氧化處理與 氧化退火處理雙方亦可》 本發明之絕緣膜之改質方法，藉由利用於例如MOSFET 等之MOS構造裝置的閘極絕緣膜的改質，可以有效果地 抑制洩漏電流的增加或硼的穿透，同時可抑制晶圓之間/ 批次之間的閘極絕緣膜的氮濃度的差異，改善半導體裝置 之可信賴性與生產率。 以上，說明了本發明的實施型態，但本發明不受限於 前述實施型態，可以進行種種變形。例如，在前述實施型 態，於電漿氧化處理使用RLSA方式的微波電漿處理裝置 ，但是也可以使用例如使用ICP電漿方式、ECR電漿方式 、表面反射波電漿方式、磁控管電漿方式等其他方式的電 漿處理裝置。此外，對於氧化退火處理’也不限於枚葉式 (single wafer processing)之退火處理裝置，亦可使用其 他方式的退火處理裝置，例如批次式之熱氧化爐等。 -45- 201234480 【圖式簡單說明】 圖1係顯示可在本發明之第1實施型態使用的電漿處 理裝置之一例之槪略剖面圖。 圖2係顯示平面天線的構造圖。 圖3係顯示控制部的構成例之說明書。 圖4係顯示相關於本發明之第1實施型態之絕緣膜之 改質方法的步驟之流程圖。 圖5係第1實施型態之電漿氮化處理步驟之說明圖。 圖6係第1實施型態之電漿氧化處理步驟之說明圖。 圖7係第1實施型態之改質處理後的氧化氮化矽膜之 說明圖。 圖8係顯示可在本發明之第2實施型態使用的退火處 理裝置之一例之槪略剖面圖。 圖9係可在本發明之第2實施型態使用的機板處理系 統之槪略構成之平面圖。 圖1 〇係顯示相關於本發明之第2實施型態之絕緣膜 之改質方法的步驟之流程圖。 圖1 1係第2實施.型態之電漿氮化處理步驟之說明圖 〇 圖1 2係第2實施型態之氧化退火步驟之說明圖。 圖1 3係第2實施型態之改質處理後的氧化氮化矽膜 之說明圖》 圖1 4係顯示相關於本發明之第3實施型態之絕緣膜 之改質方法的步驟之流程圖。 -46 - 201234480 圖15係第3實施型態之電漿氮化處理步驟之說明圖 〇 圖16係第3實施型態之電漿氧化處理步驟之說明圖 〇 圖17係第3實施型態之氧化退火步驟之說明圖。 圖18係第3實施型態之改質處理後的氧化氮化矽膜 之說明圖。 圖19係於試驗例1，顯示電漿氮化處理後之SiON膜 中的氮濃度與經過時間之關係圖。 圖20係於試驗例1，顯示電漿氮化處理步驟結束之後 經過1個小時後的Si ON膜中的氮濃度減少率與氮濃度之 關係圖。 圖2 1係電漿氮化處理後經過1 6小時之後的SiON膜 的氮濃度，與經過1小時之後的SiON膜之氮濃度的差分 (縱軸）依不同處理條件所示之圖。 圖22係顯示電漿氧化處理前後之SiON膜中的氮原子 及氧原子之XPS分析圖。 圖23係顯示電漿氮化處理後經過100小時後的氮濃 度對處理之後的SiON膜的氮濃度之減少率（縱軸）與退 火處理的條件之關係圖。 【主要元件符號說明】 1 :處理容器 2 :載置台 -47- 201234480 3 :支撐構件 5 :加熱器 1 2 :排氣管 15 :氣體導入部 1 6 :搬出入口 1 8 :氣體供給裝置 19a :惰性氣體供給源 1 9 b :含氮氣體供給源 19c :含氧氣體供給源 24 :真空泵 28 :透過板 2 9 :密封構件 3 1 ·平面天線 3 2 :微波放射孔 37 :導波管 37a :同軸導波管 37b :矩形導波管 39 :微波產生裝置 5 0 :控制部 5 1 :處理控制器 5 2 :使用者界面 5 3 :記憶部 100 :電漿處理裝置 1 0 1 :退火處理裝置 -48 201234480 200 :基板處理系統 3 0 1 :矽層 3 0 3，3 0 5 :氧化矽膜 W :半導體晶圓（基板） -49Mounting table temperature: 400 °C Microwave power: 2750W Microwave power density: 〇.97W/cm2 (permeating plate area per lem2) Processing time: 3 seconds From Fig. 2〇 and Fig. 21, it is confirmed that the SiON film is high. In the case where the plasma of either of the oxidation rate condition 1 and the low oxidation rate condition 2 is oxidized, the reduction of the nitrogen concentration can be suppressed more than when the plasma oxidation treatment is not performed. In summary, by the plasma oxidation treatment of the SiON film, the decrease in the temporal concentration of the nitrogen concentration is suppressed. In particular, in the condition 2 in which the treatment pressure is 3 33 Pa and the volume flow ratio of the oxygen gas is 13%, even if the same time passes through -42 - 201234480, the position of the dot is largely changed in the upper direction in Fig. 20 . That is, it is confirmed that the plasma oxidation treatment is performed on the SiON film for reforming, and the treatment pressure is preferably 127 Pa or more, more preferably 3 3 3 Pa or more, and the oxygen flow ratio in all the treatment gases is preferably 1% or more. '1 3 % or more is better. Further, Fig. 22 shows the results of XPS (X-ray photoelectron spectroscopy) analysis in the SiON film before and after the plasma oxidation treatment. The vertical axis of Fig. 22 shows the correlation between the nitrogen concentration and the oxygen concentration in the film, and the horizontal axis shows the depth in the film. 22, it can be seen that the oxygen concentration increases at a depth of 0.5 nm or less in the extremely shallow layer on the surface of the film by the plasma oxidation treatment, and the opposite nitrogen concentration decreases in Test Example 2 to a thickness of 6 nm formed by the dry oxidation method. The SiO 2 film was subjected to plasma nitriding treatment under the following conditions using a plasma processing apparatus having the same configuration as that of the plasma processing apparatus 1 shown in Fig. 1 to form an SiON film. [plasma nitriding treatment conditions] Air flow rate: l〇〇〇mL/min (sccm) Nitrogen flow rate: 2 0 0 m L / min (sccm) Processing pressure: 35Pa (260mTorr) Stage temperature: 400°C Microwave power : 1 900 W Treatment time: 1 1 5 seconds The SiON film was annealed under the conditions shown below. -43-201234480 Here, the annealing treatment is performed after the plasma nitriding treatment, and while maintaining the vacuum, the apparatus having the same configuration as the annealing processing apparatus 101 shown in FIG. 8 is carried into the wafer W on which the SiON film is formed. , completed within 180 seconds of the transfer. [annealing condition 1: 〇2 annealing] 〇2 gas flow rate: 2L/min (slm) [annealing condition 2: 02 · N2 annealing] 〇2 gas flow rate: N2 gas flow ratio = 1: 1 〇2 gas flow rate: lL/ Min(slm) N2 gas flow rate: lmL/min (sccm) [annealing condition 3: N2 annealing] N2 gas flow rate: 2mL/min (see) [common conditions] Treatment pressure: 1 33Pa ( ITorr ), 667Pa ( 5Torr ) or 9998Pa (75Torr) Processing temperature: 900°C, 1050°C, or ll〇〇°C Processing time: 15 seconds Figure 23 shows the nitrogen concentration after 100 MPa of plasma nitriding treatment and the SiON after treatment. The relationship between the reduction rate of the nitrogen concentration of the film (vertical axis) and the conditions of the annealing treatment. Further, the "standard" in Fig. 23 means that the state after the plasma nitriding treatment is maintained without annealing treatment - 44 - 201234480. It is understood that in order to suppress the reduction rate of the nitrogen gas concentration to less than 1% of the target enthalpy, it is preferable to anneal to the N2 of the annealing condition 3, and to anneal under the annealing condition 1 of 02 or the annealing condition 2 of 02 Ν2. Further, in the annealing after the annealing condition 1, the higher the treatment pressure and the treatment temperature, the greater the effect of suppressing the decrease in the nitrogen concentration. As described above, it was confirmed that the plasma oxidation treatment or the oxidation annealing treatment of the SiON film after the plasma nitriding treatment can improve the film quality of the yttrium nitride nitride film and suppress the nitrogen detachment. In addition, it can be understood from the above results that both the plasma oxidation treatment and the oxidation annealing treatment can be performed on the SiON film after the plasma nitriding treatment, and the modification method of the insulating film of the present invention can be utilized by using a MOS such as a MOSFET. The modification of the gate insulating film of the structural device can effectively suppress the increase of the leakage current or the penetration of boron, and at the same time suppress the difference in the nitrogen concentration of the gate insulating film between the wafers/batch, and improve The reliability and productivity of semiconductor devices. The embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made. For example, in the foregoing embodiment, the RLSA type microwave plasma processing apparatus is used for the plasma oxidation treatment, but it is also possible to use, for example, an ICP plasma method, an ECR plasma method, a surface reflected wave plasma method, or a magnetron tube. Other types of plasma processing equipment such as slurry. Further, the annealing treatment apparatus for the oxidation annealing treatment is not limited to the single wafer processing, and other annealing treatment apparatuses such as a batch type thermal oxidation furnace or the like may be used. [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing an example of a plasma processing apparatus which can be used in the first embodiment of the present invention. Fig. 2 is a structural view showing a planar antenna. Fig. 3 is a view showing a configuration example of a control unit. Fig. 4 is a flow chart showing the steps of a modification method relating to the insulating film of the first embodiment of the present invention. Fig. 5 is an explanatory view showing a step of plasma nitriding treatment of the first embodiment. Fig. 6 is an explanatory view showing a plasma oxidation treatment step of the first embodiment. Fig. 7 is an explanatory view showing a ruthenium oxynitride film after the modification treatment of the first embodiment. Fig. 8 is a schematic cross-sectional view showing an example of an annealing treatment apparatus which can be used in the second embodiment of the present invention. Fig. 9 is a plan view showing a schematic configuration of a machine plate processing system which can be used in the second embodiment of the present invention. Fig. 1 is a flow chart showing the steps of a modification method of an insulating film according to a second embodiment of the present invention. Fig. 11 is an explanatory view of a plasma nitriding treatment step of the second embodiment. Fig. 1 2 is an explanatory view of an oxidation annealing step of the second embodiment. Fig. 1 is an explanatory view of a ruthenium oxynitride film after the modification treatment of the second embodiment. Fig. 1 is a flow chart showing the steps of the modification method of the insulating film according to the third embodiment of the present invention. Figure. -46 - 201234480 FIG. 15 is an explanatory diagram of a plasma nitriding treatment step of the third embodiment. FIG. 16 is an explanatory view of a plasma oxidation treatment step of the third embodiment. FIG. 17 is a third embodiment. An illustration of the oxidation annealing step. Fig. 18 is an explanatory view showing a ruthenium oxynitride film after the modification treatment of the third embodiment. Fig. 19 is a graph showing the relationship between the nitrogen concentration in the SiON film after the plasma nitriding treatment and the elapsed time in Test Example 1. Fig. 20 is a graph showing the relationship between the nitrogen concentration reduction rate and the nitrogen concentration in the Si ON film after one hour after the completion of the plasma nitriding treatment step in Test Example 1. Fig. 2 is a graph showing the difference between the nitrogen concentration of the SiON film after the plasma nitriding treatment for 16 hours and the nitrogen concentration of the SiON film after one hour (vertical axis) according to different processing conditions. Fig. 22 is a view showing an XPS analysis of nitrogen atoms and oxygen atoms in a SiON film before and after plasma oxidation treatment. Fig. 23 is a graph showing the relationship between the nitrogen concentration of the SiON film after the treatment of the plasma nitriding treatment for 100 hours and the reduction ratio of the nitrogen concentration of the SiON film (vertical axis) and the conditions of the annealing treatment. [Description of main component symbols] 1 : Processing container 2 : Mounting table - 47 - 201234480 3 : Support member 5 : Heater 1 2 : Exhaust pipe 15 : Gas introduction portion 1 6 : Carry-out port 1 8 : Gas supply device 19a : Inert gas supply source 1 9 b : nitrogen-containing gas supply source 19c : oxygen-containing gas supply source 24 : vacuum pump 28 : transmission plate 2 9 : sealing member 3 1 · planar antenna 3 2 : microwave radiation hole 37 : waveguide 37a: Coaxial waveguide 37b: rectangular waveguide 39: microwave generating device 50: control unit 5 1 : processing controller 5 2 : user interface 5 3 : memory unit 100 : plasma processing device 1 0 1 : annealing device -48 201234480 200 : Substrate processing system 3 0 1 : germanium layer 3 0 3, 3 0 5 : hafnium oxide film W: semiconductor wafer (substrate) -49

Claims (1)

201234480 七、申請專利範園： 1. 一種絕緣膜之改質方法，其特徵爲具備： 電漿氮化處理露出於被處理體的表面之氧化矽膜，形 成氧化氮化矽膜之氮化處理步驟，及 氧化處理前述氧化氮化矽膜之表面之改質步驟； 前述氮化處理步驟結束後，在維持真空氛圍的狀態下 ，接著開始前述改質步驟。 2. 如申請專利範圍第1項之絕緣膜之改質方法，其中 在前述氮化處理步驟之後的氧化氮化矽膜之膜中氮濃 度爲NC0，前述改質步驟後的氧化氮化矽膜之膜中氮濃度 的目標値爲NCT時，以成爲Nco > NCT的方式進行前述電 漿氮化處理。 3 ·如申請專利範圍第1項之絕緣膜之改質方法，其中 前述改質步驟，包含根據藉由具有複數孔之平面天線 對處理容器內導入微波而產生處理氣體的電漿之電漿處理 裝置所進行的電漿氧化處理。 4. 如申請專利範圍第3項之絕緣膜之改質方法，其中 對一個被處理體，使前述電漿氮化處理及前述電漿氧 化處理，在前述電漿處理裝置之同一處理容器內連續地進 行。 5. 如申請專利範圍第4項之絕緣膜之改質方法，其中 前述電漿氮化處理之後，前述電漿氧化處理之前，以 抽真空或者掃氣（purge )處理除去殘留於前述處理容器 內的氮氣。 -50- 201234480 6. 如申請專利範圍第4或5項之絕緣膜之改質方法， 其中 前述電漿氧化處理之後，作爲前述改質步驟之一部分 ，進而包含在氧化氛圍下使被處理體在8 00 °C以上1100°C 以下的範圍內之溫度進行退火處理的步驟。 7. 如申請專利範圍第3至5項之任一項之絕緣膜之改 質方法，其中 前述電漿氧化處理的處理壓力爲67Pa以上1 3 3 3 Pa以 下的範圍內。 8 ·如申請專利範圍第3至5項之任一項之絕緣膜之改 質方法，其中 前述電漿氧化處理，係使氧氣體對全部處理氣體之體 積流量比率在0.1 %以上20%以下的範圍內進行的。 9. 如申請專利範圍第3至5項之任一項之絕緣膜之改 質方法，其中 前述電漿氧化處理的處理溫度，爲200°C以上600°C 以下之範圍內。 10. 如申請專利範圍第3至5項之任一項之絕緣膜之 改質方法，其中 前述電漿氧化處理的處理時間，爲1秒以上90秒以 下之範圍內。 11. 如申請專利範圍第1或2項之絕緣膜之改質方法 ，其中 藉由具有複數孔的平面天線對處理容器內導入微波而 -51 - 201234480 產生處理氣體的電漿之電漿處理裝置來進行前述氮化處理 步驟， 藉由在氧化氛圍使被處理體在800°C以上1100°C以下 的範圍內之溫度進行退火處理的退火裝置來進行前述改質 步驟。 12. 如申請專利範圍第11項之絕緣膜之改質方法，其 中 前述退火處理的處理時間，爲1 0秒以上5 0秒以下的 範圍內。 13. 如申請專利範圍第12項之絕緣膜之改質方法，其 中 被處理體由前述電漿處理裝置往前述退火裝置之移送 是在真空狀態下進行的。 1 4 ·如申請專利範圍第丨至5項之任一項之絕緣膜之 改質方法，其中 前述氧化氮化矽膜爲MOS構造裝置之閘極絕緣膜。 -52-201234480 VII. Application for Patent Park: 1. A method for modifying an insulating film, characterized in that it has: a cerium oxide film which is exposed to the surface of the object to be treated by plasma nitriding, and a nitriding treatment for forming a cerium oxide film And a step of modifying the surface of the ruthenium oxynitride film by oxidation treatment; after the nitriding treatment step is completed, the reforming step is started in a state where the vacuum atmosphere is maintained. 2. The method for modifying an insulating film according to claim 1, wherein the nitrogen concentration in the film of the cerium oxide film after the nitriding treatment step is NC0, and the cerium oxide film after the modifying step When the target 値 of the nitrogen concentration in the film is NCT, the plasma nitriding treatment is performed so as to be Nco > NCT. 3. The method for modifying an insulating film according to claim 1, wherein the modifying step comprises a plasma treatment of a plasma for generating a processing gas by introducing microwaves into the processing container by a planar antenna having a plurality of holes. Plasma oxidation treatment performed by the device. 4. The method for modifying an insulating film according to claim 3, wherein the plasma nitriding treatment and the plasma oxidation treatment are performed continuously in the same processing container of the plasma processing apparatus for a processed object Conducted. 5. The method for modifying an insulating film according to claim 4, wherein after the plasma nitriding treatment, the plasma is removed by vacuum or purging before being removed in the processing container. Nitrogen. -50- 201234480 6. The method for modifying an insulating film according to claim 4 or 5, wherein after the plasma oxidation treatment, as part of the modifying step, further comprising the object to be treated under an oxidizing atmosphere The annealing step is performed at a temperature in the range of 8 00 ° C or more and 1100 ° C or less. 7. The method of modifying an insulating film according to any one of claims 3 to 5, wherein the processing pressure of the plasma oxidation treatment is in a range of 67 Pa or more and 1 3 3 3 Pa or less. The method for modifying an insulating film according to any one of claims 3 to 5, wherein the plasma oxidation treatment is such that a volume flow ratio of the oxygen gas to the entire processing gas is 0.1% or more and 20% or less. Conducted within the scope. 9. The method of modifying an insulating film according to any one of claims 3 to 5, wherein the processing temperature of the plasma oxidation treatment is in a range of from 200 ° C to 600 ° C. 10. The method for modifying an insulating film according to any one of claims 3 to 5, wherein the treatment time of the plasma oxidation treatment is in the range of from 1 second to 90 seconds. 11. The method for modifying an insulating film according to claim 1 or 2, wherein the plasma processing device for generating a plasma of the processing gas by introducing a microwave into the processing container by a planar antenna having a plurality of holes In the nitriding treatment step, the upgrading step is performed by an annealing apparatus that anneals the object to be processed at a temperature in the range of 800 ° C to 1100 ° C in an oxidizing atmosphere. 12. The method for modifying an insulating film according to claim 11, wherein the processing time of the annealing treatment is in the range of 10 seconds or more and 50 seconds or less. 13. The method of modifying an insulating film according to claim 12, wherein the transfer of the object to be processed from the plasma processing apparatus to the annealing apparatus is carried out under vacuum. The method of modifying an insulating film according to any one of the items of the invention, wherein the yttrium oxynitride film is a gate insulating film of a MOS structure device. -52-
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