201220391 六、發明說明： 【發明所屬之技術領域】 本發明係關於—種對非晶石夕等切物進行㈣之裝置。 【先前技術】 公知有例如—面使平板顯示器用<玻璃&板等被處理物 相對喷嘴於搬送方向上進行相對移動，—面將處理氣體自 喷嘴喷附於被處理物，對被處理物之表面膜進行蝕刻處理 之蝕刻裝置（參照專利文獻卜2等一般而言，此種喷嘴之 前端面（與被處理物對向之面）成為具有某種程度之面積之 平面。藉由處理氣體紐暫停留於喷嘴之前端面與被處理物 之間而使處理反應充分地進行。於專利文獻丨、2之喷嘴中， 於被處理物之搬送方向上並列地形成有例如3個（複數個）喷 出孔。夾持著各噴出孔於搬送方向之兩側形成有一對吸入 孔。各吸入孔之下端之開口與喷出孔之下端之開口係於上 述搬送方向相互間隔。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2009-129996號公報 [專利文獻2]曰本專利特開2009-1：29998號公報 【發明内容】 [發明所欲解決之問題] 如圖14所示，發明者係使用與專利文獻i、2中記載情況 大致相同結構之噴嘴5 ’進行非晶矽之蝕刻處理。嘴嘴5之 前端面5e之沿搬送方向（圖14之左右方向）之尺寸為3〇〇 158969.doc 201220391 mm，喷嘴前端面5e之與搬送方向正交之寬度方向（圖丨斗之 與紙面正父之方向）之尺寸為640 mm。3個喷出孔5a、5a、 5&之間距為100 mm，各喷出孔53與吸入孔讣之間隔為乃 mm。各喷出孔5a及吸入孔5b係於寬度方向上延伸之狹缝 狀。一面藉由滾輪運送機6於搬送方向上搬送覆膜有非晶矽 之玻璃基板9，一面將含有HF及〇3之處理氣體自3個喷出孔 5a、5a、5a喷出。如此般，於玻璃基板9之表面上，在搬送 方向上以100 mm之間距形成有複數個分別於寬度方向上延 伸之條紋狀之處理斑。 因此，如圖15所示，噴出孔5a係利用僅1個喷嘴5X同樣地 進行非晶矽之蝕刻處理。該喷嘴5X之前端面5e之沿搬送方 向（圖15之左右方向）之尺寸為22 mm，且於其正中央部設置 有1個噴出孔5a。噴嘴5X之寬度方向（圖15之與紙面正交之 方向）之尺寸及噴出孔5a於寬度方向上延伸之狹縫狀之點 與上述喷嘴5(圖14)相同。如此般，並未形成上述條紋狀之 處理斑。另一方面，基板9之行進方向之前端部及後端部中 之钱刻處理量與中央部相比下降。 進而’如圖16所示，於供基板9搬送之高度之略下方配置 有與上述噴嘴5X對向之平坦之整流板7，且進行非晶矽之蝕 刻處理。整流板7之沿搬送方向（圖16之左右方向）之尺寸為 63 mm’整流板7之寬度方向（圖16之與紙面正交之方向）之 尺寸與喷嘴5X相同。如此般，基板9之行進方向之前後端部 與中央部之蝕刻處理量之差得到緩和’然而，於行進方向 之前端部’蝕刻處理量變大，於行進方向之後端部，蝕刻 158969.doc 201220391 處理量變小。 自喷嘴5X之噴出流速為〇 4 m/s，雷諾數為〇 〇7。因此， 可認為新喷出之處理氣體並無足夠擠出先喷出之處理完畢 之氣體之程度之衝力。因此，處理完畢之氣體滯留於噴嘴 前端面與基板9之間，使新喷出之處理氣體中之反應成分 濃度降低，其結果’可認為會招致基板之表面上之钱刻處 理置之不均^—。 本發明係基於上述見解而完成者，其目的在於於大氣壓 附近下對非晶石夕等含石夕物進行敍刻時提高姓刻處理之均一 性。 [解決問題之技術手段] p為達成上述目的，本發明係_種#刻裝置，其係於大氣 壓附近下使a有氟系反應成分之處理氣體接觸於含有含矽 物之被處理基板，對上述含矽物進行蝕刻者，其特徵在於 包括： 支樓部’其係於虛擬之平面上支樓上述被處理基板； 喷嘴’其係具有嗔出上述處理氣體之喷出孔，且於上述 虛擬平面之寬度方向上延伸；及 搬运機構，其係使上述被處理基板相對上述喷嘴於沿著 述虛擬平面且與上述寬度方向正交之搬送方向上進行相 對移動； 上述喷嘴係包含呈極細(上述搬送方向之尺寸極小)且於 上述寬度方向上延伸之前端緣、及於上述搬送方向之兩側 形成S且隨著#近上述前端緣而相互接近之傾斜側面， 158969.doc 201220391 與上述寬度方向正交之剖面係朝向上述虛擬平面變尖，上 述喷出孔係分佈於上述寬度方向上且於上述前端緣開口， 於上述前端緣與上述虛擬平面之間畫分出反應部位，於上 述一對傾斜側面與上述虛擬平面之間，畫分出隨著沿上述 搬送方向背離上述反應部位，於與上述虛擬平面正交之方 向上擴寬之擴散空間。 根據上述特徵構成，可提高含矽物之蝕刻處理之均一 性。根據發明者之實驗’即便複數個喷嘴排列於搬送方向 上’亦可防止於被處理基板之表面上形成條紋狀之處理斑 (參照下述之實施例1)。可認為其原因如下。即，處理氣體 自噴出孔噴出’於反應部位中與被處理基板接觸。藉由該 接觸而引起含矽物之蝕刻反應。於反應部位之上述搬送方 向之兩側分別連接有擴散空間。處理氣體於反應部位中進 行上述接觸後，立即朝向擴散空間擴散。由於擴散空間隨 著背離反應部位而擴寬’故幾乎不產生擴散阻力。因此， 處理氣體之喷出流速即便較小，亦可藉由新喷出之氣流而 確實將先噴出之處理氣體自反應部位擠出。因此，於反應 部位中，始終使新鮮之處理氣體與被處理基板接觸。因此， 可防止反應部位中處理氣體中之反應成分之濃度下降。上 述蝕刻反應幾乎僅局部性地產生於較狹窄之反應部位上。 反應部位中之局部之飯刻速率係無論於被處理基板之行進 方向之前端部位於反應部位内時、或者被處理基板之中央 部位於反應部位内時、或者被處理基板之行進方向之後端 位於反應部位内時均為大致相同。由於擴散空間中處理 158969.doc 201220391 氣體充分擴散，反應成分濃度大幅度下降，故幾乎不產生 蝕刻反應。因此，可對被處理基板之整體大致均—地進行 蝕刻處理。其結果，可認為即便複數個喷嘴排列於搬送方 向上，亦可防止或抑制於被處理基板之表面形成分別沿寬 度方向延伸之條紋狀之處理斑。 上述喷出孔中之上述處理氣體之平均喷出流速較佳為 〇.1 m/s〜1·〇 m/s，更佳為〇 2 m/s〜〇·6 m/s。可藉由將處理氣 體之喷出流速抑制為較小，而防止處理槽内之氣流擾動。 即便喷出流速較小’亦可充分確保蝕刻速率。且，上述擴 散阻力之降低效果與處理槽内之氣流之擾動防止效果可結 合地充分確保處理之均一性。此處，上述平均噴出流速係 藉由將喷出流量除以喷出孔之剖面面積而求得。 於上述喷嘴處形成有連接於空氣抽吸機構之吸入孔，上 述吸入孔亦可與上述喷出孔相接且於上述前端緣開口。 於進行蝕刻處理時，與處理氣體之喷出併行地藉由氣體 抽吸機構將上述前端緣之吸入孔之開口附近之氣體乃部『生 地吸入至吸入孔内。因此’處理氣體自喷出孔喷出接觸於 被處理基板後立即被吸入至吸入孔。因此，可進一步確實 防止處理完畢之氣體滞留於反應部位，從而可進一步確實 防止反應部位中之反應成分之濃度下降。進而，無需依賴 於被處理基板之行進方向之位置便可進—步確實地使反應 部位内之處理氣體之流速或流向等流動狀態均衡。藉此， 可進一步提高蝕刻處理之均一性。 以沿著上述虛擬平面之方式設置隔著上述虛擬平面與上 158969.doc 201220391 述噴嘴對向之整流板，上述整流板較佳為自上述一對傾斜 側面延伸至上述搬送方向之兩侧。藉此，即便上述虛擬平 面為虛擬之平面’亦可使處理氣體朝向擴散空間擴散之流 動狀態保持大致固定而不依賴於被處理基板之行進位置。 進而’可確實地使反應部位内之處理氣流之狀態保持大致 固定而不依賴於被處理基板之行進位置。藉此，可進一步 提向触刻處理之均一性。 較佳為’更包括將上述處理氣體供給至上述噴嘴之處理 氣體供給部，上述處理氣體供給部包含包括於彼此之間在 大氣壓附近下產生放電之一對電極之電漿產生部，且藉由 將含有含氟成分及含氫添加成分之原料氣體導入至上述一 對電極間之空間進行電漿化而產生上述氟系反應成分。 作為含氟成分，除了可列舉cf4、c2f4、c2f6、c3f8等 PFC(Perfluorocarbon，全氟碳）、及 CHF3、CH2F2、CH3F等 HFC(hydrofluorocarbon，氫氟碳）以外，亦可列舉 SF6、NF3、201220391 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a device for performing (4) on an amorphous stone. [Prior Art] It is known that, for example, a workpiece such as a flat panel display is moved relative to a nozzle in a transport direction with respect to a nozzle, and a processing gas is sprayed from a nozzle onto a workpiece, and is processed. An etching apparatus for etching a surface film of a material (see Patent Document 2, etc., generally, the front end surface of the nozzle (the surface facing the object to be processed) becomes a plane having a certain area. In the nozzle of the patent documents 丨 and 2, for example, three (multiple) are formed in parallel in the transport direction of the object to be processed. a plurality of suction holes are formed in each of the discharge holes, and the openings at the lower ends of the suction holes and the lower ends of the discharge holes are spaced apart from each other in the transport direction. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-129996 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-1:29998 As a result, as shown in Fig. 14, the inventors performed an etching treatment of an amorphous crucible using a nozzle 5' having substantially the same configuration as described in Patent Documents i and 2. The front end face 5e of the nozzle 5 is conveyed in the direction (Fig. The size of the left and right direction of 14 is 3〇〇158969.doc 201220391 mm, and the width direction of the nozzle front end surface 5e orthogonal to the conveying direction (the direction of the figure and the direction of the paper father) is 640 mm. The distance between the discharge holes 5a, 5a, 5& is 100 mm, and the distance between each of the discharge holes 53 and the suction holes is mm. Each of the discharge holes 5a and the suction holes 5b is in the shape of a slit extending in the width direction. When the glass substrate 9 coated with the amorphous crucible is conveyed in the conveyance direction by the roller conveyor 6, the processing gas containing HF and 〇3 is ejected from the three ejection holes 5a, 5a, 5a. On the surface of the glass substrate 9, a plurality of processing spots each having a stripe shape extending in the width direction are formed at a distance of 100 mm in the transport direction. Therefore, as shown in Fig. 15, only one ejection hole 5a is used. The nozzle 5X is similarly subjected to an etching treatment of amorphous germanium. Before the nozzle 5X The end surface 5e has a size of 22 mm in the transport direction (the horizontal direction in Fig. 15), and one discharge hole 5a is provided at the center portion thereof. The width direction of the nozzle 5X (the direction orthogonal to the plane of the paper in Fig. 15) The slit shape of the size and the ejection hole 5a extending in the width direction is the same as that of the above-described nozzle 5 (Fig. 14). Thus, the stripe-shaped processing spot is not formed. On the other hand, the front end of the traveling direction of the substrate 9 The amount of processing in the portion and the rear end portion is lower than that in the central portion. Further, as shown in Fig. 16, a flat rectifying plate 7 opposed to the nozzle 5X is disposed slightly below the height at which the substrate 9 is transported. And performing an etching treatment of amorphous germanium. The size of the rectifying plate 7 in the conveying direction (the horizontal direction in Fig. 16) is 63 mm. The width direction of the rectifying plate 7 (the direction orthogonal to the plane of the drawing in Fig. 16) is the same as that of the nozzle 5X. In this manner, the difference between the etching treatment amount of the rear end portion and the center portion in the traveling direction of the substrate 9 is alleviated. However, the amount of etching treatment at the end portion before the traveling direction becomes larger, and the end portion in the traveling direction is etched 158969.doc 201220391 The amount of processing becomes smaller. The discharge flow rate from the nozzle 5X is 〇 4 m/s, and the Reynolds number is 〇 〇7. Therefore, it can be considered that the newly ejected process gas does not have sufficient momentum to eject the processed gas which is ejected first. Therefore, the processed gas is retained between the front end surface of the nozzle and the substrate 9, so that the concentration of the reaction component in the newly sprayed processing gas is lowered, and as a result, it can be considered that the processing on the surface of the substrate is uneven. ^—. The present invention has been completed based on the above findings, and its object is to improve the uniformity of the surname treatment when quoting a rock-like object such as an amorphous stone in the vicinity of atmospheric pressure. [Technical means for solving the problem] p In order to achieve the above object, the present invention is a method for contacting a processing gas having a fluorine-based reaction component in contact with a substrate containing a ruthenium-containing material under the vicinity of atmospheric pressure, The etchant containing the cerium is characterized in that: the branch portion is attached to the substrate to be processed on a virtual plane; the nozzle has a discharge hole for scooping out the processing gas, and is virtual a transporting mechanism that moves the substrate to be processed relative to the nozzle in a transport direction orthogonal to the width direction and perpendicular to the width direction; the nozzle includes an extremely thin (the transport) The dimension of the direction is extremely small) and the edge of the front end extending in the width direction and the side of the transport direction are formed by S and the inclined side surface which is close to each other with the front end edge is 158969.doc 201220391 and the width direction is positive The cross section of the intersection is sharpened toward the virtual plane, and the discharge holes are distributed in the width direction and open at the front end edge. a reaction portion is formed between the front end edge and the virtual plane, and between the pair of inclined side surfaces and the virtual plane, the drawing is separated from the reaction surface along the transport direction, and is orthogonal to the virtual plane. The diffusion space is widened in the direction. According to the above characteristic configuration, the uniformity of the etching treatment of the ruthenium-containing material can be improved. According to the experiment of the inventors, "even if a plurality of nozzles are arranged in the transport direction", it is possible to prevent the formation of striped processing spots on the surface of the substrate to be processed (see Example 1 below). The reason can be considered as follows. That is, the processing gas is ejected from the ejection holes to contact the substrate to be processed in the reaction site. The etching reaction of the cerium is caused by the contact. A diffusion space is connected to each of the two sides of the transfer direction of the reaction site. Immediately after the treatment gas is subjected to the above contact in the reaction site, it diffuses toward the diffusion space. Since the diffusion space is widened as it deviates from the reaction site, almost no diffusion resistance occurs. Therefore, even if the discharge flow rate of the process gas is small, the process gas which is first ejected can be surely extruded from the reaction site by the newly ejected gas stream. Therefore, fresh processing gas is always brought into contact with the substrate to be processed in the reaction site. Therefore, the concentration of the reaction component in the treatment gas in the reaction site can be prevented from decreasing. The above etching reaction is almost exclusively generated locally on a narrow reaction site. The local cooking rate in the reaction site is located when the end portion is located in the reaction site before the traveling direction of the substrate to be processed, or when the central portion of the substrate to be processed is located in the reaction site, or the rear end of the substrate to be processed The reaction sites are all approximately the same. Due to the full diffusion of the gas in the diffusion space, the concentration of the reaction component is greatly reduced, so that almost no etching reaction occurs. Therefore, the entire substrate to be processed can be etched substantially uniformly. As a result, even if a plurality of nozzles are arranged in the transport direction, it is possible to prevent or suppress the formation of stripe-shaped process spots extending in the width direction on the surface of the substrate to be processed. The average discharge flow rate of the above-mentioned processing gas in the above-mentioned discharge holes is preferably 〇1 m/s to 1·〇 m/s, more preferably 〇 2 m/s to 〇·6 m/s. The air flow disturbance in the treatment tank can be prevented by suppressing the discharge flow rate of the treatment gas to be small. Even if the ejection flow rate is small, the etching rate can be sufficiently ensured. Further, the effect of reducing the diffusion resistance and the effect of preventing the disturbance of the airflow in the treatment tank can sufficiently ensure the uniformity of the treatment. Here, the average discharge flow rate is obtained by dividing the discharge flow rate by the cross-sectional area of the discharge hole. A suction hole connected to the air suction mechanism is formed in the nozzle, and the suction hole may be in contact with the discharge hole and open at the front end edge. In the etching process, the gas in the vicinity of the opening of the suction hole of the front end edge is sucked into the suction hole by the gas suction mechanism in parallel with the discharge of the processing gas. Therefore, the process gas is sucked into the suction hole immediately after it is ejected from the ejection hole to contact the substrate to be processed. Therefore, it is possible to further surely prevent the treated gas from remaining in the reaction site, and it is possible to further surely prevent the concentration of the reaction component in the reaction site from decreasing. Further, it is possible to surely equalize the flow rate or the flow direction of the processing gas in the reaction portion without depending on the position of the traveling direction of the substrate to be processed. Thereby, the uniformity of the etching process can be further improved. Preferably, the rectifying plate facing the nozzle is disposed along the virtual plane along the virtual plane, and the rectifying plate preferably extends from the pair of inclined side surfaces to both sides of the conveying direction. Thereby, even if the virtual plane is a virtual plane ′, the flow state in which the processing gas is diffused toward the diffusion space can be kept substantially constant without depending on the traveling position of the substrate to be processed. Further, the state of the process gas stream in the reaction site can be surely kept substantially constant irrespective of the traveling position of the substrate to be processed. Thereby, the uniformity of the etch processing can be further improved. Preferably, the method further includes: a processing gas supply unit that supplies the processing gas to the nozzle, wherein the processing gas supply unit includes a plasma generating unit that includes a pair of electrodes that generate a discharge in the vicinity of atmospheric pressure, and A raw material gas containing a fluorine-containing component and a hydrogen-containing additive component is introduced into a space between the pair of electrodes to be plasma-formed to generate the fluorine-based reaction component. Examples of the fluorine-containing component include PFC (Perfluorocarbon) such as cf4, c2f4, c2f6, and c3f8, and HFC (hydrofluorocarbon) such as CHF3, CH2F2, and CH3F, and SF6 and NF3.
XeF2、Fa等。含氫添加成分較佳為水（h2〇)，除此以外，可 列舉乙醇等含OH基化合物或過氧化氫。 本說明書中’所謂大氣壓附近係指1.013xlO4〜50.663χΙΟ4 pa之範圍，若考慮壓力調整之便利化或裝置構成之簡便 化，則較佳為 1.333xl04~10.664xl04Pa，更佳為 9.331χ104 〜 l〇.397xl〇4 pa 〇 [發明之效果] 根據本發明，可提高含矽物之蝕刻處理之均一性。 【實施方式】 158969.doc -9· 201220391 以下’根據圖式對本發明之實施形態進行說明。 虚=圖2係表示本發明第1實施形態之#刻裝置1者。被 9係包含例如液晶顯示面板之玻璃基板，且成為較 缚之平板狀。被處理基板9之厚度t例如為网.4随〜i」麵 左右於被處理基板9之表面(圖i中為上表面)覆膜有蝕刻對 象之切物(圖4)。切物例如包含非晶妙。切物不僅 Γ為非晶料，亦可為單_❹晶[亦可不限定為石夕 單質而為氮化矽、氧化矽、碳化矽等。 飯刻裝置1係於大氣屋附近τ使處理氣體接觸於被處理 基板9,對含矽物進行蝕刻處理。處理氣體係含有氟系反應 成分。作為氟系反應成分可列舉HF、c〇F2、〇F2、〇2匕等。 於含矽物為非晶矽等矽之情形時，處理氣體更含有氧化性 反應成分。作為氧化性反應成分可列舉〇3、〇自由基等。 如圖1所示，蝕刻裝置丨係包括處理槽2、處理氣體供給部 10、滾輪運送機20及喷嘴30。處理槽2係收容喷嘴30及輸送 機20之一部分。處理槽2内之壓力成為大氣壓附近。 處理氣體供給部10係包括用以產生氟系反應成分之電漿 產生部11、及氧化性反應成分供給部〗6。電漿產生部丨i係 包含相互對向之一對電極12。於兩個或一個電極12之對向 面上設置有固體介電質層（省略圖示）。於一電極12連接有電 源3 ’且另一電極〗2電性接地。藉由來自電源3之電力供給 而對一對電極12彼此之間施加例如脈衝狀之高頻電場。藉 此’於電極1.2間在大氣壓附近下產生輝光放電。 於電極12間之空間13中連接有氟原料供給部14。於連結 158969.doc 201220391 氟原料供給部14與電極間空間13之路徑中連接有添加部 b °自氟原料供給部14輸送含有含氟成分之原料氣體，且 對該原料氣體中添加來自添加部15之含氫添加成分。添加 後之原料氣體係導入至電極間空間13。藉此，於電極間空 間13内’將上述原料氣體電漿化（包括激勵、分解、自由基 化、離子化），產生HF等氟系反應成分。 作為成為氟系反應成分之原料之含氟成分，可列舉cp4、 C2F4、C2F6、C3F8 等 PFC(Perfluorocarbon)、及 CHF3、CH2F2、 CH3F 專 HFC(hydrofluorocarbon)。進而，亦可使用 sf6、NF3、XeF2, Fa, etc. The hydrogen-containing additive component is preferably water (h2〇), and other examples thereof include an OH group-containing compound such as ethanol or hydrogen peroxide. In the present specification, the term "in the vicinity of atmospheric pressure" means a range of 1.013 x 10 4 to 50.663 χΙΟ 4 Pa. When the convenience of pressure adjustment or the simplification of the device configuration is considered, it is preferably 1.333×10 4 to 10.664 x 10 4 Pa, more preferably 9.331 χ 104 〜 l 〇 .397xl〇4 pa 〇 [Effect of the Invention] According to the present invention, the uniformity of the etching treatment of the cerium-containing material can be improved. [Embodiment] 158969.doc -9 201220391 Hereinafter, embodiments of the present invention will be described based on the drawings.虚 = Fig. 2 shows the #刻刻装置1 according to the first embodiment of the present invention. The glass substrate of the liquid crystal display panel is included in the ninth system, and is formed into a flat plate shape. The thickness t of the substrate to be processed 9 is, for example, a web (4) which is coated with an etching target on the surface of the substrate 9 to be processed (the upper surface in Fig. i). The cut contains, for example, amorphous. The cut material is not only an amorphous material but also a single crystal, and may be a tantalum nitride, a tantalum oxide, a tantalum carbide or the like. The rice cooking apparatus 1 is placed in the vicinity of the atmosphere chamber to bring the processing gas into contact with the substrate to be processed 9, and etches the contents. The treatment gas system contains a fluorine-based reaction component. Examples of the fluorine-based reaction component include HF, c〇F2, 〇F2, and 〇2匕. In the case where the ruthenium is an amorphous ruthenium or the like, the treatment gas further contains an oxidizing reaction component. Examples of the oxidative reaction component include ruthenium 3, an anthracene radical, and the like. As shown in Fig. 1, the etching apparatus includes a processing tank 2, a processing gas supply unit 10, a roller conveyor 20, and a nozzle 30. The treatment tank 2 houses a portion of the nozzle 30 and the conveyor 20. The pressure in the treatment tank 2 becomes near atmospheric pressure. The processing gas supply unit 10 includes a plasma generating unit 11 for generating a fluorine-based reaction component, and an oxidizing reaction component supply unit 6. The plasma generating unit 包含i includes a pair of counter electrodes 12 opposed to each other. A solid dielectric layer (not shown) is provided on the opposite faces of the two or one electrodes 12. A power source 3' is connected to one electrode 12 and the other electrode 2 is electrically grounded. A high-frequency electric field such as a pulse is applied to the pair of electrodes 12 by power supply from the power source 3. By this, a glow discharge is generated between the electrodes 1.2 at a temperature near the atmospheric pressure. A fluorine raw material supply portion 14 is connected to the space 13 between the electrodes 12. In connection with the 158969.doc 201220391, the fluorine-containing raw material supply unit 14 and the inter-electrode space 13 are connected to the inter-electrode space 13 with an addition portion b. The fluorine-containing component-containing raw material gas is supplied from the fluorine raw material supply unit 14, and the raw material gas is added from the additive portion. 15 contains hydrogen added components. The added raw material gas system is introduced into the interelectrode space 13. Thereby, the raw material gas is plasma-formed (including excitation, decomposition, radicalization, and ionization) in the interelectrode space 13 to generate a fluorine-based reaction component such as HF. Examples of the fluorine-containing component which is a raw material of the fluorine-based reaction component include PFC (Perfluorocarbon) such as cp4, C2F4, C2F6, and C3F8, and CHF3, CH2F2, and CH3F-specific HFC (hydrofluorocarbon). Furthermore, sf6, NF3,
XeF2、F2等作為含氟成分。此處，例如使用cF4作為含氟成 分。 氣原料供給部14係藉由稀釋成分而將含氟成分稀釋。作 為稀釋成分’不僅可列舉Ar、He、Ne、Kr等稀有氣體，且 可列舉Nz等惰性氣體。稀釋成分不僅發揮稀釋含氟成分之 作用，亦發揮作為載氣之作用及作為電漿產生用之氣體之 作用。此處’例如使用^作為稀釋成分。 上述含氫添加成分係水蒸氣（H2〇)。添加部15係包含水之 氣化器。水係以液態儲存於氣化器15内。來自供給部14之 氟系原料氣體（CFdAr)係導入至氣化器15内之液體中進行 起泡。或者，亦可將上述原料氣體導入至氣化器15内之相 較液面之上側部分，且藉由上述原料氣體而將上述上側部 刀之飽和瘵氣擠出。藉此，將水蒸氣添加至上述原料氣體 中可藉由對氣化器15進行溫度調節，而調節水之蒸氣壓 進而凋節添加量。或者，亦可將上述原料氣體（CF4+Ar)之 158969.doc 201220391 一部分導入至氣化器1 5内，且使殘餘部分繞過氣化器丨5 , 藉由調節上述一部分與殘餘部分之流量比而調節水之添加 量。作為添加成分，亦可使用含〇11基化合物、過氧化氫等 而取代水》作為含OH基化合物，可列舉醇。 氧化性反應成分供給部1 6係包含臭氧產生器。臭氧產生 器16係以〇2為原料，產生ο;作為氧化性反應成分。氧化性 反應成分並不限定於〇3，亦可為〇自由基或Ν〇χ。再者，於 應蝕刻之含矽膜為氧化矽等之情形時，亦可省略氧化性反 應成分供給部16。 其次，對滾輪運送機20及喷嘴30進行說明。滾輪運送機 20係兼具作為支撐被處理基板9之支撐部之功能、及作為搬 送被處理基板9之搬送機構之功能。 眾所周知，滾輪運送機20係包括軸2 1及滚輪22。複數個 抽21係相互隔開間隔地排列於χ方向（搬送方向，圖1中為左 右）。各軸21之軸線係水平地朝向與上述χ方向正交之y方向 (寬度方向’圖1之紙面正交方向）。複數個滾輪22係於丫方向 上隔開間隔地設置於各軸2 1上。於滾輪22上以平坦之狀態 水平地載置有被處理基板9。滾輪運送機20係於滾輪22之上 端部之高度之虛擬之水平平面PL上支撐被處理基板9,且於 沿上述虚擬平面PL之X方向上搬送被處理基板9 » 如圖1所示’於處理槽2内之滾輪運送機20之上方配置有 噴嘴30。喷嘴30係由未圖示之支座支撐於處理槽2内之上側 部。如圖2及圖3所示’喷嘴3 0係較長地延伸於y方向（虛擬 平面之寬度方向）。喷嘴30之y方向之長度係充分大於該噴 158969.doc •12- 201220391 嘴30之X方向之尺寸，且較佳為大於被處理基板9之y方向之 長度。如圖1所示，與喷嘴30之延伸方向正交之剖面之中心 轴CL·係垂直地與虛擬平面pl正交，進而與被處理基板9正 交。 於喷嘴30之内部形成有喷出孔31。如圖4所示，喷出孔31 係沿著中心軸CL上下延伸。喷出孔31之乂方向之寬度w較佳 為w=l mm〜6 mm左右，更佳為w=4 mm左右。如圖2所示， 喷出孔31係遍及喷嘴30之長度方向（y方向）之大致全長地分 佈。詳細而言，喷出孔31係較長地延伸於丫方向上，且呈狹 縫狀。喷出孔31亦可包含排列於y方向上之多個小孔而取代 狹縫狀。喷出孔31之y方向之長度（分佈寬度）係略微大於被 處理基板9之y方向之長度。較佳為，於平面投影圖中喷 出孔31之y方向上之各端部為相較被處理基板9之丫方向上 之相同側之端部略微突出至外側之程度。喷出孔31亦可包 含排列於y方向上之多個小孔。 如圖1所不，喷出孔31之基端部（上端部）係連接於來自處 理氣體供給部ίο之供給路19。雖圖示省略，但於供給路19 與處理氣體供給部1G之間設置有錢部。整流料包括沿y 方向延伸之腔室、沿丫方向延伸之狹縫、及分散地配置於丫 方向上之多個小孔等°處理氣體係藉由穿過整流部，而於y 方向上均一化。 如圖3及圖4所示，喷嘴3〇中之上側部扣之與以向正交 之^面係呈長方形°相對於此’喷嘴30中之下側部分33之 與y方向正父之剖面係以朝向虛擬平面孔變尖之方式成為 158969.doc •13· 201220391 :狀。喷嘴下側部分33係包括於… 傾斜側面34，、及朝向虛擬平 =為： 斜側面34、34在士 & 又⑴螭緣35。一對傾 式相對H 隨著靠近前端緣35而相互接近之方 對傾：CL傾斜之傾斜面。於噴嘴3〇之前端(下端)， =側面34,充分接近，且於該些傾斜側一 细^彼此間形成有喷嘴前端緣35。喷嘴前端緣Μ係呈極 上」X方向之尺寸極小，且於Υ方向(圖1之紙面正交方向) 上直線狀較長地延伸。 嗜Γ孔Γ之，下端_達喷嘴前端緣35開°，構成 义口纟嘴則端緣35之大致整體成為喷出口。喷嘴取 刖编緣之X方向之寬度係與噴出孔31之乂方向之寬度一致， 例如為4 _左右。於喷嘴30之前端（下端），相較中心轴CL 相互為相同側之傾斜側面34與喷出孔”之内面以銳角交 又，構成刀口 35e。77 口 35e係於y方向（圖4之與紙面正交之 方向）上延伸。夾著中心軸CL，兩側之刀口 he、35e構成喷 嘴刖端緣3 5之X方向之兩端部。 上述中〜軸CL與傾斜側面34所成之角度θ較佳為θ=6〇。以 下°就處理之均—性之觀點而言’角度Θ愈小愈佳。另一方 若Θ過j則喷嘴30之加工變得困難。因此，角度0更 佳為Θ-20〜30。左；fe·。可藉由使角度0之下限為2〇。左右而 使喷嘴3 0之加工便利化。 就處理之均一性之觀點而言，自傾斜側面34之上端至喷 出孔31之内面為止之水平距離[愈小愈佳。另一方面，若距 離L過小，則喷嘴3〇之加工變得困難。顧及喷嘴3〇加工之水 158969.doc 201220391 平距離L較佳為L=l〇 min~30 mm左右。就處理之均一性之 觀點而言，傾斜側面34之垂直方向之高度h愈大愈佳，例如 較佳為h=10 mm以上。 於喷嘴前端緣35與虛擬平面pl之間畫分出反應部位ia。 反應部位la係於X方向上具有與喷嘴前端緣35大致相同之 寬度，且於y方向（圖1之紙面正交方向）上具有與噴嘴前端緣 3 5大致相同之長度。即，反應部位丨&係χ方向之尺寸極小（呈 極細）’且於y方向上直線狀地較長延伸。反應部位13之乂方 向之寬度例如為2 mm左右。藉由被處理基板9橫截反應部位 la，而於反應部位la中引起被處理基板9之表面之含矽膜％ 之触刻反應。 喷嘴别端緣35與被處理基板9之上表面之間隙gl較佳為 gl = l mm〜10 mm ’ 更佳為 gl=3 mm〜7 mm。 於喷嘴30之一對傾斜側面34各自與虛擬平面pL之間畫分 出擴散空間le。進而，於各傾斜側面34與被處理基板9之間 畫分出擴散空間le ^ —對擴散空間le係自乂方向之兩側失著 反應部位la。各擴散空間le係於y方向上以與傾斜側面34相 同之長度延伸。各擴散空間le係與反應部位la相連，且隨 著於X方向上背離反應部位la而在上下方向（與虛擬平面PL 正父之方向）上擴寬，從而與處理槽2内之喷嘴之周邊空 間相連。反應部位la及擴散空間le成為大氣壓附近之壓力。 如圖1所示，於喷嘴30之正下方設置有整流板4〇。整流板 40係配置於在X方向上鄰接之2個滾輪22彼此之間。如圖1 及圖2所示，整流板40係以沿著虛擬平面孔之方式成為朝向 158969.doc •15· 201220391 水平且於y方向上較長地延伸之平板狀。整流板4〇之乂方向 之中央部係正好與喷嘴30之中心軸〇^交叉。整流板4〇之乂 方向之尺寸係大於噴嘴30之X方向之尺寸，且整流板4〇之乂 方向之兩端部自一對傾斜側面34、34朝父方向之兩側延伸。 整流板40之y方向之尺寸係大於被處理基板9之丫方向之尺 寸，進而大於喷出孔31之丫方向之尺寸。整流板4〇之乂方向 之兩端部係自被處理基板9朝向y方向之外側突出，進而自 喷出孔31朝向y方向之外側突出。如圖i所示，整流板4〇之 上表面係位於虛擬平面PL之略微下側。如圖4所示，虛擬平 面PL與整流板40之上表面之間之間隙g2較佳為g2=1爪爪〜3 左右。喷嘴30與整流板40係隔著虛擬平面PL上下對向。整 流板40之X方向之兩端面係成為向下之斜面。 對以上述方式構成之蝕刻裝置丨之動作進行說明。 藉由滾輪運送機20而沿著x方向搬送被處理基板藉由 電漿產生部11而併行地將來自供給部14、15之氟系原料氣體 (CF4+Ar+H2〇)電漿化，且於該氟系原料氣體（CF4+Ar+H2〇) 中混合來自臭氧產生器16之含臭氧氣體（〇2+〇3)，獲得處理 氣體》藉由上述整流部（未圖示）而使該處理氣體於y方向上 均一化後，導入至噴出孔31，並將其自噴出孔31之前端（下 端）噴出。喷出孔31中之處理氣體之平均喷出流速較佳為〇」 m/s〜1 .〇 m/s，更佳為0.2 m/s〜0.6 m/s。可藉由將喷出流速控 制為較小，而防止處理槽2内之氣流擾動。喷出流速可藉由 處理氣體之供給流量而調節。 處理氣體於喷嘴前端緣35之正下方之反應部位la中接觸 158969.doc •16- 201220391 於被處理基板9。該處理氣體係於反應部位la内引起蝕刻反 應。具體而言’藉由處理氣體中之〇3而將非晶石夕膜9a氧化， 進而與HF進行反應’轉換為SiF4等揮發性成分。藉此，可 將非晶石夕膜9a中之配置於反應部位1 a内之部分敍刻。 於圖4中，如粗線箭頭f所示，處理氣體係於反應部位u 中接觸於被處理基板9之後，立即朝向擴散空間le擴散。由 於擴散空間le隨著背離反應部位ia而大幅度地擴寬，故幾 乎不產生擴散阻力。因此’即便處理氣體之喷出流速較小， 亦可藉由新喷出之氣流而簡單地將先喷出之處理氣體自反 應部位la中擠出。因此，於反應部位la中，新鮮之處理氣 體始終與被處理基板9接觸。因此，可防止反應部位la中之 反應成分（HF及〇3)之濃度下降，從而可提高蝕刻速率。 上述姓刻反應幾乎僅局部性地產生於狹窄之反應部位丄a 内。反應部位la中之局部之蝕刻速率無論於被處理基板9之 行進方向之前端部位於反應部位la内時、或者於被處理基 板9之中央部位於反應部位内時、以及於被處理基板9之行 進方向之後端部位於反應部位内時均為大致均衡。於擴散 二間le中處理氣體充分擴散而使反應成分濃度大幅度地降 低’因此’於擴散空間16内之基板9之表面上幾乎不產生蝕 刻反應。並且’由於整流板4〇係自一對傾斜側面34朝向X 方向之兩外側延伸’故而擴散空間le内之處理氣體之流動 狀態亦可保持大致固定而不依賴於被處理基板9之行進位 置°藉此’可對被處理基板9之整體均一地進行蝕刻處理。 進而’與喷出流速較小之處理槽2内之氣流之擾動防止效果 158969.doc -17- 201220391 相結合，可進一步提高處理之均一性。 經擴散之處理完畢之氣體係藉由未圖示之排氣機構進行 排氣。 其次’對本發明之其他實施形態進行說明。於以下之實 施形態中，對於所述之構成於圖式中標註相同符號且省略 其說明。 圖5〜圖10係表示噴嘴30之形狀之變形例者。如圖5所示， 喷嘴前端緣35A亦可略微變平（平坦地切割）而成為面狀。亦 於此情形時’前端緣35A之X方向之寬度較佳為儘量小。自 喷出孔31之内面至面狀之前端緣μα之外端之間的寬度 w2 ’較佳為w2$2mm ’更佳為W2<1 mm。反應部位1&係形 成於喷嘴3之前端緣35A與虛擬平面pl之間，進而，形成於 前端緣35A與被處理基板9之間。反應部位13之^方向之寬度 係與喷嘴前端緣35A之X方向之寬度實質上相等，且大於噴 出孔31之X方向之寬度。 傾斜側面34亦可不為平坦面。如圖6所示，傾斜側面34 亦可為平緩之凹曲面。如圖7所示，傾斜侧面34亦可為平缓 之凸曲面。如圖8所示’亦可於傾斜側面34上形成凸部36。 如圖9所示，亦可於傾斜側面34上形成槽等凹部37。凸部36 或凹部37既可為點狀，亦可為沿上下方向或y方向延伸之珠 狀或條紋狀。凸部36或凹部37之數量既可為1個，亦可為複 數個。XeF2, F2, etc. are contained as a fluorine-containing component. Here, for example, cF4 is used as the fluorine-containing component. The gas raw material supply unit 14 dilutes the fluorine-containing component by diluting the component. The diluent component' is not limited to a rare gas such as Ar, He, Ne or Kr, and an inert gas such as Nz. The diluted component not only functions to dilute the fluorine-containing component, but also functions as a carrier gas and as a gas for plasma generation. Here, for example, ^ is used as a dilution component. The hydrogen-containing additive component is water vapor (H2〇). The adding portion 15 is a gasifier including water. The water system is stored in the gasifier 15 in a liquid state. The fluorine-based source gas (CFdAr) from the supply unit 14 is introduced into the liquid in the vaporizer 15 to cause foaming. Alternatively, the raw material gas may be introduced into the upper portion of the liquid level in the vaporizer 15, and the saturated helium gas of the upper blade may be extruded by the raw material gas. Thereby, by adding water vapor to the above-mentioned raw material gas, the vapor pressure of the water can be adjusted by adjusting the vapor pressure of the vaporizer 15, and the amount of addition can be adjusted. Alternatively, a portion of the above-mentioned raw material gas (CF4+Ar) 158969.doc 201220391 may be introduced into the gasifier 15 and the residual portion may be bypassed by the gasifier crucible 5 by adjusting the flow rate of the above-mentioned portion and the residual portion. Adjust the amount of water added. As the additive component, a hydrazine-containing compound, hydrogen peroxide or the like may be used instead of water, and an OH group-containing compound may be mentioned. The oxidative reaction component supply unit 16 includes an ozone generator. The ozone generator 16 is made of ruthenium 2 as a raw material, and is produced as an oxidizing reaction component. The oxidizing reaction component is not limited to ruthenium 3, and may be ruthenium radical or ruthenium. Further, when the ruthenium-containing film to be etched is ruthenium oxide or the like, the oxidative reaction component supply unit 16 may be omitted. Next, the roller conveyor 20 and the nozzle 30 will be described. The roller conveyor 20 has both a function as a support portion for supporting the substrate to be processed 9 and a function as a transport mechanism for transporting the substrate 9 to be processed. As is known, the roller conveyor 20 includes a shaft 21 and a roller 22. A plurality of pumping lines 21 are arranged at intervals in the χ direction (transport direction, left and right in Fig. 1). The axis of each of the shafts 21 is horizontally oriented in the y direction orthogonal to the above-described χ direction (the width direction θ is orthogonal to the plane of the drawing of Fig. 1). A plurality of rollers 22 are disposed on the respective shafts 2 1 at intervals in the 丫 direction. The substrate to be processed 9 is horizontally placed on the roller 22 in a flat state. The roller conveyor 20 supports the substrate 9 to be processed on a virtual horizontal plane PL of the height of the upper end of the roller 22, and transports the substrate to be processed 9 in the X direction along the virtual plane PL. A nozzle 30 is disposed above the roller conveyor 20 in the processing tank 2. The nozzle 30 is supported by the support (not shown) on the upper side in the treatment tank 2. As shown in Fig. 2 and Fig. 3, the nozzle 30 extends longer in the y direction (the width direction of the virtual plane). The length of the nozzle 30 in the y direction is sufficiently larger than the dimension of the nozzle 30 in the X direction, and preferably greater than the length of the substrate 9 to be processed in the y direction. As shown in Fig. 1, the center axis CL of the cross section orthogonal to the extending direction of the nozzle 30 is perpendicular to the virtual plane pl and orthogonal to the substrate to be processed 9. A discharge hole 31 is formed inside the nozzle 30. As shown in Fig. 4, the discharge holes 31 extend up and down along the central axis CL. The width w of the ejection hole 31 in the meandering direction is preferably about w = 1 mm to 6 mm, more preferably about w = 4 mm. As shown in Fig. 2, the discharge holes 31 are distributed over substantially the entire length of the nozzle 30 in the longitudinal direction (y direction). Specifically, the discharge hole 31 is elongated in the weir direction and has a slit shape. The ejection hole 31 may also include a plurality of small holes arranged in the y direction instead of the slit shape. The length (distribution width) of the discharge hole 31 in the y direction is slightly larger than the length of the substrate 9 to be processed in the y direction. Preferably, each end portion of the discharge hole 31 in the y direction in the plan view is such that the end portion on the same side in the zigzag direction of the substrate to be processed 9 slightly protrudes to the outside. The ejection holes 31 may also include a plurality of small holes arranged in the y direction. As shown in Fig. 1, the base end portion (upper end portion) of the discharge hole 31 is connected to the supply path 19 from the treatment gas supply portion ίο. Although not shown in the drawings, a money portion is provided between the supply path 19 and the processing gas supply unit 1G. The rectifying material includes a chamber extending in the y direction, a slit extending in the 丫 direction, and a plurality of small holes dispersedly disposed in the 丫 direction. The processing gas system is uniform in the y direction by passing through the rectifying portion. Chemical. As shown in FIG. 3 and FIG. 4, the upper side of the nozzle 3 is buckled and has a rectangular shape with respect to the orthogonal surface. The cross section of the lower side portion 33 of the nozzle 30 and the y direction is the father. It is 158969.doc •13· 201220391 : in the way of sharpening towards the virtual plane hole. The nozzle lower side portion 33 is included on the inclined side surface 34, and is oriented toward the virtual plane = the oblique side surfaces 34, 34 are in the shovel & (1) the rim 35. A pair of tilting relative H is close to each other as it approaches the leading edge 35. The inclined surface is inclined by CL. At the front end (lower end) of the nozzle 3, the side surface 34 is sufficiently close, and a nozzle leading edge 35 is formed between the inclined sides. The tip end edge of the nozzle is extremely large in the "X" direction, and extends linearly in the Υ direction (the direction perpendicular to the plane of the drawing of Fig. 1). The lower end _ reaches the nozzle front end edge 35, and the mouth of the mouth is formed as a discharge port. The width of the nozzle in the X direction of the braided edge is the same as the width of the ejection orifice 31, for example, about 4 _. At the front end (lower end) of the nozzle 30, the inner side of the inclined side surface 34 and the ejection hole" on the same side as the central axis CL are perpendicularly intersected to form a knife edge 35e. 77 port 35e is in the y direction (Fig. 4 The paper surface extends in the direction orthogonal to the paper. The central axis CL is sandwiched, and the cutting edges he and 35e on both sides constitute the X-direction end portions of the nozzle end edge 35. The angle between the middle-axis CL and the inclined side surface 34 θ is preferably θ = 6 〇. The following angles are better in terms of the uniformity of the treatment. The other side is more difficult to process the nozzle 30. Therefore, the angle 0 is better. It is Θ-20~30. Left; fe·. The processing of the nozzle 30 can be facilitated by making the lower limit of the angle 0 to be 2 〇. From the viewpoint of uniformity of processing, the self-tilting side 34 The horizontal distance from the upper end to the inner surface of the discharge hole 31 is preferably smaller. On the other hand, if the distance L is too small, the processing of the nozzle 3〇 becomes difficult. Considering the water of the nozzle 3〇 processing 158969.doc 201220391 L is preferably about L = l 〇 min ~ 30 mm. From the viewpoint of uniformity of treatment, the sloping side 34 is sag The larger the height h of the direction, the better, for example, h=10 mm or more. The reaction site ia is drawn between the nozzle front edge 35 and the virtual plane pl. The reaction site la has a front end edge with respect to the nozzle in the X direction. 35 has substantially the same width and has substantially the same length as the nozzle front end edge 35 in the y direction (the direction perpendicular to the paper surface of Fig. 1). That is, the size of the reaction portion 丨& χ direction is extremely small (very fine) And extending in a straight line in the y direction. The width of the reaction portion 13 in the 乂 direction is, for example, about 2 mm. The substrate to be processed 9 is caused in the reaction site 1a by the substrate to be processed 9 crossing the reaction site 1a. The etch reaction of the surface containing the ruthenium film. The gap gl between the nozzle edge 35 and the upper surface of the substrate to be processed 9 is preferably gl = 1 mm to 10 mm 'more preferably gl = 3 mm to 7 mm. A diffusion space le is formed between each of the inclined side surfaces 34 of the nozzle 30 and the virtual plane pL. Further, a diffusion space le ^ is formed between each inclined side surface 34 and the substrate to be processed 9 - the diffusion space is derived from The reaction site la is lost on both sides of the 乂 direction. Each diffusion space It extends in the y direction at the same length as the inclined side surface 34. Each diffusion space le is connected to the reaction site la, and is in the up and down direction (in the direction of the father of the virtual plane PL) as it deviates from the reaction site la in the X direction. The upper portion is widened to be connected to the peripheral space of the nozzle in the treatment tank 2. The reaction site la and the diffusion space le are at a pressure near atmospheric pressure. As shown in Fig. 1, a rectifying plate 4 is provided directly below the nozzle 30. The plate 40 is disposed between the two rollers 22 adjacent in the X direction. As shown in FIGS. 1 and 2, the rectifying plate 40 is oriented toward the 158969.doc •15·201220391 level along the virtual plane hole. And a flat plate extending long in the y direction. The central portion of the direction of the rectifying plate 4 is exactly intersecting the central axis of the nozzle 30. The dimension of the rectifying plate 4 is larger than the dimension of the nozzle 30 in the X direction, and both ends of the rectifying plate 4 in the 乂 direction extend from the pair of inclined side faces 34, 34 toward both sides in the parent direction. The dimension of the rectifying plate 40 in the y direction is larger than the dimension of the substrate 9 to be processed, and is larger than the size of the ejecting hole 31 in the x direction. Both ends of the rectifying plate 4 are protruded from the substrate 9 toward the outside in the y direction, and protrude from the ejection hole 31 toward the outside in the y direction. As shown in Fig. i, the upper surface of the rectifying plate 4 is located on the slightly lower side of the virtual plane PL. As shown in Fig. 4, the gap g2 between the virtual plane PL and the upper surface of the rectifying plate 40 is preferably about g2 = 1 to 3 claws. The nozzle 30 and the rectifying plate 40 are vertically opposed to each other via the virtual plane PL. Both end faces of the flow plate 40 in the X direction are downward slopes. The operation of the etching apparatus configured as described above will be described. The substrate to be processed is transported in the x direction by the roller conveyor 20, and the fluorine-based material gas (CF4+Ar+H2〇) from the supply units 14 and 15 is plasma-parallel in parallel by the plasma generating unit 11 and The ozone-containing gas (〇2+〇3) from the ozone generator 16 is mixed with the fluorine-based source gas (CF4+Ar+H2〇) to obtain a processing gas, and the rectifying unit (not shown) is used to After the treatment gas is homogenized in the y direction, it is introduced into the discharge hole 31, and is ejected from the front end (lower end) of the discharge hole 31. The average discharge flow rate of the process gas in the discharge port 31 is preferably 〇 m / s 〜 1 . 〇 m / s, more preferably 0.2 m / s to 0.6 m / s. The air flow disturbance in the treatment tank 2 can be prevented by controlling the discharge flow rate to be small. The discharge flow rate can be adjusted by the supply flow rate of the process gas. The process gas is contacted in the reaction site la directly below the front end edge 35 of the nozzle 158969.doc •16- 201220391 on the substrate 9 to be processed. The process gas system causes an etch reaction in the reaction site la. Specifically, the amorphous austenite film 9a is oxidized by the ruthenium 3 in the treatment gas, and further reacted with HF to be converted into a volatile component such as SiF4. Thereby, the portion of the amorphous stone film 9a disposed in the reaction site 1a can be described. In FIG. 4, as shown by the thick line arrow f, the process gas system is diffused toward the diffusion space le immediately after it contacts the substrate to be processed 9 in the reaction site u. Since the diffusion space le is greatly widened as it deviates from the reaction site ia, diffusion resistance is hardly generated. Therefore, even if the discharge velocity of the process gas is small, the process gas first ejected can be simply extruded from the reaction site la by the newly ejected gas stream. Therefore, in the reaction site la, the fresh process gas is always in contact with the substrate 9 to be processed. Therefore, the concentration of the reaction components (HF and 〇3) in the reaction site la can be prevented from decreasing, and the etching rate can be increased. The above-mentioned surname reaction is generated only locally in the stenosis reaction site 丄a. The local etching rate in the reaction site 1a is in the case where the front end portion of the substrate to be processed 9 is located in the reaction site 1a, or when the central portion of the substrate to be processed 9 is located in the reaction site, and the substrate to be processed 9 When the end portion in the traveling direction is located inside the reaction site, it is substantially equalized. In the diffusion chambers, the treatment gas is sufficiently diffused to greatly reduce the concentration of the reaction components. Therefore, almost no etching reaction occurs on the surface of the substrate 9 in the diffusion space 16. And 'because the rectifying plate 4 is extended from the opposite sides of the pair of inclined side faces 34 toward the X direction, the flow state of the processing gas in the diffusion space le can be kept substantially constant without depending on the traveling position of the substrate to be processed. Thereby, the entire substrate to be processed 9 can be uniformly etched. Further, in combination with the disturbance preventing effect of the airflow in the treatment tank 2 having a small discharge flow rate, 158969.doc -17-201220391, the uniformity of the treatment can be further improved. The diffused gas system is exhausted by an exhaust mechanism (not shown). Next, other embodiments of the present invention will be described. In the following embodiments, the same components are denoted by the same reference numerals, and the description thereof will be omitted. 5 to 10 show a modification of the shape of the nozzle 30. As shown in Fig. 5, the nozzle leading edge 35A may be slightly flattened (flatly cut) to have a planar shape. Also in this case, the width of the front end edge 35A in the X direction is preferably as small as possible. The width w2' between the inner surface of the ejection orifice 31 and the outer end of the planar front edge μα is preferably w2$2 mm', more preferably W2 < 1 mm. The reaction site 1& is formed between the front end edge 35A of the nozzle 3 and the virtual plane pl, and is formed between the front end edge 35A and the substrate to be processed 9. The width of the reaction portion 13 is substantially equal to the width of the nozzle leading edge 35A in the X direction and larger than the width of the ejection hole 31 in the X direction. The inclined side surface 34 may also not be a flat surface. As shown in FIG. 6, the inclined side surface 34 may also be a gently concave curved surface. As shown in Fig. 7, the inclined side surface 34 may also be a gently convex curved surface. As shown in Fig. 8, a convex portion 36 may also be formed on the inclined side surface 34. As shown in FIG. 9, a concave portion 37 such as a groove may be formed on the inclined side surface 34. The convex portion 36 or the concave portion 37 may have a dot shape or a bead shape or a stripe shape extending in the vertical direction or the y direction. The number of the convex portions 36 or the concave portions 37 may be one or plural.
圖丨〇及圖11所示之第2實施形態係於噴嘴30之内部形成 有一對吸入孔39。一對吸入孔39係夾著噴出孔31設置於X 158969.doc -18- 201220391 方向之兩側。各吸入孔39係呈現沿丫方向延伸之狹縫狀，且 以隨著朝向下方而靠近中央之喷出孔31之方式傾斜。各吸 入孔39之下端部（吸入口）係到達喷嘴前端緣35開口。各吸入 孔39之中心轴Cl側之内面與喷出孔31之内面係於喷嘴前端 緣35以銳角交又。於喷嘴前端緣35中，以相接之方式排列 有喷出孔3 1與其兩側之吸入孔39。各吸入孔39之X方向之寬 度係小於喷出孔3 1之X方向之寬度（例如為2 m m左右），較佳 為喷出孔31之X方向之寬度的二分之一（例如} mm)左右。各 吸入孔39之X方向之寬度可與喷出孔31之^方向之寬度大致 相等，亦可大於喷出孔31之X方向之寬度。吸入孔39亦可包 含排列於y方向上之複數個小孔。 於喷嘴30之上側部分32設置有抽吸口 38 ^吸入孔39之上 端部係經由抽吸口 3 8而與抽吸泵4 (氣體抽吸機構）相連。 噴嘴30之傾斜側面34係傾斜角度於前端緣35之附近非連 續性地變化而形成脊線34c。相較脊線34c於下側’相對於 虛擬平面PL之傾斜變小》 根據本實施形態，與對喷嘴30之處理氣體供給併行地藉 由抽吸泵4將吸入孔39之下端開口附近之氣體局部性地吸 入至吸入孔39内。因此’處理氣體自喷出孔31喷出而接觸 於正下方之被處理基板9之後’立即被吸入至吸入孔39。因 此，可進一步確實地防止處理完畢之氣體滯留於反應部位 la。藉此，於反應部位la中，可確實地使被處理基板9僅與 新鮮之處理氣體接觸’從而可進一步確實地防止反應部位 la中之反應成分之濃度下降。進而，可確實地使反應部位 158969.doc •19· 201220391 la内之處理氣體之流動均衡而不依賴於被處理基板9之行 進方向之位置。藉此，可進一步提高蝕刻處理之均一性。 圖12所示之第3實施形態係設置有3個（複數個）喷嘴3〇。3 個噴嘴30係隔開間隔地排列於X方向上。對各喷嘴3〇之喷出 孔31分配處理氣體。於各喷嘴3〇之正下方配置有整流板 40。相應之喷嘴30與整流板40彼此係隔著虛擬平面pl上下 對向。各喷嘴3〇於y方向（圖12之紙面正交方向）上延伸之方 面、及下侧部分3 3錐狀變尖之方面等各喷嘴3 〇之構成係與 第1實施形態相同。 根據本發明，即便複數個喷嘴30排列於χ方向上，亦可防 止或抑制於被處理基板9上以與噴嘴30之配置間隔相同之 間隔形成沿y方向延伸之條紋狀之處理斑。 圖13係表示本發明第4實施形態者。於該實施形態中，第 3實施形態（圖12)中之χ方向之兩端之喷嘴成為排氣喷嘴 5〇。排氣喷嘴50之形狀與處理氣體喷出喷嘴3〇大致相同。 即’排氣喷嘴50係包括χ方向之兩側之一對傾斜側面54、 54、及朝向虛擬平面pL之前端緣55，且較長地延伸於y方向 (圖13之與紙面正交之寬度方向）上。傾斜側面54、54係隨著 靠近前端緣55而相互接近。前端緣55係呈極細地於y方向上 直線狀延伸。排氣喷嘴50之下側部分53之與y方向正交之刮 面以朝向虛擬平面PL變尖之方式成為錐狀。 於排氣喷嘴50之内部形成有排氣孔51。於排氣孔51之上 端部連接有抽吸路5。抽吸路5係連接於氣體抽吸機構4。排 氣孔5 1之下端部係於前端緣55開口，且遍及喷嘴之長度 158969.doc -20· 201220391 方向（圖13之與紙面正交之y方向）之大致全長地以狹縫狀分 佈。排氣孔5 1亦可取代狹縫狀而包含排列於y方向上之多個 小孔。 喷出喷嘴30係配置於兩端之排氣喷嘴50、50之正_間。 自噴出喷嘴30之中心軸CL至各排氣喷嘴50之中心軸CL50為 止之距離例如為幾十mm〜幾百min，此處為100 mm左右。 再者’亦可偏向任一排氣喷嘴5〇側地配置喷出喷嘴3〇。 例如，於自排氣喷嘴50、50彼此之正中間之位置至—排氣 喷嘴50之中心軸CL^為止之距離為1〇〇 mm左右時，亦可於 自上述中間位置相距幾十mm(較佳為2〇 mm)左右之範圍内 偏向一排氣喷嘴50側地配置喷出喷嘴3〇。 第4實施形態係藉由抽吸排氣機構4之驅動而將兩端之排 氣喷嘴50、50之周邊之氣體吸入至排氣孔51。尤其，將各 排氣噴嘴50之下端即前端緣55之周邊之氣體吸入至排氣孔 51。可藉由該吸入氣流，而使各排氣喷嘴5〇與中央之喷出 喷嘴30之間之空間之氣體之流動f穩定，從而可進一步提高 處理之均一性。 本發明並不限定於上述實施形態，於不脫離其精神之範 圍内可採用各種更改態樣。 例如，搬送機構亦可與喷嘴30連接。亦可使噴嘴3〇於搬 送方向上移動’使被處理基板9靜止。 亦可省略整流板40。 亦可使喷嘴30之前端緣與被處理基板9之上表面之間之 間隙gl相對地變大。藉此，可使處理氣體更容易自反應部 158969.doc •21 · 201220391 位1 a朝向擴散空間1 e擴散。例如’於上述實施形態中，間 隙gl之較佳範圍為gl = l mm~l〇 mm，但亦可使§1 = 1〇 mm〜30 mm左右。 亦可相互組合複數個實施形態。例如，可由圖1〇之附有 吸入孔39之噴嘴30構成圖12所示之複數個噴嘴30，亦可由 圖5〜圖9之變形形狀之喷嘴30構成圖12所示之複數個喷嘴 30。亦可使排氣喷嘴50(圖13)之形狀成為與圖5〜圖9之噴出 喷嘴30相同之形狀。 [實施例1 ] 對實施例進行說明。當然本發明並不限定於以下實施例。 使用圖1所示之蝕刻裝置丨，對玻璃基板9之表面之非晶石夕 膜知進行蝕刻。噴嘴30整體之上下方向之尺寸為55 mm，傾 斜側面3 4之垂直高度h為h=3 0 mm。自傾斜側面3 4之上端至 喷出孔31之内面為止之水平距離l為L=10 mm。傾斜側面34 之對於垂直面之角度θ略小於20。。喷出孔31之乂方向之寬度 為2 mm。噴出孔31之y方向之長度為6〇〇 mm，且相較玻璃 基板9之y方向之尺寸大1〇〇 mm。喷出孔31之丫方向之各端部 係相較玻璃基板9朝向y方向之外側突出50 整流板4〇 之上表面之X方向之尺寸為63mine 處理氣體之氟系原料氣體成分如下所述。 CF4 0.8 slmIn the second embodiment shown in Fig. 11 and Fig. 11, a pair of suction holes 39 are formed inside the nozzle 30. A pair of suction holes 39 are provided on both sides of the X 158969.doc -18-201220391 direction with the ejection holes 31 interposed therebetween. Each of the suction holes 39 has a slit shape extending in the z-direction, and is inclined so as to approach the discharge port 31 at the center as it goes downward. The lower end portion (suction port) of each of the suction holes 39 reaches the nozzle front end edge 35 opening. The inner surface of the suction shaft 39 on the central axis Cl side and the inner surface of the discharge hole 31 are attached to the nozzle leading edge 35 at an acute angle. In the nozzle front end edge 35, the discharge holes 31 and the suction holes 39 on both sides thereof are arranged in contact with each other. The width of each of the suction holes 39 in the X direction is smaller than the width of the discharge hole 31 in the X direction (for example, about 2 mm), preferably one-half of the width of the discharge hole 31 in the X direction (for example, } mm )about. The width of each of the suction holes 39 in the X direction may be substantially equal to the width of the discharge hole 31, or may be larger than the width of the discharge hole 31 in the X direction. The suction holes 39 may also include a plurality of small holes arranged in the y direction. The upper side portion 32 of the nozzle 30 is provided with a suction port 38. The upper end portion of the suction hole 39 is connected to the suction pump 4 (gas suction mechanism) via the suction port 38. The inclined side surface 34 of the nozzle 30 is non-continuously changed at an inclination angle from the vicinity of the front end edge 35 to form a ridge line 34c. In contrast to the ridge line 34c, the inclination of the lower side 'with respect to the virtual plane PL becomes smaller. According to the present embodiment, the gas near the opening of the lower end of the suction hole 39 is supplied by the suction pump 4 in parallel with the supply of the processing gas to the nozzle 30. Locally inhaled into the suction hole 39. Therefore, the process gas is sucked into the suction hole 39 immediately after being ejected from the discharge hole 31 to contact the substrate 9 to be processed immediately below. Therefore, it is possible to further surely prevent the treated gas from remaining in the reaction site la. Thereby, in the reaction site la, the substrate to be processed 9 can be surely brought into contact with only the fresh process gas, and the concentration of the reaction component in the reaction site la can be further reliably prevented from decreasing. Further, the flow of the processing gas in the reaction site 158969.doc • 19·201220391 la can be surely equalized without depending on the position of the substrate 9 to be processed. Thereby, the uniformity of the etching process can be further improved. In the third embodiment shown in Fig. 12, three (plural) nozzles 3 are provided. The three nozzles 30 are arranged in the X direction at intervals. A processing gas is dispensed to the discharge holes 31 of the respective nozzles 3''. A rectifying plate 40 is disposed directly under each nozzle 3〇. The corresponding nozzle 30 and the rectifying plate 40 are vertically opposed to each other with a virtual plane pl therebetween. The configuration of each of the nozzles 3 such as the side in which the nozzles 3 are extended in the y direction (the direction orthogonal to the plane of the paper in Fig. 12) and the lower portion of the lower portion 3 3 are tapered is the same as that of the first embodiment. According to the present invention, even if a plurality of nozzles 30 are arranged in the weir direction, it is possible to prevent or suppress formation of stripe-shaped process spots extending in the y direction at the same intervals as the arrangement intervals of the nozzles 30 on the substrate to be processed 9. Fig. 13 is a view showing a fourth embodiment of the present invention. In this embodiment, the nozzles at both ends of the χ direction in the third embodiment (Fig. 12) serve as the exhaust nozzles 5A. The shape of the exhaust nozzle 50 is substantially the same as that of the process gas discharge nozzle 3〇. That is, the 'exhaust nozzle 50' includes one of the two sides of the χ direction, the inclined side faces 54, 54 and the front edge 55 facing the imaginary plane pL, and extends longer in the y direction (the width orthogonal to the plane of the drawing in Fig. 13) Direction). The inclined sides 54, 54 are close to each other as they approach the leading edge 55. The front end edge 55 extends linearly in the y direction. The scraping surface of the lower side portion 53 of the exhaust nozzle 50 which is orthogonal to the y direction is tapered so as to be pointed toward the virtual plane PL. A vent hole 51 is formed inside the exhaust nozzle 50. A suction path 5 is connected to the upper end of the exhaust hole 51. The suction path 5 is connected to the gas suction mechanism 4. The lower end portion of the vent hole 5 1 is opened at the front end edge 55, and is distributed in a slit shape over substantially the entire length of the nozzle 158969.doc -20·201220391 direction (the y direction orthogonal to the plane of the drawing in Fig. 13). The vent hole 5 1 may include a plurality of small holes arranged in the y direction instead of the slit shape. The discharge nozzles 30 are disposed between the exhaust nozzles 50 and 50 at both ends. The distance from the central axis CL of the discharge nozzle 30 to the central axis CL50 of each of the exhaust nozzles 50 is, for example, several tens of mm to several hundreds of minutes, and here is about 100 mm. Further, the discharge nozzles 3' may be disposed on either side of the exhaust nozzle 5 side. For example, when the distance from the position in the middle of the exhaust nozzles 50 and 50 to the center axis CL^ of the exhaust nozzle 50 is about 1 mm, the distance from the intermediate position may be several tens of mm ( The discharge nozzle 3 is disposed on the side of the exhaust nozzle 50 in a range of preferably about 2 mm. In the fourth embodiment, the gas around the exhaust nozzles 50, 50 at both ends is sucked into the exhaust hole 51 by the driving of the suction and exhaust mechanism 4. In particular, the gas at the lower end of each of the exhaust nozzles 50, that is, the periphery of the front end edge 55, is sucked into the exhaust hole 51. By this suction air flow, the flow f of the gas in the space between the respective exhaust nozzles 5 and the discharge nozzles 30 in the center can be stabilized, and the uniformity of the treatment can be further improved. The present invention is not limited to the above embodiments, and various modifications may be employed without departing from the spirit thereof. For example, the conveying mechanism can also be connected to the nozzle 30. It is also possible to move the nozzle 3 in the transport direction to make the substrate to be processed 9 stationary. The rectifying plate 40 can also be omitted. It is also possible to relatively increase the gap gl between the front edge of the nozzle 30 and the upper surface of the substrate to be processed 9. Thereby, the processing gas can be more easily diffused from the reaction portion 158969.doc •21 · 201220391 bit 1 a toward the diffusion space 1 e. For example, in the above embodiment, the preferable range of the gap gl is gl = l mm to l 〇 mm, but it is also possible to make § 1 = 1 〇 mm to 30 mm. A plurality of embodiments may be combined with each other. For example, the plurality of nozzles 30 shown in Fig. 12 may be formed by the nozzles 30 having the suction holes 39 in Fig. 1A, and the plurality of nozzles 30 shown in Fig. 12 may be formed by the nozzles 30 of the deformed shape of Figs. The shape of the exhaust nozzle 50 (Fig. 13) may be the same as that of the discharge nozzles 30 of Figs. 5 to 9 . [Example 1] An example will be described. Of course, the invention is not limited to the following embodiments. The amorphous Austenite film on the surface of the glass substrate 9 is etched using the etching apparatus 图 shown in Fig. 1 . The size of the nozzle 30 as a whole in the upper and lower directions is 55 mm, and the vertical height h of the inclined side surface 34 is h = 30 mm. The horizontal distance l from the upper end of the inclined side face 3 4 to the inner face of the discharge hole 31 is L = 10 mm. The angle θ of the inclined side faces 34 to the vertical faces is slightly less than 20. . The width of the discharge hole 31 in the weir direction is 2 mm. The length of the ejection hole 31 in the y direction is 6 mm, which is 1 mm larger than the dimension of the glass substrate 9 in the y direction. Each end portion of the discharge hole 31 in the 丫 direction protrudes outward from the glass substrate 9 toward the y direction. The rectifying plate 4 尺寸 The surface of the upper surface in the X direction is 63. The fluorine-based raw material gas component of the processing gas is as follows. CF4 0.8 slm
Ar 16.2 slm 對上述CF4及Ar之混合氣體中以露點成為丨3之方式添 加水（H2〇)。於電漿產生部丨丨將添加後之氣體電漿化。電源 158969.doc •22· 201220391 3之供給電力於直流時為450 V、9.0 A，且將其轉換為 Vpp=12 kV、25 kHz之高頻脈衝電壓後供給至電極12。進 而’將來自臭氧產生器16之含臭氧氣體混合於上述電激化 後之敗系氣體中’獲付處理氣體。含臭氧氣體之流量為 12.68 slm ’臭氧濃度為230 g/m3。該處理氣體係自喷嘴3〇 之喷出孔31喷出。喷出流速為0.4 m/s。 以4 m/min之搬送速度於X方向上搬送玻璃基板9 ,於噴嘴 3〇之前端緣之正下方之反應部位ia中，使該玻璃基板9與上 述處理氣體接觸。玻璃基板9穿過反應部位ia之次數（掃描 次數）為3次。喷嘴30之前端緣與被處理基板9之上表面之間 之間隙gl為gl = 7 mm。藉此’可對被處理基板9之表面之非 晶矽膜9a均一地進行蝕刻處理。未形成依賴於被處理基板9 之行進方向之位置之處理斑，且亦未形成於7方向上延伸之 條紋狀之處理斑。 [產業上之可利用性] 本發明可應用於半導體裝置或液晶顯示裝置之製造。 【圖式簡單說明】 圖1係本發明第1實施形態之蝕刻裝置之側視圖。 圖2係圖1之沿π_π線之平面剖面圖。 圖3係上述钱刻裝置之喷嘴之立體圖。 圖4係將上述蝕刻裝置之噴嘴之一部分放大進行表示之 側面剖面圖。 圖5係表示上述蝕刻裝置之噴嘴之變形例之側面剖面圖。 圖6係表示上述蝕刻裝置之噴嘴之變形例之側面剖面圖。 158969.doc -23· 201220391 圖7係表示上述蝕刻裝置之喷嘴之變形例之側面剖面圖。 圖8係表示上述蝕刻裝置之喷嘴之變形例之側面剖面圖。 圖9係表示上述蝕刻裝置之喷嘴之變形例之側面剖面圖。 圖10係本發明第2實施形態之蝕刻裝置之喷嘴之側面剖 面圖。 圖11係上述第2實施形態之蝕刻裴置之喷嘴之沿圖10之 XI-XI線之仰視圖。 圖12係本發明第3實施形態之蝕刻裝置之側視圖。 圖13係本發明第4實施形態之蝕刻裝置之側視圖。 圖14係完成本發明之過程中作為參考例之喷嘴裝置之側 面剖面圖。 圖1 5係完成本發明之過程中作為參考例之喷嘴裝置之側 面剖面圖。 圖1 6係完成本發明之過程中作為參考例之喷嘴裝置之側 面剖面圖。 【主要元件符號說明】 1 蝕刻裝置 1 a 反應部位 1 e 擴散空間 2 處理槽 3 電源 4 抽吸泵（氣體抽吸機構） 9 被處理基板 9a 含石夕物 158969.doc -24- 201220391 10 處理氣體供給部 11 電漿產生部 12 電極 13 放電空間（電極間空間） 14 氟原料供給部 15 添加部 16 臭氧產生器（氧化性反應成分供給部） 19 供給路 20 滾輪運送機（支撐部、搬送機構） 21 軸 22 滾輪 30 喷嘴 31 喷出孔 32 上側部分 33 下側部分 34 傾斜側面 35 前端緣 35A 面狀之前端緣 35e 刀口 36 凸部 37 凹部 38 抽吸口 39 吸入孔 40 整流板 158969.doc -25- 201220391 50 排氣喷嘴 51 排氣孔 53 下側部分 54 傾斜側面 55 前端緣 CL 中心軸 PL 虛擬平面 -26- 158969.docAr 16.2 slm Water (H2 〇) is added to the mixed gas of CF4 and Ar described above so that the dew point becomes 丨3. The added gas is plasmad in the plasma generating unit. Power supply 158969.doc •22· 201220391 The supplied power is 450 V and 9.0 A at DC, and is converted to a high-frequency pulse voltage of Vpp=12 kV and 25 kHz and supplied to the electrode 12. Further, the ozone-containing gas from the ozone generator 16 is mixed in the above-mentioned electric shock-derived gas to receive the treatment gas. The flow rate of the ozone-containing gas is 12.68 slm 'the ozone concentration is 230 g/m3. This process gas system is ejected from the discharge holes 31 of the nozzles 3A. The discharge flow rate was 0.4 m/s. The glass substrate 9 was conveyed in the X direction at a conveying speed of 4 m/min, and the glass substrate 9 was brought into contact with the processing gas in the reaction portion ia immediately below the end edge of the nozzle 3〇. The number of times (the number of scans) of the glass substrate 9 passing through the reaction site ia was three times. The gap gl between the front edge of the nozzle 30 and the upper surface of the substrate to be processed 9 is gl = 7 mm. Thereby, the amorphous germanium film 9a on the surface of the substrate to be processed 9 can be uniformly etched. A processing spot depending on the position of the traveling direction of the substrate 9 to be processed is not formed, and a stripe-shaped processing spot extending in the direction of 7 is not formed. [Industrial Applicability] The present invention is applicable to the manufacture of a semiconductor device or a liquid crystal display device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a side view of an etching apparatus according to a first embodiment of the present invention. Figure 2 is a plan sectional view taken along line π_π of Figure 1. Figure 3 is a perspective view of the nozzle of the above-described money engraving device. Fig. 4 is a side cross-sectional view showing a part of the nozzle of the etching apparatus in an enlarged manner. Fig. 5 is a side cross-sectional view showing a modification of the nozzle of the etching apparatus. Fig. 6 is a side cross-sectional view showing a modification of the nozzle of the etching apparatus. 158969.doc -23 201220391 Fig. 7 is a side cross-sectional view showing a modification of the nozzle of the etching apparatus. Fig. 8 is a side cross-sectional view showing a modification of the nozzle of the etching apparatus. Fig. 9 is a side cross-sectional view showing a modification of the nozzle of the etching apparatus. Fig. 10 is a side cross-sectional view showing the nozzle of the etching apparatus according to the second embodiment of the present invention. Fig. 11 is a bottom plan view of the nozzle of the etching apparatus of the second embodiment taken along line XI-XI of Fig. 10. Figure 12 is a side view of an etching apparatus according to a third embodiment of the present invention. Figure 13 is a side view of an etching apparatus according to a fourth embodiment of the present invention. Figure 14 is a side cross-sectional view showing a nozzle device as a reference example in the course of carrying out the invention. Fig. 15 is a side sectional view showing a nozzle device as a reference example in the course of carrying out the invention. Fig. 16 is a side sectional view showing a nozzle device as a reference example in the course of carrying out the invention. [Description of main component symbols] 1 Etching device 1 a Reaction site 1 e Diffusion space 2 Treatment tank 3 Power supply 4 Suction pump (gas suction mechanism) 9 Substrate to be processed 9a Contains stone 158969.doc -24- 201220391 10 Gas supply unit 11 Plasma generating unit 12 Electrode 13 Discharge space (interelectrode space) 14 Fluorine raw material supply unit 15 Adding unit 16 Ozone generator (oxidizing reaction component supply unit) 19 Supply path 20 Roller conveyor (support unit, transport) 21) 22 shaft 22 roller 30 nozzle 31 discharge hole 32 upper side portion 33 lower side portion 34 inclined side surface 35 front end edge 35A front end edge 35e knife edge 36 convex portion 37 recess 38 suction port 39 suction hole 40 rectifying plate 158969. Doc -25- 201220391 50 Exhaust Nozzle 51 Venting Hole 53 Lower Side 54 Inclined Side 55 Front End Edge CL Central Axis PL Virtual Plane -26- 158969.doc