WO2010071005A1 - 対象物洗浄方法及び対象物洗浄システム - Google Patents
対象物洗浄方法及び対象物洗浄システム Download PDFInfo
- Publication number
- WO2010071005A1 WO2010071005A1 PCT/JP2009/069645 JP2009069645W WO2010071005A1 WO 2010071005 A1 WO2010071005 A1 WO 2010071005A1 JP 2009069645 W JP2009069645 W JP 2009069645W WO 2010071005 A1 WO2010071005 A1 WO 2010071005A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nozzle
- water
- water vapor
- pressure
- fluid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 239000012530 fluid Substances 0.000 claims abstract description 162
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 230000001678 irradiating effect Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 284
- 238000002156 mixing Methods 0.000 claims description 66
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 238000011144 upstream manufacturing Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 72
- 239000007789 gas Substances 0.000 description 53
- 230000035939 shock Effects 0.000 description 34
- 238000010586 diagram Methods 0.000 description 32
- 239000010408 film Substances 0.000 description 32
- 230000007246 mechanism Effects 0.000 description 24
- 238000012545 processing Methods 0.000 description 22
- 238000005259 measurement Methods 0.000 description 19
- 230000008859 change Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000000498 cooling water Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000005536 corrosion prevention Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010534 mechanism of action Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005468 ion implantation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910001179 chromel Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- 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
Definitions
- the present invention uses a semiconductor substrate / glass substrate / lens / disk member / precision machined member / mold resin member as an object (particularly a semiconductor substrate having an aluminum material such as aluminum wiring on the surface).
- the present invention relates to a method of treating a part or a predetermined surface and a system thereof (for example, an object cleaning method and an object cleaning system), and more specifically, cleaning of a part or a surface, and removal or peeling of unnecessary materials there ,
- a method for polishing and processing the surface of an object and a system thereof for example, a processing method in a semiconductor manufacturing apparatus such as a resist peeling apparatus, a polymer peeling apparatus and a cleaning apparatus, a printed board cleaning apparatus, a photomask cleaning apparatus, etc.
- the object of the cleaning is an organic substance such as a resist film or a polymer film, particles, or the like that affects device reliability.
- a combination of an alkali cleaning solution and an acid cleaning solution and other chemicals such as sulfuric acid / hydrogen peroxide are usually used, and a large amount of pure water is used in a rinsing step for removing the residue.
- a plasma ashing apparatus is generally used for removing the resist, but another cleaning apparatus is used for the subsequent cleaning of residues and impurities.
- amine-based organic solvents are often used for removing the polymer film. This chemical solution may also be used for resist removal.
- the chemicals used for the above-described conventional cleaning and thin film removal are 1) expensive, 2) large environmental load and special wastewater treatment equipment is required, and 3) safety and health of workers.
- the size of the equipment is increased, and cleaning with chemicals requires a large amount of pure water to wash away the chemicals. 4)
- One device cannot cover everything from thin film removal to cleaning. .
- the ultrasonic cleaning apparatus is the most widely used cleaning technique at present and is sometimes combined with various cleaning liquids as well as pure water.
- the disadvantage is that there is concern about damage to soft materials, brittle materials and fine patterns due to cavitation (which is different from the mechanism of cavitation of the present invention as will be described later). For this reason, measures such as increasing the frequency are taken, but there is a trade-off with the cleaning power.
- the water jet cleaning apparatus is applied to a relatively large cleaning object.
- the disadvantage is that a high pressure (several MPa to 20 MPa) is required, which is not suitable for an object having a fine pattern.
- the brass scrub cleaning apparatus is sometimes combined with various cleaning liquids as well as pure water.
- the disadvantage is that it is not suitable for surfaces with deep grooves or holes.
- the object surface and the brush are in direct contact with each other, there is a possibility of generating dust and scratches.
- Patent Document 1 a cleaning apparatus that irradiates a combination of water vapor and liquid fine particles.
- vaporized water water vapor
- mist-like water water mist
- paragraph number 0019 of patent document 1 describes the cavitation using a thermal effect phenomenon as a basic principle of the said technique.
- Patent Document 1 when using a cleaning device that irradiates a combination of water vapor and water as disclosed in Patent Document 1, first, a phenomenon that requires a certain amount of time for the reaction, such as penetration of water molecules, and mist-like mist Since it uses the real-time phenomenon of removing the film and dirt by directly colliding with the resist film and particles, there is a problem that the treatment time is limited by the penetration time of water molecules, and secondly, cleaning There is a problem that often the situation where the power is insufficient and the dirt on the object cannot be sufficiently removed, or on the contrary, the cleaning power is too strong to damage the object. In such a case, for example, measures have been taken to increase the ejection pressure in the former case and lower the ejection pressure in the latter case.
- a first object of the present invention is to provide means for reliably washing without damaging the object without being limited by the permeation time of water molecules.
- the present inventors have empirically found that when a semiconductor substrate is washed with a mixed phase flow of water and water vapor, aluminum formed on the surface of the semiconductor substrate is corroded early. As described above, if aluminum is corroded before the next treatment is performed, it may not function as a semiconductor device, resulting in a poor yield. Accordingly, the second aspect of the present invention provides a means for preventing the aluminum formed on the surface of the semiconductor substrate from being corroded for a long time even when the semiconductor substrate is washed with a mixed phase flow of water and water vapor. Objective.
- the present inventor pays attention to cavitation having a completely different mechanism of action from the above and controls the degree of cavitation on the object, thereby enabling effective and easy processing suitable for the object. And the present invention has been completed.
- the present inventor has focused on the speed of the droplets contained in the multiphase fluid instead of the pressure of the gas, and conducted extensive research to increase the speed. Then, when the droplet velocity is increased using a specific nozzle, the object to be removed attached to the object has a sufficient impact force without causing the object to break or the surface pattern to collapse as described above. The present invention has been completed.
- the present invention (1) includes a step of irradiating, through a nozzle, a multiphase fluid containing continuous phase water vapor and dispersed phase water droplets, which is generated by mixing water vapor and water in a mixing unit.
- the mixing section is installed on the upstream side of the nozzle, and has a water introduction section in which a part of an inner wall surface is opened;
- the nozzle is an ultra-high speed nozzle;
- the inner wall surface of the mixing part and the inner wall surface of the nozzle form a substantially continuous curved surface, Mixing water from the inner wall surface of the mixing unit with the water vapor flowing in the mixing unit, allowing water to flow from the inner wall surface of the mixing unit to the inner wall surface of the nozzle, and from the outlet of the nozzle to the mixed phase
- It is a method characterized by injecting a fluid.
- the nozzle has a divergent structure in which the diameter of the nozzle is reduced from the nozzle upstream side toward the nozzle outlet, and further, the diameter is expanded at the throat portion having the minimum cross-sectional area.
- This invention (3) is the method of the said invention (1) or (2) in which the said mixing part is cylindrical.
- the present invention (4) is the method according to any one of the above inventions (1) to (3), wherein the speed of the water droplet is in the range of 100 to 600 m / s.
- the temperature when the mixed phase fluid reaches the object is 50 ° C. or more, and the pH when the mixed phase fluid reaches the object is in the range of 7 to 9. 4) Any one of the methods.
- the present invention (6) is the method of the above invention (5), wherein the distance between the mixed-phase fluid ejection outlet and the object is 30 mm or less.
- the present invention (7) is the method according to any one of the inventions (1) to (6), wherein the object is a semiconductor substrate having an aluminum material such as aluminum wiring on its surface.
- the present invention (8) includes a water vapor supply means ⁇ for example, a water vapor supply section (A) ⁇ for supplying water vapor, a water supply means for supplying liquid water ⁇ for example, a pure water supply section (B) ⁇ , and a multiphase fluid.
- the mixing section (for example, the mixing section 144) is installed upstream of the nozzle, and is capable of mixing water from the inner wall surface with the flowing water vapor.
- the nozzle is an ultra-high speed nozzle (for example, nozzle 141); In the system, the inner wall surface of the mixing unit and the inner wall surface of the nozzle form a substantially continuous curved surface.
- the nozzle has a divergent structure in which the diameter of the nozzle is reduced from the nozzle upstream side toward the nozzle outlet, and further, the diameter is expanded at the throat portion having the minimum cross-sectional area.
- the present invention is the system according to the invention (8) or (9), wherein the mixing section is cylindrical.
- the “water droplet” is a concept including not only water droplets derived from water but also minute water droplets derived from wet saturated water vapor.
- the “multiphase fluid” is a fluid having a plurality of fluid components such as two fluids and three fluids, for example, 1) saturated water vapor and pure water droplets having a boiling point or less, and 2) heated steam and pure water droplets having a boiling point or less. 3) A combination of the above 1) or 2) with an inert gas or clean high-pressure air can be mentioned.
- oxygen gas and other active gases may be used when used in applications where the oxidation or chemical reaction of the object is not concerned.
- the “object” is not particularly limited, and examples thereof include an electronic component, a semiconductor substrate, a glass substrate, a lens, a disk member, a precision machined member, and a mold resin member.
- the “treatment” is not particularly limited as long as it is applied to an object, and examples thereof include peeling, washing, and processing.
- Water is a characteristic that is used as pure water or ultrapure water for applications such as cleaning processes in semiconductor device manufacturing where contamination of fine foreign objects or metal ions is anxious.
- a “system” is not only an “apparatus” that houses each component in an integrated manner, but also each component is placed in a physically separated position (for example, a plant), or each component is information Even if it is not connected in a communicable manner, it is applicable to the system as long as it has all the components having the functions defined in the claims.
- “Ultra-high-speed nozzle” means a nozzle capable of accelerating a droplet at a speed higher than the sound speed.
- cavitation Normally, boiling begins when the temperature of the liquid rises above the saturation temperature at that pressure, but the liquid begins to boil even when the pressure of the liquid drops below the saturation pressure at that temperature. That is, vapor bubbles are generated in the liquid. In this way, bubbles generated by boiling due to the pressure reduction effect, not due to temperature change, are usually called cavitation bubbles. When the bubbles contract and collapse, high pressure is generated, and erosion, noise, and the like are generated. This phenomenon is sometimes called cavitation.
- a sound wave is normally generated by a traveling wave that travels in the medium and a reflected wave that is reflected by the liquid surface. 11. In this case, cavitation occurs in a striped manner in the medium along the maximum sound pressure body.
- the pressure change on the free interface is reduced because an expansion wave that cancels the compression wave, that is, a pressure wave lower than the surroundings is generated and propagates into the liquid. 5.
- the expansion wave propagating into the droplet reduces the pressure inside the droplet. If the temperature of the droplet is about 30 ° C., about 0.04 atm, about 60 ° C. about 0.2 atm, about 80 ° C. If it drops to about 0.5 atm, boiling starts. Bubbles are generated and grow (FIGS. 28 and 29). 6).
- the generated vapor bubbles take in non-condensable gas in the liquid while growing and become larger. 7). Fully grown bubbles reach the growth limit and begin to rebound or shrink. Since the contraction process occurs abruptly compared to the expansion process, the bubbles contract drastically, and the pressure inside the bubbles can reach an extremely higher pressure than at the start of growth. This high pressure is called bubble collapse pressure. 8). Bubble collapse is also induced by the disturbance of the bubble ambient conditions. Also, the bubbles are not necessarily single and collapse, but rather collapse as a group of bubbles in which the bubbles are accumulated. It is reported that the bubble collapse pressure in such a case is several hundred times or more of the single bubble collapse pressure. 9.
- the bubble collapse pressure generated inside the droplet propagates inside the droplet as a pressure wave (compression wave), reaches the contact surface between the droplet and the solid surface, and generates a very large pressure on the solid surface. . This is the collapse pressure of cavitation generated at the time of droplet collision, and cleaning is performed using this pressure.
- the thermal environment around the droplets is kept at a sufficiently high temperature by water vapor or prevents heat leakage from the droplets. Therefore, even if the pressure drop due to the expansion wave inside the droplet is not severe, it is a condition that bubbles can be generated sufficiently. Because of this characteristic, it is sufficient that the droplets have a rapid velocity and can generate a certain amount of compression waves even if they do not collide with the solid surface as in other inventions. .
- cavitation is generated by droplets having a velocity generated at a pressure that is about two orders of magnitude lower than other inventions.
- cavitation at the time of droplet collision that occurs when a droplet collides with the surface of the object which is different from the conventional method in which the impact force on the object is controlled by adjusting the ejection pressure (hydrodynamic action).
- the ejection pressure hydrodynamic action
- the degree of cavitation (whether or not it occurs and the degree thereof) can be easily controlled by changing the temperature of the droplet. It is possible.
- the droplet temperature is raised, the object can be processed efficiently, and problems due to the high jet pressure can be avoided.
- the gas is water vapor, even if it causes a heat transfer from the water vapor to another medium, the temperature of the entire system decreases as a result of being utilized from the latent heat of the water vapor. It can be avoided.
- the speed of the water droplet is increased by using the ultra-high speed nozzle.
- the droplets are subdivided to reduce the droplet diameter. Therefore, it is difficult for droplets having a large diameter that cause cracking of the wafer or collapse of the pattern to be generated, and the problem is less likely to occur even if the pressure is increased.
- Example 28 If the pressure is exceeded, measurement becomes impossible (Example 28).
- the particle size does not depend on the gas pressure in a mixed phase fluid of air and water.
- Example 29 This means that there is a pressure in a region that can be measured with a mixed phase fluid of air and water but cannot be measured with a mixed phase fluid of water vapor and water. That is, at the pressure, the mixed phase fluid of water vapor and water exhibits at least some different behavior from the mixed phase fluid of air and water. Although the difference in the behavior is not clear, it can be considered that the reason why the measurement is impossible is that the droplet velocity is too high or the droplet diameter is too small.
- the nozzle used for irradiation has a divergent structure in which the diameter decreases from the upstream side of the nozzle toward the nozzle outlet and further expands at the throat where the minimum cross-sectional area is the boundary.
- the water thus formed forms a water film on the inner wall of the nozzle, and water vapor is ejected through the central portion of the nozzle. At this time, water vapor is accelerated between the throat and the nozzle outlet. Further, the water is accelerated so as to be dragged by the accelerated water vapor.
- the present invention (5) in addition to the sufficient impact obtained by the cavitation described above, even when the semiconductor substrate is washed with a mixed phase flow of water and water vapor, it is formed on the surface of the semiconductor substrate.
- the effect is that aluminum is not easily corroded for a long time. For example, after the dry etching of aluminum, if the resist on the object is peeled off by the method according to the present invention (5), the effect that the aluminum wiring is not corroded in the time until the next step is observed.
- the multiphase fluid injection outlet and the object since the distance between the multiphase fluid injection outlet and the object is short, the multiphase fluid is difficult to take in carbon dioxide in the atmosphere, and the pH is less likely to be acidic. There is an effect of demonstrating.
- the multiphase fluid in the best mode includes continuous phase water vapor and dispersed phase water droplets generated by mixing water vapor and water.
- the “water droplets” are made of pure water suitable for processing an object made of a material that dislikes chemicals (in addition, a part of water vapor with high wetness).
- the mixed phase fluid may optionally contain an inert gas such as argon or nitrogen and clean high-pressure air.
- the optional gas is preferably argon or an inert gas.
- the reason for using water vapor is that, in addition to the high specific heat, the latent heat can be used, and the temperature is almost constant even in the situation where the heat quantity of the droplet is taken away with the change of the fluid pressure. This is because it is advantageous in that it does not decrease.
- heat transfer occurs between the water droplets and the gas, or heat transfer occurs between the water droplets and the inner wall of the mixing unit or piping.
- decompression expansion occurs, so that the gas temperature decreases. At this time, whether or not the temperature of the water droplet is lowered is determined by the latent heat of the gas.
- FIG. 1 is an overall view of an object processing apparatus 100 according to an embodiment of the present invention.
- the apparatus 100 includes a water vapor supply unit (A), a pure water supply unit (B), a water vapor fluid adjustment unit (C), a mixed phase fluid irradiation unit (D), and a wafer holding / rotating / vertical mechanism unit (E). It is.
- A water vapor supply unit
- B pure water supply unit
- C water vapor fluid adjustment unit
- D mixed phase fluid irradiation unit
- E wafer holding / rotating / vertical mechanism unit
- the water vapor supply unit (A) controls the generation amount of water vapor by generating water vapor by heating to a water supply pipe 111 for supplying pure water and a predetermined temperature D1 (° C.) or higher.
- the steam generator 112 that pressurizes the steam to a predetermined value C1 (MP), the steam opening / closing valve 113 that can open and close to supply and stop the steam, and the pressure of the steam supplied downstream from the steam generator 112
- a pressure gauge 114 for measuring, a steam pressure adjusting valve 115 for adjusting the steam supply pressure to a desired value, and a heating steam generator / saturated steam with a temperature control mechanism for adjusting the amount of fine droplets in the supplied steam It comprises a wetness adjuster 116 and a pressure release valve 117 as a safety device.
- the pure water supply unit (B) includes a water supply pipe 121 for supplying pure water, a pure water temperature control mechanism additional heat unit 122 for giving pure water thermal energy, Pure water opening / closing valve 123 for controlling stop and restart of pure water, pure water flow meter 124 for confirming the flow rate of pure water, and stopping and restarting the supply of pure water downstream in the case of two fluids And a two-fluid production pure water on-off valve 125.
- the steam fluid adjusting unit (C) includes a steam fluid temperature control mechanism additional heat unit 131 for adjusting the temperature of the steam fluid and the wetness of the saturated steam.
- the multi-phase fluid irradiation unit (D) moves in the front-rear and left-right directions (X-axis nozzle scan range or Y-axis nozzle scan range in FIG. 1) for irradiating the target with the multi-phase fluid.
- the gas-liquid mixing unit 144 is introduced so as to form a water film, and the orifice 145 is used for smoothly introducing pure water into the gas pipe.
- the nozzle 141 is an ultra-high speed nozzle.
- the “ultra-high speed nozzle” is not particularly limited as long as it is a nozzle capable of accelerating the liquid droplets at a speed higher than the sound speed, and examples thereof include a sonic nozzle.
- FIG. 30 is a cross-sectional view of the sonic nozzle and the mixing unit according to the best mode.
- the shape of sonic nozzle is not particularly limited, the nozzle is abruptly reduced in diameter toward to the nozzle outlet is located in the drawing downward from the nozzle upstream of the drawings above, further, was a minimum cross-sectional area A 3 It has a divergent nozzle structure with the diameter (relatively widened) so that the fluid does not peel off from the inner wall at the position (throat), and the cross-sectional area is A 2 at the nozzle outlet.
- Sectional area of the throat portion A 3 is calculated by dividing the flow rate at the speed of sound.
- Sectional area A 3 of the throat portion is not particularly limited, for example, 3.0 ⁇ 20.0 mm 2.
- the spreading rate (A 3 / A 2 ) is calculated by the following equation (1).
- ⁇ is the specific heat ratio of gas (constant pressure specific heat / constant volume specific heat)
- P 1 is the pressure at the nozzle throat
- P 2 is the pressure at the nozzle outlet.
- The, the cross-sectional area A 3 of the spreading rate and the throat portion, the sectional area A 2 of the nozzle outlet is required.
- the sectional area A 2 of the nozzle outlet is not particularly limited, but is, for example, 7.0 to 28.0 mm 2 .
- the length of the nozzle can be appropriately set in consideration of various parameters such as nozzle material, roughness, flow rate (Reynolds number), and the like.
- the degree of diameter expansion can be appropriately set in consideration of various parameters such as viscosity, density, and flow rate.
- the shape of the nozzle outlet is not particularly limited, but may be circular.
- the inner wall surface of the mixing part and the inner wall surface of the nozzle form a substantially continuous curved surface.
- the mixing part may be joined upstream of the nozzle as a cylindrical body, or may be formed upstream of the nozzle.
- the joining part is formed so that the liquid that reaches the wall surface while forming a water film by the mixing unit flows through the nozzle wall surface also forming a water film.
- the mixing unit 144 will be described in detail later.
- the wafer holding / rotation / up / down mechanism unit (E) includes a stage 151 on which an object (wafer) can be mounted / held, and a rotation motor 152 for rotating the stage 151.
- a wafer vertical drive mechanism 153 capable of adjusting the distance between the outlet of the nozzle 141 and the wafer by moving the stage 151 in the vertical direction, and a cooling water pipe 154 for supplying cooling water for cooling the object (wafer), , An openable / closable cooling water opening / closing valve 155 for stopping and restarting the cooling water supply, a cooling water flow rate adjusting valve 156 for adjusting the flow rate of the cooling water, and a cooling water for measuring the flow rate of the cooling water A flow meter 157.
- the mixing unit 144 in the mixed phase fluid irradiation unit (D) will be described in detail.
- the mixing unit 144 is an upstream side of the nozzle that can mix water from the wall surface of the mixing unit at an angle of 90 degrees or less with respect to the water vapor in the direction of travel of the water vapor. It has an introduction part 144a (FIG. 30).
- the mixing part is preferably cylindrical, and the inner diameter of the cross section joined to the mixing part nozzle is preferably the same as the inner diameter of the inlet of the nozzle.
- FIG. 2 is a diagram showing a detailed configuration in the case where the mixing unit 144 is a mixed phase fluid / gas mixing unit with a temperature control mechanism.
- the mixing unit 144 it is important to minimize the occurrence of a phase change phenomenon such as liquefaction of water vapor or vaporization of water on the inner wall of the mixing unit. For this reason, as shown in FIG. 2, it is preferable that the mixing unit 144 has the following structure.
- the direction of each fluid of gas and liquid has an angle of less than 90 degrees at the mixing portion.
- the pipe diameter of the liquid fluid or the orifice attached to the pipe is sufficiently smaller than the cross-sectional area of the flow path of the gas fluid at the mixing section.
- the inner wall temperature of the mixing section is controlled to meet the following conditions. Further, the temperature of the inner wall does not greatly deviate from the saturation temperature of the liquid under the pressure in the mixing part (within ⁇ 20%). Further, the temperature of the inner wall should not greatly deviate from the saturation temperature of the gas under the pressure in the mixing part (within ⁇ 20%).
- the temperature of the mixing unit is sufficiently kept for applications where the time until the state of the multiphase flow becomes stable is not an issue. Under this condition, the heating function by the heater can be removed.
- the fluid mixing unit is at room temperature when the device is activated. If there is a temperature difference between the part and the water vapor, the liquid mixing device may have a temperature unevenness, which causes the discharge pressure of the multiphase fluid to be unsatisfactory due to a phase change of a part of the steam into water droplets. It becomes stable and it is difficult to stably apply a certain shock wave on the surface of the object to be processed, so that it takes time until the apparatus operates stably.
- the fluid mixing unit can be set to the same temperature as the temperature of the water vapor from the beginning of the operation, and the device is less likely to cause a gas-liquid phase change in the mixing unit.
- a stable shock wave can be applied to the target processing surface.
- the cleaning device includes a gas pressure, a water mixing flow rate in a multiphase fluid, a gas temperature, a temperature of water to be mixed, a nozzle shape, a distance from a nozzle outlet to an object, a temperature of the object, a nozzle and an object
- the flow velocity contributes to the generation of a shock wave due to the collapse of bubbles in the droplet when the droplet collides, and the temperature contributes to the generation of bubbles in the droplet.
- the higher the droplet density the higher the probability that a shock wave will occur. For example, if the number of droplets is zero, a shock wave due to droplet collision does not occur.
- droplet density refers to the total number of droplets per unit volume and time in a multiphase fluid, but measuring instruments that accurately measure micro-order droplets moving at high speed are still being developed. Therefore, the amount of pure water introduced into the mixed phase fluid should be substituted.
- the system according to the present invention includes a measurement means for measuring how much cavitation occurs under the condition after irradiating the object or the measurement sample with a multiphase flow under a certain condition. Yes.
- a measurement means for measuring how much cavitation occurs under the condition after irradiating the object or the measurement sample with a multiphase flow under a certain condition Yes.
- Physical change measuring means for quantitatively measuring the physical change of an object or a measurement sample ⁇ Roughness of the metal surface when the metal surface is irradiated with a multiphase fluid ⁇ Resist when the resist surface is irradiated Peeling area and small amount of residue ⁇ Removal rate of foreign matter adhered to the entire wafer surface
- Acoustic measurement means capable of detecting the magnitude of cavitation noise ⁇ Cavitation noise magnitude detected by an acoustic sensor
- Object Or visual change measurement means for quantitatively measuring the visual change of the measurement sample ⁇ Image data of resist stripping process taken with a high-speed camera
- the data of the multiphase fluid temperature and the degree of unevenness of the metal surface irradiated with it are confirmed as shown in FIG. Further, the correlation between the resist stripping performance and each parameter has been confirmed by a lot of data accumulated over the past three years.
- One example is the data shown in FIG.
- the pressure at which the mixed phase fluid is ejected from the nozzle is increased, the resist stripping area is increased and the residue is reduced.
- the ejection pressure is increased too much, physical damage to the object is concerned, and the superiority of the low pressure process, which is a feature of this apparatus, is impaired. Therefore, in this apparatus, the maximum ejection pressure from the nozzle is 0.3 MPa.
- Patent Document 1 also adopts a configuration that is not greatly different from the best mode in terms of apparatus, except that an ultra-high speed nozzle is used.
- shock wave the physical force
- no control has been performed to generate or not generate the shock wave on the object.
- “cavitation” occurs only in a nozzle having a tapered tip, and the generated shock wave is extremely short-lived and disappears before reaching the object. Specifically, when the multiphase fluid flowing in the nozzle reaches the tip of the nozzle, the flow velocity is increased.
- the liquid causes a cavitation phenomenon and a shock wave is generated.
- the collapse duration of hydrogen bubbles in a liquid shock wave tube is 2 to 3 ⁇ s.
- the movement time of the fluid having a flow rate of 400 m / sec for 3 ⁇ sec is only 1.2 mm, and the bubble collapse phenomenon disappears between the nozzle throat and the nozzle outlet. Further, even if bubble collapse occurs at the nozzle outlet, it is mechanically difficult to set the object distance to 1.2 mm or less.
- the nozzle mainly functions to accelerate the multiphase fluid or expand the irradiation area.
- the bubble collapse related parameters related to the occurrence of cavitation may be basically adjusted anywhere as long as the cavitation on the object is focused.
- any parameter of the fluid piping in front of the nozzle may be adjusted.
- the fluid mixing section may be used. Specifically, it may be controlled anywhere within the range of the arrow indicated by ⁇ in FIG. 1 (between the steam generator and the nozzle outlet). Later, the main bubble collapse related parameters will be described in detail.
- the object cleaning method has an aluminum corrosion prevention effect together with the above impact force.
- the corrosion prevention effect can be achieved. It is possible to control.
- the temperature when the mixed phase fluid reaches the object and the pH when the mixed phase fluid reaches the object are important.
- the shock wave is considered to be mainly generated by the cavitation generated when the droplet collides with the surface of the object to be processed and the collapse of the cavitation.
- Cavitation is a cavity generated when a low pressure portion is generated in a part of a liquid such as water, and tends to be generated more easily as the temperature of the gas and the liquid is higher. That is, the higher the temperature of the droplet, the easier it is to generate bubbles in the water droplet, and along with this, more bubble collapse occurs on the surface of the object to be processed, which is the basis of a large energy shock wave.
- the processing method is used for removing the resist film, it is possible to remove the resist film and foreign matters that are relatively strongly bonded.
- the temperature of the multiphase fluid or water droplets is set low, the generation of shock waves on the surface of the object to be treated can be suppressed and the object having a relatively low strength can be cleaned.
- the temperature there is a limit to the temperature that can be set due to the limitation due to the heat resistance of the object.
- the distance from the object becomes long when the temperature is too high, it is expected that the gas components in the droplets will escape and bubble nuclei will not easily be generated, but the distance from the nozzle outlet to the object will be 2 to 2. It can be ignored at a distance of about 30 mm.
- the temperature of the water vapor supplied into the nozzle is preferably 50 to 120 ° C., more preferably 80 to 115 ° C., and still more preferably 90 to 110 ° C.
- the temperature of the water mixed with the water vapor is preferably 0 to 40 ° C., more preferably 10 to 35 ° C., and further preferably 20 to 30 ° C.
- the temperature when the target of the multiphase fluid reaches the target is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 90 ° C. or higher.
- the temperature of the mixed phase fluid is measured by the method described in the examples. By setting it as the said range, the special film
- the speed of the droplet is 100 to 600 m / s, more preferably 200 to 500 m / s, and further preferably 250 to 350 m / s.
- the velocity of the droplet is substantially equal to the velocity of the fluid, and is [flow rate] / [nozzle cross-sectional area].
- the flow rate is the water vapor flow rate (m 3 / s)
- the nozzle sectional area is the sectional area (m 2 ) of the nozzle outlet.
- an ultra-high speed nozzle is used as described above.
- the flow velocity of the fluid changes and the magnitude of the shock wave also changes.
- using a nozzle with a large flow velocity makes it easier to obtain shock waves.
- a special behavior is observed in relation to the pressure of the water vapor and the speed and diameter of the water droplets.
- the water vapor pressure is not particularly limited as long as it is 0.05 to 0.25 MPa.
- the mixed phase fluid of water vapor and water droplets behaves significantly differently from the mixed phase fluid of air and water droplets.
- the normal adaptive value is in the range of 2 to 30 mm (optimum range 2 to 10 mm), preferably 5 mm or less, more preferably 3 mm or less, and 2 mm. Is more preferred. If the distance from the nozzle outlet to the wafer is shortened, the resist stripping performance is improved in the same manner. However, if the optimum distance exists and is too close, the stripping performance is lowered.
- the flow rate of water vapor is preferably 0.083 to 1.0 kg / min, more preferably 0.025 to 0.75 kg / min in terms of the mass flow rate of water vapor, and 0.33 to 0.50 kg / min. min is more preferable.
- the gas / liquid mixing ratio (liquid / gas) is preferably 0.00018 to 0.01.
- the droplet diameter is preferably 2 to 25 ⁇ m. The larger the droplet diameter, the smaller the surface area. Therefore, the amount of carbon dioxide in the atmosphere is reduced, so that the droplet diameter is less likely to be acidic.
- the droplet diameter is measured at a position 5 mm from the nozzle outlet by a PDA (Phase Doppler Anemometry) unless otherwise specified, using a device manufactured by TSI.
- the fluid flow rate / jet outlet cross-sectional area is preferably 0.5 to 32.0 kgcm ⁇ 2 min ⁇ 1 .
- the pressure applied to the water is such that the water does not flow backward due to the pressure of water vapor. is there.
- the pressure applied with respect to water is not specifically limited, For example, it can introduce
- the pH of the mixed phase fluid when it reaches the object is preferably 7.0 to 9.0, more preferably 7.0 to 8.0, and even more preferably 7.0 to 7.5.
- a special film is formed on aluminum on the surface of the object, so that an effect of preventing corrosion of aluminum is obtained.
- the pH measuring method shall be based on the method as described in an Example.
- FIG. 31 is a schematic diagram of a device for performing temperature measurement in the object reach the multiphase fluid.
- a thermocouple TH (Alumel-Chromel thermocouple JIS C1602) is affixed to a silicon wafer W having a diameter of 6 inches and a thickness of 0.625 mm with a tape TA, and the distance between the fluid ejection outlet of the nozzle 141 and the object, water vapor Set the various conditions such as pressure and pure water flow rate to the same values as when processing the object, and irradiate the thermocouple for 1 minute.
- FIG 32 is a schematic view of an apparatus for measuring the pH at the time of the object reaches the multiphase fluid.
- the outlet of the nozzle 141 is connected to a cooling pipe C (for example, a Graham-type pipe cooling pipe) via a pipe P, and the condensed water is collected in a container R, and the pH of the water is adjusted according to the method of JIS Z 8802. It was measured by.
- the aggregating operation is performed without touching the air.
- Example 1 Under the following conditions, the aluminum surface was irradiated with a multiphase fluid (when steam was used as a gas and when air was used) for 10 minutes. AFM photographs before and after the treatment are shown in FIG. FIG. 5 shows surface roughness data. In this example, the surface roughness was measured by the profile analysis method attached to AFM. Steam pressure: 0.2 MPa Steam temperature: 130 ° C Flow rate of pure water: 300cc / min Pure water temperature: 20 ° C GAP: 5mm Nozzle scan: Fixed
- Example 2 Under the same conditions as in Example 1, the steel surface was irradiated with a mixed phase fluid (when steam was used as a gas and when air was used) for 10 minutes. AFM photographs before and after the treatment are shown in FIG. FIG. 6 shows surface roughness data.
- Example 3 Since the vapor cleaning technique disclosed in Patent Document 1 is to remove the resist by the chemical reaction of the vapor and the mechanical action of the jet, it takes a minute time to remove the resist. Visualization using high-speed video was performed to confirm whether this method is the same mechanism.
- FIG. 7 shows the change over time when the i-line positive resist is peeled off, as observed in the lower part of the quartz wafer, irradiated with the multiphase fluid under the same conditions as in Example 1 except that the nozzle scan speed is 100 mm / sec. Show. As shown in the figure, the resist was peeled off at a very high speed while the peeled area gradually expanded.
- Example 4 Except that the nozzle scan speed was set to 40 mm / sec, the silicon wafer after the high concentration ion implantation was irradiated with the mixed phase fluid under the same conditions as in Example 1, and the change with time of i-line positive resist peeling was observed. The results are shown in FIG.
- Examples 5-8 Under the following conditions, the gas and temperature of the mixed phase fluid were changed, and the aluminum surface was irradiated with the mixed phase fluid for 10 minutes. AFM photographs before and after the treatment are shown in FIG. FIG. 10 shows surface roughness data. The surface of the aluminum to be treated before irradiation had an Ra of 34.9 nm. Gas pressure: 0.2MPa Liquid flow rate: 300cc / min Gap: 10mm
- Examples 9-10 The surface of Al alumite having a Ra of 348.8 nm was irradiated under the same conditions as in Examples 5 to 8 while changing the gas and temperature of the mixed phase fluid.
- a surface with Ra of 380 nm was obtained.
- a surface AFM photograph is shown in FIG. 11 (a)
- surface roughness data is shown in FIG. 11 (c) (Example 9).
- a surface with an Ra of 440 nm was obtained.
- a surface AFM photograph is shown in FIG. 11B, and surface roughness data is shown in FIG. 11D (Example 10).
- Example 11 An SUS surface with an Ra of 8.1 nm was irradiated under the same conditions as in Examples 5 to 8 while changing the gas and temperature of the multiphase fluid. As a result of irradiating a multiphase fluid consisting of 130 ° C. water vapor and 20 ° C. pure water droplets, a surface with an Ra of 19.9 nm was obtained. The AFM photograph of the surface is shown in FIG. 12 (a), and the surface roughness data is shown in FIG. 12 (b) (Example 11).
- Example 12 The titanium surface with an Ra of 75.5 nm was irradiated under the same conditions as in Examples 5 to 8 while changing the gas and temperature of the multiphase fluid. As a result of irradiating a mixed phase fluid consisting of 130 ° C. water vapor and 20 ° C. pure water droplets, a surface with an Ra of 98 nm could be obtained. A surface AFM photograph is shown in FIG. 13A, and surface roughness data is shown in FIG. 13B (Example 12). In titanium, interference fringes were visually observed. There is a possibility that an oxide film is formed on the surface.
- Example 13 The silicon surface with Ra of 1.9 nm was irradiated under the same conditions as in Examples 5 to 8 while changing the gas and temperature of the multiphase fluid. As a result of irradiating a mixed phase fluid consisting of 130 ° C. water vapor and 20 ° C. pure water droplets, a surface with Ra of 7.6 nm could be obtained.
- the AFM photograph of the surface is shown in FIG. 14A, and the data of the surface roughness is shown in FIG. 14B (Example 13).
- Examples 14-25 In Examples 14 to 25, it was examined whether there was a difference in the state of peeling depending on the resist coating conditions. The presence or absence of HMDS and the Bake temperature were changed to 90 ° C. and 110 ° C., and the influence of the condition change was observed. The result is considered that the surface profile after the treatment does not depend on the ground treatment HMDS. The experiment was performed under the following conditions. Sample used: I-line resist Irradiation time: Until peeling is visually observed Gas pressure: 0.2 MPa Liquid flow rate: 300cc / min Nozzle scan: Fixed Gap: 10 mm
- FIGS. 15 (d) to 15 (f) show Observations are shown in FIGS. 15 (d) to 15 (f).
- FIG. 15A shows a state in which the surface was observed with a microscope after irradiation with a mixed phase fluid composed of 20 ° C. air and 20 ° C. pure water
- FIG. 15D is a corresponding AFM photograph ( Example 14).
- FIG. 15 (b) shows a state where the surface was observed with a microscope after irradiating a mixed phase fluid composed of 130 ° C. air and 90 ° C. pure water
- FIG.15 (e) is a corresponding AFM photograph ( Example 15).
- FIG.15 (c) is a state which observed the surface with the microscope after irradiating the mixed phase fluid which consists of 130 degreeC water vapor
- FIG.15 (f) is a corresponding AFM photograph ( Example 16).
- FIGS. 16A to 16C show a state in which a resist film was applied under the conditions of HMDS and Bake 110 ° C., the sample was irradiated under the above conditions, and the treatment peeling boundary surface was observed with a microscope.
- the observations are shown in FIGS. 16 (d) to (f).
- FIG. 16A shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 20 ° C. air and 20 ° C. pure water
- FIG. 16D is a corresponding AFM photograph ( Example 17).
- FIG. 16 (b) shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 130 ° C.
- FIG. 16 (e) is a corresponding AFM photograph ( Example 18).
- FIG. 16 (c) shows a state in which the surface was observed with a microscope after irradiation with a mixed phase fluid composed of 130 ° C. water vapor and 20 ° C. pure water
- FIG. 16 (f) is a corresponding AFM photograph ( Example 19).
- FIGS. 17 (d) to 17 (f) show a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 20 ° C. air and 20 ° C. pure water
- FIG. 17D is a corresponding AFM photograph ( Example 20).
- FIG. 17 (b) shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 130 ° C. air and 90 ° C. pure water
- FIG. 17 (b) shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 130 ° C. air and 90 ° C. pure water
- FIG. 17 (e) is a corresponding AFM photograph ( Example 21).
- FIG. 17 (c) shows a state in which the surface was observed with a microscope after irradiation with a mixed phase fluid consisting of 130 ° C. water vapor and 20 ° C. pure water
- FIG. 17 (f) is a corresponding AFM photograph ( Example 22).
- FIGS. 18 (d) to (f) show a state in which the surface was observed with a microscope after irradiation with a mixed phase fluid composed of 20 ° C. air and 20 ° C. pure water
- FIG. 18 (d) is a corresponding AFM photograph ( Example 23).
- FIG. 18 (b) shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 130 ° C. air and 90 ° C. pure water
- FIG. 18 (a) shows a state in which the surface was observed with a microscope after irradiation with a multiphase fluid composed of 130 ° C. air and 90 ° C. pure water
- FIG. 18 (e) is a corresponding AFM photograph ( Example 24).
- FIG. 18 (c) shows a state of observing the surface with a microscope after irradiating a mixed phase fluid composed of 130 ° C. water vapor and 20 ° C. pure water
- FIG. 18 (f) is a corresponding AFM photograph ( Example 25).
- Example 26 The relationship between droplet diameter and flow velocity is shown in FIG.
- the water vapor pressure was constant (0.2 MPa), and the flow rate and diameter of the droplets were measured at various pure water flow rates.
- the results are shown in FIG.
- the relationship between droplet velocity v and diameter d measured by PDA is shown. Both v and d were close to a normal distribution, and the averages were about 280 m / s and 10 ⁇ m, respectively.
- the result of the mixed jet of air and droplets is also indicated by a dotted line. It can be seen from the figure that the target droplet velocity is about 200 to 300 m / s and the droplet diameter is about 10 ⁇ m.
- Example 28 (Relationship between gas pressure and droplet velocity) Using a sonic nozzle with a mixed phase fluid of water vapor and water and a mixed fluid of air and water at a flow rate of water of 200 cc / min and a gas pressure of 0.05, 0.1, 0.2 MPa. The liquid droplets were jetted, and the velocity of the liquid droplets was measured at a position 5 mm or 10 mm from the jet nozzle with an LDA (Laser Doppler Anemometer) (FIG. 33). The measurement of LDA was performed with an LDA manufactured by TSI, and when data of 10,000 droplets could be acquired, the measurement was terminated, and measurement was performed three times under each condition.
- LDA Laser Doppler Anemometer
- Example 29 (Relationship between gas pressure and droplet diameter) Using a sonic nozzle with a mixed phase fluid of water vapor and water and a mixed fluid of air and water at a flow rate of water of 200 cc / min and a gas pressure of 0.05, 0.1, 0.2 MPa. The droplet diameter was measured with a PDA at positions 5 and 10 mm from the ejection port (FIG. 34). In addition, the measurement of PDA was completed when data of 10,000 droplets could be acquired, and measurement was performed three times under each condition. In the case of a mixed phase fluid of air and water, the droplet velocity hardly changed even when the air pressure was changed.
- Example 30 pressure wave in the nozzle
- a pure water flow rate was set to 100 cc / min
- a mixed phase fluid of water vapor and water was injected using a quartz nozzle.
- a pressure wave was observed at the tip of the quartz nozzle.
- FIG. FIG. 35 (a) shows the state of injection under the condition of 0.1 MPa
- FIG. 35 (b) shows the state of injection under the condition of 0.2 MPa.
- a mixed phase fluid of air and water was irradiated using a quartz nozzle under a gas pressure of 0.1 and 0.2 MPa with a pure water flow rate of 100 cc / min.
- no pressure wave was observed at the tip of the quartz nozzle.
- FIG. FIG. 36A shows the state of injection under the condition of 0.1 MPa
- FIG. 36B shows the state of injection under the condition of 0.2 MPa.
- Examples 1-36 Using a cleaning device having a sonic nozzle (FIG. 30) according to the best mode, a mixed phase fluid of water vapor and water is sprayed on an object under the following conditions, and the cleaning effect, physical destruction and corrosion resistance of wiring The properties were evaluated (Tables 1 and 2).
- an i-line negative resist (Tokyo Ohka THMRip3300) was applied at a thickness of 1 ⁇ m, baked at 90 ° C. for 120 min, exposed at 365 nm for 20 seconds, and TMAH ([N (CH 3 ) 4 at room temperature. ]
- a silicon wafer having aluminum wiring developed by + OH ⁇ was used.
- Comparative Example Comparative Example 1 is when the fluid temperature is too low. If the fluid temperature was too low, the polymer was removed, but the wiring was eroded after 10 days. Comparative Examples 2 and 3 are cases where the droplet velocity is too slow and too fast. If it was too slow, the polymer remained, and if it was too fast, physical destruction of the wiring was observed. Comparative Examples 4 and 5 are cases where the pH is too low and too high. When the pH was too low, a protective film was not formed, and corrosion of the wiring was observed after 10 days. When the pH is too high, wiring corrosion occurs due to the high pH.
- the present invention can be applied to various kinds of processing over a very wide range of objects from materials having high strength to materials having low strength.
- materials having high strength for example, semiconductor devices, liquid crystals, magnetic heads, disks, printed circuit boards, lenses for cameras, precision-machined parts, molded resin products, etc., waste removal, cleaning, polishing, etc., and micro processing using silicon process technology
- the present invention can also be used for deburring processing in the fields of structures, mold processing, and the like.
- the present invention is particularly suitable for the treatment of materials that dislike chemicals.
- FIG. 1 is a diagram showing an overall configuration of a processing apparatus according to the best mode.
- FIG. 2 is a schematic view of a mixed phase fluid gas-liquid mixing unit with a temperature control mechanism of the processing apparatus according to the best mode.
- FIG. 3 is a diagram showing a surface observation AFM photograph 10 minutes after irradiation of the multiphase fluid on the aluminum surface in Example 1.
- FIG. 4 is a diagram showing a surface observation AFM photograph 10 minutes after irradiation of the multiphase fluid on the steel surface in Example 2.
- FIG. 5 is a diagram showing surface roughness data in Example 1 after 10 minutes of irradiation of the multiphase fluid on the aluminum surface.
- FIG. 6 is a diagram showing surface roughness data after 10 minutes of irradiation of the multiphase fluid on the steel surface in Example 2.
- FIG. 7 is a diagram illustrating a result of observing a resist peeling process from the back surface with a high-speed camera while irradiating a resist coated on a transparent wafer with a mixed phase fluid in Example 3.
- FIG. 8 is a diagram showing resist stripping data by multiphase fluid irradiation after high-concentration ion implantation in Example 4.
- FIG. 9 is a diagram showing the results of Examples 5-8.
- FIG. 10 is a diagram showing the results of Examples 5-8.
- FIG. 11 is a diagram showing the results of Examples 9 to 10.
- FIG. 12 is a diagram showing the results of Example 11. In FIG. FIG.
- FIG. 13 is a diagram showing the results of Example 12.
- FIG. 14 is a diagram showing the results of Example 13.
- FIG. 15 is a diagram showing the results of Examples 14 to 16.
- FIG. 16 shows the results of Examples 17-19.
- FIG. 17 shows the results of Examples 20-22.
- FIG. 18 is a diagram showing the results of Examples 23-25.
- FIG. 19 is a diagram showing the results of Example 26.
- FIG. FIG. 20 shows the results of Example 27.
- FIG. 21 is a diagram showing a change in the magnitude of the shock wave due to the difference in thermal energy of the multiphase fluid.
- FIG. 22 is a diagram showing a change in the magnitude of the shock wave due to the difference in velocity of the multiphase fluid.
- FIG. 21 is a diagram showing a change in the magnitude of the shock wave due to the difference in thermal energy of the multiphase fluid.
- FIG. 22 is a diagram showing a change in the magnitude of the shock wave due to the difference in velocity of the multiphase fluid.
- FIG. 21 is
- FIG. 23 is a diagram showing a change in the magnitude of the shock wave due to the difference in density of the multiphase fluid.
- FIG. 24 is a diagram showing a mechanism of cavitation generation by ultrasonic waves.
- FIG. 25 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 26 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 27 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 28 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 29 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 24 is a diagram showing a mechanism of cavitation generation by ultrasonic waves.
- FIG. 25 is a diagram showing a mechanism of cavitation that occurs at the time of droplet collision.
- FIG. 26 is a diagram showing a mechanism of
- FIG. 30 is a diagram illustrating the structure of the sonic nozzle and the mixing unit.
- FIG. 31 is a schematic view of an apparatus for measuring a multiphase fluid temperature.
- FIG. 32 is a schematic view of an apparatus for measuring the pH of a multiphase fluid.
- FIG. 33 is a diagram showing the relationship between the gas pressure and the water droplet velocity.
- FIG. 34 is a diagram showing the relationship between gas pressure and water droplet diameter.
- FIG. 35 is a diagram illustrating a state of a pressure wave generated in the quartz nozzle.
- FIG. 36 is a diagram illustrating a state in which no pressure wave is generated in the quartz nozzle.
- Object processing apparatus 111 Water supply pipe 112: Steam generator 113: Steam opening / closing valve 114: Pressure gauge 115: Steam pressure adjusting valve 116: Heated steam generator with temperature control mechanism / saturated steam wetness adjuster 117: Pressure release valve 121: Water supply pipe 122: Pure water temperature control mechanism additional heat section 123: Pure water on / off valve 124: Pure water flow meter 125: Pure water on / off valve 131 for two fluid generation 131: Steam fluid temperature control mechanism additional heat section 141: Irradiation nozzle 142: Flexible pipe 143: Pressure gauge 144: Mixed phase fluid / gas / liquid mixing section 145 with temperature control function 145: Orifice 151: Mountable / holdable stage 152: Rotating motor 153: Wafer vertical drive mechanism 154: Cooling water pipe 155 : Cooling water on-off valve 156: Cooling water flow rate adjustment valve 157: Cooling water flow meter
Landscapes
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Nozzles (AREA)
Abstract
Description
前記混合部が前記ノズルの上流側に設置されており、内壁面の一部が開口した水導入部を有し、
前記ノズルが、超高速ノズルであり、
前記混合部の内壁面とノズルの内壁面が略連続的な曲面を形成し、
前記混合部内を流動する前記水蒸気に対して前記混合部の内壁面から水を混合して、前記混合部の内壁面から前記ノズルの内壁面に水をつたわせて、前記ノズルの出口から前記混相流体を噴射することを特徴とする方法である。
前記混合部(例えば、混合部144)が前記ノズルの上流に設置されており、流動する前記水蒸気に対して内壁面から水を混合可能である、内壁面の一部が開口した水導入部(例えば、144a)を有し、
前記ノズルが、超高速ノズル(例えば、ノズル141)であり、
前記混合部の内壁面とノズルの内壁面が略連続的な曲面を形成していることを特徴とするシステムである。
通常は液体の温度が、その圧力における飽和温度より高くなると沸騰が開始するが、液体の圧力が、その温度における飽和圧力より低くなっても、液体は沸騰を開始する。すなわち蒸気泡が液体中に生成する。このように温度変化によるものではなく、減圧効果により沸騰し発生する気泡は通常キャビテーション気泡と呼ばれている。この気泡が収縮し、崩壊することによって高圧が生じ、壊食・騒音等が発生する。この現象もキャビテーションと呼ばれることがある。
1.超音波発生器により媒液中に音波が伝搬する。
2.音波は激しい周期で圧縮と減圧を繰り返して媒液中を進行する。
3.圧縮から減圧に移る過程で、局所的に飽和水蒸気圧以下にまで減圧する。
4.そこで気泡の成長(常温沸騰)が開始する。
5.また、成長蒸気気泡に媒液中に溶解している不凝縮気体も混入する。
6.気泡がさらに成長する。
7.気泡は次の圧縮力を受けて断熱的に圧縮され高いエネルギーをもつ。
8.気泡は、ついに押しつぶされて崩壊する。
9.押しつぶされるとき、局所的に極めて大きな衝撃エネルギーとなって、周囲にある汚れを解離する。
10.音波は、通常媒液中を進行する進行波と液面で反射する反射波によって定在波が生じる。
11.この場合キャビテーションは最大音圧体に沿って媒液中に縞状に発生する。
2.発生した圧力は圧力波(圧縮波)として液滴内部を上方に伝播し、液滴と周囲気体との境界面、すなわち自由界面に到達する(図26)。
3.水の音響インピーダンスは周囲気体の音響インピーダンスに比較して圧倒的に大きいためインピーダンスミスマッチングとなり、圧力波はほぼ100%反射する。すなわち、圧力波の周囲気体へと伝播は非常に小さくなるため、結果として自由界面上での圧力変化は小さく抑えられる(図27)。
4.自由界面上での圧力変化が小さくなるのは、圧縮波を打ち消す膨張波、すなわち周囲より低い圧力波が発生し、液体内部へと伝播するからである。
5.液滴内部へと伝播した膨張波は、液滴内部の圧力を低下させる。液滴の温度が30℃程度であれば、約0.04気圧、60℃程度であれば約0.2気圧、80℃程度であれば約0.5気圧まで低下すれば沸騰が開始し、気泡が発生・成長する(図28、29)。
6.発生した蒸気泡は、成長しながら液体中の不凝縮気体も取り込み、さらに大きくなる。
7.十分成長した気泡は成長限界に達し、リバウンドすなわち収縮を開始する。収縮過程は膨張過程に比較して急激に起こるため、気泡は激烈に収縮し、気泡内部圧力は成長開始時よりも極端に高い圧力にまで達しうる。この高圧力は気泡崩壊時圧力と呼ばれている。
8.気泡崩壊は気泡周囲条件の擾乱によっても誘起される。また、気泡は必ずしも単一で崩壊せず、むしろ気泡が集積した気泡群として崩壊する。そのような場合の気泡崩壊圧力は単一気泡崩壊圧力の数100倍程度以上であることが報告されている。
9.液滴内部で発生した気泡崩壊圧力は、圧力波(圧縮波)として液滴内部を伝播して、液滴と固体面との接触面に到達し、固体面上に非常に大きな圧力を発生させる。これが、液滴衝突時に発生するキャビテーションの崩壊圧力であり、この圧力を利用して洗浄を行っている。
更に、超高速ノズルを用いた場合、水蒸気と水滴を噴射する混相流体と、空気と水滴との混相流体では、下記の二点の特異な挙動を示すことが観測された。
第一に水蒸気と水の混相流体を超高速ノズルを用いて噴射することにより、ノズル内の出口付近に圧力波のようなものが観測されることが明らかとなった(例30)。これにより、ノズル内で液滴が更に細分化され液滴径が小さくなるため、圧力を上げても、ウェハの割れや、表面パターンの崩れといった問題を起さないという効果を奏する。
第二に気体圧力と液滴速度及び/又は平均粒径との関係である。気体圧力を高めた場合、空気と水との混相流体では、圧力が高まるにつれて液滴速度も高くなるのに対して、水蒸気と水の場合、所定の圧力までは計測可能であったが、所定圧力をこえると計測不可能になる(例28)。また、気体圧力と水滴の平均粒径の関係を観察すると、空気と水の混相流体では気体圧力にその粒径は依存しないが、水蒸気と水の場合、所定圧力を超えると平均粒径のデータが信憑性のないものとなってしまうことがわかった(例29)。これは、空気と水の混相流体では測定可能であるが、水蒸気と水の混相流体では測定不可能となる領域の圧力があることを意味する。即ち、当該圧力において、水蒸気と水の混相流体は、空気と水の混相流体とは少なくとも何らかの異なる挙動を示していることを意味する。当該挙動の相違点については明らかではないが、測定不可能となる要因としては、液滴速度が速すぎる又は液滴径が小さすぎるといったことが考えられる。
ノズル上流側で、前記水蒸気に対して前記混合部の壁面から水を混合することにより、壁面に水膜を形成してノズル出口から噴出して、水滴と水蒸気の混相流体を噴出する。噴出された液滴は、対象物表面に衝突することにより、先述の作用機序により液滴内に局所的に低圧部が発生して、対象物表面でキャビテーションを発生させることが可能となる。
また、照射に使用するノズルが、ノズル上流側からノズル出口へと向かうに従って縮径し、更に、最小断面積となるのど部を境に、拡径する末広構造を有するため、前記混合部において混合された水によってノズル内壁に水膜が形成されて、水蒸気がノズルの中心部分を通過して噴出される。この際、水蒸気はのど部からノズル出口の間で加速される。更に、当該加速された水蒸気に引きずられるように水が加速する。
まず、本最良形態での混相流体は、水蒸気と水とを混合することにより生成する、連続相の水蒸気と分散相の水滴を含む。ここで、「水滴」は、化学薬品を嫌う材料からなる対象物を処理するのに好適である純水からなる(加えて、湿り度の高い水蒸気の一部)。また、前記の混相流体は、任意でアルゴン、窒素等の不活性ガス、清浄高圧空気を含んでいてもよい。但し、アルミニウムの腐食防止の観点からは、任意ガスはアルゴンか不活性ガスであることが好適である。
図1は、本発明の一実施形態による対象物処理装置100の全体図である。本装置100は、水蒸気供給部(A)、純水供給部(B)、水蒸気流体調整部(C)、混相流体照射部(D)、ウェハ保持・回転・上下機構部(E)を有する構成である。以下、各部を詳述する。
水蒸気供給部(A)は、純水を供給するための水供給管111と、所定温度D1(℃)以上に加温して水蒸気を発生させ、水蒸気の発生量を制御して水蒸気を所定値C1(MP)に加圧する蒸気発生器112と、蒸気の供給及びその停止を司る開閉可能な水蒸気開閉バルブ113と、蒸気発生器112から下流に供給される水蒸気の圧力を計測するための圧力計114と、蒸気供給圧力を所望の値に調整するための水蒸気圧力調整バルブ115と、供給水蒸気内の微小液滴量を調整する温度制御機構付き加熱蒸気生成器兼飽和蒸気湿り度調整器116と、安全装置としての圧力開放バルブ117と、から構成される。
純水供給部(B)は、純水を供給するための水供給管121と、純水に熱エネルギーを持たせるための純水温度制御機構付加熱部122と、純水の供給の停止及び再開を司る純水開閉バルブ123と、純水の流量を確認するための純水流量計124と、2流体の場合に下流への純水の供給の停止及び再開を司る2流体生成用純水開閉バルブ125と、から構成される。
水蒸気流体調整部(C)は、水蒸気流体の温度や飽和水蒸気の湿り度を調整するための水蒸気流体温度制御機構付加熱部131を有している。
混相流体照射部(D)は、対象物に対して混相流体を照射するための、前後左右方向(図1のX軸ノズルスキャン範囲又はY軸ノズルスキャン範囲)に移動可能な照射ノズル141と、ノズルの移動を円滑に行うためのするためのフレキシブル配管142と、混相流体のノズル直前の圧力を計測するための圧力計143と、純水を蒸気配管に対して壁面に水膜を形成するように導入する気液混合部144と、純水が気体配管内に円滑に導入されるためのオリフィス145から構成される。ここで、ノズル141は、超高速ノズルである。「超高速ノズル」とは、液滴を音速以上に加速可能なノズルであれば、特に限定されないが、例えば、ソニックノズルが挙げられる。図30は、本最良形態に係るソニックノズル及び混合部の断面図である。ソニックノズルの形状は、特に限定されないが、ノズルの内部が、図面上方のノズル上流側から図面下方に位置するノズル出口へと向かうに従って急激に縮径し、更に、最小断面積A3となった位置(のど部)を境に、流体が内壁から剥離しないよう比較的ゆるやかに拡径し、ノズル出口で断面積がA2となる、末広ノズル構造を有する。のど部の断面積A3は、流量を音速で割り算して算出する。のど部の断面積A3は特に限定されないが、例えば、3.0~20.0mm2である。また、ひろがり率(A3/A2)は、下記の式1で示される式により算出される。
ウェハ保持・回転・上下機構部(E)は、対象物(ウェハ)を搭載・保持可能なステージ151と、ステージ151を回転させるための回転モーター152と、ステージ151を上下方向に移動させることによりノズル141の出口とウェハとの距離を調整可能なウェハ上下駆動機構153と、対象物(ウェハ)を冷却する冷却水を供給するための冷却水管154と、冷却水の供給を停止及び再開するための開閉可能な冷却水開閉バルブ155と、冷却水の流量を調整するための冷却水流量調整バルブ156と、冷却水の流量を計測するための冷却水流量計157と、から構成される。
2)液体流体の配管径又は配管に装着されたオリフィスが混合部で気体流体の流路の断面積に比較して十分小さいこと。
3)混合部にヒーターを組み込むことによって、混合部の内壁温度を以下の条件に適合するよう制御する。より内壁の温度が、混合部内の圧力下においてその液体の飽和温度から大きく外れないこと(±20%以内)。また、より内壁の温度が、混合部内の圧力下においてその気体の飽和温度から大きく外れないこと(±20%以内)。尚、時間経過により、混合部の内壁は流体の飽和温度に近づいてくるので、混相流の状態が安定するまでの時間が気にならない用途には、混合部の保温が十分に施されていることを条件下で、このヒーターによる加熱機能を外すことができる。
本最良形態に係る洗浄装置は、気体圧力、混相流体内の水混合流量、気体温度、混合される水の温度、ノズル形状、ノズル出口から対象物への距離、対象物の温度、ノズルと対象物間の相対的移動時間を調整することにより、液滴の温度、液滴の流速、液滴の大きさ、液滴の数、処理対象物表面の温度、単位時間当たりの混相流体照射面積を制御する機能を有する。これら気泡崩壊関連パラメータのうち、特に液滴の流速、温度、液滴密度が重要である。これらのパラメータを制御することにより、処理対象物表面上で、液滴によるジェットや気泡崩壊による衝撃波、前記衝撃波による連鎖反応の衝撃力を得ることができ、洗浄等において効果的な処理を行うことが出来る。流速は液滴が衝突時の液滴内の気泡の崩壊による衝撃波の発生に寄与し、温度は液滴内の気泡の発生に寄与する。また液滴密度が多いほど衝撃波の起きる確率が高まる。例えば、液滴の数が零であれば、液滴の衝突による衝撃波は生じない。但し、液滴の数が密になり過ぎても、混相流体の速度低下や温度低下をもたらして衝撃波発生確率が低下してしまう可能性がある。ここで、液滴密度とは、混相流体内の単位体積・時間当たりの総ての液滴数を示すが、高速で移動するμオーダーの微小液滴を正確に測定する測定器は未だ開発されていないため、混相流体に導入された純水量で代用するものとする。
本発明に係るシステムは、ある条件で混相流を対象物又は測定用サンプルに照射した上で、当該条件でどの程度のキャビテーションが発生しているかを測定するための測定手段を備えている。ここで、現在の技術では、キャビテーション(衝撃波)の大きさ(キャビテーションのマグニチュード)と密度(単位面積・時間当たりの発生数)をモニターしながら剥離・洗浄プロセスを行うことは不可能である。したがって、本システムでは、あらかじめの実験でキャビテーションの発生に関与するパラメータを変化させて、プロセス処理を行い、その結果得られた以下のデータからキャビテーションの大きさを判断する手法を採用している。
・金属表面に混相流体を照射したときの、金属表面の凸凹度
・レジスト表面に照射したときのレジスト剥離面積及び残渣の少なさ
・ウェハ全面に付着させた異物の除去率
(2)キャビテーションノイズの大きさを感知可能な音響的測定手段
・音響センサーで感知したキャビテーションノイズの大きさ
(3)対象物又は測定サンプルの視覚的変化を定量的に測定する視覚的変化測定手段
・高速度カメラで撮影したレジスト剥離過程の映像データ
本最良形態に係る対象物洗浄方法は、上記の衝撃力と共に、アルミニウム腐食防止効果を有する。ここでも、気体温度、混合される水の温度、ノズル形状、ノズル出口から対象物への距離、対象物の温度、ノズルと対象物間の相対的移動時間を調整することにより、腐食防止効果を制御することが可能である。これら関連パラメータのうち、特に、混相流体の対象物到達時の温度と、混相流体の対象物到達時のpHが重要である。これらのパラメータを制御することにより、アルミニウム表面上に、腐食防止効果を奏する特殊な保護膜を形成させることができる。以下、主要な気泡崩壊関連パラメータと共に、アルミニウム腐食防止に関連するパラメータについて詳述する。
当該衝撃波は、液滴が処理対象物表面に衝突した際に生じるキャビテーションとキャビテーションの崩壊により発生するものが主であると考えられる。キャビテーションは、水等の液体の一部に低圧部分が発生した際に生じる空洞であり、気体および液体の温度が高ければ高いほど発生しやすくなる傾向にある。即ち、液滴の温度が高ければ高いほど、水滴内での気泡が発生しやすくなり、それに伴い、処理対象物表面上では大きなエネルギーの衝撃波の基になる気泡崩壊が多く発生し、例えば、当該処理方法をレジスト膜の除去に用いる場合には、比較的強く接着しているレジスト膜や異物等を取り除くことができる。一方、混相流体や水滴の温度を低く設定すれば、それに伴い、処理対象物表面上では衝撃波の発生が抑えられ、比較的強度の弱い対象物の洗浄を行うことができる。但し、対象物の耐熱性による制限等で設定出来る温度の高さに制限が生じる。また、温度が高すぎる状態で対象物との距離が長くなると液滴内の気体成分が抜けてしまい気泡核が発生し難くなることが予想されるが、ノズル出口から対象物の距離が2~30mmくらいの距離では無視できるものとする。尚、ノズル内に供給する水蒸気の温度は、50~120℃が好適であり、80~115℃がより好適であり、90~110℃が更に好適である。また、前記水蒸気に対して混合する水の温度は0~40℃が好適であり、10~35℃がより好適であり、20~30℃が更に好適である。
液滴の速度は、高ければ高いほど処理対象物表面に液滴が衝突した際の衝撃が大きくなるため、内部圧力差が発生しやすくなり、結果として気泡崩壊が生じキャビテーションが発生しやすくなる。即ち、液滴の速度を高く設定すれば、それに伴い、処理対象物表面上では大きなエネルギーの衝撃波が発生し、例えば、当該処理方法をレジスト膜の除去に用いる場合には、比較的強く接着しているレジスト膜や異物等を取り除くことができる。一方、液滴の速度を低く設定すれば、それに伴い、処理対象物表面上では衝撃波の発生が抑えられ、比較的強度の弱い対象物の洗浄を行うことができる。また液滴の速度を高めることにより、混相流体はより空気に曝される時間が短くなるので、大気中の二酸化炭素を取り込みにくく、酸性に偏りにくくなるのでより好適に腐食防止効果が発揮される。液滴の速度は、100~600m/sであり、より好適には200~500m/sであり、更に好適には250~350m/sである。当該範囲の流体速度とすることにより、キャビテーションによる衝撃力を得ることができる。尚、液滴の速度は、流体の速度とほぼ一致するものとして、[流量]/[ノズル断面積]とする。尚、ここで、流量は水蒸気流量(m3/s)であり、ノズル断面積は、ノズル出口の断面積(m2)とする。
まず、ノズルに関しては、先述のように超高速ノズルを用いる。このノズルを用いることにより流体の流速が変わり衝撃波の大きさも変わる。原則として、流速の大きなノズルを使うと衝撃波を得やすくなる。また、水蒸気と水滴を含む混相流体を超高速ノズルを用いて照射することにより、水蒸気の圧力と、水滴の速度及び径との関係で、特殊な挙動が観測される。水蒸気圧は、0.05~0.25MPaであれば特に限定されないが、特に、水蒸気圧が0.15MPa以上の条件では、水蒸気と水滴の混相流体は、空気と水滴の混相流体と大きく異なる挙動を示す。次に、ノズル出口から対象物への距離に関しては、通常の適応値は2~30mmの範囲(最適範囲2~10mm)であり、5mm以下が好適であり、3mm以下がより好適であり、2mmがより好適である。ノズルの出口からウェハまでの距離を縮めていけば同様にレジスト剥離性能が向上するが、最適距離が存在し近づきすぎると剥離性能が低下する。逆に剥離性能・洗浄性能を抑えたい場合は最適距離から遠ざけていけばよい。また、ノズル出口から対象物への距離が近ければ近いほど、大気中の二酸化炭素を取り込みにくくなり、酸性に偏りにくくなる。
(水蒸気の圧力+0.02MPa)<(水導入の圧力)<(水蒸気の圧力+1.0MPa)
水導入の圧力が低すぎると、水は脈流で導入され、流体の特性が不安定になる。また、圧力が高すぎると、ノズル直径方向の中心部まで水が飛散するようになり、一様な水膜の形成が困難になるとともに、蒸気の加速も阻害される。また、噴射方向に加圧しないことが、壁面で水膜を形成するという観点から好適であり、水蒸気の進行方向に対して垂直方向から供給することが更に好適である。
図31は、混相流体の対象物到達時の温度測定を行う装置の概略図である。直径6インチ、厚さ0.625mmのシリコンウェハWの上にテープTAで熱電対TH(アルメル-クロメル熱電対 JIS C1602)を貼り付けて、ノズル141の流体噴射出口と対象物の距離や、水蒸気圧力や、純水流量等の諸条件を対象物処理時と同じ値に設定し1分間熱電対に対して照射を行い、定常状態になった際の温度を混相流体の対象物到達時の温度とする。
図32は、混相流体の対象物到達時のpHの測定を行う装置の概略図である。ノズル141の噴出口を、配管Pを介して冷却管C(例えば、グラハムタイプの陀管冷却管)に接続し、凝集した水を容器Rに回収し、当該水のpHをJIS Z 8802の方法により測定した。尚、前記の凝集作業は空気に触れないようにして行う。
以下の条件下、アルミ表面に混相流体(気体として蒸気を用いた場合と空気を用いた場合)を10分照射した。処理の前後におけるAFM写真を図3に示した。図5に表面粗さのデータを示した。尚、本例において表面粗さは、AFM付属のプロファイル分析の方法で測定した。
蒸気の圧力:0.2MPa
蒸気の温度:130℃
純水の流量:300cc/min
純水の温度:20℃
GAP:5mm
ノズルスキャン:固定
例1と同条件の下で、鋼表面に混相流体(気体として蒸気を用いた場合と空気を用いた場合)を10分照射した。処理の前後におけるAFM写真を図4に示した。図6に表面粗さのデータを示した。
特許文献1に示された蒸気洗浄技術は、蒸気の化学反応と噴流の機械的作用によりレジストを剥離するものであるため、レジストの剥離には分オーダの時間を必要とする。本手法も同様のメカニズムなのかを確認するため、高速度ビデオによる可視化を行った。ノズルスキャン速度が100mm/secであること以外は例1と同条件で、混相流体を照射し、石英ウェハの下部より観察した、i線ポジレジストが剥離する際の経時変化の様子を図7に示す。図に示されるように、レジストは、剥離した領域が徐々に広がりながら非常に高速に剥離した。
ノズルスキャン速度を40mm/secとした点以外は例1と同条件で、高濃度イオン注入後のシリコンウェハに対して混相流体を照射し、i線ポジレジスト剥離の経時変化の様子を観察した。結果を図8に示した。
以下の条件下、混相流体の気体及び温度を変化させて、アルミニウム表面に対して混相流体を10分照射した。処理の前後におけるAFM写真を図9に示した。図10に表面粗さのデータを示した。尚、照射前の処理対象のアルミニウムの表面は、Raが34.9nmであった。
気体圧力:0.2MPa
液体流量:300cc/min
Gap:10mm
Raが348.8nmのAlアルマイト表面に対して、例5~8と同条件で、混相流体の気体及び温度を変化させて照射した。20℃の空気と20℃の純水液滴からなる混相流体を照射した結果、Raが380nmの表面を得ることが出来た。表面のAFM写真を図11(a)に、表面粗さのデータを図11(c)に示した(例9)。次に、130℃水蒸気と20℃の純水液滴からなる混相流体を照射した結果、Raが440nmの表面が得られた。表面のAFM写真を図11(b)に、表面粗さのデータを図11(d)に示した(例10)。
Raが8.1nmのSUS表面に対して、例5~8と同条件で、混相流体の気体及び温度を変化させて照射した。130℃の水蒸気と20℃の純水液滴からなる混相流体を照射した結果、Raが19.9nmの表面が得られた。表面のAFM写真を図12(a)に、表面粗さのデータを図12(b)に示した(例11)。
Raが75.5nmのチタン表面に対して、例5~8と同条件で、混相流体の気体及び温度を変化させて照射した。130℃の水蒸気と20℃の純水液滴からなる混相流体を照射した結果、Raが98nmの表面を得ることが出来た。表面のAFM写真を図13(a)に、表面粗さのデータを図13(b)に示した(例12)。チタンでは、目視にて干渉縞が見られた。表面に酸化皮膜形成された可能性もある。
Raが1.9nmのシリコン表面に対して、例5~8と同条件で、混相流体の気体及び温度を変化させて照射した。130℃の水蒸気と20℃の純水液滴からなる混相流体を照射した結果、Raが7.6nmの表面を得ることが出来た。表面のAFM写真を図14(a)に、表面粗さのデータを図14(b)に示した(例13)。
例14~25では、レジスト塗布条件による剥離の様子に差があるか否かを検討した。HMDSの有無、Bake温度を90℃、110℃と変化させて、当該条件変化の影響を観察した。処理後の表面プロファイルは、下地処理HMDSに依存しないと考えられる結果が得られた。実験は以下の条件で行った。
使用サンプル:I線レジスト
照射時間:目視で剥離が観察されるまで
気体圧力:0.2MPa
液体流量:300cc/min
ノズルスキャン:固定
Gap:10mm
液滴径及び流速の関係を図19に示した。水蒸気圧力を一定(0.2MPa)として、様々な純水流量で、液滴の流速、液滴径を測定した。結果を図19に示した。PDAで計測した液滴速度v・径dの関係を示す。vとdは共に正規分布に近く、その平均はそれぞれ、280m/sと10μm程度であった。
図20に純水の流量q=100mL/minの場合のvとdに関して、蒸気圧力pおよびノズルとの距離hをパラメータとした際の結果を示す。また比較のため、空気と液滴の混合噴流の結果も点線にて示す。図より対象としている液滴速度は200~300m/s程度、液滴径は10μm程度であることがわかる。
水蒸気と水の混相流体と、空気と水の混相流体とを、水の流量を200cc/minとして、気体の圧力を0.05、0.1、0.2MPaと変化させてソニックノズルを用いて噴射し、LDA(Laser Doppler Anemometry:レーザドップラ流速計)にてその液滴の速度を噴出口から5、10mmの位置で測定した(図33)。尚、LDAの計測は、TSI社製のLDAにより行い、10000個の液滴のデータが取得できたら計測を終わりとし、各条件で3回測定した。水蒸気と水の混相流体を用いた場合には、5mmの位置よりも、10mmの位置の方が液滴の速度が高いことが観測された。また、空気と水の混相流体の場合、空気の圧力を高めれば高めるほど、液滴の速度が高くなる傾向がみられた。一方、水蒸気と水の場合、原因は不明であるが、水蒸気の圧力を高めれば、所定値までは液滴の速度が高くなることが観測されたが、0.2MPaでは、測定値によれば液滴速度が低くなった。しかし、これはエラーではないかと推測される。他の条件において、計測は10秒かからない程度であったが、水蒸気と水の混相流体で水蒸気圧0.2MPaの条件でのみ、計測に数分要した。従って、当該条件においてはほとんどノイズが観測されたものと推測できる。
水蒸気と水の混相流体と、空気と水の混相流体とを、水の流量を200cc/minとして、気体の圧力を0.05、0.1、0.2MPaと変化させてソニックノズルを用いて噴射し、PDAにてその液滴の径を噴出口から5、10mmの位置で測定した(図34)。尚、PDAの計測は、10000個の液滴のデータが取得できたら計測を終わりとし、各条件で3回測定した。空気と水の混相流体の場合、空気の圧力を変化させても、液滴の速度はほとんど変化しなかった。一方、水蒸気と水の場合、原因は不明であるが、水蒸気の圧力を高めれば、所定値までは液滴の径の変化はほとんど見られないが、0.2MPaにおいては、液滴の径が急激に小さくなるという現象が観測された。しかし、これはエラーではないかと推測される。他の条件において、計測は10秒かからない程度であったが、水蒸気と水の混相流体で水蒸気圧0.2MPaの条件でのみ、計測に数分要した。従って、当該条件においてはほとんどノイズが観測されたものと推測できる。
水蒸気圧0.1、0.2MPaの条件下で、純水流量を100cc/minとして、水蒸気と水の混相流体を石英ノズルを用いて噴射した。すると石英ノズルの先端に圧力波が観測された。その様子を図35に示した。尚、図35(a)は0,1MPaの条件での噴射の様子であり、図35(b)は0.2MPaの条件での噴射の様子である。また比較のため、気体圧力0.1、0.2MPaの条件下で、純水流量を100cc/minとして、空気と水の混相流体を石英ノズルを用いて照射した。しかし、石英ノズル先端には圧力波は観測されなかった。この様子を図36に示した。尚、図36(a)は0.1MPaの条件での噴射の様子であり、図36(b)は0.2MPaの条件での噴射の様子である。
最良形態に係るソニックノズル(図30)を有する洗浄装置を用いて、以下の条件の下で、対象物に水蒸気と水の混相流体を噴射して、その洗浄効果、物理破壊及び配線の耐腐食性を評価した(表1,2)。尚、対象物として、i線ネガレジスト(東京応化THMRip3300)を1μmの厚さで塗布し、90℃で120minベイクした後、365nmで20秒露光し、室温でTMAH([N(CH3)4]+OH―)により現像した、アルミニウム配線を有するシリコンウェハを使用した。
比較例1は流体温度が低すぎる場合である。流体温度が低すぎるとポリマーは除去されるが、10日後には配線が腐食された。
比較例2,比較例3は液滴速度が遅すぎる場合と速すぎる場合である。遅すぎるとポリマーが残存し、速過ぎると配線の物理的破壊がみられた。
比較例4,比較例5はpHが低すぎる場合と高すぎる場合である。pHが低すぎると保護膜が生成せず、10日後に配線の腐食がみられた。pHが高すぎるとpHが高いことによる配線の腐食が発生した。
111:水供給管
112:蒸気発生器
113:水蒸気開閉バルブ
114:圧力計
115:水蒸気圧力調整バルブ
116:温度制御機構付き加熱蒸気生成器兼飽和蒸気湿り度調整器
117:圧力開放バルブ
121:水供給管
122:純水温度制御機構付加熱部
123:純水開閉バルブ
124:純水流量計
125:2流体生成用純水開閉バルブ
131:水蒸気流体温度制御機構付加熱部
141:照射ノズル
142:フレキシブル配管
143:圧力計
144:温度制御機能付混相流体気液混合部
145:オリフィス
151:搭載・保持可能なステージ
152:回転モーター
153:ウェハ上下駆動機構
154:冷却水管
155:冷却水開閉バルブ
156:冷却水流量調整バルブ
157:冷却水流量計
Claims (10)
- 水蒸気と水とを混合部にて混合することにより生成する、連続相の水蒸気と分散相の水滴とを含む混相流体をノズルを介して照射する工程を含む、対象物を洗浄する方法において、
前記混合部が前記ノズルの上流側に設置されており、内壁面の一部が開口した水導入部を有し、
前記ノズルが、超高速ノズルであり、
前記混合部の内壁面とノズルの内壁面が略連続的な曲面を形成し、
前記混合部内を流動する前記水蒸気に対して前記混合部の内壁面から水を混合して、前記混合部の内壁面から前記ノズルの内壁面に水をつたわせて、前記ノズルの出口から前記混相流体を噴射することを特徴とする方法。 - 前記ノズルが、ノズル上流側からノズル出口へと向かうに従って縮径し、更に、最小断面積となるのど部を境に、拡径する末広構造を有する、請求項1記載の方法。
- 前記混合部が、筒状である、請求項1又は2記載の方法。
- 前記水滴の速度を100~600m/sの範囲とする、請求項1~3のいずれか一項記載の方法。
- 前記混相流体の対象物到達時の温度が50℃以上であり、前記混相流体の対象物到達時のpHが7~9の範囲である、請求項1~4のいずれか一項記載の方法。
- 更に、前記混相流体噴射出口と対象物の距離が、30mm以下である、請求項5記載の方法。
- 前記対象物が、アルミニウム配線等のアルミニウム素材を表面に有する半導体基板である、請求項1~6のいずれか一項記載の方法。
- 水蒸気を供給する水蒸気供給手段と、液体の水を供給する水供給手段と、混相流体を照射するノズルと、を有する、水蒸気と水滴とを含む混相流体をノズルを介して照射することにより対象物を洗浄するシステムにおいて、
前記混合部が前記ノズルの上流に設置されており、流動する前記水蒸気に対して内壁面から水を混合可能である、内壁面の一部が開口した水導入部を有し、
前記ノズルが、超高速ノズルであり、
前記混合部の内壁面とノズルの内壁面が略連続的な曲面を形成していることを特徴とするシステム。 - 前記ノズルが、ノズル上流側からノズル出口へと向かうに従って縮径し、更に、最小断面積となるのど部を境に、拡径する末広構造を有する、請求項8記載のシステム。
- 前記混合部が、筒状である、請求項8又は9記載のシステム。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980150527.XA CN102246281B (zh) | 2008-12-15 | 2009-11-19 | 对象物清洗方法及对象物清洗系统 |
US13/139,616 US20110247661A1 (en) | 2008-12-15 | 2009-11-19 | Method for cleaning object and system for cleaning object |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-318464 | 2008-12-15 | ||
JP2008318464A JP4413266B1 (ja) | 2008-12-15 | 2008-12-15 | 対象物洗浄方法及び対象物洗浄システム |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010071005A1 true WO2010071005A1 (ja) | 2010-06-24 |
Family
ID=41739272
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/069645 WO2010071005A1 (ja) | 2008-12-15 | 2009-11-19 | 対象物洗浄方法及び対象物洗浄システム |
Country Status (5)
Country | Link |
---|---|
US (1) | US20110247661A1 (ja) |
JP (1) | JP4413266B1 (ja) |
KR (1) | KR20110099130A (ja) |
CN (1) | CN102246281B (ja) |
WO (1) | WO2010071005A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7487912B2 (ja) | 2019-11-06 | 2024-05-21 | 有限会社浦野技研 | 固着物の除去方法 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5018847B2 (ja) * | 2009-08-31 | 2012-09-05 | 日立電線株式会社 | 金属部材の表面処理方法および表面処理装置 |
WO2012176060A1 (en) | 2011-06-23 | 2012-12-27 | Dynamic Micro Systems | Semiconductor cleaner systems and methods |
JP6232212B2 (ja) * | 2012-08-09 | 2017-11-15 | 芝浦メカトロニクス株式会社 | 洗浄液生成装置及び基板洗浄装置 |
CN103008299A (zh) * | 2012-11-30 | 2013-04-03 | 北京七星华创电子股份有限公司 | 一种气液两相雾化清洗装置及清洗方法 |
KR20160003636A (ko) * | 2013-05-08 | 2016-01-11 | 티이엘 에프에스아이, 인코포레이티드 | 헤이즈 소멸 및 잔류물 제거를 위한 수증기를 포함하는 프로세스 |
US9406525B2 (en) * | 2013-11-15 | 2016-08-02 | Taiwan Semiconductor Manufacturing Company Ltd. | Method for semiconductor manufacturing |
US9352263B2 (en) | 2013-12-27 | 2016-05-31 | Taiwan Semiconductor Manufacturing Co., Ltd. | Mechanisms for air treatment system and air treatment method |
JP5804131B1 (ja) * | 2014-04-16 | 2015-11-04 | 日油株式会社 | 爆薬の装填装置及びドリルジャンボ |
TWI595332B (zh) | 2014-08-05 | 2017-08-11 | 頎邦科技股份有限公司 | 光阻剝離方法 |
JP6472139B2 (ja) * | 2015-06-15 | 2019-02-20 | 富士フイルム株式会社 | オリフィス、及びこれを用いた送液装置、塗布装置、並びに光学フィルムの製造方法 |
CN105772290B (zh) * | 2016-05-11 | 2018-05-11 | 电子科技大学 | 一种超声雾化热解喷涂装置及其使用方法 |
CN109564861B (zh) * | 2016-07-29 | 2019-12-13 | 松下知识产权经营株式会社 | 微气泡清洗装置和微气泡清洗方法 |
KR102025983B1 (ko) * | 2017-05-11 | 2019-09-26 | 주식회사 뉴파워 프라즈마 | 세정장치 |
JP6639447B2 (ja) * | 2017-07-20 | 2020-02-05 | 本田技研工業株式会社 | ウォッシャ液供給システム |
TW202031374A (zh) * | 2018-11-30 | 2020-09-01 | 日商東京威力科創股份有限公司 | 基板清洗方法、處理容器清洗方法及基板處理裝置 |
JP7417191B2 (ja) * | 2020-01-30 | 2024-01-18 | セイコーエプソン株式会社 | 液体噴射装置 |
KR20210144116A (ko) * | 2020-05-21 | 2021-11-30 | 에스케이하이닉스 주식회사 | 마스크용 접착제 제거 장치, 마스크용 접착제 제거 시스템 및 방법 |
CN112845473A (zh) * | 2020-12-31 | 2021-05-28 | 苏州阿洛斯环境发生器有限公司 | 一种表面清洗装置 |
CA3153460A1 (en) | 2021-03-30 | 2022-09-30 | Kyata Capital Inc. | Systems and methods for removing contaminants from surfaces of solid material |
CN115283330A (zh) * | 2022-07-14 | 2022-11-04 | 江苏天工科技股份有限公司 | 一种钛合金板材的高压清洗固定装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1085634A (ja) * | 1996-09-12 | 1998-04-07 | Toshiba Corp | 噴流加工装置、噴流加工システムおよび噴流加工方法 |
JP2003126850A (ja) * | 2001-10-26 | 2003-05-07 | Kurita Water Ind Ltd | 有機物含有水の処理装置及び処理方法 |
JP2003249474A (ja) * | 2002-02-18 | 2003-09-05 | Lam Res Corp | 水供給装置および水供給方法 |
WO2006018948A1 (ja) * | 2004-08-20 | 2006-02-23 | Aqua Science Corporation | 対象物処理装置およびその方法 |
JP2008173628A (ja) * | 2006-12-18 | 2008-07-31 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | 微生物破砕装置 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4341869A1 (de) * | 1992-12-08 | 1994-06-09 | Flow Int Corp | Entfernung von harten Überzügen mit Ultrahochdruck-Flachstrahlen |
JP3865602B2 (ja) * | 2001-06-18 | 2007-01-10 | 大日本スクリーン製造株式会社 | 基板洗浄装置 |
JP2005216908A (ja) * | 2004-01-27 | 2005-08-11 | Aqua Science Kk | 対象物処理装置および対象物処理方法 |
-
2008
- 2008-12-15 JP JP2008318464A patent/JP4413266B1/ja active Active
-
2009
- 2009-11-19 CN CN200980150527.XA patent/CN102246281B/zh not_active Expired - Fee Related
- 2009-11-19 KR KR1020117016368A patent/KR20110099130A/ko not_active Application Discontinuation
- 2009-11-19 US US13/139,616 patent/US20110247661A1/en not_active Abandoned
- 2009-11-19 WO PCT/JP2009/069645 patent/WO2010071005A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1085634A (ja) * | 1996-09-12 | 1998-04-07 | Toshiba Corp | 噴流加工装置、噴流加工システムおよび噴流加工方法 |
JP2003126850A (ja) * | 2001-10-26 | 2003-05-07 | Kurita Water Ind Ltd | 有機物含有水の処理装置及び処理方法 |
JP2003249474A (ja) * | 2002-02-18 | 2003-09-05 | Lam Res Corp | 水供給装置および水供給方法 |
WO2006018948A1 (ja) * | 2004-08-20 | 2006-02-23 | Aqua Science Corporation | 対象物処理装置およびその方法 |
JP2008173628A (ja) * | 2006-12-18 | 2008-07-31 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | 微生物破砕装置 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7487912B2 (ja) | 2019-11-06 | 2024-05-21 | 有限会社浦野技研 | 固着物の除去方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4413266B1 (ja) | 2010-02-10 |
CN102246281B (zh) | 2015-06-17 |
KR20110099130A (ko) | 2011-09-06 |
US20110247661A1 (en) | 2011-10-13 |
CN102246281A (zh) | 2011-11-16 |
JP2010141251A (ja) | 2010-06-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4413266B1 (ja) | 対象物洗浄方法及び対象物洗浄システム | |
JP6501191B2 (ja) | マイクロ・ナノバブルによる洗浄方法及び洗浄装置 | |
JP3315611B2 (ja) | 洗浄用2流体ジェットノズル及び洗浄装置ならびに半導体装置 | |
KR101146853B1 (ko) | 강판의 세정 방법 및 강판의 연속 세정 장치 | |
US9070722B2 (en) | System and method for the sonic-assisted cleaning of substrates utilizing a sonic-treated liquid | |
Kim et al. | Visualization and minimization of disruptive bubble behavior in ultrasonic field | |
JP2007027270A (ja) | 洗浄装置及び洗浄方法 | |
JP6153110B2 (ja) | 一成分極低温微細固体粒子連続生成装置、および、その一成分極低温微細固体粒子連続生成方法 | |
Lang et al. | Near field induced defects and influence of the liquid layer thickness in Steam Laser Cleaning of silicon wafers | |
JPWO2008152717A1 (ja) | ピーニング加工による金属材料の表面改質方法及びそのシステム | |
Jiao et al. | Role of volatile liquids in debris and hole taper angle reduction during femtosecond laser drilling of silicon | |
JP2007173785A5 (ja) | ||
TWI469832B (zh) | 對象物清洗方法及對象物清洗系統 | |
JPWO2008153107A1 (ja) | 対象物洗浄方法及び対象物洗浄システム | |
KR20060136339A (ko) | 기판세정장치 및 기판세정방법 | |
JP6536884B2 (ja) | マイクロ・ナノバブルを利用した金属表面の改質方法及び金属と樹脂との接着方法 | |
JP2010070779A (ja) | 脱泡装置、気泡除去方法、めっき方法、および微少金属構造体 | |
WO2010097896A1 (ja) | 洗浄用ノズル及び洗浄方法 | |
KR101988116B1 (ko) | 미세 버블을 이용한 세정 시스템 및 방법 | |
TWI362066B (ja) | ||
Kashkoush et al. | Submicron particle removal using ultrasonic cleaning | |
JP2003209088A (ja) | エアロゾル洗浄方法及び装置 | |
Watanabe et al. | Cleaning technique using high-speed steam-water mixed spray | |
JP2002012990A (ja) | 金属被加工物表面のキャビテーションによる耐食処理法およびキャビテーション浸食の低減方法及び耐食性およびキャビテーション浸食防止性を向上させる加工処理をした加工物 | |
TW201343263A (zh) | 對象物洗淨系統及對象物洗淨方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980150527.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09833310 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13139616 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117016368 Country of ref document: KR Kind code of ref document: A |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 23.08.2011) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09833310 Country of ref document: EP Kind code of ref document: A1 |