經濟部智慧財產局員工消費合作社印製 517302 A7 --- B7 五、發明說明（1 ) 發明背景 本發明係關於包含釕、餓或這些之氧化物之固體的表 面之蝕刻處理方法。又，本發明係關於半導體裝置之製造 方法’被形成在基板之上方的上述金屬或其之氧化物之飩 刻處理以及洗淨處理，進而關於這些之c VD裝置或蝕刻 裝置之淸潔方法。 近年來伴隨半導體裝置之高集成化，具有D RAM等 之記憶體單元之元件爲了確保其之電容器的電氣容量，逐 漸成爲具有更爲複雜之立體構造。因此，上述元件之製造 工程數增加，薄膜形成·加工裕度更爲狹窄，此導致製造 成本之增加或良率之降低。因此，以增大電容器之儲存容 量爲目的，使用介電率高之新的材料以使構造簡單化成爲 必須。 現在此種之商介電率材料例如被檢討者爲 B a S r T i〇3之多元系氧化物。在形成這些氧化物之際 ，需要在氧氣氣氛中進行高溫退火。但是，電容器下部電 極之材料在使用S i之情形，很難抑制由於氧氣退伙時之 氧化所導致之電阻値增加之故，有必要選擇不易被氧化或 即使被氧化也具有導電性之新材料。 滿足此條件之電極材料例如釕、氧化釕正被檢討著。 形成這些電極材料之方法以對於物理蒸鍍，對基板之薄膜 的附著性良好，可以獲得高純度而且結晶性優異之薄膜之 C V D (化學氣相沈積法）被認爲很適合。 釕或氧化釕之薄膜形成方法例如在特開平6 — -----------------^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4 - 517302 A7 _ B7 五、發明說明（2 ) 2 8 3 4 3 8號公報、特開平9 — 2 4 6 2 1 4號公報記 載中所公開揭露的，使用特定之有機系原料氣體藉由Μ〇 一 C V D法以形成薄膜之方法。 另一方面’關於釕或氧化釕薄膜之鈾刻方法例如如特 開平8 — 7 8 3 9 6號公報記載中所公開揭露之包含使用 由氟氣體、氯氣體、碘氣體這些當中至少包含1種之鹵素 热體以及鹵化氣所形成之群選擇至少一霞或一種以上與包 含氧氣或臭氧氣之混合氣體以進行電漿蝕刻之工程的半導 體裝置之製造方法。 又’ L〇essberg、Mue 11 er(Rainer L〇essberg und U1 rich Mueller)之 ''(Zeitschrift Fuer Naturforschung， Section B, Chemical Sciences, vol. 16B，No.3，1981，pp395 )"中公開揭露 藉由在室溫中使釕與臭氧反應可以獲得純粹之四氧化釕之 方法。 進而有關於釕殘渣之去除技術，如特願平1 1 -2 4 5 1 4 3號記載中所公開揭露之使用包含過碘酸與硝 酸之洗淨液之溼洗淨方法。 發明摘要 以下所述之內容系前述之習知技術未記載者。 記載於上述習知技術之釕或釕氧化物之蝕刻方法系使 用離子補助反應之電漿蝕刻反應，使用電漿之故，要避免 對被蝕刻對象物之損傷有其困難。又，由於使用電漿之裝 置成本也變高之故，故乃期望能提供可以避免對基板之損 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -----^----"訂---------- 經濟部智慧財產局員工消費合作社印製 5- 517302 A7 一 B7 五、發明說明（3 ) 傷，而且簡易之蝕刻方法。 (請先閱讀背面之注意事項再填寫本頁) 同樣地，關於習知之去除釕殘渣或污染之洗淨方法， 在藉由電漿蝕刻反應之去除中，對基板產生損傷，又在溼 洗淨方法中需要沖洗或乾燥之工程，在此情形也期望提供 :不對基板造成損傷，而且簡易之可以處理釕殘渣或污染 之洗淨方法。 另一方面，在使用形成新材料之釕或釕氧化物用之 CVD裝置或蝕刻這些，形成圖案用之蝕刻裝置以製造 DRAM等之半導體裝置之情形，爲了減低由上述裝置來 之發塵量以便良率高地製造半導體裝置，淸潔去除包含堆 積或附著在反應處理室內或配管內之釕之反應副生成物， 以便於下一製造之方法的確立，在半導體業界也被殷切盼 望著。 一般蝕刻釕或餓之情形，可以使上述金屬變成蒸汽壓 高之金屬化合物（釕化合物或餓化合物）以去除之。 經濟部智慧財產局員工消費社印製 其中一例有關代表性之釕化合物，在圖1顯示其之蒸 汽壓之溫度依存性。其結果由圖1可以明白地，在5 0 0 °C以下之低溫下，氧化物之R u〇4之蒸汽壓最高。由此在 半導體裝置適用釕之情形，由熱預算或產出率之觀點，處 理工程之蝕刻處理溫度期望比較低之溫度，實際上在 5 0 0 °C以下之溫度範圍在使產生具有高蒸汽壓特性之 R u〇4是·很好的。 進而使產生金屬之氧化物者與製造裝置之構造或其之 維修相關連，也存在相當大之優點。即在使之產生金屬之 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（4) 鹵化物加以利用之情形，使用腐蝕性高之鹵系氣體之故， 必須施以對製造裝置或處理方法等爲萬全之安全對策。 接著，說明由釕產生R u〇4之反應。 以實現對被蝕刻物之損傷少，而且簡易之蝕刻方法爲 目的，就利用不使用電漿等之高能量進行之非電漿系之化 學反應之上述氧化物之產生方法，由熱力學之觀點來加以 檢討。 圖2 (1)〜（3)係說明由Ru產生Ru〇4之反應 中，其之吉布斯自由能變化量（△ G )與反應溫度之關係 〇 △ 0與八 反應平衡常數（K)之關係可以使用下 式表示： KK_exp (- AG/RT) 但是，R係氣體常數，T表示絕對溫度。 此式意味此能量變化量△ G隨著往正側變大，釕之氧 化反應不進展，而且△ G隨著往負側變大，氧化反應被促 進。 由圖2 (1)〜（2)之結果，使用臭氧或氧原子以 使釕反應之情形，使產生R u〇4之能量變化量△ G在負側 大之故，反應容易進行，又，很淸楚地在該反應之過程中 ，假如即使產生R U〇2，R U〇2更與臭氧或氧原子反應 而成爲R U〇4。 另一方面，如圖2 (3)所示般地，在釕與〇2之反應 中，使產生R u〇4之能量變化量△ G即使爲負，其之絕對 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 517302 A7 B7 五、發明說明（5 ) 値與臭氧或氧原子之情形相比，遠比其小之故，其之反應 不易進行。而且，與氧氣之反應下，一旦產生Ru〇2，由 該狀態幾乎不會進展爲R u〇4。 由以上之實驗結果，可以明白爲了由釕或氧化釕使之 產生R u〇4，只要使其與臭氧或氧原子反應即可。又，上 述之反應不限定於釕，餓也是相同。 然而，在上述臭氧或氧原子之氣體中微量添加鹵氣或 鹵化氫氣體，藉由使之產生釕之鹵化反應，比較安定、反 應之不易進展之R u 〇2之產生被抑制。又，藉由添加還原 性氣體，可以使產生之Ru〇2還原爲Ru。 考慮上述說明之釕的反應形態，本發明係一種蝕刻包 含由釕、氧化釕、或餓、氧化餓之群選擇至少一種之固體 表面之處理方法，藉由對此固體表面供給包含提供氧原子 性氣體之氣體，可以實現固體表面之蝕刻處理。 又，藉由對於形成由上述金屬或其之氧化物所形成之 膜之基板表面施以同樣之處理，可以進行基板表面之蝕刻 處理。 進而藉由使與上述之情形相同之方法處理包含由釕、 氧化釕、或餓、氧化餓之群選擇至少一種之膜或其粒子附 著之基板，可達成基板的洗淨處理。 進而又在基板上形成包含上述至少一種之膜之C V D 裝置之淸潔處理，或蝕刻上述之膜以進行圖案形成之飩刻 裝置之淸潔處理中，同樣可以去除包含堆積或附著在這些 裝置之至少處理室內或配管之表面之釕或餓之反應生成物 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注音？事項再填寫本頁) -----K----訂---------- 經濟部智慧財產局員工消費合作社印製 -8 - 經濟部智慧財產局員工消費合作社印製 517302 A7 ______ B7 五、發明說明（6 ) 〇 本發明之提供氧原子性氣體係由包含：臭氧、鹵化氧 氣、氧化氮、氧原子之群選擇至少一種之氣體所形成，又 ，在此氣體中添加鹵氣、鹵化氫氣、或還原性氣體，進而 添加由氟、氯、溴、氟化氯、氟化氫、、氯化氫、溴化氫、 氫、一氧化炭、氨或磷之群中選擇至少一種之氣體以供應 蝕刻處理。 而且，這些之處理反應係非電漿触刻處理，在固體或 基板之表面或這些之上方並不形成離子護層而進行。 本發明之上述反應係藉由固體或基板之表面溫度在 2 0 °C以上3 5 0 °C以下，期望在4 0 °C以上2 0 0 °C以 下，更期望在4 0°C以上1 8 0°C以下進行而達成。 合適實施例之詳細說明 利用圖面詳細說明本發明之實施例。 在以下說明中敘述之半導體裝置係意指：被形成在矽 基板上之記憶體元件等之半導體裝置、被形成在石英或玻 璃基板上之液晶顯示器用T F T元件、被形成在上述以外 之基板上之裝置全部。又，所謂基板雖意指：在表面形成 半導體裝置之矽等之半導體基板、或絕緣基板、或這些之 複合基板等，但是並不一定限制爲此。 又，以下說明之所謂非電漿蝕刻處理並非藉由利用離 子之濺鍍作用之蝕刻處理，而且也不是如反應性離子飩刻 般地，藉由加速入射被處理表面之離子之反應爲支配性之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- I-----------------^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（7) 離子補助反應之蝕刻處理，而是利用構成鈾刻氣體與被處 理表面之各別的分子彼此在主要藉由由外部供給之熱所帶 來的高能量狀態之中產生之化學反應以蝕刻處理。 因此，不會在電漿蝕刻處理之情形經常可見之在固體 或基板或裝置內之表面或彼此之上方形成離子護層也是其 一大特徵。 此處，詳細說明離子護層。所謂離子護層係意指藉由 電漿與固體相接所形成之空間電荷層。一般電漿之電子溫 度比離子溫度還高之故，在固體表面流入高速輕電子，固 體對於電漿成爲具有負的電位。因此，在固體表面附近電 子減速或被反射，形成離子變成過剩之空間電荷層，即離 子護層。因此，在以下敘述之熱氣氛中產生化學反應之情 形，在固體表面之附近電漿不存在之故，變成不會形成離 子護層。 又，在將存在於由應處理之固體隔離之空間之電漿氣 體通過配管輸送於固體表面之遙控電槳處理方法之情形， 在固體表面附近沒有形成離子護層之故，設爲被包含在非 電漿蝕刻處理中。 又，所謂氧化釕係意指：R u〇、R u〇2、R u〇3 、R u〇4之任何一種，所謂氧化餓係指：〇s〇、 〇S2〇3、〇S〇2、〇S〇3、〇S〇4之任何一種。 在實施例1中，係以半導體裝置爲例，爲進行被形成 於基板之上方之釕膜之蝕刻之情形’蝕刻工程之流程顯示 於圖3。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- -----------------^----訂--------- (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 ________ B7 五、發明說明（8 ) 圖3 ( 1 )係在晶圓3 1 (矽基板）上利用被熟知之 熱氧化膜形成法以形成氧化矽膜3 2，接著利用被熟知之 非等向性乾蝕刻法將此氧化膜3 2進行圖案形成時之半導 體裝置之剖面圖。 接著，如圖3 ( 2 )所示般地，在氧化膜3 2上利用 通常之C V D法形成釕膜3 3後，如圖3 ( 3 )所示般地 ，利用通常之乾蝕刻法去除上述釕膜3 3之一部份，使上 述氧化膜3 2與釕膜3 3之面成爲一致。 如此在利用非等向性乾蝕刻形成之孔埋入釕膜3 3， 完成由釕形成之插塞（33)。 圖4係顯示去除釕膜3 3之一部份用之鈾刻裝置之槪 要圖。此鈾刻裝置主要係由：進行蝕刻處理之處理室4 1 、與晶圓4 2、加熱晶圓之接受器加熱器4 3、供給氣體 之淋浴頭4 4所形成。供給臭氧之臭氧發生器4 5 s、產 生臭氧所必須之氧氣供給器4 6 s、氮氣供給器4 7 s、 調解臭氧濃度用之氮氣供給器4 8 s、各別之供給器之閥 門45v、46v、47v、48v透過配管49被連接 於此處理室4 1。又，透過排氣側配管4 9調整壓力之電 導閥門4 1 0、真空泵4 1 1、臭氧等之除害設備4 1 2 也被連接著。除此之外，具有搬運臂4 1 3之搬運室 4 1 4被連接於處理室41。 首先一開始爲了決定釕膜3 3之蝕刻條件，使用如圖 4所示之裝置，說明釕膜3 3之藉由含有臭氧氣體之蝕刻 特性之檢討結果。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 - -----------—A_w^-----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（9 ) 圖5係利用例如臭氧氣體鈾刻藉由C V D法之釕膜 3 3時之蝕刻率之溫度依存性。蝕刻條件係在：臭氧濃度 5%、氣體流速10s lm、處理室內之壓力1〇〇 To r r以及700To r r下進行。又，臭氧係利用無 聲放電之臭氧發生器所產生。 其結果在釕膜3 3爲利用臭氧之情形，其之處理溫度 在2 0 °C以上3 5 0 °C以下被蝕刻，了解到其之蝕刻率在 1 0 0 °C附近具有極大値。又，鈾刻率之極大値與習知所 知道之釕膜3 3之蝕刻率比較，約數倍以上。又，蝕刻率 係由利用螢光X射線分析加以量測之釕的特性X射線強度 所求得。 接著，說明釕膜3 3與臭氧氣體之蝕刻反應機制。 圖6係顯示：將使用圖4所示之蝕刻裝置進行蝕刻釕 膜3 3之際所產生之反應生成物例如在配管4 9之處安裝 QMS ( Quadrupole Mass Spectrometry )力口以量測時之 Ma s s光譜。由此結果可以明白地，反應生成物Ru、 Ru〇、Ru〇2、Ru〇3、Ru〇4被檢測出。其中光 譜強度最大之物質爲R u〇4，判明藉由釕膜3 3與臭氧氣 體之反應之主要反應生成物爲Ru〇4。又，Ru、Ru〇 、Ru〇2、Ru〇3主要被認爲係Ru〇4在QMS之離 子化室分解者。 在由釕金屬單體產生R u 〇4之際，需要反應氣體之臭 氧氣體之分解。 圖7係顯示將供給於處理室內之臭氧氣體藉由熱分解 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12- ----------------^----^--------- si (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（10) ，彼時之臭氧殘存率（由1減去臭氧分解率之値）之時間 變化。又，圖7係利用被記載於杉光英俊著「臭氧之基礎 與應用」（（株）光琳、p58(1996年發行））之 資料所計算之結果。考慮圖4所示之蝕刻裝置之臭氧氣體 之流速，被導入處理室4 1之臭氧被加熱，至與釕接觸爲 止之時間僅有數秒以下之故’處理溫度在2 0 0 °C以下時 ，臭氧幾乎未被熱分解地與釕膜接觸。 因此，在圖5所示之釕的蝕刻率顯示極大之溫度領域 中，藉由熱以外之能量臭氧被分解，而且此被認爲有助於 與釕之反應。又，上述敘述之處理溫度係以被熟知之方法 ，例如在包含釕膜3 3之晶圓4 2之表面裝置熱電對所被 量測之溫度。 臭氧藉由白金等之觸媒作用而被分解，此被記載於前 述之「臭氧之基礎與應用」或闘Q用領域廣泛之臭氧分解 觸媒"（JETI、Vol.39、No.ll、，1991 )。另一方面，釕 係屬於白金族，如考慮上述之觸媒作用，臭氧可以認爲係 藉由與釕之觸媒作用而被分解，在此情形，可以說明處理 溫度即使在1 0 0 °C程度之低溫下也可以充分發生R u〇4 生成反應。 藉由以上，釕與臭氧之反應可以認爲係依循圖8所示 之反應槪念圖，或下述之表1所示之反應式而進行。又， R u 0係極爲不安定之物質，被認爲藉由與臭氧之反應而 產生安定之Ru〇4。 本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公爱） -13- ^—訂--------- (請先閱讀背面之注意事項再填寫本頁) 517302 A7 B7 五、發明說明（11) 表1 Ru〇4之產生過程 反應過程 反應式 ① ⑴之對Ru表面之供給 ② 〇3之對Ru表面之供給 ③ 0 3分解 ④ Ru與0之反應 ⑤ 藉由Ru與〇3產生Rua ⑥ Ru〇4之脫離 0： 0 3 a d s 〇 3 a d s —^ 〇 2 + 〇 a d s Ru + 〇ads — Ru R U 〇 + 〇 3 —^ R U 〇 4 a d s RU〇4ads— Rll〇4 个 經濟部智慧財產局員工消費合作社印製 ※a d s當成顯示吸附在表面者。 接著，說明如圖5所示般地，藉由臭氧釕之蝕刻率由 1 0 0 °C前後之高溫領域降低之理由。 利用被熟知之分析法之X P S量測對於各處理溫度之 R u量之R u〇2之量的比率之結果，判明在上述之高溫領 域處理之情形，存在於釕膜表面之R u 〇2之量變多。另一 方面，圖5中，一倂記載將藉由濺鍍法所形成之R u〇2膜 單單暴露於臭氧氣體之情形的蝕刻率（記號X )。藉由此 ，了解到R u〇2膜在臭氧單體中幾乎未被蝕刻。 藉由以上之結果，於處理溫度爲高溫之情形，化學量 論而言安定之R u 〇2產生反應比表1之反應⑤所示之 R u 〇4生成反應更具支配性，可認爲生成於此表面之 Ru〇2阻礙了之後的反應。而且，Ru〇2幾乎未被蝕刻 之理由係Ru〇2沒有分解臭氧之觸媒作用，Ru〇2熱力 學上很安定，可認爲係隨著圖2所示之處理溫度上升，反 應之自由能之差（AG)由負往零或正側接近之故。 -----------------^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14- 517302 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（12) 考慮上述釕之藉由臭氧之反應，蝕刻去除被形成在圖 3所不之基板3 1之上之纟了膜3 3之一^部份之情形，下述 3點很重要：（1 )可以獲得在製造半導體裝置之際，能 確保必要產出率之鈾刻率，（2)不使釕膜33之表面變 質（氧化），(3)於晶圓3 1之面內可以做均勻之鈾刻 〇 由上述之檢討結果，利用臭氧處理溫度如在2 0。(：至 3 5 0 °C之範圍，釕膜3 3之蝕刻處理成爲可能。但是， 爲了可以獲得能確保製造上之產出率之蝕刻率，而且能抑 制釕膜3 3之表面的氧化，期望將處理溫度之範圍設定在 40 °C至200 °C。又，爲了使晶圓3 1面內可以均勻飩 刻，反應在擴散律速之領域中，對處理室4 1內使臭氧氣 體對於面內均勻地供給即可，又，在反應律速或脫離律速 之情形，使晶圓3 1面內之處理溫度均勻即可。 使用圖4所示之處理裝置，嘗試被認爲係脫離律速領 域之在處理溫度6 0°C之蝕刻。圖9係顯示其之處理程序 0 依循圖9之處理程序，利用6 0 °C之處理溫度進行形 成在晶圓3 1之基板上之釕膜3 3之一部份去除之結果， 如圖3 (3)所示般地，可以形成釕膜之插塞33。而且 ，蝕刻率之晶圓3 1面內之均勻性爲± 5 %，實用上被確認 爲不會有住何妨礙之水準。 依據本實施例，藉由利用臭氧蝕刻釕膜3 3，可以有 比較快之蝕刻。又，上述之反應並非使用電漿之反應之故 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- -----^----^--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（13) ，不會對基板3 1造成損傷。進而使用臭氧氣體之故，也 可以抑制對蝕刻裝置構件之損傷，例如金屬構件之腐蝕等 〇 在上述本實施例中，鈾刻氣體雖係使用臭氧，但是使 用鹵化氧氣、氧化氮氣、氧原子也可以獲得同樣之效果。 又’，在將氣體導入處理室4 1之前，將氧氣或氧化氮氣以 紫外線或電漿激磁後再導入處理室4 1也可以獲得同樣之 效果。 再者於本實施例中，雖然使用在氧氣與氮氣之混合氣 體中添加數％之臭氧之氣體，但是在此添加氟、氯、溴、 氟化氯、氟化氫、氯化氫以及溴化氫等之鹵氣體或鹵化氫 也可以獲得同樣之效果。 而且，替代本實施例中之在氧與氮氣中包含數％之臭 氧氣體，於添加氫、一氧化炭、氨、磷等之還原性氣體之 情形，也可以獲得同樣之效果。 以上敘述之結果對於釕氧化膜、餓、餓氧化膜也可以 獲得與釕膜之情形同樣的效果。 接著，在實施例2中，進行附著於晶圓裡面或晶圓表 面之邊緣部之釕膜或其粒子之去除。 例如在釕膜之C V D裝置中，將晶圓載置於加熱器上 加熱，此加熱器之溫度在成膜溫度或其以上之故，不單晶 圓上，在晶圓外之加熱器上也有產生釕膜之情形，而且， 藉由重複上述之C VD成膜，晶圓之裡面也會附著釕膜。 進而會有與不使晶圓表面之邊緣部形成釕膜地防止在邊緣 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- -------------$----l· — (請先閱讀背面之注意事項再填寫本頁) 1T--------- 經濟部智慧財產局員工消費合作社印製 517302 A7 B7 五、發明說明（14) 部被供給成膜氣體用之遮蔽物接觸，此遮蔽物也與加熱器 同樣地高溫之故，在遮蔽物也會形成釕膜。 而且，於此晶圓裡面或晶圓邊緣部附著釕膜下，如接 著使用其他裝置以進行別的處理，此附著之釕膜本身污染 其它裝置，最終對於半導體裝置之性能帶來壞影響。 因此，爲了防止對其它裝置之釕膜污染，CVD成膜 後或蝕刻後，不可缺少去除附著於晶圓裡面或晶圓表面之 邊緣部之釕膜或粒子用之洗淨製程。 圖10 (1)中係表示在晶圓51之表面形成裝置圖 案5 2 ，在該晶圓5 1之表面邊緣部5 3與晶圓5 1之裡 面由於釕膜5 4或釕之粒子5 5而被污染之狀態。而且， 以塗黑之領域表示利用被熟知之全反射螢光X射線量測在 晶圓5 1之表面邊緣部5 3以及裡面之釕污染量（螢光X 射線之檢測強度）在1 0 1 3 a t 〇 m s / c m 2以上之領 域。 塗1 0 ( 2 )係顯示藉由臭氧之晶圓5 1之洗淨效果 塗，將晶圓5 1暴露於臭氧前，進行以光阻覆蓋晶圓5 1 之裡面與邊緣部5 3以上之晶圓5 1之表面之處理。此係 爲了使被形成在裝置之圖案部5 2之釕膜不被蝕刻用。又 ’此晶圓5 1之裡面與邊緣部5 3之表面層係矽氧化膜。 此處，關於釕與光阻之臭氧蝕刻選擇比以改變處理溫 度（室溫至3 0 0 °C )調查之。其結果在約1 8 0 °C以下 之低溫下，釕之蝕刻率比光阻還度，在1 8 0 °C以上則以 光阻之蝕刻率比較大。此如在實施例1所示的，釕藉由其 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17- ---I-------- I I I l· I I I « — — — — — — I— Αν— _ (請先閱讀背面之注意事項再填寫本頁) 517302 A7 B7 五、發明說明（15) 之觸媒作用分解臭氧之故，於低溫下蝕刻也被促進，光阻 本身沒有觸媒作用之故，故推測乃發生上述之差。 因此，如以光阻覆蓋裝置圖案被形成之部份5 2，而 且在1 8 0 °C以下施以蝕刻處理，裝置圖案部5 2被保護 免於被蝕刻。又，爲了有效率去除釕之污染物質，考慮處 理之際之產出率，處理溫度期望在4 0 °C以上。 塗1 0 ( 2 )之結果係顯示利用上述條件洗淨處理塗 1 0 ( 1 )所示晶圓5 1之結果。由此也可以明白地，在 晶圓5 1表面之邊緣部5 3以及晶圓5 1之裡面被去除了 藉由釕被污染之領域5 5。 圖1 1係將上述之檢討結果反應於釕之乾洗淨裝置， 顯示其槪略之圖。在此例中，假定熱壁型批次式之洗淨裝 置，主要以進行洗淨處理之附有加熱機構之處理室1 1 1 、晶圓1 1 2、保持晶圓之石英製晶圓支持台1 1 3、氣 體擴散板1 1 4所構成。供給臭氧之臭氧發生器1 1 5 s 、產生臭氧所必須之氧氣供給器1 1 6 s、氮氣供給器 1 1 7 s、其它調解臭氧濃度用之氮氣洪給器1 1 8 s、 各別之供給器之閥門1 1 5 v、1 1 6 v、1 1 7 v、 1 1 8v透過配管1 1 9被連接於此處理室1 1 1。又， 透過排氣側配管1 1 9調整壓力之電導閥門1 1 1 0、真 空泵11111被連接著。除此之外，具有晶圓112搬 運用之搬蓮臂1 1 1 4之搬運室1 1 1 3透過閘門閥 1 1 1 2被設置於處理室1 1 1。 洗淨處理之方法如下述。即將以光阻覆蓋被形成在晶 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 1T--------- 經濟部智慧財產局員工消費合作社印製 -18- 517302 A7 _______ B7 五、發明說明（16) 圓1 1 2上之裝置圖案部之晶圓1 1 2 (釕污染量與圖 10 (1)爲相同程度）搬入處理室111 ，在100 °C 進行處理。此溫度之設定係考慮對於釕之蝕刻率快，而且 光阻之選擇比大（1 〇 〇程度），對於此光阻也不會有質 變。又，晶圓1 1 2之對支持台1 1 3之設置方法係使形 成光阻之面成爲向下之面朝下方式。此係爲了極力排除晶 圓裡面與邊緣部與裝置構件之接觸部。 設壓力爲700Tor r 、流量l〇s lm、臭氧濃 度1 0 %、洗淨時間3分鐘。 將處理終了之晶圓1 1 2由處理室1 1 1搬出，以前 述之全反射螢光X射線量測晶圓之釕污染料。其結果與前 述圖1 0 ( 2 )所示之情形相同，蠶留在晶圓1 1 2之邊 緣部或裡面之釕量在檢測器之檢測界限以下。進而利用被 熟知之I C P - M a s s分析裝置量測此晶圓裡面之結果 ，在5X101Qa t oms/cm2以下。由這些結果， 可以判明：藉由施以上述之洗淨處理，附著於晶圓1 1 2 之不要的部份的釕污染被排除。 依據本實施例，係乾製程之故，不需要如溼製程之沖 洗或乾燥工程，又使用不利用電漿之與臭氧氣體之化學反 應之故，基板本身或洗淨裝置構件，例如對於金屬構件也 不會造成腐蝕等之損傷，可以進行有效之洗淨。 在上述實施例中，洗淨處理雖在1 0 0 °C進行，但是 最好爲利用臭氧可以做釕之蝕刻之2 0 °C以上3 5 0 °C以 下，期望可以確保與光阻之選擇比之4 0°C以上2 0 0 t 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ------^----訂---------· 經濟部智慧財產局員工消費合作社印製 -19- 517302 A7 ______ B7 五、發明說明（I7) 以下，更好爲4 0 °C以上1 8 0 °C以下之處理溫度。 又’本實施例雖係顯示釕污染去除用之洗淨，不用說 對於當成圖案形成用之光罩形成光阻之半導體基板上之釘 膜之蝕刻處理也同樣地，可以進行簡單不會對晶圓造成損 傷，而且可以高產出率之蝕刻處理。 在上述本實施例中，洗淨用氣體雖係使用臭氧，但是 使用鹵化氧、氧化氮、氧原子也可以獲得同樣之效果。又 在事前將氧氣或氧化氮氣以紫外線或電漿激磁後再導入處 理室也可以獲得同樣之效果。而且，在上述之例中，雖然 使用在氧氣與氮氣之混合氣體中添加數％之臭氧之氣體， 但是在此添加氟、氯、溴、氟化氯、氟化氫、氯化氫以及 溴化氫等之鹵氣體或鹵化氫也可以獲得同樣之效果。再者 於添加氫、一氧化炭、氨、磷等之還原性氣體之情形，也 可以獲得同樣之效果。 又，上述洗淨效果並不限定於釕膜之情形，對於釕氧 化膜、餓、餓氧化膜之情形，也可以獲得同樣的效果。 接著，敘述適用於釕用C V D裝置之淸潔之例。 圖1 2係顯示釕或釕氧化膜之C VD裝置。 此CVD裝置之進行成膜反應之反應部係由：處理室 1 2 1、晶圓1 2 2、加熱晶圓用之陶瓷製加熱器1 2 3 、將成膜用氣體對晶圓1 2 2上均勻供給之氣體淋浴頭 1 2 4所形成。供給或排氣成膜用氣體與淸潔氣體之配管 1 2 5與處理室1 2 1爲了防止反應生成物吸附之故，藉 由加熱器1 2 6被加熱。 (請先閱讀背面之注意事項再填寫本頁) - I I--— II ^ ·111111-- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -20- 517302 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（18) 透過氣體供給配管1 2 5以及閥門1 2 7 V、 128v、129v、1210v將成膜用氣體之ru ( E t Cp) 2 (但是，E t CP係乙基茂基（ C 2 H 5 C 5 Η 4 )之略稱）氣體化供給之供給器1 2 7 s、 〇2供給器1 2 8 s、N 2供給器1 2 9 s、淸潔氣體供給 器之〇3供給器1 2 1 0 s被連接於處理室1 2 1。 又，透過排氣配管1 2 5控制處理室1 2 1內部之壓 力用之電導閥門1 2 1 1以及排氣裝置1 2 1 2也被連接 著。 此裝置係藉由載置晶圓1 2 2之加熱器1 2 3將晶圓 加熱至約3 0 0°C〜7 5 0°C爲止以成膜之冷壁型裝置。 在使用前述之成膜用氣體之情形，設成膜溫度爲3 0 0°C 之故，例如設加熱器溫度爲3 2 0 °C，又使成膜用氣體不 在裝置內壁或配管內凝縮地，處理室1 2 1或配管等也藉 由加熱器1 2 6加熱至約1 5 0 °C之程度。 但是，藉由成膜用氣體之分解反應，含有R u之不需 要的反應副生成物多量附著於處理室1 2 1之內壁等。又 ，爲了使晶圓之溫度分布均勻化，使加熱器尺寸大於晶圓 尺寸，對熱放散大之晶圓周緣部之熱投入量雖然增加，由 此此種構造之故，在加熱器1 2 3之周邊部也形成釕或氧 化釕膜。 隨著重複進行上述之CVD工程’附著於處理室 1 2 1之內壁或配管1 2 5之內壁之這些的附著物剝離， 此等由於氣流等之捲起，在成膜中下降注入晶圓1 2 2上 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -21 - -----------------^----^---------. (請先閱讀背面之注意事項再填寫本頁) 517302 經濟部智慧財產局員工消費合作社印製 A7 _____Β7__ 五、發明說明（19) 。其結果爲上述附著物變成異物，在形成裝置圖案之際， 引起短路或斷線等之不良。 因此，以下述之方法檢討藉由使用臭氧之淸潔的異物 降低效果。 (1 )釕膜之成膜方法 首先，處理室1 2 1內進行規定之排氣後，將晶圓 1 2 2載置於加熱器1 2 3上，將加熱器設定爲3 2 〇r ’使晶圓1 2 2之溫度維持在熱平衡狀態。此時，處理室 1 2 1之壁以及配管1 2 5之溫度約爲1 5 0 t。之後， 打開閥門 1 2 7 v、1 2 8 v，將 R u ( E t C p ) 2、 〇2氣體各各導入處理室1 2 1內，進行0 · 1髂之釕膜的 成膜。又，使成膜時之壓力成爲規定値地，使用電導閥門 1 2 1 1調整之。 (2 )藉由臭氧之淸潔方法 成膜完了之晶圓1 2 2上之異物數在使用同一處理室 進行之成膜工程之累積膜厚超過3髂時，有變多之傾向。 因此，處理室1 2 1之淸潔頻度係成膜次數每3 0次進行 0 可以使用於淸潔之時間係由c V D裝置之產出率與其 之稼動率算出，約在1小時以內。因此，其中一例：熱容 量大之處理室1 2 1或配管1 2 5之溫度維持爲原來者’ 將加熱器1 2 3之溫度降低至蝕刻率可以確保之溫度’例 如1 5 0 t，進行藉由臭氧之處理室淸潔。 打開閥門1 2 1 0，藉由臭氧供給器1 2 1 0 s供給 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） · 22 - -----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 517302 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（20) 臭氧氣體，與成膜時相同，藉由電導閥門調整排氣量’設 臭氧濃度爲5%、氣體流量爲l〇slm、壓力爲100 T 〇 r r ° 淸潔之終點檢測係藉由：在排氣配管1 2 5裝置 Q M S之取樣埠，如圖1 3所示般地，量測發生於淸潔中 之反應生成氣體之離子強度之時間變化以進行確認。具體 而言，將R u 0 4之離子強度減少，之後之強度變化變成極 小之時間點設爲淸潔之中了。在本實施例中，淸潔約實施 2 0分鐘後，停止臭氧氣體之供給。又，在本實施例之情 形，包含加熱器1 2 3之溫度調整、處理室1 2 1內之壓 力調整、淸潔等所需要之時間，可以在約1小時以內進行 一連串之處理。 又，關於淸潔時間之縮短如上述般地，當成添加於臭 氧氣體之氣體藉由使用5%之C 1 F3或5%之CO ’約可 縮短2 0〜3 0%之時間。 接著，假定重複實施釕之成膜以及臭氧淸潔之一連串 的作業之情形，量測該作業之晶圓1 2 2上之異物數之推 移。 圖1 4係顯示以8英吋晶圓之情形爲例’ 〇 · 3髂以 上之異物數（成膜重複進行2 0〜3 0次時之平均値）之 增減變化。由此結果可以明白地，藉由進行處理室之淸潔 ，晶圓上之異物可以降低至幾乎初期狀態。而且即使由於 其後之成膜，異物數增加，藉由再度進行淸潔’可以再度 降低異物數。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) -23- ------------------^----訂--------- 線β. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 A7 ___ B7 五、發明說明（21) 如以上說明般地，以成膜之規定的階段藉由實施臭氧 淸潔’了解到可以長期抑制處理室內之異物的發生。藉由 此，可以經常安定進行釕之成膜率。 又’以目視SS察2 0次之臭氧淸潔後之裝置內部之結 果，沒有看到使用構件之金屬腐飩等。 在本實施例中，雖在約1 5 0 °C進行淸潔，最好在臭 氧之釕蝕刻可以進行之2 0 °C以上3 5 0 °C以下，期望在 釕之蝕刻率比較大之4 0 °C以上2 0 0 °C以下，更好爲在 4 0 °C以上1 8 0 °C以下進行。 如上述般地，依據本實施例，藉由臭氧氣體淸潔可以 降低處理室內之異物，其結果可以提升半導體裝置之製造 良率。 又，不使用電漿可以蝕刻之故，可以鈾刻裝置內部之 所謂的淸潔氣體之被供給部份之故，與習知之電漿淸潔法 比較，可以減少處理室內之附著物之殘渣。 進而蝕刻氣體使用臭氧以外之鹵化氧、氧化氮、氧原 子等，又在事前將氧氣或氧化氮氣以紫外線或電漿激磁後 再導入處理室也可以獲得同樣之效果。而且，在氧氣與氮 氣中添加數％之臭氧之氣體中添加氟、氯、溴、氟化氯、 氟化氫、氯化氫以及溴化氫等之鹵氣體或鹵化氫，再者添 加氫、一氧化炭、氨、磷等之還原性氣體也可以獲得與上 述之情形同樣之效果。 又，此不限定於釕膜之情形，對於釕氧化膜、餓、餓 氧化膜之情形也相同。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -24 - -----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 517302 A7 -------- __ B7 五、發明說明（22) 接著’在實施例4中，說明適用釕用蝕刻裝置之淸潔 之例。 使用蝕刻裝置重複進行蝕刻處理之情形，藉由被蝕刻 膜或光阻膜與蝕刻氣體之反應，副生成物附著、堆積於處 理室內。此與C V D裝置之情形相同，成爲異物爲裝置之 製造良率降低之要因。 因此，檢討藉由臭氧淸潔之蝕刻裝置來之異物降低效 果。 (1 )釕膜之蝕刻（圖案形成） 首先，在進行規定排氣之處理室內，將在釕膜上光阻 被圖案化之晶圓1 2載置於電極上，將其溫度調節爲2 0 °C。之後，一邊調整處理室內之壓力一邊導入〇2、C 1 2 、N 2氣體，進行蝕刻。蝕刻終了後，搬出晶圓1 2，排氣 處理室內。 於本實施例中，晶圓之蝕刻處理每5 0次以下述之順 序實施臭氧淸潔。 (2)藉由臭氧之淸潔方法 與C V D裝置之情形相同，設淸潔時之晶圓設置電極 之溫度約1 0 0 °C，實施1 5分鐘淸潔。而且，量測此蝕 刻以及淸潔之一連串之工程重複2 0次時之異物數推移。 其結果與上述之CVD裝置之情形相同地，藉由氣體 淸潔之處理室內之異物數可以維持在低水準，在裝置內之 金屬部表面沒有腐蝕等（目視檢查）。 又，在本實施例敘述之淸潔處理溫度條件或淸潔氣體 (請先閱讀背面之注意事項再填寫本頁) -----^----訂----- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -25- 經濟部智慧財產局員Η消費合作社印製 517302 A7 — B7 五、發明說明（23) 成分等並不限定於此，例如與上述之c V D裝置之情形相 同地，藉由對使用之氣體添加鹵系氣體或還原性氣體可以 謀求淸潔率之提升。 如上述般地，藉由使淸潔條件適當化，短時間之處理 室淸潔成爲可能，其結果不單有助於橫跨長期之裝置的安 定稼動或裝置稼動率之提升，也可以提升裝置製品之製造 良率。 雖然說明了依據本發明之許多實施例，但是本發明並 不限定於此，在不脫離本發明之意旨下，不用說可以有種 種之變形。 圖面之簡單說明 圖1係說明釕化合物之蒸汽壓曲線用之圖。 圖2係顯示釕之氧化反應之自由能差與溫度之關係之 說明圖。 圖3係說明第1實施例用之半導體裝置之工程圖。 圖4係使用於第1實施例之蝕刻裝置之槪略圖。 圖5係顯示釕之蝕刻率與處理溫度之關係之說明圖。 圖6係藉由釕與臭氧之反應之反應生成物之QM S分 析例。 圖7係顯示臭氧之熱分解與晶圓上之臭氧殘存率之關 係之說明圖。 圖8係說明釕與臭氧之反應機制用之圖。 圖9係顯示第1實施例之蝕刻處理之順序之說明圖。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -26- 1 n t ϋ *^1 ί n n 1 I I ϋ n ϋ n 一- n ϋ a— I ϋ Mem— I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 517302 Α7 Β7 五、發明說明（24) 圖1 0係顯示第2實施例之釕污染晶圓之臭氧洗淨效 果圖。 圖1 1係說明第2實施例之臭氧洗淨裝置之槪略用之 圖。 •圖1 2係說明第3實施例之C V D裝置淸潔用之圖。 圖1 3係顯示說明淸潔終點檢測用之Q M S反應分析 結果圖。 圖1 4係顯示CVD裝置之淸潔與處理室內異物數之 推移圖。 元件對照表 4 1 :處理室 4 2 :晶圓 ----------------l·---訂--------- (請先閱讀背面之注意事項再填寫本頁) 4 3 : 接受 器 加 熱 器 4 4 : 淋浴 頭 4 5 S ，4 6 S J 4 7 s， ，4 8 s :臭 氧發生器 4 5 V ，4 6 V y 4 7 v， 丨4 8 v ••閥 門 4 1 0 ••電 導 閥 門 4 1 1 ••真 空 泵 4 1 3 ••搬 運 臂 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 --- B7 V. Description of the Invention (1) Background of the Invention The present invention relates to an etching treatment method for the surface of a solid containing ruthenium, starvation, or these oxides. The present invention relates to a method for manufacturing a semiconductor device, such as an etching process and a cleaning process for the above-mentioned metal or its oxide formed on a substrate, and further relates to a cleaning method for these cVD devices or etching devices. In recent years, with the high integration of semiconductor devices, in order to ensure the electrical capacity of capacitors, components with memory cells such as D RAM have gradually become more complicated three-dimensional structures. Therefore, the number of manufacturing processes of the above-mentioned elements is increased, and the film forming and processing margins are narrowed, which leads to an increase in manufacturing costs or a decrease in yield. Therefore, in order to increase the storage capacity of the capacitor, it is necessary to simplify the structure by using a new material having a high dielectric constant. Such a commercial dielectric material is, for example, a multi-element oxide of Ba S r T i 03. To form these oxides, high-temperature annealing is required in an oxygen atmosphere. However, when Si is used as the material of the lower electrode of the capacitor, it is difficult to suppress the increase in resistance due to oxidation at the time of oxygen withdrawal. Therefore, it is necessary to select a new material that is not easily oxidized or has conductivity even if oxidized. Electrode materials that meet this condition, such as ruthenium and ruthenium oxide, are being reviewed. The method of forming these electrode materials is considered to be very suitable for physical vapor deposition, good adhesion to thin films on substrates, and C V D (Chemical Vapor Deposition) which can obtain thin films with high purity and excellent crystallinity. A method for forming a thin film of ruthenium or ruthenium oxide is described in, for example, Japanese Patent Application Laid-Open No. 6 --------------------- ^ ---- order --------- line Read the notes on the reverse side and fill out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4-517302 A7 _ B7 V. Description of the invention (2) 2 8 3 4 3 8 The method disclosed in the publication of Japanese Patent Application Laid-Open No. 9- 2 4 6 2 1 4 uses a specific organic raw material gas to form a thin film by the MO-CVD method. On the other hand, a method for engraving ruthenium or a ruthenium oxide film is disclosed in, for example, Japanese Unexamined Patent Publication No. 8-7 8 3 9 6 and includes the use of at least one of fluorine gas, chlorine gas, and iodine gas. A method for manufacturing a semiconductor device in which a halogen heating body and a group formed by halogenated gas select at least one Xia or one or more mixed gas containing oxygen or ozone gas for plasma etching. Also ‘Lossberg, Mue 11 er (Rainer Lossberg und U1 rich Mueller)’ (Zeitschrift Fuer Naturforschung, Section B, Chemical Sciences, vol. 16B, No. 3, 1981, pp395) " Publicly disclosed that a pure ruthenium tetroxide can be obtained by reacting ruthenium with ozone at room temperature. Further, there are techniques for removing ruthenium residues, such as a wet cleaning method using a cleaning solution containing periodic acid and nitric acid as disclosed in Japanese Patent Application No. 1-2 4 5 1 4 3. Summary of the Invention The contents described below are those not described in the above-mentioned conventional techniques. The etching method of ruthenium or ruthenium oxide described in the above-mentioned conventional technique is a plasma etching reaction using an ion assisting reaction. Therefore, it is difficult to avoid damage to an object to be etched when using a plasma. In addition, since the cost of the equipment using plasma has also become higher, it is expected to provide a method that can avoid damage to the substrate. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) (Please note this page before filling in this page) ----- ^ ---- " Order ---------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 5-517302 A7-B7 V. Invention Explain (3) Injury and simple etching method. (Please read the precautions on the back before filling in this page.) Similarly, the conventional cleaning method for removing ruthenium residues or contamination, the substrate is damaged during the removal by plasma etching reaction, and then cleaned by wet cleaning. The method requires a process of rinsing or drying, and in this case, it is also desirable to provide a cleaning method that does not cause damage to the substrate and can easily handle ruthenium residues or contamination. On the other hand, in the case of using a CVD device for forming ruthenium or a ruthenium oxide to form a new material or etching these, and forming an etching device for patterning to manufacture a semiconductor device such as a DRAM, in order to reduce the amount of dust generated by the above device, The semiconductor device is manufactured with high yield, and the cleaning byproducts including ruthenium by-products deposited or attached in the reaction processing chamber or piping are removed to facilitate the establishment of the next manufacturing method, and it is also eagerly expected in the semiconductor industry. In the case of etching ruthenium or starvation, the above metal can be changed to a metal compound with high vapor pressure (ruthenium compound or starvation compound) to remove it. One example of a representative ruthenium compound printed by the Consumer Affairs Agency of the Intellectual Property Bureau of the Ministry of Economic Affairs is shown in Fig. 1 as the temperature dependence of its vapor pressure. As a result, it is clear from FIG. 1 that the vapor pressure of Ru 4 of the oxide is the highest at a low temperature below 500 ° C. Therefore, in the case where ruthenium is applied to a semiconductor device, from the viewpoint of thermal budget or output rate, the etching process temperature of the processing process is expected to be a relatively low temperature. Actually, the temperature range below 500 ° C is such that high steam is generated. R u〇4 of the pressure characteristics is very good. Further, there is a considerable advantage in linking the metal oxide generator to the structure of the manufacturing apparatus or its maintenance. That is to say, the metal produced by this paper is -6- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 B7 V. Description of the invention (4) Halogenation In the case of use of materials, highly corrosive halogen-based gases must be used, and safety measures must be taken against manufacturing equipment or processing methods. Next, a reaction for producing Ru 4 from ruthenium will be described. From the viewpoint of thermodynamics, in order to realize a simple etching method with less damage to the material to be etched, the above-mentioned oxide generation method using a non-plasma-based chemical reaction that does not use high energy such as plasma is considered. Review it. Fig. 2 (1) to (3) illustrate the relationship between the change in Gibbs free energy (△ G) and the reaction temperature in the reaction of Ru 〇 4 produced by Ru 〇 0 and the eight reaction equilibrium constant (K) The relationship can be expressed by the following formula: KK_exp (-AG / RT) However, R is a gas constant, and T is the absolute temperature. This formula means that as the energy change amount ΔG becomes larger toward the positive side, the oxidation reaction of ruthenium does not progress, and as the ΔG becomes larger toward the negative side, the oxidation reaction is promoted. From the results of Fig. 2 (1) to (2), when ozone or an oxygen atom is used to make ruthenium react, the amount of change in energy ΔG that produces Ru0 is large on the negative side, and the reaction is easy to proceed. Quite clearly in the process of this reaction, if even RU〇2 is produced, RU〇2 will react with ozone or oxygen atoms to become RU〇4. On the other hand, as shown in Fig. 2 (3), in the reaction between ruthenium and 〇2, even if the amount of change in energy △ G that produces Ru 0 is negative, the absolute paper size is subject to Chinese national standards. (CNS) A4 specification (210 X 297 mm) ----- ^ ---- Order --------- line (Please read the precautions on the back before filling this page) 517302 A7 B7 5 2. Description of the invention (5) As compared with the case of ozone or oxygen atom, the reaction is not easy to carry out. When RuO2 is produced by the reaction with oxygen, the state hardly progresses to Ru0. From the above experimental results, it can be understood that in order to generate Ru 4 from ruthenium or ruthenium oxide, it is only necessary to react it with ozone or an oxygen atom. The above reaction is not limited to ruthenium, and the same is true. However, by adding a trace amount of a halogen gas or a hydrogen halide gas to the above-mentioned ozone or oxygen atom gas, the ruthenium halogenation reaction is generated, and the production of Ru 2 which is relatively stable and difficult to progress is suppressed. In addition, by adding a reducing gas, the produced RuO2 can be reduced to Ru. In consideration of the reaction form of ruthenium described above, the present invention is a method for etching a solid surface containing at least one kind selected from ruthenium, ruthenium oxide, or a group of hunger and oxidization. The supply of oxygen to the solid surface includes the provision of oxygen atomicity. Gases can be used to etch solid surfaces. In addition, by subjecting the surface of the substrate on which the film formed of the metal or its oxide is formed to the same treatment, the substrate surface can be etched. Furthermore, the substrate can be cleaned by treating the substrate including at least one kind of film or particles selected from the group consisting of ruthenium, ruthenium oxide, or a group that is hungry or oxidized. Furthermore, in the cleaning process of forming a CVD device including at least one of the above-mentioned films on a substrate, or the cleaning process of an engraving device in which the above-mentioned film is etched to perform pattern formation, it is possible to remove Handle at least ruthenium or hungry reaction products on the surface of the room or piping. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page)- --- K ---- Order ---------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-8-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 ______ B7 V. Description of the Invention (6) 〇 The oxygen atomic gas system provided by the present invention is formed of at least one gas selected from the group consisting of ozone, halogenated oxygen, nitrogen oxide, and oxygen atom, and a halogen gas, hydrogen halide, or The reducing gas is further added with a gas selected from the group consisting of fluorine, chlorine, bromine, chlorine fluoride, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen, carbon monoxide, ammonia, or phosphorus to supply the etching treatment. In addition, these treatment reactions are non-plasma contact treatments, and are performed without forming an ion-protective layer on the surface of or above the solid or substrate. In the above-mentioned reaction of the present invention, the surface temperature of the solid or substrate is higher than 20 ° C and lower than 35 ° C, preferably higher than 40 ° C and lower than 2 0 ° C, and more preferably higher than 40 ° C. 1 80 ° C or lower. Detailed description of a suitable embodiment An embodiment of the present invention will be described in detail with reference to the drawings. The semiconductor device described in the following description means a semiconductor device such as a memory element formed on a silicon substrate, a TFT element for a liquid crystal display formed on a quartz or glass substrate, and a substrate other than the above. The installation is all. The term "substrate" means a semiconductor substrate such as silicon or the like on which semiconductor devices are formed on the surface, an insulating substrate, or a composite substrate of these, but it is not necessarily limited to this. In addition, the so-called non-plasma etching treatment described below is not an etching treatment by the sputtering effect of ions, nor is it dominated by accelerating the reaction of ions incident on the surface to be treated like reactive ion etching. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -9- I ----------------- ^ ---- Order --- ------ (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 B7 V. Description of the invention (7) The etching treatment of the ion subsidy reaction, but using the composition The uranium-etched gas and the respective molecules of the treated surface are chemically reacted with each other in a high-energy state mainly caused by heat supplied from the outside to be etched. Therefore, it is also a major feature that it is not often seen in the case of plasma etching to form an ion-protective layer on the surface of a solid or substrate or device or above each other. Here, the ion protective layer is explained in detail. The so-called ionic protective layer means a space charge layer formed by a plasma and a solid connected. Generally, because the plasma electron temperature is higher than the ion temperature, high-speed light electrons flow into the solid surface, and the solid has a negative potential for the plasma. Therefore, electrons decelerate or are reflected near the solid surface, forming a space charge layer that becomes an excess of ions, that is, an ion shield. Therefore, in the case where a chemical reaction occurs in the hot atmosphere described below, the plasma does not exist near the solid surface, so that an ion-protective layer is not formed. In the case of a remote-controlled electric paddle processing method in which plasma gas existing in a space separated by a solid to be processed is transported to a solid surface through a pipe, it is assumed to be included in the vicinity of the solid surface because it does not form an ion shield. Non-plasma etching process. The ruthenium oxide refers to any one of Ru u0, Ru u2, Ru u3, and Ru o4, and the so-called oxidation starvation refers to: 〇s〇, 〇S2 03, 〇 02 Any one of 0S03 and 0S04. In the first embodiment, a semiconductor device is taken as an example, and the flow of the etching process for the case of etching the ruthenium film formed on the substrate is shown in FIG. 3. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10- ----------------- ^ ---- Order ----- ---- (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 ________ B7 V. Description of the invention (8) Figure 3 (1) is on wafer 3 1 (Silicon substrate) A cross-sectional view of a semiconductor device when a well-known thermal oxide film formation method is used to form a silicon oxide film 32, and then this oxide film 32 is patterned by a well-known anisotropic dry etching method. . Next, as shown in FIG. 3 (2), after the ruthenium film 33 is formed on the oxide film 32 by a general CVD method, as shown in FIG. 3 (3), the above is removed by a normal dry etching method. A part of the ruthenium film 33 matches the surface of the oxide film 32 and the ruthenium film 33. In this way, the ruthenium film 33 is buried in the hole formed by the anisotropic dry etching to complete the plug (33) made of ruthenium. Fig. 4 is a schematic diagram showing a uranium engraving device for removing a part of the ruthenium film 33. This uranium engraving device is mainly formed by: a processing chamber 4 1 for performing an etching process, and a wafer 4 2, a receiver heater 4 for heating the wafer 3, and a shower head 4 4 for supplying gas. The ozone generator for supplying ozone is 4 5 s, the oxygen supply necessary for generating ozone is 4 6 s, the nitrogen supply is 4 7 s, the nitrogen supply for adjusting ozone concentration is 4 8 s, the valve of each supply is 45v, 46v, 47v, and 48v are connected to the processing chamber 41 through a pipe 49. In addition, a conductance valve 4 1 0 for adjusting pressure through an exhaust-side pipe 49 is connected, a vacuum pump 4 1 1, and ozone-removing equipment 4 1 2 are also connected. In addition, a transfer chamber 4 1 4 having a transfer arm 4 1 3 is connected to the processing chamber 41. First, in order to determine the etching conditions of the ruthenium film 33, the apparatus shown in Fig. 4 is used to explain the results of the review of the etching characteristics of the ruthenium film 33 by the use of an ozone gas. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -11-------------- A_w ^ ----- ^ ---- Order --- ------ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 B7 V. Description of the invention (9) Figure 5 is engraved with ozone gas such as uranium Temperature dependence of the etch rate at the time of the CVD ruthenium film 33. Etching conditions were performed at a ozone concentration of 5%, a gas flow rate of 10 slm, and a pressure in the processing chamber of 100 Torr and 700 Torr. In addition, ozone is generated by an ozone generator using silent discharge. As a result, in the case where the ruthenium film 33 is ozone, the processing temperature is etched from 20 ° C to 350 ° C, and it is understood that the etch rate is extremely high near 100 ° C. In addition, the etch rate of uranium is extremely large compared with the etch rate of the ruthenium film 33, which is conventionally known, which is several times or more. The etching rate is determined from the characteristic X-ray intensity of ruthenium measured by fluorescent X-ray analysis. Next, an etching reaction mechanism of the ruthenium film 33 and ozone gas will be described. FIG. 6 shows that the reaction product generated when the ruthenium film 3 3 is etched using the etching device shown in FIG. 4, for example, a QMS (Quadrupole Mass Spectrometry) force port is installed at the pipe 49 to measure the Ma at the time of measurement. ss spectrum. From this result, it is clear that the reaction products Ru, Ru0, Ru〇2, Ru〇3, and Ru〇4 were detected. Among them, the substance with the largest spectral intensity is Ruo4, and it is determined that the main reaction product of the reaction between the ruthenium film 33 and the ozone gas is Ruo4. In addition, Ru, Ru0, Ru02, and Ru03 are mainly considered to be those that Ru04 decomposes in the ionization chamber of QMS. When Ru 4 is produced from a ruthenium metal monomer, decomposition of the odorous oxygen gas of the reaction gas is required. Figure 7 shows that the ozone gas supplied to the processing chamber is decomposed by thermal decomposition. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12- ------------ ---- ^ ---- ^ --------- si (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 517302 A7 B7 V. Description of Invention (10) The time change of the ozone residual rate at that time (from 1 minus the ozone decomposition rate). Fig. 7 is a calculation result using data described in "The Basics and Applications of Ozone" (Sumitomo Kogyo, p58 (published in 1996)) written by Sugihiro Shuo. Considering the flow rate of the ozone gas in the etching device shown in FIG. 4, the ozone introduced into the processing chamber 41 is heated, and the time until it comes into contact with ruthenium is only a few seconds or less. When the processing temperature is below 200 ° C, Ozone is hardly decomposed into contact with the ruthenium film. Therefore, in a temperature range where the etching rate of ruthenium shown in Fig. 5 is extremely large, ozone is decomposed by energy other than heat, and this is considered to contribute to the reaction with ruthenium. In addition, the processing temperature described above is a well-known method, for example, the temperature measured by a thermoelectric pair on the surface of a wafer 4 2 including a ruthenium film 3 3. Ozone is decomposed by platinum and other catalysts. This is described in the aforementioned "Basics and Applications of Ozone" or ozone decomposing catalysts that are widely used in the field of 用 Q " (JETI, Vol. 39.No. ll ,, 1991). On the other hand, the ruthenium series belongs to the platinum family. If the above-mentioned catalyst action is considered, ozone can be considered to be decomposed by the catalyst action with ruthenium. In this case, it can be explained that the processing temperature is even at 100 ° C. The Ru 4 formation reaction can sufficiently occur even at a low temperature. From the above, the reaction between ruthenium and ozone can be considered to proceed according to the reaction scheme shown in FIG. 8 or the reaction formula shown in Table 1 below. R u 0 is a very unstable substance, and it is considered that stable RuO4 is produced by a reaction with ozone. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) -13- ^ —Order --------- (Please read the precautions on the back before filling this page) 517302 A7 B7 V. Description of the invention (11) Table 1 Production process of Ru〇4 Reaction process reaction formula ① ⑴ supply to Ru surface ② 03 supply to Ru surface ③ 0 3 decomposition ④ reaction between Ru and 0 ⑤ Ru and 〇3 produce Rua ⑥ Ru〇4 separation 0: 0 3 ads 〇3 ads — ^ 〇2 + 〇ads Ru + 〇ads — Ru RU 〇 + 〇3 — ^ RU 〇4 ads RU〇4ads — Rll〇 Printed by 4 Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ※ ads are displayed as ads that are attracted to the surface. Next, as shown in FIG. 5, the reason why the etching rate of ruthenium by ozone decreases from a high-temperature region around 100 ° C will be explained. Based on the results of the XPS measurement of the well-known analytical method for the ratio of the amount of Ru to the amount of Ru at each processing temperature, it was determined that R u 〇2 exists on the surface of the ruthenium film in the above-mentioned high-temperature processing. The amount becomes more. On the other hand, in FIG. 5, the etching rate (symbol X) in the case where the Ru 2 film formed by the sputtering method is simply exposed to ozone gas is described. From this, it is understood that the Ru 2 film is hardly etched in the ozone monomer. Based on the above results, when the processing temperature is high, the stoichiometric R u 〇 2 reaction is more dominant than the R u 〇 4 reaction shown in Table ⑤. Ru02 formed on this surface hinders subsequent reactions. Moreover, the reason why Ru〇2 is hardly etched is that Ru 02 does not have a catalytic effect of decomposing ozone. Ru 02 is thermodynamically stable. It can be considered that as the processing temperature shown in FIG. 2 increases, the free energy of the reaction The difference (AG) is approached from negative to zero or positive. ----------------- ^ ---- Order --------- (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -14- 517302 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (12) Considering the above reaction of ruthenium by ozone, the etching is removed In the case where a part of the film 3 3 is formed on the substrate 3 1 not shown in FIG. 3, the following 3 points are important: (1) It is possible to obtain necessary output when manufacturing a semiconductor device Rate of uranium engraving, (2) does not degrade (oxidize) the surface of the ruthenium film 33, (3) uniform uranium engraving can be performed on the surface of the wafer 31, and from the above review results, using ozone treatment temperature such as At 2 0. (: To a range of 3 50 ° C, etching of the ruthenium film 33 is possible. However, in order to obtain an etching rate that can ensure the production yield, and to suppress the oxidation of the surface of the ruthenium film 33, It is desirable to set the processing temperature range from 40 ° C to 200 ° C. In order to make the wafer 31 uniformly engraved on the wafer 31 surface, the reaction is in the area of diffusion law, and the ozone gas is placed on the surface of the processing chamber 41. It is only necessary to supply uniformly inside, and in the case of responding to or slowing off the speed, it is only necessary to make the processing temperature in the wafer 31 surface uniform. Using the processing device shown in FIG. 4, it is considered that it is out of the speed field. Etching at a processing temperature of 60 ° C. Fig. 9 shows the processing procedure. Following the processing procedure of Fig. 9, a processing temperature of 60 ° C is used to form a ruthenium film 3 3 on a substrate of a wafer 31. As a result of the partial removal, as shown in Fig. 3 (3), a plug 33 of a ruthenium film can be formed. In addition, the uniformity within the 1 plane of the wafer 31 with an etching rate is ± 5%, which is confirmed in practical use So as not to have any level of obstruction. According to this embodiment, by using ozone etching The film 3 3 can be etched relatively quickly. Also, the above reaction is not the reaction using plasma. Therefore, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15- ---- -^ ---- ^ --------- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 B7 V. Description of the Invention (13), Does not cause damage to the substrate 31. Furthermore, the use of ozone gas can also suppress damage to the components of the etching device, such as corrosion of metal members. In the above embodiment, although the uranium etching gas uses ozone, it is used. The same effect can be obtained by halogenated oxygen, nitrogen oxide, and oxygen atom. Also, before the gas is introduced into the processing chamber 41, the same can be obtained by introducing oxygen or nitrogen oxide into the processing chamber 41 with ultraviolet or plasma excitation. Moreover, in this embodiment, although a gas containing several percent of ozone is added to a mixed gas of oxygen and nitrogen, fluorine, chlorine, bromine, chlorine fluoride, hydrogen fluoride, hydrogen chloride, and hydrogen bromide are added here. Wait for The same effect can also be obtained with gas or hydrogen halide. Moreover, instead of the ozone gas containing several% of oxygen and nitrogen in this embodiment, in the case of adding reducing gas such as hydrogen, carbon monoxide, ammonia, phosphorus, etc., The same effect can also be obtained. The results described above can also obtain the same effect as in the case of the ruthenium film for the ruthenium oxide film, the starved, or starved oxide film. Next, in Example 2, the wafer is attached to the wafer or the wafer. Removal of ruthenium film or particles on the edge of the surface. For example, in a CVD device of ruthenium film, the wafer is placed on a heater and heated, and the temperature of the heater is not higher than the film formation temperature, and it is not single crystal On the circle, a ruthenium film may be generated on a heater outside the wafer, and by repeating the above C VD film formation, a ruthenium film is also attached to the wafer. Furthermore, it prevents the formation of a ruthenium film on the edge of the wafer surface to prevent the edge of this paper from applying Chinese National Standard (CNS) A4 (210 X 297 mm). -16- --------- ---- $ ---- l · — (Please read the notes on the back before filling out this page) 1T --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 B7 V. DESCRIPTION OF THE INVENTION The part (14) is contacted by a shield for supplying a film-forming gas. Since this shield is also as high as a heater, a ruthenium film is also formed on the shield. In addition, if the ruthenium film is attached to the inside or the edge of the wafer, if other devices are used for other processing, the attached ruthenium film itself contaminates other devices, which will eventually affect the performance of the semiconductor device. Therefore, in order to prevent contamination of the ruthenium film of other devices, after CVD film formation or after etching, a cleaning process for removing the ruthenium film or particles attached to the wafer or the edge portion of the wafer surface is indispensable. FIG. 10 (1) shows that a device pattern 5 2 is formed on the surface of the wafer 51, and a ruthenium film 5 4 or ruthenium particles 5 5 are formed inside the surface edge portion 5 3 of the wafer 5 1 and the wafer 5 1. And the state of being polluted. In addition, the area shown in black indicates that the amount of ruthenium contamination (detection intensity of fluorescent X-rays) on the surface edge portion 5 3 and the inside of the wafer 51 using the well-known total reflection fluorescent X-ray measurement is 1 0 1 3 at 〇ms / cm 2 or more. Coating 1 0 (2) shows the cleaning effect of the wafer 51 with ozone. Before exposing wafer 51 to ozone, the inside of the wafer 51 with the photoresist is covered with the edge 5 3 or more. Surface treatment of wafer 51. This is for preventing the ruthenium film formed on the pattern portion 52 of the device from being etched. The surface layer of the inner surface of the wafer 51 and the edge portion 53 is a silicon oxide film. Here, the selection ratio of ruthenium to photoresist for ozone etching was investigated to change the processing temperature (room temperature to 300 ° C). As a result, the etching rate of ruthenium is lower than that of the photoresist at a low temperature of about 180 ° C or lower, and the etching rate of the photoresist is larger than 180 ° C. As shown in Example 1, ruthenium applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) by its paper size -17- --- I -------- III l · III «— — — — — — — I— Αν— _ (Please read the precautions on the back before filling out this page) 517302 A7 B7 V. Explanation of the invention (15) Because the catalyst decomposes ozone, it is etched at low temperature It is also promoted, because the photoresist itself has no catalyst effect, so it is speculated that the above-mentioned difference occurs. Therefore, if the portion 5 2 of the device pattern formed is covered with a photoresist, and the etching process is performed below 180 ° C, the device pattern portion 5 2 is protected from being etched. In addition, in order to efficiently remove ruthenium contaminated materials, considering the output rate during processing, the processing temperature is expected to be above 40 ° C. The results of coating 1 0 (2) show the results of cleaning the coating 51 (shown in FIG. 10 (1)) using the conditions described above. It is also clear from this that the edge portion 53 of the surface of the wafer 51 and the inside of the wafer 51 are removed, and the area 55 contaminated with ruthenium is removed. Figure 11 is a diagram of the ruthenium dry-cleaning device reflecting the above review results. In this example, it is assumed that a hot-wall batch-type cleaning device is mainly supported by a processing chamber 1 1 1 with a heating mechanism and a wafer 1 1 2 for holding a wafer, and a quartz wafer holding wafer. The stage 1 1 3 is composed of a gas diffusion plate 1 1 4. Ozone generator for supplying ozone 1 1 5 s, oxygen supply necessary for generating ozone 1 1 6 s, nitrogen supply 1 1 7 s, other nitrogen flooding devices for regulating ozone concentration 1 1 8 s, each The valves of the feeder 1 1 5 v, 1 1 6 v, 1 1 7 v, 1 1 8 v are connected to the processing chamber 1 1 1 through a pipe 1 1 9. In addition, a conductance valve 1 1 10 that regulates pressure through an exhaust-side pipe 1 19 and a vacuum pump 11111 are connected. In addition, a transfer chamber 1 1 1 4 having a lotus arm 1 1 1 4 used for wafer 112 transfer is installed in the processing chamber 1 1 1 through a gate valve 1 1 1 2. The washing method is as follows. To be formed with a photoresist covering the size of the crystalline paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 1T -------- -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -18- 517302 A7 _______ B7 V. Description of the invention (16) Wafer 1 1 2 of the device pattern part on the circle 1 1 2 (To the same degree) was moved into the processing chamber 111 and processed at 100 ° C. The setting of this temperature takes into account that the etching rate for ruthenium is fast, and the selection ratio of the photoresist is large (about 1000), and there is no qualitative change for this photoresist. In addition, the method of setting the wafer 1 12 to the supporting table 1 1 3 is such that the side on which the photoresist is formed is a downward side. This is for the purpose of ruling out the contact between the inside of the wafer and the edge and the device member. The pressure was set to 700 Torr, the flow rate was 10 slm, the ozone concentration was 10%, and the washing time was 3 minutes. The processed wafer 1 1 2 is taken out of the processing chamber 11 1 and the ruthenium contamination material of the wafer is measured by the total reflection fluorescent X-ray measurement described above. The result is the same as the situation shown in Fig. 10 (2), and the amount of ruthenium left on the edge or inside of the wafer 1 12 is below the detection limit of the detector. Furthermore, the result of measuring inside the wafer using a well-known IC P-Ma s s analysis device is below 5X101Qa toms / cm2. From these results, it can be determined that the ruthenium contamination attached to the unnecessary part of the wafer 1 1 2 was eliminated by applying the above-mentioned cleaning treatment. According to this embodiment, because of the dry process, the washing or drying process such as the wet process is not required, and the chemical reaction between the plasma and the ozone gas is not used. Therefore, the substrate itself or the cleaning device components, such as metal components It does not cause damage such as corrosion, and can be effectively cleaned. In the above embodiment, although the cleaning process is performed at 100 ° C, it is preferred that the etching of ruthenium using ozone can be performed at a temperature of 20 ° C or higher and 3 50 ° C or lower. More than 40 ° C above 2 0 0 t This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ------ ^ ---- Order --------- · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- 517302 A7 ______ B7 V. Description of the invention (I7) or less, preferably 40 ° C or more 1 Processing temperature below 80 ° C. Also, although this embodiment shows cleaning for the removal of ruthenium contamination, it goes without saying that the etching process of a nail film on a semiconductor substrate that is used as a photomask for pattern formation to form a photoresist can be similarly performed. Circles cause damage and can be etched at high yields. In this embodiment described above, although ozone is used for the cleaning gas, the same effect can be obtained by using oxygen halide, nitrogen oxide, and oxygen atom. The same effect can also be obtained by introducing oxygen or nitrogen oxide into the processing room after being excited by ultraviolet or plasma beforehand. Furthermore, in the above example, although a gas in which several percent of ozone is added to a mixed gas of oxygen and nitrogen is used, halogens such as fluorine, chlorine, bromine, chlorine fluoride, hydrogen fluoride, hydrogen chloride, and hydrogen bromide are added here. The same effect can be obtained with gas or hydrogen halide. Moreover, the same effect can be obtained when reducing gases such as hydrogen, carbon monoxide, ammonia, and phosphorus are added. The above-mentioned cleaning effect is not limited to the case of a ruthenium film, and the same effect can also be obtained in the case of a ruthenium oxide film, a starved, or starved oxide film. Next, an example of cleaning applied to a C V D device for ruthenium will be described. Figure 12 shows a C VD device showing ruthenium or a ruthenium oxide film. The reaction part for the film formation reaction of this CVD apparatus is composed of a processing chamber 1 2 1, a wafer 1 2 2, a ceramic heater 1 2 3 for heating the wafer, and a film forming gas on the wafer 1 2 2 It is formed by the gas shower head 1 2 4 which is evenly supplied. The piping 1 2 5 for supplying or exhausting the film-forming gas and the cleaning gas and the processing chamber 1 2 1 are heated by a heater 1 2 6 in order to prevent adsorption of reaction products. (Please read the notes on the back before filling this page)-I I --- II ^ · 111111-- Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized according to the Chinese National Standard (CNS) A4 (210 X 297 mm) -20- 517302 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) Through the gas supply piping 1 2 5 and the valve 1 2 7 V, 128v, 129v, 1210v will be used for film formation Gas ru (E t Cp) 2 (but E t CP is an abbreviation for ethylcenelocene (C 2 H 5 C 5 Η 4)) Gas supply supplier 1 2 7 s, 〇2 supplier 1 2 8 s, N 2 feeder 1 2 9 s, and Jie gas supplier 〇3 feeder 1 2 1 0 s are connected to the processing chamber 1 2 1. Further, a conductance valve 1 2 1 1 and an exhaust device 1 2 1 2 for controlling the pressure inside the processing chamber 1 2 1 through the exhaust pipe 1 2 5 are also connected. This device is a cold-wall type device that forms a film by heating the wafer to a temperature of about 300 ° C ~ 750 ° C with a heater 1 2 3 on which the wafer 1 2 2 is placed. In the case of using the aforementioned film-forming gas, the film-forming temperature is set to 300 ° C, for example, the heater temperature is set to 320 ° C, and the film-forming gas is not condensed on the inner wall of the device or in the pipe. Ground, the processing chamber 1 2 1 or piping is also heated to a temperature of about 150 ° C. by a heater 1 2 6. However, due to the decomposition reaction of the film-forming gas, a large amount of unnecessary reaction by-products containing Ru are attached to the inner wall of the processing chamber 1 2 1 and the like. In addition, in order to make the temperature distribution of the wafer uniform and make the heater size larger than the wafer size, although the amount of heat input to the peripheral edge portion of the wafer with large heat radiation is increased, the structure of the heater 1 2 A ruthenium or ruthenium oxide film is also formed in the peripheral portion of 3. As the above-mentioned CVD process is repeated, the adhered matter attached to the inner wall of the processing chamber 1 2 1 or the inner wall of the piping 1 2 5 is peeled off, which is rolled up by the air flow and the like. The size of the paper on the circle 1 2 2 applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -21------------------ ^ ---- ^ ---------. (Please read the notes on the back before filling this page) 517302 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____ Β7__ V. Description of the Invention (19). As a result, the above-mentioned adhered matter becomes a foreign matter, causing defects such as short circuit or disconnection when the device pattern is formed. Therefore, the effect of reducing foreign substances cleaned by using ozone was reviewed in the following manner. (1) Method for forming a ruthenium film First, after a predetermined exhaust is performed in the processing chamber 1 2 1, the wafer 1 2 2 is placed on a heater 1 2 3 and the heater is set to 3 2 0r ' The temperature of the wafer 1 2 2 is maintained in a thermal equilibrium state. At this time, the temperature of the wall of the processing chamber 1 2 1 and the piping 1 2 5 is about 15 0 t. After that, the valves 1 2 7 v and 1 2 8 v were opened, and each of Ru (E t C p) 2 and 〇 2 gas was introduced into the processing chamber 1 2 1 to form a ruthenium film of 0. 1 Å. In addition, the pressure during film formation was adjusted to a predetermined level, and it was adjusted using a conductance valve 1 2 1 1. (2) The number of foreign objects on the wafer 1 2 2 after the film formation by the ozone cleaning method tends to increase when the accumulated film thickness of the film formation process using the same processing chamber exceeds 3 mm. Therefore, the cleaning frequency of the processing chamber 1 2 is that the number of film formations is performed every 30 times. 0 The time that can be used for cleaning is calculated from the output rate of the c V D device and its crop rate, within about one hour. Therefore, one of the examples is to maintain the temperature of the processing chamber 1 2 1 or the piping 1 2 5 with a large thermal capacity as the original temperature. 'Reduce the temperature of the heater 1 2 3 to a temperature that can ensure the etching rate', such as 1 50 0 t. Cleaned by ozone treatment room. Open the valve 1 2 1 0 and supply it through the ozone supplier 1 2 1 0 s. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) · 22------ ^ ---- Order --------- (Please read the notes on the back before filling out this page) 517302 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 Β7 V. Description of the invention (20) Ozone gas and film formation Similarly, the exhaust gas volume is adjusted by the conductance valve. Set the ozone concentration at 5%, the gas flow rate at 10 slm, and the pressure at 100 T 〇rr ° The end point detection of Jie Jie is performed by: installing QMS on the exhaust pipe 1 2 5 The sampling port, as shown in Fig. 13, measures the time variation of the ionic strength of the reaction-produced gas that occurs in the clean room for confirmation. Specifically, the time point when the ionic strength of Ru 0 4 was reduced and the intensity change thereafter became extremely small was set to be clean. In this embodiment, the supply of ozone gas is stopped about 20 minutes after the cleaning is performed. Also, in the case of this embodiment, the time required for the temperature adjustment of the heater 1 2 3, the pressure adjustment in the processing chamber 12 21, cleaning, and the like can be performed in a series of processes within about 1 hour. Regarding the reduction of the cleaning time, as described above, the use of 5% C 1 F3 or 5% CO 'as the gas added to the ozone gas can shorten the time by about 20 to 30%. Next, it is assumed that a series of operations of film formation of ruthenium and ozone cleaning are repeatedly performed, and the shift in the number of foreign objects on the wafer 1 2 2 during the operation is measured. Figure 14 shows the increase / decrease of the number of foreign objects (average 値 when film formation is repeated 20 to 30 times) using an 8-inch wafer as an example. From this result, it is clear that by cleaning the processing chamber, the foreign matter on the wafer can be reduced to an almost initial state. Furthermore, even if the number of foreign substances increases due to subsequent film formation, the number of foreign substances can be reduced again by cleaning again. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) -23- ------------------ ^ ---- Order ---- ----- Line β. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 A7 ___ B7 V. Description of the invention (21) As explained above, the film formation will be implemented at the prescribed stage. Ozone cleaning has learned that it can suppress the occurrence of foreign objects in the processing room for a long time. With this, the film formation rate of ruthenium can be constantly stabilized. Furthermore, the results of the inside of the device after the ozone cleaning of 20 times were visually inspected by SS, and no metal rot etc. of the used components were observed. In this embodiment, although cleaning is performed at about 150 ° C, it is preferable to perform ruthenium etching in ozone at 20 ° C or more and 3 50 ° C or less, and it is desirable that the etching rate of ruthenium is relatively large. 0 ° C or more and 2 0 0 ° C or less, more preferably 40 ° C or more and 180 ° C or less. As described above, according to the present embodiment, foreign matter in the processing chamber can be reduced by ozone gas cleaning, and as a result, the manufacturing yield of the semiconductor device can be improved. In addition, because the plasma can be etched without using a plasma, the so-called purge gas inside the uranium engraving device can be supplied. Compared with the conventional plasma purge method, it is possible to reduce the residue of the adhesion in the processing chamber. Further, the same effect can be obtained by using oxygen halide, nitrogen oxide, oxygen atom, etc. other than ozone as the etching gas, and then introducing the oxygen or nitrogen oxide in advance into the processing chamber by ultraviolet or plasma. In addition, in the gas in which several percent of ozone is added to oxygen and nitrogen, a halogen gas or hydrogen halide such as fluorine, chlorine, bromine, chlorine fluoride, hydrogen fluoride, hydrogen chloride, and hydrogen bromide is added, and hydrogen, carbon monoxide, Reducing gases such as ammonia and phosphorus can also obtain the same effects as those described above. In addition, this is not limited to the case of a ruthenium film, and the same applies to a case of a ruthenium oxide film, a starved, or starved oxide film. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -24------ ^ ---- Order --------- (Please read the precautions on the back first (Fill in this page again) 517302 A7 -------- __ B7 V. Description of Invention (22) Next, in Example 4, an example of cleaning using an etching device for ruthenium will be described. When the etching process is repeatedly performed using an etching device, by-products adhere to and accumulate in the processing chamber by the reaction of the etched film or the photoresist film with the etching gas. This is the same as the case of the C V D device, and it is a factor that reduces the manufacturing yield of the device as a foreign object. Therefore, the effect of reducing foreign substances by an ozone-cleaned etching device was reviewed. (1) Etching (pattern formation) of the ruthenium film First, in a processing chamber where a predetermined exhaust is performed, a wafer patterned with photoresist on the ruthenium film 12 is placed on an electrode, and its temperature is adjusted to 20 ° C. Thereafter, while adjusting the pressure in the processing chamber, 02, C 1 2, and N 2 gases were introduced, and etching was performed. After the etching is completed, the wafer 12 is removed and exhausted from the processing chamber. In this embodiment, the wafer is etched every 50 times by ozone cleaning in the following order. (2) Cleaning method by ozone As in the case of the CVD device, the temperature of the wafer setting electrode during cleaning is about 100 ° C, and cleaning is performed for 15 minutes. Furthermore, the number of foreign objects was measured when a series of processes of measuring the etching and cleaning were repeated 20 times. As a result, as in the case of the CVD apparatus described above, the number of foreign objects in the processing chamber cleaned by gas can be kept at a low level, and the surface of the metal part in the apparatus is not corroded, etc. (visual inspection). Also, the cleaning process temperature conditions or cleaning gas described in this example (please read the precautions on the back before filling this page) ----- ^ ---- Order ----- Intellectual Property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 (210 X 297 mm) -25- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 517302 A7 — B7 V. Description of Invention (23) Ingredients It is not limited to this. For example, as in the case of the c VD device described above, by adding a halogen-based gas or a reducing gas to the gas used, it is possible to improve the cleaning efficiency. As described above, by making the cleaning conditions appropriate, cleaning of the processing chamber in a short time becomes possible. As a result, it not only contributes to the stability of the long-term equipment or the improvement of the equipment productivity, but also improves the equipment products. Manufacturing yield. Although many embodiments according to the present invention have been described, the present invention is not limited thereto, and it goes without saying that various modifications can be made without departing from the spirit of the present invention. Brief Description of Drawings Fig. 1 is a diagram for explaining a vapor pressure curve of a ruthenium compound. Fig. 2 is an explanatory diagram showing the relationship between the free energy difference of the oxidation reaction of ruthenium and the temperature. Fig. 3 is a process diagram illustrating a semiconductor device used in the first embodiment. FIG. 4 is a schematic view of an etching apparatus used in the first embodiment. FIG. 5 is an explanatory diagram showing the relationship between the etching rate of ruthenium and the processing temperature. Fig. 6 is an example of QM S analysis of a reaction product by the reaction of ruthenium and ozone. Fig. 7 is an explanatory diagram showing the relationship between the thermal decomposition of ozone and the residual rate of ozone on a wafer. Figure 8 is a diagram illustrating the reaction mechanism of ruthenium and ozone. FIG. 9 is an explanatory diagram showing a sequence of an etching process in the first embodiment. The size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm) -26- 1 nt ϋ * ^ 1 ί nn 1 II ϋ n ϋ n a-n ϋ a— I ϋ Mem— I (please Read the notes on the back and fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517302 Α7 Β7 V. Description of the invention (24) . Fig. 11 is a diagram for explaining the outline of the ozone cleaning device of the second embodiment. Fig. 12 is a diagram for explaining the cleaning of the CVD device of the third embodiment. Figure 13 is a graph showing the results of Q M S reaction analysis used for the detection of 淸 Jie endpoint. Figures 14 and 4 show the transition of the cleaning of the CVD apparatus and the number of foreign objects in the processing chamber. Component comparison table 4 1: Processing chamber 4 2: Wafer ---------------- l · --- Order --------- (Please read the Please fill in this page again. 4 3: Receiver heater 4 4: Shower head 4 5 S, 4 6 SJ 4 7 s, 4 8 s: Ozone generator 4 5 V, 4 6 V y 4 7 v,丨 4 8 v •• Valve 4 1 0 •• Conductivity valve 4 1 1 •• Vacuum pump 4 1 3 •• Conveying arm This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -27-