200911395 九、發明說明： 【發明所屬之技術領域】 發明領域 本發明係有關於一種藉由處理液處理半導體晶圓或液 5晶顯示裝置用之玻璃基板等基板之處理裝置及處理方法。 【先前技術】 發明背景 在製造半導體裝置或液晶顯示裝置等時，有一於半導 體晶圓或玻璃基板等基板形成電路圖案之平版印刷製程。 10该平版印刷製程係如眾所皆知者，於上述基板塗布抗蝕 劑，並經由形成有電路圖案之光罩將光照射於該抗蝕劑。 接著，除去抗蝕劑未照射到光之部分或者照射到光之 部分，並反覆複數次將除去之部分進行蝕刻等一連串之步 驟，藉此於上述基板形成電路圖案。 15 上述一連串之各步驟中，若上述基板受到污染，則無 法精密地形成電路圖案，成為不良品的發生原因。因此， 於基板形成電路圖案時，要先除去附著殘留於基板之有機 物或抗蝕劑等，使用因應於其處理目的之處理液處理基 板。使用於處理基板之處理液已知有純水、蝕刻液、剝離 20 液、顯像液等。 教近，不僅單以加壓氣體對處理液加壓，還將氣體作 成微細的氣泡，使之混合於處理液中，藉此，提昇上述處 理液的處理效率。專利文獻丨中揭示了 一種處理裝置，其係 藉使微氣泡混合於處理液中，以提昇處理效率。 5 200911395 即，專利文獻1所示之處理裝置具有導入純水及氮氣之 混合泵。純水與氮氣係在氣液混合泵中加以混合，送至迴 旋加速器。迴旋加速器使純水與氮氣加速迴旋，形成氣液2 層流，然後往分散器送出。分散器以流體力學方式剪斷送 5入之氣液2層流，形成氮氣之微汽泡。然後，含有微氣泡之 純水送到處理槽，處理基板。 【專利文獻1】日本專利公開公報特開2006- i 79765 一般而言，專利文獻1所揭示之微氣泡的直徑為10〜100 从m由於微氣泡的直徑大，因此會受到浮力而在液中上 10昇’然後在液面裂開而消失。 相對於此，由於直徑在如下之奈米氣泡的内壓 低，因此在水中幾乎不會受到浮力作用。故，會在液中浮 遊，且受外壓力而漸漸縮小。當奈米氣泡縮小時，其表面 電荷會隨著表面積的縮小而濃縮，因此會形成極強的電場。 15 由於奈米氣泡的強電場會使該奈米氣泡活性化，因此 會對存在奈米氣泡之液體造成強力的影響。因此，若處理 基板之處理液中含有奈米氣泡的話，可大幅提昇該處理液 對基板的處理效果。 專利文獻1所示之處理裝置係如上所述，在使用氣液混 20合泵將氮氣與純水混合後，以迴旋加速器加速使之迴旋而 形成氣液2層流當中’利用分散器以流體力學方式來剪斷氣 液2層流’而形成氮氣的微氣泡。 也就是說’專利文獻1所揭示之處理裝置中，即使可藉 由氣液混合泵、迴旋加速器及分散器，形成直徑為10〜100 6 200911395 .· "八的微氣泡’也要在使用迴旋加速器使氮氣與純水預 先& 5 ^成氣液2層流體後，利用分散器以流體力學方式加 以剪斷。 因此由於在迴旋加速器中，氮氣會溶人純水因此 5較利用分散器並以流體力學方式將在迴旋加速器形成之 氣液2層流體料4僅紐有效率地產生微氣泡，而且專 利文獻1中’也未有任何揭示產生比微氣泡有利於基板處理 之奈米氣泡等。 【'明内穷】 10 發明概要 本發明係提供一種可有效率產生直徑比微氣泡小之奈 米氣泡’且可提高基板的處理效率之基板的處理裝置及處 理方法。 為解決上述課題，本發明提供一種基板之處理裝置， 15係藉處理液處理基板者，包含有··奈米氣泡產生機構，係 IS奈錢泡’並㈣奈以減合於料處理液者；處 、 職供給機構，雜含有由前述奈錢泡產生機構所產生 之奈米氣泡之前述處理液供給至前述基板板面者；及加壓 機構，係對由前述處理液供給機構供給至前述基板板面之 20處理液中所含之奈米氣泡進行加壓，且使該氣泡在前述基 板板面壓壞者。 又，本發明提供一種基板之處理方法，係藉處理液處 理基板者，包含有：混合步驟，係產生奈米氣泡，並使該 奈米氣泡與前述處理液混合；供給步驟，係將含有奈米氣 7 200911395 泡之前述處理液供給至前述基板板面；及壓壞步驟，係將 供給至前述基板板面之處理液所含之奈米氣泡加壓，使該 氣泡在前述基板板面壓壞。 圖式簡單說明 5 第1圖係顯示本發明之第1實施形態之處理裝置的概略 構成圖。 第2圖係沿著氣體剪斷器之軸方向之截面圖。 第3圖係由後端觀看氣體剪斷器之側面圖。 第4圖係顯示本發明之第2實施形態之螺旋處理裝置的 10 概略構成圖。 第5圖係顯示本發明之第3實施形態之螺旋處理裝置的 概略構成圖。 第6圖係顯示本發明之第4實施形態之水平搬送處理裝 置之概略構成圖。 15 第7圖係顯示本發明之第5實施形態之水平搬送處理裝 置之概略構成圖。 第8圖顯示本發明之第6實施形態之水平搬送處理裝置 之概略構成圖。 第9圖係顯示本發明之第7實施形態之水平搬送處理裝 20 置之概略構成圖。 第10圖係顯示本發明之第8實施形態之水平搬送處理 裝置之概略構成圖。 【實施方式3 較佳實施例之詳細說明 200911395 以下，參照圖式說明本發明之實施形態D 第1圖至第3圖係顯示本發明之第1實施形態，且第1圖 係顯示處理裝置之概略構成圖，該處理裝置具有處理槽i。 該處理槽1内配置有構成奈米氣泡產生機構之氣體剪斷器 5 2。該氣體剪斷器2係如第2圖所示，内具有於内部形成剪斷 室3之中空狀本體4。 上述剪斷室3之其中一端與形成於上述本體4之軸方向 前端面之噴射口 5連通，另一端與形成於上述本體4之後端 面之氣體供給口 6連通。上述剪斷室3係由後部空間部3a、 10與刚部空間部3b形成，前述後部空間部如係由連通於上述 氣體供給口 6之後端朝後端部中途部擴徑之圓錐台狀者，前 述刖部空間部3 b係由該後部空間部3 &朝前端漸漸縮徑形成 之圓錐台狀者，且於上述剪斷室3之後部空間部允與前部空 間部3b之境界部㈣齡朝切切4之外周面開口之液 15 體供給口 7。 上述氣體供給口 6設有氣體迴旋用金屬蓋151。該氣體迴 疑用金屬蓋11係與其中-端連接於氣體供給泵12之氣體供 給管13的另-端連接。該氣體供给如之中途部設有第鳩 關閥14。上述氣體供給栗12之吸^側與未圖示之高壓系等 20氣體供給源連接。該氣體供㈣係心供給氧氣。 上述氣體迴旋用金屬蓋11雖未詳細圖示，但該氣體迴 旋用金屬蓋11於内部形成有螺旋溝。藉此，若打開上述第1 開關閥14，使由上述氣體供給泵12供=之氧氣迴旋通過上 述氣體供給管13，然後由上述剪斯室3之後部空間部3a朝前 9 200911395 部空間部3b喷出，且上述剪斷 内如第2圖中虛線所示， 形成氧氣之氣體空洞部丨5。該實 貫靶形態中，氣體迴旋用金 &侧觀看為逆時鐘方向迴旋。氣體 ，，之螺旋溝係構成為使上述氣體朝由上述本體*之後 5 箭頭a所 之迴旋方向係如第2圖中 不 液體供給金屬蓋16係如第3圖所示，相對本體4之 向朝時鐘方向傾斜Θ1的角度，而且如第2圖所示，相對乾 線方向朝後端側傾斜Θ2之角度連接於上述液體供給口7。 上述液體供給金屬蓋16與液體供給管18之另— 10 接’且液體供料18之其中1連接於液體供給幻7。該 液體供給管18之中途部設有第2開關閥19。上述液體供給嚴 Π之吸引側與上述處理別之底部連接。該處理槽丨係收容 有作為處理液之純水L。 · 藉此，若打開上述第2開關閥19,由上述液體供給泵17 15而供給至上述氣體剪斷器2之純水L通過上述液體供給管18 且藉由上述液體供給金屬蓋16之傾斜角度0 1而與上迷氣 氣同様朝反時鐘徑方向迴旋，而且藉由上述液體供給金屬 蓋16之傾斜角度0 2供給至前部空間部3b側行進之方向。 藉由上述氣體供給泵12，氧氣之供給壓力設定為Pi， 20並藉由上述液體供給泵17而將純水L之供給壓力設定為 P2，且設定為P1CP2。藉此，供給至上述本體4之剪斷室3 之氧氣的迴旋速度VI與純水L之迴旋速度V2的關係為VI V2。 該實施形態中’氧氣之供給壓力P1與純水L之供給壓力 200911395 P2係設定為，氧氣的迴旋速度VI係每秒400旋轉、純水L之 迴旋速度V2係每秒600旋轉。 由上述剪斷室3之軸方向後端供給之氧氣係如箭頭a所 示，成為迴旋之氣體空洞部15’且朝喷射口 5行進。由上述 5剪斷室3之外周面供給之純水L係迴旋之氧氣的氣體空洞部 15之外周面迴旋，且朝上述噴射口 5行進。純水之迴旋方向 如第2圖中箭頭!)所示。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing apparatus and a processing method for processing a substrate such as a glass substrate for a semiconductor wafer or a liquid crystal display device by a processing liquid. [Prior Art] BACKGROUND OF THE INVENTION In the manufacture of a semiconductor device, a liquid crystal display device or the like, there is a lithography process for forming a circuit pattern on a substrate such as a semiconductor wafer or a glass substrate. In the lithographic process, as is well known, a resist is applied to the substrate, and light is irradiated onto the resist via a photomask formed with a circuit pattern. Next, a series of steps such as etching the portion where the resist is not irradiated to the light or irradiating the light and repeating the removal of the portion is performed, thereby forming a circuit pattern on the substrate. In the above-described series of steps, if the substrate is contaminated, the circuit pattern cannot be formed accurately, which may cause a defective product. Therefore, when the circuit pattern is formed on the substrate, the organic substance or the resist remaining on the substrate is removed, and the substrate is treated with the treatment liquid for the purpose of the treatment. Pure water, an etching solution, a peeling liquid, a developing liquid, and the like are known as a treatment liquid for treating a substrate. In the near future, not only the pressurized gas is used to pressurize the treatment liquid, but also the gas is made into fine bubbles and mixed in the treatment liquid, thereby improving the treatment efficiency of the treatment liquid. The patent document discloses a processing apparatus which mixes microbubbles in a treatment liquid to improve processing efficiency. 5 200911395 That is, the processing apparatus shown in Patent Document 1 has a mixing pump that introduces pure water and nitrogen. Pure water and nitrogen are mixed in a gas-liquid mixing pump and sent to a cyclotron. The cyclotron accelerates the swirling of pure water and nitrogen to form a gas-liquid two-layer flow, which is then sent to the disperser. The disperser shears the two-layer gas-liquid two-layer flow in a hydrodynamic manner to form a micro-bubble of nitrogen. Then, pure water containing microbubbles is sent to the treatment tank to treat the substrate. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-i 79765 In general, the microbubbles disclosed in Patent Document 1 have a diameter of 10 to 100. Since m has a large diameter of microbubbles, it is subjected to buoyancy in the liquid. The upper 10 liters ' then split in the liquid surface and disappeared. On the other hand, since the inner diameter of the nanobubbles having a diameter as follows is low, there is almost no buoyancy in the water. Therefore, it will float in the liquid and gradually shrink by the external pressure. When the nanobubbles are shrunk, the surface charge is concentrated as the surface area is reduced, so that an extremely strong electric field is formed. 15 Because the strong electric field of the nanobubbles activates the nanobubbles, it has a strong influence on the liquid in which the nanobubbles are present. Therefore, if the treatment liquid of the substrate is treated with nanobubbles, the treatment effect of the treatment liquid on the substrate can be greatly enhanced. The processing apparatus shown in Patent Document 1 is as described above, and after mixing nitrogen gas with pure water using a gas-liquid mixing 20-pump pump, it is accelerated by a cyclotron to swirl it to form a gas-liquid 2 laminar flow. The mechanical method is to cut off the gas-liquid two-layer flow' to form nitrogen microbubbles. In other words, in the processing apparatus disclosed in Patent Document 1, even if a gas-liquid mixing pump, a cyclotron, and a disperser can be used, a microbubble having a diameter of 10 to 100 6 200911395 can be formed. The cyclotron preliminarily combines nitrogen and pure water into a gas-liquid two-layer fluid, and then shears it hydrodynamically using a disperser. Therefore, since nitrogen gas dissolves pure water in the cyclotron, the micro-bubble is efficiently generated by the gas-liquid two-layer fluid material 4 formed in the cyclotron by using a disperser and hydrodynamically, and Patent Document 1 There is also no disclosure of nanobubbles or the like which are advantageous for substrate processing than microbubbles. [Inventive Summary] The present invention provides a processing apparatus and a processing method for a substrate which can efficiently produce a nanobubble having a smaller diameter than microbubbles and which can improve the processing efficiency of the substrate. In order to solve the above problems, the present invention provides a processing apparatus for a substrate, wherein the substrate is processed by a processing liquid, and includes a nano bubble generating mechanism, which is a method of reducing the amount of liquid to be treated by the material. a service unit that supplies the processing liquid containing the nanobubbles generated by the nemesis generating mechanism to the substrate surface; and a pressurizing mechanism that supplies the processing liquid supply unit to the foregoing The nanobubbles contained in the treatment liquid of the substrate surface of the substrate are pressurized, and the bubbles are crushed on the surface of the substrate. Moreover, the present invention provides a method for processing a substrate, which comprises: a mixing step of generating a nanobubble to mix the nanobubbles with the treatment liquid; and a supply step of containing the naphthalene The gas is supplied to the substrate surface of the substrate, and the crushing step is to pressurize the nanobubbles contained in the processing liquid supplied to the surface of the substrate to press the bubbles on the substrate. Bad. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic block diagram showing a processing apparatus according to a first embodiment of the present invention. Figure 2 is a cross-sectional view along the axial direction of the gas shear. Figure 3 is a side view of the gas cutter viewed from the rear end. Fig. 4 is a schematic block diagram showing a spiral processing apparatus according to a second embodiment of the present invention. Fig. 5 is a schematic block diagram showing a spiral processing apparatus according to a third embodiment of the present invention. Fig. 6 is a schematic block diagram showing a horizontal conveyance processing apparatus according to a fourth embodiment of the present invention. Fig. 7 is a schematic block diagram showing a horizontal conveyance processing apparatus according to a fifth embodiment of the present invention. Fig. 8 is a view showing a schematic configuration of a horizontal transport processing device according to a sixth embodiment of the present invention. Fig. 9 is a schematic block diagram showing a horizontal transport processing device 20 according to a seventh embodiment of the present invention. Fig. 10 is a schematic block diagram showing a horizontal conveyance processing apparatus according to an eighth embodiment of the present invention. [Embodiment 3] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 200911395 Hereinafter, a first embodiment of the present invention will be described with reference to the drawings. FIG. 1 to FIG. 3 show a first embodiment of the present invention, and the first embodiment shows a processing device. In a schematic configuration, the processing device has a processing tank i. A gas shearer 52 constituting a nano bubble generating mechanism is disposed in the processing tank 1. As shown in Fig. 2, the gas cutter 2 has a hollow body 4 in which a shear chamber 3 is formed inside. One end of the shearing chamber 3 communicates with the injection port 5 formed in the axial direction front end surface of the main body 4, and the other end communicates with the gas supply port 6 formed at the rear end surface of the main body 4. The shearing chamber 3 is formed by the rear space portions 3a and 10 and the rigid space portion 3b, and the rear space portion is a truncated cone that is expanded in the middle of the rear end portion by the end of the gas supply port 6 The crotch space portion 3 b is a truncated cone formed by the rear space portion 3 & gradually reducing the diameter toward the front end, and the space portion of the rear portion of the shear chamber 3 is allowed to be adjacent to the boundary portion of the front space portion 3b. (4) The liquid supply port 7 of the liquid opening to the outer peripheral surface of the cutting edge 4. The gas supply port 6 is provided with a metal cover 151 for gas swirling. The gas suspect metal cover 11 is connected to the other end of the gas supply pipe 13 whose end is connected to the gas supply pump 12. The gas supply is provided with a third closing valve 14 as in the middle. The suction side of the gas supply pump 12 is connected to a gas supply source such as a high pressure system (not shown). The gas is supplied to the (four) core to supply oxygen. Although the metal cover 11 for gas swirling is not shown in detail, the metal cover 11 for gas swirl has a spiral groove formed therein. As a result, when the first on-off valve 14 is opened, the oxygen supplied by the gas supply pump 12 is swirled through the gas supply pipe 13, and then the space portion 3a of the rear chamber 3a is turned forward to the front 9 200911395 space portion. 3b is ejected, and as shown by the broken line in Fig. 2, the above-described shearing forms a gas cavity portion 氧气5 of oxygen. In the actual target form, the gas swirl is viewed in the counterclockwise direction by the gold & side view. The spiral groove of the gas is configured such that the gas is directed to the direction of rotation of the arrow 5 after the main body*, and the metal cover 16 is not supplied with liquid as shown in Fig. 2, as shown in Fig. 3, opposite to the body 4. The angle of the Θ 1 is inclined toward the clock direction, and as shown in Fig. 2, the liquid supply port 7 is connected to the liquid supply port 7 at an angle of Θ 2 toward the rear end side with respect to the trunk direction. The liquid supply metal cover 16 is connected to the other of the liquid supply tubes 18 and one of the liquid feeds 18 is connected to the liquid supply. A second switching valve 19 is provided in the middle of the liquid supply pipe 18. The suction side of the above liquid supply is connected to the bottom of the above treatment. This treatment tank contains pure water L as a treatment liquid. When the second on-off valve 19 is opened, the pure water L supplied from the liquid supply pump 17 15 to the gas shearer 2 passes through the liquid supply pipe 18 and is tilted by the liquid supply metal cover 16 The angle 0 1 is swirled in the counterclockwise direction with the upper air, and is supplied to the direction in which the front space portion 3b side travels by the inclination angle 0 2 of the liquid supply metal cover 16. By the gas supply pump 12, the supply pressure of oxygen is set to Pi, 20, and the supply pressure of the pure water L is set to P2 by the liquid supply pump 17, and is set to P1CP2. Thereby, the relationship between the swirling velocity VI of the oxygen supplied to the shearing chamber 3 of the main body 4 and the swirling velocity V2 of the pure water L is VI V2 . In the embodiment, the supply pressure P1 of the oxygen gas and the supply pressure of the pure water L are 1111395 P2, and the swirling speed VI of oxygen is 400 rotations per second, and the swirling speed V2 of pure water L is 600 rotations per second. The oxygen supplied from the rear end of the shear chamber 3 in the axial direction is a swirling gas cavity portion 15' and travels toward the injection port 5 as indicated by an arrow a. The outer peripheral surface of the gas cavity portion 15 in which the pure water L supplied from the outer peripheral surface of the fifth shearing chamber 3 is swirled is swirled and travels toward the injection port 5. The direction of swirling of pure water is shown in the arrow in Figure 2!).
氧氣之迴旋速度VI設定成較純水L之迴旋速度V2慢。 因此，藉由氧氣與純水L之間的迴旋速度差，氧氣被純水L 1〇以流體力學方式剪斷後，藉由該剪斷作用產生氧氣之奈米 氣泡。而且，會自上述剪斷室3之前端的喷射口5噴射含有 氧氣之奈米氣泡之純水L。又，即使將氧氣之迴旋速度％ 設定成較純水L之迴旋速度V2快，也可藉由流體力學的剪 斷作用產生氧氣之奈米氣泡。 15 供給至上述剪斷室3之純水L藉在剪斷室3内之氧氣的 氣體空洞部15之周圍迴旋，而以流體力學方式剪斷氧^。' 也就是說，由於在氧氣與純水L混合後氡氣溶入純水t之 前，在剪斷室3剪斷氧氣使之產生奈米氣泡，因此可提高岑 米氧泡的產生效率。 °不 上述剪斷室3之前部空間部3b係形成朝噴射口5縮, 圓錐狀。因此，供給至剪斷器3之氧氣與純水、:之 空間部3b行進減少體積，因此壓力減少會受限。Μ 11 200911395 隨著氡氣與純水L在剪斷室3行進而可防止奈米氣泡的產生 效率降低。 如第1圖所示，洗淨處理之基板W係在浸潰於上述處理 槽1内所充滿之純水L之狀態下供給至與上述喷射口 5對向 之位置，且保持在大略垂直立起之狀態。藉此，含有由上 述喷射口 5噴射之奈米氣泡之純水L朝上述基板W之板面噴 射。 又’基板W與上述噴射口5的間隔設定成使喷射口 5所 噴射之純水L以預定之壓力作用於基板w之板面。又，由於 0使自喷射口 5喷射之純水L作用於基板界全自，因此上述氣 體剪斷益2會藉由未圖示之驅動機構而沿著基板w之板面 的上下方向及幅度方向而驅動。 由於奈米氣泡係如上所仙壓較低，因此會—面在液 15The oxygen swirl speed VI is set to be slower than the swirl speed V2 of the pure water L. Therefore, by the difference in the swirling speed between the oxygen and the pure water L, the oxygen is sheared by the pure water L 1 , and the oxygen nanobubbles are generated by the shearing action. Further, pure water L containing oxygen-containing nanobubbles is ejected from the ejection opening 5 at the front end of the above-described shearing chamber 3. Further, even if the oxygen swirling speed % is set to be faster than the swirling speed V2 of the pure water L, oxygen nanobubbles can be generated by the hydrodynamic shearing action. The pure water L supplied to the above-mentioned shearing chamber 3 is swirled around the gas cavity portion 15 of the oxygen in the shearing chamber 3, and the oxygen is sheared by hydrodynamic means. That is, since the helium gas is dissolved in the pure water t after the oxygen is mixed with the pure water L, the oxygen is cut in the shearing chamber 3 to generate nanobubbles, so that the efficiency of the generation of the xylene bubbles can be improved. ° The front space portion 3b of the above-described shearing chamber 3 is formed to be tapered toward the ejection opening 5 and has a conical shape. Therefore, the oxygen supplied to the cutter 3 and the space portion 3b of the pure water travel to reduce the volume, so the pressure reduction is limited. Μ 11 200911395 As the helium gas and the pure water L travel in the shearing chamber 3, the generation efficiency of the nanobubbles can be prevented from being lowered. As shown in Fig. 1, the substrate W to be cleaned is supplied to the position opposed to the ejection port 5 while being impregnated with the pure water L filled in the processing tank 1, and is held substantially vertically. The state of the situation. Thereby, the pure water L containing the nanobubbles sprayed from the ejection openings 5 is ejected toward the plate surface of the substrate W. Further, the interval between the substrate W and the ejection port 5 is set such that the pure water L ejected from the ejection port 5 acts on the plate surface of the substrate w with a predetermined pressure. Further, since the pure water L injected from the ejection opening 5 acts on the substrate boundary, the gas shearing effect 2 is along the vertical direction and the amplitude of the plate surface of the substrate w by a driving mechanism (not shown). Drive by direction. Since the nanobubble is as low as the above, it will be in the liquid 15
20 且因外壓1^縮小，並且藉表面電荷丨農縮而形成極強 ^電％而活性化。藉此，絲基板w喷射含有奈米氣泡之 a水L ’财有效率且確實地將基板魏淨處理。特別是， 二=液為純水L’且氣體為氧氣時，含有氧氣之奈米氣泡 、’ L可有效率地洗淨除去附著於基板％之有機物。 '供給至上述聽剪斷g2之氣體與處理液有純水與臭 離、夜2液與氧乳或空氣、飾刻液七氮氣或二氧化石炭、剝 *氧液與二氧化碳、剝離液與氮氣、顯像液 ，、虱*1、顯像液與氮氣等組合。20 And because of the external pressure 1 ^ shrink, and by the surface charge 丨 agricultural shrinkage to form a strong ^ electricity % and activated. Thereby, the silk substrate w ejects a water L' containing nano bubbles to efficiently and reliably clean the substrate. In particular, when the second liquid is pure water L' and the gas is oxygen, the nano air bubbles containing oxygen and 'L can efficiently remove and remove the organic matter adhering to the substrate. 'The gas and treatment liquid supplied to the above-mentioned listening and cutting g2 have pure water and odor, night 2 liquid and oxygen milk or air, decorative liquid seven nitrogen or carbon dioxide carbon, stripping * oxygen liquid and carbon dioxide, stripping liquid and nitrogen gas , imaging liquid, 虱*1, imaging liquid and nitrogen combination.
W ，Ϊ可由合，^ W屯水洗淨基板 9、、孔之奈米氣泡而強制於基板w上生成 12 200911395 . 氧化膜之作用、及提昇基板之潤濕性之作用。 根據蝕刻液與氧氣或空氣的組合，不僅是藉由蝕刻液 產生之蝕刻作用，還有氧氣或空氣之奈米氣泡，蝕刻液造 成之蝕刻作用所產生之陽離子性物質會因奈米氣泡表面產 5生之負離子而吸著，並可防止陰離子性物質因為排斥而往 基板w再附著。 而且，由於奈米氣泡具有吸收金屬離子等之性質，因 此可同持進行金屬離子的去除。又，可藉由已活性化之氧 氣的奈米氣泡提昇蝕刻液對基板W之反應性、也就是姓刻 10作用。 根據蝕刻液與氮氣或二氧化碳的組合，藉由於奈米氣 /包表面產生之負離子，蝕刻作用所產生之陽離子性物質會 吸著奈米氣泡，並且可防止陰離子性物質排斥，再附著於 基板W。 15 可藉由使用含有奈米氣泡之蝕刻液，不管氣體的種 類，並藉奈米氣泡的布朗運動(Brownian motion)在蝕刻液 v 中產生流動性，提升蝕刻處理的均一性。 根據剝離液與氧氣的組合，不光是具有剝離液除去抗 蝕劑的除去作用，還具有再附著防止作用，藉由氧氣之奈 20米氣泡產生的作用，防止自基板W剝離之抗蝕劑帶負電而 附著於基板W，還可藉由活性化之氧氣的奈米氣泡提昇剝 離液對基板W的反應性、也就是剝離作用。 根據剝離液與二氧化碳的組合，不僅具有剝離液除去 抗敍劑之除去作用，還具有防止強鹼化作用，藉由二氧化 13 200911395 4之奈米氣泡，防止111剝離液與水反應而產生之強驗溶液 對對鋁等配線圖案造成損害。 根據剝離液與氮氣的组合，不僅具有剝離液除去抗触 劑之除去作用’且因為藉由氮氣的奈求氣泡而使氧氣變得 5難以進人剝離液，因此還具有防止剝離液早期劣化之作用。 根據顯像液與氧氣之組合，不僅具有顯像液之顯像作 用還叮藉氧氣之示米氣泡而提高顯像液之反應性、也就 是對基板w之顯像作用。 #由麟液錢氣之組合，不僅具有顯像液之顯像作 10用’且因為藉由氮氣的奈米氣泡而使氧氣變得難以進入顯 像液，因此還具有防止顯像液早期劣化之作用。 藉使用含有奈米氣泡之顯像液而不管氣體種類，藉由 在奈米氣泡表面產生之負離子，業已顯像之陽離子性物質 會吸著奈米氣泡，防止陰離子性物質，防止再附著於基板 15 W。 藉使用3有氧氣、臭氧或氫氣之奈米氣泡之驗系洗 、 齊卜氨水或氫氧化約水，藉奈米氣泡表面帶有之負離子， 由基板W剝離之陽離子性物質會吸著奈米氣泡、排斥陰離 子性物質而防止再附著於基板W。 20 藉由純水或異丙醇（1以)洗淨90nm以下之微細圖案 時，會產生洗淨不足或圖案倒塌，但若使用含有氮氣或二 氧化碳之奈米氣泡之純水洗淨的話，則由於該純水之表面 張力降低而提高界面活性效果，因此可防止洗淨不足或圖 案倒塌。 14 200911395 再者藉上述各氣體與各處理液之組合處理基板~ 時，在處理槽1收容使用於該組合之處理液。 上述-實施形態中，分別藉由氣體供給泉與液體供給 泵设定供給至氣體剪斷器之剪斷室之氣體與處理液之壓 5力’但亦可於氣體供給管與液體供給管設置壓力調整間， 並藉由忒等壓力調整閥調整氣體與處理液之供給壓力。 又，雖然係構成為於處理槽内配置氣體剪斷器以處理 基板，但亦可在設置於使基板旋轉並進行處理之螺旋處理 裝置之旋轉台之上方之迴旋臂，安裝上述氣體剪斷器。而 10且，亦可藉使基板旋轉，且使迴旋臂迴旋後，使上述氣體 剪斷器由基板之徑方向中心部朝外方移動，並且使含有奈 米氣泡之處理液朝基板板面噴射，以處理基板。 第4圖係顯示本發明之第2實施形態。該實施形態中， 使用於液晶顯示裝置且由矩形玻璃基板構成之基板W保持 15於螺旋處理裝置21之旋轉台22。該旋轉台22收容於杯體23 内’且經由主轴24而藉由馬達25驅動旋轉。 上述旋轉台22係具有如4支支持臂26(僅圖示2支），並且 於各支持臂26之前端部設有用以支持上述基板W之角部的 下面之支持銷27、及卡合於角部的側面之一對卡合銷28(僅 2Q圖示1個）。 超音波噴嘴體31係設置於保持在上述旋轉台22之基板 W之上方。該超音波喷嘴體31係供給含有由第1實施形態所 示之作為奈米氣泡產生機構之氣體剪斷器2所產生之奈米 氣泡之處理液。超音波喷嘴體31於内部設有未圖示之振動 15 200911395 板，且該振動板對供給至内部之處理液賦與超音波振動。 上述超音波喷嘴31係安裝於搖動臂32之前端，且該搖 動臂係在保持於旋轉台22之基板W的上方朝水平方向搖動 驅動。藉此，可將由上述超音波喷嘴體31噴射之處理液均 5 一地供給到上述基板W之板面全體。 根據如此構成之螺旋處理裝置21，含有奈米氣泡之處 理液會通過超音波喷嘴體31而供給到基板W。因此，由超 曰波噴嘴體31朝基板w供給處理液時，其處理液所包含之 奈米氣泡會因為超音波振動而在基板W之板面麗壞。 10 當奈米氣泡被壓壞時’會因為其壓壞而產生氣穴作 用，並因為其氣穴作用而誘發衝擊波。藉此，可大幅促進 因應於使用於基板W之處理液的種類之處理作用。 第5圖係顯示該發明之第3實施形態。該實施形態係第2 實施形態之變形例。含有由氣體剪斷器2所產生之奈米氣泡 15的處理液供給至處理液供給喷嘴35。該處理液供給噴嘴35 係配置成朝旋轉中心將處理液供給至保持於旋轉台2 2之基 板W的板面。 另一方面，安裝於搖動臂32之超音波噴嘴體31供給之 液體係如純水。供給至超音波噴嘴體31之純水則被賦與超 20音波振動而供給至基板W之板面。 根據如此構成，含有由處理液供給噴嘴35供給至基板 w之板面之奈米氣泡之處理液會受到由超音波噴嘴體31噴 射之純水被賦與之超音波振動的作用。 藉此，處理液所含之奈米氣泡在處理液供給到基板w 16 200911395 後被賦與純水之超音波振動麼壞後，會因為其壓壞而產生 氣八作用，並因為其氣穴作用而誘發衝撃波。藉此，會大 幅促進因應於施行於基板w之處理液的種類之處理作用。 第6圖係該發明之第4實施形態，且該實施形態係藉由 5水平搬送處理裝置36將基板w水平搬運並進行處理，以取 代螺旋處理裝置2卜水平搬送處理裝置36具有以預定間隔 水平配置之複數搬送棍子37，以將基板w朝箭頭方向搬送。 在搬送之基板W的上面，沿著與基板w之搬送方向直 交之寬度方向配置有作為超音波振動賦與機構之細長超音 ⑺波嘴嘴體31A。該超音波喷嘴體31A係供給含有由氣體剪斷 器2產生之奈米氣泡之處理液。 藉此，由於含有賦與超音波振動之奈米氣泡之處理液 可涵跨寬度方向全長而供給至水平搬送之基板诃的上面， 因此當供給至基板W之上面之處理液中的奈米氣泡在基板 15 W上面被壓壞時，會因為其壓壞而產生氣穴作用，並藉由 其氧八作用而誘發衝擊波。藉此，可大幅促進對基板w進 行且因應於處理液種類之處理作用。 第7圖係顯示藉由水平搬送處理裝置36搬送基板％並 進行處理之該發明之第5實施形態。該實施形態為第6圖所 20示之第4實施形態之變形例，且自超音波喷嘴體31A朝基板 W板面供給作為賦與有超音波振動之液體的純水。 作為處理液供給喷嘴之淋浴管件41係沿著基板w之寬 度方向’配置於比上述超音波噴嘴體31A更位於基板w之搬 送方向的上游側。淋浴管件41供給含有由氣體剪斷器2產生 17 200911395 之奈米氣泡之處理液，且其處理液供給至上述基板w之上 面。 根據如此構成，當藉由淋浴管件41將含有奈米氣泡之 處理液供給至基板W的板面時，其處理液會受到賦與自超 5音波噴嘴體31A供給之純水之超音波振動的作用而被壓壞。 當奈米氣泡壓壞時，會因為其壓壞而產生氣穴作用， 並因其氣穴作用而誘發衝擊波。藉此，可大幅促進對基板 W進行且因應於處理液之種類之處理作用。 第8圖係顯示藉由水平搬送處理裝置36搬送基板评並 10進行處理之該發明之第6實施形態。該實施形態係與藉由搬 送滾子37水平搬送之基板W的上面相對向，並且配設有複 數淋浴管件41。 各淋浴管件41係具有全長涵括基板…之寬度方向之長 度，並以預定間隔與基板W之搬送方向間隔。另一方面， 15在與基板W下面之上述淋浴管件41相對向之部位配置有超 、 音波噴嘴體31A’該超音波噴嘴體係對作為液體之純水賦與 超音波振動並朝上述基板之下面喷射。 根據如此構成，由複數淋浴管件41將處理液供給至基 2〇板~上面，並且由超音波喷嘴體31A將賦與超音波振動之純 水供給至下面。藉此，賦與供給至下面之純水之超音波振 動作用於供給至基板W之上面之處理液所含之奈米氣泡， 因此藉由其超音波振動壓壞處理液所含之奈米氣泡。 當壓壞奈米氣泡時，會因為其壓壞而產生氣穴作用， 並藉由其氣穴作用而誘發衝擊波。藉此，可大幅促進對基 18 200911395 板w進行且因應於處理液種類之處理作用。 而且，由於含有奈米氣泡之處理液供給至基板w之上 面，並且經賦與超音波振動之純水供給至基板W的下面， 以壓壞處理液所含之奈米氣泡，因此供給至基板w上面之 5處職可藉由純水而稀釋m其處理液對於基板界之 上面的處理效果降低^ 第9圖係顯示藉水平搬送處理裝置36搬迸並處理基板 W之本發明之第7實施形態。該實施形態中，含有由氣體剪 斷器2生成之奈米氣泡之處理液，藉由作為加壓機構之加壓 10泵42，而加壓成如〇.7MPa以上之高壓。然後，加壓成高壓 之處理液供給至配置於水平搬送之基板w的上面且作為供 給機構之高壓淋浴管件43。 含有奈米氣泡之處理液係以高壓由高壓淋浴管件43供 給至基板W之上面。藉此，當處理液以高壓與基板w之板 15面衝突時’也就是當處理液供給至基板時，會因為其壓力 而壓壞處理液所含之奈米氣泡。 ' 當奈米氣泡壓壞時，會因為其壓壞而產生氣穴作用’ 並且因其氣六作用而誘發衝擊波。藉此，玎Λ幅促進對基 板W進行且因應於處理液之種類之處理作用。 20 又，該第7實施形態中係舉藉由水平搬送處理裝置36 水平搬送並處理基板W之例來說明，但亦町適用於使基板 W旋轉並進行處理之情況。 第10圖係顯示藉由水平搬送處理裝置36搬送並處理基 板W之該發明之第8實施形態。該實施形態係第9圖所示之 19 200911395 第實知幵九%、之憂开》例，用以供給含有由氣體剪斷器2生成 之奈米氣泡之處理液之複數淋浴管件44係沿著基板w之搬 送方向以預定間隔且沿著基板评之寬度方向配置於基板w 上面測。又，淋浴管件44亦可為1支。 5 又，用以將純水供給至前述基板W且作為液體噴射機 構之高壓淋浴管件45係沿著基板_寬度方向配置於基板 w之上面側，且為比上述淋浴管件44更位於基板w之搬送 方向之下游侧，且前述純水與含有由作為供給加屢機構之 加H42a加壓成如G.7MPa以上之高壓之奈米氣泡之處理 10液為不同之液體。 根據如此之構成，當由複數之淋浴管件44將處理液供 給至基板w之上面時，其處理液所含之奈米氣泡會因由高 C淋洛盲件45以尚壓供給至基板w上面之純水的麗力而崩 壞，且向壓淋浴管件45係配置於比前述淋浴管件44更位於 15 基板w之搬送方向的下游側者。 當奈米氣泡被壓壞時，會因為其壓壞而產生氣穴作 用，並且會因其氣穴作用而誘發衝擊波。藉此，可促進對 基板W進行且因應於處理液之種類之處理作用。 第4圖〜第1〇圖所示之各實施形態中，處理液與製作奈 20米氣泡之氣體的組合可考慮氧氣或臭氧與純水、氮氣或二 氧化碳與蝕刻液、空氣或氧氣或臭氧與剝離液、氮氣或二 氧化碳與剝離液等之組合。 含有奈米氣泡之氣體為氧氣或臭氧，且處理液為純水 %，可藉由氣穴作用之衝擊波促使來自基板w板面之有機 20 200911395 物的分解或微粒的脫離。 含有奈米氣泡之氣體為氮氣或二氧化碳，且處理液為 蝕刻液時，當因為奈米氣泡被壓壞而產生之氣穴作用誘發 衝擊波時，可藉由其衝擊波除去因蝕刻產生之殘渣。同時， 5 藉由奈米氣泡之氣體溶入處理液，具有藉由其氮氣或二氧 化碳防止基板W表面氧化之效果。 ' 含有奈米氣泡之氣體為空氣或氧氣或臭氧，且處理液 為剝離液時，藉由奈米氣泡表面之負離子而剝離之陽離子 f 性物質會吸著奈米氣泡，並且排斥陰離子性物質而防止再 10 附著於基板W。 而且，由於奈米氣泡中具有吸收金屬離子（銘系、顧 系、鎢系、銅系）等之性質，因此可同時除去金屬離子。 含有奈米氣泡之氣體為氮氣或碳氣，且處理液為剝離 液時，可藉由因奈米氣泡壓壞而產生之氣穴作用誘發之衝 15 擊波，除去剝離液之殘渣。進而，當氣體為二氧化碳時， 可藉壓壞奈米氣泡來防止液的劣化。又，以純水將基板W ^ 之表面的剝離液漂洗時，剝離液所含之二氧化碳可防止剝 離液與純水反應而成為強鹼性。 產業上之可利用性 20 根據該發明，可使氣體與處理液迴旋且供給至氣體剪 - 斷器之剪斷室，並藉由氣體與處理液之間的迴旋速度差， 以流體力學方式剪斷氣體，使之產生奈米氣泡。因此，在 氣體溶入處理液前，可有效率地產生奈米氣泡，故可藉由 含有奈米氣泡之處理液有效率地洗淨基板。 21 200911395 t圖式簡單說明1 第1圖係顯示本發明之第1實施形態之處理裝置的概略 構成圖。 第2圖係沿著氣體剪斷器之轴方向之截面圖。 5 第3圖係由後端觀看氣體剪斷器之側面圖。 第4圖係顯示本發明之第2實施形態之螺旋處理裝置的 概略構成圖。 第5圖係顯示本發明之第3實施形態之螺旋處理裝置的 概略構成圖。 10 第6圖係顯示本發明之第4實施形態之水平搬送處理裝 置之概略構成圖。 第7圖係顯示本發明之第5實施形態之水平搬送處理裝 置之概略構成圖。 第8圖顯示本發明之第6實施形態之水平搬送處理裝置 15 之概略構成圖。 第9圖係顯示本發明之第7實施形態之水平搬送處理裝 置之概略構成圖。 第10圖係顯示本發明之第8實施形態之水平搬送處理 裝置之概略構成圖。 20 【主要元件符號說明】 1.. .處理室 3b...前部空間部 2…氣體剪斷器 4.·.本體 3.. .剪斷室 5...喷射口 3a...後部空間部 6...氣體供給口 22 200911395 7...液體供給口 28…卡合銷 11...氣體迴旋用金屬蓋 31，31A...超音波喷嘴體 12…氣體供給泵 32...搖動臂 13...氣體供給管 35…液體供給喷嘴 14...第1開關閥 36...水平搬送處理裝置 15...氣體空洞部 37...搬送輥子 16…液體供給金屬蓋 41,43,44...淋浴管件 17...液體供給泵 42,42a…加壓泵 18…液體供給管 45...高壓淋浴管件 19...第2開關閥 L.··純水 21…螺旋處理裝置 P1...氧氣之供給壓力 22.··旋轉台 P2···純水之供給壓力 23...杯體 VI…氧氣之迴旋速度 24...主轴 V2...純水之迴旋速度 25...馬達 W…紐 26·.·支持臂 27...支持銷 23W, Ϊ can be combined, ^ W 屯 water to wash the substrate 9, the hole of the nano-bubble and forced to form on the substrate w 12 200911395 . The role of the oxide film, and enhance the wettability of the substrate. According to the combination of the etching solution and oxygen or air, not only the etching effect by the etching liquid, but also the oxygen bubbles of oxygen or air, the cationic substance generated by the etching action caused by the etching liquid may be produced by the surface of the nano bubble. 5 raw negative ions are attracted, and the anionic substance can be prevented from reattaching to the substrate w due to repulsion. Further, since the nanobubbles have the property of absorbing metal ions or the like, the removal of metal ions can be carried out simultaneously. Further, the reactivity of the etching liquid to the substrate W, that is, the last name, can be enhanced by the nanobubbles of the activated oxygen gas. According to the combination of the etching solution and nitrogen or carbon dioxide, the cationic substance generated by the etching action absorbs the nanobubbles by the negative ions generated on the surface of the nanogas/package, and prevents the anionic substance from repelling and adheres to the substrate W. . 15 By using an etching solution containing nanobubbles, regardless of the type of gas, and by the Brownian motion of the nanobubbles, fluidity is generated in the etching liquid v, and the uniformity of the etching treatment is improved. According to the combination of the stripping solution and the oxygen gas, not only the stripping liquid removing resist is removed, but also the re-adhesion preventing effect is provided, and the resist strip which is peeled off from the substrate W is prevented by the action of the oxygen gas 20 m bubble. Negatively attached to the substrate W, the reactivity of the stripping liquid to the substrate W, that is, the peeling action, can be enhanced by the nanobubbles of the activated oxygen. According to the combination of the stripping solution and the carbon dioxide, not only the stripping liquid removing agent is removed, but also the strong alkalizing action is prevented, and the 111 stripping liquid is prevented from reacting with water by the nanobubble of 200911395 4 The strong solution causes damage to wiring patterns such as aluminum. According to the combination of the stripping liquid and the nitrogen gas, not only the stripping liquid removing the anti-contact agent is removed, but also because the oxygen gas becomes difficult to enter the stripping liquid by the nitrogen gas, it is also possible to prevent the early peeling of the stripping liquid. effect. According to the combination of the developing liquid and the oxygen, not only the developing effect of the developing liquid but also the oxygen gas is used to increase the reactivity of the developing liquid, that is, the developing effect on the substrate w. #由麟液的气气的组合, not only has the development of imaging liquid for 10" and because oxygen bubbles become difficult to enter the developing solution by the nanobubbles of nitrogen, so it also prevents early deterioration of the imaging liquid. The role. By using a liquid containing nano bubbles regardless of the type of gas, the negative ions generated on the surface of the nanobubbles, the cationic material that has been imaged will absorb the nanobubbles, prevent anionic substances, and prevent reattachment to the substrate. 15 W. By using 3 nanometer bubbles of oxygen, ozone or hydrogen, washing with ammonia, water or hydroxide, and the negative ions on the surface of the nanobubble, the cationic material stripped from the substrate W will attract the nanometer. The bubbles repel the anionic substance to prevent reattachment to the substrate W. 20 When the fine pattern of 90 nm or less is washed by pure water or isopropyl alcohol (1), insufficient washing or pattern collapse occurs, but if it is washed with pure water containing nitrogen or carbon dioxide, it is washed. Since the surface tension of the pure water is lowered to improve the effect of the interface activity, it is possible to prevent insufficient washing or pattern collapse. 14 200911395 When the substrate is processed by the combination of the above gases and the respective treatment liquids, the treatment liquid used in the combination is accommodated in the treatment tank 1. In the above-described embodiment, the pressure of the gas and the treatment liquid supplied to the shear chamber of the gas shear is set by the gas supply spring and the liquid supply pump, respectively. However, the gas supply tube and the liquid supply tube may be provided. The pressure adjustment chamber adjusts the supply pressure of the gas and the treatment liquid by means of a pressure regulating valve such as helium. Further, although the gas cutter is disposed in the treatment tank to process the substrate, the gas shear may be attached to the swing arm provided above the rotary table of the spiral processing device that rotates the substrate and processes the substrate. . On the other hand, after the substrate is rotated and the swing arm is rotated, the gas cutter is moved outward from the center portion in the radial direction of the substrate, and the treatment liquid containing the nanobubbles is sprayed toward the substrate surface. To process the substrate. Fig. 4 is a view showing a second embodiment of the present invention. In this embodiment, the substrate W composed of a rectangular glass substrate used in the liquid crystal display device is held 15 on the turntable 22 of the spiral processing device 21. The turntable 22 is housed in the cup 23 and is driven to rotate by the motor 25 via the main shaft 24. The rotary table 22 has four support arms 26 (only two are shown), and a support pin 27 for supporting the lower surface of the corner portion of the substrate W is provided at the front end of each support arm 26, and is engaged with One of the side faces of the corner portion is a pair of engaging pins 28 (only one is shown in 2Q). The ultrasonic nozzle body 31 is provided above the substrate W held by the turntable 22. The ultrasonic nozzle body 31 supplies a treatment liquid containing nano bubbles generated by the gas cutter 2 as a nano bubble generating mechanism shown in the first embodiment. The ultrasonic nozzle body 31 is provided with a vibration 15 200911395 plate (not shown), and the vibration plate imparts ultrasonic vibration to the processing liquid supplied to the inside. The ultrasonic nozzle 31 is attached to the front end of the swing arm 32, and the rocking arm is driven to swing in the horizontal direction above the substrate W held by the turntable 22. Thereby, the processing liquid sprayed by the ultrasonic nozzle body 31 can be supplied to the entire plate surface of the substrate W. According to the spiral processing apparatus 21 configured as described above, the chemical liquid containing the nanobubbles is supplied to the substrate W through the ultrasonic nozzle body 31. Therefore, when the processing liquid is supplied from the super-chopper nozzle body 31 to the substrate w, the nano-bubble contained in the processing liquid is deteriorated on the surface of the substrate W due to the ultrasonic vibration. 10 When the nanobubble is crushed, it will cause cavitation due to its crushing, and induce shock waves due to its cavitation. Thereby, the handling action depending on the type of the treatment liquid used for the substrate W can be greatly promoted. Fig. 5 is a view showing a third embodiment of the invention. This embodiment is a modification of the second embodiment. The treatment liquid containing the nanobubbles 15 generated by the gas cutter 2 is supplied to the treatment liquid supply nozzle 35. The processing liquid supply nozzle 35 is disposed so as to supply the processing liquid to the plate surface of the substrate W held by the rotating table 22 toward the center of rotation. On the other hand, the liquid system supplied from the ultrasonic nozzle body 31 attached to the swing arm 32 is, for example, pure water. The pure water supplied to the ultrasonic nozzle body 31 is supplied with super 20-sonic vibration and supplied to the surface of the substrate W. According to this configuration, the treatment liquid containing the nanobubbles supplied to the surface of the substrate w by the treatment liquid supply nozzle 35 is subjected to the ultrasonic vibration imparted by the pure water sprayed from the ultrasonic nozzle body 31. Thereby, the nanobubbles contained in the treatment liquid are imparted to the supersonic vibration of the pure water after the treatment liquid is supplied to the substrate w 16 200911395, and the ultrasonic vibration is generated due to the crushing thereof, and because of its cavitation The action induces a wave. Thereby, the treatment effect depending on the kind of the treatment liquid applied to the substrate w is greatly promoted. Fig. 6 is a fourth embodiment of the present invention, and in this embodiment, the substrate w is horizontally conveyed and processed by the fifth horizontal transfer processing device 36, instead of the spiral processing device 2, the horizontal transfer processing device 36 has a predetermined interval. The plurality of transport sticks 37 are horizontally arranged to transport the substrate w in the direction of the arrow. On the upper surface of the substrate W to be transported, an elongated supersonic (7) wave nozzle body 31A as an ultrasonic vibration imparting mechanism is disposed in a width direction orthogonal to the transport direction of the substrate w. The ultrasonic nozzle body 31A supplies a treatment liquid containing nano bubbles generated by the gas cutter 2. In this way, since the treatment liquid containing the nanobubbles to which the ultrasonic vibration is applied can be supplied to the upper surface of the horizontally conveyed substrate crucible across the entire width direction, the nanobubbles in the treatment liquid supplied to the upper surface of the substrate W are provided. When the substrate 15 W is crushed, it is cavitation due to its crushing, and the shock wave is induced by its action of oxygen. Thereby, the substrate w can be greatly promoted and the treatment effect depending on the type of the treatment liquid can be promoted. Fig. 7 is a view showing a fifth embodiment of the invention in which the substrate is transported by the horizontal transfer processing device 36 and processed. This embodiment is a modification of the fourth embodiment shown in Fig. 6 and the pure water which is a liquid to which ultrasonic vibration is applied is supplied from the ultrasonic nozzle body 31A toward the substrate W surface. The shower tube member 41 as the processing liquid supply nozzle is disposed on the upstream side of the substrate w in the transport direction of the substrate w in the width direction of the substrate w. The shower pipe member 41 supplies a treatment liquid containing nano bubbles which are generated by the gas cutter 2, and the treatment liquid is supplied to the upper surface of the substrate w. According to this configuration, when the treatment liquid containing the nanobubbles is supplied to the plate surface of the substrate W by the shower tube member 41, the treatment liquid is subjected to ultrasonic vibration imparted to the pure water supplied from the super 5-sonic nozzle body 31A. It is crushed by the action. When the nanobubble is crushed, it will cause cavitation due to its crushing, and induce a shock wave due to its cavitation. Thereby, the substrate W can be greatly promoted and the treatment effect depending on the type of the treatment liquid can be promoted. Fig. 8 shows a sixth embodiment of the invention in which the substrate evaluation 10 is carried out by the horizontal transfer processing device 36. This embodiment is opposed to the upper surface of the substrate W horizontally conveyed by the transport roller 37, and a plurality of shower tubes 41 are disposed. Each of the shower tubes 41 has a length in the width direction of the entire length of the substrate, and is spaced apart from the conveyance direction of the substrate W by a predetermined interval. On the other hand, 15 is disposed with a super/sonic nozzle body 31A' facing the shower tube 41 below the substrate W. The ultrasonic nozzle system imparts ultrasonic vibration to the pure water as a liquid and faces the lower surface of the substrate. injection. According to this configuration, the processing liquid is supplied from the plurality of shower tubes 41 to the upper surface of the base plate, and the ultrasonic water imparted with the ultrasonic vibration is supplied to the lower surface by the ultrasonic nozzle body 31A. Thereby, the ultrasonic vibration imparted to the pure water supplied to the lower surface acts on the nanobubbles contained in the treatment liquid supplied onto the upper surface of the substrate W, so that the ultrasonic bubbles contained in the treatment liquid are crushed by the ultrasonic vibration. . When the nanobubbles are crushed, cavitation is caused by the crushing thereof, and the shock wave is induced by the cavitation. Thereby, the treatment of the base 18 200911395 plate w and the treatment liquid type can be greatly promoted. Further, since the treatment liquid containing the nanobubbles is supplied to the upper surface of the substrate w, and the pure water imparted with the ultrasonic vibration is supplied to the lower surface of the substrate W to crush the nanobubbles contained in the treatment liquid, the substrate is supplied to the substrate. The five positions on the top of w can be diluted by pure water, and the treatment effect of the treatment liquid on the upper surface of the substrate is lowered. FIG. 9 shows the seventh aspect of the present invention in which the substrate W is transferred and processed by the horizontal transfer processing device 36. Implementation form. In this embodiment, the treatment liquid containing the nanobubbles generated by the gas cutter 2 is pressurized to a high pressure of 7.5 MPa or more by the pressurizing pump 10 as a pressurizing means. Then, the treatment liquid pressurized to a high pressure is supplied to the high pressure shower pipe member 43 which is disposed on the upper surface of the substrate w which is horizontally conveyed and serves as a supply mechanism. The treatment liquid containing the nanobubbles is supplied from the high pressure shower pipe member 43 to the upper surface of the substrate W at a high pressure. Thereby, when the treatment liquid collides with the surface of the substrate 15 of the substrate w at a high pressure, that is, when the treatment liquid is supplied to the substrate, the nanobubbles contained in the treatment liquid are crushed by the pressure thereof. 'When the nanobubble is crushed, it will cause cavitation due to its crushing' and induce a shock wave due to its action. Thereby, the web is promoted to the substrate W and is treated in accordance with the type of the treatment liquid. In the seventh embodiment, the horizontal transfer processing device 36 is used to convey and process the substrate W horizontally. However, the same applies to the case where the substrate W is rotated and processed. Fig. 10 shows an eighth embodiment of the invention in which the substrate W is transported and processed by the horizontal transport processing device 36. This embodiment is an example of the 19th, 11th, 11th, and 12th, which is shown in FIG. 9 for supplying a plurality of shower tubes 44 containing a treatment liquid for the nanobubbles generated by the gas cutter 2. The transport direction of the substrate w is placed on the substrate w at a predetermined interval and along the width direction of the substrate. Further, the shower tube member 44 may be one. Further, the high-pressure shower pipe member 45 for supplying the pure water to the substrate W and serving as the liquid ejecting mechanism is disposed on the upper surface side of the substrate w along the substrate width direction, and is located on the substrate w more than the shower tube member 44. In the downstream side of the transport direction, the pure water is different from the liquid 10 containing the high-pressure nano-bubble which is pressurized by the addition of H42a as a supply-addition mechanism to a high-pressure nano-bubble of G. 7 MPa or more. According to this configuration, when the processing liquid is supplied onto the substrate w by the plurality of shower tubes 44, the nano-bubble contained in the treatment liquid is supplied to the substrate w by the high-C leaching blind member 45 at a pressure. The pressure of the pure water collapses, and the pressure shower tube 45 is disposed on the downstream side of the 15th substrate w in the transport direction of the shower tube 44. When the nanobubble is crushed, it will cause cavitation due to its crushing, and it will induce a shock wave due to its cavitation. Thereby, it is possible to promote the treatment of the substrate W in response to the type of the treatment liquid. In each of the embodiments shown in Fig. 4 to Fig. 1, the combination of the treatment liquid and the gas for producing bubbles of 20 m can be considered oxygen or ozone and pure water, nitrogen or carbon dioxide and etching liquid, air or oxygen or ozone. A combination of a stripper, nitrogen or carbon dioxide, a stripper, and the like. The gas containing the nanobubbles is oxygen or ozone, and the treatment liquid is pure water %, and the decomposing or the detachment of the particles from the surface of the substrate w can be promoted by the shock wave of the cavitation action. When the gas containing the nanobubbles is nitrogen or carbon dioxide, and the treatment liquid is an etchant, when the cavitation caused by the collapse of the nanobubbles induces a shock wave, the residue due to the etching can be removed by the shock wave. At the same time, 5 is dissolved in the treatment liquid by the gas of the nanobubbles, and has an effect of preventing oxidation of the surface of the substrate W by nitrogen gas or carbon dioxide. 'The gas containing the nanobubble is air or oxygen or ozone, and when the treatment liquid is the stripping solution, the cationic f-substance which is peeled off by the negative ions on the surface of the nanobubble will adsorb the nanobubbles and repel the anionic substance to prevent it. Further, 10 is attached to the substrate W. Further, since the nanobubbles have properties such as absorption of metal ions (Ming, Brake, Tungsten, and Copper), metal ions can be simultaneously removed. When the gas containing the nanobubbles is nitrogen gas or carbon gas, and the treatment liquid is a stripping liquid, the residue of the stripping liquid can be removed by the impact of the cavitation caused by the collapse of the nanobubbles. Further, when the gas is carbon dioxide, the deterioration of the liquid can be prevented by crushing the nanobubbles. Further, when the stripping liquid on the surface of the substrate W ^ is rinsed with pure water, the carbon dioxide contained in the stripping liquid prevents the stripping liquid from reacting with the pure water to become strongly alkaline. Industrial Applicability According to the invention, the gas and the treatment liquid can be swirled and supplied to the shear chamber of the gas shearer, and the fluid velocity can be sheared by the difference in the speed of the swirl between the gas and the treatment liquid. The gas is broken to produce nano bubbles. Therefore, since the nanobubbles can be efficiently generated before the gas is dissolved in the treatment liquid, the substrate can be efficiently washed by the treatment liquid containing the nanobubbles. 21 200911395 t. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic block diagram showing a processing apparatus according to a first embodiment of the present invention. Figure 2 is a cross-sectional view along the axial direction of the gas shear. 5 Figure 3 is a side view of the gas cutter viewed from the rear end. Fig. 4 is a schematic block diagram showing a spiral processing apparatus according to a second embodiment of the present invention. Fig. 5 is a schematic block diagram showing a spiral processing apparatus according to a third embodiment of the present invention. Fig. 6 is a schematic block diagram showing a horizontal conveyance processing apparatus according to a fourth embodiment of the present invention. Fig. 7 is a schematic block diagram showing a horizontal conveyance processing apparatus according to a fifth embodiment of the present invention. Fig. 8 is a view showing a schematic configuration of a horizontal transport processing device 15 according to a sixth embodiment of the present invention. Fig. 9 is a schematic block diagram showing a horizontal conveyance processing apparatus according to a seventh embodiment of the present invention. Fig. 10 is a schematic block diagram showing a horizontal conveyance processing apparatus according to an eighth embodiment of the present invention. 20 [Description of main component symbols] 1.. Process chamber 3b... Front space section 2... Gas shearer 4.·. Main body 3.. Cutroom 5... Injection port 3a... Rear part Space portion 6...gas supply port 22 200911395 7...liquid supply port 28...engagement pin 11...metal cover for gas swirl 31,31A...ultrasonic nozzle body 12...gas supply pump 32.. The swing arm 13 ... the gas supply pipe 35 ... the liquid supply nozzle 14 ... the first switch valve 36 ... the horizontal transfer processing device 15 ... the gas cavity portion 37 ... the transfer roller 16 ... the liquid supply metal cover 41, 43, 44... Shower tube 17 ... liquid supply pump 42, 42a ... pressure pump 18 ... liquid supply tube 45 ... high pressure shower tube 19 ... 2nd switch valve L. · pure water 21...Spiral processing device P1...Oxygen supply pressure 22.··Rotary table P2··· Pure water supply pressure 23... Cup VI... Oxygen swirl speed 24... Spindle V2... Pure Water swing speed 25...Motor W...New 26··Support arm 27...Support pin 23