1312167 玖、發明說明： 【發明所屬之技術領域】 本發明是關於用以高品質以及有效地乾燥處理例如半 導體θ曰圓、液晶顯示裝置用基板、記錄碟片用基板或光罩 用基板或其他基板表面的基板處理方法及基板處理裝置。 【先前技術】 爲了使各種基板之中例如半導體晶圓（wafer)(以下稱爲 晶圓）的表面潔淨，在利用藥液洗淨晶圓表面後，藉由純水 等的處理液進行洗淨’再使用有機溶劑例如異丙醇（以下稱 爲[IPA])(IPA:iSOpropyi aic〇h〇丨）等的有機溶劑進行使晶圓 車乙燥的處理。更具體爲此處理係由：在利用藥液以及純水洗 淨晶圓後’暴露於ΙΡΑ的蒸氣，在晶圓的表面使IpA凝結， 藉由此IPA的凝結’使到此爲止附著於晶圓的純水與ipA 置換’伴隨著此純水由晶圓的表面流下’沖洗微粒（particle) 等的污染物質之製程，以及之後使IPA蒸發，使晶圓表面 乾燥的乾燥製程構成。在此乾燥製程中，在晶圓的表面水 滴即使僅剩一點點的話，在晶圓表面也會形成有水痕（water m ark) ’此水痕與微粒一樣成爲使晶圓的品質惡化的原因。 因此’在半導體的製程中，必須不使這些污染物質等附著 於晶0 °而且，採取這種對策的晶圓等的基板表面處理方 法及處理裝置已多數被考慮實用化，在專利文獻中也有許 多被介紹。（例如參照下述專利文獻1以及2) 因此’以下一邊參照第1〇圖以及第n(a)〜（c)圖一邊說明下 述專利文獻1所揭示的基板處理裝置。此外，第10圖爲下述專 利文獻1所記載的基板處理裝置的剖面圖。此基板處理裝置1 1312167 具備：收容應處理的基板（例如晶圓）的處理: 的內部供給處理液（例如純水）的處理液導7 溶劑液（例如IP A )的蒸氣產生槽4、由處理 的處理液排出部5、供給在蒸氣產生槽4 溶劑用的加熱溶劑供給裝置6、6 _，前述基 等間距平行且垂直豎起的狀態下被傳送到| 進行各基板的表面處理。 在此基板處理裝置1藉由以下的製程， 如半導體晶圓W(以下稱爲晶圓w)的表面虔 1 )、晶圓的傳入製程 貯存有在待機狀態的處理裝置1的純水 2!被打開，複數片的晶圓W被傳送到處理 內’被投入/浸漬於純水J中，關閉蓋2 i。 供給管8,在處理槽2內供給惰性氣體例如 內的空氣被此氮氣置換。 2)、乾燥製程 其次’在晶圓W的水洗或漂洗進行後， 內供給冒泡用的氮氣N 2，使有機溶劑液例 生’產生的蒸氣由蒸氣吐出口 4,導入處理 純水：r之上的空間。 然後’內槽排液管5 ,的開關閥打開， 使內槽22內的純水]—點一點地排出，純水 晶圓W由其上端逐漸地露出到液面上。 若晶圓W的表面露出到液面上，則伴隨 內的IP A的蒸氣接觸到液面上的晶圓w的 槽2、在處理槽2 、管3、收容有機 槽2排出處理液 內被加熱的有機 板係在複數片以 蠢理槽2內，以 進行各種基板例 I理。 的處理槽2的蓋 !槽2的內槽22 然後由惰性氣體 氮氣，處理槽2 在蒸氣產生槽4 如IPA的蒸氣產 槽2內，充滿在 經由流量控制閥 J的液面下降， 丨於此，處理槽2 表面。此時，處 1312167 理槽2內的純水]因大致被設定於室溫，故晶圓w的溫度 也大致變成室溫。因此，I p A的蒸氣接觸晶圓w而急冷， IPA的蒸氣在液面上的晶圓你的表面凝聚，此凝聚的ipA 降低純水的表面張力’到此爲止附著於晶圓W的純水與此 IPA置換。完全排出純水}後’藉由自惰性氣體供給管％ 供給惰性氣體給處理槽2內，使I p A蒸發，晶圓W的表面 被乾燥處理。 3 )、晶圓的搬出製程 然後在內槽22內的純水J被排出後，經由排氣製程完 成基板處理’蓋2,被打開’晶圓W由處理槽2被取出。 如果依照此基板處理裝置，因在一個密閉的處理槽內進 行一連的處理製程，故無晶圓完全接觸大氣，可有效率地 處理晶圓，並且可抑制在晶圓表面附著微粒或水痕等的污 染物質。 但是，近年來被各種基板處理裝置處理的晶圓爲了提高 處理效率，需儘可能地將多數片晶圓插入處理槽內，由於 依照情況以50〜100片的批（lot)單位使晶圓在處理槽內同時 被處理，故各晶圓間的間隙有變的更窄的傾向，而且，晶 圓的直徑也由200mm大口徑化成300mm。因此，在直徑爲 200mm以下的較小的晶圓中雖然可抑制水痕的產生，但在 像直徑爲3 0 〇 m m的大口徑的晶圓中則會產生水痕，在習知 裝置的處理有界限。 因此，本發明者們由各種角度檢討這種水痕殘留的原因 的結果發現其原因爲乾燥氣體中的IPA蒸氣因係藉由使惰 性氣體在IPA中冒泡而得’故在未滿飽和濃度的IPA氣體 1312167 以外多羹地包含有I P A的液體粒（以下稱爲[霧滴](m 1 s t)) ’ 但此霧滴的大小（尺寸）以及質量遠比氮氣的大小（尺寸）以 及質羹籩，故很難通過窄的晶圓間的間隙，因晶圓的口徑 變成3〇Omm的話，在由IPA霧滴的供給口遠離的晶圓表面 很難供袷I P A霧滴，故無法充分地進行藉由IP A的置換。 即若乾燥氣體中所含的全IPA量相同，則IPA霧滴的尺寸 大的話其霧滴的數目減少，相反地，IPA霧滴的尺寸小的 話其霧滴的數目增加。而且，若IP A霧滴的尺寸大的話僅 該部分鸳量也重，移動速度變慢。因此，在上述2)的乾燥修 製程中，即使乾燥氣體被供給到處理槽內的複數片的晶圓 間’附菴於晶圓表面的洗淨液的水滴數與I p A霧滴的粒數 也不均衡，例如若IPA霧滴的粒數比水滴數少的話’一部 分的水滴不藉由IPA置換而殘留，成爲水痕的產生原因。 除此之外，因IPA霧滴的尺寸大且重，難以通過窄的晶 圓間的間隙，故在大口徑3 0 0 m m的晶圓中，經常在由供給 □遠離的晶圓表面，IPA霧滴在到達前就附著於附近的表 面。因此，在遠離的晶圓表面中，所供給的IPA霧滴的數 目變少，而且，IP A霧滴不會均等地供給。即雖然在接近 IPA霧滴的供給口的晶圓表面供給充分足夠的IPA霧滴， 但在比供給口還遠的晶圓表面則未被供給充分的IPA霧 滴’故在距IPA霧滴供給口遠的晶圓表面無法充分地進行 藉由附著於晶圓表面的洗淨液的IPA的置換，此點成爲水 痕的產生原因。 參照第1 1 (a)〜（C)圖說明此水滴藉由IP A置換的狀況。 此外’第1 1(a)〜（c)圖係模式地顯示乾燥處理時的IPA霧滴 1312167 與附著於晶圓W上的洗淨液的水滴（以下稱爲DIW)的關係 的剖面圖。在上述2)的乾燥製程中，如第1 1(a)圖所示，供 給包含尺寸大的IPA霧滴（液體）的IPA蒸氣與氮氣N2(氣體） 的混合氣體到處理槽內，供給到晶圓W間。於是，如第1 1 (b) 圖所示D IW被I P A蒸氣置換，但因IP A霧滴的尺寸大，故 移動速度慢，再者因在處理槽內同時處理多數片（5 0~ 1 00片） 大口徑的3 0 0 m m的晶圓，故因I P A霧滴的數量也被限定而 發生無法到達全部的DIW的情形。由於這種原因，在距乾 燥氣體的供給U遠的晶圓表面，IPA霧滴在到達前就附著φ 於附近的表面，在遠的表面IPA霧滴不被供給。因此，如 第1 1 (c)圖所示DIW殘留，此點成爲水痕的產生原因。 另一方面，在下述專利文獻2揭示無在有機溶劑中使惰 性氣體冒泡，在蒸發槽內使有機溶劑加熱蒸發，使有機溶 劑蒸氣與惰性氣體的混合氣體產生，在配管內另以惰性氣 體稀釋該混合氣體，並且用以加熱保溫由噴射噴嘴噴射而 成的基板處理裝置。在此基板處理裝置中，由配管內以及 由噴嘴噴出的氣體中的有機溶劑蒸氣完全變成氣體，若使 φ 用這種完全變成氣體的有機溶劑蒸氣，則氣體的有機溶劑 分子的大小遠比霧滴的大小還小，故使用如上述的有機溶 劑霧滴的情形的問題點不產生。 但是，即使使用完全變成氣體的有機溶劑蒸氣進行基板 處理，乾燥氣體中的有機溶劑蒸氣濃度因不爲飽和濃度以 上，故乾燥氣體中的有機溶劑的絕對量少。因此，在揭示 於下述專利文獻2的基板處理裝置中無法達成提供爲了使 有機溶劑蒸氣遍及大的基板的每一角落，與基板表面的水 -10- I312167 ^置換而相當花時間，故形成於上述基板表面的水痕少幾 $爲零，並且消除微粒的附著’乾燥處理速度高的基板處 埋方法及裝置之課題。 此外，一般[蒸氣]係顯示[氣體]’但在基板處理的技術 領域中如上述乾燥氣體，除了 [氣體]外由於包含[微小的液 體粒（霧滴）]者在慣用上也表現爲[蒸氣]乃至於[蒸汽 (vapor)]，故在本案說明書以及申請專利範圍中除了 [氣體] 外’包含[微小的液體粒（霧滴）]者也以[蒸氣]表示。 [專利文獻1 ] 日本特開200 1 - 2 7 1 1 8 8號公報（第1圖第 5頁左欄〜第6頁左欄） [專利文獻2] 日本特開平1卜1 9 1 549號公報（申請專利 範圍、段落[0018]〜[0024]、第1圖） 【發明內容】 因此，本發明者們根據上述的檢討結果重複種種檢討的 結果，發現若極度縮小構成有機溶劑的蒸氣的霧滴的尺寸 的話，可無增加有機溶劑的使用量而使有機溶劑霧滴的粒 數增大，而且可使僅各個霧滴的表面積小的但另一方面霧 滴的數目多的份以每一個霧滴的總和表示的全體的表面積 增大，而且，若將此全霧滴的表面積增大的有機溶劑蒸氣 噴射到基板表面，則可使其普遍地附著於附著在基板的水 滴，故可有效地置換此水滴成有機溶劑’達到實現本發明。 即本發明的第一目的爲提供藉由使用包含極小尺寸的 有機溶劑霧滴的乾燥氣體，實現高品質的表面處理，也縮 短處理時間的基板處理方法。 本發明的第二目的爲提供藉由調節乾燥氣體中的極小 -11 - 1312167 尺寸的有機溶劑霧滴的濃度，實現更高品質的表面 也縮短處s日寺胃自勺s f反Μ ί里方丨去° 本發明的第三目的爲提供用以可簡單地生成包 寸的有機溶劑霧滴的乾燥氣體’實現高品質的 g，也縮短處理時間的基板處理裝® ° 再者，本發明的第四目的爲提供藉由調節乾燥氣[Technical Field] The present invention relates to a high-quality and effective drying process such as a semiconductor θ circle, a substrate for a liquid crystal display device, a substrate for a recording disk, or a substrate for a photomask or the like. A substrate processing method on a substrate surface and a substrate processing apparatus. [Prior Art] In order to clean the surface of, for example, a semiconductor wafer (hereinafter referred to as a wafer) among various substrates, the surface of the wafer is washed with a chemical solution, and then washed with a treatment liquid such as pure water. 'The organic solvent such as isopropyl alcohol (hereinafter referred to as [IPA]) (IPA: iSOpropyi aic〇h) is used to carry out the treatment of drying the wafer car. More specifically, the treatment is performed by: after washing the wafer with the chemical liquid and the pure water, 'exposure to the vapor of the crucible, causing the IpA to condense on the surface of the wafer, thereby adhering to the crystal by the condensation of the IPA. The round pure water and ipA replacement are accompanied by a process in which the pure water flows down from the surface of the wafer to process the contaminated matter such as particles, and then the IPA is evaporated to dry the surface of the wafer. In this drying process, even if there is only a little water droplet on the surface of the wafer, water marks are formed on the surface of the wafer. 'This water mark is the same as the particle, which is the cause of deterioration of the quality of the wafer. . Therefore, in the process of the semiconductor, it is necessary to prevent the contamination substances from adhering to the crystal 0°, and the substrate surface treatment method and the processing apparatus such as wafers which take such countermeasures have been considered for practical use, and there are also patent documents. Many were introduced. (see, for example, the following Patent Documents 1 and 2). The substrate processing apparatus disclosed in Patent Document 1 will be described below with reference to the first drawing and the nth (a) to (c) drawings. Further, Fig. 10 is a cross-sectional view showing a substrate processing apparatus described in Patent Document 1 below. The substrate processing apparatus 1 1312167 includes a processing liquid guide for storing a substrate (for example, a wafer) to be processed: a processing liquid guide 7 for supplying a processing liquid (for example, pure water), and a vapor generating tank 4 for a solvent liquid (for example, IP A). The processing liquid discharge unit 5 to be processed and the heating solvent supply units 6 and 6 for supplying the solvent in the vapor generation tank 4 are transported to the surface in a state where the bases are equidistant and vertically erected, and the surface treatment of each substrate is performed. The substrate processing apparatus 1 stores the pure water of the processing apparatus 1 in the standby state by the following processes, such as the surface 虔1 of the semiconductor wafer W (hereinafter referred to as wafer w), and the incoming process of the wafer. ! is opened, and a plurality of wafers W are transferred into the process to be 'input/immersed in pure water J, and the lid 2 i is closed. The supply pipe 8 is supplied with air such as inert gas supplied into the treatment tank 2 by the nitrogen gas. 2) Drying process Next, after the water washing or rinsing of the wafer W is performed, the nitrogen gas N 2 for bubbling is supplied, and the vapor generated by the organic solvent liquid is generated by the steam discharge port 4, and is introduced into the treated pure water: r The space above. Then, the opening and closing valve of the inner tank discharge pipe 5 is opened to discharge the pure water in the inner tank 22, and the pure water wafer W is gradually exposed to the liquid surface from the upper end thereof. When the surface of the wafer W is exposed on the liquid surface, the vapor of the wafer W in contact with the inside of the liquid A is in contact with the groove 2 of the wafer w on the liquid surface, and is discharged into the treatment liquid in the treatment tank 2, the tube 3, and the storage tank 2. The heated organic sheet is placed in a plurality of sheets in the sloping tank 2 to carry out various substrate examples. The cover of the treatment tank 2! The inner tank 22 of the tank 2 is then filled with inert gas nitrogen, and the treatment tank 2 is filled in the steam generation tank 4 of the steam generation tank 4 such as IPA, and is filled with the liquid level falling through the flow control valve J, smashing Thus, the surface of the tank 2 is treated. At this time, since the pure water in the chamber 1312167 is set to room temperature, the temperature of the wafer w is also substantially changed to room temperature. Therefore, the vapor of I p A contacts the wafer w and is quenched, and the surface of the IPA vapor condenses on the surface of the wafer on the liquid surface. This condensed ipA lowers the surface tension of the pure water 'so pure to the wafer W. Water is replaced with this IPA. After the pure water is completely discharged, the inert gas is supplied into the treatment tank 2 from the inert gas supply pipe %, and I p A is evaporated, and the surface of the wafer W is dried. 3) Wafer unloading process After the pure water J in the inner tank 22 is discharged, the substrate processing is completed by the exhaust process, and the lid 2 is opened. The wafer W is taken out from the processing tank 2. According to the substrate processing apparatus, since a continuous processing process is performed in a closed processing tank, the wafer is completely exposed to the atmosphere, the wafer can be efficiently processed, and particles or water marks on the wafer surface can be suppressed. Contaminant. However, in recent years, in order to improve the processing efficiency of wafers processed by various substrate processing apparatuses, it is necessary to insert a plurality of wafers into the processing tank as much as possible, since the wafers are placed in units of 50 to 100 sheets in accordance with the situation. Since the processing chamber is simultaneously processed, the gap between the wafers tends to be narrower, and the diameter of the wafer is also 300 mm in diameter. Therefore, in a small wafer having a diameter of 200 mm or less, although generation of water marks can be suppressed, water marks are generated in a large-diameter wafer having a diameter of 300 μm, which is handled by a conventional device. There are boundaries. Therefore, the inventors of the present invention have examined the cause of the water mark residue from various angles and found that the reason is that the IPA vapor in the dry gas is caused by bubbling the inert gas in the IPA. The IPA gas 1312167 contains a liquid particle of IPA (hereinafter referred to as [fog] (m 1 st)). However, the size (size) and quality of the droplet are much larger than the size (size) and quality of the nitrogen.羹笾, it is difficult to pass the gap between the narrow wafers. If the diameter of the wafer becomes 3〇Omm, it is difficult to supply the IPA droplets on the surface of the wafer that is separated from the supply port of the IPA droplets. The replacement by IP A is performed. That is, if the amount of all IPA contained in the dry gas is the same, the number of droplets of the IPA droplets is large, and the number of droplets is decreased. Conversely, if the size of the IPA droplets is small, the number of droplets increases. Further, if the size of the IP A droplet is large, only the amount of the droplet is heavy, and the moving speed is slow. Therefore, in the drying process of the above 2), even if the dry gas is supplied to the wafers of the plurality of sheets in the processing tank, the number of water droplets of the cleaning liquid attached to the surface of the wafer and the particles of the I p A droplets The number is not uniform. For example, if the number of particles of the IPA droplet is smaller than the number of water droplets, a part of the water droplets do not remain by IPA replacement, and cause water marks. In addition, IPA droplets are large and heavy, and it is difficult to pass narrow gaps between wafers. Therefore, in wafers with a large diameter of 300 mm, often on the surface of the wafer away from the supply, IPA The droplets adhere to the nearby surface before they arrive. Therefore, the number of supplied IPA droplets is reduced in the far-away wafer surface, and the IP A droplets are not uniformly supplied. That is, although sufficient IPA droplets are supplied to the surface of the wafer close to the supply port of the IPA droplet, the surface of the wafer farther than the supply port is not supplied with sufficient IPA droplets, so the droplet supply is from the IPA. The replacement of the IPA of the cleaning liquid adhering to the surface of the wafer is not sufficiently performed on the surface of the wafer that is far away, and this is a cause of water marks. The state in which the water droplet is replaced by IP A will be described with reference to Figs. 1 1 (a) to (C). Further, the "1st" (a) to (c) drawings schematically show a cross-sectional view showing the relationship between the IPA droplet 1312167 during the drying process and the water droplets (hereinafter referred to as DIW) of the cleaning liquid adhering to the wafer W. In the drying process of the above 2), as shown in Fig. 1 (a), a mixed gas of IPA vapor and nitrogen gas N2 (gas) containing a large-sized IPA droplet (liquid) is supplied to the treatment tank, and supplied to the treatment tank. Wafer W. Therefore, as shown in Figure 1 1 (b), D IW is replaced by IPA vapor, but because of the large size of IP A droplets, the moving speed is slow, and the majority of the chips are processed simultaneously in the processing tank (5 0~1). 00 pieces) A large-diameter 300 mm wafer, so the number of IPA droplets is limited, and it is impossible to reach all DIWs. For this reason, on the surface of the wafer far from the supply U of the dry gas, the IPA droplets adhere to the nearby surface before reaching, and the IPA droplets are not supplied on the far surface. Therefore, as the DIW remains as shown in Fig. 1 (c), this point becomes a cause of water marks. On the other hand, Patent Document 2 listed below discloses that an inert gas is not bubbled in an organic solvent, and an organic solvent is heated and evaporated in an evaporation tank to generate a mixed gas of an organic solvent vapor and an inert gas, and an inert gas is further contained in the pipe. The mixed gas is diluted and used to heat and heat the substrate processing apparatus which is sprayed by the spray nozzle. In the substrate processing apparatus, the organic solvent vapor in the gas discharged from the inside of the pipe and from the nozzle is completely changed into a gas, and if φ is used as the organic solvent vapor which is completely changed into a gas, the size of the organic solvent molecule of the gas is much larger than that of the mist. Since the size of the droplet is still small, the problem of using the organic solvent mist as described above does not occur. However, even if the substrate treatment is carried out using an organic solvent vapor which is completely gas, the concentration of the organic solvent vapor in the dry gas is not more than the saturation concentration, so the absolute amount of the organic solvent in the dry gas is small. Therefore, in the substrate processing apparatus disclosed in the following Patent Document 2, it is not possible to provide a time for the organic solvent vapor to spread over every corner of the substrate, and it takes a considerable time to replace the water with the surface of the substrate. The problem that the water mark on the surface of the substrate is less than zero, and the adhesion of the particles is eliminated, and the method and apparatus for embedding the substrate with high drying speed are high. Further, in general, [vapor] shows [gas]', but in the technical field of substrate processing, such as the above-mentioned dry gas, in addition to [gas], it is also conventionally used because it contains [small liquid particles (fog)] [ Vapor] is a [vapor], so it is also indicated by [vapor] in addition to [gas] except for [gas] in the scope of the present specification and the patent application. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001- 2-7 1 1 8 8 (first picture, fifth page, left column, and sixth page, left column) [Patent Document 2] Japanese Special Kaiping 1 Bu 1 9 1 549 SUMMARY OF THE INVENTION The present inventors have repeated the results of various reviews based on the above-mentioned review results, and found that the vapors constituting the organic solvent are extremely reduced. When the size of the droplets is increased, the number of particles of the organic solvent droplets can be increased without increasing the amount of the organic solvent used, and the surface area of each of the droplets can be made small, but the number of droplets on the other side can be increased. The total surface area of a single mist droplet is increased, and if the organic solvent vapor having an increased surface area of the entire mist droplet is sprayed onto the surface of the substrate, it can be uniformly attached to the water droplet attached to the substrate. Effectively replacing this water droplet into an organic solvent' achieves the present invention. That is, a first object of the present invention is to provide a substrate processing method which achieves high-quality surface treatment and shortens processing time by using a drying gas containing a droplet of an organic solvent having an extremely small size. A second object of the present invention is to provide a higher quality surface and a shortened surface by adjusting the concentration of the organic solvent droplets of the size of the extremely small -11 - 1312167 in the drying gas.丨°° The third object of the present invention is to provide a substrate processing apparatus for achieving a high-quality g and a processing time for shortening the drying time of the organic solvent droplets which can be easily produced. The fourth purpose is to provide for adjusting the drying gas
^ i R寸的有機溶劑霧滴的濃度’實現更高品質的 極小八J _，也縮短處理時間的基板處理裝置° 爲了解決前述課題，與本案的申請專利範圍第1 的基板處理方法的發明係將由有機溶劑的蒸氣與惰 的混合氣體構成的乾燥氣體噴射到基板’進行基板 乾燥，其特徵爲：該有機溶劑的蒸氣包含次微米 (submicron size)的霧滴（mist) ° 而且，與本案的申請專利範圍第2項有關的發明 述申請專利範圍第1項所述之基板處理方法中，前 氣體係由在蒸氣產生部中藉由在有機溶劑中使惰性 泡而生成的有機溶劑蒸氣與惰性氣體構成的混合氣 當令前述蒸氣產生部內的溫度爲T,， 由前述蒸氣產生部到噴射噴嘴的前述有機溶劑 氣體構成的混合氣體的溫度爲τ2， 由噴射噴嘴噴出的乾燥氣體的溫度爲Τ3時，使 ®成爲如以下的關係而控制 丁丨 S Τ2$ τ3。 而且，與本案的申請專利範圍第3項有關的發明 述申請專利範圍第1項所述之基板處理方法中，前 處理， 含極小 表面處 體中的 表面處 項有關 性氣體 表面的 級尺寸 係在前 述乾燥 氣體冒 體， 與惰性 這些溫 係在前 述乾燥 -12- 1312167 板間’故乾燥處理效率提高，並且處理時間也能縮短，基 板表面的水痕的產生極少，或者可使其幾乎爲零。再者， 微粒的附著也消失’而且，因乾燥處理的速度快，故也能 防止微粒的再附著。 而且’在申請專利範圍第2項所述之基板處理方法中， 藉由在有機溶劑中使惰性氣體冒泡，得到與包含由有機溶 劑霧滴與未滿飽和濃度的有機溶劑氣體構成的有機溶劑蒸 氣之惰性氣體的混合氣體，該混合氣體因到由噴射噴嘴排 出爲止係相同溫度或慢慢地升高而進行溫度控制，故有機鲁 溶劑在移動中由有機溶劑霧滴的表面慢慢地氣化，霧滴的 粒徑變小，容易得到包含次微米級尺寸的有機溶劑霧滴的 乾燥氣體。 而且’在申請專利範圍第3項所述之基板處理方法中， 在由在蒸氣產生部中生成的有機溶劑霧滴與未滿飽和濃度 的有機溶劑氣體構成的有機溶劑蒸氣與惰性氣體的混合氣 體’更追加與冒泡所使用的惰性氣體同種的惰性氣體而稀 釋’故有機溶劑霧滴凝聚的機會減少，並且混合氣體中的馨 有機溶劑蒸氣濃度更下降，此外，可傳送（載送__carrier：^ 多IP A霧滴到晶圓與晶圓之間。因此，該混合氣體因到由 噴射噴嘴排出爲止係相同溫度或慢慢地升高而進行溫度控 制’故有機溶劑的一部分由有機溶劑霧滴的表面氣化，成 爲微霧滴（micro mist)的速度以及效率提高，雖然爲低濃度 但獲得包含多數的次微米級尺寸的有機溶劑霧滴的多量的 乾燥氣體’可連續多量的次微米級尺寸的有機溶劑霧滴， 噴射到基板表面。其結果，即使多數的大口徑基板被插入 -16- 1312167 處理槽內，因次微米級尺寸的霧滴可急速地浸入基板間， 故附著於基板的洗淨液被連續供給此多量的次微米級尺寸 的有機溶劑的蒸氣急速地置換，其結果，乾燥處理效率提 高，並且處理時間也能縮短，乾燥處理極爲快速。因此， 特別是無增加有機溶劑的使用量，乾燥處理效率提高，並 且處理時間也能縮短，基板表面的水痕的產生極少，或者 可使其幾乎爲零，而且，微粒的附著也消失，而且，因乾 燥處理的速度快，故也能防止微粒的再附著。 而且，如果依照申請專利範圍第4項所述之基板處理方 法，有機溶劑與惰性氣體的選擇寬度寬，可藉由任意的組 合適應於種種的基板處理。 再者’如果依照本案的申請專利範圍第5項所述之基板 處理裝置，得到藉由控制各處所附設的加熱器，可容易地 生成包含次微米級尺寸的有機溶劑的乾燥氣體，可容易實 施前述申請專利範圍第1項所述之基板處理方法的基板處 理裝置。 而且，如果依照申請專利範圍第6項或第7項所述之基 板處理裝置，得到可容易實施前述申請專利範圍第2項或 第3項所述之基板處理方法的基板處理裝置。 而且’如果依照申請專利範圍第8項所述之基板處理裝 置’因在則述申請專利範圍第7項所述之基板處理裝置 中’於前述第一配管與第二配管的連接點的下游，在前述 噴射噴嘴的上游配設靜態攪拌器’故得到惰性氣體、有機 溶劑霧滴、有機溶劑氣體充分地混合，均質的混合氣體， 故微霧滴的生成效率提高。 -17- 1312167 而且，如果依照申請專利範圍第9項所述之基板處理裝 置，有機溶劑與惰性氣體的選擇寬度寬，可藉由任意的組 合適應於種種的基板處理。 【實施方式】 以下一邊參照圖面一邊說明本發明的較佳實施形態。但 是，以下說明的實施形態係舉例說明用以具體化本發明的 技術思想的基板處理方法及基板處理裝置，並非意圖限定 本發明於此，包含於申請專利範圍的其他實施形態者也可 相等地適用。第1圖是顯示本發明的一實施形態的基板處φ 理裝置的剖面圖，第2圖是來自處理槽的一方側的側視 圖，第3圖是來自處理槽的他方側的側視圖，第4圖是蓋 體的俯視圖（此圖是由蓋體上部透視的俯視圖），第5圖是 弟4圖所不的蓋體的側視圖。 參照第1圖’此基板處理裝置1 〇係用以處理基板的 一例爲半導體晶圓的裝置。在此所述的處理係指包含利用 藥液蝕刻（e t c h 1 n g)晶圓W的製程、氫氟酸處理晶圓w的表 面之製程或水洗晶圓W的漂洗（rinse)處理製程，以有機溶 _ 劑乾燥水洗後的晶圓W的乾燥處理製程等。這些一連的處 理係在一個處理槽1 5內連續進行。 處理槽15如第2〜5圖所示係設置於具有可與其附屬裝 置一起收容的容積的收容室1丨。附屬裝置爲進行收容室內 的空調的空調裝置、對處理槽供給各種處理液的供給源、 晶圓傳送機構等’在圖中這些被省略。處理槽1 5具備頂面 開口的有底箱形的內槽2 0、包圍此內槽2 〇的上部外周的外 槽25、覆蓋此內槽20的開口的蓋體3〇，內外槽2〇、25係 1312167 蓋體3 0如第5圖所示由具有下部開口上部閉鎖在內部 可收容集合多數片晶圓w的晶圓集合體W ’的大小的箱狀 容器31構成’此箱狀容器31係由不易被氫氟酸或IPA等 的有機溶劑腐蝕的材料形成。此蓋體3 〇係可藉由移動裝置 5 5 (參照第3圖）朝水平方向移動。此移動裝置55如在第2 圖的箭頭所示’藉由在內槽2 0的上部使蓋體3 0朝水平方 向移動’以堵塞或打開內槽20的開口。即朝垂直方向舉起 位於內槽20上的蓋體30預定距離，朝水平方向移動，然 後’朝垂直方向的下方降下，保持於待機狀態。此蓋體3 0 的移動係在將晶圓集合體W’傳入到內槽20內以及由內槽 20內取出處理完的晶圓集合體時進行。 而且，箱狀容器31如第5圖所示，在其上部形成有略 拱狀的頂面32，在此頂面32，噴射惰性氣體的複數個噴射 噴嘴3 3 ,〜3 3 7係大致等間隔地排列成四方而配設。複數個 噴嘴3 3如第4圖所示位於晶圓集合體W ’的上方，在行方 向以大致等間隔排列的複數個噴射噴嘴33,〜3 3 7在列方向 也大致等間隔地配設有複數列。在第4圖中在行方向排列7 個爲6列，共計4 2個噴射噴嘴3 3 , ~ 3 3 7 6係配設於晶圓集合 體W ’的上部外周緣。行方向中的7個噴射噴嘴3 3 , ~ 3 3 7與 晶圓集合體W ’的關係如第5圖所示係使各噴射噴嘴3 3 , 〜3 3 7與晶圓集合體W ’的外周緣的距離大致相等而配設於頂 面3 2。藉由形成頂面3 2爲拱狀’晶圓W因成略圓板狀， 故使上述距離相等變的容易。此頂面的形狀係配合晶圓W 的形狀而變更，使上述距離大致相等較佳。 噴射噴嘴3 3如第5圖所示連接有氣體供給管3 4 2，此供 -20- 1312167 給管3 4 2被分歧’在這些分歧管3 4 2|、3 4 2 2，各個噴射噴嘴 3 3的個數相同或結合有大致相等的數目。據此，在各噴射 噴嘴可大或均等地分配氣體。這些噴射噴嘴3 3係分別使用 噴射氣體以預定角度擴散者，在由各噴射噴嘴3 3朝晶圓集 合體W ’的外周緣噴射氣體時，令接鄰的噴射噴嘴例如噴射 噴嘴3 3 2與噴射噴嘴3 3 3之間的噴射氣體在晶圓集合體W， 的外周緣b重疊而設定較佳。藉由如上述排列複數個噴射 噴嘴3 3於頂面3 2 ’可大致均勻地供給氣體給晶圓集合體 W，。 噴射噴嘴33係全體形狀呈圓錐狀，在頭細的前端形成 有開孔’由此開孔噴射乾燥氣體。而且在各噴射噴嘴3 3附 設有加熱器（省略圖示）。噴射噴嘴自身由於已經是公知， 故省略詳細的說明。再者，在氣體供給管3 4 2以及由此管 分歧的各分歧管342|、3422於管體的外周壁面附設有加熱 器（省略圖示）。此加熱器例如使用帶式加熱器（b e 11 heater)。這些加熱器係連接於CPU12，藉由此CPU控制。 在內外槽20、25與蓋體30之間如第2、3、5圖所示， 配設有中間連結構件26以及多孔板插入機構27。中間連結 構件2 6係以具有與蓋體3 0的下部開口相同大小的開口的 筒體狀形成。此筒體狀係由不易被氫氟酸或I p A等的有機 溶劑腐蝕的材料形成。此中間連結構件2 6係配設於多孔板 插入機構2 7的上方’使下方的開口 2 6 2大致對接於收容多 孔板的框體2 7 i的頂面而被定位，上方的開口 2 6 i與箱狀容 器3 1的下部開口 3 1 i嵌合。此外’用以直接嵌合蓋體3 0 於框體2 7 ,而省略中間連結構件2 6也可以。 -21 - 1312167 多孔板2 8在乾燥完成預定處理的晶圓集積體w，的製程 中’由插入內外槽20、25與中間連結構件26之間的平板 狀的平板（piate)構成，在板狀面穿設有複數個小孔。此多 孔板係由不易被氫氟酸或IPA等的有機溶劑腐蝕的材料形 成。此多孔板28被收容於框體27i內，連結於移動機構（省 略圖不）’如第2圖所示在水平方向滑動。收容多孔板28 的框體27!具有預定的縱寬（垂直方向），用以在多孔板28 被收容於框體27,時，在框體27,與多孔板28之間形成有 間隙272 。 此間隙2 7 2例如爲2 m m左右的間隙，在乾燥製程中乾燥 氣體的一部分被排放到水槽29內。因此，因在內槽20與 蓋體30之間形成有間隙2 7 2 (在第7圖中以X表示此間隙）， 故藉由此間隙X使內槽2 0與蓋體3 0之間無被密閉而是半 密閉’即乾燥處理部以及洗淨處理部與水槽29之間成爲半 密閉狀態。而且，多孔板28被插入內外槽20、25與中間 連結構件2 6之間’區分內槽2 0與蓋體3 0，即當作隔開洗 淨處理部與乾燥處理部的擋板（s h u 11 e 1.)而發揮功能。 其次，參照第1圖說明前述處理槽1 5與附屬裝置的配 管連接。在配設於內槽20底部的處理液供給部22連接有 處理液導入管22,，此導入管22i經由流量控制閥以及泵浦 (p u m p)連接於純水供給源3 8。此處理液導入管2 2 t呈現處 理液供給系配管的功能，以此配管與流量控制閥以及泵浦 構成有洗淨液供給裝置。而且，在此處理液導入管22,同 樣地經由流量控制閥也連接於藥液供給源3 9。藥液供給源 3 9具備用以調製所希望的藥液成預定濃度以及預定溫度的 -22- 1312167 接於蒸氣產生槽3 7〆朝蒸氣產生槽3 7 ,的底部供給氮氣 I ’在貯存於蒸氣產生槽37 j內的IPA內使氣泡產生（冒 泡：b U b b 11 n g ) ’生成由丨P A氣體以及霧滴構成的I P A蒸氣。 而且’由此蒸氣產生槽3 7 ,導出的配管3 7,2係經由靜態攪 泮器Μ連結於氣體供給管3 4 2，由蒸氣產生槽3 7 ,朝噴射噴 嘴33供給載氣ν2以及ίρΑ蒸氣的混合氣體。在配管35ι2、 37,2 ' 的管體的外周壁面附設有帶式加熱器（省略圖 不）’這些加熱器係藉由C Ρυ丨2進行溫度控制。此外，靜態 擾ί半器Μ係用以促進由載氣ν2以及ΙρΑ蒸氣構成的混合氣 體的混合程度使其均質化而配設。 第一惰性氣體供給源34係經由配管34ι對配管37ι2供 給惰性氣體之氮氣Ν 2。此配管3 4 !也藉由帶式加熱器控制 成預定的溫度。此氮氣&不僅爲來自蒸氣產生槽37 i的惰 性氣體與有機溶劑蒸氣的混合氣體的稀釋，也使用於處理 槽15內的沖吹（purge)或精乾燥。此外，惰性氣體除了氮氣 外’也能適宜選擇使用氬、氨。 其次，參照第6圖 '第7(a)〜（d)圖說明使用此基板處理 裝置的一連的處理。此外，第6圖係顯示一連的處理的時 序圖（time chart)，第7(a)〜⑷圖係顯示洗淨/乾燥製程，第 7 (a)圖係說明洗淨製程的剖面圖，第7 (b)圖係說明乾燥製程 1的剖面圖，第7 (c)圖係說明乾燥製程2的剖面圖’第7 (d) 圖係說明乾燥製程3的剖面圖。 參照第1、6圖，首先打開處理槽1 5的蓋體3 0 ’收容晶 圓集合體W，於內槽2 0內。此時在內槽2 0內，所希望的藥 液例如氫氟酸（H F)由藥液供給源3 9經由處理液導入管2 2 , 1312167 與處理液供給部2 2供給貯存到內槽2 0。因此，晶圓集合體 W ’藉由浸漬於此處理液，進行依照藥液的處理（例如蝕刻或 氫氟酸處理、洗淨等）。 此藥液處理終了後如第7(a)圖所示，純水DIW由純水 供給源38經由處理液導入管22,與處理液供給部22供給到 內槽2 0。此純水供給係一邊由內槽2 0的上部溢出一邊進 行。由內槽20溢出的純水DIW流入外槽25，由排洩管25, 經由排水管排出。花較長的時間進行此純水的供給，壓出 殘留於內槽20內的前述藥液HF。 此洗淨製程終了後，在第7 (b)圖所示的乾燥製程1中停 止純水DIW的連續供給，一邊供給少量的純水（〇 I w的節約 用水）’ 一邊由內槽20慢慢地（Slow up Speed)拉起晶圓集合 體W ’。與此晶圓集合體W ’的拉起同時也能供給少量的IPA 蒸氣到處理槽1 5內。 其次，在第7(c)圖所示的乾燥製程2中使處理槽15底 部的排出口 2 12的排洩機構閥動作，快速地排出處理液， 使多孔板28水平移動於框體，插入內外槽20、25 與中間連結構件2 6之間。再者，在內槽2 0內供給由被加 溫的氮氣N2與IPA蒸氣的混合氣體構成的乾燥氣體。這些 動作如圖所示係同時進行。此乾燥氣體在配管3 4 2以及噴 嘴3 3內被加熱。在此製程中，處理槽1 5內的有機溶劑的 蒸氣與各晶圓W的表面接觸，IPA的霧滴在晶圓W的表面 凝聚，形成有IPA的膜。若在晶圓W的表面形成有有機溶 劑的膜，則因到此爲止附著於晶圓W的純水與IP A置換， 故表面張力小，會由晶圓W的表面流掉，並且附著於基板 -25- 1312167 表面的IPA會蒸發。在第7(d)圖的乾燥製程3中爲了使被 置換的IPA乾燥而供給氮氣N2，乾燥製程3終了後由處理 槽1 5取出晶圓集合體W，。 在上述製程中’蓋體3 0 (乾燥處理部）內的壓力比水槽內 的壓力及其排氣根源的壓力高，且比內槽20(洗淨處理部） 的壓力及其排氣根源的壓力高。因此，乾燥處理部內的乾 燥氣體的流動變成層流，平順地由排氣管排氣到槽外，在 此過程中’乾燥氣體均勻地供給到每一片晶圓，無在基板 的表面形成有水痕’而且，也能防止微粒的除去以及附著。 而且，因無乾燥氣體在處理槽內回流，故也能阻止微粒的 再附著。 而且，此時第1圖的各處的溫度T,、TV、T4、T2''以及 Τ 3的溫度關係係藉由C P U 1 2控制各處的加熱器以滿足以下 的關係而設定。 Τ,^ Τ2'^ Τ4^ Τ2"^ Τ3 .....(1) 其中 蒸氣產生槽的溫度：1]^， 配管3 7,2內的溫度：Τγ， 配管34丨內的溫度：T4， 配管3 4 2內的溫度：Τ 2' ’， 噴射噴嘴內的溫度：Τ3， 如此，藉由各處的溫度τ,、TV、τ4、Τ，以及τ3的溫度 滿足上述（1)而設定’使由噴射噴嘴3 3噴射的I Ρ Α霧滴的 尺寸成爲極小的粒徑的霧滴。具體上，在廷德爾現象 (T y n d a 11 p h e η 〇 m e η ο η)中不會被觀察到的程度的極微粒的霧 -26- 1312167 滴，即成爲次微米級尺寸的霧滴。即若爲數微尺寸的霧滴’ 則可藉由廷德爾現象確認，但若成爲次微米級尺寸的話也 無法藉由廷德爾現象確認’需要特殊的測定裝置。在本實 施形態中，上述的IPA霧滴的尺寸因無法藉由廷德爾現象 確認，故成爲次微米級尺寸。但是，此次微米級尺寸的霧 滴並非完全氣體化，而是以液體狀態存在。此外’ T 3係不 使ΙΡΑ的霧滴完全氣化而控制於ΙΡΑ的沸點（82.4°C )以下。 藉由令構成有機溶劑的蒸氣的霧滴的尺寸爲次微米級 尺寸，無增加有機溶劑的使用量，僅使有機溶劑霧滴的粒 數增大，各個霧滴的表面積小的粒數多的份全體的表面積 增大。其結果因可使有機溶劑的蒸氣的比表面積（sPecific surface area)增大，噴射到基板，故與洗淨液的置換效率變 佳。 而且，在上述（1)式的溫度設定中，各溫度相同或慢慢 地升高較佳。即在蒸氣產生槽37,藉由在IPA中使惰性氣 體冒泡，得到與包含由IPA霧滴與未滿飽和濃度的IPA氣 體構成的IP A蒸氣之惰性氣體的混合氣體’惟該混合氣體 因到由噴射噴嘴排出爲止係相同溫度或慢慢地升高而被維 持，在配管以及噴射噴嘴內無有機溶劑的蒸氣凝聚’故混 合氣體中的有機溶劑霧滴的直徑也不會變大，此外’配管 以及噴嘴內I P A在移動中由I p A霧滴的表面慢慢地氣化’ 霧滴的粒徑變小，故容易得到包含次微米級尺寸的IPA霧 滴的乾燥氣體。 再者’由包含在蒸氣產生部37,生成的IPA霧滴與未滿 飽和濃度的I P A氣體構成的I P A蒸氣之惰性氣體構成的混 -27- 1312167 合氣體因另外被由配管3七供給的惰性氣體稀釋’前述混 合氣體中的IPA氣體濃度下降’故來自1PA霧滴的115八的 氣化更被促進，並且可供給包含多量的惰性氣體以及§午多 次微米級尺寸的IP A霧滴之乾燥氣體給處理槽1 5 °此情形 使重新供給的氮氣N2有效地混合於IP A蒸氣等’在配管3 42 的途中配設攪拌器Μ進行攪梓較佳。此攪拌器以靜態攪拌 器較佳。 如此，在乾燥氣體中若含有許多次微米級尺寸的1 ΡΑ霧 滴，則即使多數的大口徑基板被插入處理槽1 5內’因微尺 寸的霧滴可急速地浸入基板間’故附著於基板的洗淨液被 連續供給此多量的次微米級尺寸的有機溶劑的蒸氣急速地 置換，其結果，乾燥處理效率提局’並且處理時間也能縮 短，乾燥處理極爲快速。因此’特別是無增加有機溶劑的 使用量，乾燥處理效率提高’並且處理時間也能縮短’基 板表面的水痕的產生極少’或者可使其幾乎爲零’而且’ 微粒的附著也消失，而且’因乾燥處理的速度快，故也能 防止微粒的再附著。 此外，在上述樣態中雖然顯示用以由配管34,供給稀釋 用惰性氣體，惟爲了得到次微米級尺寸的ΙΡΑ霧滴，此稀 釋用惰性氣體未必需要。此情形使連結蒸氣產生槽37,與 噴嘴33的配管37]2、3 4 2、3 4 21以及3 4 2 2的溫度完全不同而 滿足上述（1)式以進行溫度控制也可以，或者維持在完全相 同的溫度Τ 2，成爲 Τ, ^ Τ, ^ τ3 而進行溫度控制也可以。 -28- 1312167 再者，配管以及噴射噴嘴內的溫度τ3設定成與供給到 蒸氣產生部的有機溶劑的溫度Τ,以及惰性氣體的溫度τ2 相同或比其還高。據此，在配管以及噴射噴嘴內無有機溶 劑的蒸氣凝聚，故乾燥氣體中的有機溶劑霧滴的直徑也不 會變大，此外，因在由噴嘴噴出前，自有機溶劑霧滴的表 面有機溶劑的一部分更氣化，故乾燥氣體中的有機溶劑霧 滴的大小可容易成爲次微米級尺寸。而且，因有機溶劑蒸 氣在配管以及噴射噴嘴內不凝聚，故也無ΙΡΑ的滴由噴嘴 落下的煩惱。 此外’在本實施樣態中，爲了防止有機溶劑霧滴彼此的 碰撞以及朝有機溶劑霧滴的機器的壁的碰撞，防止有機溶 劑霧滴直徑的增大以及霧滴的凝聚，如以下構成裝置的構 成構件較佳。即蒸氣產生部的冒泡槽作成頂部爲圓錐狀或 圓弧狀。而且’乾燥氣體供給配管作成層差少口徑未大幅 地變化。再者’蒸氣產生部的冒泡噴嘴係使用噴出徑小噴 射速度高者。 更進一步’使用包含此次微米級尺寸的ΙΡΑ霧滴的乾燥 氣體’說明附著於基板的洗淨液被此霧滴置換的狀況。第 8、9圖係模式地顯示乾燥處理時的ΙΡΑ蒸氣與基板的關係 的剖面圖’第8圖係顯示乾燥氣體包含次微米級尺寸的丨p a 霧滴但不被惰性氣體稀釋的情形，第9圖係顯示乾燥氣體 包含次微米級尺寸的IPA霧滴並且被惰性氣體稀釋的情 形。此外’第8(a)、（b)圖以及第9(a)、（b)圖係相當於第6 圖的[乾燥2]的製程’第8(c)圖以及第9(c)圖係相當於第6 圖的[乾燥3]的製程。如第8(a)圖所示，若將由次微米級尺 -29- 1312167 寸的IPA霧滴（液體）與氮氣N2(氣體）的混合氣體構成的乾 燥氣體送到處理槽1 5內’供給到晶圓W間的話’藉由此 乾燥氣體的供給，如第8(b)圖所示附著於晶圓W的DIW被 IP A置換，但因1 p A霧滴被微粒化而大大地被供給，對一 個DI W複數個I P A粒附著於D I W ’故D IW被有效地置換。 其次，如第8(c)圖所示藉由僅將I氣體送到處理槽15內’ 使IP A蒸發。此情形在[乾燥2 ]的製程（第8 (a)以及（b)圖） 中，因氮氣N 2的供給量少’故IP A霧滴的載送效果不充分’ 在藉由使用次微米級尺寸的霧滴得到大致良好的乾燥效果® 的大口徑晶圓的乾燥所使用的情形’有僅殘留DIW的水痕 剩餘的情形。 而且，乾燥氣體包含次微米級尺寸的IP A霧滴並且進一 步被惰性氣體稀釋的情形係乾燥氣體中的IPA蒸氣的濃度 低，但I P A霧滴的載送效果充分，故如第9 (a)〜（c)圖所示’ 藉由大量的載氣可連續均勻地供給次微米級尺寸的1 P A霧 滴到晶圓W的深處。因藉由包含此大量載氣的乾燥氣體’ 次微米級尺寸的IPA霧滴快速地附著於DIW ’故DIW被有鲁 效地置換。其結果，即使是在大口徑晶圓的乾燥使用的情 形，乾燥處理效率也提高’並且因處理速度提高’故可縮 短處理時間，如第9 (c)圖所示’由基板W的表面可使D IW 實質上爲零，即可完全消除水痕的產生。此外’此第9(a) 〜（c )圖所示者除了第8 (a)〜（c )圖的情形與新的氮氣混入外 均相同，故其詳細的說明省略。 【圖式簡單說明】 第1圖是顯示本發明的一實施形態的基板處理裝置的 -30- 1312167 剖面圖。 第2圖是顯示本發明的一實施形態的處理槽的側視圖。 第3圖是由他方側看圖2的處理槽的側視圖。 第4圖是由本發明的一實施形態的處理槽中的蓋體的 上部透視的俯視圖。 第5圖是第4圖所示的蓋體的側視圖。 第6圖是顯示一連的處理的時序圖的圖。 第7 (a)〜（c)圖是顯示洗淨/乾燥製程，第7 ( a )圖是說明 洗淨製程的剖面圖，第7(b)圖是說明乾燥製程1的剖面圖， 第7(c)圖是說明乾燥製程2的剖面圖，第7(d)圖是說明乾 燥製程3的剖面圖。 桌8(a)〜（c)圖是模式地顯示乾燥製程中的ιρΑ蒸氣與 基板的關係的剖面圖。 第9(a)〜（c)圖是與第8(a)〜（c)圖一樣，模式地顯示使 用稀釋用氮氣的情形的乾燥製程中的IPA蒸氣與基板的關 係的剖面圖。 第丨〇圖是顯示習知技術的基板處理裝置的剖面圖。 第11(a)〜（〇圖是模式地顯示第10圖的基板處理裝置 的乾燥製程中的IPA蒸氣與基板的關係的剖面圖。 【符號說明簡單說明】： 1 ' 1 〇 :基板處理裝置 2 ' I 5 :處理槽 2>:蓋 2 2、2 〇 :內槽 2 1 2:處理液排出孔 1312167 3、2 9 : 水槽 4 :蒸氣產生槽 4 t :蒸氣吐出口 5 ·_排氣管 5 ,:內槽排液管 7 :氮氣供給源 8 :蒸汽吐出口 8 i :惰性氣體供給管^ i R inch concentration of organic solvent droplets 'to achieve a higher quality of the extremely small J J _, and also to shorten the processing time of the substrate processing apparatus ° In order to solve the above problems, and the invention of the scope of the first application of the substrate processing method of the present invention Spraying a drying gas composed of an organic solvent vapor and an inert mixed gas onto a substrate to perform substrate drying, wherein the vapor of the organic solvent contains a submicron size mist (°), and In the substrate processing method according to the first aspect of the invention, the precursor gas system is composed of an organic solvent vapor generated by injecting an inert bubble in an organic solvent in a vapor generating portion. In the mixed gas of the inert gas, when the temperature in the steam generating portion is T, the temperature of the mixed gas composed of the organic solvent gas from the steam generating portion to the injection nozzle is τ2, and the temperature of the dry gas discharged from the injection nozzle is Τ3. At the time, the ® is controlled as follows to control Ding S Τ 2$ τ3. Further, in the substrate processing method according to the first aspect of the invention, which is related to the third aspect of the present invention, the pretreatment, the surface size of the surface of the gas-related surface in the surface containing the extremely small surface is In the case of the above-mentioned dry gas, and the inertness of these temperatures are between the aforementioned dried -12-13122167 plates, the drying treatment efficiency is improved, and the treatment time can be shortened, and the occurrence of water marks on the surface of the substrate is extremely small, or it can be made almost zero. Further, the adhesion of the fine particles also disappears. Moreover, since the drying process is fast, re-adhesion of the fine particles can be prevented. Further, in the substrate processing method according to the second aspect of the invention, the inert gas is bubbled in an organic solvent to obtain an organic solvent comprising an organic solvent gas containing a droplet of the organic solvent and an insufficient saturated concentration. a mixed gas of an inert gas of steam, which is temperature-controlled by the same temperature or slowly rising until it is discharged from the injection nozzle, so that the organic solvent is slowly gasified by the surface of the organic solvent droplet during the movement. The particle size of the mist droplets becomes small, and a dry gas containing a droplet of an organic solvent having a submicron size is easily obtained. Further, in the substrate processing method according to the third aspect of the invention, the mixed solvent of the organic solvent vapor and the inert gas composed of the organic solvent mist generated in the vapor generating portion and the organic solvent gas having a less saturated concentration 'It is diluted with the same inert gas as the inert gas used for bubbling', so the chance of coagulation of the organic solvent droplets is reduced, and the concentration of the sweet organic solvent vapor in the mixed gas is further lowered, and in addition, it can be transported (carrier __carrier :^ Multiple IP A droplets are dropped between the wafer and the wafer. Therefore, the mixed gas is temperature-controlled due to the same temperature or slowly rising from the discharge nozzle. Therefore, part of the organic solvent is made of organic solvent. The surface of the droplet is vaporized, and the speed and efficiency of the micro mist are increased. Although the concentration is low, a large amount of dry gas containing a large number of submicron-sized organic solvent droplets can be obtained continuously for a large number of times. Micron-sized organic solvent droplets are sprayed onto the substrate surface. As a result, even most large-diameter substrates are inserted at -16-13312 In the cell, the droplets of the sub-micron size can be rapidly immersed between the substrates, so that the cleaning liquid adhering to the substrate is rapidly supplied with the vapor of the organic solvent having a large amount of submicron-sized size, and as a result, drying is performed. The treatment efficiency is improved, the treatment time can be shortened, and the drying treatment is extremely fast. Therefore, in particular, the use amount of the organic solvent is not increased, the drying treatment efficiency is improved, the treatment time is also shortened, and the occurrence of water marks on the surface of the substrate is extremely small, or It can be made almost zero, and the adhesion of the particles is also lost, and since the drying process is fast, the re-adhesion of the particles can be prevented. Moreover, according to the substrate processing method according to the fourth aspect of the patent application, The organic solvent and the inert gas have a wide selection width and can be adapted to various substrate treatments by any combination. Further, if the substrate processing apparatus according to the fifth application of the present application is obtained by controlling the various parts The heater can easily generate a drying gas containing an organic solvent of a submicron size, which can be easily implemented. The substrate processing apparatus of the substrate processing method according to the first aspect of the invention, wherein the substrate processing apparatus according to the sixth or seventh aspect of the patent application is capable of easily implementing the second aspect of the aforementioned patent application. The substrate processing apparatus of the substrate processing method according to claim 3, wherein the substrate processing apparatus according to claim 8 is in the substrate processing apparatus according to claim 7 of the patent application scope. Downstream of the connection point between the first pipe and the second pipe, a static agitator is disposed upstream of the injection nozzle, so that an inert gas, an organic solvent droplet, and an organic solvent gas are sufficiently mixed to form a homogeneous mixed gas. In addition, the organic solvent and the inert gas have a wide selection width and can be adapted to various substrates by any combination, in accordance with the substrate processing apparatus of the ninth aspect of the patent application. deal with. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the embodiment described below exemplifies the substrate processing method and the substrate processing apparatus for embodying the technical idea of the present invention, and the present invention is not intended to be limited thereto, and other embodiments included in the scope of the patent application may equally Be applicable. Fig. 1 is a cross-sectional view showing a substrate processing apparatus according to an embodiment of the present invention, wherein Fig. 2 is a side view from one side of the processing tank, and Fig. 3 is a side view from the other side of the processing tank, 4 is a plan view of the cover body (this view is a plan view from the upper portion of the cover body), and FIG. 5 is a side view of the cover body not shown in FIG. Referring to Fig. 1 'this substrate processing apparatus 1 is an apparatus for processing an example of a substrate as a semiconductor wafer. The treatment described herein refers to a process including a process of etching a wafer W by a chemical solution, a process of treating a surface of a wafer by hydrofluoric acid, or a rinse process of a washed wafer W, to be organic. The solvent-drying process of the wafer W after the water-washing is dried. These successive processes are continuously performed in one processing tank 15. As shown in Figs. 2 to 5, the treatment tank 15 is provided in a storage chamber 1 having a volume that can be accommodated together with its attachment. The attached device is an air conditioner that performs air conditioning in the storage room, a supply source that supplies various processing liquids to the processing tank, a wafer transfer mechanism, etc., which are omitted in the drawings. The treatment tank 15 includes a bottomed box-shaped inner tank 20 having a top surface opening, an outer tank 25 surrounding the upper outer circumference of the inner tank 2, and a cover 3〇 covering the opening of the inner tank 20, and the inner and outer grooves 2〇 The 25-series 1312167 cover body 30 is formed of a box-shaped container 31 having a size of a wafer assembly W' having a lower opening and an upper portion that can accommodate a plurality of wafer ws therein, as shown in Fig. 5. 31 is formed of a material that is not easily corroded by an organic solvent such as hydrofluoric acid or IPA. The cover 3 can be moved in the horizontal direction by the moving device 5 5 (refer to Fig. 3). The moving device 55 moves the lid 30 in the horizontal direction by the upper portion of the inner groove 20 as shown by the arrow in Fig. 2 to block or open the opening of the inner groove 20. That is, the lid body 30 located on the inner tub 20 is lifted in the vertical direction by a predetermined distance, moved in the horizontal direction, and then lowered downward in the vertical direction to be maintained in the standby state. The movement of the cover 30 is performed when the wafer assembly W' is introduced into the inner tank 20 and the processed wafer assembly is taken out from the inner tank 20. Further, as shown in Fig. 5, the box-shaped container 31 has a slightly arched top surface 32 formed on the upper portion thereof, and a plurality of injection nozzles 3 3 to 3 3 7 for injecting an inert gas on the top surface 32 are substantially Arranged in a square arrangement at intervals. A plurality of nozzles 3 3 are disposed above the wafer assembly W' as shown in Fig. 4, and a plurality of injection nozzles 33 arranged at substantially equal intervals in the row direction are disposed at substantially equal intervals in the column direction. There are multiple columns. In Fig. 4, seven rows are arranged in six rows in the row direction, and a total of four jet nozzles 3 3 and ~ 3 3 7 6 are disposed on the upper outer periphery of the wafer assembly W'. The relationship between the seven injection nozzles 3 3 , ~ 3 3 7 in the row direction and the wafer assembly W' is as shown in Fig. 5, so that the respective ejection nozzles 3 3 , 3 3 3 7 and the wafer assembly W ' The distance between the outer circumferences is substantially equal and is disposed on the top surface 32. Since the top surface 3 2 is formed into an arch shape, the wafer W is formed into a substantially circular plate shape, so that the above-described distance is made equal. The shape of the top surface is changed in accordance with the shape of the wafer W, and it is preferable to make the distances substantially equal. The injection nozzle 3 3 is connected to the gas supply pipe 3 4 2 as shown in Fig. 5, and the -20-1312167 is supplied to the pipe 3 4 2 to be diverged 'in these branch pipes 3 4 2|, 3 4 2 2, each of the injection nozzles The number of 3 3 is the same or a combination of approximately equal numbers. According to this, the gas can be distributed in a large or equal manner in each of the injection nozzles. These injection nozzles 3 are respectively diffused at a predetermined angle using the injection gas, and when the gas is ejected toward the outer periphery of the wafer assembly W' by each of the injection nozzles 3, the adjacent injection nozzles, for example, the injection nozzles 3 3 2 and It is preferable that the ejection gas between the ejection nozzles 3 3 3 overlaps on the outer peripheral edge b of the wafer assembly W. By arranging a plurality of ejection nozzles 33 as described above, the gas can be supplied to the wafer assembly W substantially uniformly on the top surface 3 2 '. The injection nozzle 33 has a conical shape as a whole, and an opening is formed at the tip end of the tip to eject the drying gas. Further, a heater (not shown) is attached to each of the injection nozzles 3 3 . Since the injection nozzle itself is already known, detailed description is omitted. Further, a heater (not shown) is attached to the outer peripheral wall surface of the pipe body in the gas supply pipe 344 and the branch pipes 342| and 3422 which are branched from each other. This heater uses, for example, a b e 11 heater. These heaters are connected to the CPU 12 and are controlled by the CPU. The intermediate connection member 26 and the perforated plate insertion mechanism 27 are disposed between the inner and outer grooves 20, 25 and the lid body 30 as shown in the second, third, and fifth views. The intermediate connecting member 26 is formed in a cylindrical shape having an opening having the same size as the lower opening of the lid body 30. This cylindrical form is formed of a material which is not easily corroded by an organic solvent such as hydrofluoric acid or I p A . The intermediate connecting member 26 is disposed above the perforated plate insertion mechanism 27, and the lower opening 2 6 2 is positioned substantially adjacent to the top surface of the frame body 271 that houses the perforated plate, and the upper opening 26 is positioned. i is fitted to the lower opening 3 1 i of the box-shaped container 3 1 . Further, the cover member 30 may be directly fitted to the frame body 27, and the intermediate link member 26 may be omitted. -21 - 1312167 The porous plate 28 is formed of a flat plate-like flat plate inserted between the inner and outer grooves 20, 25 and the intermediate connecting member 26 in the process of drying the wafer assembly w for which the predetermined process is completed. The face is provided with a plurality of small holes. This porous plate is formed of a material which is not easily corroded by an organic solvent such as hydrofluoric acid or IPA. The perforated plate 28 is housed in the casing 27i, and is coupled to a moving mechanism (not shown) to slide in the horizontal direction as shown in Fig. 2 . The frame 27 of the perforated plate 28 has a predetermined vertical width (vertical direction) for forming a gap 272 between the frame 27 and the perforated plate 28 when the perforated plate 28 is housed in the frame 27. This gap 272 is, for example, a gap of about 2 m, and a part of the dry gas is discharged into the water tank 29 in the drying process. Therefore, since a gap 2 7 2 is formed between the inner groove 20 and the lid body 30 (this gap is indicated by X in FIG. 7), the gap between the inner groove 20 and the cover body 3 is made by the gap X. It is semi-sealed without being sealed, that is, the drying treatment unit and the washing treatment unit and the water tank 29 are in a semi-sealed state. Further, the perforated plate 28 is inserted between the inner and outer grooves 20, 25 and the intermediate connecting member 26 to distinguish between the inner groove 20 and the lid body 30, that is, a baffle that separates the washing treatment portion from the drying treatment portion (shu) 11 e 1.) and function. Next, the piping connection between the processing tank 15 and the attachment will be described with reference to Fig. 1 . The treatment liquid supply pipe 22 is connected to the treatment liquid supply unit 22 disposed at the bottom of the inner tank 20. The inlet pipe 22i is connected to the pure water supply source 38 via a flow rate control valve and a pump (p u m p). The treatment liquid introduction pipe 2 2 t functions as a treatment liquid supply system pipe, and the pipe, the flow rate control valve, and the pump constitute a cleaning liquid supply device. Further, the treatment liquid introduction pipe 22 is also connected to the chemical solution supply source 39 via the flow rate control valve. The chemical liquid supply source 39 is provided with -22- 1312167 for modulating the desired chemical liquid to a predetermined concentration and a predetermined temperature, and is connected to the vapor generating tank 37, and supplies the nitrogen gas I' to the bottom of the vapor generating tank 37. Bubble generation (bubble: b U bb 11 ng ) in the IPA in the vapor generation tank 37 j 'Generates IPA vapor composed of 丨PA gas and droplets. Further, 'the steam generating tanks 3 7 and the exported pipes 3, 2 are connected to the gas supply pipe 342 via the static damper ,, and the steam generating grooves 377 are supplied to the injection nozzles 33 and ίρΑ. a mixture of vapors. A band heater (not shown) is attached to the outer peripheral wall surface of the pipe body of the pipes 35, 2, 37, 2'. These heaters are temperature-controlled by C Ρυ丨 2 . Further, the static snubber is used to promote the degree of mixing of the mixed gas composed of the carrier gas ν2 and the ΙρΑ vapor to be homogenized. The first inert gas supply source 34 supplies the nitrogen gas Ν 2 of the inert gas to the pipe 371 via the pipe 34ι. This piping 3 4 ! is also controlled to a predetermined temperature by a band heater. This nitrogen gas & is not only used for dilution of the mixed gas of the inert gas and the organic solvent vapor from the vapor generation tank 37 i but also for purging or fine drying in the treatment tank 15 . Further, in addition to nitrogen, the inert gas can be suitably selected from the group consisting of argon and ammonia. Next, the process of using this substrate processing apparatus will be described with reference to Fig. 6(a) to (d). In addition, Fig. 6 shows a time chart of a series of processes, pages 7(a) to (4) show a washing/drying process, and Fig. 7(a) shows a sectional view of a washing process, 7 (b) shows a cross-sectional view of the drying process 1, and section 7 (c) shows a cross-sectional view of the drying process 2 '7' (d) shows a cross-sectional view of the drying process 3. Referring to Figures 1 and 6, first, the lid body 30 of the processing tank 15 is opened to accommodate the crystal aggregate W in the inner tank 20. At this time, in the inner tank 20, a desired chemical liquid such as hydrofluoric acid (HF) is supplied from the chemical liquid supply source 3 to the inner tank 2 via the treatment liquid introduction pipe 2 2 , 1312167 and the treatment liquid supply unit 2 2 . 0. Therefore, the wafer assembly W' is immersed in the treatment liquid to perform treatment according to the chemical liquid (e.g., etching, hydrofluoric acid treatment, washing, etc.). After the completion of the chemical treatment, as shown in Fig. 7(a), the pure water DIW is supplied from the pure water supply source 38 to the inner tank 20 via the treatment liquid introduction pipe 22 and the treatment liquid supply unit 22. This pure water supply system is carried out while overflowing from the upper portion of the inner tank 20. The pure water DIW overflowing from the inner tank 20 flows into the outer tank 25, and is discharged by the drain pipe 25 through the drain pipe. The supply of the pure water is carried out for a long period of time, and the chemical liquid HF remaining in the inner tank 20 is pressed out. After the completion of the cleaning process, the continuous supply of pure water DIW is stopped in the drying process 1 shown in Fig. 7(b), while a small amount of pure water (saving water for 〇I w) is supplied while the inner tank 20 is slow. Slow up (Slow up Speed) pull up the wafer assembly W '. A small amount of IPA vapor can be supplied into the treatment tank 15 at the same time as the wafer assembly W' is pulled up. Next, in the drying process 2 shown in Fig. 7(c), the discharge mechanism valve of the discharge port 2 12 at the bottom of the treatment tank 15 is operated to rapidly discharge the treatment liquid, and the perforated plate 28 is horizontally moved to the frame body, and inserted into the inside and outside. The grooves 20, 25 are interposed between the intermediate joint members 26. Further, a dry gas composed of a mixed gas of the heated nitrogen gas N2 and IPA vapor is supplied to the inner tank 20. These actions are performed simultaneously as shown. This dry gas is heated in the pipe 3 4 2 and the nozzle 3 3 . In this process, the vapor of the organic solvent in the treatment tank 15 is brought into contact with the surface of each wafer W, and the droplets of the IPA are aggregated on the surface of the wafer W to form a film of IPA. When a film of an organic solvent is formed on the surface of the wafer W, the pure water adhering to the wafer W is replaced with IP A, so that the surface tension is small and flows off the surface of the wafer W, and adheres to The IPA of the surface of the substrate -25- 1312167 will evaporate. In the drying process 3 of Fig. 7(d), in order to dry the replaced IPA, nitrogen gas N2 is supplied, and after the drying process 3 is completed, the wafer assembly W is taken out by the processing tank 15. In the above process, the pressure in the lid body 30 (drying treatment portion) is higher than the pressure in the water tank and the pressure at the exhaust source, and is higher than the pressure of the inner tank 20 (washing treatment portion) and the source of the exhaust gas. High pressure. Therefore, the flow of the dry gas in the drying treatment portion becomes a laminar flow, and is smoothly exhausted from the exhaust pipe to the outside of the tank, in which process 'dry gas is uniformly supplied to each wafer, and no water is formed on the surface of the substrate. The mark 'and also prevents the removal and adhesion of particles. Further, since no drying gas is refluxed in the treatment tank, re-adhesion of the fine particles can be prevented. Further, at this time, the temperature relationships of the temperatures T, TV, T4, T2'' and Τ3 in each of the first figures are set by controlling the heaters in each of the C P U 1 2 to satisfy the following relationship. Τ,^ Τ2'^ Τ4^ Τ2"^ Τ3 .....(1) The temperature of the steam generating tank: 1]^, the temperature in the piping 3 7,2: Τγ, the temperature inside the piping 34丨: T4 , the temperature in the pipe 3 4 2: Τ 2' ', the temperature in the injection nozzle: Τ3, so that the temperature of each of the temperatures τ, TV, τ4, Τ, and τ3 satisfies the above (1) 'The size of the I Α Α droplets ejected by the ejection nozzles 3 3 is a droplet of a very small particle size. Specifically, in the case of the Tyndall phenomenon (T y n d a 11 p h e η 〇 m e η ο η), the droplets of the polar particles -26-1312167 are not observed, that is, the droplets of the submicron size. That is, if it is a droplet of a few micrometers, it can be confirmed by the Tyndall phenomenon, but if it is a submicron size, it cannot be confirmed by the Tyndall phenomenon. A special measuring device is required. In the present embodiment, the size of the IPA droplet described above cannot be confirmed by the Tyndall phenomenon, so that it is a submicron size. However, this micron-sized droplet is not completely gasified, but exists in a liquid state. Further, the 'T 3 system does not completely vaporize the droplets of the crucible and is controlled to be below the boiling point of the crucible (82.4 ° C). By making the size of the droplets of the vapor constituting the organic solvent to a submicron size, the amount of the organic solvent droplets is increased, and the number of particles of each droplet is small, and the number of particles of each droplet is small. The total surface area of the parts is increased. As a result, the sPecific surface area of the vapor of the organic solvent can be increased and injected onto the substrate, so that the replacement efficiency with the cleaning liquid is improved. Further, in the temperature setting of the above formula (1), it is preferable that the respective temperatures are the same or slowly increased. That is, in the vapor generation tank 37, by mixing the inert gas in the IPA, a mixed gas containing an inert gas containing IPA vapor composed of IPA droplets and IPA gas having a less than saturated concentration is obtained. It is maintained at the same temperature or slowly as it is discharged from the injection nozzle, and the vapor of the organic solvent is not aggregated in the piping and the injection nozzle. Therefore, the diameter of the organic solvent droplet in the mixed gas does not become large. 'The piping and the IPA in the nozzle are slowly vaporized by the surface of the I p A droplet during movement.' The particle size of the droplet is reduced, so that it is easy to obtain a dry gas containing IPA droplets of submicron size. Further, 'the mixture of the IPA vapor contained in the vapor generation unit 37 and the IPA vapor which is not saturated with the IPA gas is a mixture of -27-13122167 gas which is additionally supplied by the piping 37. The gas dilution 'the IPA gas concentration in the aforementioned mixed gas drops', so the gasification from the 1PA mist droplets is more promoted, and the supply of a large amount of inert gas and the IP A droplets of multiple micron size can be supplied. The drying gas is supplied to the treatment tank at a rate of 15 °. In this case, the re-supplied nitrogen gas N2 is effectively mixed with the IP A vapor or the like. It is preferable to disperse the mixer while the piping 3 42 is disposed. This agitator is preferably a static agitator. As described above, when a large number of micron-sized 1 ΡΑ droplets are contained in the dry gas, even if a large number of large-diameter substrates are inserted into the processing tank 15, the micro-sized droplets can be rapidly immersed between the substrates. The cleaning liquid of the substrate is rapidly replaced by the vapor which continuously supplies the large amount of the organic solvent of the sub-micron size, and as a result, the drying treatment efficiency is improved and the processing time can be shortened, and the drying treatment is extremely fast. Therefore, 'especially without increasing the amount of organic solvent used, the drying treatment efficiency is improved' and the processing time can also be shortened 'the occurrence of water marks on the surface of the substrate is extremely small' or it can be made almost zero 'and the adhesion of the particles disappears, and 'Because of the fast drying process, it can also prevent the reattachment of particles. Further, in the above-described aspect, although the inert gas for dilution is supplied from the pipe 34, the inert gas for dilution is not necessarily required in order to obtain a helium droplet having a submicron size. In this case, the connection steam generating groove 37 is completely different from the temperature of the pipes 37] 2, 3 4 2, 3 4 21 and 3 4 2 2 of the nozzle 33 to satisfy the above formula (1) for temperature control, or may be maintained. At the same temperature Τ 2, it becomes Τ, ^ Τ, ^ τ3 and temperature control is also possible. Further, the temperature τ3 in the piping and the injection nozzle is set to be equal to or higher than the temperature 有机 of the organic solvent supplied to the steam generating portion and the temperature τ2 of the inert gas. According to this, since the vapor of the organic solvent is not aggregated in the piping and the injection nozzle, the diameter of the organic solvent mist in the dry gas does not become large, and the surface of the organic solvent droplet is organic before being ejected from the nozzle. A part of the solvent is more vaporized, so the size of the organic solvent droplets in the dry gas can easily become sub-micron size. Further, since the organic solvent vapor does not aggregate in the piping and the injection nozzle, there is no trouble that the droplets fall from the nozzle. Further, in the present embodiment, in order to prevent the collision of the organic solvent droplets with each other and the collision of the walls of the machine with the organic solvent droplets, the increase of the diameter of the organic solvent droplets and the aggregation of the droplets are prevented, as follows. The constituent members are preferred. That is, the bubble generating groove of the steam generating portion is formed into a conical shape or an arc shape at the top. Further, the dry gas supply pipe is formed to have a small difference in the diameter of the layer. Further, in the bubbling nozzle of the steam generating portion, the ejection velocity is small and the ejection speed is high. Further, the use of a dry gas containing the atomized droplets of the micron size described above indicates that the cleaning liquid adhering to the substrate is replaced by the mist. Fig. 8 and Fig. 9 are schematic cross-sectional views showing the relationship between the xenon vapor and the substrate during the drying process. Fig. 8 shows a case where the dry gas contains a submicron-sized 丨pa droplet but is not diluted with an inert gas. Figure 9 shows the case where the dry gas contains submicron size IPA droplets and is diluted with an inert gas. In addition, '8th (a), (b), and 9th (a) and (b) are equivalent to the [dry 2] process of Fig. 6 '8' and 9(c) It is equivalent to the process of [Drying 3] in Fig. 6. As shown in Fig. 8(a), if a dry gas composed of a mixed gas of IPA droplets (liquid) of sub-micrometer scale -29-1312167 inches and nitrogen gas N2 (gas) is sent to the treatment tank 15 When the wafer W is placed between the wafers, the DIW attached to the wafer W as shown in Fig. 8(b) is replaced by IP A, but the 1 p A droplet is greatly micronized. Supply, for a DI W multiple IPA particles attached to the DIW 'so D IW is effectively replaced. Next, as shown in Fig. 8(c), IP A is evaporated by feeding only I gas into the treatment tank 15. In this case, in the process of [Dry 2] (Fig. 8 (a) and (b)), since the supply amount of nitrogen N 2 is small, the carrier effect of IP A droplets is insufficient. The size of the droplets gives a generally good drying effect. The use of large-diameter wafers is dry. 'There is a residual water mark with only residual DIW. Moreover, the dry gas contains sub-micron-sized IP A droplets and is further diluted with an inert gas. The concentration of IPA vapor in the dry gas is low, but the carrier effect of the IPA droplets is sufficient, so as in paragraph 9 (a) ~(c) As shown in the figure, a sub-micron-sized 1 PA droplet is continuously and evenly supplied to the depth of the wafer W by a large amount of carrier gas. The DIW was reversibly replaced by the dry gas 'submicron size IPA droplets containing this large amount of carrier gas attached to the DIW' quickly. As a result, even in the case of drying of a large-diameter wafer, the drying treatment efficiency is improved 'and the processing speed is increased', so that the processing time can be shortened, as shown in Fig. 9(c), the surface of the substrate W can be By making D IW substantially zero, the generation of water marks can be completely eliminated. Further, the cases shown in the figures 9(a) to (c) are the same as those in the case of the eighth (a) to (c) drawings, and the detailed description thereof will be omitted. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a substrate processing apparatus according to an embodiment of the present invention, taken along the line -30-1312167. Fig. 2 is a side view showing a treatment tank according to an embodiment of the present invention. Figure 3 is a side elevational view of the processing tank of Figure 2 from the other side. Fig. 4 is a plan view showing the upper portion of the lid in the treatment tank according to the embodiment of the present invention. Fig. 5 is a side view of the lid shown in Fig. 4. Fig. 6 is a view showing a timing chart of a series of processes. Sections 7(a) to (c) show the washing/drying process, Figure 7(a) is a cross-sectional view showing the cleaning process, and Figure 7(b) is a cross-sectional view showing the drying process 1, 7th (c) is a cross-sectional view illustrating the drying process 2, and FIG. 7(d) is a cross-sectional view illustrating the drying process 3. Tables 8(a) to (c) are schematic cross-sectional views showing the relationship between the vapor and the substrate in the drying process. Figs. 9(a) to 9(c) are cross-sectional views schematically showing the relationship between the IPA vapor and the substrate in the drying process in the case of using nitrogen for dilution, similarly to the eighth (a) to (c). The figure is a cross-sectional view showing a substrate processing apparatus of the prior art. 11(a) to (b) are schematic cross-sectional views showing the relationship between the IPA vapor and the substrate in the drying process of the substrate processing apparatus of Fig. 10. [Simplified explanation of symbols]: 1 ' 1 〇: substrate processing apparatus 2 ' I 5 : treatment tank 2 >: cover 2 2, 2 〇: inner tank 2 1 2: treatment liquid discharge hole 1312167 3, 2 9 : water tank 4: steam generation tank 4 t : steam discharge port 5 ·_ exhaust Tube 5,: inner tank drain pipe 7: nitrogen supply source 8: steam discharge port 8 i: inert gas supply pipe
1 1 :收容室 12: CPU 2 1 ·.處理液排出部 2 1 i:小徑的排出口 2 12:大徑的排出口 2 2 :處理液供給部 22,:處理液導入管（處理液供給系配管） 2 2 2 ' 34, ' 3 4 2] ' 3 4 2 2 ' 35n' 3 512 ' 3 712 > 36^ 3712: 2 3 i、2 3 2:排液管 25:外槽 2 5 1 :排浅管 26:中間連結構件 27:多孔板插入機構 271:框體 272 、 X:間隙 2 8 :多孔板 3 0 :蓋體 配管1 1 : Storage chamber 12 : CPU 2 1 · Process liquid discharge unit 2 1 i: Small-diameter discharge port 2 12: Large-diameter discharge port 2 2 : Process liquid supply unit 22: Process liquid introduction pipe (treatment liquid Supply piping) 2 2 2 ' 34, ' 3 4 2] ' 3 4 2 2 ' 35n' 3 512 ' 3 712 > 36^ 3712: 2 3 i, 2 3 2: drain tube 25: outer tank 2 5 1 : shallow tube 26 : intermediate connection member 27 : perforated plate insertion mechanism 271 : frame 272 , X : gap 2 8 : perforated plate 3 0 : cover pipe
-32- 1312167 3 1 :箱狀容器 3 1 ,:下部開口 3 2 :頂面 33、33,〜3 3 7 6:噴射噴嘴 3 4 :第一惰性氣體供給源 3 4 2:氣體供給管 3 5 :第二惰性氣體供給源 36:有機溶劑（IPA)供給源 3 7 :蒸氣供給機構 · 3 7 i:蒸氣產生槽 3 7 2 :加熱槽 3 8 :純水供給源 3 9 :藥液供給源 40:排液處理設備 4 1、4 1 ,:排氣處理設備 5 0 :移動機構 50,、5 0 2:把持爪 _ 5 5 :移動裝置 60:升降機構 61:升降裝置 62:基板保持具 M:靜態攪拌器 DIW : 純水 W、W ’ ：晶圓 -33--32- 1312167 3 1 : Box-shaped container 3 1 ,: lower opening 3 2 : top surface 33, 33, 〜3 3 7 6: injection nozzle 3 4 : first inert gas supply source 3 4 2: gas supply tube 3 5: second inert gas supply source 36: organic solvent (IPA) supply source 3 7 : vapor supply mechanism · 3 7 i: steam generation tank 3 7 2 : heating tank 3 8 : pure water supply source 3 9 : chemical liquid supply Source 40: draining treatment device 4 1 , 4 1 ,: exhaust gas treatment device 50: moving mechanism 50, 5 0 2: gripping claw _ 5 5 : moving device 60: lifting mechanism 61: lifting device 62: substrate holding With M: static mixer DIW: pure water W, W ': wafer-33-