WO2013105512A1 - 熱交換器およびシリコン系材料用エッチング液の除熱方法 - Google Patents

熱交換器およびシリコン系材料用エッチング液の除熱方法 Download PDF

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Publication number
WO2013105512A1
WO2013105512A1 PCT/JP2013/000097 JP2013000097W WO2013105512A1 WO 2013105512 A1 WO2013105512 A1 WO 2013105512A1 JP 2013000097 W JP2013000097 W JP 2013000097W WO 2013105512 A1 WO2013105512 A1 WO 2013105512A1
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Prior art keywords
refrigerant
heat
heat exchanger
etching
coolant
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Ceased
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PCT/JP2013/000097
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English (en)
French (fr)
Japanese (ja)
Inventor
秀一 宮尾
岡田　淳一
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Shin-Etsu Chemical Co Ltd
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Shin-Etsu Chemical Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/0206—Heat exchangers immersed in a large body of liquid
    • F28D1/0213—Heat exchangers immersed in a large body of liquid for heating or cooling a liquid in a tank
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/0066—Multi-circuit heat-exchangers, e.g. integrating different heat exchange sections in the same unit or heat-exchangers for more than two fluids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/047—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being bent, e.g. in a serpentine or zig-zag
    • F28D1/0472—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being bent, e.g. in a serpentine or zig-zag the conduits being helically or spirally coiled
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0022—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for chemical reactors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0068—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for refrigerant cycles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0077—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for tempering, e.g. with cooling or heating circuits for temperature control of elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/02—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being helically coiled
    • F28D7/022—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being helically coiled the conduits of two or more media in heat-exchange relationship being helically coiled, the coils having a cylindrical configuration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F2013/005—Thermal joints
    • F28F2013/006—Heat conductive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/64—Wet etching of semiconductor materials
    • H10P50/642—Chemical etching

Definitions

  • the present invention relates to a heat exchanger and a method of removing heat from a silicon etching solution. More specifically, the present invention relates to silicon-based materials such as silicon crystals used in the manufacture of semiconductor devices, solar cells, etc., photomasks for photolithography, and silicon oxide-based substrates used in the production of molds for imprint lithography. The invention relates to a heat removal technology of a chemical solution for etching
  • Silicon-based materials include polycrystalline silicon and single crystal silicon used for manufacturing semiconductor devices, solar cells, etc., silicon wafers obtained by processing these, and photomasks for optical lithography or molds for imprint lithography It is widely used as a silicon oxide based substrate etc. used for preparation.
  • a chemical solution containing at least one of hydrofluoric acid (HF) and nitric acid (HNO 3 ) is used for etching these silicon-based materials.
  • HF hydrofluoric acid
  • HNO 3 nitric acid
  • a mixed solution of hydrofluoric acid and nitric acid having a relatively high concentration is used for etching for removing the surface layer portion having a predetermined depth on the surface of the silicon-based material.
  • etching reaction is an exothermic reaction
  • the etching rate depends on the temperature of the chemical solution (etching solution), and the etching rate becomes higher as the temperature of the etching solution becomes higher.
  • the temperature of the etching solution rises during the process of performing the etching process continuously, the amount of etching increases by that amount, and the product loss, the haze on the wafer surface, or the shape Problems such as nonconformity may occur. Therefore, in order to etch the silicon-based material with high accuracy by a chemical solution containing at least one of hydrofluoric acid and nitric acid, it is necessary to properly control the temperature of the etching solution.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-151779
  • a manufacturing method excellent in mass production stability in etching of a silicon crystal substrate using an acid etching solution and the realization of the manufacturing apparatus are desired
  • the silicon crystal substrate manufacturing equipment will be equipped with a means to detect the concentration of hydrofluoric acid in the mixed acid aqueous solution of nitric acid and hydrofluoric acid mixed, which enables continuous production stability and stability of quality by detecting the concentration of hydrofluoric acid.
  • the etching solution used in the etching tank is circulated to the heat exchanger through which the refrigerant sent from the chiller is circulated, and the temperature rise caused by the etching reaction is reduced. It is supposed to keep the temperature of the etching solution in a certain range.
  • temperature control of a chemical solution containing at least one of hydrofluoric acid and nitric acid used for etching a silicon-based material is performed by cooling by a heat exchanger through which a refrigerant sent from a chiller is circulated.
  • a pipe or the like for circulating a chemical solution containing at least one of hydrofluoric acid and nitric acid is lined with a fluorine resin or fluorine resin having high corrosion resistance such as PFA or PVDF (registered trademark). The material is used.
  • the neutralization operation of the refrigerant and the refrigerant replacement at a high frequency are required, but the processing cost generated along with such a measure becomes so high that it can not be ignored.
  • the present invention has been made in view of such problems, and the object of the present invention is to reduce the processing cost when etching a silicon-based material with a chemical solution containing at least one of hydrofluoric acid and nitric acid, and It is an object of the present invention to provide a heat exchanger capable of performing stable operation for a long time without any problem and a method of removing heat from a silicon-based material etching solution using the same.
  • the heat exchanger according to the present invention is a heat exchanger used in a system for etching a silicon-based material with a chemical solution containing at least one of hydrofluoric acid and nitric acid, and the chemical solution is introduced from the etching tank into the container.
  • the heat exchange system further includes a chemical solution circulation unit returned to the etching tank after heat removal by a refrigerant, and a flow passage unit for circulating a refrigerant coolant for removing heat from the refrigerant between the heat exchanger and the chiller.
  • the refrigerant is accommodated in a container of the vessel, and the refrigerant is heat-removed by the refrigerant coolant, and the heat-removed refrigerant is used to remove the heat of the chemical solution.
  • the heat exchanger further includes a refrigerant flow passage portion that circulates the refrigerant into the container.
  • the refrigerant flow path unit includes a pH control unit for adjusting the acidity of the refrigerant.
  • the refrigerant coolant is either an aqueous antifreeze solution containing alcohols or a salt solution of highly water-soluble salt.
  • the heat removal method according to the present invention is a heat removal method for an etching solution of a silicon-based material containing at least one of hydrofluoric acid and nitric acid, and the heat removal from the etching solution using a refrigerant coolant is performed. It is characterized in that heat removal of the etching solution is performed.
  • the refrigerant used for removing heat from the etching solution of the silicon-based material containing at least one of hydrofluoric acid and nitric acid is removed by the coolant, and the etching solution is removed by the removed coolant. It was decided to remove the heat.
  • the refrigerant is not circulated to the cooling system including the chiller, so that even if acid leakage occurs in the piping etc., the refrigerant contained in the heat exchanger container is replaced or its regeneration processing Just do it. Therefore, it is possible to reduce the cost of the etching process without significantly changing the design or specification of the chiller side equipment.
  • FIG. 1 is a block diagram for explaining a heat removal method (heat removal system) according to the present invention.
  • an etching tank for storing a chemical solution for etching a silicon-based material containing at least one of hydrofluoric acid and nitric acid. From 200, it leads in the container (shell) of heat exchanger 100 via circulation path 210a of the above-mentioned medical fluid.
  • a refrigerant for removing the heat of the chemical solution (etching solution) is contained in the container of the heat exchanger 100, and the removed chemical solution is returned to the etching tank 200 through the circulation path 210b and is again used as the etching solution.
  • the refrigerant Used as The refrigerant is heat-removed by the refrigerant coolant, and the heat-removed refrigerant causes heat removal of the chemical solution (etching solution).
  • etching solution chemical solution
  • symbol 220 in the figure is a circulation preparatory tank of etching liquid.
  • the refrigerant coolant contained in the heat exchanger 100 circulates with the chiller 300 via the circulation flow paths 130a and 130b, and the refrigerant coolant cooled by the chiller 300 removes heat from the refrigerant. It will be.
  • aqueous antifreeze containing alcohol salt solution of sodium sulfate, potassium sulfate, ammonium sulfate, magnesium sulfate, sodium chloride, potassium chloride, calcium chloride, sodium nitrate, potassium nitrate, potassium nitrate, ammonium nitrate, sodium carbonate
  • aqueous salt solutions in which highly water-soluble salts such as potassium carbonate, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate are dissolved alone or in combination.
  • refrigerant flow path portions 110a and 110b for circulating the refrigerant into the container.
  • a pH control unit 120 for adjusting the acidity of the refrigerant may be provided in such a refrigerant flow passage.
  • the etching solution is not directly cooled by the chiller-cooled refrigerant as in the prior art, but the chiller is designed to remove the heat of the refrigerant coolant, and this removed heat is used to remove the etching solution. Heat removal is performed. Therefore, since the refrigerant is not circulated to the cooling system including the chiller, the time for maintenance of the device is reduced, and even if the acid leaks from the piping on the etching liquid side of the heat exchanger and the pH value of the refrigerant decreases. It is only necessary to remove and replace this refrigerant. As a result, in addition to the ease of apparatus management, the amount of waste liquid of the refrigerant can be suppressed, the processing cost of etching can be reduced, and stable operation over a long period can be performed without any problem.
  • the concentration of hydrofluoric acid in a chemical solution used for etching a material such as silicon crystal is 0.1% by mass or more and 50% by mass or less, and typically about 5% by mass.
  • the nitric acid concentration is generally 5% by mass or more and 70% by mass or less, and typically about 63% by mass.
  • the concentration of hydrofluoric acid is 0.1% by mass to 10% by mass, typically about 5% by mass, and the concentration of nitric acid is 5% by mass to 70% % Or less, typically about 60% by mass.
  • FIG. 2 is a view for explaining an outline of the configuration of the heat exchanger 100 according to the present invention.
  • An etching solution circulation pipe 20 and a refrigerant coolant circulation pipe 30 are provided in the container (shell) 10, and the etching solution circulation pipe 20 and the refrigerant coolant circulation pipe 30 are respectively the above-described chemical solutions.
  • the circulation paths 210a and 210b and the refrigerant coolant circulation flow paths 130a and 130b are connected.
  • the refrigerant 40 is accommodated in the container 10, and the refrigerant 40 is circulated into the container through the refrigerant flow path portions 110a and 110b by the operation of the liquid feed pump 115, but the refrigerant 40 is circulated in the flow path After the acidity is adjusted by the pH control unit 120 provided, it is returned into the container.
  • pure water is preferably selected as the refrigerant 40, and it is preferable to use a salt solution when managing the refrigerant coolant at a value lower than 0 ° C.
  • the metal of the silicon-based material In order to avoid the possibility of contamination, it is preferable to use an ammonia salt or an organic ammonium salt, and it can also be a buffer as described later.
  • the refrigerant is supplied from the refrigerant supply passage 410 a into the container 10 and can be discharged from the refrigerant discharge passage 410 b to the outside of the container 10.
  • the cooled object is cooled by passing the cooled object and the refrigerant across the partition wall, but in order to increase the cooling efficiency, the partition wall is subjected to heat exchange.
  • the area needs to be relatively large.
  • fluorocarbon resin with excellent corrosion resistance such as PFA or PVDF (registered trademark) is used for piping etc. of the apparatus used in the etching process of silicon material which needs to avoid metal contamination and organic substance contamination as much as possible.
  • PFA polyvinyl alcohol
  • PVDF polyvinyl ether
  • a PFA tube with a tube wall thickness of 0.8 mm was used, but when continuous circulation is performed using pure water as a refrigerant for 4 weeks, the pH of the refrigerant is up to about 3 It has fallen. For this reason, in order to prevent the apparatus corrosion, it is necessary to carry out the replacement process of the refrigerant in a period of less than 4 weeks or to carry out the neutralization process on all the large amounts of refrigerant.
  • the temperature of the refrigerant should be as low as possible.
  • the etching solution In the case where nitric acid was contained in the PFA, a phenomenon was observed in which colored organic substances thought to be produced through the nitrate ester adhere to the inner and outer surfaces of the PFA pipe. The formation of such a substance not only causes the contamination of the material to be etched with organic substances, but it is necessary to avoid the formation because the nitrate ester itself is dangerous.
  • salt precipitation may occur in the antifreeze liquid, which may damage the liquid feed pump.
  • an aqueous antifreeze solution containing alcohol, a salt aqueous solution of sodium sulfate, a salt aqueous solution of ammonium sulfate, a salt aqueous solution of sodium chloride and the like can be used as the refrigerant coolant, according to the present inventors Even when water containing an alcohol such as ethylene glycol, ethanol, or methanol was used as a refrigerant coolant, the organic matter contamination of the etching solution did not occur even when the refrigerant temperature was controlled to 0 ° C. or less.
  • fluorinated saturated hydrocarbon resin examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (4, 6) Fluorinated) (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (difluorinated) (PVDF (registered trademark)), polychlorotrifluoroethylene (trifluorinated) (PCTFE), A resin group called a so-called Teflon (registered trademark) resin such as chlorotrifluoroethylene / ethylene copolymer (ECTFE) can be mentioned.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoroalkylvinylether copolymer
  • FEP tetrafluoroethylene-he
  • the pump provided in the circulation channel of the etching solution may be selected according to the size and heat generation of the etching tank, but as in the case of a commonly used pump, the wetted part is preferably an acid resistant resin. In particular, it is preferable to select one made of Teflon (registered trademark) resin as described above.
  • a general cooling device can be used as it is in a circulation system for circulating the refrigerant coolant between the heat exchanger and the chiller.
  • it is metal piping excellent in acid resistance among the said circulation systems, and it may be lined with resin with high acid resistance.
  • water when using (operating) the refrigerant coolant at a temperature of 0 ° C. or more, and there is an advantage that maintenance is not necessary for a long time when pure water is used.
  • a refrigerant coolant at a temperature of 0 ° C. or lower to increase the cooling efficiency
  • Aqueous salt solution (so-called brine) may be used. If the refrigerant coolant circulation system is metal piping, even if the refrigerant coolant contains alcohols or sodium, the etching solution removed in the heat exchanger is contaminated by these inclusions. Can be prevented.
  • a salt solution is preferable as such a refrigerant.
  • the salt solution may be any one that can obtain the required freezing point depression, but it is preferable that it does not produce harmful substances even when it reacts with silicon contained in an etching solution containing at least one of hydrofluoric acid and nitric acid.
  • refrigerants include salt solutions such as ammonium sulfate, ammonium nitrate, ammonium chloride and the like.
  • the etchant which is the object to be cooled, flows in the tube disposed in the vessel (shell) of the heat exchanger Heat exchange is performed between the above-described etchant and the refrigerant circulating between the chiller and the heat exchanger.
  • the refrigerant for removing heat of the etching solution is accommodated in the container of the heat exchanger, and the refrigerant coolant for removing the heat is between the heat exchanger and the chiller. Circulate with.
  • the shape of the container and piping of the heat exchanger used in the present invention is not particularly limited, but when piping made of Teflon (registered trademark) is adopted as piping disposed in the container, the heat exchange efficiency is From the viewpoint of enhancing the thickness, the thickness of the tube wall is preferably 0.5 mm to 2.0 mm. In addition, there is no particular restriction on the shape of the piping. However, according to the experiments of the present inventors, since the pipe for etching solution circulation is relatively easily deteriorated with time, from the viewpoint of maintenance of the apparatus, the operation such as replacement is relatively simple and the heat is relatively easy. It is preferable to use a spiral shape having a large exchange area and high heat removal efficiency.
  • FIGS. 3A and 3B are each a diagram for explaining a configuration example of the refrigerant coolant circulation pipe and the etching solution circulation pipe disposed in the container of the heat exchanger according to the present invention, both of which are spiral pipes It is assumed.
  • the spiral part of the etching solution circulation pipe shown in FIG. 3B is disposed in the container of the heat exchanger in a mode inserted in the spiral part of the refrigerant coolant circulation pipe shown in FIG. 3A, the heat exchange efficiency is improved. High and preferred.
  • the refrigerant coolant circulation pipe shown in FIG. 3A is configured to be fed from the top to the spiral portion and then returned from the bottom to the top, but directly from the lower portion of the spiral portion to the outside of the container It may be configured to return the liquid.
  • the etching solution circulation pipe shown in FIG. 3B is configured to be fed from above the straight body portion located at the center of the spiral portion and then sent upward from below the spiral portion and returned. However, the liquid may be fed directly to the spiral part from the lower part of the spiral part.
  • the shell size is designed such that a sufficient heat removal effect can be obtained with as little refrigerant as possible, in order to suppress the refrigerant processing cost.
  • an ion exchange resin may be provided in the shell in order to trap the leaked hydrofluoric acid or nitric acid.
  • the pH of the refrigerant may be managed by neutralization with an alkali to prevent the deterioration of the circulation system due to hydrofluoric acid or nitric acid leaking into the refrigerant.
  • the alkali used for the purpose is preferably aqueous ammonia or hydroxide of ammonium such as tetramethyl ammonium hydroxide.
  • an ion exchange resin may be used to capture the acid.
  • only the refrigerant circulated in the shell needs to be subjected to pH control, and pH control on the chiller side is unnecessary, so the maintenance of the apparatus is made efficient.
  • the temperature difference in the container of a heat exchanger does not arise as much as possible. If the container is of a vertical type, equalization of the temperature in the container by natural convection due to heat exchange between the refrigerant and the refrigerant in the container and heat exchange between the refrigerant and the etchant It becomes easy to be drawn.
  • the refrigerant in the container may be forced to circulate.
  • the circulating flow can be created by pumping the refrigerant from the top of the shell and sending it to the bottom of the shell.
  • a screw or the like for stirring the refrigerant may be installed in the shell.
  • pure water whose temperature was set to 7 ⁇ 1 ° C. by direct cooling with a chiller (not shown) was circulated as a refrigerant to remove heat from the etching solution.
  • the piping used for feeding the etching solution is a PFA tube (Ultra Pure Fluon (registered trademark) PFA P / 802UP manufactured by Asahi Glass Co., Ltd.) with a tube wall thickness of 0.8 mm, and the total piping length in the container is about It is 5m.
  • Table 1 is a table summarizing the changes in the pH of the refrigerant for each week for each of the above six repeated experiments.
  • the temperature of the etching solution removed with the refrigerant controlled at 7 ⁇ 1 ° C. was 31 ° C. at the maximum while the initial temperature was 20 ° C.
  • the pH of the refrigerant reached about 3 in 4 to 5 weeks. That is, it can be confirmed that the acid concentration in the refrigerant increases due to the long-term use of the tube due to the permeation and diffusion of the acid from the PFA tube.
  • the heat exchanger 100 has a structure shown in FIG. 2 and accommodates 100 L of refrigerant in the container 10, and a pipe (SUS 304) for the spiral refrigerant coolant of the aspect illustrated in FIG. 3A in the refrigerant.
  • PFA tube Ultra Pure Fluon (registered trademark) PFA P / 802UP, manufactured by Asahi Glass Co., Ltd.
  • the house was housed. Further, in order to improve the heat exchange efficiency by the in-container circulating flow, the refrigerant was circulated at a rate of 80 L / min from the bottom of the container 10 by a pump.
  • the refrigerant to be used was selected according to the control temperature of the refrigerant coolant (control accuracy is ⁇ 2 ° C.). Specifically, pure water was selected when the management temperature of the refrigerant coolant was higher than 0 ° C., and an ethylene glycol aqueous solution was selected when the management temperature of the refrigerant coolant was 0 ° C. or less.
  • concentration of the ethylene glycol aqueous solution is 5% by mass at a management temperature of 0 ° C, 10% by mass at -5 ° C, 20% by mass at -10 ° C, and 40% by mass at -15 ° C.
  • a buffer solution phosphoric acid or tetramethylammonium hydroxide (TMAH) containing potassium having a large atomic radius as a buffer was used.
  • TMAH tetramethylammonium hydroxide
  • 1 mole of K 2 HPO 4 and 1 mole of KH 2 PO 4 are mixed at 61.5: 38.5 and diluted by 1/15. It was.
  • the TMAH one having a concentration of 50 ppm was used.
  • the buffer solution may be prepared with TMAH and phosphoric acid in order to reduce the metal contamination level of the etching solution as much as possible.
  • organo-based IRA-400 1000 g
  • a filter is used as a suction port for circulating the refrigerant. installed.
  • Table 2 summarizes the results for each of the conditions 1 to 12.
  • the change in pH of the refrigerant is a value after 4 weeks.
  • the coolant for heat removal of the etching solution is cooled by a chiller, and heat removal with the coolant is performed to remove heat (temperature control) of the etching solution.
  • a heat removal method is employed in which the refrigerant is cooled using a refrigerant coolant, and the etchant is cooled by the cooled refrigerant.
  • the damage by the acid to a chiller unit is avoided and stable operation is attained.
  • pure water which is easy to handle, is used as the refrigerant coolant, it is possible to remove heat (temperature control) of the etching solution which is comparable to the conventional heat removal method.
  • continuous use for about four weeks is possible without adjusting the pH of the refrigerant.
  • the refrigerant used for removing heat from the etching solution of the silicon-based material containing at least one of hydrofluoric acid and nitric acid is removed by the coolant, and the removed heat is used to cool the removed coolant. It was decided to remove the heat of the etching solution by the agent. For this reason, it was set as the structure of the heat exchanger provided with the flow-path part which circulates the refrigerant
  • the refrigerant is not circulated to the cooling system including the chiller, so that even if acid leakage occurs in the piping etc., the refrigerant contained in the heat exchanger container is replaced or its regeneration processing Just do it. Therefore, it is possible to reduce the cost of the etching process without significantly changing the design or specification of the chiller side equipment.
  • the present invention reduces the processing cost when etching a silicon-based material with a chemical solution containing at least one of hydrofluoric acid and nitric acid, and further, a heat exchanger capable of performing stable operation for a long period without any trouble, and The heat removal method of the etching liquid for silicon-based materials which has

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  • General Engineering & Computer Science (AREA)
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PCT/JP2013/000097 2012-01-12 2013-01-11 熱交換器およびシリコン系材料用エッチング液の除熱方法 Ceased WO2013105512A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017157533A1 (de) * 2016-03-16 2017-09-21 Linde Aktiengesellschaft Sicherheitswärmeübertrager zur temperatureinstellung

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JP6329920B2 (ja) * 2015-04-14 2018-05-23 信越化学工業株式会社 多結晶シリコン塊の評価方法
JP7752465B1 (ja) * 2025-01-16 2025-10-10 直江津電子工業株式会社 半導体ウエハの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08117619A (ja) * 1994-10-19 1996-05-14 Miura Co Ltd 恒温装置
JPH09327669A (ja) * 1996-06-11 1997-12-22 Ibiden Co Ltd 蒸気洗浄装置
JP2000124184A (ja) * 1998-10-14 2000-04-28 Sony Corp 薬液用冷却水恒温装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000292040A (ja) * 1999-04-06 2000-10-20 Hitachi Building Systems Co Ltd アンモニア漏洩の危害を防止する方法、および、同危害防止装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08117619A (ja) * 1994-10-19 1996-05-14 Miura Co Ltd 恒温装置
JPH09327669A (ja) * 1996-06-11 1997-12-22 Ibiden Co Ltd 蒸気洗浄装置
JP2000124184A (ja) * 1998-10-14 2000-04-28 Sony Corp 薬液用冷却水恒温装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017157533A1 (de) * 2016-03-16 2017-09-21 Linde Aktiengesellschaft Sicherheitswärmeübertrager zur temperatureinstellung

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