JP2006255665A - Wet treatment apparatus and wet treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wet treatment apparatus and a wet treatment method which enable the reduction of the equipment cost and environmental load and are capable of treating an object of the treatment or a substrate with a fluid irrespective of the electric characteristics of the substrate i.e. being conductive or insulative. <P>SOLUTION: The wet treatment apparatus 1 comprises a nozzle 12 equipped with a perforated section 12a through which a fluid 19 passes, a planar catalyst member 13 which covers the section 12a and is permeable to water and capable of increasing ion concentration of the fluid 19, and an electrode member 14 equipped with a coaxial hole which covers the planar catalyst member 13. The apparatus ejects the fluid 19 onto an object 20 to be treated while voltage is being applied between a voltage applying section 17 of the electrode member 14 and the perforated section 12a of the nozzle 12. Thereby the wet treatment apparatus 1 feeds the fluid 19 containing an active species onto the surface of the object 20 and treats the surface of the object 20. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wet processing apparatus and a wet processing method for supplying a fluid to an object to be processed and performing a surface treatment such as cleaning of the object to be processed.

  Conventionally, the RCA cleaning method has been used to clean the surface of a substrate such as a semiconductor silicon substrate and a liquid crystal glass substrate. The RCA cleaning method is a method of cleaning a substrate surface using a concentrated chemical solution such as sulfuric acid-hydrogen peroxide solution (SPM), hydrochloric acid-hydrogen peroxide solution (HPM), and ammonia-hydrogen peroxide solution (APM) at a high temperature. is there. This method requires drainage equipment for rinsing water containing chemicals such as acid and equipment for treating volatile components such as acid gas generated in the equipment. There will be additional costs.

  Furthermore, in recent years, the mother substrates of semiconductor wafers and liquid crystal panels tend to be larger, and as a result, the amount of waste liquid in the cleaning of the substrate also increases, which increases the cost of processing the waste liquid and the burden on the environment. It is a problem. On the other hand, the design rules (minimum processing line width) of semiconductors and liquid crystals are increasingly miniaturized, and are approaching the submicron level for liquid crystals and the level of 0.1 μm or less for semiconductors. Therefore, in the cleaning of substrates and the like, improvement in cleaning power is required from the viewpoint of improving yield.

  As a method satisfying these requirements, a cleaning method using radicals composed of water components, that is, oxygen atoms and hydrogen atoms, has been proposed instead of the conventional RCA cleaning method and cleaning method using a strong water flow. Yes. Examples of radicals composed of oxygen atoms and hydrogen atoms include hydrogen radicals, oxygen radicals (atomic oxygen), hydroxyl radicals, and superoxide anion radicals. The characteristics of these radicals are so reactive that they instantly change into harmless molecules such as water, hydrogen and oxygen. Therefore, these radicals have almost no environmental burden and have a sufficient cleaning effect even at a low concentration of about several tens of ppm.

  A typical prior art is described in US Pat. The electronic material cleaning method disclosed in Patent Document 1 is a method of cleaning an electronic material with hydrogen water while applying ultrasonic vibration after cleaning the electronic material with an oxidizing cleaning liquid.

  Another conventional technique is described in Patent Document 2. In the electrolytic processing method of Patent Document 2, a substrate as an electrode and an electrode opposed to the electrode at a predetermined interval are arranged in ultrapure water, and the electrode serving as the substrate and the electrode opposed to the substrate are disposed. Water molecules in ultrapure water are formed by disposing ultrapure water dissociation and having a water-permeable catalyst member, and forming a flow of ultrapure water in the catalyst member while applying a voltage between the electrodes. Is decomposed into hydrogen ions and hydroxide ions (hydroxyl ions), the generated ions are supplied to the substrate surface, and the ions are chemically eluted or oxidized to remove the substrate or form an oxide film. This is an electrolytic processing method.

  Still another conventional technique is described in Patent Document 3. Patent Document 3 discloses a reactive ion beam etching apparatus in which active species such as radicals are formed in a gas phase and supplied to an object to be processed.

JP 2000-117208 A JP 2001-64799 A JP 59-151428 A

  The wet processing method needs to be able to generate active species capable of surface-treating an object to be processed such as a substrate, for example, cleaning active species capable of cleaning the substrate surface. Furthermore, it is necessary that the solution containing the active species can be uniformly supplied to the surface of the object to be processed.

  According to the electronic material cleaning method disclosed in Patent Document 1, by adding ultrasonic vibration to hydrogen water, hydrogen radicals that are cleaning active species are generated, and a solution containing the radicals is used to form a substrate. The surface can be cleaned. Since this method does not use a chemical solution that pollutes the environment, the load on the environment is small.

  However, in the method disclosed here, as a method of generating hydrogen radicals, by adding ultrasonic vibration to hydrogen water, the hydroxyl radicals generated by the cleavage of water molecules are reacted with hydrogen. For example, for hydrogen water having a hydrogen concentration of 1.2 ppm, the hydrogen used to generate the hydrogen radical is one of the hydrogen contained in the hydrogen water. Only about / 10. Furthermore, since the saturated dissolution concentration of hydrogen under atmospheric pressure is not so high as about 1.6 ppm, it is not expected to increase the hydrogen radicals generated by increasing the hydrogen concentration. Furthermore, even if hydrogen water having a hydrogen concentration as high as possible is used, if the hydrogen concentration increases, the propagation efficiency of ultrasonic waves may decrease, and the concentration of hydrogen radicals may decrease. Therefore, such a cleaning method using hydrogen water has a certain limit in the cleaning ability. Moreover, in order to perform this method, the apparatus for producing | generating hydrogen water is required, and the installation cost and running cost of this apparatus are needed.

  According to the electrolytic processing method disclosed in Patent Document 2, ultrapure water is electrolyzed in the presence of a catalyst that promotes ion dissociation, thereby being decomposed into hydrogen ions and hydroxide ions. Ions are supplied to a substrate which is an electrode. By doing so, ions on the surface of the substrate undergo a chemical elution reaction or oxidation reaction to generate radicals and other active species, and the substrate is removed or oxide film formed by the active species. Such a method has been studied for use in the etching process of metal and semiconductor substrates. Specifically, when the substrate is copper, molybdenum, iron, or the like, the substrate is used as an anode and the substrate surface is used. The hydroxide ions are oxidized to mainly generate hydroxyl radicals, and etching is performed by active species containing hydroxyl radicals. On the other hand, when the substrate is silicon, aluminum, or the like, the substrate is used as a cathode, hydrogen ions are reduced on the substrate surface to mainly generate hydroxyl radicals, and etching is performed with active species containing hydroxyl radicals.

  Since this method does not use chemicals that pollute the environment, it is a cleaning method with little addition to the environment, requires special equipment for wastewater and exhaust, and the cost of the chemicals is high. The cost is lower than the conventional RCA cleaning method, and ultrapure water is used as it is, so that an apparatus for generating hydrogen water or the like is not necessary.

  Furthermore, while hydrogen radicals generated by hydrogen water are defined by the saturation concentration of hydrogen water, in this method, hydrogen ions or hydroxides having a molar concentration more than 100 times the hydrogen concentration of hydrogen water Since hydroxyl radicals are generated using ions as raw materials, it is possible to generate hydroxyl radicals having a molar concentration of 100 times or more at maximum as compared with hydrogen radicals generated by hydrogen water.

  However, it is useful when the substrate to be treated with active species such as radicals is a metal, but when the substrate is a semiconductor substrate or a liquid crystal panel, the substrate constitutes one of the electrodes and is electrically destroyed. Have problems such as

  The objects to be cleaned on the substrate, that is, the inorganic fine particles and the organic resist film are present in any of the electrodes, the semiconductor film, and the insulating film, and are not necessarily present in a place having conductivity. In the manufacturing process of a semiconductor and a liquid crystal panel, a substrate which is an object to be cleaned does not necessarily have conductivity such as a conductor and a semiconductor. Furthermore, the surface of the semiconductor substrate is not uniform and has a complicated shape formed by an insulator such as a metal, a semiconductor, and an organic resist film by photolithography. Therefore, it is difficult to apply the above method to the cleaning process on the insulator substrate, the patterned semiconductor, and the metal substrate.

  When the reactive ion beam etching apparatus disclosed in Patent Document 3 is used, active species such as radicals can be formed in a gas phase and supplied to an object to be processed. Organic matter removal from the surface of the treated product can be performed. This supplies oxygen, nitrogen, helium, neon and other rare gases in the air from a nozzle equipped with an electrode. At that time, by applying a DC voltage, an AC voltage, and a pulse voltage, arc discharge and glow discharge are performed to form a plasma state. In the plasma state, the gas has a large number of active species that are radicalized and ionized by collisions between electrons and atoms, and can perform etching of metals and insulating films, and decomposition and removal of organic substances.

  However, since the process of generating the active species by making these plasma states is significantly different from the process of generating the active species in the liquid, the behavior of the generated active species is also greatly different. Further, since the treatment is performed in the gas phase, it is necessary to remove nonvolatile side reaction products such as dust and residue generated during the treatment by a treatment using a separate liquid, a so-called wet treatment.

  Also, even if liquid such as pure water is supplied to the nozzle having the electrode structure for generating plasma as described above, almost no electricity is generated unless active voltage is applied to the liquid unless a high voltage of several hundred volts or more is applied. Since no chemical reaction takes place, enormous power is consumed. Further, normally, the nozzle for generating plasma is treated with an insulator, so that an electrochemical reaction of pure water does not occur even at a high voltage.

  The object of the present invention is to realize a reduction in costs such as equipment costs and a reduction in environmental load, and further, regardless of the electrical characteristics of whether the substrate being processed is conductive or insulating. An object of the present invention is to provide a wet processing apparatus and a wet processing method capable of processing an object to be processed with a fluid.

The present invention is a wet processing apparatus for supplying a fluid to the surface of an object to be processed to process the surface of the object to be processed,
A nozzle having a region provided with a hole through which the fluid passes in order to supply the fluid to the workpiece;
A plate-shaped catalyst member that covers the region and can increase the ion concentration of the fluid and has water permeability;
Covering the catalyst member, and having an electrode member provided with holes,
In the wet processing apparatus, a voltage is applied between the region and the electrode member.

  In the invention, the electrode member is titanium, nickel, palladium, gold, platinum, or carbon.

  In the invention, the electrode member is a composite material containing titanium, nickel, palladium, gold, platinum, or carbon.

  In addition, the present invention is characterized in that an insulating film is formed between the region provided with the holes and the catalyst member.

In the present invention, the insulating film is a resin containing a fluorine-based resin.
In the invention, the insulating film is an inorganic insulator made of a metal oxide or ceramics.

  In the invention, it is preferable that the nozzle is titanium, nickel, palladium, gold, platinum or carbon.

  According to the present invention, the nozzle is a composite material containing titanium, nickel, palladium, gold, platinum, or carbon.

In the present invention, the catalyst member is an ion exchange material imparted with a strong acidic cation exchange ability or a strong basic anion exchange ability.
In the present invention, the catalyst member has a porous structure.

  In the present invention, the ion exchange material is a resin containing a fluororesin.

Further, the present invention allows a fluid to pass through a plate-shaped catalyst member having water permeability disposed between a region in which nozzle holes are provided and an electrode member in which holes are provided. An ion concentration increasing step for increasing the ion concentration;
A voltage application step of generating an active species in the fluid by applying a voltage between the region and the electrode member;
And a processing step of processing the object to be processed by supplying a fluid containing active species to the surface of the object to be processed from the discharge hole.

In the invention, it is preferable that the fluid contains water.
According to the present invention, the fluid is pure water.

In the invention, the active species includes an oxygen atom or a hydrogen atom.
In the present invention, the active species is one or more active species selected from hydrogen radical, hydroxyl radical, oxygen radical, superoxide anion radical, HO ₂ radical, HO ₃ radical, ozone and hydrogen peroxide. It is characterized by that.
Further, the present invention is characterized in that the voltage is a DC voltage of 2 V or more and 50 V or less.

  According to the present invention, the nozzle has a region provided with a hole through which a fluid passes, the region provided with the hole is covered with a water-permeable plate-shaped catalyst member, and the catalyst member is further It arrange | positions so that it may cover with the electrode member provided with the hole. By doing so, the fluid is supplied to the object to be processed through the holes provided in the nozzle, the holes provided in the catalyst member and the electrode member, and therefore all the fluid supplied to the object to be processed is the catalyst. The fluid passed through the member. Further, a voltage is applied between the region where the hole is provided and the electrode member.

  Therefore, since an electric field can be applied to the fluid and the catalyst member whose ion concentration has been increased by contacting the catalyst member, a fluid containing a large amount of active species can be supplied to the object to be treated. Wet treatment can be easily performed on objects.

  According to the invention, the electrode member is titanium, nickel, palladium, gold, platinum or carbon. Since the electrode member is exposed to an active species having high reactivity when a voltage is applied, it needs to have not only high electrical conductivity but also high resistance to chemical reactions such as chemical oxidation and reduction. These electrodes can be preferably used as electrodes because of their high electrical conductivity and high resistance to chemical reactions such as chemical oxidation and reduction.

  According to the invention, the electrode member is a composite material containing titanium, nickel, palladium, gold, platinum or carbon. Since the electrode member has a very high pressure, the electrode member needs to be able to withstand the high pressure. However, by making the electrode into a composite material containing a preferable metal as described above, the electrode member can be made to withstand the high pressure.

  Further, according to the present invention, since the insulating film is formed between the region provided with the hole and the catalyst member, it is generated when a voltage is applied between the region provided with the hole of the nozzle and the electrode member. An electrical short circuit between the area where the nozzle hole is provided and the catalyst member can be prevented.

  According to the invention, the insulating film is a resin containing a fluorine resin. Since the insulating film is exposed to highly reactive active species when a voltage is applied, it is not only an insulator but also needs to have high resistance to chemical reactions such as chemical oxidation and reduction. Since such an insulating film is an insulator and has high resistance to chemical reactions such as chemical oxidation and reduction, it can be preferably used as an insulating film.

  According to the invention, the insulating film is an inorganic insulator made of a metal oxide and a ceramic. Such an inorganic insulator can be preferably used as an insulating film because it has high resistance to chemical reactions such as chemical oxidation and reduction and has higher stability.

  According to the invention, the nozzle is titanium, nickel, palladium, gold, platinum or carbon. As with the electrode member, the nozzle is exposed to highly reactive active species when a voltage is applied, and therefore needs to have high resistance to chemical reactions such as chemical oxidation and reduction. Furthermore, the region provided with the holes needs to have high electrical conductivity. These nozzles can be preferably used as nozzles because of their high electrical conductivity and high resistance to chemical reactions such as chemical oxidation and reduction.

  According to the invention, the nozzle is a composite material containing titanium, nickel, palladium, gold, platinum or carbon. Since the nozzle becomes very high pressure, it is necessary to be able to withstand high pressure. However, by making the nozzle into a composite material containing a preferable metal as described above, it is possible to make a counter electrode plate that can withstand high pressure.

  Further, according to the present invention, the catalyst member is an ion exchange material imparted with a strong acid cation exchange ability or a strong basic anion exchange ability. Therefore, when the fluid comes into contact with the catalyst member, the fluid becomes a hydrogen ion and a hydroxyl group. It can be broken down into ions, such as ions, and ions can be increased in the fluid. Furthermore, since an electric field can be applied to the fluid and the catalyst member having increased ions, more active species can be easily generated.

  According to the present invention, since the catalyst member has a porous structure, water permeability can be sufficiently secured, and pressure loss due to passage through the catalyst member can be reduced.

  According to the invention, the ion exchange material is a resin containing a fluorine-based resin. Since ion exchange materials are exposed to highly reactive active species when a voltage is applied, it is necessary to have high resistance to chemical reactions such as chemical oxidation and reduction. Since these ion exchange materials have high resistance to chemical reactions such as chemical oxidation and reduction, they can be preferably used as ion exchange materials.

  Further, according to the present invention, the fluid is allowed to pass through a water-permeable plate-shaped catalyst member disposed between the region where the nozzle hole is provided and the electrode member provided with the hole. An active species is generated in the fluid by applying a voltage between the region where the hole is provided and the electrode member while increasing the concentration of ions therein. The object to be processed is processed by supplying a fluid containing the active species to the object to be processed.

  By doing so, an electric field can be applied to the catalyst member and the fluid while passing the fluid through the catalyst member, and active species can be easily generated in the fluid.

  Further, since the region where the nozzle holes are provided, the catalyst member, and the electrode member are arranged so as to be stacked, the fluid passes through all the catalyst members before being discharged from the discharge holes. Therefore, since the ion concentration in the fluid can be further increased, a fluid containing a large amount of active species can be generated. Since a fluid containing a large amount of such active species can be supplied to the surface of the object to be processed, the surface of the object to be processed can be wet-processed efficiently and easily.

  Further, according to the present invention, since the fluid contains water, hydrogen ions and hydroxyl ions increase in the fluid by contacting the catalyst member. Furthermore, since an electric field is applied to the fluid and the catalyst member having increased hydrogen ions and hydroxyl ions, more active species can be easily generated.

  According to the present invention, since the fluid is pure water, more active species derived from pure water can be easily generated when an electric field is applied while being in contact with the catalyst member. Moreover, such active species derived from pure water are harmless to the environment and have a low environmental load. Furthermore, since no special chemical is used, the wet treatment can be performed on the surface of the object to be processed at a lower cost compared to the case where the special chemical is used.

  Further, according to the present invention, since the active species contain oxygen atoms or hydrogen atoms, the active species become oxygen, hydrogen, and water after wet treatment of the object to be treated, so that there is no burden on the environment. small.

According to the invention, the active species is one or more active species selected from hydrogen radicals, hydroxyl radicals, oxygen radicals, superoxide anion radicals, HO ₂ radicals, HO ₃ radicals, ozone and hydrogen peroxide. It is. Such active species become oxygen, hydrogen, and water after wet processing is performed on an object to be treated, so that the load on the environment is small. In addition, since the activity is high, the object to be processed can be sufficiently processed even at a concentration of about several tens of ppm.

  Further, according to the present invention, since the voltage is a DC voltage of 2 V or more and 50 V or less, active species can be generated more efficiently in the fluid.

[Wet treatment equipment]
The wet processing apparatus according to the present invention applies an electric field to the fluid and the catalyst member while passing the fluid through the catalyst member, and supplies the fluid to the surface of the workpiece to process the surface of the workpiece. A wet processing apparatus.

  Note that the wet processing apparatus is an apparatus that supplies a liquid, which is a fluid, to an object to be processed. For example, an apparatus for manufacturing a semiconductor substrate includes an apparatus that performs wet cleaning, wet etching, wet oxidation, and the like. An apparatus that performs wet cleaning is an apparatus that removes, dissolves, peels, and decomposes organic substances and inorganic substances present on the substrate surface by supplying liquid to the substrate surface. The liquid is used to clean the substrate surface. It is a device to convert. An apparatus that performs wet etching is an apparatus that supplies a liquid to the surface of a substrate and removes, dissolves, peels, and decomposes a thin layer or the like existing on the surface of the substrate, and performs an etching using the liquid. . An apparatus that performs wet oxidation is an apparatus that oxidizes the substrate surface by supplying a liquid to the substrate surface to modify the surface of the substrate.

  In this embodiment, an apparatus that mainly performs wet cleaning will be described as a wet processing apparatus. However, wet cleaning is merely an example of a wet processing method, and the present invention is not limited to only wet cleaning. If the object to be treated can be removed, dissolved, peeled and decomposed by active species such as radicals generated in the fluid, and the object to be treated can be cleaned, surface processed and surface modified, Can be used without limitation.

  FIG. 1 is a schematic cross-sectional view showing a configuration of a wet processing apparatus 1 according to the first embodiment of the present invention. The wet processing apparatus 1 includes a fluid supply line 11, a nozzle 12, a catalyst member 13, an electrode member 14, a DC power supply device 15, an insulating film 16, and the like.

  The fluid supply line 11 is connected to the nozzle 12 and supplies the fluid 19 to the nozzle 12 by flowing the fluid 19 in the direction of the arrow 21. The nozzle 12 has a region 12 a provided with a plurality of holes for flowing the fluid 19 supplied from the fluid supply line 11. The region 12a provided with a plurality of holes of the nozzle 12 corresponds to a region provided with holes through which fluid passes. The catalyst member 13 is installed outside the nozzle 12 so as to cover the region 12a where the plurality of holes of the nozzle 12 are provided. Moreover, the catalyst member 13 has water permeability, and can increase the ion concentration in the fluid by allowing the fluid to pass therethrough. The electrode member 14 includes a voltage application unit 17 and a plate unit 18, and is further installed outside so as to cover the catalyst member 13. The plate portion 18 is formed with a hole, and the voltage application portion 17 is formed on the surface of the inner wall of the hole, and a hole for discharging the fluid 19 is formed. The DC power supply device 15 applies a voltage between the electrode member 14 and the voltage application unit 17. The insulating film 16 is disposed on the surface of the electrode member 14 on the side in contact with the catalyst member 13.

  A wet process of an object to be processed using the wet processing apparatus 1 will be described. The wet processing apparatus 1 discharges and supplies the fluid 19 to the workpiece 20 as described below while applying a voltage between the voltage applying unit 17 of the electrode member 14 and the nozzle 12. The fluid 19 supplied from the fluid supply line 11 to the nozzle 12 in the direction of the arrow 21 flows through a plurality of holes provided in the nozzle 12, flows through the catalyst member 13, and further flows into the voltage application unit 17 of the electrode member 14. The fluid 19 is supplied to the workpiece 20 by discharging from the formed hole in the direction of the arrow 22. By doing so, the fluid 19 that has passed through the catalyst member 13 generates ions in the fluid 19, and an electric field is applied to the fluid 19 in the vicinity of the catalyst member 13 with an increased ion concentration. A large amount of seed is produced. By discharging and supplying such a fluid 19 to the workpiece 20 conveyed in the direction of the arrow 23, the surface of the workpiece 20 can be easily processed.

  The nozzle 12 and the electrode member 13 are preferably titanium, nickel, palladium, gold, platinum, or carbon. Since the nozzle 12 and the electrode member 13 are exposed to highly reactive active species when a voltage is applied, the nozzle 12 and the electrode member 13 need not only have high electrical conductivity but also have high resistance to chemical reactions such as chemical oxidation and reduction. is there. Such a material can be preferably used as a counter electrode plate because of its high electrical conductivity and high resistance to chemical reactions such as chemical oxidation and reduction. More preferably, it is a composite material containing titanium, nickel, palladium, gold, platinum or carbon. Since the nozzle 12 and the electrode member 13 become very high pressure, it is necessary to be able to withstand the high pressure. Therefore, the nozzle 12 and the electrode member 13 that can withstand high pressure can be obtained by using a composite material containing the above preferred materials. For example, platinum doped with about 5% of nickel or tungsten can be used.

  The insulating film 16 is formed on the electrode member 14. By doing so, the distance between the nozzle 12 and the electrode member 14 can be mechanically set to a certain distance or more, and an electrical short circuit that occurs when a voltage is applied between the nozzle 12 and the electrode member 14 is prevented. Can do. The insulating film 16 is preferably a resin containing a fluorine resin. Since the insulating film 16 is exposed to active species having high reactivity when a voltage is applied, it is necessary not only to be an insulator but also to have high resistance to chemical reactions such as chemical oxidation and reduction. Since such an insulating film is an insulator and has high resistance to chemical reactions such as chemical oxidation and reduction, it can be preferably used as an insulating film. Further, an inorganic insulator made of a metal oxide and ceramic can be used as the insulating film. Such an inorganic insulator can be preferably used as an insulating film because it has high resistance to chemical reactions such as chemical oxidation and reduction and has higher stability.

  The catalyst member 13 is preferably an ion exchange material imparted with strong acidic cation exchange ability or strong basic anion exchange ability. By doing so, when the fluid 19 comes into contact with the catalyst member 13, the ion concentration in the fluid 19 can be increased. Furthermore, since an electric field is applied to a fluid having an increased ion concentration, more active species can be easily generated. For example, when water is contained in the fluid 19, the fluid 19 passes through the catalyst member 13, so that the water becomes hydrogen ions and hydroxyl ions, and hydrogen ions and hydroxyl ions are increased in the fluid 19. Can do. Furthermore, since an electric field is applied to the fluid 19 in which hydrogen ions and hydroxyl ions are increased, more active species derived from water can be easily generated. Moreover, it is preferable that the catalyst member 13 has a porous structure. By doing so, sufficient water permeability can be secured and pressure loss due to passing through the catalyst member can be reduced. Furthermore, the catalyst member 13 is preferably a resin containing a fluorine resin. Examples include Teflon (registered trademark), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), polyperfluoro (alkyl vinyl ether), Viton (registered trademark), and the like. . Since the catalytic member 13 is exposed to highly reactive active species when a voltage is applied, it needs to have high resistance to chemical reactions such as chemical oxidation and reduction. Since these catalyst members have high resistance to chemical reactions such as chemical oxidation and reduction, they can be preferably used as catalyst members.

  When the active species is an active species having a very short lifetime, the fluid 19 discharged from the discharge hole of the wet processing apparatus 1 needs to have a high discharge speed. It is necessary to shorten the distance to the processed object. For example, radicals are very reactive, but have very short lifetimes and half-lives on the order of microseconds. Therefore, the discharge speed is preferably 10 m / second or more and 100 m / second or less, and the distance between the discharge hole of the wet processing apparatus 1 and the object to be processed is preferably 5 mm or more and 10 mm or less.

  FIG. 2 is a schematic view showing a first embodiment of the wet processing apparatus 1 according to the present invention. FIG. 2A is a schematic view that is perpendicular to the conveyance direction 23 of the workpiece 20 and is viewed from the side of the workpiece 20. FIG. 2B is a schematic view seen from the upper surface of the workpiece 20.

  As shown in FIG. 2A, the fluid 19 is discharged from the wet processing apparatus 1 in the direction of the arrow 25 and supplied to the surface of the workpiece 20. The arrow 25 is not perpendicular to the workpiece 20 but is inclined in the direction opposite to the arrow 23 which is the conveyance direction of the workpiece 20. Furthermore, the wet processing apparatus 1 and the workpiece 20 are brought close to each other. By doing so, even if the active species has a short lifetime, the fluid 19 having a high concentration of active species can be supplied to the surface of the workpiece 20 before the active species generated in the fluid 19 disappear. Furthermore, since the workpiece 20 is transported by the transport means 24, the active species concentration of the fluid 19 that contacts the surface of the workpiece 20 can be kept high. Therefore, the surface of the workpiece 20 can be processed efficiently. Further, as shown in FIG. 2B, the wet processing apparatus 1 can discharge the fluid 19 by a width perpendicular to the conveyance direction 23 of the object to be processed 20, so that the entire surface of the object to be processed 20 can be discharged. Can be processed.

  FIG. 3 is a schematic view showing a mechanism for increasing the ion concentration in the fluid 19 by the catalyst member 13. The catalyst member 13 is a catalyst member that contacts the fluid 19 to promote an ion exchange reaction and increase the ion concentration of the fluid 19. For example, in the case of the fluid 19 containing water, as shown in FIG. 3, the water contained in the fluid 19 is decomposed into hydrogen ions 26 and hydroxyl ions 27 while passing through the catalyst member 13. The hydrogen ions 26 move so as to be attracted to the voltage application unit 17 of the electrode member 14 that is a cathode. Further, the hydroxyl ions 27 move so as to be attracted to the nozzle 12 which is an anode. Next, radicals which are active species are generated by an electrochemical reaction on the electrode member 14 and on the surface of the nozzle 12 and its periphery. Hereinafter, a radical generation mechanism in the voltage application unit 17 and the nozzle 14 will be described.

  FIG. 4 is a schematic diagram illustrating a mechanism for generating active species on the voltage application unit 17 and the nozzle 14 of the wet processing apparatus 1 of the present invention. FIG. 4A is a schematic diagram showing a mechanism for generating hydrogen radicals 28 on the voltage application unit 17. FIG. 4B is a schematic diagram showing a mechanism for generating the hydroxyl radical 29 on the nozzle 12.

As shown in FIG. 4A, the hydrogen ions 26 are attracted to the voltage application unit 17 by an electric field and receive electrons 30 from the voltage application unit 17, that is, the hydrogen ions 26 are reduced to reduce the hydrogen ions 26. A radical 28 is generated. Further, as shown in FIG. 4B, the hydroxyl ions 27 are attracted to the nozzle 12 by an electric field, and the electrons 30 are taken away from the nozzles 12, that is, the hydroxyl ions 27 are oxidized, whereby the hydroxyl radicals are oxidized. 29 is generated.
The above reaction is represented by the chemical reaction formula as follows.

  Chemical formula 1 is a chemical reaction formula showing a mechanism for generating radicals by the above-described method. Reaction formula (I), reaction formula (II), and reaction formula (III) are one stage of the radical generation mechanism. A generation mechanism of hydrogen ions 26 and hydroxyl ions 27, a generation mechanism of hydroxyl radicals 29 in electrode oxidation, and a reaction formula for generating hydrogen radicals 28 in electrode reduction are shown. Reaction formula (IV), reaction formula (V), reaction formula (VI), and reaction formula (VII) show the formation reaction of other active species contributing to the wet treatment.

  Since the active species generated as described above are highly reactive, for example, the silanol bond formed by the fine particle surface and the silicon substrate or the glass substrate is cleaved, and the fine particle binding activity on the surface of the silicon substrate, etc. By inactivating the site (dangling bond), the adhesion between the fine particles and the substrate can be reduced, and the removal ability of the fine particles can be improved. It is also effective in removing contamination from organic components such as organic resist thin film residues. In this case, strong bonds such as covalent bonds such as carbon-carbon bonds and carbon-hydrogen bonds in organic substances are used. By cutting and oxidizing it, it is decomposed into carbon dioxide and water and removed.

  FIG. 5 is a schematic view showing a second embodiment of the wet processing apparatus 1 according to the present invention. FIG. 5A is a schematic view seen from the arrow 32 that is the conveyance direction of the workpiece 20. FIG. 5B is a schematic view seen from the upper surface of the workpiece 20.

  When processing the workpiece 20, the wet processing apparatus 1 is inclined with respect to the direction in which the workpiece 20 is transported, supported by the workpiece support tool 31, and transported by the transport roller 24. Process with leaf method. By doing so, it is possible to prevent the retention of the fluid 19 on the surface of the workpiece 20 as compared with the case where the workpiece 20 is conveyed and processed in a horizontal state, and the replacement efficiency of the fluid 19 is improved. By improving the supply rate of the active species to the surface of the object to be processed 20 and improving the transmission efficiency of the physical force due to the flow of the fluid, the processing capacity of the object to be processed 20 can be improved.

  The angle A with respect to the horizontal of the workpiece 20 is preferably more than 30 degrees and not more than 90 degrees. By doing so, the effect of improving the replacement efficiency of the fluid 19 is remarkable. Replacement efficiency is an important factor for the effectiveness of processing. In particular, when an active species having a short life is used, it is necessary to quickly supply the fluid 19 discharged from the wet processing apparatus 1 to the entire surface of the workpiece 20. By tilting the workpiece 20 from the horizontal with the conveyance direction as an axis, the retention of the fluid 19 on the surface of the workpiece 20 is suppressed, and the active species reach the surface of the workpiece 20 from the wet treatment apparatus 1. Time can be reduced.

  The angle B between the discharge hole of the wet processing apparatus 1 and the conveyance direction of the workpiece 20 is preferably more than 15 degrees and 80 degrees or less. By doing so, since the fluid 19 used in the wet process does not touch the processed object 20 after processing, the surface of the processed object 20 after processing can be kept clean. If the angle B is 15 degrees or less, the area that can be processed becomes too small. If the angle B exceeds 80 degrees, the fluid 19 that has processed the upper portion of the workpiece 20 is mixed with the fluid 19 that processes the lower portion of the workpiece 20. , Processing efficiency will fall.

  Furthermore, the discharge holes of the wet processing apparatus 1 are preferably installed in parallel to the surface of the workpiece 20. By doing so, the to-be-processed object 20 can be processed uniformly.

  FIG. 6 is a schematic view showing a third embodiment of the wet processing apparatus 1 according to the present invention. FIG. 5A is a schematic view seen from the side surface of the workpiece 20. FIG. 5B is a schematic view seen from the upper surface of the workpiece 20.

  When the wet processing apparatus 1 processes the workpiece 20, the workpiece 20 is rotated by the rotating means 33 and processed. The rotating means 33 includes a rotating table 34, a rotating shaft 35, and the like. The rotating means 33 fixes the workpiece 20 on the rotating table 34 and rotates the rotating shaft 35 connected to the rotating table 34 by a motor (not shown). By processing the workpiece 20 while being rotated by the rotating means 35, the fluid 19 is prevented from staying on the surface of the workpiece 20 as compared with the case where the workpiece 20 is conveyed and processed in a horizontal state. It is possible to improve the processing efficiency for the object to be processed by improving the replacement efficiency of the fluid 19, improving the supply speed of the active species to the surface of the object to be processed, and improving the transmission efficiency of physical force by the flow of the fluid Can be achieved.

  The number of rotations is preferably 100 rpm or more and 500 rpm or less. By doing so, the retention of the fluid 19 supplied to the workpiece 20 can be prevented, so that the fluid 19 having a high active species concentration can always be supplied to the surface of the workpiece 20. Therefore, the workpiece 20 can be processed efficiently.

  Moreover, it is preferable that the discharge hole of the wet processing apparatus 1 be installed in parallel to the surface of the workpiece 20. By doing so, the to-be-processed object 20 can be processed uniformly.

  FIG. 7 is a schematic cross-sectional view showing the configuration of the wet processing apparatus 2 according to the second embodiment of the present invention. The wet processing apparatus 2 includes a nozzle 36. The nozzle 36 has a nozzle body 36a and a hole forming portion 36b. The hole forming part 36b is detachable from the nozzle body 36a. The hole forming portion 36b corresponds to a region provided with a hole through which a fluid passes. The wet processing apparatus 2 is the same as the wet processing apparatus 1 except that the nozzle 12 is the nozzle 36 configured as described above.

  FIG. 8 is a schematic cross-sectional view showing the configuration of the wet processing apparatus 3 according to the third embodiment of the present invention. The wet processing apparatus 3 includes a nozzle 37, an electrode member 40, and an insulating film 41. The nozzle 37 has a nozzle body 37a and a hole forming portion 37b. The hole forming part 37b is detachable from the nozzle body 37a. The hole forming portion 37b corresponds to a region provided with a hole through which a fluid passes. The hole forming part 37 b includes a voltage applying part 38 and a plate part 39. The plate portion 39 is formed with a hole, and the voltage application portion 38 is formed on the surface of the inner wall, and a discharge hole for discharging the fluid 19 is formed. The catalyst member 13 is installed inside the nozzle 37 so as to cover the nozzle hole forming portion 37b. The electrode member 40 is formed with a plurality of holes, and is further installed inside so as to cover the catalyst member 13. The insulating film 41 is installed between the electrode member 40 and the nozzle body 37a. By doing so, the electrical short circuit between the electrode member 40 and the nozzle main body 37a can be prevented at the time of voltage application. The wet processing apparatus 3 is the same as the wet processing apparatus 1 except for the configuration of the nozzle 37, the electrode member 40, and the insulating film 41.

  FIG. 9 is a schematic cross-sectional view showing a configuration of a wet processing apparatus 4 according to the fourth embodiment of the present invention. The wet processing apparatus 4 includes a nozzle 42, a first electrode member 43, a second electrode member 44, and an insulating film 45. The nozzle 42 has a fluid supply line connection part 42a and a hole forming part 42b. The hole forming portion 42b is formed with a hole for discharging the fluid 19, and the catalyst member 13, the insulating film 16, the first electrode member 43, the second electrode member, and the insulating film 45 are formed so as to cover the hole. Further, it can be provided and can be detached from the fluid supply line connecting portion 42a. That is, the catalyst member 13, the insulating film 16, the first electrode member 43, the second electrode member 44, and the insulating film 45 can be provided inside the nozzle 42 in a replaceable manner. By doing so, the nozzle 42 can make the inside of the nozzle 42 further high in pressure, and can further increase the discharge speed of the fluid.

The second electrode member 44 has a voltage application part 44a and a plate part 44b. The plate portion 44b is formed with a hole, and the voltage application portion 44a is formed on the surface of the inner wall, and a discharge hole for discharging the fluid 19 is formed. The second electrode member 44 corresponds to a region provided with a hole through which a fluid passes. The catalyst member 13 is installed inside the nozzle 42 so as to cover the second electrode member 44. The DC power supply device 15 applies a voltage between the first electrode member 43 and the second electrode member 44, and the first electrode member 43 corresponds to an electrode member. The insulating film 45 is installed between the first electrode member 43 and the hole forming portion 42b. By doing so, the electrical short circuit between the 1st electrode member 43 and the hole formation part 42b can be prevented at the time of a voltage application. The wet processing apparatus 4 is the same as the wet processing apparatus 1 except for the configuration of the nozzle 42, the first electrode member 43, the second electrode member 44, and the insulating film 45.

[Wet treatment method]
In the wet treatment method according to the present invention, an electric field is applied to the fluid and the catalyst member while passing the fluid through the catalyst member to generate active species in the fluid. The object to be processed is processed by supplying a fluid containing the active species to the surface of the object to be processed.

  Note that the wet treatment method is a method of supplying a fluid to an object to be processed. For example, methods for manufacturing a semiconductor substrate include wet cleaning, wet etching, wet oxidation, and the like. Wet cleaning is a method of removing, dissolving, peeling, and decomposing organic substances and inorganic substances existing on the substrate surface by supplying a fluid to the substrate surface, and a method of cleaning the substrate surface using a fluid. It is. Wet etching is a method in which a fluid is supplied to the substrate surface to remove, dissolve, peel, and decompose a thin layer or the like present on the substrate surface, and is etching performed using a fluid. In addition, wet oxidation is a method in which a substrate surface is modified by oxidizing a substrate surface by supplying a fluid to the substrate surface.

  FIG. 10 is a process diagram showing an embodiment of the present invention. In the ion concentration increasing step A1, the fluid is allowed to pass through a water-permeable plate-like catalyst member disposed between the region where the nozzle hole is provided and the electrode member provided with the hole. Increase the ion concentration inside. In the voltage application step A2, a voltage is applied so that an electric field is applied to the fluid by applying a voltage between the region where the hole is provided and the electrode member while increasing the ion concentration in the fluid in the ion concentration increasing step A1. To generate active species in the fluid. In the processing step A3, the surface of the object to be processed can be efficiently and easily cleaned by supplying the fluid containing the large amount of active species to the surface of the object to be processed.

  In this embodiment, wet cleaning will be mainly described as a wet processing method. However, wet cleaning is merely an example of a wet processing method, and the present invention is not limited to only wet cleaning. In the case where the object to be treated can be removed, dissolved, peeled and decomposed by the active species such as radicals generated in the fluid, which is a fluid, so that the object to be treated can be cleaned, surface processed and modified. If there is, it can be used without limitation.

  An object to be cleaned by wet cleaning according to the present embodiment is a substrate such as a semiconductor substrate or a glass substrate on which contaminants such as organic substances and inorganic substances exist on the surface. In the present invention, since the substrate is not used as an electrode, the substrate does not have to be a conductive substrate such as a metal, and may be a nonconductive substrate such as a glass substrate and a transparent resin substrate. In addition, the substrate needs to be one that does not react with the fluid during cleaning, or one that does not adversely affect the substrate during and after cleaning.

  Objects to be cleaned such as contaminants present on the surface of the substrate refer to those that are attached, coated, adhered or deposited on the substrate, and may be removed, dissolved, stripped or decomposed depending on the generated active species. Any substance that can be cleaned can be cleaned regardless of whether the object to be cleaned is an organic substance or an inorganic substance. Even if it takes any form such as a liquid, a solid, a gel, and an adhesive, it can be washed. Examples of the case where the object to be cleaned is an inorganic substance include adhesion contamination of metal, metal oxide and inorganic fine particles to the object to be treated. Moreover, as a case where a washing | cleaning target object is organic substance, the adhesion contamination derived from the organic substance which comprises an organic resist thin film etc. can be mentioned, for example.

In the wet cleaning according to the present embodiment, first, a fluid is passed through the catalyst member, and a voltage is applied to generate active species. Examples of the active species include radicals, ions, oxidizing substances, and reducing substances. Preferably, it is an active species containing at least one of an oxygen atom and a hydrogen atom. Specifically, a hydrogen radical, a hydroxyl radical, an oxygen radical, a superoxide anion radical, a HO ₂ radical, a HO ₃ radical, ozone and hydrogen peroxide. More preferred are hydrogen radical, oxygen radical and hydroxyl radical. Hydrogen radicals, oxygen radicals and hydroxyl radicals have very high reactivity, so that they have a sufficient cleaning effect even at a concentration as low as several tens of ppm and instantly change into harmless molecules such as water and hydrogen. There is almost no load on.

  The fluid used in the present embodiment is a fluid containing a raw material of active species, and preferably contains a radical generating species. For example, a fluid containing water can be used. More preferably, it is pure water. Even more preferably, it is ultrapure water. By using pure water or ultrapure water, the present invention can be preferably used even in the semiconductor manufacturing field, which is a field that requires a clean environment such as a liquid crystal panel and a semiconductor manufacturing process.

  Further, the fluid state may be a liquid state, or a state in which a gas and a liquid coexist. Pure water or ultrapure water is obtained by sterilizing microorganisms or the like by ultraviolet irradiation and removing dissolved organic substances and inorganic substances to the limit with a membrane filter. Pure water is purified water having a specific resistance value of 1 MΩ · cm or more and 10 MΩ · cm or less, and ultrapure water is purified water having a specific resistance value greater than 10 MΩ · cm and 18.3 MΩ · cm or less. is there. When the specific resistance value is smaller than 1 MΩ · cm, the efficiency of generating active species by applying an electric field is lowered.

Examples of the catalyst member used in the present embodiment include a catalyst member that increases the ion concentration of the fluid. The catalyst member that increases the ion concentration of the fluid is a substance that has a function of promoting the ion exchange reaction in the fluid and increasing the ion product, and is a substance that is in the same state before and after the reaction. For example, an ion exchange resin is mentioned as a preferable catalyst member. The ion exchange resin refers to an insoluble synthetic resin having an ion exchangeable acidic group or basic group. Examples of ion exchange resins include cation exchange resins, anion exchange resins, and amphoteric ion exchange resins. As a more preferable catalyst member, a strongly acidic cation exchange resin and a strong base anion resin imparted with a function of increasing the ionic product of water as a fluid are preferable. For example, a resin into which a sulfone group and a quaternary ammonium group are introduced is used. Can be mentioned. More preferably, an ion exchange resin that can increase the ionic product Kw of water, which is a fluid, within a range of 14 ≧ −log Kw can be used. When such a catalyst member is used, for example, when a voltage of 50 V is applied to pure water having a specific resistance value of 18.2 MΩ · cm without using the catalyst member, the current value is about 10 ⁻² mA / cm ^2. It can only be. On the other hand, when a voltage of 50 V is applied to pure water having a specific resistance value of 18.2 MΩ · cm using the catalyst member as described above, the current value is about 10 ⁴ mA / cm ² which is 10 ⁶ times. become. This current value is closely related to the amount of active species generated in the fluid, and since the current value and the amount of active species generated are linearly related, the catalyst member is used compared to the case where no catalyst member is used. If you were, the concentration of the active species is obtained 10 ⁶ times higher fluid. That is, when the catalyst member is used, the ion concentration in the fluid can be increased, so that more active species can be generated and the substrate surface can be more efficiently cleaned.

  Further, in order to increase the contact area with the fluid and further increase the ion concentration of the fluid, the catalyst member is provided with an ion exchange capability, that is, a porous shape, a mesh shape, a fibrous shape into which an ion exchange group is introduced, It is preferable that the catalyst member has water permeability such as particulate and non-woven fabric. Such a catalyst member is produced by, for example, a radiation graft polymerization method in which a resin having an appropriate porosity is irradiated with γ rays and then graft polymerization is performed. Furthermore, the nonwoven fabric into which the ion exchange group is introduced is more preferable because it is easily sandwiched between the counter electrode plate and the discharge hole plate and can be used stably. In addition, the concentration of active species generated in the fluid can be controlled by changing the type and amount of ion exchange groups.

  In this embodiment, a catalyst member is arranged between the hole-provided region and the electrode member, and a voltage is applied between the hole-provided region and the electrode member while the fluid passes through the catalyst member. To do. By doing so, an electric field can be applied to the fluid while the fluid passes through the catalyst member, and a large amount of active species can be generated in the fluid. The voltage applied at that time is preferably a DC voltage of 2V to 50V. By doing so, active species can be generated more efficiently in the fluid.

  As described above, the present invention can generate active species in a fluid simply by applying an electric field to the fluid while passing a fluid containing active species such as water through the catalyst member. Therefore, it is not necessary to use special equipment and chemicals. Therefore, it is possible to realize cost reduction such as equipment cost and reduction of environmental load. Furthermore, the treatment can be performed regardless of the electrical characteristics of whether the object to be treated is conductive or insulating.

Below, the Example using the wet processing apparatus 1 is shown.
In the embodiment, the fluid supplied from the fluid supply line 11 is pure water having a specific resistance of 10 MΩ · cm to 18.3 MΩ · cm. A glass substrate was used as the workpiece 20. The electrode member 14 was made of titanium or platinum alloy having a thickness of 0.3 mm. As the insulating film 16, a resin film made of a copolymer of fluororesin and polyimide having a thickness of 10 μm was used. The nozzle 12 used was one in which ejection holes with a diameter of 20 μm were formed in a row at a pitch of 40 μm or more and 80 μm or less. As the nozzle 12, titanium or a platinum alloy having a thickness of 0.1 mm to 1.0 mm was used. In the nozzle 12, a rectangular hole having a width of 0.5 mm is formed on the row of ejection holes. As the catalyst member 13, a sheet having a thickness of 0.5 mm or more and 1.0 mm or less using a non-woven fabric made of a strongly acidic cation exchange resin which is a fluororesin into which a sulfonic acid group is introduced was used. This sheet has a network structure in which pores of 0.1 mm to 1.0 mm are formed. The nozzle 12 and the electrode member 14 were installed so as to be mechanically separated by a distance of 0.2 mm or more and 1.5 mm or less using the catalyst member 13 and a spacer. Even when pure water was filled between the nozzle 12 and the electrode member 14, the resistance was 1 kΩ or more. For example, the DC voltage applied between the nozzle 12 and the electrode member 14 is 5 V when the distance between the nozzle 12 and the electrode member 14 is 0.5 mm. The current flowing through such a device affects the amount of radicals that are active species.

The flow rate of pure water, which is the fluid 19 supplied from the wet treatment apparatus 1, is Q (L / min), and the flowing current value I (A) is a radical concentration C (mol / L) in the pure water to be generated. It is expressed by the following formula.
C = 60I / 96500Q

  For example, when the flow rate of pure water is 40 L / min and the current value is 8 A, the radical concentration C in pure water is 120 μmol / L as described above. Further, this pure water was supplied at a flow rate of 100 m / sec. As a result, pure water having a radical concentration of 4 μmol / L could be supplied to the surface of the glass substrate as the object to be processed.

  This radical concentration is 100 times higher than that in the case of using the conventional method of applying ultrasonic waves to hydrogen water. The present invention can supply such a high active species concentration fluid to an object to be processed.

It is a schematic sectional drawing which shows the structure of the wet processing apparatus 1 which is the 1st Embodiment of this invention. It is the schematic which shows the 1st embodiment of the wet processing apparatus 1 which is this invention. FIG. 5 is a schematic diagram showing a mechanism for increasing the ion concentration in a fluid 19 by a catalyst member 13. It is a schematic diagram which shows the mechanism which produces | generates the active species on the voltage application part 17 and the nozzle 14 of the wet processing apparatus 1 of this invention. It is the schematic which shows the 2nd embodiment of the wet processing apparatus 1 which is this invention. It is the schematic which shows the 3rd embodiment of the wet processing apparatus 1 which is this invention. It is a schematic sectional drawing which shows the structure of the wet processing apparatus 2 which is the 2nd Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the wet processing apparatus 3 which is the 3rd Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the wet processing apparatus 4 which is the 4th Embodiment of this invention. It is process drawing which shows one Embodiment of this invention.

Explanation of symbols

1, 2, 3 Wet treatment device 11 Fluid supply line 12, 36, 37, 42 Nozzle 13 Catalyst member 14, 40 Electrode member 15 DC power supply device 16, 41, 45 Insulating film 17, 38 Voltage application unit 18, 39 Plate unit 19 Fluid 20 Object 21, 22, 23, 25, 32 Arrow 24 Transport roller 26 Hydrogen ion 27 Hydroxyl ion 28 Hydrogen radical 29 Hydroxyl radical 30 Electron 31 Object support 33 Rotating means 34 Rotating table 35 Rotating shaft 43 First electrode member 44 Second electrode member

Claims (17)

A wet processing apparatus for supplying a fluid to the surface of an object to be processed to process the surface of the object to be processed,
A nozzle having a region provided with a hole through which the fluid passes in order to supply the fluid to the workpiece;
A plate-shaped catalyst member that covers the region and can increase the ion concentration of the fluid and has water permeability;
Covering the catalyst member, and having an electrode member provided with holes,
A wet processing apparatus, wherein a voltage is applied between the region and the electrode member.   The wet processing apparatus according to claim 1, wherein the electrode member is titanium, nickel, palladium, gold, platinum, or carbon.   The wet processing apparatus according to claim 1, wherein the electrode member is a composite material containing titanium, nickel, palladium, gold, platinum, or carbon.   The wet processing apparatus according to claim 1, wherein an insulating film is formed between the region in which the hole is provided and the catalyst member.   The wet processing apparatus according to claim 4, wherein the insulating film is a resin containing a fluorine-based resin.   The wet processing apparatus according to claim 4, wherein the insulating film is an inorganic insulator made of a metal oxide or ceramics.   The wet processing apparatus according to claim 1, wherein the nozzle is titanium, nickel, palladium, gold, platinum, or carbon.   The wet processing apparatus according to claim 1, wherein the nozzle is a composite material containing titanium, nickel, palladium, gold, platinum, or carbon.   The wet processing apparatus according to any one of claims 1 to 8, wherein the catalyst member is an ion exchange material imparted with a strong acidic cation exchange ability or a strong basic anion exchange ability.   The wet processing apparatus according to claim 1, wherein the catalyst member has a porous structure.   The wet apparatus according to claim 10, wherein the ion exchange material is a resin containing a fluorine-based resin. Increasing the ion concentration in the fluid by passing the fluid through the water-permeable plate-like catalyst member disposed between the nozzle hole-provided region and the electrode member provided with the hole. An ion concentration increasing process;
A voltage application step of generating an active species in the fluid by applying a voltage between the region and the electrode member;
And a processing step of processing the object to be processed by supplying a fluid containing active species to the surface of the object to be processed from the discharge hole.   The wet processing method according to claim 12, wherein the fluid includes water.   The wet processing method according to claim 12, wherein the fluid is pure water.   15. The wet treatment method according to claim 12, wherein the active species includes an oxygen atom or a hydrogen atom. The active species is one or more active species selected from hydrogen radicals, hydroxyl radicals, oxygen radicals, superoxide anion radicals, HO ₂ radicals, HO ₃ radicals, ozone and hydrogen peroxide. The wet processing method as described in any one of Claims 12-15.   The wet processing method according to any one of claims 12 to 16, wherein the voltage is a DC voltage of 2 V or more and 50 V or less.

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