201002849 六、發明說明： 【發明所屬之技術領域】 本發明係關於在半導體晶圓等之被處理體形成鈦膜或 氮化鈦膜等之成膜方法及成膜裝置，尤其，關於抑制產生 粒子之成膜方法、成膜裝置以及記憶媒體。 【先前技術】 一般，爲了製造半導體積體電路，對半導體晶圓等之 基板，重複執行成膜和圖案蝕刻等。 又’連接構成半導體積體電路之元件間之配線，謀求 對各元件之電性接觸之接觸金屬，或是當作抑制基板之s i 之擴散的對策使用之阻障金屬，必須使用電阻低、耐腐餓 性優良之材料。 作爲可以對應於如此要求之材料，則有使用T i (鈦） 、W (鎢）、Mo (鉬）等之高溶點金屬材料之傾向，即使 在其中由於電性及耐腐蝕性等之特性等爲良好，故有多使 用Ti及該氮化膜之氮化鈦（TiN )之傾向。該些Ti膜或[Technical Field] The present invention relates to a film forming method and a film forming apparatus for forming a titanium film or a titanium nitride film or the like on a semiconductor wafer or the like, and particularly for suppressing generation of particles. Film forming method, film forming apparatus, and memory medium. [Prior Art] In general, in order to manufacture a semiconductor integrated circuit, film formation, pattern etching, and the like are repeatedly performed on a substrate such as a semiconductor wafer. In addition, it is necessary to use a low-resistance and resistance to the barrier metal that is used to connect the components of the semiconductor integrated circuit, the contact metal for electrical contact between the components, or the countermeasure for suppressing the diffusion of the Si of the substrate. A material with good hunger. As a material which can be used in accordance with such a requirement, there is a tendency to use a high-melting-point metal material such as T i (titanium), W (tungsten), or Mo (molybdenum), even if it is characterized by electrical properties and corrosion resistance. If it is good, there is a tendency to use Ti and titanium nitride (TiN) of the nitride film. The Ti film or
TiN膜係在能夠抽真空之處理容器內，藉由設置有載置晶 圓之載置台之葉片式之成膜裝置被形成（專利文獻1〜4) 〇The TiN film is formed in a processing chamber capable of evacuating by a blade type film forming apparatus provided with a mounting table on which crystals are placed (Patent Documents 1 to 4) 〇
Ti膜一般係藉由使用TiCl4 (四氯化鈦）氣體和氫（ H2)氣體作爲原料氣體之電漿 CVD ( Chemical VaporThe Ti film is generally a plasma CVD (Chemical Vapor) using TiCl4 (titanium tetrachloride) gas and hydrogen (H2) gas as raw material gases.
Deposition)成膜。再者，TiN膜係藉由使用當作原料氣 體之TiCl4和氮（N2 )氣體之電漿CVD，或是原料氣體使 201002849 用TiCl4和NH3氣體藉由熱CVD而被成膜。 在此，參照第1圖針對一般之成膜裝置之一例之槪略 構成予以說明。該成膜裝置具有能夠真空排氣之處理容器 4，在該處理容器4內，設置有由例如氮化鋁（A1N )所構 成之載置台2，在載置台2上載置半導體晶圓W。然後’ 以對向於該載置台2之方式，在處理容器4之天井設置有 噴淋頭部6，以對處理容器4內供給所需之氣體。再者’ 於必要之場合，在噴淋頭部6連接電漿產生用之高頻電源 8爲佳，以能夠在該處理容器4內形成電槳。在此’爲了 形成例如Ti膜或TiN膜，使用TiCl4、H2、N2、Ar等之 氣體。 上述般之成膜雖然在製程溫度爲例如650 °C左右之製 程條件下對晶圓連續進行，但是Ti膜或TiN膜不僅在晶 圓表面，在處理容器之內壁面或容器內構造物尤其在噴淋 頭部6之表面則必然附著不需要之膜。因當該不需要之膜 剝落時產生粒子，使得半導體製品之良率降低’故定期性 或因應所需使C1F3或NF3等之洗淨氣體流入處理容器內 ，執行除去不需要之膜的洗淨。 該洗淨因當溫度高時洗淨氣體之腐蝕性過大’故使載 置台之溫度從比較高之製程溫度一次降低至低溫度而予以 執行。 然後，於洗淨後，爲了整理處理容器內之熱性條件’ 在內部無收容晶圓之狀態下，以與成膜時相同之製程條件 ，流通成膜時相同之氣體，執行對處理容器之內壁面或容 -6- 201002849 器內構造物之表面施予預塗敷膜的預塗敷（乾燥法）。然 後，製造線則開始。 〔專利文獻1〕曰本特開2002-167673號公報 〔專利文獻2〕日本特開2004-307939號公報 〔專利文獻3〕日本特開2004-273648號公報 〔專利文獻4〕日本特開2005-68559號公報 【發明內容】 (發明所欲解決之課題） 又，上述載置台2 —般係藉由陶瓷材、例如氮化銘（ A1N)所形成，該氮化鋁當被曝露於上述CIF3或NF3等之 洗淨氣體時，兩者則反應，生成氟化鋁（A1F )系物質。 然後，當爲了成膜提高載置台2之溫度時，該A1F系物質 飛散附著於與載置台2對向之噴淋頭部6表面或處理容器 4之內壁面。之後，於成膜之時，在附著於噴淋頭部6表 面之A1F系物質上又附著上述不需要之膜。該A1F系物質 和金屬之密接性弱，因此，於成膜之時所附著之上述不需 要之膜極容易剝落，有於對晶圓施予成膜處理之時剝落而 產生粒子之問題點。 於是，在以往之洗淨中，使載置台之溫度降低至屬於 載置台之構成材料之氮化鋁即使曝露於C1F3或NF3等之 洗淨氣體，也難以產生A1F系物質之溫度，例如200 °C左 右，在維持該溫度之狀態下執行洗淨。 但是，此時使具有相當大之熱容量之載置台之溫度由 201002849 成膜溫度例如65〇t降溫至洗淨溫度的200 °C，於洗淨後 必需再次升溫至6 5 0。(：。降溫及再升溫則有花例如大約3 小時的非常長之時間的情形。因此，有大幅度降低生產率 之問題。 本發明係注目於上述般之問題點，爲了有效解決此而 所創作出者。本發明之目的在於提供成膜方法、成膜裝置 及記憶媒體，該成膜方法、成膜裝置及記憶媒體不僅於洗 淨時即使生成A1F系物質，亦可以改質使成爲難以飛散， 而且可以於成膜處理時抑制顆粒產生，可以在高於以往洗 淨溫度的溫度下執行洗淨，依此可以提高生產率。 (用以解決課題之手段） 本發明之第1態樣係提供係使用成膜裝置以第1溫度 在被處理體形成薄膜的成膜方法，該成膜裝置具備：被構 成能夠真空排氣之處理容器；被設置在處理容器內，載置 被處理體之氮化鋁製之載置台；用以加熱被處理體之加熱 部；和配置成與載置台對向，對處理容器內導入氣體之噴 淋頭部。該成膜方法包含：使用含氟系氣體之洗淨氣體， 以低於第1溫度之第2溫度洗淨處理容器內之洗淨工程； 藉由維持在第2溫度以下之第3溫度，將氮化氣體導入至 處理容器內，改質被生成在載置台之A1F系物質之改質工 程；將載置台之溫度升溫至第1溫度，在處理容器內形成 預塗敷膜之預塗敷工程；和以第1溫度在被處理體形成薄 膜之成膜工程。 -8- 201002849 本發明之第2態樣係第1態樣之成膜方法中，提供洗 淨工程中之第2溫度爲400 °C以下之成膜方法。 本發明之第3態樣係第1或第2態樣之成膜方法中， 提供改質工程中之第3溫度爲40(rC以下之成膜方法。 本發明之第4態樣係第1至第3態樣中之任一態樣的 成膜方法中，提供第2溫度和第3溫度爲相同之成膜方法 〇 本發明之第5態樣係第1至第4態樣中之任一態樣的 成膜方法中，提供在改質工程中，氮化氣體間歇性被供給 至處理容器內之成膜方法。 本發明之第6態樣係第1至第4態樣中之任一態樣的 成膜方法中，提供在改質工程中，氮化氣體和氫氣被供給 至處理容器內之成膜方法。 本發明之第7態樣係第1至第4態樣中之任一態樣的 成膜方法中，提供在改質工程中，氮化氣體和爲了形成薄 膜所使用之原料氣體被供給至處理容器內之成膜方法。 本發明之第8態樣係第7態樣之成膜方法中，提供氮 化氣體和原料氣體互相間歇性並且交互被供給之成膜方法 〇 本發明之第9態樣係第1至第8態樣中之任一態樣的 成膜方法中，提供氟系氣體爲從由 cif3、nf3、c2f6、f2 所構成之群中選擇出之一個以上之氣體之成膜方法。 本發明之第1 〇態樣係第1至第9態樣中之任一態樣 的成膜方法中，提供氮系氣體爲藉由NH3、聯胺、聯胺化 201002849 合物所構成之群中選擇出之一個以上之氣體之成膜方法。 本發明之第11態樣係第1至第1 〇態樣中之任一態樣 的成膜方法中，提供薄膜爲鈦膜或氮化鈦膜之成膜方法。 本發明之第1 2態樣係第1至第1 1態樣中之任一態樣 的成膜方法中，提供原料氣體爲從由 TiCl4、TDMAT ( Tetrakis Dimethyl Amino Titanium) 、TDEAT ( Tetraki s Diethyl Amino Titanium)所構成之群中選擇出之一個以上 之氣體的成膜方法。 本發明之第1 3態樣係第1至第1 2態樣中之任一態樣 的成膜方法中，提供第2溫度和第3溫度爲2 0 0 °C以上之 成膜方法。 本發明之第1 4態樣係提供一種成膜裝置，具備：能 夠真空排氣之處理容器；被配置在處理容器內，載置被處 理體之氮化鋁製之載置台；用以加熱被處理體之加熱部； 被配置成與載置台相向，對處理容器內導入氣體之噴淋頭 部；和控制裝置全體之動作的控制部，其特徵爲：控制部 控制成實行第1至第1 3態樣中之任一態樣所記載之成膜 方法。 本發明之第1 5態樣係提供一種記憶媒體’記憶有電 腦可讀取之程式，其特徵爲：於使用成膜裝置以第1溫度 在被處理體形成薄膜之時，該成膜裝置具備：能夠真空排 氣之處理容器；被配置在處理容器內，載置被處理體之氮 化鋁製之載置台；用以加熱被處理體之加熱部；和被配置 成與載置台相向，對處理容器內導入氣體之噴淋頭部’以 -10- 201002849 實行第1至第1 3態樣中之任一態樣所記載之成膜方法之 方式控制成膜裝置。 〔發明效果〕 若藉由本發明之實施型態，則提供於成膜處理時可以 抑制粒子產生，可以利用高於以往洗淨中之溫度的溫度執 行洗淨，而且可以提高生產率之成膜方法及成膜裝置。 【實施方式】 在藉由本發明之實施型態的在被處理體表面形成薄膜 之成膜方法中，因追加有邊導入氮化氣體至處理容器內邊 維持至第2溫度以下之第3溫度的改質工程，故即使於洗 淨之時生成A1F系物質，亦可以藉由改質A1F系物質，使 成爲難以飛散。因此，於成膜處理之時，可以抑制粒子之 產生。而且，可以以高於以往之洗淨中之溫度的溫度來執 行洗淨，依此，可以提高生產率。 以下，根據附件圖面詳細說明本發明所涉及之成膜方 法及成膜裝置之最佳實施型態。 第2圖爲表示實施本發明所涉及之成膜方法的成膜裝 置之一例的剖面構成圖。並且，在此薄膜係以藉由電漿 CVD形成鈦膜（Ti膜）之時爲例予以說明。 如圖示般，該成膜裝置12具有藉由例如鋁成型圓筒 體狀之處理容器14，該處理容器14被接地。在該處理容 器14之天井部設置有噴淋頭部18，該噴淋頭部18下面具 -11 - 201002849 有多數氣體噴出口 16以當作氣體導入手段，依此形成可 以將各種所需氣體導入處理容器14內之處理空間S。並 且，在該噴淋頭部18內，在其中區劃成屬於原料氣體之 TiCl4和屬於還原氣體之H2不會混合，成爲於兩氣體噴出 至處理空間S之時開始混合，即所謂的後混料構造。再者 ，並不限定於此，即使使用在噴淋頭部18內混合兩氣體 的所謂預混料構造之噴淋頭部亦可。 噴淋頭部1 8係藉由例如鎳或赫史特（Hastelly :產品 名）、鋁或該些材料之組合而構成。噴淋頭部1 8全體具 有導電性，當作平行平板電極之上部電極而發揮功能。屬 於該上部電極之噴淋頭部1 8之外圍或上方，藉由例如由 石英或氧化鋁（Al2〇3 )等所構成之絕緣體20覆蓋全體， 噴淋頭部18經絕緣體20被安裝固定於處理容器14。依此 ，噴淋頭部18自處理容器14絕緣。並且，在噴淋頭部18 和絕緣體20之間以及絕緣體20和處理容器14之間，存 在有由例如〇型環等所構成之密封構件22，依此能夠氣 密維持處理容器14。 然後，在該噴淋頭部18連接有電槳形成手段28。具 體而言，該電漿形成手段28具有例如產生4 5 0kHz之高頻 電壓的高頻電源24，該高頻電源24經匹配電路26連接於 噴淋頭部1 8，因應所需對屬於上部電極之噴淋頭部1 8施 加高頻電壓。並且，該高頻電壓之頻率並不限定於 450kHz，例如在300kHz〜27MHz之範圍內即可，具體而 言即使爲13.56MHz等亦可。 -12- 201002849 然後’在該處理容器14之側壁形成有用以搬出搬入 晶圓之搬出搬入口 3 0 ’依此在此設置有閘閥3 2而能夠開 關。在閘閥32，連接有不用將半導體晶圓曝露於大氣而予 以搬運之無圖式的裝載鎖定室或轉移腔室等。 處理容器14之底部之中央朝下方成型凹部狀，在該 側面設置有連接於無圖式之真空泵等之排氣口 34，依此因 應所需能夠使處理容器1 4內真空排氣。然後，在處理容 器14內’爲了載置當作被處理體之半導體晶圓w，設置 有藉由自處理容器14之底部延伸之支柱36而被支撐之載 置台38。該載置台38兼作下部電極，在載置台38之上部 周緣部’以包圍晶圓W之周圍之方式設置有環狀之聚焦 環40。然後’藉由對屬於上部電極之噴淋頭18施加高頻 電壓’則能夠在屬於下部電極之載置台3 8和屬於上部電 極之噴淋頭部1 8之間之處理空間S生成電漿。 具體而言，載置台38例如全體係以屬於陶瓷材之氮 化鋁（A1N )所形成，在氮化鋁製之載置台38之內部沿著 特定圖案形狀埋入有例如由鉬或鎢線等之電阻體所構成之 加熱器4 2 ’以作爲加熱手段。在加熱器4 2經配線4 6連接 有加熱器電源44。因應所需從加熱器電源44供給電力至 加熱器4 2 ’晶圓W能夠被加熱至特定溫度。並且，在載 置台38之內部，因發揮下部電極之功能，故在面內方向 大略全區域埋入有以例如鉬線等之網目（網）所形成之電 極本體4 8。然後，電極本體4 8經配線5 0被接地。並且， 即使對電極本體48施加當作偏壓電壓之高頻變壓亦可。 -13- 201002849 然後，在載置台38形成有貫通於上下方向之3根插 銷孔52(第2圖中僅表示2個）。在各插銷孔52中可自 由移動地插通其下端與圓弧狀之連結環54共通被支撐的 例如石英製之推上銷56。連結環54貫通容器底部而被支 撐於可上下移動之出沒桿58之上端，該出沒桿58之下端 被連接於制動器60。依此，推上銷56於晶圓W搬入搬出 時，可以從各插銷孔52之上端朝上方突出，或下降至比 上端更低處。再者，被設置在出沒桿58之容器底部之貫 通部，設置有能夠伸縮之伸縮管62，可以邊維持處理容器 14之氣密性，邊使出沒桿62升降。 在噴淋頭部1 8之氣體導入口 64連接有供給處理所需 之各種氣體之氣體供給系66。具體而言，氣體供給系66 包含流通當作原料氣體之例如TiCl4氣體之原料氣體管68 、流通當作電漿生成用氣體等之稀有氣體、流通例如Ar 氣體之稀有氣體管70、流通當作還原氣體之例如h2氣體 之還原氣體管72、流通當作沖洗氣體等之N2氣體之仏氣 體管74、流通當作洗淨氣體之例如氟系氣體的洗淨氣體管 7 6 ’以及流通當作氮化氣體之例如NH3氣體的氮化氣體管 ΊΊ。 在氣體管68、70、72、74、76、77各設置有控制所 對應之氣體之供給量的例如質量流量控制器般之流量控制 部68八、70人、72人、74人、76八、77人，和開關閥688、 70B、72B、74B、76B、77B。作爲氟系氣體，在本實施型 態中使用C 1F 3氣體。 -14- 201002849 然後，該裝置全體係藉'由例如由電腦所構成之控制部 7 8而被控制，例如控制各氣體之供給開始、停止、各氣體 流量控制、載置晶圓W之載置台3 8之溫度控制、處理容 器14內之壓力控制、電漿產生用之高頻電力之供給及供 給停止等。再者，該控制所需之電腦可讀取程式被記憶於 記憶媒體 80。該記憶媒體 80係由例如軟碟、CD ( Compact Disc) 、CD-ROM、硬碟、快閃記憶體或DVD等 所構成。 接著，針對藉由使用如上述般構成之成膜裝置而執行 之本發明之實施型態所產生之成膜方法，亦參照第3圖及 第4圖予以說明。第3圖爲表不依據本發明之實施型態的 成膜方法中各工程和載置台溫度之關係的工程圖，第4圖 爲用以說明在本實施型態中以洗淨所生成之A1 F系物質之 舉動的槪略說明圖。在此，如上述般以對半導體晶圓 W 表面執行Ti膜成膜爲例。 如上述般，於在特定片數半導體晶圓連續性形成Ti 膜之後，執行除去附著於處理容器14內之不需要膜的洗 淨、於洗淨後使處理容器內之熱性條件安定化之預塗敷（ 乾燥法），以及後述之除去處理以及排出處理等。首先， 針對成膜工程予以說明。 在成膜工程中，首先打開設置於處理容器1 4側壁之 閘閥3 2，自無圖式之裝載鎖定室等經搬出搬入口 3 0將未 處理之例如矽基板之半導體晶圓W搬入至處理容器14內 。接著，晶圓W藉由推上銷56被接取，藉由推上銷56 -15- 201002849 之下降，被載置在屬於下部電極之載置台38上。 接著，關閉閘閥3 2封閉處理容器14內，增加供給至 加熱器42之供給電力，將預熱之載置台38之溫度升溫至 屬於製程溫度之第1溫度而予以維持。在此，第1溫度例 如爲65 0°C。然後，同時打開各開關閥68B、70B、72B， 自屬於上部電極之噴淋頭部1 8將電漿生成氣體之Ar氣體 、還原氣體之H2氣體以及原料氣體之TiC 14氣體邊各予以 流量控制，邊供給至處理容器14內。與此同時，自排氣 口 34使處理容器14內排氣成真空而將處理容器14內維 持在特定之製程壓力。 並且，藉由驅動高頻電源24，在屬於上部電極之噴淋 頭部1 8和屬於下部電極之載置台 3 8之間，施加例如 450kHz之高頻電壓而在處理空間S生成電漿，藉由電漿 分解TiCl4氣體，使Ti膜堆積在晶圓W表面。 在此，針對藉由本發明之實施型態之方法，參照第3 圖予以說明。在該實施型態中，如第3圖所示般，具有以 第1溫度，例如低於6 5 (TC之第2溫度，例如在3 00 °c中 ，使用屬於洗淨氣體之氟系氣體，例如C1F 3將處理容器 1 4內予以洗淨之洗淨工程；邊將氮化氣體，例如NH3導 入至處理容器14內’邊維持在第2溫度以下之第3溫度 ，依此改質被生成在載置台38之A1F系物質之改質工程 :使載置台38之溫度升溫至上述第1溫度而在處理容器 1 4內形成預塗敷膜之預塗敷工程；和對被處理體以第1溫 度形成薄膜之成膜工程，該些各工程重複被執行。在第3 •16- 201002849 圖中，表示洗淨工程之第2溫度和改質工程之第3溫度爲 相同之時（3 0 0 °C )。 具體而言’首先’如上述般，當在第1溫度，例如 65 0 °C重複執行對半導體晶圓W成膜時，成爲粒子原因之 不需要的膜附著於處理容器1 4內，故於對某程度之片數 之晶圓執行成膜之後’即是完成成膜工程之後，使載置台 3 8之溫度下降至第2溫度例如3 0 0。(：，在其溫度下執行洗 淨。該洗淨係僅以特定流量流通屬於氟系氣體之C 1F 3氣 體而除去附著於處理容器14之內壁面或處理容器14內之 構造物表面之不需要的膜。C1F3因具有非常高之反應性（ 腐蝕性），故即使不生成電漿亦可以與不需要之膜反應， 依此除去不需要之膜。 再者’ C1F3氣體不僅與不需要的膜反應，亦與處理容 器14內之構造物之一個的載置台38之構成材料之氮化鋁 (A1N )反應，在載置台38表面生成A1F系物質。該A1F 系物質因成爲容易飛散之粒子源，故必須抑制生成。因洗 淨溫度越高越生成多量之A1F系物質，故以往之洗淨係將 洗淨溫度設定成200°C左右之低溫度而抑制A1F系物質之 生成。但是，爲了使載置台38之溫度降溫至200 °C，需要 較多時間，不得已大幅度下降生產率。再者，爲了於洗淨 後執行成膜，因使該下降至20(TC之載置台38之溫度再次 升溫至6 5 0 °C ’也需要較多時間，從該點來看也不得已大 幅度下降生產率。 對此，在本發明之實施型態中，由於將洗淨溫度設定 -17- 201002849 成高於2 0 0 °C例如3 0 0 °C，故減少載置台3 8之升降溫所需 之時間，其部分雖然可以謀求提高生產率，但是僅洗淨溫 度高之部分，則生成大量A1F系物質。但是’藉由執行在 此所說明之改質工程，可以使A1F系物質難飛散。並且， 洗淨時間雖然依存於成膜處理後之晶圓之片數’但是在將 厚度爲l〇nm左右之Ti膜形成在500片之晶圓之後，例如 大約5 0分鐘即可。 如上述般，於洗淨工程結束後，執行A1F系物質之改 質處理（改質工程）。在該改質處理中，邊使屬於氮化氣 體之例如NH3氣體流通，邊將載置台3 8之溫度維持在第 2溫度以下之第3溫度。在此，如上述般，載置台3 8之溫 度（第3溫度）被維持與洗淨工程之溫度之第2溫度相同 。再者，第3溫度爲低於屬於A1F系物質之氟化鋁飛散之 溫度低的溫度。 依此，上述A1F系物質與NH3氣體反應而被改質，成 爲難以飛散。A1F系物質係由混有 AlFx ( X = 1〜3 )之形 態所形成，X越小的低次氟化物，昇華溫度則越低。以下 表示低次氟化物之反應室和300°C及40(TC中之吉布斯（ Gibbs )之自由能變化。Deposition) film formation. Further, the TiN film is formed by plasma CVD using TiCl4 and nitrogen (N2) gas as a raw material gas, or a raw material gas to make 201002849 by thermal CVD using TiCl4 and NH3 gas. Here, a schematic configuration of an example of a general film forming apparatus will be described with reference to Fig. 1. This film forming apparatus has a processing container 4 capable of vacuum evacuation, and a mounting table 2 made of, for example, aluminum nitride (A1N) is placed in the processing container 4, and a semiconductor wafer W is placed on the mounting table 2. Then, a shower head 6 is provided on the ceiling of the processing container 4 so as to supply the required gas to the inside of the processing container 4 so as to face the mounting table 2. Further, it is preferable to connect the high-frequency power source 8 for plasma generation to the shower head 6 as necessary to form an electric paddle in the processing container 4. Here, in order to form, for example, a Ti film or a TiN film, a gas of TiCl4, H2, N2, Ar or the like is used. Although the above film formation is continuously performed on the wafer under a process temperature of, for example, about 650 ° C, the Ti film or the TiN film is not only on the surface of the wafer, but also on the inner wall surface of the processing container or the structure inside the container. The surface of the shower head 6 necessarily adheres to an undesired film. When the particles are generated when the unnecessary film is peeled off, the yield of the semiconductor article is lowered. Therefore, the cleaning gas such as C1F3 or NF3 is allowed to flow into the processing container periodically or in response to the necessity, and the cleaning of the unnecessary film is performed. . This cleaning is performed because the corrosion of the cleaning gas is too large when the temperature is high, so that the temperature of the stage is lowered from the relatively high process temperature to a low temperature. Then, after the cleaning, in order to arrange the heat conditions in the processing container, in the state where the wafer is not contained inside, the same gas as that at the time of film formation is passed, and the same gas is formed during the film formation, and the inside of the processing container is executed. The surface of the wall or the surface of the structure is applied to the precoat of the pre-coated film (drying method). Then the manufacturing line begins. [Patent Document 1] JP-A-2002-167673 (Patent Document 2) JP-A-2004-307939 (Patent Document 3) JP-A-2004-273648 (Patent Document 4) JP-A-2005- SUMMARY OF THE INVENTION (Problem to be Solved by the Invention) Further, the mounting table 2 is generally formed of a ceramic material such as Niobium (A1N), which is exposed to the CIF 3 or When a cleaning gas such as NF3 is used, the two react to form an aluminum fluoride (A1F)-based substance. Then, when the temperature of the mounting table 2 is raised for film formation, the A1F-based substance is scattered and adhered to the surface of the shower head 6 opposed to the mounting table 2 or the inner wall surface of the processing container 4. Thereafter, at the time of film formation, the above-mentioned unnecessary film adheres to the A1F-based substance adhering to the surface of the shower head 6. Since the adhesion between the A1F-based material and the metal is weak, the above-mentioned unnecessary film adhered at the time of film formation is easily peeled off, and there is a problem that particles are peeled off when the wafer is subjected to a film formation treatment. Therefore, in the conventional cleaning, if the temperature of the mounting table is lowered to the aluminum nitride which is a constituent material of the mounting table, even if it is exposed to a cleaning gas such as C1F3 or NF3, it is difficult to generate the temperature of the A1F-based substance, for example, 200 °. Around C, the washing is performed while maintaining the temperature. However, at this time, the temperature of the stage having a relatively large heat capacity is lowered from the 201002849 film forming temperature, for example, 65 Torr, to 200 °C of the washing temperature, and it is necessary to raise the temperature to 650 again after washing. (: The temperature drop and the temperature rise again have a situation such as a very long time of about 3 hours. Therefore, there is a problem that the productivity is greatly reduced. The present invention pays attention to the above-mentioned problems, and is created to effectively solve the problem. An object of the present invention is to provide a film forming method, a film forming apparatus, and a memory medium. The film forming method, the film forming apparatus, and the memory medium can be modified not only to form an A1F-based substance during cleaning, but also to be difficult to fly. Further, it is possible to suppress the generation of particles during the film formation treatment, and it is possible to perform the cleaning at a temperature higher than the conventional cleaning temperature, whereby the productivity can be improved. (Means for Solving the Problem) The first aspect of the present invention provides A film forming method for forming a film on a target object at a first temperature by using a film forming apparatus, the film forming apparatus comprising: a processing container configured to be evacuated; and a nitrogen contained in the processing container and placed on the object to be processed a mounting table made of aluminum; a heating portion for heating the object to be processed; and a shower head disposed to face the mounting table to introduce a gas into the processing container. The method includes: using a cleaning gas of a fluorine-containing gas, washing the cleaning process in the processing container at a second temperature lower than the first temperature; and maintaining the nitriding gas by maintaining the third temperature below the second temperature Introduced into the processing container to modify the A1F-based material to be reformed on the mounting table; to raise the temperature of the mounting table to the first temperature, to form a pre-coating process of the pre-coated film in the processing container; The first temperature is formed into a film forming process of the film to be processed. -8- 201002849 The second aspect of the present invention is a film forming method according to the first aspect, wherein the second temperature in the cleaning process is 400 ° C or less. The third aspect of the present invention provides a film forming method according to the first or second aspect, wherein the third temperature in the upgrading process is 40 (rC below the film forming method. The fourth aspect of the present invention) In the film forming method of any of the first to third aspects, the film forming method in which the second temperature and the third temperature are the same is provided. The fifth aspect of the present invention is the first to the fourth In any of the film forming methods of the aspect, the nitriding gas is intermittently supplied to the treatment in the upgrading process. The film forming method in the container. In the film forming method according to any one of the first to fourth aspects of the present invention, the nitriding gas and the hydrogen gas are supplied to the processing in the upgrading process. Film forming method in a container. The seventh aspect of the present invention is a film forming method according to any one of the first to fourth aspects, which provides a nitriding gas and a film for forming a film in a upgrading process. The film forming method in which the material gas is supplied to the processing container. The eighth aspect of the present invention is a film forming method according to the seventh aspect, which provides a film forming method in which a nitriding gas and a material gas are intermittently and alternately supplied to each other. In the film forming method of any of the first to eighth aspects of the ninth aspect of the present invention, the fluorine-based gas is selected from the group consisting of cif3, nf3, c2f6, and f2. A film forming method of more than one gas. In the film forming method of any of the first to ninth aspects of the first aspect of the present invention, the nitrogen-based gas is a group consisting of NH3, hydrazine, and hydrazino 201002849. A film forming method of one or more selected gases. In the eleventh aspect of the present invention, in the film forming method of any of the first to first aspects, a film forming method of the film of titanium film or titanium nitride film is provided. In the film forming method of any of the first to eleventh aspects of the first aspect of the present invention, the raw material gas is supplied from TiCl4, TDMAT (Tetrakis Dimethyl Amino Titanium), TDEAT (Tetraki s Diethyl). A method of forming a film of one or more gases selected from the group consisting of Amino Titanium. In the film forming method of any of the first to twelfth aspects of the first aspect of the present invention, a film forming method in which the second temperature and the third temperature are 200 ° C or higher is provided. According to a fourth aspect of the present invention, there is provided a film forming apparatus comprising: a processing container capable of vacuum evacuation; and a mounting table made of aluminum nitride placed in the processing container and placed on the object to be processed; a heating unit that processes the body; a shower head that is disposed to face the mounting table and that introduces a gas into the processing container; and a control unit that controls the operation of the entire device, wherein the control unit controls the first to the first The film formation method described in any of the three aspects. According to a fifteenth aspect of the present invention, there is provided a memory medium having a computer readable program, wherein the film forming apparatus is provided when a film forming device forms a film at a first temperature at a first temperature. a processing container capable of vacuum evacuation; a mounting table made of aluminum nitride placed in the processing container, placing the object to be processed; a heating portion for heating the object to be processed; and being disposed to face the mounting table, The shower head in which the gas is introduced into the container is controlled to form a film forming apparatus in such a manner that the film forming method described in any of the first to third aspects is performed in -10-201002849. [Effect of the Invention] According to the embodiment of the present invention, it is possible to provide a film formation method which can suppress the generation of particles during the film formation process, can be washed at a temperature higher than the temperature in the conventional cleaning, and can improve productivity. Film forming device. [Embodiment] In the film forming method for forming a film on the surface of a target object according to the embodiment of the present invention, the nitriding gas is introduced into the processing container while maintaining the third temperature lower than the second temperature. Since the A1F-based substance is produced at the time of washing, it is possible to make it difficult to fly by modifying the A1F-based substance. Therefore, at the time of film formation treatment, generation of particles can be suppressed. Further, the cleaning can be performed at a temperature higher than the temperature in the conventional washing, whereby the productivity can be improved. Hereinafter, the film forming method and the film forming apparatus according to the present invention will be described in detail based on the attached drawings. Fig. 2 is a cross-sectional structural view showing an example of a film forming apparatus which performs the film forming method according to the present invention. Further, the film is described as an example in which a titanium film (Ti film) is formed by plasma CVD. As shown, the film forming apparatus 12 has a processing container 14 formed of a cylindrical shape by, for example, aluminum, and the processing container 14 is grounded. A shower head 18 is disposed on the patio portion of the processing container 14, and the shower head 18 has a plurality of gas discharge ports 16 as a gas introduction means under the mask -11 - 201002849, thereby forming various desired gases. The processing space S in the processing container 14 is introduced. Further, in the shower head 18, TiCl4 which is divided into a material gas and H2 which is a reducing gas are not mixed, and mixing is started when the two gases are ejected to the processing space S, that is, a so-called post-mixing structure. Further, the present invention is not limited thereto, and a shower head of a so-called premix structure in which two gases are mixed in the shower head 18 may be used. The shower head 18 is constructed by, for example, nickel or Hastelly (product name), aluminum, or a combination of these materials. The shower head 18 has electrical conductivity and functions as an upper electrode of the parallel plate electrode. The periphery or the upper side of the shower head 18 belonging to the upper electrode is covered with an insulator 20 made of, for example, quartz or alumina (Al 2 〇 3 ), and the shower head 18 is mounted and fixed via the insulator 20 . The container 14 is processed. Accordingly, the shower head 18 is insulated from the processing vessel 14. Further, between the shower head 18 and the insulator 20, and between the insulator 20 and the processing container 14, a sealing member 22 composed of, for example, a 〇-shaped ring or the like is present, whereby the processing container 14 can be hermetically maintained. Then, an electric paddle forming means 28 is connected to the shower head 18. Specifically, the plasma forming means 28 has, for example, a high-frequency power source 24 that generates a high-frequency voltage of 4500 kHz, which is connected to the shower head 18 via the matching circuit 26, and the required pair belongs to the upper portion. The shower head 18 of the electrode applies a high frequency voltage. Further, the frequency of the high-frequency voltage is not limited to 450 kHz, and may be, for example, in the range of 300 kHz to 27 MHz, and specifically, it may be 13.56 MHz or the like. -12- 201002849 Then, the side wall of the processing container 14 is formed with a gate valve 3 2 for carrying out the loading/unloading port 3 0 for loading and unloading the wafer. The gate valve 32 is connected to a load-free lock chamber or transfer chamber that is transported without exposing the semiconductor wafer to the atmosphere. The center of the bottom of the processing container 14 is formed into a concave shape toward the lower side, and an exhaust port 34 connected to a vacuum pump or the like without a drawing is provided on the side surface, whereby the inside of the processing container 14 can be evacuated as needed. Then, in the processing container 14, in order to mount the semiconductor wafer w as the object to be processed, a mounting table 38 supported by the stay 36 extending from the bottom of the processing container 14 is provided. The mounting table 38 also serves as a lower electrode, and an annular focus ring 40 is provided on the periphery of the upper portion of the mounting table 38 so as to surround the periphery of the wafer W. Then, by applying a high-frequency voltage to the shower head 18 belonging to the upper electrode, plasma can be generated in the processing space S between the mounting table 38 belonging to the lower electrode and the shower head 18 belonging to the upper electrode. Specifically, the mounting table 38 is formed of, for example, aluminum nitride (A1N) which is a ceramic material, and the inside of the mounting table 38 made of aluminum nitride is embedded in a specific pattern shape, for example, by molybdenum or tungsten wire. The heater 4 2 ' formed of the resistor body serves as a heating means. A heater power source 44 is connected to the heater 42 via the wiring 46. Power is supplied from the heater power source 44 to the heater 4 2 ' as needed. The wafer W can be heated to a specific temperature. Further, since the function of the lower electrode is exerted inside the mounting table 38, the electrode body 48 formed of a mesh (mesh) such as a molybdenum wire is buried in the entire area in the in-plane direction. Then, the electrode body 48 is grounded via the wiring 50. Further, even if the electrode body 48 is applied with a high frequency transformation as a bias voltage. -13- 201002849 Then, three insertion holes 52 (only two are shown in Fig. 2) penetrating in the vertical direction are formed in the mounting table 38. A push pin 56 made of, for example, quartz, which is supported by the lower end and the arc-shaped connecting ring 54, is movably inserted into each of the latch holes 52. The connecting ring 54 extends through the bottom of the container and is supported by the upper end of the detachable rod 58 which is movable up and down. The lower end of the ejector rod 58 is connected to the brake 60. Accordingly, when the wafer W is carried in and out of the wafer W, the push pin 56 can protrude upward from the upper end of each of the pin holes 52 or be lowered to a lower position than the upper end. Further, the extending portion provided at the bottom of the container of the ejector rod 58 is provided with a telescopic tube 62 which can be expanded and contracted, and the outlet rod 62 can be raised and lowered while maintaining the airtightness of the processing container 14. A gas supply system 66 for supplying various gases required for the treatment is connected to the gas introduction port 64 of the shower head 18. Specifically, the gas supply system 66 includes a raw material gas pipe 68 that flows, for example, a TiCl 4 gas as a material gas, a rare gas that flows as a plasma generating gas, a rare gas pipe that flows, for example, an Ar gas, and a flow. A reducing gas pipe 72 of a reducing gas such as h2 gas, a helium gas pipe 74 that circulates N2 gas as a flushing gas, a purge gas pipe 74 of a fluorine-based gas that is used as a cleaning gas, and a circulation gas are used as a flow. A nitriding gas tube such as a NH3 gas of a nitriding gas. Each of the gas tubes 68, 70, 72, 74, 76, 77 is provided with a flow rate control unit 68 such as a mass flow controller for controlling the supply amount of the gas corresponding thereto. Eight, 70, 72, 74, 76 , 77 people, and switching valves 688, 70B, 72B, 74B, 76B, 77B. As the fluorine-based gas, C 1F 3 gas is used in the present embodiment. -14- 201002849 Then, the entire system is controlled by a control unit 78 composed of, for example, a computer, for example, controlling the start and stop of supply of each gas, control of each gas flow, and mounting of the wafer W. The temperature control of 3 8 , the pressure control in the processing container 14 , the supply of high frequency power for plasma generation, and the supply stop. Furthermore, the computer readable program required for this control is memorized in the memory medium 80. The memory medium 80 is composed of, for example, a floppy disk, a CD (Compact Disc), a CD-ROM, a hard disk, a flash memory, or a DVD. Next, a film forming method which is produced by the embodiment of the present invention which is carried out by using the film forming apparatus configured as described above will be described with reference to Figs. 3 and 4 . Fig. 3 is a drawing showing the relationship between the temperature of each project and the stage in the film forming method according to the embodiment of the present invention, and Fig. 4 is a view for explaining the A1 generated by the washing in the present embodiment. A schematic diagram of the behavior of the F-based substance. Here, as described above, the Ti film formation is performed on the surface of the semiconductor wafer W as an example. As described above, after the Ti film is continuously formed on the specific number of semiconductor wafers, the removal of the unnecessary film attached to the processing container 14 is performed, and the thermal conditions in the processing container are stabilized after the cleaning. Coating (drying method), and removal processing, discharge processing, and the like described later. First, explain the film forming project. In the film forming process, first, the gate valve 3 2 provided on the side wall of the processing container 14 is opened, and the unprocessed semiconductor wafer W such as a substrate is carried into the processing from the unloading lock chamber or the like through the loading and unloading port 30. Inside the container 14. Next, the wafer W is picked up by the push-up pin 56, and is placed on the mounting table 38 belonging to the lower electrode by pushing down the pin 56 -15-201002849. Next, the gate valve 3 2 is closed to close the inside of the processing container 14, the supply electric power supplied to the heater 42 is increased, and the temperature of the preheating stage 38 is raised to the first temperature belonging to the process temperature and maintained. Here, the first temperature is, for example, 65 °C. Then, each of the on-off valves 68B, 70B, and 72B is simultaneously opened, and the shower heads 18 belonging to the upper electrode respectively control the flow rate of the Ar gas of the plasma generating gas, the H 2 gas of the reducing gas, and the TiC 14 gas of the source gas. And supplied to the processing container 14. At the same time, the exhaust gas is evacuated from the processing vessel 14 from the exhaust port 34 to maintain the process vessel 14 at a specific process pressure. Further, by driving the high-frequency power source 24, a high-frequency voltage of, for example, 450 kHz is applied between the shower head 18 belonging to the upper electrode and the mounting table 38 belonging to the lower electrode, and plasma is generated in the processing space S. The TiCl4 gas is decomposed by the plasma to deposit the Ti film on the surface of the wafer W. Here, a method by which the embodiment of the present invention is applied will be described with reference to FIG. In this embodiment, as shown in FIG. 3, a fluorine-based gas belonging to a purge gas is used at a first temperature, for example, a temperature lower than 6 5 (the second temperature of TC, for example, 300 ° C). For example, C1F 3 cleans the inside of the processing container 14 by washing, and the nitriding gas, for example, NH3, is introduced into the processing container 14 to maintain the third temperature below the second temperature, thereby being modified. A modification process of the A1F-based substance formed on the mounting table 38: a pre-coating process for forming a pre-coated film in the processing container 14 by raising the temperature of the mounting table 38 to the first temperature; and The film formation process of the first temperature forming film is repeated, and in the 3rd - 16th - 201002849 figure, when the second temperature of the cleaning process and the third temperature of the upgrading process are the same (3) 0 0 ° C. Specifically, as described above, when the semiconductor wafer W is repeatedly formed at the first temperature, for example, 65 ° C, the film which is an unnecessary particle is attached to the processing container. In 1 4, after performing film formation on a certain number of wafers, the film formation is completed. After the process, the temperature of the mounting table 38 is lowered to the second temperature, for example, 300. (: The cleaning is performed at the temperature. The cleaning is performed by flowing only the C 1F 3 gas belonging to the fluorine-based gas at a specific flow rate. The unnecessary film attached to the inner wall surface of the processing container 14 or the surface of the structure in the processing container 14 is removed. Since C1F3 has a very high reactivity (corrosiveness), it can be used with an unnecessary film even if no plasma is formed. The reaction is carried out to remove the unnecessary film. Further, the 'C1F3 gas reacts not only with the undesired film but also with aluminum nitride (A1N) which is a constituent material of the mounting table 38 which is one of the structures in the processing container 14, An A1F-based substance is formed on the surface of the mounting table 38. Since the A1F-based substance is a particle source that is easily scattered, it is necessary to suppress the formation of the A1F-based substance. Since the A1F-based substance is formed as the washing temperature is higher, the conventional cleaning system is washed. The temperature is set to a low temperature of about 200 ° C to suppress the formation of the A1F-based substance. However, in order to lower the temperature of the mounting table 38 to 200 ° C, it takes a lot of time, and the productivity is drastically reduced. Net When the film formation is performed, it takes a lot of time to lower the temperature to 20 (the temperature of the stage 38 of the TC is raised again to 650 ° C.) From this point of view, the productivity must be drastically lowered. In the embodiment of the invention, since the cleaning temperature is set to -17-201002849 to be higher than 200 °C, for example, 300 ° C, the time required for the lifting and lowering of the mounting table 38 is reduced, although part of it can be In order to improve productivity, a large amount of A1F-based substances are generated only in a portion where the temperature is high. However, the A1F-based substance can be prevented from scattering by performing the upgrading process described herein. Further, although the cleaning time depends on the number of wafers after the film formation process, the Ti film having a thickness of about 10 nm is formed on 500 wafers, for example, about 50 minutes. As described above, after the completion of the cleaning process, the A1F-based substance is modified (reformed). In the reforming process, while the NH 3 gas belonging to the nitriding gas is circulated, the temperature of the mounting table 38 is maintained at the third temperature equal to or lower than the second temperature. Here, as described above, the temperature (third temperature) of the stage 38 is maintained to be the same as the second temperature of the temperature of the cleaning process. Further, the third temperature is a temperature lower than a temperature at which the aluminum fluoride belonging to the A1F-based substance is scattered. Accordingly, the A1F-based substance is reacted with the NH3 gas to be modified, so that it is difficult to fly. The A1F system is formed by mixing AlFx (X = 1~3), and the lower the X, the lower the sublimation temperature. The following shows the reaction chamber of the low-fluorinated fluoride and the free energy of 300 ° C and 40 ( Gibbs in TC).
A1F3 + NH3-> AIN + 3HF 263.3 (300。。） 235.1 (400 〇C) A1F2 + NH3 —A1N + 2HF + 1/ 2H2 -68.5 ( 3 00 °C ) -59.6 ( 400°C ) A1F+NH3— A1N+HF+H2 18- 201002849 -154.8 ( 300 °C ) -133.4 ( 400 °C ) 可知上述反應系於自由能減少方向進行，如上述 在A1F、A1F2之低次氟化物中自由能變化成爲負，自 與NH3氣體產生反應。aif系物質係藉由混在其中之 氟化物與nh3氣體反應，而選擇性被還原及氮化而變 安定之A1N。如此被改質之A1F系物質即使提高溫度 會引起昇華，其結果如上述般飛散被抑制。該狀況表 第4圖中，被生成在載置台38表面之A1F系物質84 ΝΑ氣體之改質，被變換成A1N (氮化鋁）85。該改 程執行例如5分鐘左右。 如此一來改質工程結束後，使載置台3 8之溫度 至成膜溫度（製程溫度）之第1溫度，即是6 5 0 °C， 預塗敷。此時之升溫速度例如爲1 0 °C / m i η左右。在 塗敷中，藉由不將晶圓W搬入至處理容器14內，與 時相同，流通TiCl4、H2、Ar並生成電漿，使處理容] 內維持與成膜時相同之壓力，例如666Pa左右。依此 理容器14之內壁面在載置台38等之容器內構造物之 形成由Ti膜所構成之預塗敷膜，依此處理容器1 4內 性狀態則安定化。 該預塗敷工程之時間例如爲60分鐘左右。可以 置台38之溫度從3 00°C升溫至65 0 °C所需之時間，比 往之成膜方法中從200°C升溫至650 °C所需之時間短。 如此一來，於預塗敷工程結束之後，將未處理之 W搬入至處理容器14內，執行上述般之成膜。在該 般， 發性 低次 化成 也不 示在 藉由 質工 升溫 執行 該預 成膜 器14 ，處 表面 之熱 使載 在以 晶圓 成膜 -19- 201002849 中，如上述般，將TiCl4、H2、Ar氣體導入至處理容器14 內而生成電漿，在晶圓W表面形成Ti膜。對該晶圓W之 成膜被重複執行至應執行下一個洗淨之時期。在該成膜中 ，屬於第1溫度之成膜溫度爲65 0 °C，處理容器14內之壓 力爲666Pa左右。並且，該製程條件僅爲一例，當然並不 限定於此。 如此一來，於對特定片數之晶圓 W成膜結束之後， 使載置台3 8之溫度降溫至第2溫度，例如3 00 °C，再次執 行洗淨。此時之降溫速度例如爲4°C /min左右。以後，以 上述般之程序重複執行各工程。 在此從成膜工程移行至洗淨工程之時，可以使載置台 38之溫度從65 0°C降溫至300°C所需之時間，比在以往之 成膜方法中從65 0 °C降溫至200°C所需之時間大幅縮短’ 其部分可以提高晶圓處理之生產率。具體而言，在以往之 成膜方法中，對一次之升溫操作也需要兩小時40分左右 ，但是在本實施形態之方法之時，可以短縮至1小時3 0 分鐘左右。 〔0061 〕 再者，在洗淨工程中，被生成在載置台38之表面之 A1F系物質，藉由氮化氣體氮化而變換至A1N，依此因可 以使飛散成爲困難，故於成膜處理之時，可以大幅度抑制 粒子產生。 並且，在此雖然將執行洗淨工程之第2溫度設定成 3 00 °C，但是該第2溫度並不限定於300°C，即使如後述般 -20- 201002849 設定成40(TC以下之溫度亦可。當將該洗淨溫度設定成 如400 °C時，因可以更縮短載置台38之升降溫所需之時 ，故可以更提高晶圓處理之生產率。並且，此時改質工 之溫度也以設定成40CTC爲佳。 如上述般，若藉由本發明之實施形態時，邊將氮化 體例如NH3導入至處理容器1 4內，邊維持屬於洗淨溫 之第2温度以下之第3溫度，依此因改質被生成在載置 38之A1F系物質，故於洗淨時即使生成A1F系物質， 可以改質A1F系物質，而且不僅可以抑制成膜時產生粒 ’亦可以在高於以往之溫度下執行洗淨，其部份可以提 生產率。 在上述實施形態中，在改質工程中雖然對處理容器 供f«虽作氮化氣體之nh3氣體，但是如後述般，即使將 NH3氣體單獨供給至處理容器ι4亦可，即使與其他氣 同日寸供給亦可。例如’於僅將NH3氣體供給至處理容 1 4之時’即使連續性流通該N Η3氣體亦可，即使間歇 例如脈衝狀流通亦可。 再者’於將ΝΗ3氣體與其他氣體同時供給之時，因 求增加還原力，故即使與NH;氣體同時流通η2氣體亦 ’即使將在該成膜所使用之原料氣體（TiCI4氣體） NH3氣體同時供給亦可。並且，NH3氣體具有氮化作用 還原作用。 (本實施型態之評估） 例 間 程 氣 度 台 亦 子 筒 14 該 體 Π-Σ£. 器 性 謀 可 與 和 -21 - 201002849 接著’因執行與上述實施型態有關之試驗，故針對其 評估結果予以說明。第5圖爲用以說明在該試驗中所利用 之評估方法的說明圖，第6圖爲表示洗淨溫度與飛散之 A1F系物質之量的關係曲線圖，第7圖爲表示在不同洗淨 溫度下於洗淨後將載置台升溫至65(TC之過程中飛散之 A1F系物質之量的曲線圖，第8圖爲表示本實施形態與比 較例之評估結果的直線圖，第9圖A及第9圖B爲在該試 驗中所利用之各氣體之供給之一例的時序圖。 該實驗係如下述般被執行。首先，使T i C14、Η 2、A r 氣體流通於無收容晶圓之處理容器i 4，產生電漿，執行 700nm膜厚之預塗敷處理，接著，在該處理容器14內供 給CIF3氣體’不生成電漿，將載置台溫度設定成200〜 6 5 0 °C (按試驗而有所不同），執行洗淨工程。此時，在 載置台38表面生成A1F系物質，此藉由溫度而飛散。 該試驗之評估係藉由如第5圖所示般測量來自載置台 38表面之A1F系物質之飛散量而執行。即是，如第5圖 所示般’半導體晶圓W係鏡面8 8邊維持朝下，邊被搬入 至處理容器14內，以不接觸於載置台38之方式，藉由推 上銷56被支撐於載置台38之上方。此時，載置台38之 上面和晶圓W之朝下之鏡面8 8之間的距離Η1設定成 3 mm。然後，在將晶圓W維持如此之狀態下，將載置台 38之溫度從200°C升溫至65〇t (按試驗有所不同），於 經過特定時間後，自處理容器1 4取出晶圓W，測量附著 於晶圓W之鏡面88之A1F系物質之量。 -22- 201002849 〔A1F系物質之特性〕 首先，針對於洗淨工程之時’被生成在載置台3 8表 面之A1F系物質之特性予以評估。具體而言，調查相對於 在洗淨工程中飛散之A1F系物質之量之洗淨溫度的依存性 ，和相對於在使載置台溫度從洗淨溫度升溫至成膜溫度（ 650°C)之期間飛散之A1F系物質之量的洗淨溫度的依存 性。 如第5圖所示般，將晶圓W之鏡面朝下設置，流通 當作洗淨氣體之C1F3氣體，在洗淨溫度執行洗淨。並且 ，在晶圓表面形成有對C1F3氣體具有耐蝕性之Si02膜。 在洗淨中附著於晶圓W之鏡面之A1F系物質之量使用 XRF (螢光X射線分析器）予以評估。具體而言，於洗淨 後’自處理容器14取出晶圓W，藉由XRF，求出自附著 於晶圓之A1F系物質所含之A1原子產生之螢光X射線之 強度，將該強度當作代替指標使用。以不同之洗淨溫度多 次重複以上順序。將如此所取得之結果表示於第6圖。在 第6圖之曲線圖中’橫軸設爲洗淨溫度，縱軸設爲來自附 著於晶圓W之A1F系物質中之A1原子的螢光X射線強度 。再者’ A1F系物質之附著量以洗淨溫度爲2〇(rc之時之 附著量爲基準而予以表示。若藉由第5圖所示之配置，從 載置台38之表面飛散之A1F系物質因全部附著於晶圓w ’故A1F系物質朝晶圓附著之附著量相當於來自載置台 38之飛散量。 -23- 201002849 如第6圖所示般，在此於將洗淨溫度變更成各種溫度 200。。、300。。、 400。。、4 5 0 °C、500 〇C 之時，在 200 〜40〇 。(：之範圍中，看不見A1F系物質之飛散量變化，但是當洗 淨溫度超過400 °C時，A1F系物質之飛散量也急速增多。 因此，可以理解洗淨工程中之洗淨溫度，即是第2溫 度之上限爲400 °C。此時，洗淨溫度之下限當考慮隨著洗 淨效率之下降及載置台38之升降溫的生產率之下降時， 則爲2 5 0 °C左右。 接著，於不同洗淨溫度之洗淨之後，不執行改質工程 ，求出在將載置台之溫度升溫至屬於成膜溫度之650°C之 過程中飛散之A1F系物質的量。具體而言，在不同洗淨溫 度下洗淨之後，半導體晶圓W係鏡面8 8邊維持朝下，邊 被搬入至處理容器14內，以不接觸於載置台38之方式， 藉由推上銷56被支撐於載置台38之上方（參照第5圖） 。接著，使載置台3 8之溫度升溫至6 5 〇t。之後，自處理 容器14取出晶圓W，並藉由XRF求出附著於晶圓W之 A1F系物質之附著量。將其結果表示於第7圖。在第7圖 之曲線圖中，橫軸設爲洗淨時之溫度，縱軸設爲來自附著 於晶圓W之A1F系物質中之A1原子的螢光X射線強度。 並且，洗淨溫度如第7圖所示般，設爲40(TC、450°C 、5 0(TC及65 0 °C。於洗淨之後，雖然將載置台38之溫度 提高至屬於成膜溫度之6 5 (TC，但是於洗淨溫度爲6 5 0 °C 之時，並不升溫。 由第7圖可知，於洗淨溫度爲400 °C之時，即使之後 -24- 201002849 將載置台溫度升溫至650 °C，A1F系物質也幾乎不飛散， 表示良好結果。對此，當洗淨溫度超過400 1之時，A1F 系物質之飛散量急速變大，爲不理想。因此，由該結果， 可以理解將洗淨溫度設定在400°C以下爲佳。 〔改質工程之評估〕 接著，與比較例同時說明在洗淨工程之後執行藉由執 行本發明之實施形態所產生之方法中之改質工程之時的評 估結果。在此，求出於執行洗淨之後，執行改質處理之後 ，或是不執行改質處理而將晶圓W搬入至處理容器內， 之後將載置台升溫至650°c之時之附著於晶圓W之A1F系 物質的附著量。該A1F系物質之附著量與上述相同，藉由 XRF求出。第8圖表示本發明之實施例和比較例之評估結 果之直條圖，第9圖A爲表示執行後述試驗8 (本發明之 實施例之一）之時之各氣體之供給模式的時序圖，第9圖 B爲表示執行後述試驗9(本發明之實施例之一）之時的 各氣體之供給模式的時序圖。 在第8圖中，試驗1〜試驗4表示比較例，試驗5〜 試驗9表示在改質工程中使用NH3氣體之本發明之實施例 。縱軸表示AIF系物質朝晶圓之附著量，該相當於來自載 置台之A1F系物質之飛散量。在此，使用C1F3當作洗淨 氣體。 試驗1爲以往方法。即是，在試驗1中，以不生成 A1F系物質之2 00 °C執行洗淨，之後不執行改質處理，載 -25- 201002849 置台38之溫度升溫至65 0°C。 在試驗2中，以3 0(TC執行洗淨，之後不執行改質處 理’載置台3 8之溫度升溫至6 5 0 t。 在試驗3中’以3 00 °C執行洗淨，之後邊流通TiCl4 ( 原料氣體）邊以300 °C進行改質處理，接著載置台38之溫 度升溫至6 5 0 °C。 在試驗4中’以3 0(TC執行洗淨，之後邊同時流通 TiCl4和Ha邊以3 00 °C進行改質處理，接著載置台38之溫 度升溫至6 5 0 °C。 在試驗5中，以3 0 (TC執行洗淨，之後邊流通N Η 3邊 以300 °C進行改質處理，接著載置台38之溫度升溫至650 °C。此時，NH3間歇性（脈衝狀）被供給5次，於停止供 給NH3之期間（NH3停止期間）流通N2或Ar之沖洗氣體 。1脈衝之供給期間爲60sec，一次之NH3停止期間（沖 洗期間）爲60sec。 在試驗6中，以3 0 0 °C執行洗淨，之後邊流通N Η 3邊 以3 0(TC進行改質處理，接著載置台38之溫度升溫至650 °C。此時，ΝΗ3間歇性（脈衝狀）被供給20次，於ΝΗ3 停止期間流通Ν2或Ar之沖洗氣體。1脈衝之供給期間爲 1 5sec，一次之NH3停止期間（沖洗期間）爲1 5sec。 在試驗7中，以3 0 0 °C執行洗淨，之後邊流通NH3和 H2邊以30(TC進行改質處理，接著載置台38之溫度升溫 至65 0°C。此時，NH3和H2同時且間歇性（脈衝狀）被供 給5次，於停止期間流通N2或Ar之沖洗氣體。1脈衝之 -26- 201002849 供給期間爲60sec，一次之停止期間（沖洗期間）爲60sec 〇 在試驗8中，以3 00 °C執行洗淨，之後邊流通TiCU 和NH3邊以300°C進行改質處理，接著載置台38之溫度 升溫至65 0°C。此時，TiCl4及NH3如第9圖A被供給。 即是，TiC 14和NH3互相間歇性（脈衝狀）並且交互被供 給5次（5循環），於沖洗期間流通N2或Ar之沖洗氣體 。1脈衝之供給期間T1爲60sec ’ 一次之間歇期間（沖洗 期間）T2爲60sec。藉由供給如此之氣體，在載置台38 形成TiN膜。即是，產生藉由Atomic Layer Deposition ( ALD)所產生之成膜。 在試驗9中，以3 00 °C執行洗淨，之後邊流通TiCl4 和NH3邊以300 °C進行改質處理，接著載置台38之溫度 升溫至650°C。此時，TiCl4及NH3如第9圖B所示般流 動。即是，間歇性（脈衝狀）供給TiC 14，NH3係以短於 TiCl4之脈衝寬間歇性（脈衝狀）且與TiCl4同時供給。並 且，該NH3即使於TiCl4之停止期間，也以短於期間T5 之脈衝寬供給。A1F3 + NH3-> AIN + 3HF 263.3 (300.) 235.1 (400 〇C) A1F2 + NH3 — A1N + 2HF + 1/ 2H2 -68.5 ( 3 00 °C ) -59.6 ( 400 ° C ) A1F+NH3 — A1N+HF+H2 18- 201002849 -154.8 ( 300 °C ) -133.4 (400 °C) It can be seen that the above reaction is carried out in the direction of free energy reduction, and the free energy in the lower-fluoride of A1F and A1F2 is changed as described above. Negative, reacting with NH3 gas. The aif-based substance is A1N which is stabilized by reduction and nitridation by reacting fluoride mixed therein with nh3 gas. The A1F-based substance thus modified causes sublimation even if the temperature is raised, and the result is suppressed as described above. In the fourth table, the A1F-based substance 84 gas generated on the surface of the mounting table 38 is reformed and converted into A1N (aluminum nitride) 85. This change is performed, for example, for about 5 minutes. After the completion of the upgrading process, the temperature of the mounting table 38 is brought to the first temperature of the film forming temperature (process temperature), that is, 650 ° C, and pre-coated. The temperature increase rate at this time is, for example, about 10 ° C / m i η. In the coating, by not carrying the wafer W into the processing container 14, as in the case, TiCl4, H2, and Ar are flowed to generate a plasma, and the same pressure as in the film formation is maintained in the processing volume, for example, 666 Pa. about. According to the inner wall surface of the container 14, a pre-coated film made of a Ti film is formed on the inner structure of the mounting table 38 or the like, and the inner state of the container 14 is stabilized. The time of the precoating process is, for example, about 60 minutes. The time required for the temperature of the stage 38 to be raised from 300 ° C to 65 ° C can be made shorter than the time required to raise the temperature from 200 ° C to 650 ° C in the film formation method. As a result, after the precoating process is completed, the untreated W is carried into the processing container 14, and the film formation as described above is performed. In this case, the low-level formation of the hair is not shown to be performed by the temperature rise of the pre-film former 14, and the heat of the surface is carried in the wafer-forming film -19-201002849, as described above, TiCl4 The H2 and Ar gases are introduced into the processing container 14 to generate plasma, and a Ti film is formed on the surface of the wafer W. The film formation of the wafer W is repeated until the next cleaning period is performed. In the film formation, the film formation temperature belonging to the first temperature was 65 °C, and the pressure in the processing container 14 was about 666 Pa. Further, the process conditions are only an example, and are of course not limited thereto. In this manner, after the film formation of the specific number of wafers W is completed, the temperature of the mounting table 38 is lowered to the second temperature, for example, 300 ° C, and the cleaning is performed again. The temperature drop rate at this time is, for example, about 4 ° C / min. In the future, each project will be repeatedly executed in the same procedure as above. Here, when moving from the film forming process to the cleaning process, the time required for the temperature of the mounting table 38 to be lowered from 65 ° C to 300 ° C can be lowered from 65 0 ° C in the conventional film forming method. The time required to reach 200 °C is greatly reduced's part of it can increase the productivity of wafer processing. Specifically, in the conventional film forming method, it takes about two hours and 40 minutes for the primary temperature increasing operation, but in the case of the method of the present embodiment, it can be shortened to about 1 hour and 30 minutes. [0061] In the cleaning process, the A1F-based substance formed on the surface of the mounting table 38 is converted to A1N by nitriding by nitriding gas, whereby scattering can be made difficult, so that film formation is performed. At the time of treatment, particle generation can be greatly suppressed. In addition, although the second temperature at which the cleaning process is performed is set to 300 ° C, the second temperature is not limited to 300 ° C, and is set to 40 (temperature below TC) -20-201002849 as will be described later. When the cleaning temperature is set to 400 ° C, the time required for the temperature rise and fall of the mounting table 38 can be further shortened, so that the productivity of the wafer processing can be further improved. The temperature is also set to 40 CTC. As described above, in the embodiment of the present invention, a nitride such as NH3 is introduced into the processing container 14 while maintaining the second temperature below the cleaning temperature. (3) Since the temperature is generated by the A1F-based substance which is placed on the 38th, the A1F-based substance can be modified even when the A1F-based substance is formed during the cleaning, and it is possible to suppress not only the occurrence of particles during film formation but also In the above-described embodiment, the processing container is supplied with nh3 gas of a nitriding gas, but as described later, even if it is described later. Supply NH3 gas separately to the processing vessel 4, even if it is supplied with other gas, it is also possible to supply the N 3 gas evenly when the NH 3 gas is supplied to the treatment volume 1 4, even if it is intermittently pulsed. In addition, when the ΝΗ3 gas is supplied simultaneously with other gases, the reducing power is increased. Therefore, even if the η2 gas flows simultaneously with the NH gas, the raw material gas (TiCI4 gas) used in the film formation is NH3 gas. At the same time, the supply is also possible. Moreover, the NH3 gas has a nitriding reduction effect. (Evaluation of this embodiment) The intermediate gas metering table is also a sub-cylinder 14 The body Π-Σ. 器性性可和和-21 - 201002849 Next, 'the test results related to the above-mentioned embodiment are performed, and the evaluation results are explained. Fig. 5 is an explanatory diagram for explaining the evaluation method used in the test, and Fig. 6 is a view showing the washing temperature and A graph showing the relationship between the amount of the scattered A1F-based substance, and Fig. 7 is a graph showing the amount of the A1F-based substance which is scattered in the process of washing the substrate to 65 (TC) at different washing temperatures, 8 In order to show a straight line diagram of the evaluation results of the present embodiment and the comparative example, FIGS. 9A and 9B are timing charts showing an example of supply of each gas used in the test. The experiment is performed as follows. First, the gas of T i C14, Η 2, and A r is circulated to the processing container i 4 having no containing wafer, plasma is generated, and a precoating process of a film thickness of 700 nm is performed, and then CIF3 is supplied in the processing container 14. The gas 'does not generate plasma, sets the stage temperature to 200 to 65 ° C (depending on the test), and performs a cleaning process. At this time, an A1F-based substance is formed on the surface of the mounting table 38. The temperature is scattered. The evaluation of this test was carried out by measuring the amount of scattering of the A1F-based substance from the surface of the mounting table 38 as shown in Fig. 5. In other words, as shown in FIG. 5, the semiconductor wafer W is moved into the processing container 14 while being kept facing downward, and is pushed onto the pin 56 so as not to contact the mounting table 38. Supported above the mounting table 38. At this time, the distance Η1 between the upper surface of the mounting table 38 and the mirror surface 88 of the wafer W facing downward is set to 3 mm. Then, while maintaining the wafer W in this state, the temperature of the mounting table 38 is raised from 200 ° C to 65 〇t (depending on the test), and after a certain period of time, the wafer is taken out from the processing container 14 W. Measure the amount of the A1F-based substance attached to the mirror surface 88 of the wafer W. -22- 201002849 [Characteristics of A1F-based substances] First, the characteristics of the A1F-based substances generated on the surface of the mounting table 38 were evaluated at the time of the cleaning process. Specifically, the dependence on the washing temperature of the amount of the A1F-based substance scattered in the washing process and the temperature of the mounting table from the washing temperature to the film forming temperature (650 ° C) are investigated. The dependence of the cleaning temperature of the amount of A1F-based material scattered during the period. As shown in Fig. 5, the wafer W is placed face down, and C1F3 gas, which is a cleaning gas, is circulated, and is washed at the cleaning temperature. Further, an SiO 2 film having corrosion resistance to C1F3 gas is formed on the surface of the wafer. The amount of the A1F-based substance attached to the mirror surface of the wafer W during the cleaning was evaluated using an XRF (fluorescent X-ray analyzer). Specifically, after the cleaning, the wafer W is taken out from the processing container 14 and the intensity of the fluorescent X-rays generated from the A1 atom contained in the A1F-based substance attached to the wafer is obtained by XRF. Used as a substitute indicator. Repeat the above sequence several times with different cleaning temperatures. The results thus obtained are shown in Fig. 6. In the graph of Fig. 6, the horizontal axis represents the cleaning temperature, and the vertical axis represents the intensity of the fluorescent X-rays from the A1 atom in the A1F-based substance attached to the wafer W. In addition, the amount of the A1F-based substance adhered is based on the amount of adhesion at the time of rc (the amount of adhesion at the time of rc). The A1F system scattered from the surface of the mounting table 38 by the arrangement shown in Fig. 5 Since all the substances adhere to the wafer w', the adhesion amount of the A1F-based substance to the wafer corresponds to the amount of scattering from the mounting table 38. -23- 201002849 As shown in Fig. 6, the cleaning temperature is changed here. In various temperatures of 200, 300, 400, 400 ° C, 500 ° C, 500 〇 C, in the range of 200 ~ 40 〇. (: In the range, the amount of scattering of the A1F material is not visible, but When the washing temperature exceeds 400 °C, the amount of scattering of the A1F-based substance increases rapidly. Therefore, it can be understood that the washing temperature in the washing process is the upper limit of the second temperature of 400 ° C. At this time, the washing is performed. When the lower limit of the temperature is considered to decrease as the washing efficiency decreases and the productivity of the lifting and lowering temperature of the mounting table 38 decreases, it is about 250 ° C. Then, after washing at different washing temperatures, the reforming is not performed. In the project, it is determined that the temperature of the mounting table is raised to 650 ° C which belongs to the film forming temperature. Specifically, after washing at different washing temperatures, the semiconductor wafer W is moved downward into the processing container 14 while being kept facing downward, so as not to be in contact with the carrier. The stage 38 is supported by the push-up pin 56 above the mounting table 38 (see Fig. 5). Then, the temperature of the mounting table 38 is raised to 65 〇t. Thereafter, the crystal is taken out from the processing container 14. The round W and the adhesion amount of the A1F-based substance adhering to the wafer W are obtained by XRF. The result is shown in Fig. 7. In the graph of Fig. 7, the horizontal axis is the temperature at the time of washing. The vertical axis is the intensity of the fluorescent X-rays from the A1 atom in the A1F-based substance attached to the wafer W. The cleaning temperature is set to 40 (TC, 450 ° C, 5 0 as shown in Fig. 7). (TC and 65 ° C. After the cleaning, the temperature of the mounting table 38 was increased to 6 5 (TC) which is a film formation temperature, but the temperature was not raised when the cleaning temperature was 605 °C. It can be seen from Fig. 7 that when the cleaning temperature is 400 °C, even if the temperature of the stage is raised to 650 °C after -24-201002849, the A1F substance is almost When the washing temperature exceeds 400 1 , the amount of scattering of the A1F-based substance is rapidly increased, which is not preferable. Therefore, it can be understood from the results that the washing temperature is set at 400 ° C. [Evaluation of Modification Project] Next, the evaluation results at the time of performing the upgrading process in the method of the embodiment of the present invention after the cleaning process will be described together with the comparative example. After the cleaning process is performed, the wafer W is carried into the processing container without performing the reforming process, and then the substrate is heated to 650 ° C and attached to the wafer W. The amount of A1F-based substance attached. The amount of adhesion of the A1F-based substance was the same as described above, and was determined by XRF. Fig. 8 is a bar graph showing the evaluation results of the examples and comparative examples of the present invention, and Fig. 9 is a timing chart showing the supply mode of each gas at the time of performing the test 8 (one of the embodiments of the present invention) described later. Fig. 9B is a timing chart showing a supply mode of each gas when the test 9 (one of the embodiments of the present invention) described later is executed. In Fig. 8, Tests 1 to 4 show comparative examples, and Tests 5 to 9 show examples of the present invention using NH3 gas in a reforming process. The vertical axis indicates the amount of adhesion of the AIF-based substance to the wafer, which corresponds to the amount of scattering of the A1F-based substance from the mounting table. Here, C1F3 is used as the cleaning gas. Test 1 is a conventional method. That is, in Test 1, the cleaning was performed at 200 °C where the A1F-based substance was not produced, and then the reforming treatment was not performed, and the temperature of the stage 38 was raised to 65 °C at -25-201002849. In the test 2, the temperature was raised to 650° at a temperature of 30 (the TC was performed, and then the reforming process was not performed.) In the test 3, the cleaning was performed at 300 ° C, and then The TiCl4 (feed gas) was subjected to a reforming treatment at 300 ° C, and then the temperature of the mounting table 38 was raised to 65 ° C. In the test 4, 'washing was performed at 30 (TC), and then TiCl4 was simultaneously flowed. The Ha side was reformed at 300 ° C, and then the temperature of the mounting table 38 was raised to 65 ° C. In the test 5, the washing was performed at 30 (TC), and then the N Η 3 side was passed at 300 °. C is reformed, and the temperature of the mounting table 38 is raised to 650 ° C. At this time, NH 3 is intermittently supplied (pulsed) five times, and N2 or Ar is flushed during the period in which the supply of NH 3 is stopped (during the NH 3 is stopped). Gas. The supply period of one pulse is 60 sec, and the NH3 stop period (washing period) is 60 sec. In test 6, washing is performed at 300 ° C, and then N Η 3 is passed and 3 0 (TC is performed). After the modification treatment, the temperature of the mounting table 38 was raised to 650 ° C. At this time, ΝΗ 3 was intermittently (pulsed) was supplied 20 times, at ΝΗ 3 The rinsing gas of Ν2 or Ar flows during the stop period. The supply period of one pulse is 15 sec, and the NH3 stop period (flush period) of one time is 15 sec. In test 7, washing is performed at 300 ° C, and then circulated. The NH3 and H2 sides were reformed by 30 (TC), and then the temperature of the stage 38 was raised to 65 ° C. At this time, NH3 and H2 were simultaneously and intermittently (pulsed) supplied five times, and N2 was flowed during the stop period. Or Ar flushing gas. 1 pulse -26- 201002849 The supply period is 60 sec, and the one stop period (flush period) is 60 sec. In the test 8, the cleaning is performed at 300 ° C, and then the TiCU and NH 3 sides are circulated. The reforming treatment was carried out at 300 ° C, and then the temperature of the mounting table 38 was raised to 65 ° C. At this time, TiCl 4 and NH 3 were supplied as shown in Fig. 9. That is, TiC 14 and NH 3 were intermittent (pulsed). And the interaction is supplied 5 times (5 cycles), and the flushing gas of N2 or Ar flows during the flushing. The supply period T1 of 1 pulse is 60 sec', and the intermittent period (flushing period) T2 is 60 sec. By supplying such a gas, A TiN film is formed on the mounting table 38. That is, it is produced by Atom. Film formation by ic layer Deposition (ALD). In Test 9, the cleaning was performed at 300 ° C, and then the modification was performed at 300 ° C while flowing TiCl 4 and NH 3 , and then the temperature of the mounting table 38 was raised to 650 ° C. At this time, TiCl4 and NH3 flow as shown in Fig. 9B. That is, the intermittent (pulsed) supply of TiC 14, NH3 is intermittently (pulsed) with a pulse width shorter than that of TiCl4 and supplied simultaneously with TiCl4. Further, this NH3 is supplied in a pulse width shorter than the period T5 even during the stop of TiCl4.
再者，在同時不供給TiC 14和NH3之沖洗期間，流通 Ar或N2之沖洗氣體。氣體之供給全體執行5循環，TiC 14 之供給期間T3爲6sec，TiCl4之停止期間T4爲8sec， NH3之供給期間T5、T6各爲 3_5sec、5sec。藉由供給如 此之氣體，在載置台38形成薄TiN膜。爲了方便說明， 將如此之成膜方法稱爲Sequential Flow Deposition ( SFD -27- 201002849 將上述試驗1〜試驗9之結果表示於第8圖。 圖，在改質工程中不使用NH3之試驗2〜試驗4中 往方法之試驗1中之A1F系物質之量相同程度之量 系物質飛散，另外在改質工程中使用NH3之試驗5 9中A1F系物質之飛散量減少至以往方法中之飛散 半以下。依此，可理解藉由本發明實施例能得到良 果。 尤其，若藉由該試驗結果，於洗淨時不需要將 溫度如以往方法般過度降低至200 °C，若至少降低 °C則足夠。確認出藉由在3 00 °C之溫度下執行洗淨 處理，比起以往方法可以大幅度且確實抑制來自載 A1F系物質之飛散。 並且，在上述實施形態中，雖然第1溫度之成 以65 0 °C之時爲例予以說明，但是該第1溫度並不 650°C，例如藉由膜種等而改變，例如即使在5 00〜 之範圍內改變亦可。 再者，在此雖然執行改質工程之時可以使用之 體以使用nh3之情形爲例予以說明，但是並不限定 亦可以使用由nh3、具有比nh3更強之還原及氮化 N2H4 (聯胺）、聯胺化合物所構成之群中選擇出之 上之氣體。 再者，在此雖然原料氣體以使用TiCl4氣體之 予以說明，但是並不限定於此，若爲含Ti氣體即 見第8 ，與以 的A1F 〜試驗 量的一 好之結 載置台 至 3 00 及改質 置台之 膜溫度 限定於 ^ 700 °C 氮化氣 於此， 作用之 —個以 時爲例 可，例 -28- 201002849 如亦可以使用 TDMAT ( Tetrakis Dimethyl Amino Titanium )、TDEAT ( Tetrakis Diethyl Amino Titanium)等作爲 有機鈦。 再者，在上述實施型態中，雖然針對形成Ti膜之成 膜方法予以說明，但是並不限定於此，亦可以適用於形成 TiN膜或其他金屬膜，或是含該金屬之薄膜的成膜方法。 再者，作爲洗淨工程所使用之洗淨氣體之氟系氣體， 並不限定於C1F3，可以使用從由C1F3 ' NF3、C2F6、F2所 構成之群所選擇出之一個以上之氣體。 再者，在此雖然成膜裝置以具有電槳形成部之成膜裝 置爲例予以說明，但是並不限定於此，本發明亦可以適用 於不具有電漿形成部，設置有噴淋頭部18或載置台38之 熱 CVD ( Chemical Vapor Deposition)用之成膜裝置。 再者’在此雖然被處理體以半導體晶圓爲例予以說明 ，但是並不限定於此，玻璃基板、LCD基板、陶瓷材基板 等亦可以適用本發明。 【圖式簡單說明】 第1圖爲表示關聯技術之成膜裝置之一例的槪略圖。 第2圖爲表示實施藉由本發明之實施型態所產生之成 膜方法的成膜裝置之一例的剖面圖。 第3圖爲表示藉由本發明之實施型態所產生之成膜方 法之各工程和載置台溫度之關係的工程圖。 第4圖爲用以說明本實施型態中在洗淨所生成之aif -29- 201002849 系物質之舉動的槪略說明圖。 第5圖爲說明本發明之實施例中之評估方法的說明圖 〇 第6圖爲表示洗淨溫度和飛散之A1F系物質之量的關 係曲線圖。 第7圖爲表示以不同洗淨溫度執行洗淨之後，將載置 台升溫至6 5 0 °C之過程中飛散之A1F系物質之量，對洗淨 溫度的曲線圖。 第8圖爲表示本發明之實施例和比較例之評估結果之 直條圖。 第9圖A爲表示執行本發明之實施例時之各氣體之供 給型態之一例的時序圖。 第9圖B爲表示執行本發明之其他實施例時之各氣體 之供給型態之一例的時序圖。 【主要元件符號說明】 12 :成膜裝置 1 4 :處理容器 噴淋頭（氣體導入部） 2 4 :高頻電源 2 8 :電漿形成部 38 :載置台 4 2 :加熱器（加熱部） 6 6 :氣體供給系 -30- 201002849 7 8 :控制部 8 0 :記憶媒體Further, during the flushing in which TiC 14 and NH3 are not supplied at the same time, the flushing gas of Ar or N2 is circulated. The supply of gas was performed for 5 cycles in total, the supply period T3 of TiC 14 was 6 sec, the stop period T4 of TiCl4 was 8 sec, and the supply periods T5 and T6 of NH3 were 3_5 sec and 5 sec, respectively. A thin TiN film is formed on the mounting table 38 by supplying such a gas. For convenience of explanation, the film formation method is referred to as Sequential Flow Deposition (SFD -27-201002849. The results of the above Test 1 to Test 9 are shown in Fig. 8. Fig. 2, Test 2 in which NH3 is not used in the upgrading process. In Test 4, the amount of the A1F-based substance in the test 1 of the method is the same amount, and the amount of scattering of the A1F-based substance in the test using NH3 in the upgrading process is reduced to the scattering half in the conventional method. In the following, it can be understood that good results can be obtained by the embodiment of the present invention. In particular, if the test result is obtained, it is not necessary to excessively reduce the temperature to 200 ° C as in the prior art, and at least reduce the ° C. It is sufficient to confirm that the washing treatment is carried out at a temperature of 300 ° C, and the scattering of the A1F-containing substance can be largely and surely suppressed compared with the conventional method. Further, in the above embodiment, the first temperature is obtained. The example is described at 65 ° C. However, the first temperature is not 650 ° C, and is changed by, for example, a film type, for example, even within a range of 500 〜. Although here The case in which the body can be used at the time of the upgrading process is exemplified by the case of using nh3, but it is not limited to the use of nh3, which has a stronger reduction and nitriding N2H4 (amine) and a hydrazine compound than nh3. In addition, although the raw material gas is described by using TiCl4 gas, it is not limited to this. If it is a Ti-containing gas, see the eighth, and the A1F~ test amount. The temperature of the film is set to 300 °C and the temperature of the modified substrate is limited to ^ 700 °C. The nitriding gas is used here. The effect can be used as an example. Example -28- 201002849 If you can also use TDMAT ( Tetrakis Dimethyl Amino Titanium), TDEAT (Tetrakis Diethyl Amino Titanium), etc. are used as the organic titanium. In the above embodiment, the film formation method for forming the Ti film will be described, but the method is not limited thereto. A film forming method for forming a TiN film or another metal film or a film containing the metal. Further, the fluorine-based gas used as the cleaning gas used in the cleaning process is not limited to C1F3. One or more gases selected from the group consisting of C1F3 'NF3, C2F6, and F2 are used. Here, although the film forming apparatus is described as an example of a film forming apparatus having an electric pad forming portion, it is not described. In addition, the present invention is also applicable to a film forming apparatus for thermal CVD (Chemical Vapor Deposition) which does not have a plasma forming portion and is provided with a shower head 18 or a mounting table 38. Further, although the semiconductor wafer is described as an example of the object to be processed, the present invention is not limited thereto, and the present invention can also be applied to a glass substrate, an LCD substrate, a ceramic substrate, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing an example of a film forming apparatus of the related art. Fig. 2 is a cross-sectional view showing an example of a film forming apparatus which performs a film forming method produced by the embodiment of the present invention. Fig. 3 is a view showing the relationship between the respective processes of the film formation method and the temperature of the stage by the embodiment of the present invention. Fig. 4 is a schematic explanatory view for explaining the behavior of the aif -29-201002849-based substance produced by the cleaning in the present embodiment. Fig. 5 is an explanatory view for explaining the evaluation method in the embodiment of the present invention. Fig. 6 is a graph showing the relationship between the washing temperature and the amount of the scattered A1F-based substance. Fig. 7 is a graph showing the amount of A1F-based substance scattered in the process of heating the substrate to 650 °C after washing at different washing temperatures, and the washing temperature. Fig. 8 is a bar graph showing the evaluation results of the examples and comparative examples of the present invention. Fig. 9A is a timing chart showing an example of the supply pattern of each gas when the embodiment of the present invention is executed. Fig. 9B is a timing chart showing an example of a supply pattern of each gas when another embodiment of the present invention is executed. [Description of main component symbols] 12: Film forming apparatus 1 4 : Processing container shower head (gas introduction unit) 2 4 : High-frequency power supply 2 8 : Plasma forming unit 38 : Mounting table 4 2 : Heater (heating unit) 6 6 : Gas supply system -30- 201002849 7 8 : Control unit 8 0 : Memory media
8 4 : A 1F系物質 85 ： A1N W :半導體晶圓（被處理體） -318 4 : A 1F substance 85 : A1N W : semiconductor wafer (subject to be processed) -31