TW201107521A - Method for forming silicon nitride film, method for manufacturing semiconductor memory device, and plasma cvd apparatus - Google Patents

Method for forming silicon nitride film, method for manufacturing semiconductor memory device, and plasma cvd apparatus Download PDF

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TW201107521A
TW201107521A TW099109920A TW99109920A TW201107521A TW 201107521 A TW201107521 A TW 201107521A TW 099109920 A TW099109920 A TW 099109920A TW 99109920 A TW99109920 A TW 99109920A TW 201107521 A TW201107521 A TW 201107521A
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gas
film
nitride film
tantalum nitride
plasma cvd
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TW099109920A
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Tatsuo Nishita
Minoru Honda
Junya Miyahara
Toshio Nakanishi
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Tokyo Electron Ltd
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
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    • H01L29/401—Multistep manufacturing processes
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]

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Abstract

A method for forming a silicon nitride film is provided with a silicon nitride film forming step wherein plasma is generated by supplying a processing gas which contains a silicon-containing compound gas and a nitrogen-containing gas into a processing container, and a silicon nitride film is formed on a subject to be processed, and an oxygen atom-containing gas introducing step wherein the generation of plasma is stopped during the silicon nitride film forming step, an oxygen atom-containing gas is introduced into the processing container, and a trap is formed by exposing the silicon nitride film to the oxygen atom-containing gas, while the film is being formed. The silicon nitride film forming step can be provided with: a first step wherein a silicon nitride film is grown by means of plasma prior to the oxygen atom-containing gas introducing step, and a second step wherein a silicon nitride film is grown by means of plasma after the oxygen atom-containing gas introducing step.

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201107521 六、發明說明： 【發明所屬之技術領域】 本發明是有關氮化矽膜的成膜方法'半導體記憶體裝 置的製造方法及使用於該等的方法之電漿CVD裝置。 【先前技術】 目前，可電性改寫動作的 EEPROM ( Electrically Erasable and Programmable ROM)等代表性的非揮發性半 導體記憶體裝置，有被稱爲 SONOS ( Silicon-Oxide-Nitride-Oxide-Silicon ) 型或 MONOS ( Metal-Oxide-Nitride-Oxide-Silicon )型的層疊構造者。在該等型態的 非揮發性半導體記憶體裝置是以被二氧化矽膜（Oxide ) 夾著的1層以上的氮化矽膜（Nitride)作爲電荷儲存區域 來進行資訊的保持。亦即，上述非揮發性半導體記憶體裝 置是在半導體基板（silicon)與控制閘極電極（Silicon或 Metal)之間施加電壓，藉此在電荷儲存區域的氮化砂膜 注入電子而保存資料，或除去被儲存於氮化矽膜的電子， 進行資料的保存及消去的改寫。在上述非揮發性半導體記 憶體裝置中，可想像資料寫入特性是與往電荷儲存區域的 氮化矽膜之電子的注入容易度有關係，特別是與存在於氮 化矽膜中的電荷捕獲中心（陷阱）有關係。 有關非揮發性半導體記億體裝置的技術，在特開平5-1 45 07 8號公報中記載：基於使氮化矽膜與頂部氧化膜的界 面的陷阱密度增加之目的，在該等的膜的中間部分設有含 -5- 201107521 多量Si的遷移層。 【發明內容】 隨著近年來半導體裝置的高集成化，非揮發性半導體 s己憶體裝置的兀件構造也急速地微細化。爲了使非揮發性 半導體記憶體裝置微細化，在各個的非揮發性半導體記億 體裝置中’需要使電荷儲存層的氮化矽膜的陷讲增加，提 高資料寫入性能。 然而，減壓 CVD (Chemical Vapor Deposition)法或 熱CVD法的成膜方法’技術上難以在氮化砂膜的形成過 程控制膜中的陷阱形成。又，雖可想像電漿CVD法藉由 將處理容器內的處理壓力設定於高真空狀態（例如3Pa以 下）來提高電漿的離子性，可在氮化矽膜中形成多數的陷 阱’但爲了將熱壁（腔室被加熱）的處理容器內維持於高 真空狀態，而需要可耐高真空狀態的真空密封技術、耐壓 容器、高性能的排氣裝置等，裝置負荷會增大，成本也會 有變高的缺點。並且，在離子變多高真空狀態下，因爲電 漿能量會變高，所以往處理容器內的零件等之濺射作用會 變強，重金屬或粒子等所造成污染的危險性會增加，或氮 化矽膜形成的覆蓋性能會變低等，在製程的一面也會有問 題。 而且，在以往的電漿CVD法所成膜的氮化矽膜，陷 阱偏在於與鄰接的膜的界面之情況多，不可能控制氮化矽 膜的膜厚方向之陷阱的分佈。 201107521 本發明是有鑑於上述情事而硏發者，其目的是在於提 供一種陷阱多數存在，且一邊控制陷阱的膜厚方向的分佈 ，一邊藉由電漿CVD法來形成有用的氮化矽膜作爲非揮 發性半導體記憶體裝置的電荷儲存層之方法。 本發明的氮化矽膜的成膜方法，係於電漿CVD裝置 的處理容器內，藉由電漿CVD法在被處理體上使氮化矽 膜堆積之氮化矽膜的成膜方法，其特徵爲具備： 氮化矽膜形成工程，其係對前述處理容器內供給包含 含矽化合物氣體及含氮氣體的處理氣體，而使電漿生成， 在被處理體上形成氮化矽膜；及 含氧原子氣體導入工程，其係於前述氮化矽膜形成工 程的途中，使前述電漿停止，對前述處理容器內導入含氧 原子氣體，將形成途中的前述氮化矽膜暴露於氧，而形成 陷阱。 在本發明的氮化矽膜的成膜方法中，前述氮化矽膜形 成工程較理想是具備： 在前述含氧原子氣體導入工程之前，藉由前述電漿來 使氮化矽膜成長之第1工程；及 在前述含氧原子氣體導入工程之後，藉由前述電漿來 使氮化矽膜成長之第2工程。 此情況，較理想是在前述氮化矽膜對目標膜厚成長成 30%以上70%以下的範圍內的厚度之階段進行前述含氧原 子氣體導入工程。 本發明的氮化矽膜的成膜方法更理想是重複2次以上 201107521 進行前述含氧原子氣體導入工程。 又’本發明的氮化矽膜的成膜方法較理想是前述電漿 CVD裝置爲：藉由具有複數個孔的平面天線來對前述處理 容器內導入微波而生成電漿之電漿CVD裝置。 本發明的半導體記憶體裝置的製造方法，係於矽層上 ’形成有隧道氧化膜、作爲電荷儲存層的氮化矽膜、阻絕 氧化矽膜及閘極電極而成的半導體記億體裝置的製造方法 ，其特徵爲： 作爲前述電荷儲存層的氮化矽膜的成膜係藉由氮化矽 膜的成膜方法來進行，該氮化矽膜的成膜方法係具備： 氮化矽膜形成工程，其係對電漿CVD裝置的處理容 器內供給包含含矽化合物氣體及含氮氣體的處理氣體，而 使電漿生成，藉由電漿CVD法在被處理體上形成氮化矽 膜；及 含氧原子氣體導入工程，其係於前述氮化矽膜形成工 程的途中使前述電漿停止，對前述處理容器內導入含氧原 子氣體，將形成途中的前述氮化矽膜暴露於氧，而形成陷 阱。 本發明的電漿CVD裝置，其特徵係具備： 處理容器，其係將被處理體載置於載置台而收容； 氣體供給裝置，其係對前述處理容器內供給處理氣體 > 排氣裝置，其係將前述處理容器內予以減壓排氣；及 控制部，其係控制成可進行氮化矽膜的成膜方法，該 -8 - 201107521 氮化矽膜的成膜方法係包含： 氮化矽膜形成工程，其係於前述處理容器內藉由電漿 CVD法在被處理體上使氮化矽膜堆積時，對前述處理容器 內供給包含含矽化合物氣體及含氮氣體的處理氣體，而使 電漿生成，在被處理體上形成氮化矽膜；及 含氧原子氣體導入工程，其係於前述氮化矽膜形成工 程的途中使前述電漿停止，對前述處理容器內導入含氧原 子氣體，將形成途中的前述氮化矽膜暴露於氧而形成陷阱 〇 若根據本發明的氮化矽膜的成膜方法，則在電漿CVD 法之氮化矽膜的堆積的途中，暫時的使電漿停止，對前述 處理容器內導入含氧原子氣體，將成膜途中的氮化矽膜暴 露於氧，藉此可形成陷阱多的氮化矽膜。又，藉由謀求氧 導入的時機，可簡單地控制氮化矽膜的膜厚方向之陷阱的 分佈。如此，若根據本發明的方法，則可以氣體系的控制 之簡易的手法來製造多數的陷阱會以預定的分佈存在之氮 化矽膜。 又，根據本發明的方法所成膜的氮化矽膜，因爲在膜 中存在多數陷阱，且膜厚方向的陷阱的分佈被控制於最適 的位置，所以藉由使用此膜來作爲非揮發性半導體記憶體 裝置的電荷儲存層，可取得寫入特性佳的非揮發性半導體 記憶體裝置。 【實施方式】 -9 - 201107521 [第1實施形態] 以下，參照圖面來詳細說明有關本發明的實施形態。 圖1是模式性地顯示可利用於本發明的氮化矽膜的成膜方 法之電槳CVD裝置100的槪略構成的剖面圖。 電漿CVD裝置100是藉由具有複數個狹縫狀的孔的 平面天線，特別是 RLSA( Radial Line Slot Antenna;徑 向線縫隙天線）來對處理容器內導入微波，而使電漿產生 ，藉此構成可使產生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CVD裝置100是具 有 lxl01Q〜5xl012/cm3的電漿密度且0.7〜2eV的低電子 溫度之電漿的處理可能。因此，電漿CVD裝置100是可 適合利用在各種半導體裝置的製造過程中電漿CVD之氮 化矽膜的成膜目的。 電漿CVD裝置100的主要構成是具備： 構成氣密的處理容器1 ; 對處理容器1內供給處理氣體的氣體供給裝置18; 作爲用以將處理容器1內減壓排氣的排氣機構之排氣 裝置24 ; 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 ;及 至少控制該等電漿CVD裝置100的各構成部之控制 部50。 處理容器1是藉由被接地的大致圓筒狀的容器所形成 。另外’處理容器1亦可藉由方筒形狀的容器所形成。處 -10- 201107521 理容器1是具有由鋁等的材質所構成的底壁la及側壁lb 〇 在處理容器1的內部是設有用以水平支撐被處理體的 矽晶圓（以下簡稱爲「晶圓」）w的載置台2。載置台2 是藉由熱傳導性高的材質例如A1N等的陶瓷所構成。此載 置台2是藉由從排氣室11的底部中央延伸至上方的圓筒 狀的支撐構件3所支撐。支撐構件3是例如藉由A1N等的 陶瓷所構成。 並且，在載置台2設有覆蓋其外緣部，引導晶圓W 的覆蓋環4。此覆蓋環4是例如以石英、AIN、Al2〇3、 SiN等的材質所構成的環狀構件。 而且，在載置台2埋入有作爲溫度調節機構的電阻加 熱型的加熱器5。此加熱器5是藉由從加熱器電源5 a給電 來加熱載置台2，而以該熱來均一地加熱被處理基板的晶 圓W。 又，在載置台2插入有熱電偶（TC) 6。藉由此熱電 偶6來進行溫度計測，可將晶圓W的加熱溫度，例如控 制於室溫〜90CTC的範圍。 又’在載置台2具有用以支撐晶圓W而使昇降的晶 圓支撐銷（未圖示）。各晶圓支撐銷是設成可對載置台2 的表面突沒。 在處理容器1的底壁la的大致中央部形成有圓形的 開口部1 0。在底壁1 a設有與此開口部1 〇連通，朝向下方 突出的排氣室11。在此排氣室11連接排氣管12，經由此 [ -11 - 201107521 排氣管12來連接至排氣裝置24。 閉 材 狀 是 第 孔 入 孔 管 導 氣 漿 W 17 N Si 供 、 器 在處理容器1的上部配置具有作爲使處理容器1開 的蓋體（lid)機能的板材13。板材13是具有開口，板 13的內周部會朝內側（處理容器內空間）突出，形成環 的支撐部13a » 在處理容器1的上部設有氣體導入部。氣體導入部 設有：形成於板材13，作爲至少導入1種類的氣體的「 1氣體導入孔」之氣體導入孔14'及形成於此氣體導入 I4的下方，作爲至少導入1種類的氣體的「第2氣體導 孔」之氣體導入孔15。亦即，在氣體導入部，氣體導入 14’ 15是設成上下2段。各氣體導入孔是經由氣體導入 來連接至供給處理氣體的氣體供給裝置1 8。另外，氣體 入孔I4及15亦可設成噴嘴狀或淋浴頭狀。又，亦可將 體導入孔14與氣體導入孔15設於單一的淋浴頭》 而且，在處理容器1的側壁lb設有：用以在電 CVD裝置1〇〇與鄰接的搬送室（未圖示）之間進行晶圓 的搬出入的搬出入口 16、及開閉此搬出入口 16的閘閥 〇 氣體供給裝置18是具有：氣體供給源（例如含氮（ )氣體供給源19a、含氧原子氣體供給源19b、含砂（ )氣體供給源19c、非活性氣體供給源19d及洗滌氣體 給源19e)、及氣體導入管（例如氣體導入管20a、20b 2 0 c、2 〇 d、2 0 e )、及流量控制裝置（例如質量流控制 21a、21b、21c、21d、21e)、及閥（例如開閉閥 22a -12- 201107521 22b、22c、22d、22e)。含氮氣體供給源19a及含氧原子 氣體供給源19b是經由氣體導入管2〇a，20b來連接至上 段的氣體導入孔14。並且，含Si氣體供給源19c、非活 性氣體供給源19d及洗滌氣體供給源19e是經由氣體導入 管20c，20d，20e來連接至下段的氣體導入孔15。洗滌氣 體供給源1 9e是被使用於洗滌附著在處理容器1內的不必 要的膜。另外，氣體供給裝置18亦可具有上述以外未圖 示的氣體供給源，例如在置換處理容器1內的環境時使用 的淨化氣體供給源等。 在本發明，含氧原子氣體可例如使用氧（〇2 )、臭氧 (03 )、一氧化氮（NO)、二氧化氮（N〇2)、一氧化二 氮（N20)等。又，含矽（Si)氣體可例如使用矽烷（ SiH4)、乙矽烷（Si2H6)、四氯矽烷（SiCl4)、六氯二 矽烷（Si2Cl6 )、二氯矽烷（SiH2Cl2 )、三氯矽烷（ Si2HCl3 )、丙矽烷（Si3H8 )、三甲矽烷胺（（SiH3 ) 3N )等，但其中又以使用由矽原子及氯原子所構成的化合物 的氣體，例如四氯矽烷（SiCl4 )或六氯二矽烷（Si2Cl6 ) 爲理想。又，含氮（N)氣體可使用氮氣體（N2)、氨（ nh3 )、聯胺（N2H4 )、單甲基聯胺（ch6n2 )等’但以 使用不含氫的n2氣體爲理想。由矽原子及氯原子所構成 的四氯矽烷（SiCl4)或六氯二矽烷（Si2ci6)與N2的組 合是因爲在原料氣體分子中不含氫，所以在本發明中爲可 理想使用的組合。又，非活性氣體是例如以添加稀有氣體 爲更理想，例如可使用Ar氣體' Kr氣體、Xe氣體、 -13- 201107521 氣體等。淨化氣體是以Ar氣體、氮氣體等的非活性 爲理想。 含N氣體及含氧原子氣體是從氣體供給裝置is 氮氣體供給源l9a及含氧原子氣體供給源經由氣 入管20a、20b來分別至氣體導入孔14，從氣體導入3 導入處理容器1內。另一方面，含Si氣體、非活性 及洗滌氣體是從含Si氣體供給源19c、非活性氣體供 19d及洗滌氣體供給源19e分別經由氣體導入管20c、 、20e來至氣體導入孔15，導入處理容器1內。在連 各氣體供給源的各個氣體導入管20a〜20e是設有質 控制器21a〜21e及其前後的開閉閥22a〜22e。藉由 的氣體供給裝置1 8的構成，可進行所被供給之氣體 換或流量等的控制。另外，Ar等的電漿激發用的稀 體是任意的氣體，並非一定要與處理氣體（含Si氣 含N氣體）同時供給，但由使電漿安定化的觀點來看 加更爲理想。尤其是使用Ar氣體作爲用以安定的流 將含Si氣體供給至處理容器內的載氣時更爲理想。 排氣裝置24是具備渦輪分子泵等的真空泵（圖 略）。真空泵是經由排氣管12來連接至處理容器1 氣室11。藉由使該真空泵作動，處理容器1內的氣體 均一地流至排氣室1 1的空間1 1 a內，更從空間1 1 a 排氣管12來排氣至外部。藉此，可將處理容器1內 地，例如高速減壓至0.133Pa。 其次’說明有關微波導入機構27的構成。微波 氣體 的含 體導 I 14 氣體 給源 20d 接至 量流 如此 的切 有氣 體、 是添 量來 示省 的排 會被 經由 均一 導入 -14- 201107521 機構27，主要的構成是具備透過板28、平面天線3 1、慢 波材33、金屬製罩構件34、導波管37及微波產生裝置39 〇 透過微波的透過板28是配備於板材13中突出至內周 側的支撐部13a上。透過板28是由電介體、例如石英或 陶瓷（Al2〇3、A1N等）所構成。在此透過板28與支撐部 1 3 a之間是經由密封構件2 9來密封成氣密。因此，處理容 器1內是被保持成氣密》 平面天線31是在透過板28的上方，設成與載置台2 對向。平面天線31是成爲圓板狀。另外，平面天線3 1的 形狀並非限於圓板狀，例如亦可爲四角板狀。此平面天線 3 1是配置於板材1 3的上面。 平面天線3 1是例如由表面鍍金或銀的銅板、鎳板、 SUS板或鋁板所構成。平面天線31是具有放射微波的多 數個狹縫狀的微波放射孔3 2。微波放射孔3 2是以預定的 圖案來貫通平面天線3 1所形成^ 例如圖2所示，微波放射孔32是成細長的長方形狀 (狹縫狀），鄰接的2個微波放射孔會成對。而且，典型 的是鄰接的一對微波放射孔32會以預定的圖案來配置成 「T」字形或「V」字形。並且，如此組合成形狀而配置的 微波放射孔32是配置成同心圓狀，微波會以同心圓偏波 來導入至處理容器1內，形成均一的電槳。 微波放射孔3 2的長度或配列間隔是因應微波的波長 (Xg )來決定。例如，微波放射孔32的間隔可配置成 [ -15- 201107521BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a tantalum nitride film, a method for fabricating a semiconductor memory device, and a plasma CVD device used in the method. [Prior Art] At present, a representative non-volatile semiconductor memory device such as an EEPROM (Electrically Erasable and Programmable ROM), which is electrically rewritable, is called a SONOS (Silicon-Oxide-Nitride-Oxide-Silicon) type or A laminated structure of the MONOS (Metal-Oxide-Nitride-Oxide-Silicon) type. In these types of nonvolatile semiconductor memory devices, one or more layers of a tantalum nitride film (Nitride) sandwiched by a ruthenium dioxide film (Oxide) are used as a charge storage region for information retention. That is, the non-volatile semiconductor memory device applies a voltage between a semiconductor substrate and a control gate electrode (Silicon or Metal), thereby depositing electrons in the silicon nitride film of the charge storage region to store data. Or the electrons stored in the tantalum nitride film are removed, and the data is saved and erased. In the above nonvolatile semiconductor memory device, the imaginable data writing characteristic is related to the ease of implantation of electrons into the tantalum nitride film of the charge storage region, particularly with charge trapping existing in the tantalum nitride film. The center (trap) has a relationship. In the technique of the non-volatile semiconductor device, it is described in Japanese Laid-Open Patent Publication No. Hei. The middle part is provided with a migration layer containing a large amount of Si from -5 to 201107521. SUMMARY OF THE INVENTION With the recent increase in the integration of semiconductor devices, the structure of the non-volatile semiconductor s-resonance device has been rapidly miniaturized. In order to refine the nonvolatile semiconductor memory device, it is necessary to increase the trapezing of the tantalum nitride film of the charge storage layer in each of the nonvolatile semiconductor devices, thereby improving data writing performance. However, the film forming method of the CVD (Chemical Vapor Deposition) method or the thermal CVD method is technically difficult to form a trap in the process of forming a nitrided film. Further, although it is conceivable that the plasma CVD method can increase the ionicity of the plasma by setting the treatment pressure in the processing container to a high vacuum state (for example, 3 Pa or less), a large number of traps can be formed in the tantalum nitride film. The processing vessel of the hot wall (the chamber is heated) is maintained in a high vacuum state, and a vacuum sealing technology capable of withstanding a high vacuum state, a pressure vessel, a high-performance exhaust device, etc. are required, and the load of the device is increased, and the cost is increased. There will also be disadvantages of getting higher. Further, in the case where the ion is highly vacuumed, since the plasma energy is increased, the sputtering action of the parts and the like in the conventional processing container becomes strong, and the risk of contamination by heavy metals or particles or the like increases, or nitrogen The coverage of the ruthenium film formation will be low, and there will be problems in the process side. Further, in the tantalum nitride film formed by the conventional plasma CVD method, the trap is too much in the interface with the adjacent film, and it is impossible to control the distribution of the trap in the film thickness direction of the tantalum nitride film. 201107521 The present invention has been made in view of the above circumstances, and an object thereof is to provide a useful tantalum nitride film by a plasma CVD method while controlling the distribution of a trap in the film thickness direction. A method of charge storage layer of a non-volatile semiconductor memory device. The method for forming a tantalum nitride film according to the present invention is a method for forming a tantalum nitride film in which a tantalum nitride film is deposited on a target object by a plasma CVD method in a processing container of a plasma CVD apparatus. The present invention provides a tantalum nitride film forming process for supplying a processing gas containing a ruthenium-containing compound gas and a nitrogen-containing gas to a processing chamber to form a plasma, and forming a tantalum nitride film on the object to be processed; And an oxygen atom-containing gas introduction process for stopping the plasma in the middle of the formation of the tantalum nitride film, introducing an oxygen-containing atom gas into the processing chamber, and exposing the tantalum nitride film in the middle of formation to oxygen And form a trap. In the method for forming a tantalum nitride film according to the present invention, it is preferable that the tantalum nitride film forming process includes: growing the tantalum nitride film by the plasma before the oxygen atom-containing gas introduction process 1); and a second project in which the tantalum nitride film is grown by the plasma after the introduction of the oxygen-containing atom gas. In this case, it is preferable that the oxygen-containing atomic gas introduction process is performed at a stage in which the thickness of the target film is increased by 30% or more and 70% or less. More preferably, the film formation method of the tantalum nitride film of the present invention is repeated twice or more. 201107521 The oxygen atom-containing gas introduction process is carried out. Further, in the film forming method of the tantalum nitride film of the present invention, it is preferable that the plasma CVD apparatus is a plasma CVD apparatus which generates a plasma by introducing microwaves into the processing chamber by a planar antenna having a plurality of holes. A method of manufacturing a semiconductor memory device according to the present invention is a semiconductor device in which a tunnel oxide film, a tantalum nitride film as a charge storage layer, a ruthenium oxide film, and a gate electrode are formed on a germanium layer. A method for producing a tantalum nitride film as the charge storage layer is formed by a film formation method of a tantalum nitride film, and the method for forming a tantalum nitride film includes: a tantalum nitride film a forming process for supplying a processing gas containing a cerium-containing compound gas and a nitrogen-containing gas to a processing vessel of a plasma CVD apparatus to generate a plasma, and forming a tantalum nitride film on the object to be processed by a plasma CVD method And an oxygen atom-containing gas introduction process for stopping the plasma in the middle of the formation of the tantalum nitride film, introducing an oxygen-containing atom gas into the processing chamber, and exposing the tantalum nitride film in the middle of formation to oxygen And form a trap. A plasma CVD apparatus according to the present invention includes: a processing container that stores a workpiece to be placed on a mounting table; and a gas supply device that supplies a processing gas to the processing chamber; And the control unit is controlled to form a film of a tantalum nitride film, and the film forming method of the tantalum nitride film comprises: nitriding In a ruthenium film forming process, when a tantalum nitride film is deposited on a target object by a plasma CVD method in the processing container, a processing gas containing a ruthenium-containing compound gas and a nitrogen-containing gas is supplied into the processing container. And the plasma is formed to form a tantalum nitride film on the object to be processed; and the oxygen atom-containing gas introduction process is performed to stop the plasma in the middle of the formation of the tantalum nitride film, and the introduction into the processing container The oxygen atom gas exposes the tantalum nitride film in the middle of formation to oxygen to form a trap. According to the film formation method of the tantalum nitride film according to the present invention, in the middle of deposition of the tantalum nitride film by the plasma CVD method, So that when the plasma is stopped, gas containing oxygen atoms introduced into the process vessel, the way of forming a silicon nitride film is exposed to oxygen, whereby the number of traps silicon nitride film can be formed. Further, by the timing of introduction of oxygen, the distribution of traps in the film thickness direction of the tantalum nitride film can be easily controlled. Thus, according to the method of the present invention, it is possible to manufacture a niobium nitride film in which a plurality of traps are present in a predetermined distribution by a simple method of controlling the gas system. Further, since the tantalum nitride film formed by the method of the present invention has a large number of traps in the film and the distribution of traps in the film thickness direction is controlled to an optimum position, the film is used as a nonvolatile property. The charge storage layer of the semiconductor memory device can obtain a nonvolatile semiconductor memory device with excellent writing characteristics. [Embodiment] -9 - 201107521 [First Embodiment] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Fig. 1 is a cross-sectional view schematically showing a schematic configuration of an electric pad CVD apparatus 100 which can be used in a film forming method of a tantalum nitride film of the present invention. The plasma CVD apparatus 100 is a planar antenna having a plurality of slit-shaped holes, in particular, a RLSA (radiial line Slot Antenna), which introduces microwaves into the processing container to generate plasma. This configuration makes it possible to produce a high density and low electron temperature microwave excited plasma RLSA microwave plasma processing apparatus. The plasma CVD apparatus 100 is a treatment of a plasma having a plasma density of lxl01Q to 5xl012/cm3 and a low electron temperature of 0.7 to 2eV. Therefore, the plasma CVD apparatus 100 is suitable for the film formation purpose of the ruthenium nitride film of the plasma CVD in the manufacturing process of various semiconductor devices. The main structure of the plasma CVD apparatus 100 includes: a processing container 1 that is airtight; a gas supply device 18 that supplies a processing gas into the processing container 1, and an exhaust mechanism that decompresses the inside of the processing container 1 The exhaust unit 24 is provided in the upper portion of the processing container 1, the microwave introducing unit 27 that introduces microwaves into the processing container 1, and the control unit 50 that controls at least the respective constituent units of the plasma CVD apparatus 100. The processing container 1 is formed by a substantially cylindrical container that is grounded. Further, the processing container 1 can also be formed by a rectangular tube-shaped container. -10-201107521 The container 1 is a bottom wall 1a and a side wall lb which are made of a material such as aluminum. The inside of the processing container 1 is provided with a silicon wafer for horizontally supporting the object to be processed (hereinafter referred to as "crystal". The mounting table 2 of the circle "). The mounting table 2 is made of a material having a high thermal conductivity such as A1N or the like. This stage 2 is supported by a cylindrical support member 3 extending from the center of the bottom of the discharge chamber 11 to the upper side. 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 that covers the outer edge portion and guides the wafer W. The cover ring 4 is, for example, an annular member made of a material such as quartz, AIN, Al2〇3, or SiN. Further, a heater 5 of a resistance heating type as a temperature adjustment mechanism is embedded in the mounting table 2. This heater 5 heats the stage 2 by supplying electricity from the heater power source 5a, and uniformly heats the crystal W of the substrate to be processed by the heat. Further, a thermocouple (TC) 6 is inserted into the mounting table 2. By performing the thermometer measurement by the thermocouple 6, the heating temperature of the wafer W can be controlled, for example, at a temperature ranging from room temperature to 90 CTC. Further, the mounting table 2 has a crystal supporting pin (not shown) for supporting the wafer W to be raised and lowered. Each of the wafer support pins is provided to protrude from the surface of the mounting table 2. A circular opening portion 10 is formed in a substantially central portion of the bottom wall 1a of the processing container 1. The bottom wall 1a is provided with an exhaust chamber 11 that communicates with the opening 1 and projects downward. Here, the exhaust chamber 11 is connected to the exhaust pipe 12, and is connected to the exhaust device 24 via the [-11 - 201107521 exhaust pipe 12. The closed material is the first hole inlet pipe. The gas slurry W 17 N Si is disposed on the upper portion of the processing container 1 and has a plate 13 functioning as a lid for opening the processing container 1. The plate member 13 has an opening, and the inner peripheral portion of the plate 13 protrudes toward the inner side (the space inside the processing container), and the support portion 13a for forming a ring is provided with a gas introduction portion at the upper portion of the processing container 1. The gas introduction portion is provided with a gas introduction hole 14' formed in the "one gas introduction hole" in which at least one type of gas is introduced, and is formed below the gas introduction I4 to introduce at least one type of gas. The gas introduction hole 15 of the second gas guide hole. That is, in the gas introduction portion, the gas introduction 14' 15 is set in two stages. Each gas introduction hole is connected to a gas supply device 18 that supplies a processing gas via gas introduction. Further, the gas inlet holes I4 and 15 may be formed in a nozzle shape or a shower head shape. Further, the body introduction hole 14 and the gas introduction hole 15 may be provided in a single shower head. Further, the side wall 1b of the processing container 1 is provided for the electric CVD apparatus 1 and the adjacent transfer chamber (not shown). The carry-in port 16 for carrying in and out of the wafer between the display and the gate valve gas supply device 18 for opening and closing the carry-in port 16 have a gas supply source (for example, a nitrogen-containing gas supply source 19a and an oxygen-containing gas supply) a source 19b, a sand-containing gas supply source 19c, an inert gas supply source 19d, a scrubbing gas supply source 19e), and a gas introduction pipe (for example, gas introduction pipes 20a, 20b 2 0 c, 2 〇d, 2 0 e ), And flow control devices (for example, mass flow control 21a, 21b, 21c, 21d, 21e) and valves (for example, on-off valves 22a-12-201107521 22b, 22c, 22d, 22e). The nitrogen-containing gas supply source 19a and the oxygen-containing atomic gas supply source 19b are connected to the upper gas introduction hole 14 via the gas introduction pipes 2a, 20b. Further, the Si-containing gas supply source 19c, the inert gas supply source 19d, and the scrubbing gas supply source 19e are connected to the lower gas introduction hole 15 via the gas introduction pipes 20c, 20d, and 20e. The washing gas supply source 9e is an unnecessary film used for washing and adhering to the processing container 1. Further, the gas supply device 18 may have a gas supply source (not shown), for example, a purge gas supply source used when replacing the environment in the processing container 1. In the present invention, the oxygen atom-containing gas may, for example, be oxygen (?2), ozone (03), nitrogen monoxide (NO), nitrogen dioxide (N?2), nitrous oxide (N20) or the like. Further, as the cerium (Si)-containing gas, for example, decane (SiH4), ethane hydride (Si2H6), tetrachloro decane (SiCl4), hexachlorodioxane (Si2Cl6), chlorin (SiH2Cl2), chloroform (Si2HCl3) may be used. , propane (Si3H8), trimethylmethaneamine ((SiH3) 3N), etc., but in which a gas using a compound composed of a halogen atom and a chlorine atom, such as tetrachlorosilane (SiCl4) or hexachlorodioxane (Si2Cl6) ) is ideal. Further, as the nitrogen-containing (N) gas, nitrogen gas (N2), ammonia (nh3), hydrazine (N2H4), monomethyl hydrazine (ch6n2) or the like can be used, but it is preferred to use n2 gas containing no hydrogen. The combination of tetrachloromethane (SiCl4) or hexachlorodioxane (Si2ci6) and N2 composed of a ruthenium atom and a chlorine atom is a combination which can be desirably used in the present invention because hydrogen is not contained in the material gas molecules. Further, the inert gas is preferably a rare gas, for example, and an Ar gas 'Kr gas, Xe gas, -13-201107521 gas, or the like can be used. The purge gas is preferably inert to Ar gas or nitrogen gas. The gas containing N gas and the oxygen-containing atom are supplied from the gas supply device is a nitrogen gas supply source 19a and an oxygen-containing gas supply source to the gas introduction holes 14 through the gas inlet pipes 20a and 20b, and are introduced into the processing container 1 from the gas introduction 3. On the other hand, the Si-containing gas, the inactive gas, and the scrubbing gas are introduced from the Si-containing gas supply source 19c, the inert gas supply 19d, and the scrubbing gas supply source 19e to the gas introduction hole 15 through the gas introduction pipes 20c and 20e, respectively. Processing inside the container 1. Each of the gas introduction pipes 20a to 20e connected to each of the gas supply sources is provided with quality controllers 21a to 21e and front and rear opening and closing valves 22a to 22e. By the configuration of the gas supply device 18, it is possible to control the gas exchange or flow rate to be supplied. Further, the thin body for plasma excitation such as Ar is an arbitrary gas, and it is not necessarily supplied simultaneously with the processing gas (including the N gas containing N gas), but it is more preferable from the viewpoint of making the plasma stable. In particular, it is more preferable to use Ar gas as a flow for stabilization to supply a Si-containing gas to a carrier gas in the processing container. The exhaust device 24 is a vacuum pump (not shown) including a turbo molecular pump or the like. The vacuum pump is connected to the process vessel 1 gas chamber 11 via an exhaust pipe 12. By operating the vacuum pump, the gas in the processing container 1 uniformly flows into the space 11a of the exhaust chamber 1 1 and is further exhausted from the space 1 1 a exhaust pipe 12 to the outside. Thereby, the inside of the processing container 1 can be decompressed, for example, at a high speed to 0.133 Pa. Next, the configuration of the microwave introducing mechanism 27 will be described. The microwave gas containing body I 14 gas is supplied to the source 20d to the metering flow. The gas is cut, and the amount is added. The row is introduced through the uniform introduction-14-201107521 mechanism 27, and the main component is provided with a transparent plate 28, The planar antenna 3 1 , the slow wave material 33 , the metal cover member 34 , the waveguide 37 , and the microwave generating device 39 . The transmitting plate 28 that transmits the microwaves is provided on the support portion 13 a that protrudes from the plate member 13 to the inner peripheral side. The transmission plate 28 is made of a dielectric material such as quartz or ceramic (Al2〇3, A1N, etc.). Here, the gap between the transmission plate 28 and the support portion 13a is sealed by airtightness through the sealing member 29. Therefore, the inside of the processing container 1 is kept airtight. The planar antenna 31 is disposed above the transmitting plate 28 and opposed to the mounting table 2. The planar antenna 31 has a disk shape. Further, the shape of the planar antenna 3 1 is not limited to a disk shape, and may be, for example, a quadrangular plate shape. This planar antenna 3 1 is disposed on the upper surface of the plate member 13. The planar antenna 31 is composed of, for example, a copper plate, a nickel plate, a SUS plate or an aluminum plate plated with gold or silver on the surface. The planar antenna 31 is a plurality of slit-shaped microwave radiation holes 32 having a microwave. The microwave radiation hole 32 is formed by penetrating the planar antenna 3 1 in a predetermined pattern. For example, as shown in FIG. 2, the microwave radiation hole 32 is formed in an elongated rectangular shape (slit shape), and two adjacent microwave radiation holes are formed. Correct. Further, it is typical that the adjacent pair of microwave radiation holes 32 are arranged in a predetermined pattern in a "T" shape or a "V" shape. Further, the microwave radiation holes 32 arranged in such a shape are arranged in a concentric shape, and the microwaves are introduced into the processing container 1 by concentric circular waves to form a uniform electric paddle. The length or arrangement interval of the microwave radiation holes 32 is determined in accordance with the wavelength (Xg) of the microwave. For example, the interval of the microwave radiation holes 32 can be configured as [ -15- 201107521

Xg/4〜Xg。在圖2中，是以Ar來表示形成同心圓狀之鄰 接的微波放射孔3 2彼此間的間隔。另外，微波放射孔3 2 的形狀亦可爲圓形狀、圓弧狀等其他的形狀。又，微波放 射孔32的配置形態並無特別限定，同心圓狀以外，例如 亦可配置成螺旋狀、放射狀等。 在平面天線31的上面是設有慢波材33，其係具有比 真空大的介電常數。此慢波材33是因爲在真空中微波的 波長會變長，所以具有縮短微波的波長來調整電漿的機能 〇 另外，平面天線31與透過板2 8之間，且慢波材3 3 與平面天線3 1之間，雖可使分別接觸或離間，但較理想 是使接觸。 在處理容器1的上部是以能夠覆蓋該等平面天線31 及慢波材33的方式設有金屬製罩構件34。金屬製罩構件 34是例如藉由鋁或不銹鋼等的金屬材料所形成，與平面天 線31 —起構成偏平導波管。板材13的上端與金屬製罩構 件34是藉由密封構件35來密封。在金屬製罩構件34的 內部是形成有冷卻水流路34a°藉由在此冷卻水流路34a 使冷卻水流通’可冷卻金屬製罩構件34、慢波材33、平 面天線31及透過板28。另外，金屬製罩構件34是被接地 〇 在金屬製罩構件34的上壁（頂部）的中央是形成有 開口部36，在此開口部36是連接有導波管37»導波管37 的另一端側是經由匹配電路3 8來連接產生微波的微波產 -16- 201107521 生裝置39。 導波管37是具有：從上述金屬製罩構件34的開口部 36往上方延伸之剖面圓形狀的同軸導波管37a、及連接於 此同軸導波管37a的上端部之水平方向延伸的矩形導波管 37b ° 在同軸導波管37a的中心延伸有內導體41。此內導體 41是以金屬製的銅等所構成，在其下端部連接固定於平面 天線3 1的中心。藉由如此的構造，微波是傳播於同軸導 波管37a的內導體41來往平面天線31導入，而放射狀地 效率佳均一傳播於偏平導波管。 藉由以上那樣構成的微波導入機構27，在微波產生裝 置39所產生的微波可經由導波管37來傳播至平面天線31 ，更經由透過板28來導入至處理容器1內。另外，微波 的頻率，例如較理想是使用 2.45GHz，其他亦可使用 8.35GHz ' 1 .98GHz 等。 電漿CVD裝置1 00的各構成部是形成連接至控制部 5 〇而控制的構成。控制部5 0是具有電腦，例如圖3所示 ，具有：具備CPU的製程控制器5 1、及連接至此製程控 制器51的使用者界面52及記憶部53。製程控制器51是 在電漿CVD裝置100中，例如統括控制有關溫度、壓力 、氣體流量、微波輸出等的製程條件的各構成部（例如加 熱器電源5a、氣體供給裝置18、排氣裝置24、微波產生 裝置3 9等）之控制手段。 使用者介面52是具有鍵盤及顯示器等。該鍵盤是 -17- 201107521 程管理者爲了管理電漿CVD裝置loo而進行指令的輸入 操作等。該顯示器是使電漿CVD裝置1〇〇的操業狀況可 視化顯示。並且，在記憶部5 3中保存處方等，其係記錄 有用以在製程控制器51的控制下實現在電漿CVD裝置 】〇〇所被實行的各種處理之控制程式（軟體）或處理條件 資料等。 然後，因應所需，以來自使用者介面5 2的指示等， 從記憶部5 3叫出任意的處方，而使實行於製程控制器51 ，在製程控制器51的控制下，於電漿CVD裝置100的處 理容器1內進行所望的處理。又，上述控制程式或處理條 件資料等的處方，可利用被儲存於電腦可讀取的記憶媒體 '例如CD-ROM、硬碟、軟體、快閃記憶體、DVD、藍光 碟（Blu-ray Disc)等的狀態者，或亦可從其他的裝置例 如經由專線來隨時傳送連線利用。 其次，說明有關使用RLSA方式的電漿CVD裝置1〇〇 之氮化矽膜的成膜處理的程序。在此是舉使用 Si Cl4作爲 含Si氣體，使用N2氣體作爲含N氣體，使用〇2氣體作 爲含氧原子氣體時爲例。圖4是氮化矽膜的成膜處理的微 波、SiCl4氣體、N2氣體及〇2氣體的導入的時序圖。首先 ，開啓閘閥17，從搬出入口 16來將晶圓W搬入至處理容 器1內，載置於載置台2上加熱。其次，一邊將處理容器 1內予以減壓排氣，一邊分別以預定的流量，從氣體供給 裝置18的含氮氣體供給源19a經由氣體導入孔14來將N2 氣體導入至處理容器1內，另外從含Si氣體供給源19c -18- 201107521 及非活性氣體供給源1 9d經由氣體導入孔1 5來將SiCU氣 體及因應所需將Ar氣體導入至處理容器1內（圖4的t〇 )。而且，將處理容器1內設定於預定的壓力。有關此時 的條件會在以後敘述。 其次，使在微波產生裝置39所產生之預定頻率例如 2.45GHz的微波經由匹配電路38來引導於導波管37 (圖 4的h)。被導波管37引導的微波是依序通過矩形導波管 3 7b及同軸導波管37a，經由內導體41來供給至構成偏平 導波管的平面天線31。微波是從同軸導波管37a來往平面 天線31放射狀地傳播。而且，微波是從平面天線31的狹 縫狀的微波放射孔3 2經由透過板2 8在處理容器1內的晶 圓W的上方空間成爲圓偏波而放射。 藉由從平面天線31透過透過板28來放射至處理容器 1的微波，在處理容器1內形成電磁場，分別使N2氣體、 SiCl4氣體、Ar氣體電漿化。然後，在電漿中，原料氣體 的解離會有效率地進展，藉由活性種（離子、自由基等） 的反應，氮化矽（SiN ;在此，Si與N的組成比並非一定 化學計量性地決定，依成膜條件取相異的値，以下同樣） 的薄膜會被堆積》此電漿CVD工程是從圖4的tl到t4爲 止的區間進行。 本實施形態的氮化矽膜的成膜方法是具備： CVD工程之氮化矽膜的成膜的途中，僅預定時間（圖4的 t2〜h的區間）使電發停止，從含氧原子氣體供，給源 經由氣體導入孔I4來導入〇2氣體等的含氧原子氣 -19- 201107521 理容器1內之含氧原子氣體導入工程（在此，因爲是代表 性地使用〇2氣體，所以有記載「〇2氣體流動」的情形） 。就此〇2氣體流動而言，是將形成途中的氮化矽膜暴露 於氧’而使產生Si-o結合，以形成陷阱爲目的。如此， 本實施形態的氮化矽膜的形成方法是藉由使02氣體流動 介在，將氮化矽膜形成工程分割成：在〇2氣體流動之前 ，藉由電漿來使氮化矽膜成長的第1工程（圖4的n〜t2 的區間）、及在〇2氣體流動之後，藉由電漿來使氮化矽 膜成長的第2工程（圖4的t3〜t4的區間）。亦即，藉由 電漿來形成第1氮化矽膜，使第1氮化矽膜暴露於含氧原 子氣體來形成陷阱，在其上藉由電漿來形成第2氮化矽膜 。並且，在含氧原子氣體導入工程，亦可使Si-O結合形 成平面性均一地散佈，陷阱可均一地散佈。 圖5A〜圖5D是顯示在電漿CVD裝置100中進行的 氮化矽膜的成膜處理的工程之晶圓W的表面附近的剖面 圖。如圖5A所示，例如在任意的底層（在此是Si〇2膜60 )之上，使用電漿CVD裝置100來生成SiCl4/N2氣體電 漿，藉由電漿CVD法來形成氮化矽膜（SiN膜）7〇a (第 1工程）。此第1工程的SiN膜70a的形成是供給作爲含 Si氣體的SiCl4氣體、及作爲含氮氣體的含N2氣體的處 理氣體至處理容器1內，可在以下的條件下進行。此情況 ，亦可與添加稀有氣體而安定後的電漿生成安定供給氣體 〇 處理壓力是O.lPa以上6.7Pa以下的範圍內爲理想， -20- 201107521 更理想是O.lPa以上4Pa以下的範圍內。爲了容易解離 SiCl4，最好處理壓力低。一旦處理壓力超過 6.7Pa，則 Si Cl4氣體的解離少，與氮的反應不會進展，無法充分的 成膜，不理想。 又，將SiCl4氣體對合計處理氣體流量的流量比（ SiCl4氣體/合計處理氣體流量的百分率）設於〇.〇3%以上 1 5 %以下爲理想，更理想是〇 . 〇 3 %以上1 %以下。另外， SiCl4氣體的流量是設定於 〇.5mL/min ( seem )以上 10mL/min ( seem ) 以下爲理想，更理想是設定於 0.5mL/min ( seem)以上 2mL/min ( seem)以下。另外， 使用其他種類的含Si氣體時也是同樣的。 又，將N2氣體流量對合計處理氣體流量的比（N2氣 體/合計處理氣體流量的百分率）設於5%以上99%以下爲 理想，更理想是40%以上99%以下。另外，N2氣體的流量 是設定於 100mL/min(sccm)以上 5000mL/min(sccm) 以下爲理想，更理想是設定於 l〇〇mL/min(sccm)以上 2000mL/min(sccm)以下。另外，使用其他種類的含N 氣體時也是同樣的。 又，將Ar氣體對合計處理氣體流量的流量比（例如 Ar氣體/合計處理氣體流量的百分率）設於10%以上90% 以下爲理想，更理想是10%以上60%以下。另外，Ar等稀 有氣體的流量是設定於 10mL/min(sccm) 以上 1000mL/min(sccm)以下爲理想，更理想是設定於 1 0 m L / m i n ( s c c m )以上 5 0 0 m L / m i n ( s c c m )以下。 -21 - 201107521 又，電漿CVD處理的溫度是將載置台2的 於3 00°C以上，較理想是400°C以上600°C以下的 可。 又，電漿CVD裝置100的微波輸出是每透兒 面積的功率密度設於0.25〜2.56W/cm2的範圍內 微波輸出是例如可從500〜5〇〇OW的範圍內按照 擇形成上述範圍內的功率密度。藉由在以上的條 ，可均一地形成不含氫的氮化矽膜。 其次，如圖5B所示，在第1工程後，停止 含氧原子氣體供給源19b短時間供給〇2氣體（ 氣體導入工程）。亦即，一時的（圖4的t2〜t3 停止往處理容器1內之微波、SiCl4及N2的供給 漿，且在處理容器1內將〇2氣體導入處理容器 藉由第1工程的電漿CVD處理所成膜的SiN膜 面暴露於氧。藉此，可將極微量的氧導入至SiN 表面。另外，含氧原子氣體，亦可取代02氣體 用〇3氣體、NO氣體、N02氣體、N20氣體等。 〇2氣體流動時，可在不損及〇2氣體流動效果的 稀有氣體或氮氣體等作爲載氣來與〇2氣體一起 如，在圖4雖是停止N2氣體的供給，但N2氣體 可不停止。 〇2氣體流動是以SiN膜70a的成長在膜厚方 標膜厚（SiN膜70的全膜厚）的中央附近的時 標膜厚的30〜70 %的範圍內進行〇2氣體流動爲 溫度設定 範圍內即 I板28的 爲理想。 目的來選 件下成膜 電漿，從 含氧原子 的期間） ，熄滅電 1內，將 70a的表 膜7〇a的 ，例如使 並且，在 範圍，以 導入。例 的供給亦 向接近目 機例如目 理想，在 -22 - 201107521 40〜60%的範圍內進行〇2氣體流動更爲理想。藉此，如後 述般，作爲非揮發性半導體記憶體裝置的電荷儲存層用時 ，可取得良好的資料寫入特性。1次的〇2氣體流動的時間 是例如1 0秒以上3 0 0秒以下的範圍內爲理想’ 3 0秒以上 1 2 0秒以下的範圍內更爲理想。 〇2氣體流動時的〇2氣體（含氧原子氣體）的流量是 例如 10mL/min(sccm)以上 2000mL/min( seem)以下爲 理想，更理想是設定於 l〇〇mL/min ( seem )以上 2000mL/min ( seem )以下，最好是設定於 l〇〇mL/min ( seem)以上l〇〇〇mL/min(sccm)以下。另外’在使用其 他種類的含氧原子氣體時也是同樣的。 02氣體流動時的處理容器1內的壓力，較理想是設定 成與其前後進行的電漿CVD的第1工程（圖4的M〜t2 的區間）或第2工程（圖4的t3〜t4的區間）同等以上的 壓力，例如0.1〜133.3Pa。另外，藉由將〇2氣體流動時 的壓力設定成比氮化矽膜形成時的壓力更高，拉長處理容 器1內之〇2氣體的滯留時間（residence time)，可更提 高02氣體流動的效果。 〇2氣體流動終了後，在與上述第1工程同條件下，再 開始電漿CVD處理（第2工程）。亦即，.如圖5C及圖 5D所示，再度往處理容器1內，再開始微波、SiCl4及N2 的供給，使生成SiCl4/N2氣體電漿，在第1工程，在成膜 後的第ISiN膜70a上使堆積第2SiN膜70b而層疊。如此 —來，可在目標膜厚例如2nm〜300nm的範圍內，較理想 [ -23- 201107521 是以2nm〜50nm的範圍內的膜厚來形成SiN膜70。一旦 SiN膜70成長至目標膜厚，則關閉（OFF )微波產生裝置 39的功率，而使電漿停止（圖4的t4)。然後，停止 SiCl4及N2的供給（圖4的t5 )。如以上那樣，對一片晶 圓 W的成膜處理會終了，因此以和前述相反的程序來從 電漿CVD裝置100搬出晶圓W。 在圖5D是依虛線來顯示在形成目標膜厚的SiN膜70 中導入〇2氣體的位置。〇2氣體的導入是在停止電漿的狀 態下進行，所以往S iN膜7 0中之氧的混入是微量’即使 針對SiN膜70進行TEM (透過型電子顕微鏡）或XPS( X線光電子分光）分析等也未被觀察明確的層構造。但’ 藉由〇2氣體流動，可想像在圖5D所示的SiN膜70中的 〇2氣體的導入位置，至少平面地Si-Ο結合會被形成單層 或數單層程度，形成高陷阱密度的區域（陷阱層）。而且 ，在接近目標膜厚（SiN膜70的全膜厚）的中央附近的 時機例如目標膜厚的30〜70%的範圍內（較理想是40〜 60%的範圍內）進行〇2氣體流動’藉此可將〇2氣體流動 所產生的陷阱層形成於離SiN膜70的膜厚方向的中心 ± 2 0 %以內，較理想是± 1 0 %以內的厚度的範圍內，在將 SiN膜70作爲非揮發性半導體記憶體裝置的電荷儲存層 用時，可取得良好的資料寫入特性。 以上的條件是作爲處方來保存於控制部50的記憶部 53。然後，製程控制器51會讀出該處方來往電獎CVD裝 置1〇〇的各構成部例如加熱器電源5a、氣體供給裝置18 -24- 201107521 、排氣裝置24、微波產生裝置39等送出控制信號，藉此 實現在所望的條件下的電漿CVD處理。 以上那樣取得的SiN膜70因爲陷阱多，所以例如作 爲半導體記憶體裝置的電荷儲存層使用時，資料寫入特性 會被改善。並且，藉由適用本發明的方法所形成的氮化矽 膜來作爲例如半導體記憶體裝置的電荷儲存區域，可製造 具備良好的資料寫入特性的半導體記憶體裝置。 [第2實施形態] 其次，一邊參照圖6及圖7，一邊說明有關本發明的 第2實施形態的氮化矽膜的成膜方法。圖6是本實施形態 的氮化矽膜的成膜處理的微波、SiCl4氣體、N2氣體及02 氣體的導入的時序圖。又，圖7是表示在本實施形態所被 成膜的氮化矽膜的〇2氣體的導入位置。另外，在本實施 形態也是使用SiCl4氣體及N2氣體作爲處理氣體，有關使 用其他含Si氣體或含N氣體時也是同樣。 第1實施形態是在電漿CVD工程的期間僅1次（圖4 的t2〜t3的區間）進行〇2氣體流動，但在本實施形態是 將〇2氣體流動重複進行2次以上，此點與第1實施形態 不同。本實施形態是除了將〇2氣體流動重複進行2次以 上的點以外，其餘則和第1實施形態同樣，所以在以下是 以相異點爲中心進行說明。在圖0及圖7也是對於和第1 實施形態同一構成附上同一符號’而省略說明。 本實施形態的電漿CVD工程是在圖6的的區ι -25- 201107521 間進行，形成SiN膜70。在該電漿CVD工程的途 預定時間（圖6的t12〜tl3的區間及t14〜t15的區 止電漿，而實施〇2氣體流動。亦即’在第1工程 的t,】〜t12的區間）之後，停止往處理容器1內之 SiCl4氣體及N2氣體的供給’而從含氧原子氣體 19b將02氣體往處理容器1內短時間供給（第1 : 氣體流動；圖6的ti2〜ti3的區間）。 第1次的〇2氣體流動終了後，再度往處理容 供給微波、SiCl4氣體及N2氣體，在與第1工程同 ，再開始電漿CVD處理之SiN膜70的形成（第2 圖6的t13〜t14的區間）。其次，再度停止往處理 內之微波、SiCl4氣體及N2氣體的供給，而從含氧 體供給源1 9b將02氣體往處理容器1內短時間供雜 次的〇2氣體流動；圖6的t14〜t15的區間）。另外 6中，區間ti2〜tl3與區間tl4〜ti5的長度可爲相同 ，各例如1 〇〜3 0 0秒爲理想’更理想是3 0秒〜1 2 0 在第2次的02氣體流動終了後，再度往處理 內供給微波、SiCl4氣體及N2氣體，在與第丨工程 下，再開始電漿CVD處理（第3工程；圖6的t15 區間）。此第3工程是除了工程時間以外，實質上 工程相同。另外，雖圖示省略，但實際在第1工程 後第1次的〇2氣體流動之前及第2工程的終了後 的〇2氣體流動之前，分別將淨化氣體導入至處理 內，而去除残留成膜氣體爲理想，藉此可提高〇2 中，僅 間）停 (圖6 微波、 供給源 欠的〇2 器1內 條件下 工程； 容器1 原子氣 Ϊ (第2 ，在圖 或相異 秒。 容器1 同條件 〜ti6的 與第2 的終了 第2次 容器1 氣體流 -26- 201107521 動的效果。 圖7是表示在電漿CVD工程的期間進行2次〇2氣體 流動，藉此所被成膜之SiN膜70的膜厚方向的〇2氣體的 導入位置。在進行2次以上〇2氣體流動時也是與第1實 施形態同樣，以SiN膜70的成長在膜厚方向接近目標膜 厚的1/2附近的時機例如成膜的目標膜厚的30〜70 %的範 圍內進行〇2氣體流動爲理想，更理想是在40〜60%的範 圍內進行〇2氣體流動。例如’在進行2次02氣體流動時 ，是在到達SiN膜70的成膜的目標膜厚的30%的時間點 以後的時機進行第1次的〇2氣體流動’在到達成膜的目 標膜厚的70%的以前的時機實施第2次的02氣體流動爲 更理想。如此一來，可將〇2氣體流動所產生的陷阱層形 成於離SiN膜70的膜厚方向的中心±2 0 %以內，較理想是 ±10%以內的厚度的範圍內，在將具有此陷阱的SiN膜70 作爲非揮發性半導體記憶體裝置的電荷儲存層用時，可取 得良好的資料寫入特性。 如以上那樣，藉由在電漿CVD工程的期間進行複數 次〇2氣體流動，可在SiN膜70中將陷阱形成層狀，可形 成具有多數的陷阱之SiN膜70。藉由如此形成多數的陷 阱，相較於只進行1次02氣體流動時，可更提高將SiN 膜70作爲非揮發性半導體記憶體裝置的電荷儲存層利用 時的寫入特性。另外，〇2氣體流動的次數並非限於2次， 亦可重複進行3次以上。在重複進行3次以上02氣體流 動時’可組合02氣體流動與第2工程來予以重複。 -27- 201107521 本實施形態的其他構成及效果是與第 [試驗例] 其次，說明有關成爲本發明的基礎之 ，作成如圖8所示那樣的SONOS構造的| 的符號60是Si02膜，符號70是具有陷 符號80是阻絕Si02膜，符號90a是由單 Si基板，符號90b是多結晶矽膜，SiN Jg 層，多結晶矽膜90b是具有作爲控制閘電 試驗中是將矽基板90a設爲接地電位，韵 以預定範圍來使電壓變化而施加（向前（ 逆向地使變化而施加（反向（reverse)) 電壓施加過程的電容，由向前及反向的各 曲線）來求取AVfb ( Vfb磁滯）。之所以 加下CV曲線變化，是因爲電壓施加，而 ，正孔（hole)被設陷阱的結果，爲了消 生電壓的變化，Vfb磁滞越大，SiN膜70 示寫入特性佳。本試驗是對圖8的試驗用 的範圍的電壓，計測ΔνΠί，評價資料寫乂 試驗例1 : 在本試驗是將SiN膜70以1-Α)通 1-B )電漿CVD成膜+〇2氣體流動（1次 1實施形態同樣 實驗資料。首先 ΐ驗用裝置。圖8 ί阱的氮化矽膜， .結晶矽所構成的 I 7〇爲電荷儲存 :極的機能。在此 [多結晶矽膜90b forward ))後， ，計測此往復的 CV曲線（磁滯 在往復的電壓施 在SiN膜70中 除其電荷，而產 中陷阱越多，顯 裝置施加4〜6V .特性。 常的電漿CVD、 ;膜厚方向中央 -28- 201107521 部）、1-C)電漿CVD成膜+02氣體流動（2次；界面附 近）、1-D )電漿CVD (全區間02氣體導入；SiON膜形 成）的4種成膜方法來成膜。各成膜方法的條件是如以下 般。 1-A)通常的電漿CVD之氮化矽膜的成膜： 使用電漿CVD裝置1 00。Xg/4~Xg. In Fig. 2, the interval between the adjacent microwave radiation holes 3 2 forming concentric circles is indicated by Ar. Further, the shape of the microwave radiation holes 3 2 may be other shapes such as a circular shape or an arc shape. Further, the arrangement of the microwave radiation holes 32 is not particularly limited, and may be arranged in a spiral shape or a radial shape, for example, in addition to the concentric shape. On the upper surface of the planar antenna 31, a slow wave material 33 having a dielectric constant larger than a vacuum is provided. This slow wave material 33 is because the wavelength of the microwave is long in the vacuum, so that it has the function of shortening the wavelength of the microwave to adjust the plasma. In addition, between the planar antenna 31 and the transmission plate 28, and the slow wave material 3 3 and the plane Although the antennas 31 can be contacted or separated from each other, it is preferable to make contact. A metal cover member 34 is provided on the upper portion of the processing container 1 so as to cover the planar antenna 31 and the slow wave member 33. The metal cover member 34 is formed of, for example, a metal material such as aluminum or stainless steel, and constitutes a flat waveguide as opposed to the planar antenna 31. The upper end of the plate 13 and the metal cover member 34 are sealed by a sealing member 35. In the inside of the metal cover member 34, a cooling water flow path 34a is formed. The cooling water flow path 34a is used to circulate the cooling water. The metal cover member 34, the slow wave material 33, the planar antenna 31, and the transmission plate 28 can be cooled. Further, the metal cover member 34 is grounded to the center of the upper wall (top) of the metal cover member 34, and an opening portion 36 is formed. Here, the opening portion 36 is connected to the waveguide 37»waveguide 37. The other end side is connected to the microwave generating device 39 which generates microwaves via the matching circuit 38. The waveguide 37 has a coaxial coaxial waveguide 37a having a circular cross section extending upward from the opening 36 of the metal cover member 34, and a rectangular extending horizontally connected to the upper end of the coaxial waveguide 37a. The waveguide 37b° has an inner conductor 41 extending in the center of the coaxial waveguide 37a. The inner conductor 41 is made of metal copper or the like, and is connected and fixed to the center of the planar antenna 31 at its lower end portion. With such a configuration, the microwave is propagated to the inner conductor 41 of the coaxial waveguide 37a and introduced to the planar antenna 31, and the radiation efficiency is uniformly propagated uniformly to the flat waveguide. According to the microwave introducing mechanism 27 configured as described above, the microwave generated by the microwave generating device 39 can be transmitted to the planar antenna 31 via the waveguide 37, and introduced into the processing container 1 via the transmissive plate 28. In addition, the frequency of the microwave is preferably 2.45 GHz, and the other is 8.35 GHz '1.98 GHz. Each component of the plasma CVD apparatus 100 is configured to be connected to the control unit 5 to be controlled. The control unit 50 has a computer. For example, as shown in Fig. 3, the control unit 50 includes a process controller 51 having a CPU, a user interface 52 connected to the process controller 51, and a memory unit 53. The process controller 51 is a constituent unit (for example, a heater power source 5a, a gas supply device 18, and an exhaust device 24) that collectively controls process conditions related to temperature, pressure, gas flow rate, microwave output, and the like in the plasma CVD apparatus 100. Control means for the microwave generating device 39, etc.). The user interface 52 has a keyboard, a display, and the like. The keyboard is an input operation of the commander to manage the plasma CVD device loo, -17-201107521. This display allows the visual state of the plasma CVD apparatus 1 to be visually displayed. Further, a prescription or the like is stored in the storage unit 53 for recording a control program (software) or processing condition data for realizing various processes performed in the plasma CVD apparatus under the control of the process controller 51. Wait. Then, if necessary, an arbitrary prescription is called from the memory unit 53 by an instruction from the user interface 52, etc., and is executed in the process controller 51 under the control of the process controller 51 in plasma CVD. The desired processing is performed in the processing container 1 of the apparatus 100. Further, the prescription of the control program or the processing condition data and the like can be stored in a computer-readable memory medium such as a CD-ROM, a hard disk, a software, a flash memory, a DVD, or a Blu-ray Disc (Blu-ray Disc). The state of the device or the like may be transmitted from any other device, for example, via a dedicated line. Next, a procedure for forming a film of a tantalum nitride film using a plasma CVD apparatus of the RLSA method will be described. Here, SiCl4 is used as the Si-containing gas, N2 gas is used as the N-containing gas, and 〇2 gas is used as the oxygen-containing atom gas. Fig. 4 is a timing chart showing the introduction of the micronization of the film formation process of the tantalum nitride film, the SiCl4 gas, the N2 gas, and the helium gas. First, the gate valve 17 is opened, and the wafer W is carried into the processing container 1 from the carry-out port 16, and is placed on the mounting table 2 for heating. Then, while the inside of the processing container 1 is evacuated, the N 2 gas is introduced into the processing container 1 from the nitrogen-containing gas supply source 19 a of the gas supply device 18 through the gas introduction hole 14 at a predetermined flow rate. The Si gas is introduced into the processing container 1 from the Si gas supply source 19c -18-201107521 and the inert gas supply source 19d via the gas introduction hole 15 via the gas introduction hole 15 (T〇 of Fig. 4). Further, the inside of the processing container 1 is set to a predetermined pressure. The conditions at this time will be described later. Next, the microwave of a predetermined frequency generated by the microwave generating device 39, for example, 2.45 GHz, is guided to the waveguide 37 via the matching circuit 38 (h of Fig. 4). The microwave guided by the waveguide 37 is sequentially supplied to the planar antenna 31 constituting the flat waveguide via the inner conductor 41 through the rectangular waveguide 37b and the coaxial waveguide 37a. The microwave propagates radially from the coaxial waveguide 37a to the planar antenna 31. Further, the microwave is radiated from the slit-shaped microwave radiation hole 3 2 of the planar antenna 31 via the transmission plate 28 in a space above the crystal W in the processing container 1 as a circular wave. By radiating the microwaves radiated to the processing container 1 from the planar antenna 31 through the transmission plate 28, an electromagnetic field is formed in the processing container 1, and the N2 gas, the SiCl4 gas, and the Ar gas are respectively plasmad. Then, in the plasma, the dissociation of the material gas proceeds efficiently, and the reaction of the active species (ion, radical, etc.), tantalum nitride (SiN; here, the composition ratio of Si and N is not necessarily stoichiometric It is determined that the film according to the film formation conditions is different, and the film of the following is stacked. The plasma CVD process is performed from the range of t1 to t4 in Fig. 4 . In the film formation method of the tantalum nitride film of the present embodiment, in the middle of the film formation of the tantalum nitride film of the CVD process, the electric power is stopped only for a predetermined period of time (the interval of t2 to h in FIG. 4), and the oxygen atom is contained. In the gas supply, the source of the oxygen-containing atomic gas such as the 〇2 gas is introduced into the gas through the gas introduction hole I4-19-201107521 The oxygen-containing atom gas introduction process in the chemical container 1 (here, since the 〇2 gas is typically used, There is a case of "〇2 gas flow". In the case of this gas flow, the tantalum nitride film on the way of formation is exposed to oxygen to cause Si-o bonding to form a trap. As described above, in the method for forming a tantalum nitride film according to the present embodiment, the formation of the tantalum nitride film is carried out by interposing the 02 gas, and the tantalum nitride film is grown by plasma before the flow of the helium gas. The first work (the interval of n to t2 in Fig. 4) and the second process in which the tantalum nitride film is grown by plasma after the flow of the 〇2 gas (the interval of t3 to t4 in Fig. 4). That is, the first tantalum nitride film is formed by plasma, and the first tantalum nitride film is exposed to the oxygen-containing gas to form a trap, and the second tantalum nitride film is formed thereon by plasma. Further, in the oxygen atom-containing gas introduction process, the Si-O bonding can be uniformly spread in a planar manner, and the trap can be uniformly dispersed. Figs. 5A to 5D are cross-sectional views showing the vicinity of the surface of the wafer W of the process of forming the tantalum nitride film by the plasma CVD apparatus 100. As shown in FIG. 5A, for example, on any of the underlayers (here, the Si〇2 film 60), a plasma CVD apparatus 100 is used to generate a SiCl4/N2 gas plasma, and a tantalum nitride is formed by a plasma CVD method. Membrane (SiN film) 7〇a (first project). The SiN film 70a of the first process is formed by supplying a SiCl gas containing Si gas and a treatment gas containing N 2 gas as a nitrogen-containing gas into the processing container 1, and can be carried out under the following conditions. In this case, it is preferable to form a stable supply gas with a plasma which is stabilized by the addition of a rare gas, and the treatment pressure is preferably in the range of 0.1 LPa or more and 6.7 Pa or less, and -20-201107521 is more preferably O.lPa or more and 4 Pa or less. Within the scope. In order to easily dissociate SiCl4, it is preferable to have a low processing pressure. When the treatment pressure exceeds 6.7 Pa, the dissociation of the Si Cl 4 gas is small, and the reaction with nitrogen does not progress, and the film formation is not sufficient, which is not preferable. Further, it is preferable that the flow ratio of the SiCl4 gas to the total flow rate of the processing gas (the percentage of the flow rate of the SiCl4 gas/total processing gas flow rate) is 〇3% or more and 15% or less, more preferably 〇. 〇3 % or more and 1%. the following. Further, it is preferable that the flow rate of the SiCl 4 gas is set to 10 mL/min or more and 10 mL/min or less, and more preferably set to 0.5 mL/min or more and 2 mL/min or less. In addition, the same is true when other types of Si-containing gas are used. Further, the ratio of the N2 gas flow rate to the total process gas flow rate (the percentage of the N2 gas/total process gas flow rate) is preferably 5% or more and 99% or less, more preferably 40% or more and 99% or less. Further, the flow rate of the N2 gas is preferably set to 100 mL/min (sccm) or more and 5000 mL/min (sccm) or less, and more preferably set to 1 mL/min (sccm) or more and 2000 mL/min (sccm) or less. In addition, the same is true when other types of N-containing gas are used. Further, the flow rate ratio of the Ar gas to the total processing gas flow rate (for example, the percentage of the Ar gas/total processing gas flow rate) is preferably 10% or more and 90% or less, more preferably 10% or more and 60% or less. Further, the flow rate of the rare gas such as Ar is preferably set to 10 mL/min (sccm) or more and 1000 mL/min (sccm) or less, and more preferably set to 10 m L / min (sccm) or more and 500 m L / min. (sccm) below. Further, the temperature of the plasma CVD treatment is set to be 300 ° C or higher, and preferably 400 ° C or higher and 600 ° C or lower. Further, the microwave output of the plasma CVD apparatus 100 is such that the power density per area of the transparent area is set in the range of 0.25 to 2.56 W/cm 2 , and the microwave output is, for example, in the range of 500 to 5 〇〇 OW. Power density. By the above strip, a tantalum nitride film containing no hydrogen can be uniformly formed. Next, as shown in Fig. 5B, after the first process, the oxygen-containing atom gas supply source 19b is stopped and the 〇2 gas is supplied for a short time (gas introduction process). That is, at a time (t2 to t3 in FIG. 4, the supply of the microwave, SiCl4, and N2 in the processing container 1 is stopped, and the 〇2 gas is introduced into the processing container in the processing container 1 by the plasma CVD of the first process. The surface of the SiN film formed by the treatment is exposed to oxygen, whereby a very small amount of oxygen can be introduced to the surface of the SiN. In addition, the oxygen-containing gas can also replace the 气体3 gas, the NO gas, the N02 gas, and the N20 for the 02 gas. Gas, etc. When the gas flows, the rare gas or the nitrogen gas that does not impair the gas flow effect of the helium gas can be used as the carrier gas together with the helium gas. For example, in Fig. 4, the supply of the N2 gas is stopped, but N2 The gas flow is not performed in the range of 30 to 70% of the time-scale film thickness in the vicinity of the center of the film thickness of the SiN film 70a (the total film thickness of the SiN film 70). It is desirable that the gas flow is within the temperature setting range, that is, the I plate 28. The purpose is to form a plasma under the option of the plasma, from the period of containing oxygen atoms, to extinguish the electricity inside the cell, and to make the surface of the 70a film 7a, for example Also, in the range to import. The supply of the example is also ideal for close to the camera, for example, it is more desirable to carry out the 〇2 gas flow in the range of -22 - 201107521 40~60%. As a result, as described later, when used as a charge storage layer of a nonvolatile semiconductor memory device, good data writing characteristics can be obtained. The time during which the primary enthalpy gas flows is, for example, in the range of 10 seconds or more and 300 seconds or less, which is preferably in the range of preferably more than 30 seconds and not more than 1 to 20 seconds. The flow rate of the 〇2 gas (oxygen atom-containing gas) when the gas is 〇2 is, for example, 10 mL/min (sccm) or more and 2000 mL/min or less, and more preferably set to 10 mL/min (see). The above 2000 mL/min (them) or less is preferably set to 1 〇〇mL/min (see) or more and 10 〇〇〇mL/min (sccm) or less. In addition, the same is true when other types of oxygen-containing atomic gases are used. 02 The pressure in the processing container 1 at the time of gas flow is preferably set to the first process (the section of M to t2 in FIG. 4) or the second process (the t3 to t4 of FIG. 4) of the plasma CVD performed before and after. The interval is equal to or higher than the pressure, for example, 0.1 to 133.3 Pa. Further, by setting the pressure at which the helium gas is flowing to be higher than the pressure at which the tantalum nitride film is formed, the residence time of the helium gas in the processing container 1 is elongated, and the 02 gas flow can be further enhanced. Effect. After the end of the gas flow of 〇2, the plasma CVD treatment (second work) is started under the same conditions as the above-mentioned first project. That is, as shown in FIG. 5C and FIG. 5D, the microwave, SiCl4, and N2 are again supplied into the processing container 1, and the SiCl4/N2 gas plasma is generated, and in the first project, after the film formation The second SiN film 70b is deposited on the ISiN film 70a and laminated. In this manner, the SiN film 70 can be formed in a range of a target film thickness of, for example, 2 nm to 300 nm, preferably [-23-201107521] in a film thickness in the range of 2 nm to 50 nm. Once the SiN film 70 is grown to the target film thickness, the power of the microwave generating device 39 is turned off (OFF), and the plasma is stopped (t4 of Fig. 4). Then, the supply of SiCl4 and N2 is stopped (t5 of Fig. 4). As described above, since the film formation process for one wafer W is completed, the wafer W is carried out from the plasma CVD apparatus 100 in the reverse procedure. In Fig. 5D, the position at which the 〇2 gas is introduced into the SiN film 70 forming the target film thickness is shown by a broken line. The introduction of the gas of 〇2 is performed while the plasma is stopped, and the mixing of oxygen in the conventional SiN film 70 is a small amount. Even TEM (transmission electron micromirror) or XPS (X-ray photoelectron spectroscopy) is performed on the SiN film 70. ) Analytical layers, etc., which are also unobserved. However, by the flow of 〇2 gas, it is conceivable that at least the planar Si-Ο bond is formed into a single layer or a single layer to form a high trap at the introduction position of the 〇2 gas in the SiN film 70 shown in FIG. 5D. The area of density (trap layer). Further, the gas flow of 〇2 is performed in a range of 30 to 70% (preferably 40 to 60%) of the target film thickness near the center of the target film thickness (the total film thickness of the SiN film 70). 'By this, the trap layer generated by the flow of the 〇2 gas can be formed within ±20% from the center of the SiN film 70 in the film thickness direction, and preferably within a range of ±10% or less, in the SiN film. When used as a charge storage layer for a non-volatile semiconductor memory device, 70 can achieve good data writing characteristics. The above conditions are stored in the memory unit 53 of the control unit 50 as a prescription. Then, the process controller 51 reads out the prescription and sends the control to each component of the credit CVD apparatus 1 such as the heater power source 5a, the gas supply device 18-24-201107521, the exhaust device 24, the microwave generating device 39, and the like. Signal, thereby achieving plasma CVD processing under the desired conditions. Since the SiN film 70 obtained as described above has many traps, the data writing characteristics are improved when used as a charge storage layer of a semiconductor memory device, for example. Further, by using the tantalum nitride film formed by the method of the present invention as a charge storage region of, for example, a semiconductor memory device, a semiconductor memory device having excellent data writing characteristics can be manufactured. [Second Embodiment] Next, a film forming method of a tantalum nitride film according to a second embodiment of the present invention will be described with reference to Figs. 6 and 7 . Fig. 6 is a timing chart showing the introduction of microwaves, SiCl 4 gas, N 2 gas, and 02 gas in the film formation process of the tantalum nitride film of the present embodiment. Further, Fig. 7 shows the introduction position of the krypton gas of the tantalum nitride film formed in the present embodiment. Further, in the present embodiment, SiCl 4 gas and N 2 gas are also used as the processing gas, and the same applies to the case of using other Si-containing gas or N-containing gas. In the first embodiment, the 〇2 gas flow is performed only once during the plasma CVD process (the interval t2 to t3 in Fig. 4). However, in the present embodiment, the 〇2 gas flow is repeated twice or more. It is different from the first embodiment. The present embodiment is the same as the first embodiment except that the flow of the helium gas is repeated twice or more. Therefore, the following description will focus on the difference. In Figs. 0 and 7, the same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof will be omitted. The plasma CVD process of this embodiment is performed between the regions ι -25 - 201107521 of Fig. 6 to form the SiN film 70. At the predetermined time of the plasma CVD process (the interval between t12 and t13 in Fig. 6 and the interval between t14 and t15), the gas flow of 〇2 is performed. That is, 't in the first project, 】~t12 After the interval, the supply of the SiCl4 gas and the N2 gas in the processing container 1 is stopped, and the 02 gas is supplied from the oxygen-containing atomic gas 19b to the processing container 1 for a short period of time (first: gas flow; ti2 to ti3 of Fig. 6) Interval). After the first 〇2 gas flow is completed, the microwave, the SiCl4 gas, and the N2 gas are again supplied to the treatment volume, and the formation of the SiN film 70 by the plasma CVD treatment is started again as in the first process (t13 of FIG. 6). ~ t14 interval). Next, the supply of the microwave, the SiCl4 gas, and the N2 gas in the treatment is stopped again, and the 〇2 gas which supplies the 02 gas into the processing container 1 for a short time from the oxygen donor supply source 19b flows; t14 of Fig. 6 ~ t15 interval). In the other six, the length of the interval ti2 to t13 and the interval tl4 to ti5 may be the same, and each of the intervals of 1 〇 to 30,000 is ideal, and more preferably, it is 30 seconds to 1 2 0. Thereafter, microwaves, SiCl4 gas, and N2 gas are supplied again into the process, and plasma CVD processing (third process; t15 section of Fig. 6) is started again under the second process. This third project is essentially the same except for the engineering time. In addition, although the illustration is omitted, the purge gas is introduced into the treatment before the flow of the first 〇2 gas after the first project and before the flow of the 〇2 gas after the end of the second project, and the residual gas is removed. Membrane gas is ideal, which can improve the 〇2, only between) (Fig. 6 microwave, supply source under the condition of 〇2 device 1; container 1 atomic gas Ϊ (2, in the figure or different seconds The effect of the container 1 with the condition ti6 and the second end of the second container 1 gas flow -26-201107521. Fig. 7 shows the flow of 〇2 gas twice during the plasma CVD process. The introduction position of the 〇2 gas in the film thickness direction of the SiN film 70 to be formed is similar to that of the first embodiment, and the growth of the SiN film 70 approaches the target film in the film thickness direction. It is preferable to carry out the gas flow of the helium 2 in the range of 30 to 70% of the target film thickness of the film formation in the vicinity of the thickness of 1/2, and it is more preferable to carry out the gas flow of the helium 2 in the range of 40 to 60%. When the 02 gas flow is performed twice, the film formation of the SiN film 70 is reached. It is more preferable to carry out the second 02 gas flow at the timing until the 70% of the target film thickness of the film is reached at the timing after the time point of 30% of the film thickness. In the first place, the trap layer generated by the flow of the 〇2 gas can be formed within ±20% of the center of the SiN film 70 in the film thickness direction, and preferably within ±10% of the thickness of the SiN film 70. When the SiN film 70 is used as a charge storage layer of a nonvolatile semiconductor memory device, good data writing characteristics can be obtained. As described above, by performing a plurality of 〇2 gas flows during the plasma CVD process, The trap is formed into a layered shape in the SiN film 70, and the SiN film 70 having a large number of traps can be formed. By forming a plurality of traps as described above, the SiN film 70 can be further improved as compared with the case where only one gas flow is performed once. The writing characteristics of the charge storage layer of the non-volatile semiconductor memory device are not limited to two, and may be repeated three times or more. When the gas flow is repeated three or more times. Can combine 02 gas The flow and the second work are repeated. -27- 201107521 Other configurations and effects of the present embodiment are the same as the first [test example] Next, the basis of the present invention is described, and the SONOS structure as shown in Fig. 8 is created. The symbol 60 is a SiO 2 film, the symbol 70 is a recessed symbol 80 is a blocking SiO 2 film, the symbol 90 a is a single Si substrate, the symbol 90 b is a polycrystalline germanium film, the SiN Jg layer, and the polycrystalline germanium film 90b is provided as a control gate. In the electric test, the tantalum substrate 90a is set to the ground potential, and the rhythm is applied in a predetermined range to change the voltage (forward (reversely applying a change (reverse)) voltage application process, forward and Reverse each curve) to find AVfb (Vfb hysteresis). The reason why the CV curve change is added is because the voltage is applied, and the hole is trapped. As the voltage is changed, the Vfb hysteresis is larger, and the SiN film 70 shows good writing characteristics. This test is for the voltage range of the test in Fig. 8, and the measurement data is ΔνΠί, and the evaluation data is written. Test Example 1: In this test, the SiN film 70 is formed into a film by 1-V) plasma CVD + 〇 2 gas flow (1 time 1 embodiment of the same experimental data. First of all, the test device. Figure 8 ί 的 nitride film, I 〇 矽 矽 〇 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷 电荷After the crystallization film 90b is forward), the reciprocating CV curve is measured (the hysteresis is applied to the SiN film 70 in addition to the electric charge in the reciprocating voltage, and the more traps are produced, the display device applies 4 to 6 V. Characteristics. Plasma CVD, film thickness direction center -28-201107521), 1-C) plasma CVD film formation + 02 gas flow (2 times; near the interface), 1-D) plasma CVD (full interval 02 gas Four kinds of film formation methods of introduction and formation of SiON film were used to form a film. The conditions of each film formation method are as follows. 1-A) Film formation of a conventional plasma CVD tantalum nitride film: A plasma CVD apparatus 100 is used.

Ar 氣體流量；40mL/min ( seem) N2 氣體流量；450mL/min(sccm)Ar gas flow; 40mL/min (see) N2 gas flow; 450mL/min (sccm)

SiCl4 氣體流量；lmL/min ( seem) 處理壓力；2.7Pa(20mTorr) 處理溫度（載置台）：400°C 微波功率：3kW 處理時間；11 0秒 目標膜厚；8nm 1-B)根據電漿CVD + 02氣體流動之具有陷阱的氮化 矽膜（1次；膜厚方向中央部附近）： i )第1次的電漿CVD (氮化矽膜形成） 處理時間與目標膜厚以外，是以和上述1 - A )的《 漿CVD同條件來進行電漿CVD * 處理時間；5 5秒 目標膜厚；4nm ii ) 〇2氣體流動（陷阱層形成） 第1次的電漿CVD之後，停止電漿，在以下的條 件下實施〇2氣體流動。 | -29- 201107521 〇2 氣體流量；600mL/min(SCCm) 處理時間；60秒間 iii)第2次的電漿CVD (氮化矽膜形成） 處理時間與目標膜厚以外，是與上述第1次的電漿 CVD同樣地實施。 處理時間；5 5秒 目標膜厚：4nm 1-C )根據電漿CVD + 02氣體流動之具有陷阱的氮化 矽膜（2次；界面附近）： i )第1次的〇2氣體流動（界面陷阱層形成） 即將電漿CVD之前，在以下的條件下實施〇2氣體 流動。 〇2 氣體流量；600mL/min ( seem) 處理時間；6 0秒間 ii) 電漿CVD (氮化矽膜形成） 也包含處理時間與目標膜厚，以和上述 漿CVD同條件來進行電漿CVD。 iii) 第2次的02氣體流動（界面陷阱層形$ > 剛電漿CVD之後，停止電漿，在以下的條件T實 施〇2氣體流動。 〇2 氣體流量；600mL/min(scem) 處理時間；60秒間 ^ - η N膜开^成 1-D )電漿CVD (全區間02氣體導入；ηκ -30- 201107521 使用電漿CVD裝置100。SiCl4 gas flow rate; lmL/min (see) processing pressure; 2.7Pa (20mTorr) processing temperature (mounting table): 400°C microwave power: 3kW processing time; 11 0 second target film thickness; 8nm 1-B) according to plasma A tantalum nitride film with a trap of CVD + 02 gas flow (1 time; near the center of the film thickness direction): i) The first plasma CVD (formation of tantalum nitride film) The processing time and the target film thickness are The plasma CVD* treatment time is the same as the above-mentioned 1 - A) "Pulp CVD * processing time; 5 5 seconds target film thickness; 4 nm ii ) 〇 2 gas flow (trap layer formation) after the first plasma CVD, The plasma was stopped, and the 〇2 gas flow was carried out under the following conditions. -29- 201107521 〇2 gas flow rate; 600mL/min (SCCm) processing time; 60 seconds iii) second plasma CVD (yttrium nitride film formation) treatment time and target film thickness are the same as above Secondary plasma CVD is performed in the same manner. Processing time; 5 5 seconds target film thickness: 4 nm 1-C) Tantalum nitride film with traps according to plasma CVD + 02 gas flow (2 times; near the interface): i) 1st 〇2 gas flow ( Interface trap layer formation) Immediately before plasma CVD, the 〇2 gas flow was carried out under the following conditions. 〇2 gas flow rate; 600mL/min (see) processing time; 60 seconds ii) plasma CVD (tantalum nitride film formation) also includes processing time and target film thickness to perform plasma CVD under the same conditions as the above slurry CVD . Iii) The second 02 gas flow (interfacial trap layer shape > After the plasma CVD, the plasma is stopped, and the gas flow is performed under the following conditions T. 〇2 gas flow rate; 600 mL/min (scem) treatment Time; 60 seconds ^ - η N film opening ^ 1-D) plasma CVD (full interval 02 gas introduction; η κ -30 - 201107521 using plasma CVD device 100.

Ar 氣體流量；40mL/min(sccm) N2 氣體流量；450mL/min(sccm) ◦ 2 氣體流量；lmL/min(sccm)Ar gas flow rate; 40 mL/min (sccm) N2 gas flow rate; 450 mL/min (sccm) ◦ 2 gas flow rate; lmL/min (sccm)

SiCl4 氣體流量；lmL/min ( seem) 處理壓力；2.7Pa(20mTorr) 處理溫度（載置台）：500°C 微波功率：3kW 處理時間；150秒 目標膜厚；8nm 圖9是表示顯示朝上述各條件下所被成膜的氮化矽膜 (包含氮化氧化矽膜）的寫入特性之AVfb的測定結果。 另外，圖9的橫軸是資料寫入時間，刻度的「1 E-n」、「 1Ε + η」 （η爲數字）是分別意味「lxi〇_n」、「ixi〇n」（ 圖11也同樣）。在目標膜厚的約一半（膜厚方向的中央 附近）實施〇2氣體流動時，與完全不進行氧導入的通常 電漿CVD所產生的氮化矽膜作比較，顯示較高的Δνα。 另一方面，在氮化矽膜的形成前後實施02氣體流動時， 或在全區間進行氧導入時，與完全不進行氧導入的通常電 漿CVD所產生的氮化矽膜作比較，在Δνη幾乎未見差異 〇 在此’一邊參照圖10Α〜圖10C —邊說明有關〇2氣 體流動的實施對氮化矽膜中的陷阱分佈造成的影響。圖 10Α是在通常的條件下進行電漿CVD而形成氮化矽膜時 -31 - 201107521 ，圖10B是在電漿CVD工程的途中進行1次的02氣體流 動而形成氮化矽膜時，圖10C是在SiN膜70即將成膜之 前及剛成膜之後的時機分別（合計2次）實施〇2氣體流 動時之氮化矽膜中的陷阱的分佈模型，分別在與圖8同樣 構成的SONOS構造的層疊體的能帶圖中模式性顯示者。 另外，圖10B是將SiN膜70的成膜分成2次，在其間實 施1次〇2氣體流動時。圖10A〜圖10C中的符號意義是 與圖8同樣。 如圖10A所示，藉由通常的電漿CVD來形成SiN膜 70時，陷阱T是集中分佈於與鄰接的底層的Si02膜60的 界面附近。另一方面，在SiN膜70的成膜途中，實施1 次〇2氣體流動時，如圖10B所示，陷阱T是集中分佈於 SiN膜70的膜厚方向的中央附近（膜中）。並且，在SiN 膜70即將成膜之前及剛成膜之後的時機合計實施2次02 氣體流動時，如圖10C所示，陷阱T是分佈於與SiN膜 70鄰接的底層的Si 02膜60的界面附近。另外，在圖10C 中，在SiN膜70與阻絕Si02膜80的界面，藉由在SiN 膜70的形成後實施〇2氣體流動所產生的陷阱會在阻絕 Si02膜80的成膜時被初期化而消滅，所以在該界面幾乎 無陷阱T殘留。因此，可想像在SiN膜70即將成膜之前 及剛成膜之後的時機合計實施2次的02氣體流動的圖 10C是陷阱T的分佈結果與圖10A同樣。 在將圖10A〜圖10C所示構造的層疊體想像成 SONOS構造的半導體記憶體裝置時，在資料寫入時是以矽 -32- 201107521 基板90a的電位作爲基準’對成爲閘極電極的多結晶矽膜 9〇b施加預定的正電壓。此時’在通道形成區域（圖示省 略）儲存電子而形成反轉層，該反轉層內的電荷的一部分 會因隧道現象而經由Si〇2膜60來移動至SiN膜70。移動 至SiN膜70的電子是被形成於其內部的陷阱所捕獲，進 行資料的儲存。在此’若比較圖l〇A〜圖i〇c所示的層疊 構造的資料寫入特性’則顯示寫入速度快，最佳的寫入特 性的是圖10B所示的構造。另一方面，在siN膜70即將 成膜之前及剛成膜之後的時機合計實施2次02氣體流動 的圖10C所示的構造是與圖i〇A所示的構造同等，若與圖 1 0B所示的構造作比較’則寫入速度慢，只能取得低的寫 入特性。 藉由在SiN膜70的膜厚方向的中央附近導入〇2氣體 而成爲圖10B所示的構造時，Si02膜60/SiN膜70界面的 陷阱分佈是與藉由通常的電漿CVD而形成的圖10A的構 造同等。但，在圖10B所不的構造，鄰接於Si〇2膜60與 SiN膜70的界面附近的陷阱分佈，因爲有更多的陷阱分 佈在SiN膜70的膜厚方向的中央部，所以通過Si 02膜60 的電荷容易注入至比SiN膜70的膜中更深的位置（中央 部附近）。其結果，圖1 〇B所示的構造，相較於圖1 0A的 構造，可想像寫入速度快，可取得良好的資料寫入性能。 另外，在SiN膜70即將成膜之前及剛成膜之後的時機合 計實施2次02氣體流動的圖10C所示的構造時也是陷阱 T的分佈會最終與圖l〇A同樣，因此無法取得像圖10B那 [ -33- 201107521 樣良好的寫入特性。如以上般，依圖10A〜圖10C 樣的陷阱T分佈的不同，可合理地說明圖9所示的 性的試驗結果。 根據以上，可想像02氣體的導入是只要在藉 CVD來使堆積的SiN膜70的膜厚方向的膜中則在 行而形成陷阱層皆可，特別是在目標膜厚的30%〜 範圍內成長的時機進行而形成陷阱層爲理想。如此 可使陷阱集中地分佈於SiN膜70的膜中。亦即， 的方法是具有可藉由調節〇2氣體的導入時機來控 膜70的膜中之陷阱的膜厚方向的存在分佈之優點 想是使陷阱集中於SiN膜70的膜厚方向的中央附 此可製作出正好該位置形成的陷阱層那樣的構造。 膜中具有陷阱的分佈峰値的SiN膜70是藉由例如 揮發性半導體記憶體裝置的電荷儲存層用，可取得 資料寫入特性。 試驗例2 : 在本試驗是將SiN膜70以2-A)通常的電漿 2-B )電漿CVD + 02氣體流動（1次；膜厚方向中央 2-C)電漿CVD + 02氣體流動（2次；膜厚方向中央 2-D)熱CVD等4種的成膜方法來成膜。各成膜方 件是如以下般。 2-A )通常的電漿CVD : 使用電漿CVD裝置1〇〇〇 所示那 寫入特 由電漿 何處進 7 0 %的 一來， 本發明 制 SiN 。較理 近，藉 然後， 作爲非 良好的 CVD、 部）、 部）、 法的條 -34- 201107521SiCl4 gas flow rate; lmL/min (where) processing pressure; 2.7Pa (20mTorr) processing temperature (mounting table): 500 °C microwave power: 3kW processing time; 150 seconds target film thickness; 8nm Figure 9 shows the display toward each The measurement result of the AVfb of the write characteristics of the tantalum nitride film (including the tantalum nitride film) formed by the film under the conditions. In addition, the horizontal axis of Fig. 9 is the data writing time, and the scales "1 En" and "1Ε + η" (η is a number) mean "lxi〇_n" and "ixi〇n" respectively (the same applies to Fig. 11). ). When the 〇2 gas flow is performed in about half of the target film thickness (near the center in the film thickness direction), a higher Δνα is exhibited as compared with the tantalum nitride film produced by the normal plasma CVD in which oxygen introduction is not performed at all. On the other hand, when the 02 gas flow is performed before and after the formation of the tantalum nitride film, or when the oxygen introduction is performed in the entire section, the tantalum nitride film produced by the normal plasma CVD in which oxygen is not introduced at all is compared with Δνη. There is almost no difference. The effect of the implementation of the 〇2 gas flow on the trap distribution in the tantalum nitride film will be described with reference to FIGS. 10A to 10C. Fig. 10A is a case where plasma CVD is performed under normal conditions to form a tantalum nitride film -31 - 201107521, and Fig. 10B is a case where a 02 gas gas is flowed in the middle of a plasma CVD process to form a tantalum nitride film. 10C is a distribution model of traps in the tantalum nitride film when the SiN film 70 is formed immediately before the film formation and immediately after the film formation (two times in total), and the SONOS is formed in the same manner as in FIG. A pattern displayer in the energy band diagram of the constructed laminate. In addition, Fig. 10B is a case where the film formation of the SiN film 70 is divided into two, and the gas flow of the helium gas is performed once. The symbol meanings in Figs. 10A to 10C are the same as those in Fig. 8. As shown in Fig. 10A, when the SiN film 70 is formed by ordinary plasma CVD, the trap T is concentratedly distributed in the vicinity of the interface with the adjacent underlying SiO 2 film 60. On the other hand, when the 〇2 gas flow is performed once during the formation of the SiN film 70, as shown in Fig. 10B, the trap T is concentrated in the vicinity of the center (in the film) of the SiN film 70 in the film thickness direction. Further, when the 02 gas flow is performed twice before the film formation of the SiN film 70 and immediately after the film formation, as shown in FIG. 10C, the trap T is the Si 02 film 60 distributed on the bottom layer adjacent to the SiN film 70. Near the interface. Further, in Fig. 10C, at the interface between the SiN film 70 and the blocking SiO2 film 80, the trap generated by the flow of the 〇2 gas after the formation of the SiN film 70 is initialized when the film formation of the SiO 2 film 80 is blocked. And eliminated, so there is almost no trap T remaining at this interface. Therefore, it is conceivable that Fig. 10C in which the 02 gas flow is performed twice before the film formation of the SiN film 70 and immediately after the film formation is the same as Fig. 10A. When the laminated body of the structure shown in FIG. 10A to FIG. 10C is assumed to be a semiconductor memory device of the SONOS structure, the data is written with the potential of the substrate of the 90-32-201107521 substrate 90a as the reference electrode. The crystalline ruthenium film 9〇b applies a predetermined positive voltage. At this time, electrons are stored in the channel formation region (not shown) to form an inversion layer, and a part of the charge in the inversion layer is moved to the SiN film 70 via the Si 2 film 60 due to the tunneling phenomenon. The electrons moved to the SiN film 70 are captured by traps formed inside the material, and the data is stored. Here, the comparison of the data writing characteristics of the laminated structure shown in Figs. 1A to i〇c shows that the writing speed is fast, and the optimum writing characteristics are the ones shown in Fig. 10B. On the other hand, the structure shown in FIG. 10C in which the 02 gas flow is performed twice before the film formation of the siN film 70 and immediately after the film formation is the same as the structure shown in FIG. The configuration shown is a comparison of 'the write speed is slow, only low write characteristics can be achieved. When the 〇2 gas is introduced in the vicinity of the center of the SiN film 70 in the film thickness direction to form the structure shown in FIG. 10B, the trap distribution at the interface of the SiO 2 film 60 / SiN film 70 is formed by ordinary plasma CVD. The structure of Fig. 10A is equivalent. However, in the structure shown in FIG. 10B, the trap distribution adjacent to the interface between the Si〇2 film 60 and the SiN film 70 is distributed in the central portion of the SiN film 70 in the film thickness direction, so that Si is passed through the Si. The charge of the film 60 is easily injected into a position deeper than the film of the SiN film 70 (near the center portion). As a result, the structure shown in Fig. 1 〇B is comparable to the structure of Fig. 10A, and it is conceivable that the writing speed is fast and good data writing performance can be obtained. In addition, in the structure shown in FIG. 10C in which the 02 gas flow is performed twice before the film formation of the SiN film 70 and immediately after the film formation, the distribution of the trap T is finally the same as that of FIG. 10A, and thus the image cannot be obtained. Figure 10B [-33- 201107521 good write characteristics. As described above, the test results of the nature shown in Fig. 9 can be reasonably explained based on the difference in the trap T distribution of Figs. 10A to 10C. According to the above, it is conceivable that the introduction of the 02 gas is performed by forming a trap layer in the film thickness direction of the deposited SiN film 70 by CVD, particularly in the range of 30% to the target film thickness. It is ideal to form a trap layer when the timing of growth proceeds. Thus, the traps can be concentratedly distributed in the film of the SiN film 70. That is, the method has the advantage that the existence distribution of the film thickness direction of the trap in the film of the film 70 can be controlled by adjusting the timing of introduction of the 〇2 gas, so that the trap is concentrated in the center of the film thickness direction of the SiN film 70. Attached here is a structure in which a trap layer formed at the position is formed. The SiN film 70 having a distribution peak of traps in the film is obtained by, for example, a charge storage layer of a volatile semiconductor memory device, and data writing characteristics can be obtained. Test Example 2: In this test, the SiN film 70 was subjected to 2-A) normal plasma 2-B) plasma CVD + 02 gas flow (1 time; film thickness direction center 2-C) plasma CVD + 02 gas Four types of film formation methods, such as flow (2 times; center 2-D in the film thickness direction), thermal CVD, etc. are formed. Each film forming member is as follows. 2-A) Normal plasma CVD: The SiN is produced by the present invention using a plasma CVD apparatus 1 写入 which is written to the special plasma where it is 70%. More closely, borrowed, then, as a non-good CVD, ministry, department), law strip -34- 201107521

Ar 氣體流量；40mL/min(sccm) N2 氣體流量；450mL/min ( seem)Ar gas flow rate; 40 mL/min (sccm) N2 gas flow rate; 450 mL/min (see)

SiCl4 氣體流量；lmL/min(sccm) 處理壓力；2.7Pa(20mTorr) 處理溫度（載置台）：400°C 微波功率：3kW 處理時間；1 1 0秒 目標膜厚；8nm 2-B )電漿CVD + 02氣體流動（1次；膜厚方向中央部 附近）： ’SiCl4 gas flow rate; lmL/min (sccm) treatment pressure; 2.7Pa (20mTorr) treatment temperature (mounting table): 400 °C microwave power: 3kW processing time; 1 10 seconds target film thickness; 8nm 2-B) plasma CVD + 02 gas flow (1 time; near the center of the film thickness direction): '

i)第1次的電漿CVD 處理時間與目標膜厚以外，是以和上述1 - A )的電 漿CVD同條件來進行電漿CVD。 處理時間；5 5秒 目標膜厚；4nm i〇 〇2氣體流動 第1次的電漿CVD之後，停止電漿，在以下的條 件下實施〇2氣體流動。 〇2 氣體流量；600mL/min ( seem)i) In addition to the first plasma CVD treatment time and the target film thickness, plasma CVD is performed under the same conditions as the above-mentioned 1 - A) plasma CVD. Processing time; 5 5 seconds Target film thickness; 4 nm i〇 〇 2 gas flow After the first plasma CVD, the plasma was stopped, and the 〇2 gas flow was carried out under the following conditions. 〇2 gas flow rate; 600mL/min (see)

處理時間；6 0秒間 iii )第2次的電漿C VD 處理時間與目標膜厚以外，是以和上述第1次的電 漿CVD同樣實施。 處理時間；5 5秒 -35- 201107521 目標膜厚；4nm 2-C )電漿CVD + 02氣體流動（2次；膜厚方向中央部 附近）：Processing time; 60 seconds iii) The second plasma C VD processing time and the target film thickness are performed in the same manner as the first plasma CVD described above. Processing time; 5 5 seconds -35- 201107521 target film thickness; 4nm 2-C) plasma CVD + 02 gas flow (2 times; near the center of the film thickness direction):

i )第1次的電漿CVD 處理時間與目標膜厚以外，是以和上述1-A)的電 漿CVD同條件來進行電漿CVD。 處理時間；3 4秒 目標膜厚；2.6rm Π)第1次的〇2氣體流動 第1次的電漿CVD之後，停止電漿，在以下的條 件下實施〇2氣體流動》 〇2 氣體流量；600mL/min ( seem)i) In addition to the first plasma CVD treatment time and the target film thickness, plasma CVD is performed under the same conditions as the plasma CVD of the above 1-A). Processing time; 3 4 seconds target film thickness; 2.6 rm Π) The first 〇2 gas flow After the first plasma CVD, the plasma is stopped, and the 〇2 gas flow is carried out under the following conditions: 〇2 Gas flow ;600mL/min (see)

處理時間；60秒間 iii )第2次的電漿CVD 和上述第1次的電漿CVD同樣地實施。 處理時間；34秒 目標膜厚；2.6 n m iv) 第2次的02氣體流動 第2次的電漿CVD之後，停止電漿，在以下的條 件下實施〇2氣體流動。 〇2 氣體流量；600mL/min ( seem) 處理時間；60秒間Processing time; 60 seconds iii) The second plasma CVD was carried out in the same manner as the first plasma CVD described above. Processing time; 34 seconds Target film thickness; 2.6 n m iv) The second 02 gas flow After the second plasma CVD, the plasma was stopped, and the 〇2 gas flow was carried out under the following conditions. 〇2 gas flow rate; 600mL/min (see) processing time; 60 seconds

v) 第3次的電漿CVD 和上述第1次的電漿CVD同樣地實施。 -36- 201107521 處理時間；3 4秒 目標膜厚；2.6nm [熱CVD條件] 處理溫度：780°C 處理壓力；133Pav) The third plasma CVD is carried out in the same manner as the first plasma CVD described above. -36- 201107521 Processing time; 3 4 seconds Target film thickness; 2.6 nm [thermal CVD condition] Processing temperature: 780 ° C Processing pressure; 133 Pa

SiH2Cl2 氣體+NH3 氣體：1 00+1 000mL/min(sccm) 目標膜厚；8nm 圖11是表示顯示朝上述各條件下所被成膜的氮化矽 膜的寫入特性之AVfb的測定結果。實施02氣體流動，在 氮化矽膜中導入氧而取得的實驗2-B及實驗2-C的氮化矽 膜，相較於通常的電漿CVD所產生的氮化矽膜（實驗2-A )、或熱CVD所產生的氮化矽膜（實驗2-D )，顯示特別 高的 AVfb。並且，在目標膜厚的約一半（膜厚方向的中 央附近）實施〇2氣體流動的實驗2-B及2-C的比較中， 比起只進行1次的〇2氣體流動的實驗2-B，進行2次的 〇2氣體流動的實驗2_C是AVfb較大，陷阱會被多數形成 。由以上的結果，顯示爲了使作爲半導體記憶體裝置的電 荷儲存層利用時的寫入特性形成更良好者，而在電漿CVD 工程的期間，將〇2氣體流動進行1次以上，較理想是2 次以上，而在氮化矽膜中形成陷阱層有效。較理想是在氮 化矽膜的目標膜厚的30〜70%的範圍內成膜的階段進行〇2 氣體流動。 -37- 201107521 [半導體記憶體裝置的製造之適用例] 其次，一邊參照圖12，一邊說明有關將本實施形態的 氮化矽膜的製造方法適用於半導體記億體裝置的製造過程 的例子。圖12是表示半導體記億體裝置201的槪略構成 的剖面圖。半導體記億體裝置201是具有：作爲半導體層 的P型的矽基板101、及在此p型的矽基板101上被層疊 形成的複數個絕綠膜、及更形成於其上的閘極電極〗〇3。 在矽基板101與閘極電極103之間設有作爲隧道氧化膜的 第1絕緣膜1 Π、第2絕緣膜1〗2、及第3絕緣膜1 1 3。其 中，第2絕緣膜1 1 2爲氮化矽膜，形成半導體記憶體裝置 201的電荷儲存層。 並且，在矽基板101，以能夠位於閘極電極103的兩 側之方式，從表面以預定的深度來形成有η型擴散層的第 1源極.汲極1〇4及第2源極.汲極105，兩者之間是形成 通道形成領域1 〇 6。另外，半導體記憶體裝置2 0 1亦可形 成於半導體基板內所形成的ρ阱或ρ型矽層。而且，在此 雖是舉η通道MOS裝置爲例來進行說明，但即使在ρ通 道MOS裝置實施也無妨。因此，以下記載的內容全部可 適用於η通道MOS裝置、及ρ通道MOS裝置。 第1絕緣膜111是例如藉由熱氧化法來氧化矽基板 101的表面而形成的二氧化矽膜（3丨02膜）。 第2絕緣膜112是形成於第1絕緣膜ηι的表面之氮 化矽膜（SiN膜）。 第3絕緣膜113是在第2絕緣膜112上，例如藉由 -38- 201107521 CVD法來使堆積的二氧化矽膜（Si 〇2膜）。此| 膜113是在電極103與第2絕緣膜112之間具有 層（屏蔽層）的機能。 閘極電極103是例如藉由CVD法成膜的多 所構成，具有作爲控制閘（CG )電極的機能。又 極1 〇 3亦可爲例如含鎢（W )，鈦（Ti )，鉬（ (Cu)，鋁（A1)，金（Au)，白金（Pt )等金 閘極電極1 03並非限於單層，基於降低閘極電極 電阻，使半導體記億體裝置201的動作速度高速 ，亦可形成例如含鎢（W )、鉬（Mo )、鉅（Ta Ti )、白金（Pt )等該等的矽化物、氮化物、合 疊構造。閘極電極103是被連接至未圖示的配線J 並且，在半導體記憶體裝置201中，第2絕 是主要儲存電荷的電荷儲存區域。因此，在第 112的形成時，可適用本發明的氮化矽膜的成膜 制陷阱量及其分佈，藉此來調節半導體記憶體裝j 資料寫入性能或資料保持性能。 在此是舉代表性的程序來說明有關將本發明 用於半導體記憶體裝置201的製造例。首先， LOCOS ( Local Oxidation of Silicon )法或 STI Trench Isolation)法等的手法來形成元件分離膜 )的矽基板101’在其表面，例如藉由熱氧化法 1絕緣膜1 1 1。第1絕緣膜1 1 1爲Si〇2膜》 其次’在第1絕緣膜1 1 1的上面，利用電發 肖3絕緣 作爲阻絕 結晶砂膜 ，閘極電 Ta )，銅 屬的層。 1 0 3的比 化的目的 )、鈦（ 金等的層 譽0 緣膜1 12 2絕緣膜 方法，控 置201的 的方法適 準備一以 (Shallow (未圖示 來形成第 ί CVD 裝 -39- 201107521 置1 00藉由電漿CVD法來形成第2絕緣膜112。 在形成第2絕緣膜112時，是在電漿CVD的途 預定的時機來實施〇2氣體流動，藉此於膜中形成多 阱的同時，控制膜厚方向的陷阱的分佈。藉此，可使 體記億體裝置201的寫入特性與讀出特性形成優越者 其次，在第2絕緣膜112的上面形成第3絕緣膜 。此第3絕緣膜1 13是Si02膜，可例如藉由CVD法 成。另外，亦可使用低溫的電漿CVD來形成。而且 第3絕緣膜1 1 3的上面，例如藉由CVD法來使多晶 或金屬層、或金屬矽化物層等成膜，而形成成爲閘極 103的金屬膜。 其次，利用光學独刻（Photolithography)技術， 成圖案的光阻劑作爲光罩，蝕刻前述金屬膜、第3絕 113〜第1絕緣膜111，藉此可取得具有被形成圖案的 電極103及複數的絕緣膜之閘極層疊構造體。其次， 接於閘極層疊構造體的兩側之矽表面，高濃度地離子 η型雜質，形成第1源極.汲極104及第2源極.汲極 。如此一來，可製造圖12所示構造的半導體記憶體 201。 說明有關以上那樣構造的半導體記憶體裝置20 1 作例。首先，在資料寫入時，以矽基板1 〇 1的電位作 準，將第1源極.汲極1〇4及第2源極.汲極1〇5保 0V，對閘極電極103施加預定的正電壓。此時，在通 成區域106儲存電子而形成反轉層，該反轉層內的電 中以 數陷 半導 〇 113 來形 ，在 砂層 電極 以形 緣膜 鬧極 在鄰 注入 105 裝置 的動 爲基 持於 道形 荷的 -40- 201107521 一部分會藉由隧道現象經由第1絕緣膜111來移動至第2 絕緣膜112。移動至第2絕緣膜112的電子是被形成於其 內部的電荷捕獲中心的陷阱（trap )所捕獲，進行資料的 儲存。 在資料讀出時，以矽基板101的電位作爲基準，對第 1源極.汲極1 04或第2源極.汲極1 05的其中任一方施加 0V的電壓，對另一方施加預定的電壓。更在閘極電極103 也施加預定的電壓。藉由如此施加電壓，通道的電流量或 汲極電壓會按照有無被儲存於第2絕緣膜112內的電荷或 被儲存的電荷量來變化。因此，藉由檢測出此通道電流或 汲極電壓的變化來將資料讀出至外部。 在資料的消去時，是以矽基板1 0 1的電位作爲基準， 對第1源極·汲極104及第2源極.汲極105的雙方施加 OV的電壓，對閘極電極1 〇3施加預定大小的負電壓。藉 由如此電壓的施加，被保持於第2絕緣膜112內的電荷會 經由第1絕緣膜111來抽出至矽基板101的通道形成區域 106。藉此，半導體記憶體裝置201會回到第2絕緣膜1 12 內的電子儲存量低的消去狀態。 另外，半導體記憶體裝置201的資訊的寫入、讀出、 消去的方法並非被限定者，亦可使用和上述不同的方式來 進行寫入 '讀出及消去。並且，在圖12是舉具有第2絕 緣膜112的構成爲例，作爲電荷儲存區域，但本發明的方 法亦可適用於層疊2層以上的氮化矽膜的構造作爲電荷儲 存層的半導體記億體裝置時。 -41 - 201107521 以上’敘述本發明的實施形態，但本發明並非限於上 述實施形態，亦可實施各種的變形。例如，上述實施形態 是在電漿處理使用RLSA方式的微波電漿處理裝置，但可 使用其他方式的電漿處理裝置，例如ICP電漿方式、ECR 電漿方式、表面波電漿方式、磁控管電漿方式等其他方式 的電漿處理裝置。 【圖式簡單說明】 圖1是表示適於氮化矽膜的形成之電漿CVD裝置的 一例槪略剖面圖。 圖2是表示平面天線的構造圖面。 圖3是表示控制部的構成說明圖。 圖4是表示第1實施形態的氮化矽膜的成膜方法的時 序圖的圖面。 圖5A是說明第1實施形態的電漿CVD工程的圖面。 圖5B是說明第1實施形態的含氧原子氣體導入工程 的圖面。 圖5C是說明第1實施形態的電漿CVD工程的圖面。 圖5D是說明第1實施形態的成膜後的氮化矽膜的剖 面構造的圖面。 圖6是表示第2實施形態的氮化矽膜的成膜方法的時 序圖的圖面》 圖7是表示氮化矽膜的膜厚方向的〇2的導入位置的 說明圖 -42- 201107521 圖8是在試驗例所使用的S0N0S構造的層疊體的說 明圖。 圖9是表示試驗例1的AVfb的測定結果的圖表。 圖10A是表示在通常的條件下進行電漿CVD而形成 之氮化矽膜中的陷阱的分佈的能帶圖° 圖10B是表示在電漿CVD的途中進行1次的02氣體 流動而形成之氮化矽膜中的陷阱的分佈的能帶圖。 圖10C是表示在電漿CVD的前後進行2次的02氣體 流動而形成之氮化矽膜中的陷阱的分佈的能帶圖。 圖11是表示試驗例2的AVfb的測定結果的圖表。 圖12是表示可適用本發明方法的半導體記憶體裝置 的構成例的槪略剖面圖。 【主要元件符號說明】 1 :處理容器 1 a :底壁 1 b :側壁 2 :載置台 3 :支撐構件 4 :覆蓋環 5 :加熱器 5 a :加熱器電源 6 :熱電耦 -43- 201107521 1 1 :排氣室 1 1 a :空間 1 2 :排氣管 13 :板 13a :支撐部 1 4，1 5 :氣體導入孔 16 :搬出入口 1 7 :閘閥 1 8 :氣體供給裝置 19a :含氮（N)氣體供給源 19b :含氧原子氣體供給源 19c :含矽（Si)氣體供給源 19d :非活性氣體供給源 19e :洗滌氣體供給源 20a、 20b ' 20c、 20d 、 20e ：氣體導入管 21a、 21b、 21c、 21d、 21e:質量流控制器 22a > 22b 、 22c 、 22d 、 22e :開閉閥 24 :排氣裝置 27 :微波導入機構 2 8 :透過板 3 1 ·平面天線 32 :微波放射孔 3 3 :慢波材 34 :金屬製罩構件 -44- 201107521 3 6 :開口部 37 :導波管 37a :同軸導波管 3 7b :矩形導波管 3 8 :匹配電路 39 :微波產生裝置 41 :內導體 5 0 :控制部 5 1 :製程控制器 5 2 :使用者介面 5 3 :記憶部 60 ： Si02 膜 70 : SiN 膜 70a : SiN 膜 9 0 a :砂基板 9 0b :多結晶砂膜 1 00 :電漿CVD裝置 101 : p型的矽基板 1 〇 3 :閘極電極 104 :第1源極.汲極 105 :第2源極.汲極 106 :通道形成領域 1 1 1 :第1絕緣膜 1 1 2 :第2絕緣膜 -45 201107521 1 1 3 :第3絕緣膜 201 :半導體記憶體裝置 W :晶圓 -46-SiH2Cl2 gas + NH3 gas: 1 00 + 1 000 mL/min (sccm) Target film thickness; 8 nm Fig. 11 shows measurement results of AVfb showing the writing characteristics of the tantalum nitride film formed under the above respective conditions. Experiment 2-B obtained by introducing 02 gas flow, introducing oxygen into the tantalum nitride film, and tantalum nitride film of Experiment 2-C, compared with the conventional tantalum nitride film produced by plasma CVD (Experiment 2 A), or a tantalum nitride film produced by thermal CVD (Experiment 2-D), shows a particularly high AVfb. Further, in the comparison of Experiments 2-B and 2-C in which the gas flow of 〇2 was performed in about half of the target film thickness (near the center in the film thickness direction), the experiment 2 of the 〇2 gas flow was performed only once. B. Experiment 2_C of performing 〇2 gas flow twice is that AVfb is large, and traps are formed by a large number. From the above results, it is shown that the writing characteristics are better when the charge storage layer is used as the semiconductor memory device, and the 〇2 gas is flowed once or more during the plasma CVD process, preferably. More than 2 times, it is effective to form a trap layer in the tantalum nitride film. It is preferable to carry out the gas flow of the 〇2 gas at the stage of film formation in the range of 30 to 70% of the target film thickness of the ruthenium nitride film. -37-201107521 [Application Example of Manufacturing Semiconductor Memory Device] Next, an example of a method of manufacturing the method of manufacturing a tantalum nitride film of the present embodiment to a semiconductor device will be described with reference to Fig. 12 . Fig. 12 is a cross-sectional view showing a schematic configuration of a semiconductor device 201. The semiconductor body device 201 includes a P-type germanium substrate 101 as a semiconductor layer, a plurality of green films laminated on the p-type germanium substrate 101, and a gate electrode formed thereon. 〗 〇 3. Between the ruthenium substrate 101 and the gate electrode 103, a first insulating film 1 作为, a second insulating film 1 2, and a third insulating film 1 1 3 as tunnel oxide films are provided. The second insulating film 112 is a tantalum nitride film, and forms a charge storage layer of the semiconductor memory device 201. Further, the first substrate, the first source, the drain 1〇4, and the second source of the n-type diffusion layer are formed on the germanium substrate 101 so as to be located on both sides of the gate electrode 103 with a predetermined depth from the surface. Bungee 105, between the two forms a channel formation area 1 〇 6. Further, the semiconductor memory device 210 may be formed in a p-well or p-type germanium layer formed in the semiconductor substrate. Further, although the n-channel MOS device is described as an example, it may be implemented even in the p-channel MOS device. Therefore, all of the contents described below are applicable to the n-channel MOS device and the p-channel MOS device. The first insulating film 111 is, for example, a ruthenium dioxide film (3丨02 film) formed by oxidizing the surface of the ruthenium substrate 101 by a thermal oxidation method. The second insulating film 112 is a hafnium nitride film (SiN film) formed on the surface of the first insulating film ηι. The third insulating film 113 is a ceria film (Si 〇 2 film) deposited on the second insulating film 112 by, for example, the -38-201107521 CVD method. This film 113 is a function of providing a layer (shield layer) between the electrode 103 and the second insulating film 112. The gate electrode 103 is composed of, for example, a plurality of films formed by a CVD method, and has a function as a control gate (CG) electrode. Further, 1 〇3 may be, for example, a tungsten gate electrode such as tungsten (W), titanium (Ti), molybdenum ((Cu), aluminum (A1), gold (Au), platinum (Pt), etc. The layer is formed such that tungsten (W), molybdenum (Mo), giant (Ta Ti ), platinum (Pt ), etc. are formed, for example, by lowering the gate electrode resistance and increasing the operating speed of the semiconductor device 201. The gate electrode 103 is connected to a wiring J (not shown), and in the semiconductor memory device 201, the second is a charge storage region in which charges are mainly stored. At the time of formation of 112, the trapping amount and distribution of the film formation of the tantalum nitride film of the present invention can be applied, thereby adjusting the data writing performance or the data retention performance of the semiconductor memory device. Here is a representative program. A description will be given of a manufacturing example in which the present invention is applied to the semiconductor memory device 201. First, a germanium substrate 101' on which the element separation film is formed by a method such as the LOCOS (Local Oxidation of Silicon) method or the STI Trench Isolation method is formed on the surface thereof. For example, the insulating film 1 1 1 is formed by thermal oxidation. The first insulating film 1 1 1 is a Si 〇 2 film. Next, the upper surface of the first insulating film 1 1 1 is insulated by an electric radiance 3 as a resistive crystalline sand film, a gate electrode Ta), and a copper layer. The purpose of the comparison of 1 0 3), the method of titanium (gold and other layers of the edge film 1 12 2 insulating film method, the method of controlling 201 is suitable for one (Shallow (not shown to form the ί CVD device - 39-201107521 The second insulating film 112 is formed by a plasma CVD method. When the second insulating film 112 is formed, the gas flow of the 〇2 gas is performed at a predetermined timing of the plasma CVD. In the middle of the formation of the multi-well, the distribution of the trap in the thickness direction is controlled. Thereby, the writing characteristics and the readout characteristics of the body device 201 are superior, and the second insulating film 112 is formed on the upper surface of the second insulating film 112. 3. The insulating film 136 is an SiO 2 film, which can be formed, for example, by a CVD method. Alternatively, it can be formed by plasma CVD at a low temperature, and the upper surface of the third insulating film 141 can be formed, for example, by In the CVD method, a polycrystalline or metal layer, a metal telluride layer or the like is formed into a film to form a metal film to be the gate electrode 103. Next, a patterned photoresist is used as a photomask by photolithography. By etching the metal film and the third anode 113 to the first insulating film 111, it is possible to obtain The gate electrode 103 and the gate laminated structure of the plurality of insulating films are connected to the surface of both sides of the gate laminated structure, and the n-type impurity is ionized at a high concentration to form the first source and the drain 104. In this way, the semiconductor memory device 201 having the structure shown in Fig. 12 can be manufactured. An example of the semiconductor memory device 20 1 having the above configuration will be described. First, when data is written, The potential of the substrate 1 〇1 is normal, and the first source, the drain 1〇4, and the second source, the drain 1〇5 are kept at 0 V, and a predetermined positive voltage is applied to the gate electrode 103. The region 106 stores electrons to form an inversion layer, and the electricity in the inversion layer is shaped by a plurality of trapped semiconductors 113, and the sand layer electrodes are held in the shape of the device by the action of the edge film on the adjacent device 105. A part of the charged -40 to 201107521 is moved to the second insulating film 112 via the first insulating film 111 by the tunneling phenomenon. The electrons moving to the second insulating film 112 are traps of the charge trapping center formed inside the trap (trap) Captured, stored data. Read data At the time of applying the potential of the ruthenium substrate 101 as a reference, a voltage of 0 V is applied to one of the first source, the drain 10 04 or the second source and the drain 205, and a predetermined voltage is applied to the other. A predetermined voltage is also applied to the gate electrode 103. By applying a voltage in this way, the current amount or the drain voltage of the channel varies depending on the amount of charge stored in the second insulating film 112 or the amount of stored charge. The data is read out to the outside by detecting a change in the current or the drain voltage of the channel. When the data is erased, the voltage of OV is applied to both the first source/drain 104 and the second source and the drain 105 based on the potential of the germanium substrate 110, and the gate electrode 1 〇3 is applied. A negative voltage of a predetermined magnitude is applied. By the application of such a voltage, the electric charge held in the second insulating film 112 is extracted to the channel formation region 106 of the ruthenium substrate 101 via the first insulating film 111. As a result, the semiconductor memory device 201 returns to the erased state in which the amount of electrons stored in the second insulating film 1 12 is low. Further, the method of writing, reading, and erasing information of the semiconductor memory device 201 is not limited, and writing 'reading and erasing' can be performed using a different method from the above. In addition, in FIG. 12, a structure having the second insulating film 112 is taken as an example of a charge storage region. However, the method of the present invention can also be applied to a structure in which two or more layers of a tantalum nitride film are stacked as a semiconductor of a charge storage layer. When the body is installed. The present invention is not limited to the above embodiments, and various modifications can be made. For example, in the above embodiment, the RLSA type microwave plasma processing apparatus is used for plasma processing, but other types of plasma processing apparatuses such as ICP plasma method, ECR plasma method, surface wave plasma method, and magnetron control can be used. Other plasma processing devices such as tube plasma. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a plasma CVD apparatus suitable for forming a tantalum nitride film. Fig. 2 is a structural view showing a planar antenna. 3 is a view showing the configuration of a control unit. Fig. 4 is a view showing a timing chart of a method of forming a tantalum nitride film according to the first embodiment. Fig. 5A is a view showing a plasma CVD process of the first embodiment; Fig. 5B is a view for explaining an oxygen-containing atom gas introduction process of the first embodiment. Fig. 5C is a view for explaining a plasma CVD process of the first embodiment. Fig. 5D is a view showing a cross-sectional structure of a tantalum nitride film after film formation in the first embodiment. 6 is a timing chart showing a method of forming a tantalum nitride film according to a second embodiment. FIG. 7 is an explanatory view showing a position of introduction of 〇2 in the film thickness direction of the tantalum nitride film. FIG. 8 is an explanatory view of the laminated body of the SONOS structure used in the test example. FIG. 9 is a graph showing the measurement results of AVfb in Test Example 1. FIG. Fig. 10A is an energy band diagram showing the distribution of traps in a tantalum nitride film formed by plasma CVD under normal conditions. Fig. 10B is a view showing the flow of 02 gas once in the middle of plasma CVD. An energy band diagram of the distribution of traps in a tantalum nitride film. Fig. 10C is an energy band diagram showing the distribution of traps in the tantalum nitride film formed by the 02 gas flow twice before and after the plasma CVD. FIG. 11 is a graph showing the measurement results of AVfb in Test Example 2. FIG. Fig. 12 is a schematic cross-sectional view showing a configuration example of a semiconductor memory device to which the method of the present invention is applicable. [Main component symbol description] 1 : Processing container 1 a : bottom wall 1 b : side wall 2 : mounting table 3 : support member 4 : cover ring 5 : heater 5 a : heater power supply 6 : thermocouple - 43 - 201107521 1 1 : Exhaust chamber 1 1 a : Space 1 2 : Exhaust pipe 13 : Plate 13 a : Support portion 1 4, 1 5 : Gas introduction hole 16 : Carry-out port 1 7 : Gate valve 1 8 : Gas supply device 19a : Nitrogen-containing (N) gas supply source 19b: oxygen-containing gas supply source 19c: cerium-containing (Si) gas supply source 19d: inert gas supply source 19e: washing gas supply source 20a, 20b' 20c, 20d, 20e: gas introduction tube 21a, 21b, 21c, 21d, 21e: mass flow controller 22a > 22b, 22c, 22d, 22e: opening and closing valve 24: exhaust device 27: microwave introduction mechanism 2 8 : transmission plate 3 1 · planar antenna 32: microwave Radiation hole 3 3 : slow wave material 34 : metal cover member - 44 - 201107521 3 6 : opening portion 37 : waveguide 37a : coaxial waveguide 3 7b : rectangular waveguide 3 8 : matching circuit 39 : microwave generation Device 41: inner conductor 50: control unit 5 1 : process controller 5 2 : user interface 5 3 : memory portion 60 : SiO 2 film 70 : SiN 70a : SiN film 9 0 a : sand substrate 9 0b : polycrystalline sand film 1 00 : plasma CVD apparatus 101 : p-type germanium substrate 1 〇 3 : gate electrode 104 : first source. drain 105 : 2 source. drain 106: channel formation region 1 1 1 : first insulating film 1 1 2 : second insulating film - 45 201107521 1 1 3 : third insulating film 201 : semiconductor memory device W : wafer - 46 -

Claims (1)

201107521 七、申請專利範圍： 1. 一種氮化矽膜的成膜方法，係於電漿CVD 處理容器內，藉由電漿CVD法在被處理體上使氮 堆積之氮化矽膜的成膜方法，其特徵爲具備： 氮化矽膜形成工程，其係對前述處理容器內供 含矽化合物氣體及含氮氣體的處理氣體，而使電漿 在被處理體上形成氮化矽膜；及 含氧原子氣體導入工程，其係於前述氮化矽膜 程的途中，使前述電漿停止，對前述處理容器內導 原子氣體，將形成途中的前述氮化矽膜暴露於含氧 體，而形成陷阱。 2. 如申請專利範圍第1項之氮化矽膜的成膜 其中，前述氮化矽膜形成工程係具備： 在前述含氧原子氣體導入工程之前，藉由前述 使氮化砍膜成長之第1工程；及 在前述含氧原子氣體導入工程之後，藉由前述 使氮化砂膜成長之第2工程。 3. 如申請專利範圍第2項之氮化矽膜的成膜 其中，在前述氮化矽膜對目標膜厚成長成30%以上 下的範圍內的厚度之階段進行前述含氧原子氣體導 〇 4. 如申請專利範圍第1項之氮化矽膜的成膜 其中，重複2次以上進行前述含氧原子氣體導入工; 5 .如申請專利範圍第1項之氮化矽膜的成膜 裝置的 化矽膜 給包含 生成， 形成工 入含氧 原子氣 方法， 電漿來 電漿來 方法， 7 0 %以 入工程 方法， 呈。 方法， -47- 201107521 其中，前述電漿CVD裝置爲：藉由具有複數個孔的平面 天線來對前述處理容器內導入微波而生成電漿之電漿CVD 裝置。 6. —種半導體記億體裝置的製造方法，係於矽層上 ，形成有隧道氧化膜、作爲電荷儲存層的氮化矽膜、阻絕 氧化矽膜及閘極電極而成的半導體記億體裝置的製造方法 ，其特徵爲： 作爲前述電荷儲存層的氮化矽膜的成膜係藉由氮化矽 膜的成膜方法來進行，該氮化矽膜的成膜方法係具備： 氮化矽膜形成工程，其係對電漿CVD裝置的處理容 器內供給包含含矽化合物氣體及含氮氣體的處理氣體，而 使電漿生成，藉由電漿CVD法在被處理體上形成氮化矽 膜；及 含氧原子氣體導入工程，其係於前述氮化矽膜形成工 程的途中使前述電漿停止，對前述處理容器內導入含氧原 子氣體，將形成途中的前述氮化矽膜暴露於含氧原子氣體 ，而形成陷阱。 7. —種電漿CVD裝置，其特徵係具備： 處理容器，其係將被處理體載置於載置台而收容； 氣體供給裝置，其係對前述處理容器內供給處理氣體 t 排氣裝置，其係將前述處理容器內予以減壓排氣；及 控制部，其係控制成可進行氮化矽膜的成膜方法，該 氮化矽膜的成膜方法係包含： -48- 201107521 氮化矽膜形成工程，其係於前述處理容器內藉由電漿 CVD法在被處理體上使氮化矽膜堆積時，對前述處理容器 內供給包含含矽化合物氣體及含氮氣體的處理氣體，而使 電漿生成，在被處理體上形成氮化矽膜，·及 含氧原子氣體導入工程，其係於前述氮化砂膜形成工 程的途中使前述電漿停止，對前述處理容器內導入含氧原 子氣體，將形成途中的前述氮化矽膜暴露於氧而形成陷讲 -49-201107521 VII. Patent application scope: 1. A film formation method of tantalum nitride film, which is formed by film formation of a tantalum nitride film in which a nitrogen is deposited on a workpiece by a plasma CVD method in a plasma CVD processing vessel. The method comprising: a tantalum nitride film forming process for supplying a ruthenium-containing compound gas and a nitrogen-containing gas to a processing gas in the processing container to form a tantalum nitride film on the object to be processed; The oxygen atom-containing gas introduction process is performed in the middle of the tantalum nitride film process to stop the plasma, and expose the tantalum nitride film in the middle of the formation of the tantalum nitride film in the processing container to the oxygen-containing body. Form a trap. 2. The film formation of the tantalum nitride film according to the first aspect of the patent application, wherein the tantalum nitride film formation engineering system includes: the first step of growing the nitride film by the aforesaid oxygen atom gas introduction process 1); and the second project of growing the nitrided sand film after the introduction of the oxygen-containing atom gas. 3. The film formation of the tantalum nitride film according to the second application of the patent scope, wherein the oxygen atom-containing gas is guided at a stage in which the thickness of the tantalum nitride film is increased to 30% or more. 4. In the film formation of the tantalum nitride film according to the first application of the patent scope, the introduction of the oxygen atom-containing gas is repeated twice or more; 5. The film formation device of the tantalum nitride film according to claim 1 The ruthenium film is supplied to form a method of forming an oxygen-containing atomic gas, and the plasma is fed to the slurry method, 70% of which is incorporated into the engineering method. The method of the plasma CVD apparatus is a plasma CVD apparatus which generates a plasma by introducing microwaves into the processing chamber by a planar antenna having a plurality of holes. 6. A method for manufacturing a semiconductor device, which is formed on a germanium layer, and has a tunnel oxide film, a tantalum nitride film as a charge storage layer, a germanium oxide film, and a gate electrode. In the method of manufacturing a device, the film formation of the tantalum nitride film as the charge storage layer is performed by a film formation method of a tantalum nitride film, and the film formation method of the tantalum nitride film includes: nitridation A ruthenium film forming process for supplying a processing gas containing a ruthenium-containing compound gas and a nitrogen-containing gas to a processing vessel of a plasma CVD apparatus to generate a plasma, and forming a nitridation on the object to be processed by a plasma CVD method a ruthenium film; and an oxygen atom-containing gas introduction process, wherein the plasma is stopped during the formation of the tantalum nitride film, and an oxygen-containing atom gas is introduced into the processing chamber to expose the tantalum nitride film in the middle of formation Contains oxygen atoms to form a trap. A plasma CVD apparatus characterized by comprising: a processing container for accommodating a workpiece to be placed on a mounting table; and a gas supply device for supplying a processing gas t to the inside of the processing container; The method further comprises: depressurizing and decompressing the inside of the processing container; and controlling the portion to control a film forming method of the tantalum nitride film, wherein the film forming method of the tantalum nitride film comprises: -48- 201107521 nitriding In a ruthenium film forming process, when a tantalum nitride film is deposited on a target object by a plasma CVD method in the processing container, a processing gas containing a ruthenium-containing compound gas and a nitrogen-containing gas is supplied into the processing container. In the plasma processing, a tantalum nitride film is formed on the object to be processed, and an oxygen atom-containing gas is introduced into the project, and the plasma is stopped in the middle of the formation of the nitrided sand film, and the inside of the processing container is introduced. An oxygen-containing gas gas, which exposes the foregoing tantalum nitride film formed on the way to oxygen to form a trap-49-
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