TW201023986A - Object cleansing method and object cleansing system - Google Patents

Abstract

The present invention provides a method for cleansing an object by injecting multiphase fluid comprising vapor and droplet, which is characterized in obtaining preferred impact force by controlling the level of cavitation resulted from the impact of the droplet of the multiphase fluid upon the object.

Description

[Technical Field] The present invention relates to a semiconductor substrate/glass substrate/lens/disc member/precision machined member/molded resin member or the like (particularly ^ a method of processing a predetermined portion or a predetermined surface of the object on a semiconductor substrate having an aluminum material such as aluminum wiring on the surface, and the system (for example, an object cleaning method and an object cleaning system), and more specifically, a method of cleaning a part or a surface, removing and peeling off a substance not used in the part, polishing and processing the surface of the object surface, and the like (for example, a resist stripping device, a polymer stripping device, and a cleaning device) Processing methods such as a semiconductor manufacturing apparatus, a printed circuit board cleaning apparatus, and a mask cleaning apparatus. [Prior Art] In the processing step of the semiconductor, the cleaning of the i wafer is repeated from 100 to 100 times. The object to be cleaned is an organic substance or a fine particle such as a resist film or a polymer film which affects the reliability of the element. In this cleaning step kicking, the combination of the cleaning solution and the acid cleaning solution is mixed with other sulfuric acid and hydrogen peroxide, and in addition, the residue is washed in the waste == use a large amount of pure water . In addition, one ▲ use electric ash and each class to wash the line using other cleaning devices "(4) residue and miscellaneous f clear

The use of an amine-based organic second is used to remove the polymer film. This liquid can also be used for the removal of the resist. Here, the conventional technical liquid system shown by Shangshen has the following disadvantages: n. The drainage treatment equipment of the 认 认 〜 云 云 云 云 云 云 云 云 , , 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 There is a special ', ', to ensure that the safety and health of the staff must be 320816 201023986 must be large, and in the cleaning of the used liquid, in order to rinse the liquid must have a large amount of pure water, 4) can not use one device The process of removing the film to the cleaning is performed. Further, if it is limited to the washing step in which the chemical liquid is not used, the following main techniques are currently available. First, ultrasonic cleaning devices are now the most widely used cleaning technology. In addition to pure water, they can be combined with various cleaning solutions. Disadvantages are due to the cavitation phenomenon (which is different from the cavitation phenomenon described later in the present invention), which may damage the soft material, the brittle material, and the fine pattern. Therefore, although the frequency is increased, etc., there is a conflict with the cleaning power. Secondly, the water spray cleaning device is suitable for cleaning large-scale systems. The disadvantage is that there must be high pressure (several Mpa to 20 MPa), but not for objects with fine patterns. Moreover, the brush cleaning device can be combined with various cleaning liquids in addition to pure water. Disadvantages are not suitable for surfaces with deep grooves and holes. Moreover, since the surface of the object is in direct contact with the brush, there is a possibility of generating dust and scratches. In addition, there is a cleaning device that illuminates only water vapor. The environmental load of the device is also very small when the device is not used. However, 'this device has the following disadvantages: 1) Since the droplets are not used, the effect of strongly bonding the object such as the photoresist on the wafer and the foreign matter is small ' 2) Since the pressure of the vapor generator is unique The parameters, so it is impossible to adjust the optimum conditions of the object. Therefore, in recent years, it has been proposed to use a cleaning device that combines water vapor with liquid fine particles (for example, Patent Document 1 to be described later). In this technique, 'the first vaporized water (water vapor) infiltrates into the resist film and reaches the interface between the resist film and the surface of the object, and weakens the bond of the resist film of the interface 4 320816 201023986, so that The resist film is lifted off from the surface of the object. Next, a county is produced, and (4) a mist-like water (water mist) containing liquid water microparticles having a constant cutting pressure physically acts on the resist film to peel the resist film from the interface. Then, in the patent literature! The paragraph number is deleted as 9, and the cavitation phenomenon using the thermal effect phenomenon as a basic principle of the technique is described. Specifically, it is a mechanism that generates a vibration having a certain frequency (ΙΟΚΗζ to 1 MHz) by mixing the above-mentioned heat exchange with pure water of normal temperature and high water vapor. Then, by using this vibration, the water molecules are decomposed into hydrogen ions and hydroxide ions, and the high energy generated when the unstable ions are returned to the water molecules again is converted into a mechanical impact. [Patent Document 1] W020061/018948 [Problem to be Solved by the Invention] However, when a cleaning device that combines water vapor and water shown in Patent Document 1 is used, the following problems occur: First, Water molecules are soaked by the phenomenon of a certain amount of time required for the water-molecular impregnation reaction, and the fog-like mist directly collides with the resist film and the particles to remove the film and the dirt. The problem of the time limit processing time, and the second 'cleaning force is insufficient enough to sufficiently remove the dirt of the object, or conversely, the cleaning power is too strong to damage the object. At this time, 'take some measures', for example, the former is used to increase the discharge pressure, and the latter is to lower the discharge pressure. Thus, in the current state, the cleaning force can be adjusted only by the action of fluid mechanics (collision force, etc.). However, at this time, there is some doubt that in the former, the vapor temperature rises due to the increase of the pressure of the spray 320816 5 201023986, and the material with low heat resistance cannot be used as the object 'or the collision force is too strong and the object may occur. Damage. On the other hand, in the latter, there is a problem in that the ejection pressure is low and the situation of the object is prevented from being damaged, but the cleaning of the object is insufficient. Accordingly, a first object of the present invention is to provide a means for ensuring that the permeation time of water molecules is not restricted and that the cleaning is carried out before the object is not damaged. Further, the inventors of the present invention have found from their experience that when a semiconductor substrate is cleaned by a multiphase flow of water and water vapor, aluminum formed on the surface of the semiconductor substrate is quickly corroded. As a result, the semiconductor device may not operate when it is subjected to corrosion before the next process, and it also causes a situation in which the yield is deteriorated. Accordingly, a second object of the present invention is to provide a means for forming aluminum on the surface of the semiconductor substrate to be less susceptible to long-term corrosion even when the semiconductor substrate is cleaned by multiphase flow of water and water vapor. (Means for Solving the Problem) The inventors of the present invention focused on the aforementioned cavitation phenomenon completely different from the previous action sequence, and found that the degree of the cavitation phenomenon on the object can be effectively and easily implemented. The present invention has been completed in accordance with the treatment of an object. Further, in order to improve the detergency, the inventors of the present invention did not pay attention to the pressure of the gas but focused on the velocity of the liquid (four) contained in the multiphase fluid, and continually conducted careful research to increase the speed. Therefore, it has been found that when a specific nozzle is used to increase the droplet velocity, the above-described object can be removed without causing cracking of the object and collapse of the surface pattern, and sufficient impact force can be used to remove the removed object attached to the object. The present invention has been completed. 201023986 The present invention (1) is a method for cleaning an object, comprising the step of irradiating a multiphase fluid containing water droplets of a continuous phase and water droplets of a dispersed phase which are produced by mixing water vapor and water with a mixing portion through a nozzle. In the method of cleaning the object, the mixing unit is provided on the upstream side of the nozzle, and has a water introduction portion that is partially open in the inner λ wall surface, and the nozzle is an ultrahigh-speed nozzle, and the inner wall surface of the mixing portion and the nozzle The inner wall surface forms a substantially continuous curved surface, and water is mixed from the inner wall surface of the mixing portion to the water vapor flowing in the mixing portion, and water is caused to flow along the inner wall surface of the nozzle from the inner wall surface of the mixing portion In the method of the invention (1), the nozzle has a diameter reduction from the upstream side of the nozzle toward the nozzle outlet, and The structure in which the throat of the small cross-sectional area is a boundary and the end of the diameter is widened. The invention (3) is the method of the invention (1) or (2), the aforementioned In the method of any one of the inventions (1) to (3), the speed of the water droplets is in the range of 100 to 600 m/s. The invention (5) is based on In any one of the above inventions (1) to (4), the temperature at which the multiphase fluid reaches the object is 50 ° C or higher, and the pH of the multiphase fluid reaching the object is in the range of 7 to 9. The invention (6) is the method of the invention (5), wherein the distance between the ejection outlet of the multiphase fluid 7 320816 201023986 and the object is 30 mm or less. The invention (7) is based on the aforementioned inventions (1) to (6) In any one of the methods, the object is a semiconductor substrate having a material such as a wiring on the surface. The invention (8) is a system for cleaning an object by irradiating a multiphase fluid containing water vapor and water droplets through a nozzle. And a water vapor supply means for supplying water vapor (for example, 'reduction gas supply part (A)); a water supply means for supplying water (for example, a pure water supply part (B)); and a nozzle for irradiating the multiphase fluid; The feature is: a description mixing unit (for example, 'mixing unit 144) is provided in the foregoing a nozzle upstream of the nozzle and having a water introduction portion (for example, 144a) that can mix water to the inner wall surface of the water vapor flowing from the inner wall surface, and the nozzle system is a super high speed nozzle (for example, the nozzle 141). According to a seventh aspect of the invention, in the method of the invention (8), the nozzle has a nozzle that faces from the upstream side of the nozzle toward the nozzle outlet. In the system of the invention (8) or the system of the invention (8), the mixing portion is cylindrical, and the end portion of the invention is (8). Next, the meaning of each term in this manual is explained. First, the month, the drop, for example, refers to the concept of tiny droplets of water that are saturated with vapor, in addition to water droplets from water. The "multi-phase fluid" refers to a fluid having a plurality of fluid components such as two fluids and three fluids, and examples thereof include 1) saturated water vapor and pure water droplets having a boiling point or less, and 2) heating water 8 320816 201023986 vapor With pure water droplets below the boiling point, 3) complex inert gas or clean high pressure air in the above 1} or 2). However, oxygen gas and other reactive gases can also be used when it is used without ignoring the oxidation and chemical reaction of the object. Further, from the viewpoint of using aluminum to prevent corrosion, it is preferable to use a two-phase flow which is only water and water vapor or a combination of the above two-phase flow and an inert gas. The "object" is not particularly limited, and examples thereof include an electronic component, a semiconductor substrate, a glass substrate, a lens, a disk member, and a precision machined member' molded resin member. The term "treatment" is not particularly limited as long as it is applied to the object, and examples thereof include peeling, π washing, and processing. The term "water" refers to a cleaning step in the manufacture of a semiconductor device. In the use of a small foreign matter or a metal ion or the like, the water is used as a characteristic of pure water or ultrapure water, and the foreign matter and metal ions which are generated on the object are not contaminated. In use, it includes a layer of tap water with a low level. The term "system" refers to a position (for example, a device) in which each of the 10 constituent elements is physically separated from each other except for the "1" setting in which each component is stored as a body, or between the components. When connected in such a way as to convey information, the overall constituent elements having the functions specified in the scope of the patent application are in compliance with the system. The term "super south speed nozzle" means a nozzle that accelerates a droplet above the speed of sound. Here, in order to clarify the difference between the cavitation phenomenon of the other action sequence known in the field of object processing, the cavitation phenomenon at the time of collision of the droplet of the present invention will be described in detail with reference to the drawings. Furthermore, the operational sequence described herein is only predictive. Therefore, the present invention is not limited by this action sequence 9 320816 201023986. First, the general concept of cavitation is explained below. In general, when the temperature of the liquid is higher than the saturation temperature of the pressure, boiling starts, and even if the pressure of the liquid becomes lower than the saturation pressure of the temperature, the liquid starts to boil. That is, vapor bubbles are generated in the liquid. Therefore, it is not a bubble that is caused by a change in temperature but is caused by a decompression effect. It is usually called a cavitation bubble. High pressure is generated due to shrinkage and collapse of the bubble, and erosion, noise, and the like are generated. This phenomenon is called cavitation. Conventionally, in the ultrasonic cleaning device used for cleaning, cavitation is generated by the following action sequence (Fig. 24). 1. Use the ultrasonic generator to transmit sound waves into the medium. 2. The sound wave is compressed and decompressed in a fast cycle and passed through the medium. 3. During the transfer from compression to decompression, local pressure is reduced to below the saturated water vapor pressure. 4. At this point, the growth of bubbles (normal temperature boiling) begins to occur. 5. In addition, non-condensable gases dissolved in the vehicle are also mixed into the enlarged growth vapor bubbles. 6. Bubbles continue to grow. 7. The bubble is compressed in a heat-insulated manner by the subsequent compressive force and has high energy. 8. The bubble collapses and collapses at the end. 9. When crushed, it becomes a localized impact energy and decomposes the dirt around it. 10 320816 201023986 * ίο. Sound waves usually generate standing waves by passing the traveling waves in the medium and the reflected waves reflected at the liquid level. 11. At this time, the gas six phenomenon is streaked in the vehicle liquid along the maximum sound pressure body. Then, according to the method of the present invention, the mechanism for generating cavitation in the collision of the generated droplets can be considered, and the example of the past report is used as a reference (martin Rein, Drop-Surface Interaction (Cism).

Internation Centre For Mechanical Sciences Courses and

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Lectures) pp.39-102, Martin Eein ed., Springer-Verlag, 2002,) ° 1. When a droplet collides with a solid boundary interface at a certain velocity, the kinetic energy of the droplet is converted to a pressure energy 'in the droplet High pressure is generated in the contact surface of the solid boundary interface (Fig. 25). 2. The generated pressure acts as a pressure wave (compressed wave) that propagates the inside of the droplet to the upper side and reaches the boundary interface between the droplet and the surrounding gas, that is, the free interface (Fig. 20). 3. The acoustic impedance of water is much larger than the acoustic impedance of the surrounding gas, and the I-force wave system is approximately as far as % reflection. That is, since the propagation of the gas around the pressure wave becomes very small, the pressure change at the free interface can be suppressed to a small extent (Fig. π). Since the pressure change on the interface becomes smaller, the expansion wave which cancels the compression wave is generated, and the A _ force generates a lower pressure wave than the surroundings, and propagates to the inside of the liquid. 5 · Propagation into the droplets The internal expansion of the wave system reduces the pressure inside the droplets. 11 320816 201023986 Force. When the temperature of the droplet is about 30 ° C, it is reduced by about 0.04 atmosphere. If it is about 60 ° C, it is reduced by about 0.2 atmosphere. If it is about 80 ° C, it is lowered by about 0.5 atmosphere, so that boiling starts and bubbles are generated. And grow up (Figures 28, 29). 6. The generated vapor bubbles are also introduced into the liquid and become larger than the non-condensable gas in the liquid. 7. When the bubble of full growth reaches the limit of growth, it begins to rebound and shrinks. Since the shrinkage process is sharply generated compared to the expansion process, the bubble is rapidly contracted, and the internal pressure of the bubble is higher than the pressure at the start of growth, and an extremely high pressure can be achieved. This high pressure is called pressure when the bubble collapses. 8. Bubble collapse is also induced by disturbances in the surrounding conditions of the bubble. In addition, the bubbles do not necessarily collapse alone, but collapse as a group of bubbles that accumulate bubbles. According to the report, the bubble collapse pressure at this time is more than a hundred times the pressure of a single bubble collapse. 9. The bubble collapse pressure generated inside the droplet propagates as a pressure wave (compression wave) inside the droplet and reaches the contact surface between the droplet and the solid surface, causing a very large pressure on the solid surface. This is the collapse pressure of the cavitation phenomenon that occurs when the droplet collides, and is cleaned by this pressure. It is essential in the present invention to maintain the thermal environment around the droplets at a sufficiently high temperature by water vapor or to prevent the leakage of heat caused by the droplets. Therefore, even if the pressure drop caused by the expansion wave inside the droplet is not significant, it is a condition that a sufficient bubble can be generated. Because of this characteristic, as in other inventions, even if the droplets have a rapid velocity without colliding with the solid surface, it is sufficient as long as a certain degree of compression wave can be generated. 12 320816 201023986 In the comparison of inventions, the point of generating cavitation by the droplets with a 2-digit degree-speed is the most special (the effect of the invention) 々 according to the invention, and the gambling of the (four) pressure (The method of fluid mechanics is used to control the impact force on the object, and the method is to treat the object by the cavitation phenomenon when the droplet collides with the surface of the object. Therefore, the following problems can be solved by solving the following problems and problems, which are conventional problems due to the level of the discharge pressure, specifically, the fact that the collision force becomes too strong and causes damage to the object. Suspicion and the problem that the object is damaged due to the low discharge pressure, but the cleaning of the object is insufficient. Moreover, the temperature of the droplet at the time of collision is highly correlated with the cavitation phenomenon at the time of collision of the droplet, so that the degree of the gas pocket (the presence or absence and degree of occurrence) can be easily controlled by changing the temperature of the helium. Further, under the low discharge pressure, the treatment of the object can be performed efficiently by increasing the temperature of the droplet, so that the problem caused by the high discharge pressure can be avoided. Further, when the gas is water vapor, even if the heat of the water vapor is transferred to another medium, the temperature of the entire system can be prevented from being lowered as a result of the latent heat of the water vapor. More specific effects and effects of the present invention are as follows. (i) a shock wave caused by a high-speed side jet and a bubble collapse caused by a collision of a droplet, and an impact force (cavitation phenomenon) caused by a chain reaction by a shock wave, which is caused by a film peeling cause Cracks and holes. (2) Producing a jet-and-shock wave due to droplets and a chain reaction due to shock waves and a jet on the high-speed side 13 320816 201023986, and rolling up the film with the crack and hole as described in (1) Stripping. (3) The object material is embrittled by the vapor of water having a large heat temperature energy, or stress is generated to weaken the adhesion of the interface between the object and the substrate. (4) The combination of the above functions can be changed in accordance with the object, whereby the cleaning object and the removal object can be expanded. (5) The present invention can be applied not only to the removal of impurities but also to the removal of the photoresist which is not used after the etching-step and ion implantation steps, and the use of the polymer which is not used after the etching step. Further, according to the inventions (1) to (4) and (8) to (10), the speed of water droplets is made faster by using an ultrahigh speed nozzle. Therefore, the droplets are subdivided to make the droplet diameter smaller. Therefore, it is difficult to produce droplets having a diameter which is a cause of cracking of the wafer and collapse of the pattern, and the problem is not easily generated even if the pressure is increased. Further, when an ultrahigh-speed nozzle is used, an action indicating the following two points is observed in the multiphase fluid which ejects water vapor and water droplets, and the multiphase fluid of air and water droplets. First, it is clear that an object such as a pressure wave is observed near the outlet in the nozzle by using an ultra-high-speed nozzle to eject a multiphase fluid of water vapor q and water (the 30th example). According to this, the effect is obtained in that the droplets are more subdivided in the nozzle and the droplet diameter is made smaller, so that even if the pressure is raised, the problem of cracking of the wafer and collapse of the surface pattern is not caused. Second, the relationship between gas pressure and droplet velocity and/or average particle size. When the gas pressure is increased, in the multiphase fluid of air and water, the droplet velocity becomes higher as the pressure increases, and conversely, in the case of water vapor and water, the measurement can be performed until the predetermined pressure is reached, but When the predetermined pressure is exceeded, it is not possible to enter 14 320816 201023986 'line measurement (28th case). Furthermore, it can be known that when observing the relationship between the gas pressure and the average particle size of the water droplets, in the multiphase fluid of air and water, the particle diameter does not depend on the gas pressure, but in the case of water vapor and water. 'The data of the average particle size when the pressure exceeds the predetermined pressure becomes the unbelief (the 29th case). This refers to the pressure of a zone that is measurable in the multiphase fluid of air and water and not unmeasurable in the multiphase fluid of water vapour and water. That is, under this pressure, the multiphase fluid of water and fluorine is distilled, and the multiphase fluid of air and water represents at least a different action of sand. The difference between the = is not clear, and as for the main reason for the measurement, it may be that the droplet velocity is too fast or the liquid crystal diameter is too large. By mixing the water from the wall surface of the present housing portion on the upstream side of the nozzle As a result, the water vapor forms a water film on the wall surface and is ejected from the nozzle outlet, and a multiphase fluid of water droplets and water vapor is ejected. The ejected wave drowner can generate cavitation on the surface of the object by colliding with the surface of the object and locally generating a low % portion in the wave droplet by the aforementioned action sequence. Since the structure has a widened end, even if it is used for irradiation, the diameter is reduced from the upstream side of the nozzle toward the nozzle outlet, and the diameter is expanded by the throat of the mixed and sectional area. According to the structure, the water film is formed on the inner wall of the nozzle by the water which is caused by the spray, and the water vapor is ejected through the central portion of the nozzle 1 .蛑.^ ^ ^ Between the mouths ‘and the mouth, the water is steamed in the throat to the nozzle water. The way of accelerating the steaming of the steam makes it better, and the effect of the town can be achieved. In addition to the full impact of the 'cavity phenomenon, the water and the multi-phase flow of 320816 15 201023986 come. When the semiconductor substrate is cleaned, it is formed during the length of the ... For example, after the surface of the conductor substrate is etched by 5, the method of (5) of the present invention is used, and the effect is: in the case of the aluminum dry agent, the wiring is not in the next step, and the object is not removed from the object. According to the invention (6), the following corrosion can be achieved. Since the distance between the outlet and the object is short, the multiphase flow does not cause the effect of the corrosion of the aluminum in the atmosphere because the carbon dioxide is injected into the fluid, so that the pH is not easily biased toward acidity. It can be more effectively prevented. [Embodiment]: The state is only an optimum example, and the following is the best mode. The following is the best mode, and the use of twins as the object processing device to specifically describe the washing device of the present invention is Example: The best form of the 2 multiphase fluid' is a water droplet containing a continuous phase of water vapor and water produced by mixing water with water and a dispersed phase. Here, the "water droplet" is composed of pure water which is an object which is formed by appropriately processing a material which is resistant to chemicals (in addition, a part of water vapor having a high humidity). Further, the above-mentioned multiphase fluid may optionally contain inert gas such as argon or nitrogen, and clean high-pressure air. However, from the viewpoint of preventing corrosion of aluminum, any gas is preferably argon or an inert gas. Here, the reason for using water vapor is that, in addition to being higher than the heat, it is possible to use the potential, and even if the heat of the liquid droplets is taken away with the change of the pressure of the fluid, the temperature is almost * It is advantageous to reduce the point. 320816 16 201023986 *There is a heat transfer between the water droplets and the gas when the water is mixed with the gas mixing portion or between the water droplets and the mixing portion and the inner wall of the pipe or the like. In addition, since the pressure of the gas is lowered when the nozzle portion is accelerated and released to the atmosphere, the temperature of the gas is lowered. At this time, whether the temperature of the water droplet is lowered is determined by the latent heat of the gas. For example, when an inert gas or clean high-pressure air is mixed with pure water, the temperature of the gas is lowered and it is difficult to control the temperature. On the other hand, when the gas is water vapor, 'because of a predetermined amount of latent heat, it is relatively low-temperature water droplets. When mixing, when the inner wall takes away heat, 'the heat can also be used to make the temperature of the gas not easy to decrease' and the latent heat of the falling water can be easily controlled. Insufficient, and with a part of the water, 、, 滴, 茈 # IA zL Μ each vapor liquefaction liquid production will be the balance of the surface of the object to be treated, this multiphase fluid is finally in the nozzle Although the throat is increased, the degree is lowered, but the latent heat of the steam is used to reduce the temperature of the fluid. ❹ The processing method of the apparatus is shown in Fig. 1 is an object processing apparatus according to an embodiment of the present invention. The overall configuration of the device 100. The configuration of the device 100 includes a steam supply unit (A), a pure water supply unit (B), a steam fluid adjustment unit (C), and a multi-phase fluid irradiation unit (D). And the wafer holding/rotating and the upper and lower mechanism parts (E). The following sections detail each part. (A) Water vapor supply part steaming 1.11; The gas supply part (A) consists of: supply of pure water The water is heated to a predetermined temperature DirC) to generate water vapor, and 320816 17 201023986 controls the amount of water vapor generated and pressurizes the water vapor to a predetermined 値Cl(MP)* vapor generator 112; Supply and stop switchable - water vapor switch valve 113; for measurement The steam generator 112 supplies a pressure gauge 114 to the pressure of the downstream water vapor; a water vapor pressure regulating valve 115 for adjusting the steam supply pressure to the desired enthalpy; and adjusting the amount of the minute droplets in the supply water vapor~ The heating steam generator of the temperature control mechanism and the saturated vapor humidity regulator 116; and the pressure relief valve 117 as a safety device. (B) The pure water supply unit 〇 the pure water supply unit (B) comprises: for supplying pure a water supply pipe 121; a heating portion 122 with a pure water temperature control mechanism for making pure water having thermal energy; a pure water switching valve 123 for stopping and resupply the supply of pure water; for confirming pure water A pure water flow meter 124 for flow rate; and a pure water switching valve 125 for generating 2 fluids for stopping supply and resupply of pure water downstream for 2 fluids. (C) The steam fluid adjusting unit (C) has a heating unit 131 (D) with a steam fluid temperature control mechanism for adjusting the temperature of the steam fluid and the humidity of the saturated steam. The multiphase fluid irradiation unit multiphase fluid irradiation unit (D) includes a movable front and rear direction (the X-axis nozzle scanning range or the Y-axis nozzle scanning range in FIG. 1) for irradiating the multi-phase fluid to the object. Irradiation nozzle 141; elastic pipe 142 for smoothly moving the nozzle; pressure gauge 143 for measuring the pressure of the multiphase fluid nozzle before 18 320816 201023986 *; forming a water film on the wall surface with respect to the steam pipe In this manner, the gas-liquid mixing portion 144 of the pure water is introduced; and the orifice 145 for smoothly introducing the pure water into the gas pipe is introduced. Here, the nozzle 141 is an ultra high speed nozzle. The "high-speed nozzle" is not particularly limited as long as it can accelerate the droplet to the speed of sound < Above, for example, a sonic nozzle can be cited. • Figure 30 is a cross-sectional view of the sonic nozzle and mixing section of this best mode. The shape of the sonic nozzle is not particularly limited, and has an end widening nozzle structure which is formed by the nozzle opening, which is rapidly reduced in diameter from the upstream side of the nozzle above the drawing toward the nozzle outlet located below the pattern G, and is minimized. The position (throat) of the sectional area a3 is a boundary, and the diameter is relatively gently expanded so that the fluid does not peel off from the inner wall, and the cross-sectional area at the nozzle outlet becomes a2. The sectional area of the throat A3 is calculated by dividing the flow rate by the speed of sound. The sectional area A3 of the throat is not particularly limited, and is, for example, 3.0 to 20.0 mm 2 . Further, the expansion ratio (A3/A2) is calculated by the equation expressed by the following mathematical formula 1. [Math 1]

Α3 φ2 _ \jc+ if aH- A2 φ3 2 fil

, 2/ (*-i) 2/r <1 a (wide 1) /r ftH-l NIX (r-1) Μ \/κ fc+l ——一[卜(五) (d)八, > J i κ — 1 L UJ (Formula 1) Here, K is the specific heat of the gas (constant pressure ratio / constant volume specific heat), and Ρ! is the pressure of the throat of the nozzle, and the pressure of the outlet of the P2 nozzle. The cross-sectional area A2 of the nozzle outlet is obtained by the expansion ratio and the sectional area A3 of the throat. Here, the sectional area A2 of the nozzle outlet is not particularly limited, and is, for example, 7.0 to 28.0 mm2. In addition, the length of the nozzle is determined by considering the material of the nozzle, the roughness, and various parameters such as the flow rate of 19 320816 201023986 (Reynolds number). Further, the degree of expansion is considered in consideration of various parameters such as the degree of investigation, the density, the flow rate, and the like, and the shape suitable for the π of the nozzle is not particularly limited, and may be circular. Further, the inner wall surface of the mixing portion and the inner wall surface of the nozzle are formed into a substantially continuous curved surface. The mixing portion may be joined as a cylindrical body upstream of the nozzle or formed upstream of the nozzle. The mixing portion wall surface and the spray enchantment (4) are joined, and the secret portion is preferably formed by a liquid which is formed along the wall surface by forming a water film by the mixing portion, and also flows by squirting into a water film. There is no special setting, but it can also be a joint with piping, etc., and it is preferable to smoothly form the obstacle by the degree of the obstacle that the financial core is (4). In addition, the hybrid H4 will be described in detail later. (E) Wafer holding, rotation, upper and lower mechanism, wafer holding, rotation, and up-and-down mechanism unit (8) include a base 151 for holding an object (wafer); The rotation motor 152 is cooled by cooling the cooling object (wafer) by moving the susceptor 151 in the vertical direction by the distance between the outlet of the nozzle 141 and the wafer. The water pipe 154 is used to open and close the switchable cooling water for stopping the supply of the cooling water; the cooling water flow regulating valve w _ for adjusting the flow rate of the cooling water and the cooling for measuring the flow rate of the cooling water Water flow meter? In the above, the object processing of the present preferred embodiment is described as a structure, and then the mixing unit 144 of the multiphase fluid irradiation unit (1) is described. The mixing portion 144 has a water enthalpy that is partially open to the inner wall surface. The entangled portion 32 〇 8l6 20 201023986 • 144a (Fig. 30) is on the upstream side of the nozzle, and is 90 degrees or less based on the direction of the water vapor. The angle can mix water from the wall surface of the aforementioned mixing portion to water vapor. Preferably, the mixing portion has a cylindrical shape, and the inner diameter of the cross section joined to the nozzle of the mixing portion is preferably the same as the inner diameter of the inlet of the nozzle. Here, Fig. 2 is a detailed configuration diagram in which the mixing unit 144 is provided with a multiphase fluid amount mixing unit of a temperature controller. It is important to reduce the occurrence of the mutual northward phenomenon of the liquefaction of water vapor and the vaporization of water to the minimum α in the mixing portion 144 in the mixing portion 144. Therefore, as shown in Fig. 2, the mixing portion 144 is preferably the same. It is constructed as follows. 1) The direction in which the fluids of the gas and the liquid are stably mixed is at an angle of less than 90 degrees in the mixing portion. 2) The direct control of the liquid fluid or the orifice installed in the piping is much smaller than the cross-sectional area of the flow path of the gas fluid in the _ mixing section. 3) By installing a heater in the mixing section, the temperature of the inner wall of the mixing section is controlled to suit the following conditions. The temperature of the inner wall is not too large (±20% or less) from the saturation temperature of the liquid under the pressure φ force in the mixing portion. Further, the temperature of the inner wall is not too large (±20% or less) from the saturation temperature of the gas under the pressure in the mixing portion. Further, as the time passes, the inner wall of the mixing portion approaches the saturation temperature of the fluid, so that it is not intended to be used until the state of the multiphase flow is stabilized, and under the condition that the heat retention of the mixing portion is sufficiently performed, Remove the heating function of this heater. In the apparatus for processing an object by using a multiphase fluid in which a droplet and a gas are mixed, the fluid mixing portion is at a normal temperature at the time of starting the apparatus. Then, when there is a difference between the temperature and the temperature of the water vapor, the temperature is not uniform in the interior of the liquid mixing device 21 320816 201023986, whereby a part of the vapor is phase-changed and becomes a water droplet or the like. The delivery pressure of the multiphase fluid becomes unstable, and it is difficult to stably supply a certain shock wave to the surface of the object to be processed, so that it takes time until the device operates stably. That is, when the heater is provided to the multi-phase fluid adjusting portion, the fluid mixing portion can be set to the same temperature as the water vapor and the gas temperature, so that it is less likely to generate a gas-liquid phase in the mixing portion. The device can apply a stable shock wave to the object processing surface. 1- Attacking Phenomenon (Air Bubble Dregs Related Parameters) This best mode cleaning device is based on adjusting the gas pressure, the water mixing flow in the multiphase helium fluid, the gas temperature, the temperature of the mixed water, and the nozzle shape. The distance from the nozzle outlet to the object, the temperature of the object, and the relative movement time between the nozzle and the object, and the temperature of the droplet, the flow rate of the droplet, the size of the droplet, the number of droplets, and the treatment The function of the temperature of the surface of the object and the irradiation area of the multiphase fluid per unit time. Among the above parameters related to bubble collapse, the flow rate, temperature, and droplet density of the droplets are particularly important. By controlling the above parameters, the jet generated by the droplet and the shock wave caused by the collapse of the bubble, and the impact of the chain reaction generated by the shock wave can be obtained on the surface of the object to be processed, and can be cleaned, etc. In the effective processing. The flow rate contributes to the generation of shock waves caused by the collapse of the bubbles in the droplets at the time of droplet collision, and the temperature contributes to the generation of fluoro bubbles in the droplets. In addition, the higher the droplet density, the higher the probability of generating a shock wave. For example, if the number of droplets is zero, no shock wave due to collision of droplets will occur. However, when the number of droplets becomes too dense, the speed of the 爹 phase fluid may be lowered and the temperature may be lowered to reduce the probability of generation of the shock wave. 32〇816 22 201023986 • Here, the density of droplets means the number of droplets per unit volume in a multiphase fluid • every * unit time, and correctly measures the droplets of the high speed moving / order The measuring device has not been developed yet, so it is substituted with the amount of pure water introduced into the multiphase fluid. ^ Measurement method of cavitation phenomenon' The system of the present invention has a measuring means for measuring the degree of cavitation under the condition of irradiating the multiphase flow to the object or the measurement sample under certain conditions. phenomenon. Here, according to the current technology, it is impossible to monitor the cavitation phenomenon (shock wave) (the intensity of cavitation) and the density (the number of occurrences per unit time) while performing the peeling and cleaning process. Therefore, the technique used in the present system changes the parameters related to the generation of cavitation in a prior experiment, and performs program processing, and s determines the size of the cavitation phenomenon from the following data obtained from the result. (1) Measurement method of physical change of physical change of object or measurement sample by quantitative method ^ Concavity and convexity of metal surface when irradiating multiphase fluid on metal surface • Resistor when irradiated on resist surface The area of the peeling area and the amount of the residue • The removal rate of the foreign matter attached to the entire surface of the wafer (2) The measuring method of the sound that can detect the noise of the cavitation phenomenon • The size of the noise of the cavitation phenomenon perceived by the acoustic sensor (3) Measuring means for visually measuring changes in the visual value of an object or a measuring sample in a quantitative manner. Image data of a resist stripping process photographed by a high-speed camera, for example, multiphase fluid temperature and irradiation of the multiphase fluid 23 320816 201023986 The surface of the metal is as confirmed in Section 9. The correlation between these parameters is determined by the peeling performance of the agent. The data of the mouth map is its product, the product of the f, the majority of the data is indeed the second resistance _ the area will be physically injured, and the damage to the equipment = = the maximum of the nozzle _ force two:: also does not produce _ high-pressure parts As a result, and manufacturing a safe device. The distance between the objects of the county and the county is as follows: Table 1: Fig. 2, Fig. 23. r d±..., the table is unfavorable for the unit of the weight Z, ', and the weight of the droplet generated by the fast collision, which is expressed as the relative unit of no unit. 11 'In the conventional technology (for example, in addition to the use of more than 2 mouthpieces, the difference between the device and the best form is not large = composition. But in the conventional technology, in the object At the time of the treatment, there is no such thing as the physical force of the so-called "shock wave". Therefore, the jade is not controlled on the object, and the control of the shock wave is not performed. In addition, under the condition of the prior art, "the cavitation phenomenon" It is completely inside the mouth of the thin-tailed shape of the front end of the shirt. The life of the shock wave generated is extremely short, and when the object is reached, the specific phase of the shock wave is lost, and the multiphase fluid flowing in the nozzle is accelerated near the tip of the nozzle. Money. Then 'causes that the flow rate is accelerated to become the result of the decompression L, the liquid causes cavitation and generates shock waves. According to Kato Yang / σ, the "cavitation phenomenon" published by the bookstore, the nitrogen in the liquid shock wave tube The duration of the bubble collapse is 2 to 3 seconds. The flow rate is 4〇〇m/sec. 24 320816 201023986 ' The movement time of the body is only 1.2mm, and the bubble collapses between the nozzle throat and the mouth. The phenomenon will disappear. Again, that is, Bubble collapse occurs at the nozzle outlet, and it is difficult to set the object distance to 1.2 mm or less. On the other hand, in the present invention, the nozzle is used to accelerate or expand the irradiation area of the multiphase 'fluid. The function of the bubble is related to the bubble collapse related parameters related to the occurrence of fluorine and acupoint phenomenon. As long as the cavitation phenomenon on the object is focused on, it can be adjusted basically in any place, for example, in front of the nozzle. The fluid mixing section of any space of the fluid piping is carried out. Specifically, it can be controlled in any space as shown by the arrow symbol shown by α in Fig. 1 (between the steam generating device and the nozzle outlet). In the following, the main parameters related to bubble collapse will be described in detail. The method of cleaning the object in the best form of the aluminum alloy button, in addition to the above-mentioned impact force, also has the effect of preventing the money of the rot. By adjusting the temperature of the gas, the temperature of the mixed water, the shape of the nozzle, the distance from the nozzle outlet to the object, the temperature of the object, the relative between the nozzle and the object The movement time can be controlled to prevent the corrosion effect. Among the above related parameters, in particular, the temperature at which the multiphase fluid reaches the object and the ρΗ when the multiphase fluid reaches the object are particularly important. By controlling the above parameters, it is possible to On the surface, a special protective film for preventing corrosion is formed. Hereinafter, the parameters related to the prevention of aluminum corrosion are detailed together with the parameters related to the main bubble collapse. (1) Temperature of the fluid The shock wave system is mainly a droplet collision. When the surface of the object is treated, the cavitation phenomenon of 320816 25 201023986 and the collapse of the cavitation phenomenon occur. The cavitation phenomenon is a cavity generated when a part of the liquid such as water generates a low pressure portion, and the temperature of the gas and the liquid is higher. The higher the temperature of the droplets, the higher the temperature of the droplets, and the more easily the bubbles in the water droplets occur. Accordingly, the bubble collapse which is the basis of the shock wave that becomes a large energy source on the surface of the object to be treated occurs. When the treatment method is utilized for the removal of the resist film, the resist film and foreign matter which are relatively bonded can be removed.On the other hand, if the temperature of the multiphase fluid and the water droplets is set to a low level, the generation of the shock wave can be suppressed on the surface of the object to be treated, and the object having a weak strength can be cleaned. However, there is a limit to the height at which the temperature can be set due to the limitation of the heat resistance of the object or the like. Further, when the distance from the object becomes long in a state where the temperature is too high, there is a possibility that the gas component in the droplet falls off and the bubble core is not easily generated, and the distance from the nozzle outlet to the object is about 2 to 30 mm. The distance is set to be negligible. Further, the temperature of the water vapor supplied into the nozzle is preferably from 50 to 120, more preferably from 80 to 115. (:, more preferably 90 to 11 (TC. Further, the temperature of the water mixed with the aforementioned steam is preferably 0 to 40. (: 'It is desirable to be 10 to 35. (:, better yet 20 to 3 〇. (: Here, in particular, the temperature at which the multiphase fluid reaches the object is preferably 5 〇ΐ or more, more preferably 80 Å or more, and more preferably 9 〇 or more. The measurement of the temperature of the multiphase fluid is carried out by the method described in the examples. By setting it in this range, the aluminum on the surface of the object is formed into a special film which prevents the effect of the rot #2. The speed of the drop is 320816 26 201023986 • The higher the velocity of the droplet is, the larger the impact becomes when the droplet collides with the surface of the object to be treated. Therefore, the internal pressure difference is likely to occur, and as a result, the bubble collapses and gas is generated. Acupoint phenomenon, that is, if the velocity of the droplet is set to a high degree, a large shock wave of the energy is generated on the surface of the object to be processed, for example, the treatment method is utilized for the removal of the resist film. It can remove the relatively strong resist film and foreign matter. On the other hand, if the speed of the liquid droplets is set to a low level, the generation of the shock wave can be suppressed on the surface of the object to be processed, and the object of the weaker object can be cleaned and washed. The speed makes the time for exposing the multiphase fluid to the air to be short, so it is difficult to introduce carbon dioxide in the atmosphere, and it is difficult to be biased toward acidity, so that the effect of preventing corrosion can be more appropriately exhibited. The velocity of the droplets is 100 to 600 m/s, It is preferably 200 to 500 m/s, more preferably 250 to 350 m/s. By setting the fluid velocity in this range, the impact of cavitation can be obtained. Furthermore, the velocity of the droplet and the fluid are set. The speed is approximately the same, and is set to "flow rate" / "nozzle sectional area". Here, the flow rate is set to @ water vapor flow rate (m3/s), and the nozzle sectional area is set to the sectional area of the nozzle outlet (m2) 〇(3) Other parameters First, regarding the nozzle, the ultrahigh-speed nozzle is used as described above. By using this nozzle, the flow velocity of the fluid is changed and the magnitude of the shock wave is also changed. In principle, it is easy to obtain a shock wave when using a nozzle having a large flow velocity. Furthermore, by using an ultra-high-speed nozzle to irradiate a multi-phase fluid containing water vapor and water droplets, a special action is observed by the relationship between the pressure of the water vapor and the speed and diameter of the water droplets. The water vapor pressure is 0.05. Up to 0.25Mpa, there is no special 27 320816 201023986. Especially when the water vapor pressure is above 015MPa, the multiphase flow system of water vapor and water droplets shows a different action from the multiphase fluid of air and water droplets. Then, Regarding the distance from the nozzle outlet to the object, the general adaptation 値 is in the range of 2 to 3 mm (optimal range 2 to 1 〇 ηπη), preferably 5 mm or less 'more preferably 3 mm or less, more preferably 2 mm. If the distance from the exit of the nozzle to the wafer is reduced, the resist stripping performance is improved as well, and when the optimum distance is too close, the peeling performance is lowered. On the contrary, it is desirable to suppress the peeling performance and the cleaning performance as long as it is far from the optimum distance. Furthermore, the closer the distance from the nozzle outlet to the object, the more difficult it is to introduce carbon dioxide in the atmosphere, and it becomes difficult to be acidic. In addition, when it is desired to obtain a particularly high impact force, it is important that the liquid droplets are covered by the water droplets when they collide with the object. Here, the flow rate of water vapor, preferably the mass flow rate of water vapor is 〇〇83 to 1 〇kg/min, more preferably 疋0.025 to 0.75 kg/min, more preferably 〇33 to 〇5〇kg/ Min. Further, the gas-liquid mixture ratio (liquid/gas) is preferably 〇 〇 18 to 〇 〇1. The droplet diameter is preferably from 2 to 25. When the droplet diameter is increased, the surface area is reduced, so that the amount of carbon dioxide introduced into the atmosphere is small, and it becomes difficult to be acidic. Further, the droplet diameter was a machine manufactured by Ding 81 Co., Ltd., and PDA 〇Phase D〇ppiei· Anem〇metry: phase Doppler method), and when there was no special load, it was set at 5 mm from the nozzle outlet. The position is measured. The cross-sectional area of the fluid flow/discharge port is preferably 〇.5 to 32 〇 kgcm-2min-i. In order to form water into the water film on the wall surface and to mix the water into the multiphase fluid, for example, it is preferable to set the pressure applied to the water to such an extent that the water does not flow back by the pressure of the water vapor. The pressure applied to the water is not particularly limited. For example, 28 320816 201023986 ' If it is introduced above the water vapor pressure and the pressure is not applied, the pressure can be introduced. More specifically, the pressure of water introduction preferably satisfies the following formula. (pressure of water vapor + 〇.〇2MPa) < (pressure of water introduction) < (pressure of water vapor + 1.0 MPa) When the pressure of water introduction is too low, the water is introduced as a pulsating flow, and the characteristics of the fluid become Unstable. In addition, when the pressure is too high, the water will scatter to the center of the diameter direction of the nozzle, and it is difficult to form the same water film, and it also hinders the acceleration of the vapor ©. Further, from the viewpoint of forming a water film on the wall surface, it is preferable not to pressurize the spray direction, and it is more preferable to supply it in the vertical direction against the passage direction of the water vapor. The pH of the multiphase fluid reaching the object is preferably 7.0 to 9.0, more preferably 7.0 to 8.0, more preferably 7.0 to 7.5. Since a special film is formed on the surface of the object by setting the pH in this range, the corrosion preventing effect of aluminum can be obtained. Further, the pH measuring method is a method described in accordance with the examples. [Embodiment] Method for measuring temperature when multiphase fluid reaches an object Fig. 31 is a schematic view showing a device for measuring temperature when a multiphase fluid reaches an object. A thermocouple TH (aluminum chrome thermocouple JIS C1602) is attached to the dream wafer W having a diameter of 6 leaves and a thickness of 0.625 mm, and the distance between the fluid ejection outlet of the nozzle 141 and the object is compared with the water vapor pressure. The conditions such as the pure water flow rate and the like are set to the same enthalpy as when the object is processed, and the thermocouple is irradiated for 1 minute, and the temperature at which the temperature is stabilized is 29 320816 201023986, and the temperature at which the multiphase fluid reaches the object is set. . Multiphase, Measure method of pH when the body reaches the object Fig. 32 is a schematic view of a device for measuring the pH when the multiphase fluid reaches the object. The discharge port of the nozzle 141 is connected to a cooling pipe C (for example, a Graham condenser) via a pipe P, and the agglomerated water is recovered to the vessel r, and the pH of the water is measured by the method of HSZ8802. Further, the aforementioned agglutination operation is carried out without contact with air. First Example Under the following conditions, a multiphase fluid (a case where steam was used as a gas and air was used) was irradiated on an aluminum surface for 10 minutes. The AFM (atomic force microscopy) photograph before and after the treatment is shown in Fig. 3. Figure 5 shows the surface roughness data. Further, in this example, the surface roughness was measured by the AFM-affiliated profile analysis method. Vapor pressure: 〇.2Mpa Vapor temperature: 13〇°C Pure water flow rate: 300cc/min Pure water temperature: 20°C GAP 5 mm Nozzle scan: Fixed the second case under the same conditions as the first case The multiphase fluid (as a gas for the vapor and the use of air as a gas) was irradiated on the steel surface for 1 minute. The AFM photographs before and after the treatment are shown in Fig. 4. Figure 6 shows the table 320816 30 201023986 * Surface roughness data. . . . - 3rd example The steam cleaning technique shown in Patent Document 1 utilizes the mechanical action of the strip gas and the mechanical action of the jet to peel off the resist, so the stripping of the resist needs to be calculated in minutes. This method also visualizes high-speed video in order to confirm whether it is the same mechanism. Fig. 7 is a view showing the case where the multi-phase fluid is irradiated under the same conditions as in the first example except that the nozzle scanning speed is io 〇 mm/sec, and the one-line positive photoresist is removed from the lower portion of the quartz wafer. The case of time-dependent changes. As shown in Fig. 7, the area where the resist is peeled off gradually expands and rapidly peels off. ΆΛΜ. In the same conditions as in the first example, the multi-phase fluid was irradiated against the dream wafer implanted with high-concentration ions, and the i-line positive photoresist was peeled off, except that the nozzle scanning speed was set to 40 mm/sec. The situation of change over time. The results are shown in Fig. 8. From ft to eighth, the gas and temperature of the multiphase fluid were changed under the following conditions, and the multiphase fluid was irradiated against the aluminum surface for 10 minutes. The AFM photographs before and after the treatment are shown in Fig. 9. The surface roughness data is shown in Figure 1. Further, the surface Ra of the aluminum to be treated before the irradiation was Ra of 34.9 nm. Gas pressure: 〇.2Mpa Liquid flow rate: 300cc/min Gap : 10mm The result of irradiation with a large amount of 31 320816 201023986 phase fluid composed of low temperature air (20 ° C) and low temperature pure water droplets (20 ° C), obtained Ra It is a surface of 30.5 nl Vt. The AFM photograph of the surface is shown in Fig. 9(a), and the data of the surface roughness is shown in Fig. 10(a) (the fifth example). Next, as a result of irradiating a multiphase fluid composed of high-temperature air and low-temperature pure water droplets (2 ° C), a surface of 96.4 nm was obtained. The AFM photo of the surface is shown in Fig. 9(b) and the surface roughness data is shown in Fig. 10(b) (sixth example). Then, the irradiation is performed by high temperature air (13 〇 ° C) and high temperature pure As a result of the multi-purpose fluid composed of water droplets (6 〇 ° C), a surface having an Ra of 86.3 nm was obtained. The photograph of the surface is shown in Fig. 9(c)' and the data of the surface roughness is shown in Fig. (c) (the seventh example). The surface coarse rotation of (c) is slightly smaller than (b) and the density of the portion of the thick wheel is larger than (b), so it can be seen that (c) is more affected by shock waves than (b). Further, the result of irradiation of a multiphase fluid composed of water vapor and low-temperature pure water droplets (203⁄4) was used to obtain a surface having Ra of 257 nm. The photograph of the surface is shown in Fig. 9(d), and the data of the surface roughness is shown in Fig. (d) (8th example). As a result of the above, as the shock wave is increased in temperature, especially when water vapor is used in the gas, it is clear that the maximum shock wave is applied to the surface to be treated. The surface of the A1 anti-money surface having a Ra of 348.8 nm was irradiated with the gas and temperature of the multiphase fluid under the same conditions as in the fifth to eighth examples. As a result of irradiating a multi-camera composed of 2 (the air of TC and 20 t of pure water droplets), a surface having an Ra of 380 nm was obtained. The AFM of the surface was shown in Fig. 11 (a) 'and the surface roughness was The data is shown in Figure U (c) (Example 9). Next, the result of irradiating a multiphase fluid consisting of 130 〇C water vapor and 2 (η: pure water 320816 32 201023986 • droplets gives Ra Surface of 440 nm. 'AFM photograph of the surface is shown in Fig. 11(b), and the surface roughness data is shown in Fig. 11(d) (10th example). In the eleventh case, the Ra is 8.1 nm. The SUS surface was irradiated with the gas and temperature of the multiphase fluid under the same conditions as in the fifth to eighth examples. The irradiation consisted of water vapor at 130 ° C and pure water droplets at 20 ° C. As a result of the phase fluid, a surface having an Ra of 19. gnm was obtained. The AFM of the surface was shown in Fig. 12(a), and the surface roughness data was shown in Fig. 12(b) (the eleventh example). In the twelfth case, the surface of the titanium having a Ra of 75.5 nm is subjected to the change of the gas and temperature of the multiphase fluid under the same conditions as in the fifth to eighth examples. As a result of irradiating a multiphase fluid composed of water vapor of 130 ° C and 2 (a pure water droplet of TC), a surface having an Ra of 98 nm was obtained. The AFM photograph 10 of the surface is shown in Fig. 13 (a), and The surface roughness data is shown in Fig. 13(b) (12th example). With titanium, interference fringes can be visually observed. It is also possible to form an oxide film on the surface. The thirteenth case has a Ra surface of Ra of 1.9 nm. Irradiating the gas and temperature of the multiphase fluid under the same conditions as in the fifth to eighth examples. Irradiating the multiphase fluid composed of water vapor at 130 ° C and pure water droplets at 20 ° C As a result, a surface having Ra of 7.6 nm was obtained. The AFM photograph of the surface was shown in Fig. 14 (a), and the surface roughness data was shown in Fig. 14 320816 201023986 (b) (13th example). From the 14th case to the 25th case, in the 14th to the 25th cases, it is reviewed whether there is a difference in the peeling condition under the resist coating condition. The presence or absence of HMDS (hexamethyldiazepine, hexamethyldisilazane), Bake The temperature change was 9 ° ° C, 11 ° ° C, and the effect of the change in the condition was observed. The profile may not depend on the results of the substrate treatment of HMDS. The experiment was carried out under the following conditions: Sample use: I line resist irradiation time: visually observed the gas pressure after peeling: 〇. 2Mpa liquid flow rate: 300cc/min nozzle scanning : Fixed Gap : 10 mm Fig. 15 (a) to (c) shows that the peeling boundary interface was treated by microscopic observation after coating the sample under the conditions described above without HMDS and Bake9 (Jc) and irradiating the sample under the above conditions. In the case of Fig. 15, (4) to (1) are observed by AFM. Fig. 15(a) is an AFM photograph corresponding to the case where the surface is observed by a microscope after the irradiation of 2 (Γ(: air and a multiphase fluid composed of pure water of 2 °C), and Fig. 15 (d) The 14th example). The 15th _) is the AFM photo corresponding to the radiation of 30: (: the air of the thief and the pure water of the thief, and the surface is observed by a microscope] and Fig. 15 (e) (15th example) Fig. 15 (4) is a case where the surface is observed by a microscope after irradiating a multiphase fluid composed of 13 (r water vapor and paper pure water, Fig. 15 (1) 320816 34 201023986 * corresponding AFM Photograph (16th example). The resist film was applied under the conditions of no HMDS and BakellCTC, and after irradiating the sample under the above conditions, the boundary interface was peeled off by microscope/observation treatment, and the 16th to the (1) In the case of observation, Fig. 16 (4) is an AFM photograph corresponding to the multi-phase fluid consisting of 2 (the air of TC and 2 〇C of water, and the surface is observed by a microscope) (Fig. 16(d)) 17 cases). Figure 16 (Using the external 1', the 130C gas and the 90 C pure water, the multiphase fluid is used. Micromirror observation of the surface, f 16 (4) corresponds to the 18th case of the photo. Figure 16 (4) is the multi-phase fluid composed of the water vapor of the city and the captured window water, the microscopic observation table _ In the case, the 16th figure «) corresponds to the AFM photograph (19th example). Figure 17 (a) to (c) show that 'in the case of HMDS, 赃% of the privately coated squid' and under the above conditions (4) After the sample, the peeling boundary interface is treated by microscopic observation. Fig. 17 (6) to (10) show the case of 2/FM observation. Fig. 17 (4) is the irradiation of the multiphase composed of the jumping air and C pure water. After the fluid, the surface of the surface is observed by a microscope. Figure 17 (4) corresponds to the AFM photograph (2nd example). Figure 17 is a photograph (4) 130. (: Air and 9G. (3) Pure water constitutes a ❹ phase The fluid is shown in the microscope and is observed by a microscope. The 7th figure (e) corresponds to the film (21st case) and the 17th figure (^) is irradiated by 13〇. (: water vapor and 2〇 pure After the multiphase fluid consisting of water, the surface is observed by a microscope, and Fig. 17 (f) corresponds to the AFM photograph (22nd example). Fig. 18 (4) to (c) show that HMDs, ^ke11〇t>c strip 320816 35 201023986 coated resist film, and irradiated the sample under the above conditions, and observed the peeling boundary interface by microscopic t-mirror, Fig. 18 (d) (f) is the case of observation by AFM. [Fig. 18 (4) is a case where the surface of the multiphase fluid composed of pure air is added and the surface is observed by a microscope, Fig. 18 (d) Corresponding AFM photograph (23rd example). Fig. 18 is a case where a multiphase fluid composed of 13 〇t of air and 90 °C of pure water is irradiated, and the surface is observed by a microscope, Fig. 18 ) A corresponding AFM photograph (24th example). Figure 18 (4) is irradiated with water vapor of 130eC and 20 . (A: A multi-phase fluid composed of pure water, and a condition of observing the surface by a microscope. Fig. 18(f) corresponds to an AFM photograph (the first example). The 26th example relates the relationship between the droplet diameter and the flow rate. It is shown in Fig. 19. The water vapor pressure is set to - (G. 2 MPa), and the flow rate of the droplets is measured at various pure water flows, and the results are shown in Fig. 19. The relationship between the droplet velocity V and the diameter d. Both V and d are close to the regular knife cloth's average value is 28 〇 oil and 1 〇 "

No. 27, L Figure 20 shows the flow rate of pure water (the result of setting the vapor pressure P and the distance h from the nozzle as a parameter at T100 mL/min. hi is more mixed with 'air and liquid droplets. The result of the jet flow is also π ° as shown in the figure. The droplet velocity is 200 to 300 m/s: right' and the droplet diameter is about 1 。. '''''' Relationship, change the shape of the water to 200cc/min' JL to change the pressure of the gas 36 320816 201023986 'Multi-phase fluid of 0.05, (U, 0.2Mpa 'and use sonic nozzle to spray water vapor and water', and air The multiphase fluid with water, and the LDA (LaserDopplerAnemometry) is used to measure the velocity of the droplet at 5, 10 mm from the discharge port (Fig. 33). In addition, the measurement system of 'LDA The measurement was performed using LD A manufactured by TSI Corporation until three times of measurement was possible, and three measurements were performed under each condition. When a multiphase fluid of water vapor and water was used, a position of 5 mm was observed. At a position of 10mm, the velocity of the droplet is faster. In addition, the air and the water are In the case of the phase fluid, it can be seen that the higher the pressure of the air, the higher the tendency of the droplet to become higher. On the other hand, the case of water vapor and water is unknown, but the higher the pressure of the water vapor is observed, the liquid The speed of the drop becomes southerly and two to the predetermined 値 'under 〇.2Mpa'. The droplet velocity will become lower depending on the measurement. But 'presumably this may be an error. Under other conditions, the measurement is less than 10 seconds. The multiphase fluid of water vapor and water only needs to be measured for several minutes under the condition of water vapor pressure of .2Mpa. Therefore, it is speculated that most of the noise is observed under the condition of this condition. The relationship between the pressure and the droplet diameter, the flow rate of water is set to 200 cc/min', and the pressure of the gas is changed to 0.05, 0.1, M.2 MPa, and the sonic nozzle is used to spray the multiphase fluid of water vapor and water, and the air and The multiphase fluid of water' and the diameter of the droplet are measured by pDA at a position of 5, 10 mm from the discharge port (Fig. 34). In addition, the measurement of the PDA is measured until the data of 10,000 droplets is obtained. , measured 3 times under various conditions. Air In the case of a multiphase fluid with water, the velocity of the droplets hardly changes even if the pressure of the air changes. 320816 37 201023986 On the other hand, in the case of water vapor and water, the eyebrows are not clear. Increase the water vapor pressure until the predetermined (four) stop can hardly see the change of the droplet, and under 0.2 Zheng, the diameter of the observation_drop is rapidly reduced. However, it is speculated that this may be an error. Under other conditions, The measurement is not to the extent of ι〇秒, and the multiphase fluid of qi and water is only measured for several minutes under the conditions of money pressure && Therefore, it is speculated that most of the noise is observed under this condition. 'Thirtyth case (the pressure inside the nozzle is in water vapor (U, 〇. 2Mpa, the pure water flow rate is set to 1〇〇CC/min, and the quartz nozzle is used to spray the multiphase fluid of water vapor and water) In this way, the force wave is observed at the tip of the quartz nozzle. This is shown in Figure 35. In addition, the '35th _ series is the case under the condition of Q ¥, Fig. 35 (b) In the case of the injection of 〇2Mpa conditions. In addition, for comparison, the pure water flow rate 5 is i QQee/min under the condition of gas force 0.1, 0.2Mpa, and quartz nozzle is used to take λ work 1 and water. Multiphase fluid. However, no pressure wave is observed at the tip of the quartz nozzle. This is shown in Fig. 36. In addition, Fig. 36 (4) is the case of injection under the condition of 〇., Fig. 36 (b) The case of the nozzle under the condition of 22Mpa. (The first embodiment to the thirty-sixth embodiment) The cleaning device having the best form of the sonic nozzle (Fig. 30) under the following conditions 'water vapor and The multiphase fluid of water is sprayed onto the object, and the washing effect, physical damage, and corrosion resistance of the wiring (Table 1, 2矣, clothing) ° Again, in terms of the object 'use the aluminum wiring 38 320816 201023986 • after the wafer, which is tied to the i-line negative photoresist (Tokyo should THMRip3300), coated 1 / zm The thickness was dried at 90 ° C for 120 minutes, and exposed at 365 nm for 20 seconds, and developed at room temperature using TMAH ([N(CH3)4) + ΟΚΓ).

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In Ο 00 _> 0 inch 1001- 100 10 0 '6 00 _ 0 inch 1001. 320816 ο 201023986^ 2nd table e item _璲*38 Corrosion of wiring after 10 days 墀m Alkali dish alkali mm dish mmm 墀m 墀磲峨 physical destruction 1_ medium mm alkali 磔墀m disc #. m 磲m polymer removal I ! Μ 4i • Μ Μ droplet diameter 〇 > σ > 1 1 C0 r - CO 〇 > 〇 > 1 1 00 GO σ> 03 1 1 Ming? :S , \φ v! 〇ο 5 〇Ύ—〇〇〇δ Ο τ-~ ο 〇〇〇Τ Ο Ο ο 〇τ~ ο δ Ο τ- Ο ο τ- Ο Ο »— Ο 〇Ϊ — 〇 T— 〇ο 〇〇〇ό 〇d 6 Ο ο ο Ο Ο 6 〇Water vapor pressure / MPa 0. 20 0; 20 0. 23 0. 23 0.05 0. 05 0. 20 0. 20 0. 23 0. 23 0. 05 0. 05 0. 20 0. 20 0. 23 0. 23 铋鳋 _ dare to run I 10 10 10 1〇ΙΟ ΙΟ ΙΟ to u> to ΙΟ ΙΟ tD ίΩ ΙΟ Ι \ \ 〇 Ο 〇 〇 〇 〇〇 〇〇 gt ό ό ό ό & & & & & & & & & & ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴 液滴Ο - ο ο t — 〇〇c〇ο ο C0 ο S ο (Ο ο ο r* ο τ- Ο g ο § 〇〇 〇〇〇 &〇〇〇; 〇〇〇 < D mixed water temperature / 3⁄4 Guide 〇 σ Ο ο 〇ο ο ο Ο Ο 〇 流体 fluid temperature / ° C g 1 - to ο τ ~ g ο τ - SS τ - · T - τ - ο CSI Τ TM * · S τ - 8 ΊΤ ~ S τ - r — SS | <Μ CM to <Μ inch 1Ω ΟΙ 苳Φ < &Amp; C0 Csl benzene 0) CM ο C0 5 ΟΙ C9 3ε Ο CO 10 CQ CO CO: s remote Μ 4Κ ίΚ 41 320816 201023986 Comparative Example 1 Comparative Example of case-based fluid temperature is too low. When the fluid temperature was too low, the polymer was removed and the wiring was corroded after 10 days. In the second comparative example and the third comparative example, the case where the droplet velocity is too slow is too fast. When the polymer is too slow, the polymer remains, and when it is too fast, the physical damage of the wiring can be seen. The fourth comparative example and the fifth comparative example are cases where the pH is too low and the case is too high. When the pH is too low, no protective film is produced, and after 10 days, the wiring is corroded. When the pH is too high, corrosion of the wiring due to high pH occurs. 42 320816 201023986 ^ Table 3

Corrosion of wiring after 10 days of wiring corrosion II Physical damage after processing m _ I Polymer removal | Removal 梛 Removal II Removal I Removal ι Processing conditions 诨趔 f ^ ^ \ σ> 〇〇 TC • •. CD Ό> Liquid/gas mixture ratio 0.010 0.010 0.010 〇 _ 〇〇 0.010 丨Water vapor pressure / MPa 〇CO 〇〇κ ο 〇ο Nozzle object distance /mm to IO ΙΟ u> to 乂 乂 CD CD 〇 cad ο ο5 to cd To o (4)7« Ο TO to 〇E> Ο石ο 〇〇o « Mixed water temperature / XS ο 04 ο CM ss Fluid temperature / 3⁄4 ü in o to o Comparative Example 1 j Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparison Example 201023986 [Industrial use and utilization] The present invention is a process for processing liquid crystals, magnetic heads, magnetic micro-such as 'semiconductor devices, machined parts, moldings=substrates, cameras, etc., precision machine polishing, etc. 2 In the field of removal of unusable materials, cleaning, processing, etc., the fine structure of the stone-making process, molding, and the present invention are preferably used. In addition, [simplified description of the drawings], processing of materials for heart sputum chemicals.整体 The overall structure of the second device. The multi-phase fluid gas-liquid mixing part is attached with a temperature control mechanism. Fig. 3 shows the surface roughness of the 10th ring after 4th 4-.. minutes. A diagram of the data of the fluid 10 coarse wheel. Table 7 of the data of the surface roughness of the steel surface after irradiation of the multiphase fluid for 10 minutes in the first example of the table. Side 2:7:2 shows the result of the stripping agent-i (a ^ , , , L ~ side coated on the transparent wafer in the third example), and the result of peeling off the resist from the back side by a high-speed camera. The figure shows the multi-phase 320816 201023986' of the resist stripping data by fluid irradiation in the fourth example after injecting high-concentration ions. - Figure 9 shows the results of the fifth to eighth examples. Fig. 10 is a view showing the results of the fifth to eighth examples. Fig. 11 is a view showing the results of the ninth to tenth examples. < Fig. 12 is a view showing the results of the eleventh example. Fig. 14 is a view showing the results of the thirteenth example. Fig. 14 is a view showing the results of the twelfth example. Fig. 15 (4) to (1) are diagrams showing the results of the fourteenth to sixteenth examples. a) to (f) are graphs showing the results of the 17th to the 19th examples. Fig. 17 (8) to (1) show the results of the 20th to 22nd examples. Fig. 18 (4) to (1) indicate the 23rd. Fig. 19 is a diagram showing the results of the twenty-sixth example. Fig. 20 is a diagram showing the results of the twenty-seventh example. Fig. 21 is a diagram showing the difference in thermal energy due to the multiphase fluid. Cited The size variation of the shock wave in FIG. FIG. 22 are diagrams Wei vary the speed of a multiphase fluid due to the overshoot

G The map of the magnitude of the shock wave. Fig. 23 is a view showing changes in the magnitude of the shock wave due to the difference in density of the multiphase fluid. Figure 24 is a diagram showing the mechanism of cavitation caused by ultrasonic waves. Fig. 25 is a view showing the mechanism of the cavitation phenomenon generated when the droplet collides. Figure 26 is a diagram showing the mechanism of cavitation caused by droplet collisions. 45 320816 201023986 Figure 27 is a diagram showing the mechanism of the cavitation phenomenon generated when a droplet collides. Figure 28 is a diagram showing the mechanism of cavitation generated when a droplet collides. Fig. 29 is a view showing the mechanism of the mechanism of the cavitation phenomenon generated when the liquid droplet collides. Fig. 30 is a view showing the structure of a sonic nozzle and a mixing portion. Figure 31 is a schematic view of a measuring device for the temperature of a multiphase fluid. Figure 32 is a schematic view of a measuring device for the pH of a multiphase fluid. Figure 33 is a graph showing the relationship between gas pressure and water droplet velocity. Figure 34 is a graph showing the relationship between the gas pressure and the diameter of the water droplets. Fig. 35 (a) and (b) are views showing a state of pressure waves generated in the British nozzle. Fig. 36 (a) and (b) are views showing a state in which no pressure wave is generated in the quartz nozzle. [Description of main components] 100 Object processing device 111 Water supply pipe 112 Vapor generator 113 Water vapor switching valve 114 Pressure gauge 115 Water vapor pressure regulating valve with temperature control mechanism heating steam generator and saturated steam 46 320816 116 201023986 'Humidity regulator-117 Pressure relief valve 121 Water supply pipe 122 Heating section with pure water temperature control mechanism ^ 123 Pure water switching valve 124 Pure water flow meter 125 2 Pure water switching valve for fluid generation 131 Water vapor fluid Temperature control unit heating unit 141 141 Irradiation nozzle 142 Elastic piping 143 Pressure gauge 144 Multiphase fluid gas-liquid mixing unit 145 with temperature control function Hole 151 Mounting and holding object pedestal 152 Rotating motor ^ 153 Wafer Upper and lower drive mechanism 154 cooling water pipe 155 cooling water switching valve 156 cooling water flow adjustment valve 157 cooling water flow meter 47 320816

Claims (1)

201023986 VII. Patent application scope: 1. A method for cleaning an object, comprising the step of passing a multiphase fluid containing a continuous phase of water vapor and a dispersed phase of water droplets generated by mixing a water vapor and water through a mixing nozzle; In the method of cleaning the object, the mixing unit is provided on the upstream side of the nozzle, and has a water inlet portion that is partially open on the inner wall surface, and the nozzle is an ultrahigh-speed nozzle, and the inner wall surface of the mixing portion and the inside of the nozzle The wall surface forms a substantially continuous curved surface, and water is mixed from the inner wall surface of the mixing portion to the water vapor flowing in the mixing portion, and water is moved along the inner wall surface of the nozzle from the inner wall surface of the mixing portion. And spraying the aforementioned multiphase fluid from the outlet of the aforementioned nozzle. 2. The method of cleaning an object according to the first aspect of the invention, wherein the nozzle has a diameter that decreases in diameter from a nozzle upstream side toward a nozzle outlet, and an end portion that expands in diameter with a throat portion that is a minimum sectional area. The structure of widening. 3. The object cleaning method according to Item 1 or Item 2 of the patent application, wherein the mixing portion is cylindrical. 4. The object cleaning method according to any one of claims 1 to 3, wherein the speed of the water droplets is set to be in the range of 100 to 600 m/s. The object cleaning method according to any one of the items 1 to 4, wherein the temperature at which the multiphase fluid reaches the object is 50 ° C or more, and the multiphase fluid reaches The pH of the object is in the range of 7 to 9. 6. The object cleaning method according to claim 5, wherein the distance between the multiphase fluid ejection outlet and the object is 30 mm or less. 7. The object cleaning method according to any one of claims 1 to 6, wherein the object is a semiconductor substrate having a material such as a wiring on the surface. 8. An object cleaning system which is a system for cleaning an object by irradiating a multiphase fluid containing water vapor and water droplets through a nozzle, and has: a water vapor supply means for supplying water vapor; and a water water supply for supplying the liquid And a nozzle for illuminating the multiphase fluid, wherein the mixing portion is provided upstream of the nozzle, and has a water introduction portion that can mix water to the inner wall surface of the water vapor flowing through the inner wall surface, and a part of the opening. Further, in the nozzle-type ultrahigh-speed nozzle, the inner wall surface of the mixing portion forms a substantially continuous curved surface with the inner wall surface of the nozzle. 9. The object cleaning system according to claim 8, wherein the nozzle has a diameter that is reduced in diameter from the upstream side of the nozzle toward the nozzle outlet, and the end of the diameter is expanded with the throat having the smallest cross-sectional area as a boundary. The structure of widening. 10. The object cleaning system of claim 8 or 9, wherein the mixing portion is cylindrical. 49 320816