201250807 六、發明說明： 【發明所屬之技術領域】 本發明，係與利用氣體群集束對形成於半導體 被處理體之表面的金屬膜進行加工之金屬膜的加工 加工裝置相關。 【先前技術】 超LSI之配線，現在係以銅鑲嵌法來形成。銅 ，係利用光刻技術及乾蝕刻技術於絕緣膜形成圖案 再以銅阻障膜被覆其表面後，將銅鍍塡埋於溝，以 Chemical Mechanical Polishing)硏磨除去不要之 來形成金屬圖案的方法（參照非專利文獻1) » 銅鑲嵌法，需要：將銅阻障膜良好地被覆於微 製程、將銅鍍種膜良好地被覆於銅阻障膜上之製程 鍍良好地塡埋於微細構造之製程，而難以適用於更 圖案。並且，在圖案形成上，因爲CMP製程爲必 用以連結於TSV( Through Silicon Via)之焊墊的 形成製程，使得成本提高。 鑲嵌法以外之金屬膜圖案形成製程之一，係濕 。其係於金屬膜上實施遮罩之圖案化，再以稀鹽酸 蝕刻除去無遮罩之金屬膜部分的手法。然而，因爲 係等向蝕刻金屬，微細構造的話，則無法控制側蝕 難以確保良好之圖案形成。 另一手法’係 RIE( Reactive Ion Etching)法 晶圓等 方法及 鑲嵌法 化溝， CMP ( 上層部 細溝之 、將銅 微細之 要，如 大圖案 蝕刻法 等來濕 該手法 刻量而 。該手 201250807 法，係利用反應性電漿蝕刻未遮罩之金屬部的方法，以 RIE法蝕刻鹵化物之蒸氣壓較高之金屬元素的A1、Ti、Ta 、W等時，已確認可以得到良好的圖案形成（參照非專利 文獻2 )。 然而，以RIE法蝕刻鹵化物之蒸氣壓較低之金屬的 Co、Ni、Cu、Pt、Ru等來實施圖案形成時，爲了使鹵化 金屬氣化來去除並防止再附著於反應容器之壁，必須將基 板及反應容器之壁的溫度保持於高溫。 而且，此種高溫RIE製程時，屬於電漿之活性種的鹵 離子及自由基腐蝕由蝕刻所形成之開口（溝及孔）的側壁 ，而難以保持良好的圖案形狀（參照非專利文獻3 )。並 且，該等RIE法時，電漿所分解之蝕刻液以聚合物及化合 物之形式而以殘渣殘留下來，而經常發生以蝕刻後之濕洗 也難以除去的問題。 另一方面，也有人提出利用使洗淨及蝕刻氣體隔熱膨 脹所發生之氣體群集束來實施洗淨處理及加工處理的方案 (專利文獻1、2)。此時，也可以使上述氣體群集束進行 離子化來加速的方式來實施。而且，上述氣體群集束衝擊 材料表面時，所發生之熱及化學反應也會使表面清淨化或 對材料進行餓刻。 非專利文獻 非專利文獻 1 : D. Edelstein et al，IEDM Technical Digest, IEEE ( 1 997 ). 非專利文獻 2 : Y. Yasuda，Thin Solid Films, Volume 201250807 90, Issue 3, 23 April 1 982, Pages259-270. 非專利文獻 3 : B. J. Howard and C. Steinbruchel， Applied Physics Letters，59 ( 8 )，19p914， ( 1991) · 專利文獻 專利文獻1 :日本特開2009-043975號公報 專利文獻2 :國際公開第201 0/021265 【發明內容】 如上面所述，利用氣體群集束時，可以對矽膜充份實 施蝕刻加工係眾所皆知的事。然而，由如前面所述之Cu 、Co、Pt、Ru等金屬所形成之金屬鹵化物的蒸氣壓相當 低。所以，使如前面所述之氣體群集束衝擊由Cu、Co、 Pt、RU等金屬所形成之金屬鹵化物時，依然有難以保持良 好之圖案形成的問題。 本發明之目的，係提供專注於以上之問題並可有效解 決的方案。本發明，係藉由使用了氧化氣體、錯合氣體、 及稀有氣體之群集束來蝕刻傳統無法以群集束法進行蝕刻 之金屬膜的金屬膜加工方法及加工裝置。 依據本發明之實施方式，提供一種金屬膜加工方法， 係含有：在可真空排氣之處理容器內，使氧化前述金屬膜 之元素來形成氧化物之氧化氣體、與前述氧化物反應來形 成有機金屬錯合物之錯合氣體、以及稀有氣體的混合氣體 隔熱膨脹，來形成氣體群集束的形成步驟；及藉由使前述 氣體群集束衝擊形成於前述被處理體表面之金屬膜，來對 201250807 前述金屬膜進行蝕刻的加工步驟。 依據本發明之其他實施方式，提供一種加工裝 藉由使氣體群集束對形成於被處理體表面之金屬膜 工的金屬膜加工裝置，其具備：可真空排氣之處理 用以保持前述被處理體之保持手段；以及與前述保 相對配置，而且，使前述金屬膜之元素氧化而形成 之氧化氣體、與前述氧化物反應而形成有機金屬錯 錯合氣體、以及稀有氣體之混合氣體，在前述處理 隔熱膨脹而形成氣體群集束之氣體群集束形成手段 述氣體群集束衝擊形成於前述被處理體表面之金屬 前述金屬膜進行蝕刻。 依據本發明，可以藉由利用了氧化氣體、錯合 及稀有氣體之群集束來對金屬膜進行蝕刻加工。 【實施方式】 以下，依據圖式，針對本發明之一實施方式之 加工方法及加工裝置的一例進行詳細說明。第1圖 明之一fl施方式之金屬膜加工裝置之一例的構成圖 施方式時，係以針對金屬膜之銅薄膜施圖案化鈾刻 爲例來進行說明。 如第1圖所示，該加工裝置2，具有特定長度 的處理容器4。該處理容器4，係由鋁、鋁合金、 鋼等耐壓性優良材料所形成。該處理容器2內，由 容器內中央之撇渣板10區分成左右2個之：供設 置，係 進行加 容器： 持手段 氧化物 合物之 容器內 ，使前 膜來對 氣體、 金屬膜 係本發 。本實 加工時 之箱形 或不鏽 設置於 置屬於 -8 - 201250807 被處理體之例如半導體晶圓W之處理空間6、及用以發生 以加工爲目的之後述氣體群集束的束形成空間8。於該撇 渣板10之中央部’形成有只有高直進性之氣體群集束可 通過的氣體撇渣孔12。 該氣體撇渣孔1 2之開口面積非常小’透過該氣體撇 渣孔1 2，上述處理空間6及束形成空間8成爲連通狀態。 而且，於上述處理空間6內，設有用以保持上述半導體晶 圓W之保持手段14。具體而言，該保持手段14，具有以 保持晶圓W爲目的之例如圓板狀的保持台16。該保持台 16立設於上下方向，晶圓W之背面抵接於其中一側面， 而以夾持具18固定晶圓W之周邊部。該保持台16，由設 於處理容器4之天花板部的掃描致動器20所支撐。 具體而言，該掃描致動器20，具有朝下方延伸的支臂 22，上述保持台16裝設固定於該支臂22。該支臂22，可 以分別往圖中之上下方向〔Y方向〕、左右方向〔Z方向 〕、及圖面之垂直方向〔X方向〕（未圖示）移動。朝X 方向及Y方向，只以晶圓W之至少半徑長度進行掃描移 動，藉由該掃描移動，從圖中左側直進之氣體群集束對晶 圓W全面進行照射。 此外，於區隔成上述處理空間6及束形成空間8之處 理容器4的各底部，分別設有排氣口 24、26，於各排氣口 24、26，連接著執行真空吸引之排氣系28。具體而言，該 排氣系28，具有共同連接於上述2個排氣口 24、26之排 氣通路30。而且，於該排氣通路30，從其上游側朝下游 -9 - 201250807 側依序介設著以執行壓力調整爲目的之壓力調整閥 1真空泵34、及第2真空泵36，可進行上述處理容 之全體的壓力調整並維持於高真空狀態。上述第1 34 ’例如，可以使用渦輪分子栗，上述第2真空泵 如，可以使用乾式泵。 其次，於該處理容器4內，以與上述保持台1 之方式配設著氣體群集束形成手段38。具體而言， 群集束形成手段38，具有高速噴射氣體群集之噴 40。該噴射機構40，係由：某種程度大小之容量的 留腔室42、及設於該橫長滯留腔室42之前端側並 方向逐漸擴徑之喇叭狀噴嘴部44所構成，整體而 如，構成爲拉瓦噴嘴。 其次，於該滞留腔室42，連接著以導入氣體群 形成上所必要的各種氣體爲目的之氣體導入通路46 氣體導入通路46，共同地連接著供氧化氣體流通之 體通路48、及供錯合氣體流通之錯合氣體通路50 ，於上述氧化氣體通路4 8，由其上游側朝下游側， 設著如質量流量控制器之氣體用流量控制器52、及 54，在執行高壓力之氧化氣體的流量控制下進行供 處，氧化氣體係使用例如〇2 (氧）。 本實施方式時，係使用在室溫爲液體之錯合劑 ，於上述錯合氣體通路50，係由其上游側朝下游側 介設著如液體用質量流量控制器之流量控制器5 6、 58、及氣化器60。而且，於上述氣化器60，連接 32、第 器4內 真空泵 36，例 6相對 該氣體 射機構 橫長滯 朝噴射 言，例 集束之 。於該 氧化氣 。而且 依序介 開關閥 應。此 。所以 ，依序 開關閥 著以供 -10- 201250807 發揮載體氣體之機能的稀有氣體流通爲目的之稀有氣體通 路62。而且，該稀有氣體通路62，由其上游側朝下游側 依序介設著如質量流量控制器之氣體用流量控制器64、及 開關閥66’在將高壓力之稀有氣體當作載體氣體進行流量 控制下執行供應。 此處，上述錯合劑係使用在室溫下爲液體之六氟乙醯 丙酮（l，l，l，5,5,5-Hexafluoro-2,4-pentanedione : H ( hfac ))’並且，作爲載體氣體之稀有氣體係使用 Ar。上述 液體之錯合劑係以高壓力進行壓送而流通，於氣化器60 氣化而成爲錯合氣體，並在與高壓力之載體氣體（Ar)之 混合狀態朝下游流去。 其次’氧化氣體、錯合氣體、及稀有氣體（載體氣體 )處於混合狀態，在高壓狀態下，由氣體導入通路46被 導入滯留腔室42，並由該前端之噴嘴部44，朝真空狀態 之束形成空間8，藉由隔熱膨脹而形成氣體群集束70。此 時，上述噴射機構40，係以噴嘴部44及氣體撇渣孔12之 開口部的中央位於相同高度之位置而使噴射之氣體群集束 70的中心通過氣體撇渣孔12之方式來設置。此處，上述 氧化氣體，具有使形成於半導體晶圓W表面之金屬膜的 元素氧化而形成氧化物之作用。此外，上述錯合氣體，係 具有與上述氧化物反應而形成有機金屬錯合物之作用。並 且，上述稀有氣體，係具有作爲形成氣體群集時之核的作 用。 而且，此處，係於通路之中途混合氧化氣體及錯合氣 -11 - 201250807 體（包含載體氣體），然而，並未受限於此，也可分別將 該兩種氣體導入滯留腔室42再於滯留腔室42內形成混合 氣體。並且，對於錯合氣體不需要稀有氣體之載體氣體時 ，亦可在通路途中使稀有氣體、與氧化氣體及錯合氣體進 行混合來形成混合氣體，或者，直接將稀有氣體導入滞留 腔室42內再形成混合氣體。 如以上之構成之加工裝置2的全體之動作，例如，係 由電腦等所構成之裝置控制部72來控制，執行該動作之 電腦程式，則記憶於記憶媒體74。該記憶媒體74，例如 ，係由軟碟、CD ( CompactDisc )、硬碟、快閃記憶體、 或DVD等所構成。具體而言，依據來自該裝置控制部72 之指令，執行各種氣體之供應的開始、停止、流量控制、 處理壓力之控制等。 此外，上述裝置控制部72，係具有：裝置控制部72 、及連接由作業員所操作之裝置的使用者介面（未圖示） ，使用者介面，也可以爲作業員以管理裝置爲目的而用以 執行指令之輸出入操作等的鍵盤、或可見化顯示裝置之運 轉狀況的顯示器等。此外，裝置控制部72連接於通訊線 路（未圖示），透過通訊線路對上述裝置控制部72執行 上述各控制之資訊的通信。 <加工方法> 其次，參照第1圖〜第3圖，針對利用以上構成之加 工裝置2所執行之本實施方式的金屬膜加工方法進行說明 -12- 201250807 。第2A圖〜第2C圖，係表示本實施方式之金屬膜加工方 法之一例的製程圖，第3圖係表示銅蝕刻時所發生之反應 衍生物Cu(hfac) 2的蒸氣壓曲線圖。 首先，藉由以夾持具18固定被處理體之半導體晶圓 W，將半導體晶圓W保持於設在處理容器4內之保持手段 14的保持台16上。此時，晶圓W之被加工面係朝向圖之 左側，而以面對氣體群集束形成手段38之狀態配置。參 照將晶圓W表面放大表示之第2A圖〜第2C圖的話，首 先，如第2A圖所示，預先於該晶圓W表面之被加工面， 形成蝕刻之加工對象的金屬膜72，於該金屬膜72之表面 ，形成有圖案化之遮罩74。此處，如前面所述，上述金屬 膜係使用銅（Cxi)，此外，上述遮罩74，係使用由對氣 體群集束具有耐性之材料之例如利用電漿CVD ( Chemical Vapor Deposition)所形成之矽氧化膜（Si02)或矽氮化 膜（Si3N4 ) » 接著，如上面所述，使晶圓W保持於保持台16，密 閉該處理容器4內且驅動排氣系28對處理容器4內實施 真空吸引，使處理空間6內及束形成空間8內成爲高真空 狀態。 其次，驅動氣體群集束形成手段38而產生氣體群集 束70。亦即’氧化氣體、錯合氣體、及稀有氣體分別在高 壓力下流動，並分別在流量控制下供應》錯合氣體之原料 的錯合劑’亦即，H ( hfac )，因爲在室溫下爲液體，在 高壓力及流量控制下被壓送’而於氣化器60氣化成錯合 -13- 201250807 氣體。該錯合氣體，與對氣化器60供應之載體氣體的Ar 氣體（稀有氣體）混合並流動。而且，上述氧化氣體、錯 合氣體、及稀有氣體成爲混合氣體通過氣體導入通路46, 並對噴射機構40之滞留腔室42內進行供應。該混合氣體 成爲高壓狀態，由該混合氣體噴嘴部44朝高真空狀態之 束形成空間8內，利用隔熱膨脹來進行放射或噴射。此時 ，因爲處理容器4內處於高真空狀態，混合氣體隔熱膨脹 而放射，而形成氣體群集束70並對晶圓W進行照射。 該氣體群集束70，擴散之氣體群集在途中爲撇渣板 10所阻隔，只有高直進性之氣體群集束70通過設於撇渣 板10之氣體撇渣孔12，並如第2B圖所示，對晶圓W進 行照射。上述滯留腔室42內之壓力，例如，爲20氣壓程 ft 度，束形成空間8內及處理空間6內之壓力，則爲l〇-3Pa 以上、105Pa以下之壓力。 構成上述氣體群集束70之氣體群集70A，藉由在前 方之噴嘴部44之混合氣體之隔熱膨脹所產生的冷卻，以 稀有氣體之Ar作爲核，使氧化氣體之原子或分子、及錯 合氣體之原子或分子逐漸成爲受到拘束的狀態。亦即，1 個氣體群集70A，例如，係由數個〜數千個原子、或分子 所構成，氧化氣體、錯合氣體、及稀有氣體係以原子等級 或分子等級混合存在之狀態。 上述氣體群集束70，如第2B圖所示，照射於由Cu 所構成之金屬膜72的話，藉由此時之衝擊能量產生部分 之熱。此時’首先’銅及氧化氣體反應而形成氧化物，該 -14- 201250807 氧化物及錯合氣體反應而形成蒸氣壓較高之有機金屬 物。藉由該有機金屬錯合物氣化並排氣，由Cu所構 金屬膜72，如第2B圖及第2C圖所示，被進行蝕刻 以，露出於圖案化之遮罩74的圖案溝74內之金屬膜 藉由氣體群集束之蝕刻而被除去。 此外，藉由以掃描致動器20使保持台16於X方 Y方向進行掃描，可以使氣體群集束70照射晶圓W 面並進行蝕刻。並且，藉由朝Z方向移動保持台16 圓W接近或離開噴射機構40來進行蝕刻。該蝕刻時 、氧化氣體之〇2、及錯合氣體之H( hfac )的反應如 示。 4 C u + Ο 2 ~2 C u 2 〇 ( C u : 1 價） 2Cu + 02— 2CuO ( Cu : 2 價）[Technical Field] The present invention relates to a processing apparatus for a metal film which is processed by a gas cluster to form a metal film formed on a surface of a semiconductor object to be processed. [Prior Art] The wiring of the ultra LSI is now formed by a copper damascene method. Copper is formed by patterning an insulating film by a photolithography technique and a dry etching technique, and then coating the surface with a copper barrier film, then burying the copper plating in the trench and removing it by chemical mechanical polishing to form a metal pattern. (Refer to Non-Patent Document 1) » Copper damascene method requires: a copper barrier film is well coated on a micro-process, and a copper plating film is well coated on a copper barrier film. The process of construction is difficult to apply to more patterns. Further, in the pattern formation, since the CMP process is a process for forming a pad to be bonded to the TSV (Through Silicon Via), the cost is increased. One of the metal film pattern forming processes other than the damascene method is wet. It is a method in which a mask is patterned on a metal film, and the portion of the maskless metal film is removed by etching with dilute hydrochloric acid. However, since the metal is formed in an isotropic manner and the microstructure is fine, it is impossible to control the side etching. It is difficult to ensure good pattern formation. The other method is a method such as RIE (Reactive Ion Etching) method wafer and damascene groove, CMP (the upper part of the fine groove, the copper is fine, such as large pattern etching method, etc. to wet the method. This method of 201250807 is a method of etching a non-masked metal portion by reactive plasma, and it is confirmed that an A1, Ti, Ta, W, etc. of a metal element having a high vapor pressure of a halide is etched by the RIE method. Good pattern formation (see Non-Patent Document 2). However, when patterning is performed by etching a pattern of Co, Ni, Cu, Pt, Ru, etc. of a metal having a low vapor pressure of a halide by RIE, in order to vaporize the halogenated metal In order to remove and prevent reattachment to the wall of the reaction vessel, the temperature of the substrate and the wall of the reaction vessel must be maintained at a high temperature. Moreover, in such a high-temperature RIE process, halide ions and radical corrosion belonging to the active species of the plasma are etched. The side walls of the openings (grooves and holes) are formed, and it is difficult to maintain a good pattern shape (see Non-Patent Document 3). Moreover, in the RIE method, the etching liquid which is decomposed by the plasma is a polymer and a compound. In the form of residue, the residue is often difficult to remove by wet cleaning after etching. On the other hand, it has also been proposed to carry out the cleaning treatment by a gas cluster bundle generated by heat-insulating and expanding the cleaning and etching gas. And a processing method (Patent Documents 1 and 2). In this case, the gas cluster beam may be ionized and accelerated. Further, when the gas cluster beam hits the surface of the material, heat and chemistry occur. The reaction also purifies the surface or hungry the material. Non-Patent Document Non-Patent Document 1: D. Edelstein et al, IEDM Technical Digest, IEEE (1 997). Non-Patent Document 2: Y. Yasuda, Thin Solid Films , Volume 201250807 90, Issue 3, 23 April 1 982, Pages 259-270. Non-Patent Document 3: BJ Howard and C. Steinbruchel, Applied Physics Letters, 59 (8), 19p914, (1991) · Patent Document Patent Document 1: JP-A-2009-043975 PATENT DOCUMENT 2: International Publication No. 201 0/021265 [Disclosed from the Invention] As described above, when a gas cluster is used, the diaphragm can be charged. It is well known to carry out the etching process. However, the vapor pressure of the metal halide formed by a metal such as Cu, Co, Pt or Ru as described above is relatively low. Therefore, the gas group as described above is used. When the cluster impacts a metal halide formed of a metal such as Cu, Co, Pt, or RU, there is still a problem that it is difficult to maintain a good pattern formation. It is an object of the present invention to provide a solution that focuses on the above problems and can be effectively solved. The present invention is a metal film processing method and processing apparatus for etching a metal film which cannot be etched by a cluster beam method by using a cluster of oxidizing gas, a mixed gas, and a rare gas. According to an embodiment of the present invention, there is provided a metal film processing method comprising: oxidizing an element of the metal film to form an oxide oxidizing gas in a vacuum evacuated processing container, and reacting with the oxide to form an organic a step of forming a gas cluster bundle by thermally insulating and expanding a mixed gas of a metal complex and a mixed gas of a rare gas; and a metal film formed on the surface of the object to be processed by impacting the gas cluster beam 201250807 The processing step of etching the foregoing metal film. According to another embodiment of the present invention, there is provided a metal film processing apparatus for processing a metal beam to form a metal film formed on a surface of a workpiece, wherein the vacuum processing is performed to maintain the aforementioned processed And a gas mixture formed by oxidizing an element of the metal film, reacting with the oxide to form an organic metal error-missing gas, and a mixed gas of a rare gas, as described above The gas clustering forming means for forming the gas cluster bundle by the heat insulating expansion means that the gas cluster beam impacts the metal formed on the surface of the object to be processed to etch the metal film. According to the present invention, the metal film can be etched by using a cluster of oxidizing gas, mismatched, and rare gas. [Embodiment] Hereinafter, an example of a processing method and a processing apparatus according to an embodiment of the present invention will be described in detail based on the drawings. Fig. 1 is a view showing a configuration of an example of a metal film processing apparatus according to one embodiment of the present invention, in which a patterned uranium engraving is applied to a copper film of a metal film as an example. As shown in Fig. 1, the processing apparatus 2 has a processing container 4 of a specific length. The processing container 4 is formed of a material having excellent pressure resistance such as aluminum, aluminum alloy, or steel. In the processing container 2, the slag plate 10 in the center of the container is divided into two left and right sides: for installation, the container is placed: the container is placed in the container of the oxide compound, and the front film is applied to the gas or metal film system. This issue. The box shape or the stainless state at the time of the actual processing is set in the processing space 6 of the semiconductor wafer W, which is placed on the object to be processed -8 - 201250807, and the beam forming space 8 for generating a gas cluster bundle to be processed for the purpose of processing. . At the central portion of the slag plate 10, a gas slag hole 12 through which only a high-straight gas cluster is passed is formed. The opening area of the gas slag hole 12 is extremely small. The gas slag hole 12 is transmitted through the gas slag hole 12, and the processing space 6 and the beam forming space 8 are in a communicating state. Further, in the processing space 6, a holding means 14 for holding the semiconductor wafer W is provided. Specifically, the holding means 14 has a holding plate 16 of, for example, a disk shape for the purpose of holding the wafer W. The holding table 16 is erected in the up and down direction, and the back surface of the wafer W abuts against one of the side faces, and the peripheral portion of the wafer W is fixed by the holder 18. The holding table 16 is supported by a scanning actuator 20 provided on the ceiling portion of the processing container 4. Specifically, the scanning actuator 20 has an arm 22 extending downward, and the holding table 16 is attached and fixed to the arm 22. The arms 22 are movable in the upper and lower directions (Y direction), the left and right directions (Z direction), and the vertical direction (X direction) (not shown) of the drawing. In the X direction and the Y direction, scanning movement is performed only by at least the radius length of the wafer W, and by this scanning movement, the gas cluster bundle straight from the left side in the figure illuminates the crystal circle W in full. Further, exhaust ports 24 and 26 are respectively provided at the bottoms of the processing containers 4 partitioning into the processing space 6 and the beam forming space 8, and exhaust ports for performing vacuum suction are connected to the respective exhaust ports 24 and 26. Department 28. Specifically, the exhaust system 28 has an exhaust passage 30 that is commonly connected to the two exhaust ports 24, 26. Further, in the exhaust passage 30, the pressure regulating valve 1 vacuum pump 34 and the second vacuum pump 36 for performing pressure adjustment are sequentially disposed from the upstream side toward the downstream side -9 - 201250807, and the above-described processing capacity can be performed. The entire pressure is adjusted and maintained in a high vacuum state. For the first 34'', for example, a turbol pump can be used, and for the second vacuum pump, for example, a dry pump can be used. Next, a gas clustering beam forming means 38 is disposed in the processing container 4 so as to be in contact with the holding table 1. Specifically, the cluster beam forming means 38 has a spray 40 of a high velocity jet gas cluster. The injection mechanism 40 is composed of a chamber 42 having a capacity of a certain size and a flared nozzle portion 44 provided on the front end side of the horizontally long retention chamber 42 and gradually expanding in diameter. , configured as a lava nozzle. Then, the gas introduction passage 46, the gas introduction passage 46, for the purpose of introducing various gases necessary for the formation of the gas group is connected to the retention chamber 42, and the body passage 48 through which the oxidizing gas flows is connected in common, and the error is supplied. The gas-converting gas passage 50 is provided on the upstream side of the oxidizing gas passage 48, and the gas flow controllers 52 and 54 such as the mass flow controller are disposed to perform high-pressure oxidation. The supply is controlled under the flow control of the gas, and the oxidizing gas system uses, for example, 〇2 (oxygen). In the present embodiment, a liquid-based cross-linking agent is used, and in the above-described misaligned gas passage 50, a flow controller such as a mass flow controller for liquid is disposed downstream from the upstream side to the downstream side. And gasifier 60. Further, in the above-described gasifier 60, the vacuum pump 36 in the third and fourth units is connected 32, and the example 6 is bundled with respect to the gas jet mechanism. In the oxidizing gas. And in turn, the switch valve should be applied. This. Therefore, the in-situ switching valve is provided for the rare gas passage 62 for the purpose of circling the rare gas which functions as a carrier gas. Further, the rare gas passage 62 is provided with a gas flow controller 64 such as a mass flow controller and an on-off valve 66' from the upstream side toward the downstream side in order to treat the noble gas of high pressure as a carrier gas. Supply is performed under flow control. Here, the above-mentioned complexing agent is a hexafluoroacetone (1,1,5,5,5-Hexafluoro-2,4-pentanedione:H(hfac))' which is liquid at room temperature and Ar is used in the rare gas system of the carrier gas. The liquid dissimilaring agent is pumped at a high pressure to flow, and is vaporized in the vaporizer 60 to become a mixed gas, and flows downstream in a state of being mixed with a high-pressure carrier gas (Ar). Next, the 'oxidizing gas, the mixed gas, and the rare gas (carrier gas) are in a mixed state, and are introduced into the retentate chamber 42 by the gas introduction passage 46 in a high pressure state, and the nozzle portion 44 of the front end is in a vacuum state. The beam forming space 8 forms a gas cluster bundle 70 by thermal expansion. At this time, the injection mechanism 40 is disposed such that the center of the nozzle portion 44 and the opening of the gas slag hole 12 are at the same height, and the center of the injected gas cluster bundle 70 is passed through the gas slag hole 12. Here, the oxidizing gas has an action of oxidizing an element of a metal film formed on the surface of the semiconductor wafer W to form an oxide. Further, the above-mentioned miscible gas has an action of reacting with the above oxide to form an organic metal complex. Further, the above-mentioned rare gas has a function as a core when a gas cluster is formed. Further, here, the oxidizing gas and the miscible gas -11 - 201250807 body (including the carrier gas) are mixed in the middle of the passage. However, the present invention is not limited thereto, and the two gases may be separately introduced into the retentate chamber 42. A mixed gas is formed in the retention chamber 42. Further, when a carrier gas of a rare gas is not required for the mixed gas, a rare gas, an oxidizing gas, and a mixed gas may be mixed in the passage to form a mixed gas, or the rare gas may be directly introduced into the retention chamber 42. A mixed gas is formed again. The entire operation of the processing device 2 configured as described above is controlled by, for example, a device control unit 72 composed of a computer or the like, and the computer program for executing the operation is stored in the memory medium 74. The memory medium 74 is composed of, for example, a floppy disk, a CD (Compact Disc), a hard disk, a flash memory, or a DVD. Specifically, the start, the stop of the supply of various gases, the flow rate control, the control of the processing pressure, and the like are performed in accordance with an instruction from the device control unit 72. Further, the device control unit 72 includes a device control unit 72 and a user interface (not shown) that connects the device operated by the operator, and the user interface may be used for the operator to manage the device. A keyboard for performing an input/output operation of a command or the like, or a display for visualizing the operation state of the display device. Further, the device control unit 72 is connected to a communication line (not shown), and communicates the information of the above-described respective controls to the device control unit 72 via the communication line. <Processing Method> Next, a metal film processing method according to the present embodiment executed by the processing device 2 having the above configuration will be described with reference to Figs. 1 to 3, and -12 to 201250807. Figs. 2A to 2C are process diagrams showing an example of a metal film processing method according to the present embodiment, and Fig. 3 is a graph showing a vapor pressure curve of a reaction derivative Cu(hfac) 2 which occurs during copper etching. First, the semiconductor wafer W is held by the holding means 16 of the holding means 14 provided in the processing container 4 by fixing the semiconductor wafer W of the object to be processed by the holder 18. At this time, the processed surface of the wafer W is oriented to the left side of the figure, and is disposed in a state of facing the gas clustering beam forming means 38. Referring to FIG. 2A to FIG. 2C showing the surface of the wafer W in an enlarged manner, first, as shown in FIG. 2A, a metal film 72 to be processed is formed in advance on the surface to be processed of the surface of the wafer W. A patterned mask 74 is formed on the surface of the metal film 72. Here, as described above, the metal film is made of copper (Cxi), and the mask 74 is formed of, for example, a chemical vapor CVD (Chemical Vapor Deposition) using a material resistant to a gas cluster.矽Oxide film (SiO 2 ) or 矽 nitride film (Si 3 N 4 ) » Next, as described above, the wafer W is held in the holding stage 16 , the inside of the processing container 4 is sealed, and the exhaust system 28 is driven into the processing container 4 . The vacuum suction causes the inside of the processing space 6 and the inside of the beam forming space 8 to be in a high vacuum state. Next, the gas clustering means 38 is driven to generate a gas cluster bundle 70. That is, 'oxidizing gas, mismatched gas, and rare gas flow under high pressure, respectively, and supply the wrong agent of the raw material of the wrong gas under flow control, that is, H (hfac), because at room temperature It is a liquid, which is pumped under high pressure and flow control' and is vaporized in gasifier 60 into a miscible -13 - 201250807 gas. The mixed gas is mixed with and flows with Ar gas (rare gas) of the carrier gas supplied from the gasifier 60. Further, the oxidizing gas, the staggered gas, and the rare gas pass through the gas introduction passage 46 as a mixed gas, and are supplied into the retentate chamber 42 of the injection mechanism 40. The mixed gas is in a high pressure state, and the mixed gas nozzle portion 44 is formed into a space 8 in a high vacuum state, and is radiated or ejected by thermal expansion. At this time, since the inside of the processing container 4 is in a high vacuum state, the mixed gas is thermally inflated and radiated, and the gas cluster bundle 70 is formed and the wafer W is irradiated. The gas cluster bundle 70, the diffused gas cluster is blocked by the skim plate 10 on the way, and only the highly straightforward gas cluster bundle 70 passes through the gas skim hole 12 provided in the skim plate 10, and as shown in FIG. 2B The wafer W is irradiated. The pressure in the retention chamber 42 is, for example, 20 rpm, and the pressure in the beam forming space 8 and the processing space 6 is a pressure of l 〇 -3 Pa or more and 105 Pa or less. The gas cluster 70A constituting the gas cluster bundle 70 is cooled by the thermal expansion of the mixed gas of the nozzle portion 44 in the front, and the atom of the oxidizing gas or the molecule is misaligned by using Ar as a core of the rare gas. The atoms or molecules of the gas gradually become constrained. That is, one gas cluster 70A is composed of, for example, several to several thousand atoms or molecules, and the oxidizing gas, the mixed gas, and the rare gas system are mixed in an atomic level or a molecular level. As shown in Fig. 2B, the gas cluster bundle 70 is irradiated with a metal film 72 made of Cu, and a part of the heat is generated by the impact energy at this time. At this time, 'first' copper reacts with the oxidizing gas to form an oxide, and the -14-201250807 oxide reacts with the mixed gas to form an organic metal having a high vapor pressure. By vaporizing and venting the organometallic complex, the Cu-formed metal film 72 is etched as shown in FIGS. 2B and 2C to be exposed to the patterned trench 74 of the patterned mask 74. The inner metal film is removed by etching of a gas cluster. Further, by scanning the holding stage 16 in the X-direction Y by the scanning actuator 20, the gas cluster beam 70 can be irradiated onto the wafer W surface and etched. Further, etching is performed by moving the holding table 16 in the Z direction to the circle W to approach or leave the ejection mechanism 40. The reaction at the time of etching, enthalpy 2 of the oxidizing gas, and H (hfac) of the mixed gas is as shown. 4 C u + Ο 2 ~2 C u 2 〇 ( C u : 1 valence) 2Cu + 02— 2CuO ( Cu : 2 valence)
Cu2〇 + 2H ( hfac ) -^-Cu + Cu ( hfac) 2 个 +H2〇 个 CuO + 2H ( hfac) -> Cu ( hfac) 2 个 +H2〇 个 此處，箭頭t係表示成爲氣體並飛散。以反應衍 方式形成之有機金屬錯合物的錯合物Cu( hfac ) 2， 蒸氣壓相對較高而容易昇華去除。此處，未氧化之銅 要至少不是在26 5 °C以上，就不會與H (hfac)產生 ，然而，如上面所述，氧化成1價或2價之銅，因 1 50 °C程度即容易與H ( hfac )產生反應，以氣體群 70之衝擊能量容易使局部成爲150°C以上，藉此，可 蒸氣壓較局，換言之容易昇華的Cu( hfac) 2錯合物 機金屬錯合物）。 錯合 成之 。是 72， 向及 之全 使晶 之銅 下所 生物 因爲 ，只 反應 爲在 集束 形成 (有 -15- 201250807 該錯合物，如上面所述，因爲蒸氣壓較高，即使未將 晶圓W本身加熱成高溫也容易昇華除去。第3圖係表示 錯合物Cu ( hfac) 2之蒸氣壓曲線，例如，溫度150°C程 度時，蒸氣壓爲10〇Torr程度。所以，氣體群集束70之 衝擊能量被轉換成熱能量，以微觀而言，容易成爲150°C 程度之溫度，而且，處理空間6內之處理壓力，例如，因 爲低於lOOTorr，可知CU(hfac) 2可容易昇華除去》 此外，如上面所述，氣體群集束70在開始衝擊Cu之 金屬膜72時，氧化氣體之〇2在其衝擊面與Cu之氧化反 應幾乎被消耗用完，因爲衝擊面而漫射於周圍之分子中， 幾乎不含氧。假設，即使存在著未反應之02，因爲二次 漫射也失去運動能量，即使衝擊於側壁，也不會產生氧化 反應。所以，漫射分子產生2次蝕刻的機率非常小，側蝕 刻獲得抑制，結果，可以使金屬蝕刻溝之側壁保持平滑形 狀。 此時，尤其是，藉由將有助於銅之氧化的氧化氣體量 設定成少於錯合氣體之量，可以消除過剩氧化氣體，而可 進一步抑制上述側蝕刻之發生。爲了充份發揮該側飩刻之 抑制效果，以將錯合氣體之量設定成氧化氣體量之5倍以 上的大小爲佳。尤其是，藉由適度控制上述氧化氣體量及 錯合氣體量之比，也可調整且抑制上述側蝕刻之發生量。 並且，稀有氣體之量以較少爲佳，例如，氧化氣體之1/10 程度之量即足夠，然而，其流量並無特別限制。 是以，本實施方式時，因爲係使例如由銅所構成之金 -16- 201250807 屬膜72之元素氧化來形成氧化物之氧化氣體、例如使〇2 及上述氧化物錯合來形成有機金屬錯合物之錯合氣體、以 及例如H ( hfac )與稀有氣體的混合氣體進行隔熱膨脹而 形成氣體群集束70,使上述氣體群集束衝擊上述被處理體 ，例如半導體晶圓W之金屬膜來對上述金屬膜進行蝕刻 ，故可對傳統之群集束法無法蝕刻的金屬膜，藉由利用了 氧化氣體、錯合氣體、及稀有氣體之群集束來進行蝕刻加 工。 <變形例> 其次，針對本發明之變形例的加工裝置進行說明。在 前面之實施方式，係使氣體群集束形成手段38所形成之 氣體群集束70直接衝擊半導體晶圓W，然而，並未受限 於此，也可於途中使該氣體群集束70離子化並且進一步 進行加速再衝擊晶圓。此種加工裝置之變形例，如第4圖 所示。 第4圖，係本發明之變形例之加工裝置的一例圖。此 外，第4圖中，與第1圖中所示之構成部分相同的構成部 分，賦予相同參照符號並省略其說明。如第4圖所示，在 該加速裝置，於處理容器4之處理空間6側，設有平行於 撇渣板10之區隔壁80,於該區隔壁80及上述撇渣板10 之間，形成離子化空間82。 其次，於該區隔壁80之中央部，以上述撇渣板1〇之 氣體撇渣孔12與噴射機構40之噴嘴部44位於直線上的 -17- 201250807 方式，形成小孔徑之照射孔84，氣體群集束70通過該處 。而且，於區隔該離子化空間82之處理容器4的底部， 也形成有排氣口 86，該排氣口 86連接於排氣系28之排氣 通路30，可以對離子化空間82內進行真空吸引。 其次，於離子化空間82內，設有對應氣體群集束70 通過之路徑的離子化器88，通過該離子化器88內之氣體 群集束70被離子化。該離子化器88，例如，可以使用具 有釋放以離子化爲目的之熱電子的白熾燈（未圖示）之電 子衝搫離子化器。 於該離子化器88之下游側的路徑，設有用以對上述 離子化之氣體群集束70進行加速的加速電極部90。該加 速電極部90，具有沿著氣體群集束70之進行方向並列配 設的複數組環狀電極92。而且，於該複數組電極92之間 ，連接加速電源（未圖示）來施加束加速用之高電壓。 依據該變形，不但可發揮與前面實施方式相同之作用 效果，因爲以加速電極部90對離子化器88所離子化之氣 體群集束70進行加速並衝擊晶圓W，如此一來可以對應 而更有效率地實施金屬膜之蝕刻加工。 如以上所述，依據上述實施方式及變形例之金屬膜加 工方法及加工裝置，可以發揮如下所示之優良作用效果。 因爲係非電漿製程，不會有鹵自由基或離子對側壁表 面之腐蝕》是以，相較於RIE法，可以得到良好之蝕刻形 狀。同樣地，由電漿活化之蝕刻氣體，不會聚合物化而堆 積於遮罩表面及蝕刻側壁。所以，蝕刻後之加工基板之洗 18- 201250807 淨製程被大幅簡化。 因爲由被導入之氣體形成高蒸氣 並進行排氣，可以大幅降低處理容器 。所以，可以減少裝置處理容器之內 裝置之高使用效率。 對形成於被處理體表面之金屬膜 使：使金屬膜之元素氧化而形成氧化 述氧化物反應而形成有機金屬錯合物 氣體之混合氣體，進行隔熱膨脹來形 由使上述氣體群集束衝擊上述被處理 述金屬膜，可以藉由利用了氧化氣體 氣體之群集束來對傳統之群集束法無 蝕刻加工。 以上，係參照附錄圖式來針對本 進行詳細說明，然而，本發明並未受 爲具有本發明所屬技術分野之一般知 利範圍所記載之技術思想範疇，當然 或修正例，該等也當然地屬於本發明 例如’以上之實施方式時，係以 體時爲例來進行說明，然而，本發明 氣體可以使用從由o2、h2o、及h2< 擇之1種以上的材料。 此外’以上之實施方式時，係以 使用有機酸之1的H(hfac)時爲例 壓之有機金屬錯合物 側壁之衍生物附著量 壁洗淨次數，而保持 進行加工時，因爲係 物之氧化氣體、與上 之錯合氣體、及稀有 成氣體群集束，並藉 體之金屬膜來鈾刻上 、錯合氣體、及稀有 法蝕刻之金屬膜進行 發明之良好實施方式 限於該等實例。只要 識者的話，在申請專 可以想到各種變更例 之技術範園。 氧化氣體使用〇2氣 並未受限於此，氧化 32所構成之群組所選 錯合氣體（錯合劑） I來進行說明，然而， -19- 201250807 本發明並未受限於此，錯合氣體可以使用從由乙醯丙酮、 /、氟乙醯丙酮（l，l，l，5,5,5-Hexafluoro-2,4-pentanedione :H ( hfac))、三氟乙酸（ trifluoroaceticacid : TFA)、 蟻酸、醋酸、丙酸、酪酸、及吉草酸所構成之群組所選擇 之1種以上的材料。 此外’以上之實施方式時，係以稀有氣體使用Ar時 爲例來進行說明，然而，本發明並未受限於此，也可以使 用He、Ne、Kr、Xe等之其他稀有氣體。而且，以上之實 施方式時，係以被蝕刻之金屬膜72的材料爲銅來進行蝕 刻時爲例’實施說明，然而，本發明並未受限於此，對金 屬膜72爲從由Cu、Co、Ni、Pt、及Ru所構成之群組所 選擇之1種材料進行蝕刻時，也可適用本發明。 此外’在上述實施方式，係以被處理體爲半導體晶圓 之例來進行說明，然而，於本發明之半導體晶圓，也包含 矽基板、GaAs、SiC、GaN等之化合物半導體基板，而且 ，本發明並未受限於該等基板，也可適用於液晶顯示裝置 用玻璃基板及陶瓷基板等。 本國際專利申請，依據2011年1月25日提出申請之 日本國特許出願20 1 1 -0 1 3 3 1 3號來主張優先權，其全部內 容皆援用於本國際專利申請》 【圖式簡單說明】 第1圖係表示本發明之一實施方式之金屬膜加工裝置 之一例的構成圖。 -20- 201250807 第2A圖係表示本發明之一實施方式之金屬膜加工方 法之一例的製程圖。 第2B圖係表示本發明之一實施方式之金屬膜加工方 法之一例的製程圖。 第2C圖係表示本發明之一實施方式之金屬膜加工方 法之一例的製程圖。 第3圖係表示蝕刻銅時所發生之反應衍生物Cu ( hfac )2之蒸氣壓曲線圖》 第4圖係表示本發明之一實施方式之加工裝置的變形 例圖。 【主要元件符號說明】 2 :加工裝置 4 :處理容器 14 :保持手段 1 6 :保持台 28 :排氣系 38:氣體群集束形成手段 40 :噴射機構 42 :貯留腔 44 :噴嘴部 48 :氧化氣體通路 50 :錯合氣體通路 60 :氣化器 -21 - 201250807 62 :稀有氣體通路 70 :氣體群集束 70A :氣體群集 72 :金屬膜 74 :遮罩 W:半導體晶圓（被處理體） -22Cu2〇+ 2H ( hfac ) -^-Cu + Cu ( hfac) 2 + H 2 Cu CuO + 2H ( hfac ) - > Cu ( hfac ) 2 + H 2 〇 here, arrow t means gas And scattered. The complex Cu( hfac ) 2 of the organometallic complex formed by the reaction diffraction method has a relatively high vapor pressure and is easily removed by sublimation. Here, the unoxidized copper should not be produced with H (hfac) at least not above 26 5 ° C. However, as described above, it is oxidized to monovalent or divalent copper due to the degree of 1 50 °C. That is, it is easy to react with H (hfac), and the impact energy of the gas group 70 is likely to be locally 150 ° C or higher, whereby the vapor pressure can be compared with the local, in other words, the Cu( hfac) 2 complex metal which is easy to sublimate Compound). Wrong into it. It is 72, the total of the crystals under the copper, because only the reaction is formed in the bundle (there are -15-201250807 the complex, as described above, because the vapor pressure is higher, even if the wafer W is not It is easy to sublimate and remove by heating itself to a high temperature. Fig. 3 shows the vapor pressure curve of the complex compound Cu (hfac) 2, for example, at a temperature of about 150 ° C, the vapor pressure is about 10 Torr. Therefore, the gas cluster bundle 70 The impact energy is converted into thermal energy, and at a microscopic level, it is easy to become a temperature of 150 ° C, and the processing pressure in the processing space 6, for example, because it is lower than 100 Torr, it can be known that CU (hfac) 2 can be easily sublimated. Further, as described above, when the gas cluster bundle 70 starts to impinge on the metal film 72 of Cu, the oxidizing gas 〇2 is almost consumed by the oxidation reaction of the impact surface with Cu, and is diffused around the surface due to the impact surface. In the numerator, almost no oxygen is contained. It is assumed that even if there is unreacted 02, the kinetic energy is lost because of the second diffusion, and even if it hits the side wall, no oxidation reaction occurs. Therefore, the diffusion molecule produces two etchings. The probability of the etching is very small, and the side etching is suppressed, and as a result, the side wall of the metal etching groove can be kept in a smooth shape. At this time, in particular, the amount of the oxidizing gas contributing to the oxidation of copper is set to be less than that of the mixed gas. The amount of the excess oxidizing gas can be eliminated, and the occurrence of the side etching can be further suppressed. In order to sufficiently exert the effect of suppressing the side etching, it is preferable to set the amount of the mixed gas to be 5 times or more the amount of the oxidizing gas. In particular, by appropriately controlling the ratio of the amount of the oxidizing gas and the amount of the mixed gas, the amount of occurrence of the side etching can be adjusted and suppressed. Further, the amount of the rare gas is preferably less, for example, 1 of the oxidizing gas. The amount of /10 is sufficient, however, the flow rate thereof is not particularly limited. Therefore, in the present embodiment, the oxide of the film of the gold film 16-201250807, which is composed of, for example, copper is formed to form an oxide. An oxidizing gas, for example, a misaligned gas in which ruthenium 2 and the above oxide are combined to form an organic metal complex, and a mixed gas such as H (hfac) and a rare gas is thermally inflated. The gas cluster bundle 70 is formed, and the gas cluster beam is caused to impinge on the metal object of the object to be processed, for example, the semiconductor wafer W, to etch the metal film, so that the metal film which cannot be etched by the conventional clustering method can be utilized. The etching process of the oxidizing gas, the mixed gas, and the rare gas is performed. <Modification> Next, a processing apparatus according to a modification of the present invention will be described. In the foregoing embodiment, the gas cluster is bundled. The gas cluster bundle 70 formed by the forming means 38 directly impinges on the semiconductor wafer W. However, it is not limited thereto, and the gas cluster bundle 70 may be ionized on the way and further accelerated to impact the wafer. A modification of such a processing apparatus is shown in Fig. 4. Fig. 4 is a view showing an example of a processing apparatus according to a modification of the present invention. In the fourth embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted. As shown in Fig. 4, in the acceleration device, a partition wall 80 parallel to the slag plate 10 is provided on the processing space 6 side of the processing container 4, and is formed between the partition wall 80 and the slag plate 10 in the region. Ionization space 82. Next, in the central portion of the partition wall 80 of the area, a small aperture illumination hole 84 is formed by a method in which the gas slag hole 12 of the slag plate 1 and the nozzle portion 44 of the injection mechanism 40 are located on a straight line, -17-201250807, The gas cluster bundle 70 passes therethrough. Further, an exhaust port 86 is formed at the bottom of the processing container 4 partitioning the ionization space 82, and the exhaust port 86 is connected to the exhaust passage 30 of the exhaust system 28, and can be performed in the ionization space 82. Vacuum suction. Next, in the ionization space 82, an ionizer 88 corresponding to the path through which the gas cluster bundle 70 passes is provided, and the gas cluster bundle 70 in the ionizer 88 is ionized. For the ionizer 88, for example, an electron pumping ionizer having an incandescent lamp (not shown) for releasing hot electrons for ionization can be used. An accelerating electrode portion 90 for accelerating the ionized gas cluster bundle 70 is provided on a path on the downstream side of the ionizer 88. The accelerating electrode portion 90 has a plurality of array annular electrodes 92 arranged in parallel along the direction in which the gas clusters 70 are conducted. Further, an acceleration power source (not shown) is connected between the plurality of array electrodes 92 to apply a high voltage for beam acceleration. According to this modification, not only the same operational effects as those of the above-described embodiment can be exhibited, but the gas cluster bundle 70 ionized by the ionizer 88 is accelerated by the accelerating electrode portion 90 and impacts the wafer W, so that it can be correspondingly The etching process of the metal film is efficiently performed. As described above, according to the metal film processing method and the processing apparatus of the above-described embodiments and modifications, the following advantageous effects can be exhibited. Because it is a non-plasma process, there is no halogen radical or ion corrosion on the sidewall surface. Therefore, a good etched shape can be obtained compared to the RIE method. Similarly, the plasma-activated etching gas is not polymerized and accumulates on the mask surface and etches the sidewalls. Therefore, the processing of the processed substrate after etching 18-201250807 net process is greatly simplified. Since the introduced gas forms high vapor and is vented, the processing container can be greatly reduced. Therefore, it is possible to reduce the high efficiency of use of the device within the device processing container. The metal film formed on the surface of the object to be processed is formed by oxidizing the element of the metal film to form a mixed gas of the oxide compound oxide to form an organic metal complex gas, and performing thermal expansion and expansion to cause the gas cluster to be shocked. The metal film to be processed described above can be processed without etching by a conventional clustering method by using a cluster of oxidizing gas gases. The above is a detailed description of the present invention with reference to the appended drawings. However, the present invention is not intended to be limited to the technical scope of the present invention. In the present invention, for example, the above embodiment is described by taking the body time as an example. However, the gas of the present invention may be one or more selected from the group consisting of o2, h2o, and h2. In addition, in the above embodiment, when the H(hfac) of the organic acid 1 is used, the number of times of the deposition of the amount of the derivative of the side wall of the organometallic complex which is exemplified is maintained, and the process is maintained because the compound is used. Good embodiments of the invention are exemplified by the oxidizing gas, the mismatched gas, and the rare gas-forming cluster, and the metal film of the uranium engraved, the mismatched gas, and the rare-etched metal film. . As long as you know the person, you can apply for a variety of examples of changes in the technology. The use of the oxidizing gas in the oxidizing gas is not limited thereto, and the oxidized gas 32 is selected from the group of the selected gas (coupling agent) I. However, the present invention is not limited thereto, and the present invention is not limited thereto. The gas can be used from acetamidine, /, fluoroacetone (1, 1, 1, 5, 5, 5-Hexafluoro-2, 4-pentanedione: H (hfac)), trifluoroacetic acid (TFA) And one or more materials selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and geishic acid. Further, in the above embodiment, the case where Ar is used as a rare gas is taken as an example. However, the present invention is not limited thereto, and other rare gases such as He, Ne, Kr, and Xe may be used. Further, in the above embodiment, the etching is performed by using the material of the etched metal film 72 as copper as an example. However, the present invention is not limited thereto, and the metal film 72 is made of Cu, The present invention is also applicable to etching of a material selected from the group consisting of Co, Ni, Pt, and Ru. In addition, the above-described embodiment is described as an example in which the object to be processed is a semiconductor wafer. However, the semiconductor wafer of the present invention also includes a germanium substrate, a compound semiconductor substrate such as GaAs, SiC, or GaN, and The present invention is not limited to such substrates, and can be applied to a glass substrate for a liquid crystal display device, a ceramic substrate, or the like. This international patent application claims priority based on the Japanese privileged offer 20 1 1 -0 1 3 3 1 3 filed on January 25, 2011, the entire contents of which are applied to this international patent application. Description of the Drawings Fig. 1 is a configuration diagram showing an example of a metal film processing apparatus according to an embodiment of the present invention. -20-201250807 Fig. 2A is a process diagram showing an example of a metal film processing method according to an embodiment of the present invention. Fig. 2B is a process diagram showing an example of a metal film processing method according to an embodiment of the present invention. Fig. 2C is a process diagram showing an example of a metal film processing method according to an embodiment of the present invention. Fig. 3 is a graph showing a vapor pressure curve of a reaction derivative Cu (hfac) 2 which occurs when copper is etched. Fig. 4 is a view showing a modification of the processing apparatus according to an embodiment of the present invention. [Description of main component symbols] 2: Processing apparatus 4: Processing container 14: Holding means 1 6 : Holding stage 28: Exhaust system 38: Gas clustering means 40: Injection mechanism 42: Storage chamber 44: Nozzle portion 48: Oxidation Gas passage 50: misaligned gas passage 60: gasifier-21 - 201250807 62: rare gas passage 70: gas cluster bundle 70A: gas cluster 72: metal film 74: mask W: semiconductor wafer (subject to be processed) - twenty two