WO2020075844A1 - Dispositif et procédé de nettoyage à fines bulles - Google Patents

Dispositif et procédé de nettoyage à fines bulles Download PDF

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Publication number
WO2020075844A1
WO2020075844A1 PCT/JP2019/040253 JP2019040253W WO2020075844A1 WO 2020075844 A1 WO2020075844 A1 WO 2020075844A1 JP 2019040253 W JP2019040253 W JP 2019040253W WO 2020075844 A1 WO2020075844 A1 WO 2020075844A1
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Prior art keywords
cleaning
bubble
cleaning liquid
nano
bubbles
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PCT/JP2019/040253
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English (en)
Japanese (ja)
Inventor
日高　義晴
義勝 上田
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パナソニックＩｐマネジメント株式会社
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Priority to JP2020551246A priority Critical patent/JPWO2020075844A1/ja
Publication of WO2020075844A1 publication Critical patent/WO2020075844A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/02—Cleaning by the force of jets or sprays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a cleaning device and a cleaning method using fine bubbles.
  • a method of using a brush, a method of jetting a gas and a liquid at the same time to form a droplet (two-fluid cleaning), and a method of vibrating the liquid with ultrasonic waves are widely used.
  • the surface potential of the foreign matter is controlled. The surface potential of the foreign matter is controlled by controlling the pH of the liquid to the alkaline side.
  • Nano bubbles Fine bubbles are divided into nano bubbles of 1 nm to less than 1 ⁇ m (hereinafter referred to as “nano bubbles”) and micro bubbles of 1 ⁇ m to 100 ⁇ m (hereinafter referred to as “micro bubbles”). Among them, it was found that the lifetime of nano bubbles is as long as several months, but the lifetime of micro bubbles is much shorter than that of nano bubbles.
  • the micro bubbles in the cleaning liquid are destroyed and disappear during the transfer by the pipe, and unless the object to be cleaned can be reached, the energy at the time of the destruction of the micro bubbles cannot be effectively utilized. There were challenges.
  • the present invention was conceived in view of the above problems. From the phenomenon that the bubble diameter increases due to the nozzle injection of the fine bubble cleaning liquid described later, it has been found that the combination of the cleaning nozzle and the collision processing body is suitable as the bubble spontaneous collapse device of Patent Document 2. Furthermore, the inventors have found an invention in which a combination of a cleaning nozzle and a collision processing body is provided immediately before being supplied to a cleaning target. Thus, of the fine bubbles, micro-order fine bubbles are generated in the vicinity of the object to be cleaned, and a cleaning device is provided that effectively utilizes the energy at the time of destruction of the fine bubbles to improve the cleaning capability. Is.
  • the fine bubble cleaning device according to the present invention, A micro-bubble generator that generates at least nano-order micro bubbles in the cleaning liquid to generate nano-bubble cleaning liquid, A cleaning nozzle for ejecting the nano-bubble cleaning liquid toward the object to be cleaned, It has a collision processing body provided between the cleaning nozzle and the object to be cleaned.
  • the micro-bubble cleaning device changes the nano-bubbles into micro-bubbles by hitting the nano-bubbles once on the collision-treated body before ejecting the nano-bubbles onto the object to be cleaned. That is, micro bubbles are generated from the nano bubbles just before the object to be cleaned, and the nano bubbles and the micro bubbles are supplied to the object to be cleaned.
  • a high-speed camera analyzes the results of what kind of bubbles are generated after purified water with a dissolved oxygen content of 32 ppm and a dissolved oxygen content of 7 ppm collides with the liquid surface in a state where the spray force is small (spray height 180 mm). Show. It is a graph which shows the result of having measured the temperature change when a nano-bubble cleaning liquid is applied to the slope with a thermocouple. It is a figure which shows the structure which performed the Example which confirms the effect at the time of making a collision process body into a liquid. It is a figure which shows the state below 1 mm of liquid level. It is an enlarged view of FIG.8 (b). It is a photograph which shows the result at the time of using a nano bubble cleaning liquid and purified water. 14 is a graph showing the result of image processing of the result of FIG. 13.
  • the fine bubble cleaning apparatus 1 is mainly used in a chemical treatment process and a cleaning process of semiconductors and electronic parts formed by photolithography.
  • the fine bubble cleaning device 1 performs cleaning by removing deposits adhering to these surfaces and replacing chemical liquid components with cleaning water.
  • the fine bubble cleaning device 1 can also be used for cleaning the inner wall in the liquid supply pipe.
  • FIG. 1 shows the configuration of a fine bubble cleaning device 1 according to the present invention.
  • the fine bubble cleaning device 1 according to the present invention includes a fine bubble generating device 10 and a cleaning tank 14. An object to be cleaned Pro is placed in the cleaning tank 14. Further, a cleaning nozzle 14 a and a collision processing body 26 are also arranged in the cleaning tank 14. Further, the fine bubble cleaning device 1 may have a storage tank 16.
  • the fine bubble generator 10 is a device that generates nano bubbles nB having a bubble diameter of at least nano-order (1 nm or more and less than 1 ⁇ m) in the cleaning liquid W to generate the nano bubble cleaning liquid WnB.
  • the nanobubble cleaning liquid WnB may include microbubbles ⁇ B having a diameter of micron order (1 ⁇ m or more and 100 ⁇ m or less). However, even if the micro bubbles ⁇ B are mixed in the cleaning liquid W at the point of the fine bubble generator 10, a considerable portion of the micro bubbles ⁇ B disappear while being transferred to the cleaning tank 14.
  • the cleaning liquid W pure water, ion-exchanged water, or the like can be preferably used. However, other polar solvents or non-polar solvents may be used.
  • the cleaning liquid W is supplied from a cleaning water supply source (not shown).
  • the nano bubbles nB may be air, but N 2 (nitrogen), O 2 (oxygen), H 2 (hydrogen), Ar (argon), Xe (xenon), and O 3 (ozone) may be used alone or in combination. It may be used as a mixed gas of.
  • a gas supply source Gas may be provided when using a gas other than air.
  • the cleaning tank 14 is a container for bringing the short-life bubble cleaning liquid WBs, which will be described later, into contact with the cleaning target Pro.
  • the contacting includes a method of spraying the short-lived bubble cleaning liquid WBs on the cleaning target Pro (discharging: also including a shower), and immersing the cleaning target Pro in the short-life bubble cleaning liquid WBs (dip).
  • FIG. 2 shows the inside of the cleaning tank 14 more specifically.
  • the cleaning nozzle 14a, the collision processing body 26, and the cleaning target Pro are arranged.
  • the object to be cleaned Pro is a semiconductor substrate or an electronic device produced by photolithography, and one that has been exposed can be illustrated as a typical example.
  • the cleaning tank 14 may be provided with a chemical solution device 70 that processes the exposed cleaning object Pro with a chemical solution.
  • the chemical liquid device 70 includes a disk 71 to which the cleaning target Pro is sucked and fixed, a chemical liquid nozzle 72 that discharges the chemical liquid to the cleaning target Pro, a chemical liquid tank 73 that supplies the chemical liquid to the chemical liquid nozzle 72, a pump 74, and a filter 75. Is formed by.
  • the chemical treatment means a kind of treatment for removing the resist from the cleaning target Pro after the development.
  • the cleaning tank 14 is provided with a cleaning nozzle 14a for ejecting the nano-bubble cleaning liquid WnB toward the cleaning target Pro.
  • the collision processing body 26 is disposed between the cleaning nozzle 14a and the cleaning target Pro.
  • the nano-bubble cleaning liquid WnB becomes the short-lived bubble cleaning liquid WBs after colliding with the collision processing body 26 at least once, and is brought into contact with the cleaning target Pro.
  • the fine bubble cleaning apparatus 1 mainly includes the cleaning liquid W, the fine bubble generating apparatus 10, the cleaning nozzle 14a, and the collision processing body 26. Further, the storage tank 16, the first bubble monitor 20, the second bubble monitor 22, and the control device 30 can be further provided.
  • the storage tank 16 is a container for storing the nano bubble cleaning liquid WnB generated by the fine bubble generating device 10.
  • the volume of the storage tank 16 can be appropriately determined depending on the scale of the fine bubble cleaning device 1.
  • the first bubble monitor 20 and the second bubble monitor 22 are devices that measure the density of the nano bubbles nB in the nano bubble cleaning liquid WnB. This is an apparatus for measuring the number of nanobubbles nB in a unit volume or the density of nanobubbles nB using a laser.
  • the first bubble monitor 20 and the second bubble monitor 22 may be devices that measure heat or energy such as temperature between a certain distance between the pipe r2 and the return pipe r3 as a method other than laser. This is because the number of nanobubbles nB or the density of nanobubbles nB in a unit volume can be measured from the difference between the measured values.
  • control device 30 a computer including an MPU (Micro Processor Unit) and a memory can be preferably used.
  • the control device 30 is connected to the first bubble monitor 20 and the second bubble monitor 22. Further, it may be connected to a pump or the like that determines the flow rate. Each pump is configured so that its movement can be controlled by a signal from the control device 30.
  • the storage tank 16 is provided with a circulation pipe r1.
  • a fine bubble generator 10 is arranged in the circulation pipe r1. Further, a gas supply source Gas may be connected to the fine bubble generator 10.
  • the circulation pipe r1 is provided with a pump P1 that determines the circulation amount of the nanobubble cleaning liquid WnB.
  • a pipe r2 through which the stored nano-bubble cleaning liquid WnB passes is arranged.
  • a pump P2 that determines the flow rate of the nanobubble cleaning liquid WnB is provided in the pipe r2.
  • a drain pipe rx is provided in the cleaning tank 14. Further, the cleaning tank 14 may be provided with a return pipe r3 through which the short-lived bubble cleaning liquid WBs flows up to the storage tank 16 and can be used when the cleaning liquid W is circulated and used.
  • the return pipe r3 is provided with a pump P3 that determines the amount of return.
  • a second bubble monitor 22 may also be provided in the return pipe r3.
  • the cleaning liquid W is supplied to the fine bubble generator 10 from a cleaning water supply source (not shown).
  • the cleaning liquid W is supplied to the storage tank 16 once, and the cleaning liquid W is supplied from the stored water 16 to the fine bubble generator 10 by the pump P1.
  • a gas supply source Gas is connected to the fine bubble generator 10, and nanobubbles nB are generated in the cleaning liquid W to generate nanobubble cleaning liquid WnB.
  • the generated nano bubble cleaning liquid WnB returns to the storage tank 16. Therefore, not only the cleaning liquid W but also the nano bubble cleaning liquid WnB may be supplied to the fine bubble generator 10. Further, the nanobubble cleaning liquid WnB is stored in the storage tank 16.
  • the nanobubble cleaning liquid WnB stored in the storage tank 16 is transferred to the cleaning tank 14 through the pipe r2 by the pump P2.
  • the transferred nano bubble cleaning liquid WnB is discharged from the cleaning nozzle 14 a in the cleaning tank 14.
  • the collision processing body 26 is disposed between the cleaning nozzle 14a and the cleaning target Pro.
  • nanobubble cleaning liquid WnB collides with the collision treatment body 26 to shorten the life of the nanobubbles nB, and further part of the nanobubbles nB grows into microbubbles ⁇ B.
  • nanobubble nB has a shortened life is synonymous with “nanobubble nB undergoes a short life treatment”.
  • micro bubbles ⁇ B are generated by the impact when the collision processing body 26 collides. That is, the nanobubble cleaning liquid WnB after having collided with the collision processing body 26 becomes the cleaning liquid W containing the nanobubbles nB having a shortened life and the microbubbles ⁇ B. This is called short-lived bubble cleaning liquid WBs.
  • the short-lived air bubble cleaning liquid WBs covers the entire object to be cleaned Pro, and the nano-bubbles nB and the micro bubbles ⁇ B whose lifespan has been shortened are destroyed, so that the adhered substances of the object to be cleaned Pro can be peeled off. Further, the micro bubbles ⁇ B are generated almost immediately before contact with the cleaning target Pro. Therefore, the problem that the micro bubbles ⁇ B disappear during the transfer of the pipe r2 is also solved.
  • the collision treatment body 26 is one in which the nanobubble cleaning liquid WnB ejected from the cleaning nozzle 14a flies in space and physically collides, and it is sufficient that it has at least the collision surface 26a.
  • FIG. 3 illustrates the shape of the collision processing body 26.
  • FIG. 3 (a) shows a collision processing body 26 that has a discharge port 26o on the bottom and is configured by a cylindrical body 26t that is open at the top.
  • the nano-bubble cleaning liquid WnB discharged from the cleaning nozzle 14a collides with the inner wall 26ta and the liquid surface 26s accumulated inside, so that the diameter of the nano-bubbles nB becomes large, that is, the life thereof is shortened, and further the micro-bubbles ⁇ B are reduced. Is generated.
  • the cleaning liquid W containing the short-life processed nano bubbles nB and the micro bubbles ⁇ B, that is, the short-life bubble cleaning liquid WBs is discharged from the discharge port 26o.
  • the short-life bubble cleaning liquid WBs comes into contact with the cleaning target Pro.
  • the collision surface 26a may be a solid surface (inner wall 26ta in FIG. 3A) or a liquid surface (in FIG. 3A, liquid surface). 26s).
  • FIG. 3B shows a case where the collision surface 26a of the collision processing body 26 is formed of only solid.
  • Other shapes of the plate-like object 26f are not particularly limited as long as the plate surface 26fa becomes the collision surface 26a. That is, as long as it has the flat plate surface 26fa, the shape of the other portion may be arbitrary.
  • the nano bubble cleaning liquid WnB ejected from the cleaning nozzle 14a collides with the plate surface 26fa, so that the nano liquid nB subjected to the short life treatment and the micro bubbles are contained in the cleaning liquid W. ⁇ B is generated and becomes short-lived bubble cleaning liquid WBs. The short-life bubble cleaning liquid WBs comes into contact with the cleaning target Pro.
  • the solid collision surface 26a may be a flat surface, but may be a surface having irregularities.
  • the solid collision surface 26a may be given a motion such as rotation. This is because impact upon collision is likely to occur and micro bubbles ⁇ B are likely to be generated.
  • FIG. 3 (c) shows the interior of the collision processing body 26 that is partitioned in the vertical direction, and is formed, for example, in the shape of a honeycomb structure having openings on both sides.
  • the nano-bubble cleaning liquid WnB collides with the portion of the crosspiece (vertical wall) forming the partition, and the nanobubbles nB are subjected to a short life treatment.
  • micro bubbles ⁇ B are generated by the impact when colliding with the nano bubbles nB.
  • the nano-bubble cleaning liquid WnB becomes the short-lived bubble cleaning liquid WBs, and drops and contacts the cleaning object Pro below.
  • the height of the partition may be short or may be mesh-like.
  • FIG. 3D shows a case where the collision processing body 26 is composed of only the liquid surface 26s.
  • the cleaning target Pro is immersed in a liquid having a certain depth (which may be the cleaning liquid W or the short-lived bubble cleaning liquid WBs), and the nano bubble cleaning liquid WnB is jetted from above by the cleaning nozzle 14a.
  • the nanobubble cleaning liquid WnB that has collided with the liquid surface 26s undergoes a short life treatment.
  • micro bubbles ⁇ B are generated by the impact when they partially collide with the nano bubbles nB.
  • the chemical solution remaining on the surface of the object to be cleaned Pro may constitute the collision processing body 26.
  • FIG. 4 shows a case where the end of the collision processing body 26 is immersed in the short-life bubble cleaning liquid WBs. From the examples described below, it was found that the nanobubble cleaning liquid WnB, when hitting a wall and flowing down, generated a large number of microbubbles ⁇ B from the flowing-down liquid. Further, in the nanobubble cleaning liquid WnB, when the collision speed is slow, the microbubbles ⁇ B are generated only near the liquid surface. On the other hand, when the nanobubble cleaning liquid WnB hits the wall and flows down, it was confirmed that the microbubbles ⁇ B were generated deep in the water.
  • FIG. 4 shows a configuration in which the end of the collision processing body 26 is immersed in the liquid surface.
  • the nano bubble cleaning liquid WnB collides with the collision processing body 26 and then flows down through the collision processing body 26 to reach the cleaning liquid W (short-lived bubble cleaning liquid WBs) in which the cleaning target Pro is immersed. Then, micro bubbles ⁇ B are generated from the entry point to a certain depth.
  • the collision processing body 26 is immersed in the short-life bubble cleaning liquid WBs with a tilt of 45 degrees, but it may be immersed vertically (90 degrees), and the tilt angle is not limited.
  • the cleaning object Pro need only be arranged at the depth where the micro bubbles ⁇ B are generated, and it is not necessary to strictly control the depth from the liquid surface. As a result, it is possible to obtain the fine bubble cleaning device 1 that is extremely easy to adjust. Further, the nano-bubble cleaning liquid WnB collides with the collision processing body 26 to become the short-lived bubble cleaning liquid WBs, and then, the damage to the cleaning target Pro is far less than that when the nano-bubble cleaning liquid WnB drops and collides with the cleaning target Pro. Small. Therefore, it is almost unnecessary to consider the damage to the cleaning target Pro during cleaning. Therefore, even the object Pro to be cleaned that has been subjected to ultrafine processing can be safely cleaned.
  • the collision processing body 26 is disposed between the object to be cleaned Pro and the cleaning nozzle 14a, and when the nano bubble cleaning liquid WnB discharged from the cleaning nozzle 14a collides, the physical force is applied to the nano bubble cleaning liquid. It is given to WnB.
  • the fine bubble cleaning device 1 may include a control device 30.
  • the control device 30 receives the signals S1 and S2 from the first bubble monitor 20 and the second bubble monitor 22, and in order to adjust the production amount of bubbles, an instruction signal CB0 to the fine bubble generation device 10 and a pump P1, The instruction signals CP1, CP2, CP3 to P2, P3 are transmitted.
  • Fig. 5 shows the structure of the experiment. Ion-exchanged water was prepared as the cleaning liquid W.
  • the cleaning liquid W is poured into the storage tank 16 and is supplied to the fine bubble generation device 10 by the circulation pipe r1 provided in the storage tank 16.
  • Buvitas HYK-32D manufactured by Ligaric was used as the fine bubble generator 10.
  • a gas (oxygen) supply source Gas was connected to the fine bubble generator 10 to generate a nano bubble cleaning liquid WnB having an oxygen concentration of 18 ppm. Further, the fine bubble generator 10 can generate a nano bubble cleaning liquid WnB by flowing 700 mL of gas for 1 minute.
  • the nano-bubble cleaning liquid WnB stored in the storage tank 16 was sent to the pressurizing device 94, pressurized, and sent to the cleaning nozzle 14a.
  • a stainless pressure container 2.5 L TA100N was used as the pressure device 94. The pressurizing device 94 adjusted the discharge pressure.
  • a nozzle (TPU650033 manufactured by Spraying Systems Co., Ltd.) having an injection angle of 65 degrees was used.
  • a graduated cylinder 96 having a diameter of about 70 mm was used as a discharge target.
  • Nanosight LM-10 manufactured by Malvern was used as the bubble concentration measuring device 98. This uses a red laser (wavelength: 638 nm) and was able to detect bubbles having a bubble diameter of 30 to 1000 nm.
  • the procedure of the experiment was as follows. Into the graduated cylinder 96, 1 L of the nano bubble cleaning liquid WnB generated by the fine bubble generator 10 was placed. Next, the nano bubble cleaning liquid WnB was discharged from the cleaning nozzle 14a at a predetermined pressure. The nano bubble cleaning liquid WnB collides with the inner wall and the liquid surface of the graduated cylinder 96. The cleaning liquid W after the collision was collected from the vicinity of the liquid surface of the measuring cylinder 96, and the distribution of bubbles was measured by the bubble concentration measuring device 98.
  • the measurement results are shown in FIG.
  • the horizontal axis represents the bubble diameter (nm), and the vertical axis represents the concentration (10 6 cells / mL).
  • the line A indicates the distribution of the nano bubble cleaning liquid WnB generated in the fine bubble generator 10 before being discharged to the graduated cylinder 96. There is a main region of distribution from 80 nm to 150 nm.
  • the line B is the bubble distribution of the cleaning liquid W after collision when discharged at a pressure of 0.1 MPa. It can be seen that the distribution becomes broader than that of the line A, and the distribution around 300 nm is larger than that before the collision. As described above, the nanobubble nB has a large bubble diameter, so that the stability is destroyed and the life of the nanobubble nB is shortened.
  • FIG. 7A shows a photograph when pure water is put into the graduated cylinder 96 and then the pure water is discharged from the cleaning nozzle 14a.
  • FIG. 7B shows a photograph when the nano bubble cleaning liquid WnB is put into the measuring cylinder 96 and then the nano bubble cleaning liquid WnB is ejected from the cleaning nozzle 14a. That is, FIG. 7B shows the state of line B in FIG.
  • the area C in FIG. 7A and the area D in FIG. 7B are both areas where micro bubbles ⁇ B are generated.
  • the micro bubbles ⁇ B are generated by the impact when the liquid is discharged from the cleaning nozzle 14a and collides with the inner wall of the measuring cylinder 96 and the liquid surface.
  • the portion in which micro bubbles ⁇ B are generated appears cloudy on the photograph.
  • area C and area D area D is observed larger. That is, in the case of the nano bubble cleaning liquid WnB (FIG. 7 (b)), more micro bubbles ⁇ B are generated as compared with the pure water (FIG. 7 (a)). It is considered that this is because not only the micro bubbles ⁇ B due to the impact at the time of collision but also the nano bubbles nB grew into the micro bubbles ⁇ B.
  • the nano-bubble cleaning liquid WnB has an initial dissolved gas amount of 18 ppm, which is higher than pure water and higher than the saturation concentration. Therefore, the nano-bubble cleaning liquid WnB becomes a bubble of the dissolved gas when ejected (pressurized to depressurized) to make the droplet finer, and the nano-bubble nB in the droplet whose pressure balance is broken when ejected. It is considered that the droplet is made smaller when a part of it becomes large and breaks.
  • pure water has a small amount of dissolved gas and thus has larger droplets after being ejected than the nano-bubble cleaning liquid WnB, colliding with the liquid surface and entraining air on the liquid surface to form millibubbles.
  • FIG. 8A shows a spray height from the liquid surface of 40 mm
  • FIG. 8B shows a spray height from the liquid surface of 100 mm
  • FIG. 8C shows a spray height from the liquid surface. Is 120 mm
  • FIG. 8D shows a case where the spray height from the liquid surface is 180 mm.
  • the spray pressure was 0.3 MPa.
  • the nanobubble cleaning liquid WnB having an oxygen concentration of 18 ppm was used.
  • micro bubbles ⁇ B were generated from the liquid surface to a deep position at the portion which hits the wall surface and flows down the wall surface to reach the liquid surface (H part). From this, it was found that the microbubbles ⁇ B can be generated at a deep position by causing the nanobubble cleaning liquid WnB to once collide with the wall surface and allowing the colliding surface to flow down and reach the liquid surface.
  • the spray striking force has an appropriate strength for the pattern, and it is considered that the cleaning effect is enhanced by the generation of the micro bubbles ⁇ B.
  • FIG. 9 shows a state where the spray hitting force is small (spray height) by using dissolved water amount of 32 ppm (the dissolved oxygen amount was increased from the above experiment) and purified water of dissolved oxygen amount of 7 ppm (normal water oxygen concentration).
  • the result of analyzing with a high-speed camera what kind of bubbles are generated after colliding with the liquid surface at 180 mm) is shown.
  • the dissolved oxygen amount of 32 ppm was described as "oxygen UFB water”, and the purified water was shown as "purified water”.
  • the horizontal axis represents the bubble diameter ( ⁇ m), and the vertical axis represents the number (number / in-plane).
  • in-plane refers to the inside of one screen of the high-speed camera. It was found from the graph that when the oxygen content was high, the amount of microbubbles ⁇ B generated was much higher than when the oxygen content was low (approximately 27 times per unit volume). It is considered that this is because cavitation bubbles were generated with the dissolved gas and the nano bubbles nB as nuclei.
  • the nanobubble cleaning liquid WnB having a high dissolved gas concentration generates a large amount of microbubbles ⁇ B without strongly colliding with the liquid surface, and the short-lived bubble cleaning liquid WBs expected to have a cleaning effect is generated. .
  • FIG. 10 shows the temperature change when the nano-bubble cleaning liquid WnB was applied to the slope, and the temperature was measured by attaching a thermocouple to the back surface of the silicon substrate.
  • FIG. 10A is a side view conceptual diagram of the experimental apparatus.
  • the cleaning nozzle 14a (jet angle 65 °) was arranged at a point 120 mm away from the inclined surface, and the nanobubble cleaning liquid WnB with purified water was sprayed at a pressure of 0.3 MPa.
  • the temperatures at three points on the inclined surface were examined by attaching thermocouples to the back surface of the silicon substrate.
  • the ejection center is represented by "o center”
  • the point 25 mm above the ejection center is represented by “ ⁇ upper part”
  • the point 25 mm below the ejection center is represented by "x lower part”.
  • FIG. 10 (b) shows the temperature at each point in the case of the nano bubble cleaning liquid WnB using purified water.
  • the horizontal axis is the elapsed time (seconds: described as “sec”) after the start of measurement after ejection, and the vertical axis is the temperature (° C.).
  • the temperature changes in the central part (marked with ⁇ ) and the lower part (marked with x) are almost the same.
  • the upper part (marked by ⁇ ) the temperature was constant for a few seconds after the start of the ejection measurement and after 180 seconds, the central portion, the upper portion and the lower portion of the ejection were constant and stable.
  • the upper part is shown as “ ⁇ Water CH1”
  • the central part is shown as “ ⁇ Water CH2”
  • the lower part is shown as “ ⁇ Water CH3”.
  • FIG. 10C shows the result in the case of the nano bubble cleaning liquid WnB containing 32 ppm of oxygen.
  • the upper part (marked with ⁇ ) was the lowest, and the central part (marked with ⁇ ) was higher by about 0.7 ° C.
  • the lower part (marked with x) was clearly higher than the center part (marked with ⁇ ) by about 1 ° C., and these relationships were stable. It is considered that this is because the nano-bubble cleaning liquid WnB collides with the slope to become the short-lived bubble cleaning liquid WBs having the micro bubbles ⁇ B, and heat is generated at the point where the micro bubbles ⁇ B are destroyed after a lapse of the subsequent flow time.
  • FIG. 11 shows an embodiment in which the collision processing body 26 is composed of only the liquid surface 26s (see FIG. 3D).
  • the object to be cleaned Pro "GKE cleaning indicator (Distributor by gke: Meiyu Co. Ltd.)" was used. This is composed of sheets with pseudo stains L1 to L4. Each of the sheets L1 to L4 has different types of pseudo stains formed on the base material. Since it is an indicator for various detergency, neither of the sheets can be completely cleaned with water.
  • This pseudo stain is a stain that can be taken with temperature, or a stain that can be taken with the pH of the wash water.
  • L2 dirty that can be taken at pH
  • the experimental apparatus fixed the object to be cleaned Pro (GKE cleaning indicator) to the bottom of the container 40 and filled the container 40 with 10 mL of the alkaline cleaning liquid 42.
  • the depth from the liquid surface of the container 40 to the cleaning object Pro was about 1 mm.
  • the pH of the alkaline cleaning liquid 42 was 13 or more at the concentration usually used, whereas the alkaline cleaning liquid 42 was diluted 100 times to weaken the dissolving power, and the pH was about 10-12.
  • the spray nozzle 14a (TPU650017 manufactured by Spraying Systems Co., Ltd.) was set at a position 100 mm away from the cleaning target Pro.
  • FIG. 12A is an enlarged view of FIG. 8B
  • FIG. 12B is a partially enlarged view thereof.
  • FIG. 8B shows the case where the spray height from the liquid surface is 100 mm. The point 1 mm below the sprayed liquid surface is the portion indicated by the arrow in FIG.
  • Micro bubble ⁇ B was generated in this part (near collision part F), and it was a region where the direct spray hitting force did not hit. That is, in FIG. 11A, below 1 mm from the liquid surface, the spraying force of the spray is not directly applied, and the sprayed nano-bubble cleaning liquid WnB has a thickness of 1 mm when it hits the generation area of micro bubbles generated by cavitation from the interface. It can be said that this is a region in which the short-life cleaning liquid WBs is obtained by subjecting the water of the above-mentioned water to the collision processing body 26 to undergo the short-life processing.
  • the nano bubble cleaning liquid WnB using oxygen and purified water were applied to the liquid surface from the nozzle 14a at a spray pressure of 0.5 MPa.
  • the liquid level of the alkaline cleaning liquid 42 is gradually increased by spraying, and the influence of the spray hitting force on the object to be cleaned Pro (GKE cleaning indicator) is further reduced. Since the nano-bubble cleaning liquid WnB is also a mixture of purified water with oxygen nano-bubbles, the pH in the container 40 becomes thin with the passage of time. The spray time was 2 minutes.
  • FIG. 13 shows the result.
  • 13A and 13B show the case of the nanobubble cleaning liquid WnB
  • FIGS. 13C and 13D show the case of purified water.
  • 13A and 13D are photographs of the sheet in the container 40 immediately after the spraying is stopped.
  • 13B and 13D are enlarged views of the soiled portion of the sheet after cleaning.
  • 13 (b) and 13 (d) are the stain components after cleaning. This image was subjected to image processing with image processing software (color spatial plotter), and the intensity of green and frequency analysis were performed.
  • FIG. 14 shows the result.
  • FIG. 14A shows the case where the nanobubble cleaning liquid WnB is used
  • FIG. 14B shows the case where purified water is used.
  • the horizontal axis represents green intensity
  • the vertical axis j represents frequency.
  • the nano-bubble cleaning liquid WnB was used, the average intensity of green color was 0.590, whereas that of purified water was 0.621. That is, it was possible to reduce the intensity of the green color by using the nano bubble cleaning liquid WnB. This is a result of removing the green pseudo stain, and it was confirmed that the nanobubble cleaning liquid WnB has a cleaning power.
  • the nano-bubble cleaning liquid WnB As described above, by colliding the nano-bubble cleaning liquid WnB with the collision treatment body 26, it is possible to treat the nano-bubbles nB for a short life and further increase the generation amount of the micro-bubbles ⁇ B. Further, even if the nano-bubble cleaning liquid WnB collides with the collision processing body 26, many millimeter bubbles are not generated and the cleaning power is not impaired.
  • micro-bubble cleaning device can be suitably used in the cleaning process of semiconductors and electronic devices. Further, it can be suitably used for cleaning the inner wall of piping and the like.
  • Micro Bubble Cleaner 10 Micro Bubble Generator 14 Cleaning Tank 14a Cleaning Nozzle 16 Storage Tank 20 First Bubble Monitor 22 Second Bubble Monitor 26 Collision Processing Body 26a Collision Surface 26o Discharge Port 26t Cylindrical Body 26ta Inner Wall 26s Liquid Surface 26f Plate-like Object 26fa Plate surface 30
  • Control device 40 Container 42 Alkaline cleaning liquid 44 Dirt component 70 Chemical liquid device 71 Disk 72 Chemical liquid nozzle 73 Chemical liquid tank 74 Pump 75 Filter 90 Cleaning liquid tank 92 Oxygen cylinder 94 Pressurizing device 96 Messy cylinder 98 Bubble concentration measuring device W Cleaning liquid nB nano bubbles ⁇ B micro bubbles WnB nano bubbles cleaning liquid Gas gas supply source WBs short life bubble cleaning liquid Pro to be cleaned r1 circulation pipe r2 pipe rx drain pipe r3 return pipe P1 pump P2 Pump P3 Pump

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

La présente invention aborde le problème selon lequel, lorsqu'il est souhaité d'utiliser de fines bulles pour nettoyer un semi-conducteur ou un dispositif électronique, il n'est pas possible d'utiliser efficacement l'énergie lors de la destruction de bulles fines car les nano-bulles sont stables et ont une longue durée de vie, et des micro-bulles disparaissent principalement lorsqu'elles sont transportées par la tuyauterie. Ce dispositif de nettoyage à fines bulles est caractérisé en ce qu'il comprend : un dispositif de génération de fines bulles qui amène au moins des bulles fines d'ordre nanométrique à être générées dans une solution de nettoyage pour générer une solution de nettoyage à nano-bulles ; une buse de nettoyage pour éjecter la solution de nettoyage à nano-bulles vers un objet à nettoyer ; et un corps de traitement de collision disposé entre la buse de nettoyage et l'objet à nettoyer. Le dispositif de nettoyage à fines bulles génère des micro-bulles juste avant que les micro-bulles ne soient mises en contact avec l'objet à nettoyer, ce qui permet d'effectuer un nettoyage efficace.
PCT/JP2019/040253 2018-10-12 2019-10-11 Dispositif et procédé de nettoyage à fines bulles WO2020075844A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008087903A1 (fr) * 2007-01-15 2008-07-24 Shibaura Mechatronics Corporation Appareil et procédé de traitement de substrat
WO2011101936A1 (fr) * 2010-02-18 2011-08-25 シャープ株式会社 Procédé de décapage et dispositif de décapage
JP2016092340A (ja) * 2014-11-10 2016-05-23 旭有機材工業株式会社 基板の洗浄方法及び装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008087903A1 (fr) * 2007-01-15 2008-07-24 Shibaura Mechatronics Corporation Appareil et procédé de traitement de substrat
WO2011101936A1 (fr) * 2010-02-18 2011-08-25 シャープ株式会社 Procédé de décapage et dispositif de décapage
JP2016092340A (ja) * 2014-11-10 2016-05-23 旭有機材工業株式会社 基板の洗浄方法及び装置

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