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WO2025234055A1 - Système et procédé de traitement - Google Patents

Système et procédé de traitement

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Publication number
WO2025234055A1
WO2025234055A1 PCT/JP2024/017266 JP2024017266W WO2025234055A1 WO 2025234055 A1 WO2025234055 A1 WO 2025234055A1 JP 2024017266 W JP2024017266 W JP 2024017266W WO 2025234055 A1 WO2025234055 A1 WO 2025234055A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
filter
flow path
liquid
pfas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/017266
Other languages
English (en)
Japanese (ja)
Inventor
真二 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Electron Ltd
Original Assignee
Tokyo Electron Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Electron Ltd filed Critical Tokyo Electron Ltd
Priority to PCT/JP2024/017266 priority Critical patent/WO2025234055A1/fr
Publication of WO2025234055A1 publication Critical patent/WO2025234055A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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

  • This disclosure relates to a processing system and a processing method.
  • Patent Document 1 describes a wastewater treatment system that includes a treatment device that reduces the content of organic fluorine compounds, etc., an anion exchange building filled with ion exchangers including anion exchangers, and a decomposition device that decomposes the regenerated liquid that has circulated through the anion exchange building.
  • This disclosure provides a treatment system and method that can smoothly detoxify organic fluorine compounds.
  • a processing system includes a concentrating unit that concentrates waste liquid containing organic fluorine compounds discharged from semiconductor manufacturing equipment, and a chemical processing unit that decomposes and volatilizes the concentrated liquid concentrated by the concentrating unit.
  • This disclosure makes it possible to smoothly detoxify organic fluorine compounds.
  • FIG. 1 is a schematic diagram of a PFAS detoxification system according to an embodiment of the present invention.
  • FIG. 2 is a block diagram of the PFAS detoxification system shown in FIG. 1.
  • FIG. 1 is a diagram illustrating the filtration of a liquid containing PFAS.
  • FIG. 10 is a diagram illustrating cleaning of a filter by backflowing filtrate.
  • FIG. 1 is a diagram illustrating gas separation.
  • FIG. 2 is a diagram illustrating the function of a gas filter.
  • FIG. 10 is a diagram illustrating separation of taken-in outside air.
  • FIG. 2 is a diagram illustrating concentration and decomposition of a positive developer.
  • FIG. 10 is a diagram illustrating cleaning of a filter by backflowing filtrate.
  • FIG. 10 is a diagram illustrating the discharge of SPM waste liquid.
  • FIG. 10 is a diagram illustrating cleaning of a filter with SPM waste liquid.
  • FIG. 10 is a diagram illustrating a decomposition processing chamber according to
  • the processing system is a PFAS detoxification system 1 that detoxifies PFAS discharged from semiconductor manufacturing equipment 100.
  • Figure 1 shows an outline of the configuration of the PFAS detoxification system 1, and some components (for example, the components related to TMAH (tetramethylammonium hydroxide) waste liquid, which will be described later) are not shown.
  • PFAS refers to per- and polyfluoroalkyl substances (PFAS: Per- and PolyFluoroAlkyl Substances), which are organic fluorine compounds.
  • PFAS is a compound containing at least one aliphatic molecule of -CF2- or -CF3, and includes organic polymers such as Teflon.
  • PFAS is found, for example, in fire extinguishing foams, plating solutions, aircraft hydraulic fluids, water repellents, and floor waxes.
  • PFAS is also found, for example, in textiles, medical products, electronic circuit boards, automobiles, food packaging, stone, flooring, and leather.
  • non-polymer PFAS is used in photoresists, for example.
  • Polymer PFAS is also used in liquid-contacting components such as piping, valves, and pumps in semiconductor manufacturing equipment, as well as in anti-reflective coatings.
  • the PFAS detoxification system 1 of this embodiment is a system that detoxifies PFAS discharged from semiconductor manufacturing equipment 100, thereby preventing PFAS from being discharged to the outside.
  • the PFAS detoxification system 1 is configured to include a concentrator 11 (concentration section, waste liquid storage section), a sulfuric acid treatment tank 12 (chemical treatment section, decomposition treatment section), a cooler 13 (collection section), and a detoxification device 14 (combustion detoxification device). While this embodiment describes the PFAS detoxification system 1 as a group of devices, the PFAS detoxification system 1 may also be configured as a single device. Furthermore, the semiconductor manufacturing equipment 100 is configured to include a lithography device 111, a cleaning device 112, an etching device 113, and a film deposition device 114. Each component of the semiconductor manufacturing equipment 100 discharges substances containing PFAS as it performs processing.
  • the processing sections that make up the PFAS detoxification system 1 may or may not be installed in the same space (location).
  • each processing unit may be installed inside the building in which the lithography apparatus 111, cleaning apparatus 112, or etching apparatus 113 is installed, or may be installed outside the building or in an adjacent space.
  • Each processing unit may be installed separately, one inside the building and the other outside the building.
  • sulfuric acid treatment tank 12, cooler 13, and detoxification apparatus 14 those that are not in use do not need to be installed all the time.
  • the lithography system 111 includes a coating/developing system and an exposure system.
  • the exposure system performs exposure processing on the resist film. Specifically, it irradiates the exposure target portion of the resist film (photosensitive coating) with energy rays using methods such as immersion exposure.
  • the coating/developing system forms a resist film on the surface of the substrate before exposure processing by the exposure system, and then develops the resist film after exposure processing.
  • PFAS is contained in the liquids and gases discharged from the lithography system 111.
  • PFAS is contained in resist waste liquid, alkaline waste liquid (positive developer) from development processing, acid waste liquid from resist stripping, organic exhaust, thermal exhaust, solidified sublimate, etc.
  • organic solvent waste liquid from negative development processing can be considered extremely diluted resist waste liquid, and contains PFAS. In this embodiment, it may be treated the same as the resist waste liquid described above.
  • PFAS contained in resist waste liquid and PFAS contained in positive developer will be mainly described.
  • Examples of PFAS contained in resist waste liquid include photo acid generators (PAGs), surfactants, and F-modified polymers.
  • Resist waste liquid discharged from the lithography equipment 111 is introduced into the concentrator 11 of the PFAS detoxification system 1.
  • the cleaning device 112 performs cleaning processing on substrates.
  • the cleaning device 112 uses SPM (Sulfuric Acid Hydrogen Peroxide Mixture), a mixture of H2O2 and sulfuric acid, to remove organic matter such as resist.
  • the cleaning device 112 uses a mixed aqueous solution (SC2: Standard Clean 2) of H2O2 and hydrochloric acid to remove metals, and a mixed aqueous solution (SC1) of H2O2 and ammonia to remove particles.
  • Hot concentrated sulfuric acid alone is also produced during waste liquid treatment.
  • the cleaning device 112 discharges SPM waste liquid containing PFAS.
  • the SPM waste liquid and hot concentrated sulfuric acid discharged from the cleaning device 112 are introduced into the sulfuric acid treatment tank 12.
  • the cleaning device 112 also discharges acid waste gas containing PFAS.
  • the acid waste gas discharged from the cleaning device 112 is introduced into the detoxification device 14.
  • the etching device 113 performs an etching process to remove the oxide film and thin film according to the pattern of the formed resist film.
  • the etching device 113 discharges exhaust gas containing PFAS.
  • the exhaust gas discharged from the etching device 113 is introduced into the detoxification device 14.
  • the film forming device 114 forms wiring films and insulating films on the substrate.
  • the film forming device 114 uses various process gases (PFAS-containing or non-containing gases) and emits exhaust gases.
  • PFAS-containing or non-containing gases process gases
  • the exhaust gases emitted from the film forming device 114 are introduced into the detoxification device 14.
  • the concentrator 11 concentrates the PFAS-containing resist waste liquid discharged from the lithography tool 111 of the semiconductor manufacturing equipment 100. That is, the concentrator 11 concentrates the substrate processing waste liquid in the lithography tool 111 as a PFAS-containing waste liquid.
  • the concentrator 11 uses, for example, an ultrafiltration membrane or a reverse osmosis membrane to concentrate the resist waste liquid and separate the solvent contained in the resist waste liquid (details will be described later).
  • the concentrated resist waste liquid is a concentrated liquid containing polymer, and therefore has a high viscosity.
  • the concentrated resist waste liquid is introduced into the sulfuric acid treatment tank 12. Note that when the alkaline waste liquid discharged from the lithography tool 111 is concentrated by the concentrator 11, the alkaline waste liquid may be introduced into the reverse osmosis membrane after being neutralized.
  • the solvent separated from the resist waste liquid may be used as recycled solvent for purposes such as cup cleaning in semiconductor manufacturing equipment 100, or may be collected by a solvent recovery company.
  • solvent recovery companies attempt to refine recycled solvent from resist waste liquid by analyzing its components, there is a risk that they may also recover waste liquid containing confidential materials held by the resist manufacturer.
  • the solid components are contained in the concentrated liquid, preventing confidential information from being leaked to the solvent recovery company.
  • the sulfuric acid treatment tank 12 decomposes and volatilizes the concentrated liquid concentrated by the concentrator 11 using the SPM waste liquid.
  • the sulfuric acid treatment tank 12 utilizes the SPM waste liquid from the cleaning device 112.
  • the solvent and polymer undergo oxidation and dehydration decomposition reactions, resulting in lower molecular weights (lower viscosity).
  • the temperature of the SPM waste liquid rises due to the exothermic reaction (the temperature of the hot concentrated sulfuric acid in the SPM waste liquid rises).
  • SPM waste liquid is treated by adding catalase to prevent foaming.
  • the sulfuric acid treatment tank 12 reacts with organic matter to use up the H2O2 components and degas the SPM waste liquid, foaming does not occur in the downstream sulfuric acid waste liquid, making treatment easier.
  • the amount of catalase can be reduced. This reaction generates heat, for example, at approximately 300°C. This reaction can be used for temperature-difference power generation using the exhaust heat, or for steam generation using steam generated from the circulating water used to cool the sulfuric acid treatment tank 12.
  • the sulfuric acid waste liquid discharged from the sulfuric acid treatment tank 12 is recovered, for example, by a recycling company.
  • This sulfuric acid waste liquid has a higher sulfuric acid purity than conventional waste liquids.
  • the sulfuric acid treatment tank 12 is preferably operated in an inert nitrogen atmosphere to prevent accidental ignition.
  • the SPM waste liquid may also be hot concentrated sulfuric acid waste liquid.
  • hot concentrated sulfuric acid a dehydration decomposition reaction occurs in the solvent and polymer, resulting in a lower differentiation (lower viscosity).
  • the temperature of the hot concentrated sulfuric acid increases due to an exothermic reaction, volatilizing PFAS, PAG, and other compounds.
  • the sulfuric acid treatment tank 12 As concentrated resist waste liquid is added to the SPM waste liquid stored in the sulfuric acid treatment tank 12 and treated, H2O2 is gradually consumed, resulting in a decrease in treatment capacity. After an appropriate amount of concentrated resist waste liquid is supplied, the sulfuric acid treatment tank 12 is placed on standby until the reaction calms down and gas generation ceases. Because a large amount of SPM waste liquid is produced from the cleaning device 112, it is necessary to treat this waste liquid without delay. For this reason, the sulfuric acid treatment tank 12 may be composed of multiple treatment tanks. In this case, while one treatment tank is being treated, preparations such as the injection of liquid may be made in other treatment tanks. Furthermore, liquid may be flowed downstream, depending on the progress of the reaction, from the first treatment tank, then the second treatment tank, and then the third treatment tank. Note that if the resist waste liquid is a metal-containing resist, the metal components precipitate without volatilization and are treated together with the sulfuric acid waste liquid in the same processes as those described above.
  • SPM waste liquid contains hydrogen peroxide, so if it is disposed of as waste liquid, it may foam, putting a strain on the equipment, or the foaming gas may cause environmental damage.
  • the configuration of this embodiment makes effective use of the remaining hydrogen peroxide, and the foaming gas is also burned as fuel in the detoxification device 14, thereby reducing the burden on the equipment and the environment.
  • the cooler 13 liquefies and collects the PFAS-containing gas volatilized by the sulfuric acid treatment tank 12.
  • the cooler 13 separates and collects the gas into low-molecular-weight gases, which are gaseous components, and hydrocarbon (HC) extract, which is a liquid component.
  • HC hydrocarbon
  • the gas from the sulfuric acid treatment tank 12 is cooled in the cooler 13, and the liquefied gas is collected as HC (hydrocarbon) extract, and the low-molecular-weight gas that did not condense is also collected.
  • the gas generated from the sulfuric acid treatment tank 12 is treated in a nitrogen atmosphere, so it is a mixed gas with nitrogen. Mixed gases containing a large amount of nitrogen require a large amount of processing in the subsequent detoxification device 14. Therefore, for example, the low-molecular-weight gas that did not condense in the cooler 13 may be separated into nitrogen and other components using a nanosubceramic filter and concentrated.
  • PFAS such as PAG are also discharged as gases. While it is possible to introduce these gases directly into the detoxification device 14, transportability can be improved for gases that are liquid at room temperature by first liquefying them in the cooler 13. Note that if the gases are transported without being liquefied, liquid may accumulate in the piping, making control difficult. PFAS are contained in both the liquefied HC extract and the uncondensed low-molecular-weight gas. The HC extract and low-molecular-weight gas are introduced into the detoxification device 14. Note that to further improve gas transportability, all gases, including the low-molecular-weight gas, may be liquefied before being introduced into the detoxification device.
  • the detoxification device 14 detoxifies the substances after treatment by the cooler 13.
  • the detoxification device 14 may be a combustion detoxification device that detoxifies the substances after treatment by the cooler 13 by combustion.
  • the detoxification device 14 incinerates the HC extract and low molecular weight gases introduced from the cooler 13.
  • Most HC extracts are hydrocarbons, so they can be burned as fuel.
  • Most low molecular weight gases are hydrocarbons with a carbon number of 10 or less, so they can also be burned as fuel.
  • combustion detoxification devices have used propane gas or city gas as fuel, but as the HC extract, etc. is used as fuel as described above, the amount of propane gas, etc. can be reduced.
  • the detoxification device 14 may simultaneously combust and detoxify the exhaust gas introduced from the etching device 113, the exhaust gas introduced from the film formation device 114, and the acid waste gas introduced from the cleaning device 112. These gases are exhaust gases containing PFAS used in each device. By simultaneously combusting and detoxifying these gases, the amount of propane gas and other gases can be further reduced. During combustion and detoxification, electricity may be generated by burning them using an internal combustion engine such as a gas turbine. Detoxified gases such as carbon dioxide may be recovered and used to synthesize organic substances such as formic acid and methanol.
  • the detoxification device 14 may also be a subcritical treatment device that performs subcritical treatment on materials treated by the cooler 13, or a supercritical treatment device that performs supercritical treatment.
  • the detoxified waste gas may also be passed through a scrubber device (a device that washes the exhaust gas with water, neutralizes it with chemicals, or adsorbs it and releases it into the atmosphere) to process it into scrubber water containing F ions and waste gas.
  • This scrubber water can be reacted with calcium to produce calcium fluoride or fluorite. Fluorite is the starting material for fluorine compounds, making it a resource that can be recycled.
  • Figure 2 is a configuration diagram of the PFAS detoxification system 1 shown in Figure 1.
  • Figure 2 also illustrates configurations that are omitted from Figure 1 (such as the configuration related to TMAH waste liquid).
  • the PFAS detoxification system 1 further includes a waste liquid supply path 15 (second supply path), a circulation path 16 (first path), a first filtrate path 17 (second path), a second filtrate path 18 (fourth path), a third filtrate path 19 (third path), a first reservoir 20x, and a second reservoir 20y.
  • the PFAS detoxification system 1 further includes a bypass path 21.
  • the PFAS detoxification system 1 further includes a first gas filter 22, a vacuum pump 23, and a distiller 24.
  • the PFAS detoxification system 1 further includes a second gas filter 25.
  • the PFAS detoxification system 1 further includes a waste liquid supply path 26 (first supply path), a concentrator 27 (developer concentrating section), a circulation path 28, a developer path 29, a recycled developer storage section 30, a developer treatment tank 31 (chemical treatment section), a third gas filter 32, and a generator 33.
  • the PFAS detoxification system 1 further includes a bypass path 34, a backflow liquid storage section 35, and a recovery path 36.
  • the PFAS detoxification system 1 further includes a discharge path 37.
  • the PFAS detoxification system 1 further includes an SPM supply path 38.
  • FIG 3 is a diagram explaining the filtration of resist waste liquid, which is a liquid containing PFAS.
  • the concentrator 11 concentrates the resist waste liquid containing PFAS discharged from the lithography apparatus 111.
  • the circulation flow path 16 is a circulation flow path connected to the concentrator 11, and a filter 39 (first filter) that removes polymers is provided midway through the flow path.
  • the filter 39 is, for example, a hollow fiber filter.
  • the provision of the filter 39 concentrates the resist waste liquid.
  • the filtrate (solvent) that passes through the filter 39 flows through the first filtrate flow path 17 and is stored in the first reservoir 20x (filtrate reservoir). Such filtrate is a low-concentration PFAS solution.
  • the first reservoir 20x is a reservoir connected to the first filtrate flow path 17 and stores the filtrate.
  • the second filtrate flow path 18 (filtrate reservoir) is a flow path that connects the first reservoir 20x and the second reservoir 20y.
  • a filter 40 (second filter) is provided in the second filtrate flow path 18.
  • the filter 40 is, for example, an ion exchange resin filter.
  • FIG. 4 is a diagram illustrating cleaning of filter 39 by backflowing filtrate. It is conceivable that filter 39 may become clogged with polymer components and the like over time. To eliminate such clogging, filtrate flowing through third filtrate flow path 19 may be introduced into filter 39 from its outlet side. That is, a bypass flow path 21 may be provided to connect third filtrate flow path 19 and first filtrate flow path 17, and by pressurizing the filtrate in bypass flow path 21, the filtrate may be reversed in first filtrate flow path 17 and introduced into circulation flow path 16 from the outlet side of filter 39. Such liquid pressurization may be achieved, for example, by gas pressure or by a liquid delivery unit such as a pump. By using filtrate to reverse flow through filter 39, it is possible to unclog and refresh filter 39. The reversed filtrate may also be the filtrate flowing through second filtrate flow path 18.
  • Figure 5 is a diagram explaining gas separation.
  • the concentrated liquid concentrated by the concentrator 11 is decomposed and volatilized with SPM waste liquid in the sulfuric acid treatment tank 12. This causes decomposition reactions such as oxidation and dehydration, resulting in decomposition into gases containing carbon monoxide, carbon dioxide, nitrogen, water vapor, hydrocarbon gases, and PFAS.
  • the gas released in this case reaches a temperature of 100°C or higher.
  • the gas volatilized in the sulfuric acid treatment tank 12 is then separated by the first gas filter 22.
  • the first gas filter 22 is a filter that separates the gas volatilized in the sulfuric acid treatment tank 12 into PFAS-rich gas and gas from which PFAS has been removed.
  • the first gas filter 22 is, for example, a pervaporation filter, and may also be a ceramic filter.
  • the first gas filter 22 is heated to a temperature higher than that of the concentrated liquid before decomposition due to the heat generated in the sulfuric acid treatment tank 12.
  • the first gas filter 22 may be disposed in the same space as the sulfuric acid treatment tank 12, or may be connected to the sulfuric acid treatment tank 12 by a conductive member such as metal, thereby receiving heat generated in the sulfuric acid treatment tank 12.
  • PFAS-rich gas refers to gas in which the PFAS concentration is higher than in gas before being affected by the predetermined action.
  • separation by the first gas filter 22 corresponds to the predetermined action.
  • the predetermined action is not limited to separation by the first gas filter 22; if PFAS-rich gas is generated, the action that causes it to be generated can be considered the predetermined action.
  • Figure 6 is a diagram explaining the function of the first gas filter 22 when a pervaporation filter is used as the first gas filter 22.
  • the first gas filter 22 which is a pervaporation filter, is a filter that separates gases by utilizing differences in momentum due to differences in molecular weight. That is, by reducing the pressure on the downstream side, for example, the first gas filter 22 allows gases with relatively small molecular weights (nitrogen, carbon monoxide, carbon dioxide, water vapor, etc.) to pass (flow downstream) while preventing gases with relatively large molecular weights (PFAS, hydrocarbons) from passing. This makes it possible to roughly separate PFAS-rich gas from gas from which PFAS has been removed.
  • gases with relatively small molecular weights nitrogen, carbon monoxide, carbon dioxide, water vapor, etc.
  • PFAS gases with relatively large molecular weights
  • the vacuum pump 23 is a pump that reduces the pressure downstream of the first gas filter 22, achieving the gas separation by the first gas filter 22 described above.
  • the cooler 13 liquefies and collects the gas containing PFAS.
  • the collected liquid and gas are stored in the distiller 24.
  • the liquid PFAS and hydrocarbons, as well as the gaseous PFAS and hydrocarbons (and ozone, described below) are introduced from the distiller 24 into the detoxification device 14.
  • FIG 7 is a diagram explaining the separation of taken-in outside air.
  • the PFAS detoxification system 1 takes in outside air and separates it into nitrogen and oxygen using the second gas filter 25. That is, the second gas filter 25 separates the outside air into a first diverted gas (hereinafter simply referred to as nitrogen) having a higher nitrogen concentration than air, and a second diverted gas (hereinafter simply referred to as oxygen) having a higher oxygen concentration than air.
  • the second gas filter 25 then supplies the nitrogen to the sulfuric acid treatment tank 12. This prevents ignition in the sulfuric acid treatment tank 12.
  • the second gas filter 25 also supplies oxygen to the detoxification device 14. This promotes combustion in the detoxification device 14.
  • the detoxification device 14 may be supplied with ozone generated from the oxygen described above. Such ozone may be supplied to the distiller 24 and introduced into the detoxification device 14, or may be introduced directly into the detoxification device 14. Methods for generating ozone from oxygen include, for example, UV irradiation or electrical discharge.
  • FIG 8 is a diagram explaining the concentration and decomposition of a positive developer.
  • TMAH waste liquid which is a positive developer
  • the TMAH waste liquid discharged from the lithography apparatus 111 of the semiconductor manufacturing equipment 100 is concentrated in the concentrator 27.
  • the first concentrated liquid which is a concentrated liquid of the positive developer concentrated by the concentrator 27, is decomposed and volatilized in the developer treatment tank 31.
  • the waste liquid supply path 26 is a supply path that supplies TMAH waste liquid introduced from the lithography device 111 to the concentrator 27.
  • the waste liquid supply path 26 and the waste liquid supply path 15, which supplies resist waste liquid to the concentrator 11, are provided separately.
  • the waste liquid supply path 26 is provided with a filter 41 that removes polymers.
  • the circulation path 28 is a circulation path connected to the concentrator 27, and is provided with a filter 42 midway through the path to increase the concentration of PFAS.
  • the developer that passes through the filter 42 (PFAS-free developer) passes through the developer path 29 and is stored in the recycled developer storage section 30. This type of developer can be used as recycled developer.
  • the concentrated solution (developer with a high concentration of PFAS) concentrated in the concentrator 27 is supplied to the developer treatment tank 31 via the concentrated solution flow path 45.
  • the developer treatment tank 31 is provided in contact with the sulfuric acid treatment tank 12 (a decomposition processing unit for the second concentrated solution, which has a higher resist concentration than the first concentrated solution, which is a concentrated solution of a positive developer) described above.
  • the developer treatment tank 31 is provided so as to surround the sulfuric acid treatment tank 12 from below. This allows the developer treatment tank 31 to receive heat from the sulfuric acid treatment tank 12, which can decompose and volatilize the first concentrated solution.
  • the method for decomposing the first concentrated solution is not limited to heat; for example, the first concentrated solution may be decomposed by exposure to microorganisms.
  • the first concentrated solution may also be used as a cooling solvent for the SPM in the sulfuric acid treatment tank 12.
  • TMAH decomposed by heat breaks down into trimethylamine and dimethyl ether. These gases can be used as fuel in the detoxification device 14.
  • PFAS is not decomposed by heat and is released as a gas, which is burned in the detoxification device 14.
  • the gas released from the developer treatment tank 31 contains nitrogen, water vapor, hydrocarbons, trimethylamine, dimethyl ether, PFAS, etc.
  • the third gas filter 32 reduces the pressure downstream, allowing gases with relatively small molecular weights (nitrogen, water vapor, etc.) to pass (flow downstream) while blocking gases with relatively large molecular weights (trimethylamine, dimethyl ether, PFAS, hydrocarbons).
  • PFAS-rich gas This allows the PFAS-rich gas to be largely separated from the gas from which PFAS has been removed. Nitrogen, water vapor, etc. are released outside the system. The released water vapor is converted back into water in the generator 33, allowing electricity to be generated using the pressure difference.
  • the gas containing PFAS and the like sent to the detoxification device 14 may be compressed before being sent to the detoxification device 14.
  • the detoxification device 14 may have a combustion chamber that mixes and burns gas associated with the first concentrated liquid vaporized by the developer treatment tank 31 and gas associated with the second concentrated liquid vaporized by the sulfuric acid treatment tank 12.
  • FIG. 9 illustrates cleaning of filter 41 by backflowing filtrate. It is conceivable that filter 41 may become clogged with polymer components and the like over time. To eliminate such clogging, filtrate flowing through third filtrate flow path 19 may be introduced into filter 41 from its outlet side. Specifically, a bypass flow path 34 is provided that is connected to bypass flow path 21, which is connected to third filtrate flow path 19, and is connected downstream of filter 41 in waste liquid supply path 26. The filtrate in bypass flow path 34 may be pressurized to cause the filtrate to flow back through waste liquid supply path 26 and to flow into filter 41 from its outlet side. This liquid pressurization may be achieved, for example, by gas pressure or by a liquid delivery unit such as a pump.
  • the filtrate to be backflowed may be the filtrate flowing through second filtrate flow path 18. Because polymer removal by filter 41 is not possible during this filter cleaning, multiple filters 41 may be configured in parallel (multiple configurations).
  • the backflow liquid storage section 35 is connected to the concentrator 11 by a recovery flow path 36.
  • the recovery flow path 36 is a flow path that sends backflow liquid from the backflow liquid storage section 35 to the concentrator 11.
  • FIG 10 is a diagram explaining the discharge of SPM waste liquid.
  • the hydrogen peroxide in the SPM is deactivated, significantly reducing its reactivity.
  • the SPM becomes concentrated sulfuric acid, and although a dehydration reaction can occur, carbonization of the organic matter progresses, causing the liquid to turn yellow or brown. Therefore, for example, when the liquid turns yellow, the SPM waste liquid is discharged from the discharge flow path 37. At this time, carbonized matter is filtered out by a filter 43 installed in the discharge flow path 37.
  • the discharged SPM waste liquid is free of hydrogen peroxide, and the purity of the sulfuric acid has been increased by filtering through the filter 43, so it can be used as recycled sulfuric acid.
  • FIG 11 is a diagram illustrating the cleaning of filter 43 with SPM waste liquid.
  • part of the SPM waste liquid can be introduced into filter 43 from the outlet side to clean filter 43, which traps carbonized matter.
  • SPM waste liquid by flowing SPM waste liquid into a flow path connected to the outlet of filter 43 within SPM supply path 38, which supplies new SPM waste liquid to sulfuric acid treatment tank 12, the SPM waste liquid can be made to react with the carbonized matter trapped in filter 43.
  • the carbonized matter trapped in filter 43 becomes carbon dioxide, which is exhausted, and filter 43 is cleaned.
  • the PFAS detoxification system 1 of this embodiment includes a concentrator 11 that concentrates PFAS-containing resist waste liquid discharged from the lithography tool 111 of the semiconductor manufacturing equipment 100.
  • the PFAS detoxification system 1 also includes a sulfuric acid treatment tank 12 that decomposes and volatilizes the concentrated liquid concentrated by the concentrator 11.
  • the concentrated liquid is decomposed and volatilized. As a result, polymers, solvents, etc. are broken down into smaller molecules through the decomposition reaction of the dehydration reaction, and PFAS is volatilized.
  • This PFAS detoxification system 1 allows for smooth detoxification of PFAS.
  • the sulfuric acid treatment tank 12 may decompose and volatilize the concentrated liquid using a liquid containing hot, concentrated sulfuric acid. In this way, by mixing the concentrated liquid with a liquid containing hot, concentrated sulfuric acid, polymers, solvents, etc. are decomposed into smaller molecules through a dehydration reaction, and PFAS is volatilized. By degassing the mixed liquid through an organic reaction, the liquid is less likely to foam in subsequent treatments, making the subsequent treatments easier.
  • the PFAS detoxification system 1 further comprises a circulation flow path 16 connected to the concentrator 11 and having a filter 39 installed midway through the circulation flow path, and a first filtrate flow path 17 through which the filtrate of the concentrated liquid that has passed through the filter flows.
  • the PFAS detoxification system 1 also comprises a first reservoir 20x connected to the first filtrate flow path 17 and for storing the filtrate. With this configuration, the waste liquid can be appropriately concentrated using the filter 39, and the filtrate that has passed through the filter 39 can be stored and used, for example, as a regenerated solvent.
  • the PFAS detoxification system 1 further includes a third filtrate flow path 19 downstream of the second reservoir 20y, and a bypass flow path 21 connecting the third filtrate flow path 19 and the first filtrate flow path 17.
  • pressurizing the liquid in the bypass flow path 21 causes the liquid to flow back in the first filtrate flow path 17 and into the circulation flow path 16 from the outlet side of the filter 39. In this way, by allowing the filtrate to flow from the outlet side of the filter 39 via the bypass flow path 21, clogging of the filter 39 can be eliminated and the filter 39 can be properly cleaned.
  • the PFAS detoxification system 1 further includes a second filtrate flow path 18 equipped with a filter 40, which connects the first reservoir 20x and the second reservoir 10y.
  • a filter 40 which connects the first reservoir 20x and the second reservoir 10y.
  • the PFAS detoxification system 1 may further include a first gas filter 22 that separates the gas volatilized by the sulfuric acid treatment tank 12 into a PFAS-rich gas and a PFAS-removed gas.
  • a first gas filter 22 that separates the gas volatilized by the sulfuric acid treatment tank 12 into a PFAS-rich gas and a PFAS-removed gas.
  • the first gas filter 22 may be heated to a temperature higher than that of the concentrated liquid by receiving heat generated in the sulfuric acid treatment tank 12. By heating the first gas filter 22 to a high temperature in this way, the PFAS to be sorted passes through the first gas filter 22 less easily than other gases, and the difference in flow rate change due to heating can be used to properly separate the gases.
  • the PFAS detoxification system 1 further includes a second gas filter 25 that takes in outside air and separates it into a first diverted gas having a higher nitrogen concentration than air, and a second diverted gas having a higher oxygen concentration than air.
  • the second gas filter 25 may supply the first diverted gas to the sulfuric acid treatment tank 12. In this way, supplying gas with a high nitrogen concentration to the sulfuric acid treatment tank 12 can prevent fire in the sulfuric acid treatment tank 12.
  • the PFAS detoxification system 1 further includes a detoxification device 14 that combusts and detoxifies the PFAS contained in the gas volatilized by the sulfuric acid treatment tank 12, and the second gas filter 25 may supply the second diverted gas to the detoxification device 14. In this way, supplying gas with a high oxygen concentration to the detoxification device 14 can promote combustion in the detoxification device 14.
  • the PFAS detoxification system 1 further includes a concentrator 27 that concentrates waste liquid containing a positive developer discharged from the lithography apparatus 111 of the semiconductor manufacturing equipment 100, and a developer treatment tank 31 that decomposes and volatilizes the first concentrated liquid concentrated by the concentrator 27.
  • a concentrator 27 that concentrates waste liquid containing a positive developer discharged from the lithography apparatus 111 of the semiconductor manufacturing equipment 100
  • a developer treatment tank 31 that decomposes and volatilizes the first concentrated liquid concentrated by the concentrator 27.
  • the concentrated liquid is decomposed and volatilized.
  • polymers, solvents, etc. are decomposed into lower molecular weight compounds by the decomposition reaction of the dehydration reaction, and PFAS is volatilized.
  • This PFAS detoxification system 1 allows for smooth detoxification of PFAS.
  • the PFAS detoxification system 1 further includes a waste liquid supply channel 26 that supplies waste liquid containing positive developer to a concentrator 27, and a waste liquid supply channel 15 that supplies waste liquid with a higher resist concentration than waste liquid containing positive developer to a sulfuric acid treatment tank 12, which is a decomposition processing unit corresponding to the waste liquid.
  • the waste liquid supply channel 26 and the waste liquid supply channel 15 are provided separately. In this way, by providing a supply channel for waste liquid containing positive developer (waste liquid supply channel 26) and a supply channel for waste liquid with a high resist concentration (waste liquid supply channel 15) separately from each other, it is possible to suppress the generation of excess salts due to, for example, acid-alkali reactions.
  • the developer treatment tank 31 may decompose and volatilize the first concentrated liquid using heat. In this way, the first concentrated liquid can be decomposed appropriately by decomposing it using heat.
  • the developer treatment tank 31 may be provided in contact with the sulfuric acid treatment tank 12, which is a decomposition treatment unit for the second concentrated liquid, which has a higher resist concentration than the first concentrated liquid.
  • the first concentrated liquid can be appropriately separated using the heat of reaction in the sulfuric acid treatment tank 12, which is a decomposition treatment unit for the second concentrated liquid.
  • the container of the sulfuric acid treatment tank 12 (and therefore the SPM waste liquid) can be cooled.
  • the PFAS detoxification system 1 further includes a detoxification device 14 that combusts and detoxifies PFAS.
  • the detoxification device 14 has a combustion chamber that mixes and burns gas associated with the first concentrated liquid volatilized by the developer treatment tank 31 and gas associated with the second concentrated liquid volatilized by the sulfuric acid treatment tank 12. In this way, the gas associated with the first concentrated liquid decomposed and volatilized by the developer treatment tank 31 and the gas associated with the second concentrated liquid decomposed and volatilized by the sulfuric acid treatment tank 12 are used for combustion in the combustion chamber. This reduces the amount of fuel introduced into the detoxification device 14, suppresses overall CO2 emissions, and avoids the need for larger incineration facilities.
  • the PFAS detoxification system 1 may pressurize the filtrate in the bypass flow path 34, causing the liquid to flow back in the waste liquid supply path 26 and for the filtrate to flow into the filter 41 from the outlet side. In this way, by forcing the filtrate to flow into the filter 41 from the outlet side via the bypass flow path 34, clogging of the filter 41 can be eliminated and the filter 41 can be properly cleaned.
  • the PFAS detoxification system 1 is equipped with a backflow liquid storage section 35 that stores the backflow liquid that flows out from the inlet side of the filter 41 when filtrate flows in from the outlet side of the filter 41.
  • the system may also be equipped with a recovery flow path 36 that connects the backflow liquid storage section 35 to the concentrator 11 and sends the backflow liquid from the backflow liquid storage section 35 to the concentrator 11. This allows the liquid that has been backflowed to clean the filter 41 to be properly recovered.
  • the present embodiment has been described above, but the present disclosure is not limited to the above.
  • the chemical treatment unit for waste liquid containing a positive developer has been described as being provided in contact with the sulfuric acid treatment tank 12, which is a chemical treatment unit for resist waste liquid
  • the present disclosure is not limited to this.
  • the decomposition treatment chamber 135, which is a chemical treatment unit for waste liquid containing a positive developer may be provided separately from the sulfuric acid treatment tank 12.
  • the sulfuric acid treatment tank 12 may be cooled by a refrigerant tank 131 containing a refrigerant.
  • a flow path 150 may be provided connecting the concentrator 27 and the developer treatment tank 31, and a heat exchanger 151 may be provided in the flow path 150.
  • the first concentrated liquid in the developer treatment tank 31 can be returned to the concentrator 27 via the flow path 150.
  • the processing system includes a concentrating section that concentrates waste liquid containing organic fluorine compounds discharged from a semiconductor manufacturing device, and a chemical processing section that decomposes and volatilizes the concentrated liquid concentrated by the concentrating section.
  • the treatment system according to [E1] or [E2] further comprises: a first flow path connected to the concentration unit and having a first filter provided therein; a second flow path through which a filtrate of the concentrated liquid that has passed through the first filter flows; and a filtrate storage unit connected to the second flow path and configured to store the filtrate.
  • the processing system according to [E3] further includes a third flow path downstream of the filtrate reservoir, and a bypass flow path connecting the third flow path and the second flow path, and further includes a liquid delivery unit that pressurizes the liquid in the bypass flow path to cause the liquid to flow back in the second flow path and flow into the first flow path from the outlet side of the first filter.
  • the treatment system described in [E8] further comprises a combustion detoxification device that combusts and detoxifies organic fluorine compounds contained in the gas volatilized by the chemical treatment device, and the second gas filter supplies the second diverted gas to the combustion detoxification device.
  • a treatment method including: a concentration step of concentrating waste liquid containing an organic fluorine compound discharged from a semiconductor manufacturing device; and a chemical treatment step of decomposing and volatilizing the concentrated liquid concentrated in the concentration step.
  • a developer concentrating unit for concentrating waste liquid containing a positive developer discharged from a semiconductor manufacturing device; a chemical treatment unit that decomposes and volatilizes the first concentrated solution concentrated by the developer concentrating unit.
  • the processing system according to [E14] further comprises a first supply path for supplying the waste liquid containing the positive developer to the developer concentrating section, the first supply path being provided separately from a second supply path for supplying the waste liquid having a higher resist concentration than the waste liquid containing the positive developer to a decomposition processing section corresponding to the waste liquid.
  • the processing system further comprises: a first supply path that supplies waste liquid containing the positive developer to the developer concentrating section, the first supply path having a filter for waste liquid containing the positive developer disposed therein; a filtrate flow path through which flows filtrate that has passed through a filter for concentrating waste liquid having a higher resist concentration than the waste liquid containing the positive developer; and a bypass flow path that connects the filtrate flow path and the first supply path.
  • the processing system further comprises: a liquid delivery section that pressurizes the filtrate in the bypass flow path to reverse the flow of the filtrate in the first supply path and causes the filtrate to flow from an outlet side of the filter for waste liquid containing the positive developer.
  • a waste liquid storage section for storing waste liquid having a higher resist concentration than the waste liquid containing the positive developer, and a backflow liquid storage section for storing backflow liquid flowing out from the inlet side of a filter for waste liquid containing the positive developer when the filtrate flows in from the outlet side of the filter.
  • the processing system according to [E19] further comprises a recovery flow path connecting the backflow liquid storage section and the waste liquid storage section and sending the backflow liquid from the backflow liquid storage section to the waste liquid storage section.
  • a processing method including: a developer concentrating step of concentrating waste liquid containing a positive developer discharged from a semiconductor manufacturing device; and a chemical treatment step of decomposing and volatilizing a first concentrated liquid concentrated in the developer concentrating step.
  • the processing method according to [E21] or [E22] further comprises a filter washing step of washing the filter used in the developer concentrating step by introducing, from an outlet side of the filter used in the developer concentrating step, filtrate that has passed through a filter other than the filter used in the developer concentrating step and that is used to concentrate a waste liquid having a higher resist concentration than the waste liquid containing the positive developer.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

Le système de traitement de l'invention comprend : une unité de concentration qui concentre un liquide résiduaire évacué d'un dispositif de fabrication de semi-conducteur, le liquide résiduaire contenant un composé de fluor organique; et une unité de traitement de liquide chimique qui décompose et volatilise le liquide concentré qui a été concentré par l'unité de concentration.
PCT/JP2024/017266 2024-05-09 2024-05-09 Système et procédé de traitement Pending WO2025234055A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004298680A (ja) * 2003-03-28 2004-10-28 Asahi Eng Co Ltd フォトレジスト現像の廃液処理方法
WO2013031621A1 (fr) * 2011-08-26 2013-03-07 Tdk株式会社 Membrane de séparation de gaz
JP2018527872A (ja) * 2015-08-19 2018-09-20 アーベーベー・シュバイツ・アーゲー 電気エネルギーの生成、伝送、配給および／または使用を行うための電気装置の絶縁媒体から少なくとも１つの物質を再生するための方法
JP2024031788A (ja) * 2022-08-25 2024-03-07 東京エレクトロン株式会社 処理システム及び処理方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004298680A (ja) * 2003-03-28 2004-10-28 Asahi Eng Co Ltd フォトレジスト現像の廃液処理方法
WO2013031621A1 (fr) * 2011-08-26 2013-03-07 Tdk株式会社 Membrane de séparation de gaz
JP2018527872A (ja) * 2015-08-19 2018-09-20 アーベーベー・シュバイツ・アーゲー 電気エネルギーの生成、伝送、配給および／または使用を行うための電気装置の絶縁媒体から少なくとも１つの物質を再生するための方法
JP2024031788A (ja) * 2022-08-25 2024-03-07 東京エレクトロン株式会社 処理システム及び処理方法

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