JP2015088740A - Method and device for processing substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for processing a substrate, capable of further suppressing corrosion or oxidation of a metal wire exposed on a substrate surface.SOLUTION: The present invention relates to a substrate processing device 1 having a processing chamber 2 in which a substrate W is disposed and to which a substrate processing liquid for processing the substrate W is supplied. The device includes: an inert gas filling mechanism (18, 39, 41) for filling with inert gas the interior of the processing chamber 2 in which the substrate W is disposed; and a catalytic unit 21 installed near or inside the processing chamber 2, and filled with a platinum-group metal catalyst allowing hydrogen-dissolved water to pass therethrough, the hydrogen-dissolved water comprising ultra-pure water added with hydrogen. A hydrogen-dissolved processing liquid is supplied as the substrate processing liquid into the processing chamber 2, the hydrogen-dissolved processing liquid being obtained by passing the hydrogen-dissolved water through the platinum-group metal catalyst.

Description

  The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. In particular, the present invention relates to a substrate processing method and a substrate processing apparatus used for circuit board cleaning processing, chemical processing, or immersion processing. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, field emission display substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, A ceramic substrate is included.

  High integration and high speed of semiconductor integrated circuit elements are market demands. In order to meet this demand, lower resistance copper wiring has been used in place of the conventionally used aluminum wiring. If a multilayer wiring is formed by combining a copper wiring with a low dielectric constant insulating film (a so-called low-k film; an insulating film made of a material having a relative dielectric constant smaller than that of silicon oxide), an integrated circuit that operates at a very high speed. A circuit element can be realized.

  In the manufacturing process of such integrated circuit elements, cleaning is performed for the purpose of removing fine particles, organic substances, metals, natural oxide films, etc. adhering to the surface of an object to be processed such as a wafer or a substrate, and a high degree of cleanliness is achieved. Achieving and maintaining this is important for maintaining product quality and improving yield. This cleaning is performed, for example, using a chemical solution such as a sulfuric acid / hydrogen peroxide solution mixed solution or a hydrofluoric acid solution, and rinsing with ultrapure water is performed after the cleaning. In recent years, the number of cleanings has increased due to miniaturization of semiconductor devices, diversification of materials, and complexity of processes. For example, in the formation of the multilayer wiring, a metal wiring serving as a first wiring layer is formed on a substrate, the metal wiring is filled with an insulating material, and the surface of the insulating material covering the metal wiring is planarized by CMP. Then, a procedure is repeated in which a metal wiring serving as a second wiring layer is formed on the surface, the metal wiring is filled with an insulating material, and the surface of the insulating material is flattened by CMP. In such a process, the substrate is cleaned every time the polishing step is completed.

  For the production of ultrapure water, an ultrapure water production apparatus comprising a pretreatment system, a primary pure water system, and a secondary pure water system (hereinafter referred to as a subsystem) is generally used. The role of each system in the ultrapure water production system is as follows. The pretreatment system is a process for removing suspended substances and colloidal substances contained in raw water by, for example, coagulation sedimentation or sand filtration. The primary pure water system uses, for example, an ion exchange resin or a reverse osmosis (RO) membrane to remove the ionic components and organic components of the raw water from which the suspended substances have been removed by the pretreatment system. This is a process for obtaining water. As shown in FIG. 1, the subsystem includes an ultraviolet oxidizer (UV), a membrane deaerator (MD), a non-regenerative ion exchanger (eg, cartridge polisher (CP)), and a membrane separator (eg, ultrafiltration). This is a process for producing ultrapure water by further increasing the purity of primary pure water obtained by the primary pure water system using a water flow line in which a device (UF)) and the like are made continuous.

  When the ultrapure water obtained in this way is used for a semiconductor substrate, there are the following various problems, and countermeasures have been proposed for each problem.

  If the concentration of dissolved oxygen contained in the cleaning water is high, a natural oxide film is formed on the wafer surface by the cleaning water, thereby preventing precise control of the film thickness and film quality of the gate oxide film, contact holes, vias, and plugs. The contact resistance such as may increase. Further, the wiring metal is exposed on the surface of the substrate after the polishing process in the multilayer wiring forming process. Since tungsten (W), copper (Cu), and the like are metals that are easily corroded by oxygen dissolved in water, the thickness of the wiring may be reduced during the cleaning of the substrate with the ultrapure water. In addition, when the resist residue on the substrate surface caused by polishing is removed with the polymer removal liquid, the polymer removal liquid touches the air in the processing chamber, and oxygen dissolves in the polymer removal liquid, so that the polymer removal liquid with a high oxygen concentration. Is supplied to the substrate. Even in this case, the metal film (copper film, tungsten film, etc.) on the substrate is oxidized by the dissolved oxygen in the polymer removing solution, and there is a possibility that the performance of the integrated circuit element formed from the substrate is deteriorated.

  As a countermeasure against these problems, the above-described subsystem performs degassing using a membrane deaerator to reduce the amount of gas dissolved in water, but it is described in Patent Document 1 and Patent Document 2 as well. In order to reduce dissolved oxygen in water, an inert gas or hydrogen gas is dissolved in degassed ultrapure water. Patent Document 1 also employs a method of replacing the atmosphere near the surface of the substrate to be processed with an inert gas.

  In the above-mentioned subsystem, water is also decomposed and removed by irradiating water with ultraviolet rays using an ultraviolet oxidizer, so that water molecules are also oxidized by this ultraviolet irradiation, producing hydrogen peroxide, an oxidizing substance. Is done. That is, the ultrapure water contains hydrogen peroxide.

  As a method of removing hydrogen peroxide in water, a method of removing hydrogen peroxide in water using a platinum group metal catalyst such as palladium (Pd) is known as in Patent Document 3. Furthermore, as described in Patent Document 4, a catalyst formed by supporting a platinum group metal on a monolithic organic porous anion exchanger and a water to be treated containing hydrogen peroxide are brought into contact with each other. There is also a method for efficiently decomposing and removing hydrogen peroxide from water. Patent Document 5 discloses a method in which hydrogen is dissolved in oxygen-dissolved water and then the hydrogen-dissolved water is brought into contact with a catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. In the method described in Patent Document 5, treated water from which dissolved hydrogen peroxide and oxygen are removed with high efficiency can be produced.

JP 2010-56218 A JP 2003-136077 A JP 2010-17633 A JP 2010-240641 A Japanese Patent No. 2010-240642

  By the way, as the pattern dimensions of the integrated circuit element are further miniaturized, the thickness of the wiring is further reduced, and therefore, there is a concern that slight corrosion of the wiring deteriorates the performance of the integrated circuit element.

  Due to the layout of the semiconductor manufacturing line, there are few cases where the substrate processing apparatus and the subsystem can be placed adjacent to each other, so the piping for supplying ultrapure water from the subsystem to the processing chamber extends over a long distance. . In general, in semiconductor manufacturing lines, pipes using a fluororesin such as polyvinyl chloride (PVC), PFA, PTFE and the like having resistance to chemicals are used.

  However, air (oxygen) may enter the pipe from the pipe joint or flange. In addition, piping made of fluororesin such as PFA and PTFE has high oxygen permeability. Therefore, as described above, even if the dissolved oxygen in the water is reduced from a predetermined amount in the subsystem when producing ultrapure water, oxygen enters the pipe from the outside of the pipe in the water supply process to the substrate processing chamber. There is a risk. When oxygen enters the pipe, the dissolved oxygen of water applied to the substrate becomes a predetermined amount or more, and the problem of corrosion of metal wiring such as Cu exposed on the substrate surface recurs. That is, the applicant has found that the proposal for removing oxygen from ultrapure water with respect to the subsystem cannot completely suppress the corrosion of metal wiring such as Cu exposed on the surface of the object to be processed.

  Therefore, the present invention has been made in view of the problem, and it is an object of the present invention to provide a substrate processing method and a substrate processing apparatus that can further suppress the corrosion of metal wiring exposed on the substrate surface.

  One embodiment for achieving the above object relates to a substrate processing method in which a substrate is disposed in a processing chamber of a substrate processing apparatus and the substrate is processed. In this method, a platinum group metal catalyst is installed in the vicinity of the processing chamber or in the processing chamber, an inert gas is filled in the processing chamber in which the substrate is disposed, and hydrogen is added to the liquid to be processed. A hydrogen-dissolved processing solution obtained by passing the solution through a platinum group metal catalyst is supplied into a processing chamber filled with an inert gas, and the substrate is processed with the hydrogen-dissolving processing solution.

  Another embodiment of the present invention relates to a substrate processing apparatus having a processing chamber in which a substrate is disposed and a substrate processing liquid for processing the substrate is supplied. This apparatus includes an inert gas filling mechanism for filling an inert gas into a processing chamber in which a substrate is disposed, and a hydrogen that is installed in the vicinity of the processing chamber or in the processing chamber and adds hydrogen to the liquid to be processed. And a catalyst unit filled with a platinum group metal catalyst through which the solution is passed. The hydrogen dissolution treatment liquid obtained by passing the hydrogen solution through the platinum group metal catalyst is used as a substrate treatment liquid in the processing chamber. It is characterized by supplying to.

  In the above method and apparatus, the inert gas is filled in the processing chamber so that the oxygen gas concentration in the processing chamber is 2% or less, and the dissolved hydrogen concentration in the hydrogen solution is adjusted to 8 μg / L or more. Hydrogen is added to the treatment liquid, and by passing the hydrogen solution through a platinum group metal catalyst, the dissolved oxygen concentration in the hydrogen solution is 2 μg / L or less, and the hydrogen peroxide concentration in the hydrogen solution is It is desirable to be 2 μg / L or less.

  According to the present invention, a hydrogen-dissolved treatment solution obtained by passing a hydrogen-dissolved solution (dissolved hydrogen concentration of 8 μg / L or more) through a platinum group metal catalyst disposed in the vicinity of or in the treatment chamber is treated. A method of filling the processing chamber with an inert gas while supplying the chamber is employed. As a result, in the processing chamber in which the oxygen gas concentration on the surface of the substrate to be processed is reduced to a predetermined value (2%) or less, oxygen and hydrogen peroxide are less than a predetermined value (dissolved oxygen concentration is 2 μg / L or less, hydrogen peroxide The substrate to be processed can be processed using a hydrogen-dissolved processing solution whose concentration is reduced to 2 μg / L or less. For this reason, corrosion (metal oxidation and elution) of the wiring exposed on the surface of the substrate to be processed can be further suppressed as compared with the conventional substrate processing apparatus. Further, according to the present invention, the amount of oxygen dissolved in the processing liquid for processing the substrate can be reduced to a value that does not corrode regardless of the material and distance of the pipe between the ultrapure water production apparatus and the substrate processing apparatus.

  According to another aspect, the diluted chemical solution may be prepared by mixing the hydrogen-dissolving treatment solution and the chemical solution in a pipe or a dilution tank. The diluted chemical prepared in the pipe or in the dilution tank is suppressed or prevented from increasing in oxygen concentration due to contact with air.

  In the processing chamber in which the oxygen gas concentration on the surface of the substrate to be processed is reduced to a predetermined value (2%) or less, the hydrogen-dissolving processing solution or the diluting chemical solution can be applied to the substrate. It is possible to suppress or prevent an increase in oxygen concentration in the chemical solution by touching the air. That is, it is possible to apply the hydrogen dissolution treatment liquid or the diluted chemical liquid to the substrate while maintaining the state in which the oxygen concentration is reduced.

  Furthermore, according to another aspect, by providing a blocking member having a surface facing the substrate, the atmosphere on the substrate surface can be blocked from the surrounding atmosphere. Thereby, an increase in the oxygen concentration of the atmosphere on the substrate surface can be more reliably suppressed or prevented. In this case, the amount of inert gas used can be suppressed.

Examples of chemical solutions include hydrofluoric acid (HF), hydrochloric acid (HCl), IPA (isopropyl alcohol), a mixture of hydrofluoric acid and IPA (isopropyl alcohol), ammonium fluoride (NH ₄ F), ammonia ( NH ₃ ) can be exemplified. When hydrofluoric acid is used, dilute hydrofluoric acid (DHF) is generated by mixing (preparing) hydrofluoric acid stock solution and catalyst-treated water at a predetermined ratio.

  The substrate to be processed has a metal pattern exposed on the surface, and the metal pattern may be a metal wiring. The metal pattern may be a single film of copper, tungsten, or other metal, or may be a multilayer film in which a plurality of metal films are stacked. As an example of the multilayer film, a laminated film in which a barrier metal film for preventing diffusion is formed on the surface of a copper film can be cited.

  A typical example of the inert gas is nitrogen gas, but an inert gas such as argon gas or helium gas can also be used.

  As another aspect, by supplying an inert gas to a tank for storing a chemical solution or the above-described dilution tank, it is possible to suppress or prevent an increase in oxygen concentration in the liquid in the tank. Therefore, it is possible to suppress or prevent the dilute chemical solution having an increased oxygen concentration from being supplied into the processing chamber.

  Further, the pipe connected to the processing chamber is structured to include an inner pipe through which the liquid flows and an outer pipe surrounding the inner pipe, and by supplying an inert gas between the inner pipe and the outer pipe, It can be surrounded by an inert gas. Therefore, even when the inner pipe is made of an oxygen permeable material such as a fluororesin, the amount of oxygen that enters the inner pipe through the inner pipe can be reduced. Thereby, it can suppress or prevent that oxygen melt | dissolves in the liquid which distribute | circulates the inside piping, and the oxygen concentration in the said liquid rises. As the outer pipe, for example, a pipe made of PVC or a fluororesin can be used.

  As described above, according to the present invention, it is possible to further suppress the wiring exposed on the substrate surface from being corroded by the substrate processing liquid as compared with the prior art. Therefore, it is possible to provide a substrate processing that hardly degrades the performance of the manufactured integrated circuit element.

It is a schematic diagram which shows the general aspect of the manufacturing apparatus of ultrapure water. 1 is a schematic configuration diagram of a substrate processing apparatus according to a first embodiment. The figure which shows the piping line which supplies a process liquid from the subsystem shown in FIG. 1 to the substrate processing apparatus of this invention. The figure which shows the deformation | transformation aspect 1 of the substrate processing apparatus which concerns on 1st embodiment. The figure which shows the deformation | transformation aspect 2 of the substrate processing apparatus which concerns on 1st embodiment. The figure which shows the deformation | transformation aspect 3 of the substrate processing apparatus which concerns on 1st embodiment. The figure which shows the deformation | transformation aspect 4 of the substrate processing apparatus which concerns on 1st embodiment. The figure which shows the deformation | transformation aspect 5 of the substrate processing apparatus which concerns on 1st embodiment. The figure which shows the preferable aspect of piping used for the substrate processing apparatus which concerns on this invention. It is a typical block diagram of the substrate processing apparatus which concerns on 2nd embodiment. It is a figure which shows the substrate processing apparatus of Example 3 based on the aspect of FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[First embodiment]
FIG. 2 is a schematic configuration diagram for explaining the configuration of the substrate processing apparatus according to the first embodiment. The substrate processing apparatus 1 of the first embodiment is a single-wafer type apparatus that processes substrates W one by one. In this embodiment, the substrate W is a circular substrate such as a semiconductor wafer.

  Referring to FIG. 2, the substrate processing apparatus 1 has one or a plurality of processing chambers 2 partitioned by a partition wall. In each processing chamber 2, a spin chuck 3 (substrate holding mechanism, substrate holding and rotating mechanism) that holds and rotates a single substrate W horizontally, and a processing liquid on the upper surface of the substrate W held by the spin chuck 3. And a treatment liquid nozzle 4 for supplying the liquid.

  The spin chuck 3 includes a disc-shaped spin base 8 (holding base) that is horizontally attached to an upper end of a rotating shaft extending in a vertical direction, a plurality of clamping members 6 disposed on the spin base 8, And a chuck rotation driving mechanism 7 coupled to the rotation shaft. The spin base 8 is a disk-shaped member having a diameter larger than that of the substrate W, for example. The upper surface of the spin base 8 (the surface of the holding base) is a circular plane having a diameter larger than that of the substrate W.

  The plurality of clamping members 6 can clamp (hold) one substrate W in a horizontal posture in cooperation with each other on the upper surface of the spin base 8. The substrate W held by the clamping member 6 is rotated around a vertical rotation axis passing through the center by the driving force of the chuck rotation driving mechanism 7.

  The processing liquid nozzle 4 can discharge a target processing liquid such as a cleaning process or etching onto the upper surface of the substrate W held by the spin chuck 3. The treatment liquid nozzle 4 is attached to the tip of a nozzle arm 19 that extends horizontally. The treatment liquid nozzle 4 is disposed above the spin chuck 3 with its discharge port directed downward.

  A support shaft 20 extending along the vertical direction is coupled to the nozzle arm 19. The support shaft 20 can swing around its central axis. The support shaft 20 is coupled to a nozzle swing driving mechanism configured by, for example, a motor. The treatment liquid nozzle 4 and the nozzle arm 19 are horizontally moved integrally around the central axis of the support shaft 20 by the driving force of the nozzle swing drive mechanism. Thereby, the processing liquid nozzle 4 can be disposed above the substrate W held by the spin chuck 3, and the processing liquid nozzle 4 can be retracted from above the spin chuck 3. Further, while the substrate W is rotated by the spin chuck 3, the processing liquid nozzle 4 is swung in a predetermined angle range while supplying the processing liquid droplets from the processing liquid nozzle 4 to the upper surface of the substrate W. Thus, the processing liquid supply position on the upper surface of the substrate W can be moved.

  A processing liquid supply pipe 27 is connected to the processing liquid nozzle 4 through the hollow arm 19 and the support shaft 20.

  The processing liquid supply pipe 27 is provided with a processing liquid valve 28 for switching between supply and stop of processing liquid supply to the processing liquid nozzle 4.

  Further, a gas supply pipe 39 is inserted into the processing chamber 2. Nitrogen gas, which is an example of an inert gas, is supplied into the processing chamber 2 from the gas supply pipe 39. Thereby, the air existing in the space above the substrate W can be replaced with the inert gas. For this reason, the inert gas is preferably supplied around the substrate W held by the spin chuck 3, particularly in the space between the processing liquid nozzle 4 and the spin chuck 3.

  The gas supply pipe 39 is provided with a gas valve 18 for switching between supply and stop of supply of the inert gas to the gap, and a gas flow rate adjustment valve 41 for adjusting the supply flow rate of the inert gas to the gap. ing.

  The opening / closing operations of the processing liquid valve 28, the gas valve 18 and the gas flow rate adjusting valve 41 are controlled by the control unit 5. Instead of the gas valve 18 and the gas flow rate adjustment valve 41, a valve capable of simultaneously opening and closing and adjusting the flow rate may be used.

  Further, in the present invention, as shown in FIG. 3, ultrapure water (liquid to be processed) from the subsystem 9 (see FIG. 1 for details) of the ultrapure water production apparatus is supplied to each processing chamber 2 ( To the cleaning mechanism). The outlet 9b from the ultrapure water (liquid to be processed) circulation pipe 9a of the subsystem 9 and the ultrapure water (liquid to be processed) inlet 1a of each substrate processing apparatus 1 are PVC or PFA mainly used in the semiconductor manufacturing line. Are connected through a main pipe 10 made of a fluororesin such as PTFE. Each main pipe 10 extends in each substrate processing apparatus 1 and branches, and is connected to a processing liquid supply pipe 27 that communicates with the processing liquid nozzle 4 of each processing chamber 2 in the substrate processing apparatus 1. The processing liquid supply pipe 27 is also made of a fluororesin such as PVC, PFA, or PTFE.

  A catalyst unit 21 (see FIG. 2) is installed near the ultrapure water inlet 1a of the substrate processing apparatus 1 in the main pipe 10, and further, a membrane separation unit 22 (see FIG. 2) is placed downstream of the catalyst unit 21 in the main pipe 10. ) Is installed.

  The ultrapure water (treatment liquid) supplied from the main pipe 10 to the catalyst unit 21 is a hydrogen-dissolved treatment liquid having a dissolved hydrogen concentration of 8 μg / L or more (preferably 15 μg / L or more, more preferably 66 μg / L or more). It has been adjusted. The ultrapure water (liquid to be treated) discharged from the subsystem 9 to the main pipe 10 is treated by a hydrogen dissolution treatment apparatus (see FIG. 1) of the subsystem 9 and has a predetermined dissolved hydrogen concentration. It is. However, if the dissolved hydrogen concentration of the hydrogen-dissolved water is not more than 8 μg / L (preferably 15 μg / L or more, more preferably 66 μg / L or more) at the position immediately before the catalyst unit 21 in FIG. Hydrogen is added to the hydrogen-dissolved water so that the dissolved hydrogen concentration of the hydrogen-dissolved water is adjusted to 8 μg / L or more (preferably 15 μg / L or more, more preferably 66 μg / L or more). In this case, a hydrogen gas introducing device (not shown) is provided in the piping portion immediately before the catalyst unit 21.

  The catalyst unit 21 is a platinum group metal catalyst that reduces the dissolved oxygen concentration to 2 μg / L or less and the hydrogen peroxide concentration to 2 μg / L or less in the hydrogen-dissolved treatment liquid obtained by passing hydrogen-dissolved water through the catalyst unit 21. It has a filled aspect. For example, a catalyst unit filled with a palladium catalyst or a catalyst unit in which a palladium catalyst is supported on a monolithic organic porous anion exchanger can be mentioned, and more specific examples of the platinum group metal catalyst will be described later. (Refer to the third embodiment).

  In the present embodiment, the catalyst unit 21 is located near the ultrapure water inlet 1 a (FIG. 3) of the substrate processing apparatus 1 in the main pipe 10. However, the catalyst unit 21 is not limited to this position. What is necessary is just to be arrange | positioned inside the chamber 2. FIG.

  In addition, “the vicinity of the processing chamber” specifically includes the following several positions (first to fifth examples). As a first example, supply of ultrapure water (liquid to be treated) from the outlet (branch port) 9b from the ultrapure water circulation pipe 9a of the subsystem 9 shown in FIG. A catalyst unit 21 is installed on the road. As a second example, the catalyst unit 21 is installed in the ultrapure water supply path from the outlet 9 b from the ultrapure water circulation pipe 9 a of the subsystem 9 to the ultrapure water inlet 1 a of the substrate processing apparatus 1. . As a third example, the catalyst unit 21 is installed in the ultrapure water supply path within 10 m (more preferably within 5 m) upstream from the ultrapure water inlet 1 a of the substrate processing apparatus 1. As a fourth example, the catalyst unit 21 is installed in the ultrapure water supply path from the ultrapure water inlet 1 a of the substrate processing apparatus 1 to the first branch point 10 a of the main pipe 10 that goes to each processing chamber 2. . As a fifth example, the catalyst unit 21 is installed in the processing liquid supply pipe 27 connected to each processing chamber 2.

  Furthermore, the catalyst unit 21 may be located not only in the vicinity of the processing chamber 2 but also in the processing chamber 2. Specifically, the “inside of the processing chamber” includes the following several positions. . That is, the catalyst unit 21 may be disposed in any one of the hollow support shaft 20, the nozzle arm 19, or the treatment liquid nozzle 4, which is an ultrapure water supply path in the treatment chamber 2 shown in FIG. 2. .

  Further, in the present embodiment, the membrane separation unit 22 is arranged in the piping portion from the catalyst unit 21 to the first branch point 10a as shown in FIG. . As the membrane separation unit 22, a microfiltration membrane (MF), an ultrafiltration membrane (UF), or a nanofilter (NF) can be used.

  According to the aspects of the present invention, the following problems can be solved.

  Even if ultrapure water in which dissolved oxygen is reduced is produced by the subsystem 9, air is supplied from the subsystem 9 to the substrate processing apparatus 1 through a long pipe, and the air is connected to the joint portion of the pipe. The amount of dissolved oxygen in the ultrapure water in the pipe increases due to intrusion into or through the pipe from the flange. When this ultrapure water is used as a substrate processing solution, there is a problem that the wiring exposed on the surface of the substrate to be processed is corroded (that is, metal is eluted or oxidized). Due to the recent miniaturization of pattern dimensions, the film thickness of wiring made of copper, tungsten, molybdenum or the like has also been reduced, so even a slight corrosion is expected to have a great influence on the performance of semiconductor circuit elements.

  In view of such a problem, in the aspect of the present invention, a mechanism (gas supply pipe 39) in which the catalyst unit 21 is provided in the vicinity of the processing chamber 2 or in the processing chamber 2 as described above and the processing chamber 2 is filled with an inert gas. In the processing chamber 2 in which the oxygen gas concentration on the surface of the substrate to be processed is reduced to a predetermined value or less by providing the gas valve 18 or the like, a hydrogen-dissolved processing solution in which oxygen and hydrogen peroxide are reduced to a predetermined value or less is provided. It is possible to process the substrate to be processed. For this reason, corrosion of the wiring exposed on the surface of the substrate to be processed can be further suppressed as compared with the conventional substrate processing apparatus.

  As a method for removing oxygen from ultrapure water, there is a method using vacuum deaeration (including membrane deaeration). However, vacuum deaeration removes all gas components including oxygen (such as nitrogen) from ultrapure water. Therefore, there is a problem that the gas partial pressure becomes low and it becomes easy to draw outside air into the ultrapure water. Since only dissolved oxygen is removed by deoxidation by catalytic reduction, there is an effect that fluctuation of the partial pressure of gas contained in ultrapure water is suppressed and water quality is easily maintained.

  In addition, the catalyst unit 21 is installed in the vicinity of the processing chamber 2 or in the processing chamber 2, and “the vicinity of the processing chamber” or “the inside of the processing chamber” physically includes the place as described above. explained. This place is described in terms of a functional expression. “Near the processing chamber” or “the inside of the processing chamber” means that the dissolved oxygen concentration is 2 μg / L or less in the processing liquid discharge portion of the processing chamber 2 and the hydrogen peroxide concentration. Is a position where 2 μg / L or less.

  Further, in the present invention, the above-described problems can be solved even if the “membrane separation unit (22)” is not installed. However, if the membrane separation unit 22 is installed at the subsequent stage of the catalyst unit 21, the treatment is performed. It is preferable because fine particles can be removed from the substrate processing liquid supplied to the room. Therefore, in this specification, the membrane separation unit 22 is illustrated in the subsequent stage of the catalyst unit 21.

<Deformation mode 1>
2 described above removes dissolved oxygen and hydrogen peroxide from hydrogen-dissolved water using a means including a catalyst unit 21 and a membrane separation unit 22, and then removes the hydrogen-dissolved treatment liquid from which each of them has been removed. Although it sends to the processing chamber 2, this invention can also take the aspect of FIG. In the embodiment of FIG. 4, means including a catalyst unit 21 and a membrane separation unit 22 is installed for each processing liquid supply pipe 27 disposed in each processing chamber 2. According to this aspect, the means including the catalyst unit 21 and the membrane separation unit 22 can be disposed closer to the processing chamber 2 than in the aspect of FIG. For this reason, the piping from the membrane separation unit 22 of the means to the processing liquid nozzle 4 of the processing chamber 2 is also shortened, and therefore the probability that oxygen is contained in the processing liquid discharged to the substrate in the processing chamber 2 is further reduced. be able to.

  Further, in the embodiment of FIG. 4, a drain pipe 23 is connected to a pipe portion from the membrane separation unit 22 to the treatment liquid valve 28. A drainage valve 24 for switching between drainage and drainage stop is interposed in the drainage pipe 23. The opening / closing operation of the drain valve 24 is also controlled by the control unit 5. While the substrate processing in the processing chamber 2 is stopped, the hydrogen-dissolving processing liquid may stagnate in the catalyst unit 21, and in this case, impurities may be eluted into the processing liquid supply pipe 27. For this reason, when the substrate processing in the processing chamber 2 is stopped for a certain time, the hydrogen-dissolved processing liquid in the processing liquid supply pipe 27 is drained (blowed) from the drain pipe 23 and then a new hydrogen-dissolving processing liquid is supplied to the substrate W. It is made to supply.

  As another method of discharging impurities eluted into the processing liquid supply pipe 27, the processing liquid nozzle 28 is opened with the position of the processing liquid nozzle 4 being removed from the upper part of the substrate W, and the process liquid supply pipe 27 stays in the processing liquid supply pipe 27. A method for discharging the hydrogen-dissolving treatment liquid can also be used. In this case, the drain pipe 23 and the drain valve 24 are unnecessary.

<Deformation mode 2>
In the embodiment of FIG. 2 described above, after the dissolved oxygen and hydrogen peroxide are removed from the hydrogen-dissolved water using the means including the catalyst unit 21 and the membrane separation unit 22, the hydrogen-dissolved treatment liquid from which they have been removed is used for each of them. Although it has sent to the processing chamber 2, this invention can also take the aspect of FIG. That is, in this embodiment, a chemical solution is mixed with the hydrogen-dissolved processing solution from which dissolved oxygen and hydrogen peroxide have been removed to prepare a diluted chemical solution, which is supplied to the processing solution nozzle 4. This is effective when a chemical solution that cannot be passed through the catalyst unit 21 is used.

  Referring to FIG. 5, a chemical liquid preparation unit 51 is added to the processing liquid supply pipe 27 in the mode shown in FIG.

  The chemical solution preparation unit 51 is a pipe capable of mixing the hydrogen-dissolved treatment solution from which dissolved oxygen and hydrogen peroxide have been removed using means including the catalyst unit 21 and the membrane separation unit 22 and the chemical solution therein. The mixing part 52 is comprised.

  A first chemical solution supply pipe 53 that supplies a chemical solution is connected to the mixing unit 52. A chemical liquid valve 54 and a chemical liquid flow rate adjustment valve 55 are interposed in the first chemical liquid supply pipe 53.

The “chemical solution” means a chemical solution before mixing with the inert gas-dissolved water. Examples of chemical solutions include hydrofluoric acid (HF), hydrochloric acid (HCl), IPA (isopropyl alcohol), a mixture of hydrofluoric acid and IPA (isopropyl alcohol), ammonium fluoride (NH ₄ F), ammonia ( NH ₃ ) can be exemplified. When hydrofluoric acid is used as the chemical solution for the purpose of etching, hydrofluoric acid and hydrogen-dissolved treatment liquid are mixed (prepared) at a predetermined ratio in the mixing unit 52, and dilute hydrofluoric acid (DHF) is generated. Is done.

  By opening the chemical liquid valve 54, the chemical liquid having a predetermined flow rate adjusted by the chemical liquid flow rate adjusting valve 55 can be supplied to the mixing unit 52. By opening the chemical liquid valve 54 with the processing liquid valve 28 open, the chemical liquid is injected (injected) into the hydrogen-dissolving processing liquid circulating in the mixing section 52 to mix the chemical liquid and the hydrogen-dissolving processing liquid. Can be made. Therefore, a chemical solution diluted to a predetermined ratio can be prepared by adjusting the supply amount of the chemical solution to the mixing unit 52 and the supply amount of the hydrogen dissolution treatment liquid.

  Further, by opening only the processing liquid valve 28 without opening the chemical liquid valve 54, only the hydrogen-dissolving processing liquid can be supplied to the mixing unit 52. Thereby, the hydrogen-dissolved treatment liquid can be supplied as it is to the treatment liquid nozzle 4 as a rinse liquid without mixing the chemical solution with the hydrogen-dissolved treatment liquid.

  The end of the first chemical liquid supply pipe 53 is inserted into a chemical liquid tank 56 that stores the chemical liquid. The chemical liquid tank 56 is a sealed container, and the internal space of the chemical liquid tank 56 is blocked from the external space. A pump 57 is interposed between the chemical solution valve 54 and the chemical solution tank 56 in the first chemical solution supply pipe 53. Furthermore, it is preferable that a filter and a deaeration unit (not shown) are interposed in the first chemical solution supply pipe 53 on the downstream side of the pump 57. The first chemical liquid supply pipe 53 is divided into two branches downstream of the pump 57: a path toward the chemical liquid valve 54 and the mixing unit 52 and a path toward another processing chamber.

  Further, a second chemical liquid supply pipe 75 is connected to the chemical liquid tank 56. A chemical solution from a chemical solution supply source (not shown) is supplied to the chemical solution tank 56 via a chemical solution supply pipe 75. The second chemical liquid supply pipe 75 is provided with a chemical liquid valve 76 for switching supply and stop of supply of the chemical liquid to the chemical liquid tank 56. For example, an unused chemical solution is supplied to the chemical solution tank 56 when the amount of the liquid in the chemical solution tank 56 becomes a predetermined amount or less. Thereby, the chemical tank 56 can be replenished with unused chemical liquid.

  Further, an inert gas supply pipe 77 is connected to the chemical tank 56. The chemical liquid tank 56 is supplied with an inert gas from an inert gas supply source (not shown) via an inert gas supply pipe 77. The inert gas supply pipe 77 is provided with an inert gas valve 78 for switching between supply and stop of supply of the inert gas to the chemical tank 56. For example, an inert gas is constantly supplied to the chemical tank 56. In this modification, an inert gas supply means is constituted by the inert gas supply pipe 77 and the inert gas valve 78.

  By supplying an inert gas to the chemical liquid tank 56, air can be expelled from the chemical liquid tank 56. Therefore, it is possible to suppress or prevent the oxygen contained in the air in the chemical liquid tank 56 from being dissolved in the chemical liquid stored in the chemical liquid tank 56 and increasing the amount of dissolved oxygen in the chemical liquid. It is also possible to pressurize the chemical liquid stored in the chemical liquid tank 56 to the first chemical liquid supply pipe 53 by pressurizing the chemical liquid tank 56 with an inert gas.

  The chemical solution in the chemical solution tank 56 is pumped out of the chemical solution tank 56 by the pressure of the inert gas and the suction force by the pump 57 and sent to the first chemical solution supply pipe 53. At this time, if a filter and a deaeration unit are provided immediately downstream of the pump 57, the chemical liquid pumped out by the pump 57 passes through the filter to remove foreign substances in the liquid. Furthermore, the chemical solution that has passed through the filter is degassed by the degassing unit, and the amount of dissolved oxygen is reduced. As a result, a chemical solution with a reduced dissolved oxygen amount can be supplied to the mixing unit 52, and the effects of the present invention can be further enhanced. Regarding the installation of the filter and the deaeration unit, they may be installed downstream of the pump 57 in the order of the deaeration unit and the filter. Even in this case, the same effect can be obtained.

  In addition, you may apply this deformation | transformation aspect 2 to the deformation | transformation aspect 1 shown in FIG. In this case, it is preferable that the chemical solution preparation unit 51 is configured in a pipe portion between the catalyst unit 21 and the membrane separation unit 22 in the modification 1.

<Deformation mode 3>
In the embodiment of FIG. 5 described above, the chemical liquid is injected into the hydrogen-dissolved processing liquid flowing in the mixing unit 52 that is a part of the processing liquid supply pipe 27, and the chemical liquid and the hydrogen-dissolving processing liquid are mixed. However, the present invention can also take the form of FIG. In other words, a hydrogen-dissolving treatment liquid that circulates in the treatment liquid supply pipe 27 and a chemical solution are introduced into the tank, and the chemical solution is diluted with the hydrogen-dissolving treatment solution and supplied to the treatment liquid nozzle 4. This is effective when a chemical solution that cannot be passed through the catalyst unit 21 is used and when it is difficult to achieve the target dilution rate in the embodiment of FIG. 5 (mixing unit 52 in the pipe).

  Referring to FIG. 6, a chemical liquid preparation unit 81 is added to the processing liquid supply pipe 27 in the aspect shown in FIG.

  The chemical solution preparation unit 81 receives a hydrogen-dissolved treatment solution from which dissolved oxygen and hydrogen peroxide have been removed using means including the catalyst unit 21 and the membrane separation unit 22 and a chemical solution to prepare a diluted chemical solution. A dilution tank 82 is provided. The chemical solution dilution tank 82 is a closed container, and the internal space of the chemical solution dilution tank 82 is blocked from the external space.

  One end of a diluted chemical solution supply pipe 83 for supplying a diluted chemical solution is inserted into the chemical solution dilution tank 82. The other end of the diluted chemical supply pipe 83 is connected to a portion of the processing liquid supply pipe 27 that is downstream from the processing liquid valve 28. The diluted chemical solution supply pipe 83 is provided with a diluted chemical solution valve 84 for switching between supply and stop of supply of the diluted chemical solution to the treatment liquid supply tube 27.

  Further, a pump 57 is interposed between the diluted chemical solution valve 84 and the chemical solution dilution tank 82 in the diluted chemical solution supply pipe 83. It is preferable that a filter and a deaeration unit (not shown) are interposed in the portion of the diluent supply pipe 83 on the downstream side of the pump 57. The diluting chemical liquid supply pipe 83 is branched into two paths downstream of the pump 57: a path toward the diluting chemical liquid valve 84 and a path toward another processing chamber.

  In addition, one end of a second processing liquid supply pipe 85 that supplies a hydrogen-dissolving processing liquid is inserted into the chemical liquid dilution tank 82. The other end of the second processing liquid supply pipe 85 is connected to a portion of the processing liquid supply pipe 27 that is upstream of the processing liquid valve 28. The second treatment liquid supply pipe 85 is supplied with a treatment liquid valve 86 for switching between supply and stop of supply of the hydrogen dissolution treatment liquid to the chemical dilution tank 82 and a hydrogen dissolution treatment liquid supplied to the chemical dilution tank 82. And a processing liquid flow rate adjustment valve 87 for adjusting the flow rate of the liquid.

  A chemical solution supply pipe 75 is connected to the chemical solution dilution tank 82. A chemical solution from a chemical solution supply source (not shown) is supplied into the chemical solution dilution tank 82 via a chemical solution supply pipe 75. The chemical solution supply pipe 75 includes a chemical solution valve 76 for switching supply and stop of supply of the chemical solution to the chemical solution dilution tank 82, and a chemical solution flow rate adjusting valve 79 for adjusting the chemical solution supplied to the chemical solution dilution tank 82 to a predetermined flow rate. , Is intervening.

  Further, an inert gas supply pipe 77 is connected to the chemical solution dilution tank 82. An inert gas from an inert gas supply source (not shown) is supplied to the chemical solution dilution tank 82 via an inert gas supply pipe 77. The inert gas supply pipe 77 is provided with an inert gas valve 78 for switching between supply and stop of supply of the inert gas to the chemical solution dilution tank 82. For example, an inert gas is constantly supplied to the chemical dilution tank 82. The inert gas supply pipe 77 and the inert gas valve 78 constitute an inert gas supply means.

  In this aspect, by opening another processing liquid valve 86 without opening the processing liquid valve 28, a predetermined flow rate of hydrogen-dissolved processing liquid adjusted by the processing liquid flow rate adjustment valve 87 is supplied to the chemical dilution tank 82. Can do. In addition, by opening the chemical liquid valve 76 without opening the processing liquid valve 28, the chemical liquid having a predetermined flow rate adjusted by the chemical liquid flow rate adjusting valve 79 can be supplied to the chemical liquid dilution tank 82. By these operations, the chemical solution and the hydrogen dissolution treatment solution can be mixed in the chemical solution dilution tank 82. Therefore, the chemical solution diluted to a predetermined ratio is adjusted by adjusting the supply amount of the chemical solution and the supply amount of the hydrogen-dissolving treatment liquid by using the treatment liquid flow rate adjustment valve 87 and the chemical solution flow rate adjustment valve 79. Can be prepared in-house. Then, it is possible to supply the diluted chemical liquid to the processing liquid nozzle 4 by opening only the diluted chemical liquid valve 84 without opening the processing liquid valve 28.

  On the other hand, by opening only the processing liquid valve 28 without opening the diluting chemical liquid valve 84, only the hydrogen-dissolving processing liquid can be supplied to the processing chamber 2. Thereby, the hydrogen-dissolved treatment liquid can be supplied as it is to the treatment liquid nozzle 4 as a rinse liquid without mixing the chemical solution with the hydrogen-dissolved treatment liquid.

  Further, by supplying an inert gas to the chemical solution dilution tank 82 using the inert gas supply pipe 77, air can be expelled from the chemical solution dilution tank 82. Therefore, it is possible to suppress or prevent the oxygen contained in the air in the chemical solution dilution tank 82 from being dissolved in the diluted chemical solution stored in the chemical solution dilution tank 82 and increasing the amount of dissolved oxygen in the diluted chemical solution. . It is also possible to pressurize the diluted chemical solution in the chemical solution dilution tank 82 to the diluted chemical solution supply pipe 83 by pressurizing the chemical solution dilution tank 82 with an inert gas.

  The diluted chemical solution in the chemical solution dilution tank 82 is pumped out of the chemical solution dilution tank 82 and sent to the diluted chemical solution supply pipe 83 by the pressure of the inert gas or the suction force by the pump 57. At this time, if a filter and a deaeration unit are provided immediately downstream of the pump 57, the diluted chemical liquid pumped out by the pump 57 passes through the filter to remove foreign substances in the liquid. Furthermore, the diluted chemical solution that has passed through the filter is degassed by the degassing unit, and the amount of dissolved oxygen is reduced. As a result, it is possible to supply the treatment liquid supply pipe 27 with a diluted chemical solution with a reduced amount of dissolved oxygen, and the effects of the present invention can be further enhanced. Regarding the installation of the filter and the deaeration unit, they may be installed downstream of the pump 57 in the order of the deaeration unit and the filter. Even in this case, the same effect can be obtained.

  In addition, you may apply this deformation | transformation aspect 3 to the deformation | transformation aspect 1 shown in FIG. In this case, it is preferable to arrange the chemical solution preparation unit 81 in the piping portion between the catalyst unit 21 and the membrane separation unit 22 in the modified embodiment 1.

  Furthermore, in this modification 3, the other process liquid supply pipe 90 that supplies another process liquid (for example, process water that does not require hydrogen addition, such as ozone water) to the process liquid nozzle 4 is provided. The processing liquid supply pipe 27 may be connected to the downstream side of the processing liquid valve 28. The processing liquid supply pipe 90 is provided with a processing liquid valve 91 for switching between supply and stop of supply of other processing liquids to the processing liquid nozzle 4. By switching the opening / closing operation of each of the processing liquid valve 28, the processing liquid valve 91, and the diluting chemical liquid valve 84 by the control unit 5, the processing liquid can be selected.

<Deformation aspect 4>
Although the processing liquid nozzles 4 of the various modes described above are held by the nozzle arm 19 and the support shaft 20, the mode shown in FIG. Instead of the treatment liquid nozzle 4 held by the nozzle arm 19 and the support shaft 20, the embodiment of FIG.

  Referring to FIG. 7, the blocking plate 11 is a disk-like member having a substantially constant thickness. The diameter of the blocking plate 11 is larger than that of the substrate W. The blocking plate 11 is disposed horizontally above the spin chuck 3 so that the central axis thereof is located on the same axis as the rotation axis of the spin chuck 3.

  The blocking plate 11 has a flat plate portion 33 having a disk shape. The lower surface of the flat plate portion 33 is formed in a plane and is parallel to the upper surface of the substrate W held by the spin chuck 3. The lower surface of the flat plate portion 33 is a substrate facing surface 34 that faces the substrate W held by the spin chuck 3. The substrate facing surface 34 faces the substrate W held by the spin chuck 3 and faces the upper surface of the spin base 8. Preferably, as shown in FIG. 7, the outer peripheral portion of the blocking plate 11 is bent downward over the entire circumference to form a cylindrical peripheral wall portion 32. In other words, the peripheral wall portion 32 protruding from the periphery of the substrate facing surface 34 toward the spin chuck 3 may be formed.

  A central portion of the blocking plate 11 has a hollow support shaft 31 that supports the blocking plate 11, and a processing liquid supply pipe 27 is inserted into the support shaft 31. One or more discharge ports (not shown) are formed in the blocking plate 11 and communicate with the internal space of the support shaft 31. The processing liquid is supplied to the internal space of the support shaft 31 through the processing liquid supply pipe 27. Thereby, the processing liquid can be discharged from the discharge port formed in the blocking plate 11 toward the upper surface portion of the substrate W held by the spin chuck 3.

  Further, a gas supply pipe 39 is inserted into the support shaft 31. Nitrogen gas, which is an example of an inert gas, is supplied from the gas supply pipe 39 to the internal space of the support shaft 31. The inert gas supplied to the internal space of the support shaft 31 is discharged downward from a discharge port (not shown) formed in the blocking plate 11. For this reason, an inert gas can be supplied to the space (gap) between the shielding plate 11 and the substrate W held by the spin chuck 3.

  The gas supply pipe 39 is provided with a gas valve 18 for switching between supply and stop of supply of the inert gas to the gap, and a gas flow rate adjustment valve 41 for adjusting the supply flow rate of the inert gas to the gap. ing.

  Further, the support shaft 31 is coupled with a shield plate lifting drive mechanism (a shield member moving mechanism) and a shield plate rotation drive mechanism. By the driving force of the blocking plate lifting / lowering drive mechanism, the support shaft 31 and the blocking plate 11 are moved between a processing position where the substrate facing surface 34 approaches the upper surface of the spin base 8 and a retreat position where the substrate facing surface 34 is far away from the upper surface of the spin base 8. Can be moved up and down integrally. Furthermore, the support shaft 31 and the blocking plate 11 can be rotated integrally around the common axis with the substrate W by the driving force of the blocking plate rotation drive mechanism. Thereby, for example, the support shaft 31 and the blocking plate 11 can be rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or with slightly different rotational speeds).

  In the embodiment of FIG. 7, when the blocking plate 11 is positioned at the processing position while the substrate W is held on the spin chuck 3, and the inert gas is discharged from the discharge port positioned on the substrate facing surface 34, The active gas spreads outward in the space between the upper surface of the substrate W held by the spin chuck 3 and the substrate facing surface 34. Therefore, the air existing in the space between the upper surface of the substrate W and the substrate facing surface 34 is pushed outward by the inert gas, and is formed between the tip edge of the peripheral wall portion 32 and the upper surface of the spin base 8. It is discharged from the gap. Thereby, the atmosphere between the upper surface of the substrate W and the substrate facing surface 34 can be replaced with an inert gas.

  Further, when the blocking plate 11 is positioned at the processing position while the substrate W is held on the spin chuck 3, the space between the upper surface of the substrate W and the substrate facing surface 34 can be surrounded by the peripheral wall portion 32. It is possible to suppress or prevent the surrounding air from entering the outer peripheral portion of the space. Thereby, after the atmosphere between the upper surface of the substrate W and the substrate facing surface 34 is replaced with an inert gas atmosphere, air enters the space between the upper surface of the substrate W and the substrate facing surface 34, and An increase in the oxygen concentration in the space can be suppressed or prevented.

<Deformation mode 5>
The various modes described so far are the nozzle mode in which the processing liquid nozzle 4 is disposed above the spin check 3 holding the substrate W, or the blocking plate 11 in which the processing liquid discharge port is formed is the spin check 3. It was either of the shielding board aspects arrange | positioned above. However, the present invention may include both the nozzle mode and the blocking plate mode as shown in FIG.

  Further, the number of the processing liquid nozzles is not limited to one, and may be provided for each purpose of processing such as cleaning and etching, or for each type of processing liquid. For example, as shown in FIG. 8, a processing liquid nozzle 4 a for cleaning the peripheral edge of the substrate W may be installed in the processing chamber 2. A treatment liquid nozzle (not shown) for cleaning the blocking plate 11, particularly the substrate facing surface 34, may be provided. Alternatively, a mode in which the processing liquid is supplied to the lower surface of the substrate W through the processing liquid supply pipe 27 inside the spin chuck 3 that is the substrate holding mechanism can also be adopted.

  Further, the treatment liquid nozzle may be, for example, a two-fluid nozzle that generates a droplet of the treatment liquid by mixing the treatment liquid supplied into the nozzle and an inert gas.

<Deformation mode 6>
FIG. 9 is a view showing a preferred mode of piping used in the substrate processing apparatus 1 according to the present invention.

  The above-described piping from the catalyst unit 21 to the discharge port formed in the processing liquid nozzle 4 or the blocking plate 11, piping from the catalyst unit 21 to the chemical dilution tank 82, and from the chemical dilution tank 82 to the processing liquid nozzle 4 or the blocking plate 11 It is preferable that any or all of the pipes extending to the discharge port are formed in the form shown in FIG. In this description, all the pipes are collectively referred to as “pipe 100”.

  Referring to FIG. 9, the pipe 100 has a double structure, and has an inner pipe 101 through which the processing liquid flows and an outer pipe 102 surrounding the inner pipe 101. The inner pipe 101 is supported inside the outer pipe 102 by a support member (not shown) interposed between the inner pipe 101 and the outer pipe 102. The inner pipe 101 is supported in a non-contact state with respect to the outer pipe 102. A cylindrical space is formed between the inner pipe 101 and the outer pipe 102. The inner pipe 101 is made of, for example, a fluororesin such as PFA or PTFE having excellent chemical resistance and heat resistance. The fluororesin can transmit oxygen. As the outer pipe, for example, a pipe made of PVC or a fluororesin can be used.

  The outer pipe 102 is connected to an inert gas supply pipe 104 provided with an inert gas valve 103 and an exhaust pipe 106 provided with an exhaust valve 105. By opening the inert gas valve 103, an inert gas from an inert gas supply source (not shown) (for example, nitrogen gas) can be supplied into the outer pipe 102 through the inert gas supply pipe 104. Thereby, it is possible to fill the inert gas between the inner pipe 101 and the outer pipe 102. The inert gas valve 103 and the inert gas supply pipe 104 constitute an inert gas filling means. Further, by opening the exhaust valve 105, gas can be exhausted from between the inner pipe 101 and the outer pipe 102.

  By opening the inert gas valve 103 while the exhaust valve 105 is opened, air can be expelled from between the inner pipe 101 and the outer pipe 102, and the atmosphere in the meantime can be replaced with an inert gas atmosphere. Thereby, the inner side piping 101 can be surrounded by an inert gas. Then, after the atmosphere between the inner pipe 101 and the outer pipe 102 is replaced with an inert gas atmosphere, the inner pipe 101 is surrounded by the inert gas by closing the inert gas valve 103 and the exhaust valve 105. Can be maintained.

  By enclosing the inner pipe 101 with an inert gas, the amount of oxygen that enters the inner pipe 101 through the pipe wall of the inner pipe 101 can be reduced. Thereby, it can suppress or prevent that oxygen melt | dissolves in the process liquid which distribute | circulates the inside of the inner side piping 101, and the oxygen concentration in the said process liquid rises.

[Second Embodiment]
Although the processing chamber 2 of the first embodiment described above has a single wafer cleaning mechanism, the processing chamber included in the present invention is not limited to this, and is a processing chamber having a batch cleaning mechanism. May be.

  FIG. 10 shows an example in which the processing chamber in the mode (modified mode 2) in FIG. 5 is replaced with a processing chamber having a batch type cleaning mechanism. However, this figure is an example, and not only the above-described modification 2 but also each of or all of the above-described other modifications 1 to 6 are applied to the processing chamber 2 equipped with the batch-type cleaning mechanism. Can do. In addition, the same code | symbol is attached | subjected to the same component as 1st embodiment, and since it is the same as 1st embodiment, the description of the component is omitted.

  Referring to FIG. 10, the processing chamber 2 of the substrate processing apparatus 1 according to the second embodiment has a processing tank 201 for storing a processing solution and cleaning the substrate W with the processing solution. On the outer periphery of the processing tank 201, an overflow unit 202 that receives the processing liquid overflowing from the processing tank 201 is provided.

  In the processing chamber 2, a substrate transport mechanism (not shown) for transporting the substrate W into the processing tank 201 is also provided. A lifter and a chuck are used as the substrate transport mechanism. The chuck conveys a plurality of substrates W from outside the processing chamber 2 to above the processing bath 201 in a state where the plurality of substrates W are collectively held. The lifter receives a plurality of substrates W from the chuck above the processing tank 201, descends in a state where the plurality of substrates W are collectively supported, and is immersed in the processing liquid stored in the processing tank 201. To do.

  A processing liquid nozzle 203 for supplying a processing liquid into the processing tank 201 is disposed at the bottom of the processing tank 201. A pipe branched from the treatment liquid supply pipe 27 is connected to each treatment liquid nozzle 203. Each treatment liquid nozzle 203 is formed with a large number of ejection openings for ejecting the treatment liquid toward the substrate W.

  As described in the first embodiment, the treatment liquid is a hydrogen-dissolved treatment liquid from which dissolved oxygen and hydrogen peroxide have been removed using means including the catalyst unit 21 and the membrane separation unit 22.

  The ejected processing liquid is stored in the processing tank 201 and overflows from the upper end of the processing tank 201. The substrate W is uniformly washed by the upward flow of the processing liquid at this time.

  The processing liquid that has been used for the cleaning process of the substrate W and has overflowed from the upper end of the processing tank 201 is temporarily stored in an overflow unit 202 formed on the outer periphery of the processing tank 201. A drain pipe 206 having a resistivity meter 205 is connected to the bottom of the overflow part 202. For this reason, the pure water temporarily stored in the overflow unit 202 passes through the specific resistance meter 205 and is then discharged out of the substrate processing apparatus 1.

  The specific resistance meter 205 measures the cleanliness of the processing liquid by measuring the specific resistance value of the processing liquid used for cleaning the substrate W, and determines the cleaning degree of the substrate W based on the measured value. Used for purposes.

  Further, in order to quickly discharge the processing liquid stored in the processing tank 201, a discharge port 204 having a relatively large diameter is formed at the bottom of the processing tank 201. A drain pipe 207 for discharging the processing liquid to the outside of the substrate processing apparatus 1 is connected to the discharge port 204. A drain valve 208 that is opened and closed by the control unit 5 is interposed in the drain pipe 207.

  A pair of lid members 209 that operate to open and close the opening of the processing tank 201 are disposed above the processing tank 201. Each lid member 209 has a discharge opening, and a pipe branched from the gas supply pipe 39 is connected to the discharge opening. As a result, the inert gas can be supplied into the processing tank 201 covered with the lid member 209 and the space above the processing liquid in the processing tank 201 can be purged with the inert gas.

  As described above, the inert gas discharge port is formed in the lid member 209 without providing the nozzle for supplying the inert gas in the treatment tank 201, so that the space in the vertical direction composed of the processing tank 201 and the lid member 209 is formed. It is possible to prevent the substrate processing apparatus 1 from becoming large. Further, since the distance between the liquid level of the processing liquid stored in the processing tank 201 and the lower surface of the lid member 209 can be reduced, the amount of inert gas supplied into the processing tank 201 can be reduced. Is possible.

[Third embodiment]
A specific example of the catalyst for removing dissolved oxygen and removing hydrogen peroxide used in the catalyst unit 21 of the substrate processing apparatus 1 described above will be described in detail.

<Catalyst for removing dissolved oxygen and hydrogen peroxide>
Examples of the platinum group metal catalyst include a granular ion exchange resin on which a platinum group metal is supported, a metal ion type granular cation exchange resin, a non-particulate organic porous material on which a platinum group metal is supported, or a platinum group. Examples thereof include a non-particulate organic porous ion exchanger carrying a metal.

<Platinum group metal-supported non-particulate organic porous body, platinum group metal-supported non-particulate organic porous ion exchanger>
As the platinum group metal-supported non-particulate organic porous body, fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the non-particulate organic porous body, and the non-particulate organic porous body is a continuous skeleton phase. The continuous skeleton has a thickness of 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, the total pore volume is 0.5 to 50 ml / g, and the supported amount of platinum group metal is A platinum group metal-supported non-particulate organic porous material that is 0.004 to 20% by weight in a dry state.

  Further, as the platinum group metal-supported non-particulate organic porous ion exchanger, fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the non-particulate organic porous ion exchanger. The ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5 to 50 ml / g. The ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the ion exchange groups are uniformly distributed in the organic porous ion exchanger, and the supported amount of the platinum group metal is in the dry state. And a platinum group metal-supported non-particulate organic porous ion exchanger of 0.004 to 20% by weight.

  In addition, the average diameter of the opening of a non-particulate organic porous body or a non-particulate organic porous ion exchanger is measured by the mercury intrusion method, and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method. Further, the structure of the non-particulate organic porous body or the non-particulate organic porous ion exchanger and the thickness of the continuous skeleton are determined by SEM observation. The particle diameter of the platinum group metal nanoparticles supported on the non-granular organic porous material or the non-granular organic porous ion exchanger is determined by TEM observation.

The platinum group metal-supported non-particulate organic porous material or the platinum group metal-supported non-particulate organic porous ion exchanger has a mean particle diameter of 1 to 100 nm. since the platinum group metal is supported, it shows a high hydrogen peroxide decomposition catalytic activity, and, 200～20000H ^-1 preferably be passed through the treated water at a space velocity (SV) of 2000～20000H ^-1 Can do.

  In the platinum group metal-supported non-particulate organic porous body, the carrier on which the platinum group metal is supported is a non-particulate organic porous body. This non-particulate organic porous exchanger is a monolithic organic porous exchange. Is the body. In the platinum group metal-supported non-particulate organic porous ion exchanger, the carrier on which the platinum group metal is supported is a non-particulate organic porous ion exchanger. A monolithic organic porous ion exchanger, in which an ion exchange group is introduced into the monolithic organic porous body.

  The monolithic organic porous body is a porous body having a skeleton formed of an organic polymer and a large number of communication holes serving as a flow path for a reaction solution between the skeletons. The monolithic organic porous ion exchanger is a porous body introduced so that ion exchange groups are uniformly distributed in the skeleton of the monolithic organic porous body. In the present specification, “monolithic organic porous material” is also simply referred to as “monolith”, and “monolithic organic porous ion exchanger” is also simply referred to as “monolith ion exchanger”, and is also an intermediate in the production of monoliths. The “monolithic organic porous intermediate” that is the body (precursor) is also simply referred to as “monolith intermediate”.

  Examples of the structure of such a monolith or monolith ion exchanger are disclosed in Japanese Patent Application Laid-Open No. 2002-306976 and Japanese Patent Application Laid-Open No. 2009-62512, and Japanese Patent Application Laid-Open No. 2009-67982. A co-continuous structure, a particle aggregation type structure disclosed in JP 2009-7550 A, a particle composite type structure disclosed in JP 2009-108294 A, and the like.

  Examples of monoliths serving as carriers for the above monolith, that is, platinum group metal particles (hereinafter also referred to as monolith (1)) and monolith ion exchangers, that is, monolith ion exchangers serving as the carrier for platinum group metal particles Examples of the form (hereinafter also referred to as monolith ion exchanger (1)) include monoliths and monolith ion exchangers having a co-continuous structure disclosed in JP-A No. 2009-67982.

  That is, the monolith (1) is a monolith before the ion exchange group is introduced, and has an average thickness composed of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. Is a co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 100 μm in a dry state and three-dimensionally continuous pores having an average diameter of 1 to 1000 μm in a dry state between the skeletons, It is a monolith that is an organic porous body having a total pore volume of 0.5 to 50 ml / g in a dry state.

  In addition, the monolith ion exchanger (1) has a three-dimensional average thickness of 1 to 100 μm in a dry state of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. A co-continuous structure composed of a continuous skeleton and three-dimensionally continuous pores having an average diameter of 1 to 1000 μm in a dry state between the skeletons, and the total pore volume in the dry state is 0 5 to 50 ml / g, having an ion exchange group, an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, and the ion exchange group in the organic porous ion exchanger It is a monolith ion exchanger that is a monolith ion exchanger that is uniformly distributed.

  The monolith (1) or the monolith ion exchanger (1) has a three-dimensional continuous skeleton having an average thickness of 1 to 100 μm, preferably 3 to 58 μm in a dry state, and an average diameter between the skeletons in a dry state. A co-continuous structure composed of three-dimensionally continuous pores of 1 to 1000 μm, preferably 15 to 180 μm, particularly preferably 20 to 150 μm. The co-continuous structure is a structure in which a continuous skeleton phase and a continuous vacancy phase are intertwined, and both are three-dimensionally continuous. The continuous pores have higher continuity of the pores than the conventional open-cell type monolith and the particle aggregation type monolith, and the size thereof is not biased. Moreover, since the skeleton is thick, the mechanical strength is high.

  If the average diameter of the three-dimensionally continuous pores is less than 1 μm in the dry state, it is not preferable because the pressure loss at the time of passing the liquid increases, and if it exceeds 1000 μm, the reaction solution and the monolith or monolith ion exchanger are not preferred. As a result, the contact with the catalyst becomes insufficient, resulting in insufficient catalytic activity. Moreover, when the average thickness of the skeleton is less than 1 μm in a dry state, the monolith or the monolith ion exchanger is greatly deformed when the liquid is passed at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolith or monolith ion exchanger is lowered, and the catalytic effect is lowered, which is not preferable. On the other hand, if the thickness of the skeleton exceeds 100 μm, the skeleton becomes too thick, and the pressure loss during liquid passage increases, which is not preferable.

  The average diameter of the opening of the monolith (1) in the dry state, the average diameter of the opening of the monolith ion exchanger (1) and the opening of the monolith intermediate (1) in the dry state obtained by the I treatment in the production of the monolith described below The average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore distribution curve obtained by the mercury intrusion method. The average thickness of the skeleton of the monolith (1) or the monolith ion exchanger (1) in the dry state is determined by SEM observation of the dry monolith (1) or the monolith ion exchanger (1). Specifically, the SEM observation of the dried monolith (1) or monolith ion exchanger (1) is performed at least three times, the thickness of the skeleton in the obtained image is measured, and the average value thereof is calculated as the average thickness. Say it. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  Moreover, the total pore volume per weight in the dry state of the monolith (1) or the monolith ion exchanger (1) is 0.5 to 50 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of liquid passing is increased, which is not preferable. Further, the permeation amount per unit cross-sectional area is decreased, and the processing amount is decreased. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 50 ml / g, the mechanical strength is lowered, and the monolith or the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction liquid and the monolith (1) or the monolith ion exchanger (1) is lowered, the catalyst efficiency is also lowered, which is not preferable. If the three-dimensionally continuous pore size and total pore volume are within the above ranges, the contact with the reaction solution is extremely uniform, the contact area is large, and the solution can be passed under a low pressure loss. .

  In the monolith (1) or the monolith ion exchanger (1), the material constituting the skeleton is 0.1 to 5 mol%, preferably 0.5 to 3.0 mol% of a crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, styrene-divinylbenzene copolymer has the advantage of easy co-continuous structure formation, ease of ion exchange group introduction and high mechanical strength, and high stability to acids or alkalis. A polymer or vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  In the monolith ion exchanger (1), the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution status of the ion exchange groups can be easily confirmed by using EPMA. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the monolith, the physical and chemical properties of the surface and the interior can be made uniform, so that they are resistant to swelling and shrinkage. Improves.

  The ion exchange group introduced into the monolith ion exchanger (1) is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. Examples of anion exchange groups include trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, quaternary ammonium group, tertiary sulfonium group, phosphonium group. Etc.

  The monolith ion exchanger (1) has an ion exchange capacity of 1 to 6 mg equivalent / g of ion exchange capacity per weight in a dry state. Since the monolith ion exchanger (1) has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while keeping the pressure loss low. When the ion exchange capacity per weight is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, and thereby the catalyst activity is increased. When the monolith ion exchanger (1) is a monolith anion exchanger, an anion exchange group is introduced into the monolith anion exchanger (1), and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the monolith ion exchanger (1) is a monolith cation exchanger, a cation exchange group is introduced into the monolith cation exchanger (1), and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

  The monolith (1) can be obtained by carrying out the method for producing a monolithic organic porous material disclosed in Japanese Patent Application Laid-Open No. 2009-66792. That is, the production method prepares a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain an ion-exchange group, a surfactant, and water, and then polymerizes the water-in-oil emulsion to form all pores. I treatment for obtaining a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (1)) having a continuous macropore structure having a volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, one In all oil-soluble monomers having at least two vinyl groups in the molecule, 0.3 to 5 mol% of the crosslinking agent, aromatic vinyl monomer and crosslinking agent are dissolved, but the aromatic vinyl monomer is polymerized to form. Preparation of a mixture comprising an organic solvent in which the polymer does not dissolve and a polymerization initiator II treatment, a monolith intermediate obtained by standing the mixture obtained by the II treatment and by the I treatment Polymerization was conducted in the presence of 1), including III treatment, to obtain a monolith (1) is an organic porous material is a co-continuous structure.

  A platinum group metal is supported on the platinum group metal-supported non-particulate organic porous body or the platinum group metal-supported non-particulate organic porous ion exchanger. The platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals, and more than one metal may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.

  The average particle diameter of the platinum group metal particles supported on the platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger is 1-1000 nm, preferably 1-200 nm, More preferably, it is 1-20 nm. If the average particle diameter is less than 1 nm, the possibility that the platinum group metal particles will be detached from the carrier increases, which is not preferable. On the other hand, if the average particle diameter exceeds 1000 nm, the surface area per unit mass of the metal decreases. This is not preferable because the catalytic effect cannot be obtained efficiently. In addition, the average particle diameter of a platinum group metal particle is calculated | required by image-analyzing the TEM image obtained by a transmission electron microscope (TEM) analysis.

  Platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger supported amount of platinum group metal particles ((platinum group metal particles / platinum group metal-supported catalyst in dry state) × 100 ) Is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. If the supported amount of platinum group metal particles is less than 0.004% by weight, the catalytic activity becomes insufficient, such being undesirable. On the other hand, when the amount of platinum group metal particles is more than 20% by weight, metal elution into water is observed, which is not preferable.

  There are no particular restrictions on the method for producing the platinum group metal-supported non-particulate organic porous material or the platinum group metal-supported non-particulate organic porous ion exchanger. A platinum group metal-supported catalyst can be obtained by supporting fine particles of a platinum group metal on a monolith or a monolith ion exchanger by a known method. Examples of the method for supporting the platinum group metal on the non-particulate organic porous body or the non-particulate organic porous ion exchanger include the method disclosed in JP 2010-240641 A. For example, a dried monolith ion exchanger is immersed in a methanol solution of a platinum group metal compound such as palladium acetate, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then contacted with a reducing agent to form palladium metal fine particles. And the monolith ion exchanger is immersed in an aqueous solution of a platinum group metal compound such as a tetraammine palladium complex, and the palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then the reducing agent and In this method, palladium metal fine particles are supported on a monolith ion exchanger by contact.

  The granular ion exchange resin carrying a platinum group metal is one in which a platinum group metal is carried on a granular ion exchange resin. The particulate ion exchange resin that serves as the platinum group metal carrier is not particularly limited, and examples thereof include strongly basic anion exchange resins. Then, the granular ion exchange resin is loaded with a platinum group metal by a known method to obtain a granular ion exchange resin loaded with the platinum group metal.

  The metal ion type granular cation exchange resin on which a metal is supported is obtained by supporting a metal such as iron ion, copper ion, nickel ion, chromium ion or cobalt ion on a granular cation exchange resin. The granular cation exchange resin to be a carrier is not particularly limited, and examples thereof include strongly acidic cation exchange resins. And metal, such as an iron ion, copper ion, nickel ion, chromium ion, and cobalt ion, is carry | supported by a granular cation exchange resin by a well-known method, and a metal ion type granular cation exchange resin is obtained.

  Hereinafter, the catalyst of the catalyst unit 21 used in the present invention will be described more specifically, but this is merely an example and does not limit the present invention.

<Production of platinum group metal-supported non-particulate organic porous ion exchanger>
(Production of monolith intermediate (I treatment))
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.25 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was stirred under reduced pressure to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate (dry body) thus obtained was observed by SEM. From the SEM image, although the wall section that divides two adjacent macropores is very thin and rod-shaped, it has an open cell structure, and the average of the openings (mesopores) where the macropores and macropores overlap measured by the mercury intrusion method The diameter was 40 μm and the total pore volume was 18.2 ml / g.

(Manufacture of monoliths)
Subsequently, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (II treatment). Next, the above monolith intermediate is placed in a reaction vessel, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and degassed in a vacuum chamber. The reaction vessel was sealed and allowed to polymerize at 50 ° C. for 24 hours. After completion of the polymerization, the content was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure (III treatment).

  The internal structure of the monolith (dry body) containing 1.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. From the SEM observation, the monolith has a co-continuous structure in which the skeleton and the vacancies are three-dimensionally continuous, and both phases are intertwined. Moreover, the average thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 70 μm, and the total pore volume was 4.4 ml / g. The average diameter of the pores was determined from the maximum value of the pore distribution curve obtained by the mercury intrusion method.

(Production of monolith anion exchanger)
The monolith produced by the above method is put into a column reactor, and a solution consisting of 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride and 2500 ml of dimethoxymethane is circulated and passed through, and reacted at 30 ° C. for 5 hours to give a chloromethyl group Was introduced. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1600 ml of THF and 1400 ml of 30% aqueous solution of trimethylamine were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolith anion exchanger.

  The obtained monolith anion exchanger had an anion exchange capacity of 4.2 mg equivalent / g in a dry state, and it was confirmed that quaternary ammonium groups were quantitatively introduced. Further, the thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average diameter in the dry state of the three-dimensional continuous pores of the monolith anion exchanger determined from the measurement by the mercury intrusion method. Was 70 μm and the total pore volume in the dry state was 4.4 ml / g.

  Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . As a result, it was confirmed that the chloride ions were uniformly distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. It was.

(Supporting platinum group metals)
The monolith anion exchanger was ion-exchanged into Cl form, cut into a cylindrical shape in a dry state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. This dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 100 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged to the palladium chloride acid form. After completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in an aqueous hydrazine solution for 24 hours for reduction treatment. The chloropalladium acid form monolith anion exchanger was brown, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium fine particles. The sample after the reduction was washed several times with pure water and then dried by drying under reduced pressure.

  The amount of palladium supported was determined by ICP emission spectrometry, and the amount of palladium supported was 3.9% by weight. In order to confirm the distribution state of palladium supported on the monolith anion exchanger, the distribution state of palladium was observed by EPMA. It was confirmed that palladium was distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the inside was relatively uniformly distributed although the concentration was slightly higher. In order to measure the average particle diameter of the supported palladium particles, observation with a transmission electron microscope (TEM) was performed. The average particle diameter of the palladium fine particles was 8 nm.

  Below, the measurement result obtained by processing the board | substrate W with the substrate processing apparatus 1 is demonstrated.

[Substrate to be processed (sample)]
A test wafer was used in which copper, molybdenum, and tungsten were each formed to a thickness of 200 nm on a 4-inch silicon wafer by sputtering. In addition, about copper and tungsten, it forms into a film after forming titanium into a film beforehand by 50 nm sputtering as a base. In recent years, molybdenum has been used as a wiring material for MOS type elements in addition to tungsten and copper.

[Evaluation method]
The sheet resistance before and after the cleaning treatment was measured using a 4-probe sheet resistance measuring instrument (Σ-5 +, manufactured by NP Corporation), and the difference was recorded. As the metal elutes and the film thickness decreases, the sheet resistance increases.

[Substrate processing equipment (cleaning equipment)]
As the substrate processing apparatus (cleaning apparatus), the single wafer type substrate processing apparatus 1 shown in FIG. 2 was used. 99.999% nitrogen gas was used as the inert gas, the wafer rotation speed was kept constant at 500 rpm, and the test wafer was cleaned by supplying process water from the process liquid nozzle for 60 minutes.

[Raw water (ultra pure water)]
As for ultrapure water, secondary pure water of an ultrapure water production apparatus installed in Organo Corporation Development Center was used. The water quality at the outlet of the ultrapure water production apparatus is as shown in Table 1 below. Note that the outlet of the ultrapure water production apparatus corresponds to, for example, the outlet 9b from the ultrapure water circulation pipe 9a of the subsystem 9 shown in FIG. 3, and from the outlet 9b to the ultrapure water inlet 1a of the substrate processing apparatus 1 Between them, they were connected by a pipe of about 50 m (pipe and joint made of PFA), and the dissolved oxygen concentration at the ultrapure water inlet 1a was 8 μg / L.

[Evaluated treated water]
The hydrogen peroxide-removed water was obtained by passing the above ultrapure water through a palladium-supported monolith. At this time, the hydrogen peroxide concentration was 2 μg / L or less.

  The hydrogen-dissolved water was obtained by adding hydrogen to the above ultrapure water through a hollow fiber membrane. The hydrogen concentration was measured with a dissolved hydrogen meter (DHDI-1, manufactured by Toa DKK Corporation). The hydrogen concentration was controlled by a mass flow controller for the amount of hydrogen gas supplied to the hollow fiber membrane.

  The water from which oxygen and hydrogen peroxide were removed was obtained by passing the hydrogen-dissolved water through a palladium-supported monolith. At this time, the palladium-supporting monolith is located between the outlet 9b from the ultrapure water circulation pipe 9a of the subsystem 9 shown in FIG. The ultrapure water (liquid to be treated) was placed in an ultrapure water supply path within 5 m upstream from the inlet 1. The dissolved oxygen concentration was measured using a model 410 made by Orbis Fair.

[Example 1]
With the oxygen gas concentration in the processing chamber of the single wafer cleaning apparatus set to 2% or less, the test wafer was processed by changing the type of processing water. The results (increase in sheet resistance) are shown in Table 2 below.

  Copper corrosion occurs in the above-described ultrapure water and hydrogen peroxide-removed water. In the above hydrogen-dissolved water, the copper corrosion is not completely suppressed. Even removing dissolved oxygen and hydrogen peroxide from ultrapure water still does not completely inhibit the corrosion.

  However, if the water obtained by removing dissolved oxygen and hydrogen peroxide from the above ultrapure water and adding more than the prescribed concentration of hydrogen is used to clean the substrate in a low oxygen atmosphere, copper corrosion is completely suppressed. did it. This was the same for the test wafer with tungsten deposited on the surface (not shown in Table 2).

  From the evaluation results in Table 2, the following can be understood. When a wafer with copper exposed on the surface is washed with ultrapure water, copper is corroded and eluted by oxygen and hydrogen peroxide contained in the ultrapure water.

  Therefore, when oxygen and hydrogen peroxide are removed from the ultrapure water, copper elution (thickness reduction) is suppressed, and when hydrogen is added to ultrapure water from which oxygen and hydrogen peroxide have been removed, copper is removed. It was found that elution of was further suppressed.

  The treated copper water has a dissolved oxygen concentration of 2 μg / L or less, a hydrogen peroxide concentration of 2 μg / L or less, and a dissolved hydrogen concentration of 8 μg / L or more, preferably 15 μg / L or more, more preferably 66 μg / L. It can be seen from Table 2 that it is most effective when adjusted to L or more.

  It can also be seen from Table 2 that when processing a test wafer having molybdenum deposited on its surface, corrosion of molybdenum can be significantly suppressed by removing hydrogen peroxide from the ultrapure water. The sheet resistance increment at this time is almost the same as that of the hydrogen-dissolved water. Furthermore, when water obtained by adding hydrogen to hydrogen peroxide-removed water at a predetermined concentration or more is used for processing a molybdenum-exposed substrate in a low oxygen atmosphere, the sheet resistance can be reduced below the detection limit.

  From the evaluation results in Table 2, it is preferable that the treated water of molybdenum has at least a hydrogen peroxide concentration of 2 μg / L or less, a dissolved oxygen concentration of 2 μg / L or less, and a hydrogen peroxide concentration of 2 μg / L or less. It can be seen from Table 2 that the most effective results are obtained when the dissolved hydrogen concentration is adjusted to 8 μg / L or more, preferably 15 μg / L or more, more preferably 66 μg / L or more.

[Example 2]
The oxygen gas concentration in the processing chamber of the single wafer cleaning apparatus was adjusted, and water from which oxygen and hydrogen peroxide had been removed was used. Under the adjusted oxygen gas concentration, the test wafer was processed. Table 3 shows.

  When the oxygen gas concentration in the processing chamber for performing the processing of Example 1 was 2% or less, copper corrosion could be completely suppressed. This was the same for the silicon wafer having a molybdenum film formed on the surface.

  From this evaluation result, the following can be understood. A treatment that removes oxygen and hydrogen peroxide from the above ultrapure water, and uses the treated water obtained by adding hydrogen to the ultrapure water from which oxygen and hydrogen peroxide have been removed, and then performs substrate treatment with the treated water. When the oxygen gas concentration in the room is 2% or less, elution of copper and molybdenum exposed on the substrate surface can be completely suppressed.

  Therefore, it can be said that the provision of the catalyst unit 21 and the separation membrane unit 22 as in the substrate processing apparatus 1 of the various aspects described above has an effect of completely suppressing elution of copper and molybdenum.

[Example 3]
Next, an evaluation result in the case where the substrate is processed with a diluted chemical solution is shown. In this example, the substrate processing apparatus 1 having the aspect shown in FIG. 11 was used. This apparatus is almost the same as the substrate processing apparatus of the aspect shown in FIG. 5, and the same components as those in FIG.

  The configuration changed or added to the mode shown in FIG. 5 is as follows. An exhaust gas pipe 212 having an exhaust gas valve 211 is connected to the upper part of the chemical liquid tank 56. Two level sensors 210 for monitoring the upper limit and lower limit of the liquid level are disposed on the side wall of the chemical liquid tank 56. A processing liquid supply pipe 27 extending between the membrane separation unit 22 and the mixing unit 52 is provided with a processing liquid valve 213 and a flow meter 214. Further, three measurement pipes 215, 216, and 217 are connected to the processing liquid supply pipe 27 extending from the processing liquid valve 28 to the inside of the support shaft 20 of the processing chamber 2. A pH meter 218 is interposed in the measurement pipe 215, a conductivity meter 219 is interposed in the measurement pipe 216, and a dissolved oxygen concentration meter 220 is interposed in the measurement pipe 217. The processing liquid valve 28, the chemical liquid valve 54, the pump 57, the processing liquid valve 213, and the flow meter 214 are controlled by the control unit 5.

  Further, piping (processing liquid supply pipe 27, some main piping 10, chemical liquid supply pipes 53 and 75, exhaust gas pipe 212, measurement pipes 215, 216, and 217, which are directly or indirectly connected to the processing chamber 2 and the chemical liquid tank 56. , Etc.) are arranged in an inert gas seal chamber 221 as shown in FIG. An inert gas introduction port 222 and an inert gas discharge port 223 are provided on the peripheral wall of the inert gas seal chamber 221. The inert gas seal chamber 221 is hermetically sealed except for these ports. A branch pipe of an inert gas supply pipe 77 is connected to the inert gas inlet 222. In addition, the inert gas is introduced into the inert gas seal chamber 221 by bubbling through the liquid in the transparent tank 224 while the inert gas is discharged from the inert gas discharge port 223 to the exhaust port. It has come to understand that.

The substrate processing apparatus 1 according to the above-described embodiment is prepared, and a 1 L-volume PP chemical liquid tank 56 is filled with ammonia water (25% NH ₃ ) as a chemical liquid, and the inert gas supply pipe 77 stores the chemical liquid tank 56. Nitrogen gas (purity 99.999%) was supplied to the gas phase as an inert gas. Prior to the filling of the chemical liquid tank 56 with ammonia water, the air in the empty chemical liquid tank 56 was previously replaced with nitrogen by using the nitrogen gas in order to eliminate the influence of the air and the like existing in the chemical liquid tank 56.

  The exhaust gas valve 211 of the exhaust gas pipe 212 connected to the upper part of the chemical liquid tank 56 was opened, and the supply of nitrogen gas was continued for 4 minutes at a flow rate of 5 L / min. After 4 minutes, the exhaust gas from the exhaust port of the exhaust gas pipe 212 was collected in a plastic bag in which an oxygen monitor sensor had been previously inserted, and the oxygen concentration was measured to be 0.02% to 0.03%. Met. As this oxygen monitor, a low concentration oxygen monitor JKO-02LJD3 (manufactured by Zico Corporation) was used.

  When supplying nitrogen gas after filling the chemical liquid tank 56 with ammonia water, control was performed with the gas supply pressure, and the pressure was adjusted to 5 kPa. This pressure may be a level that does not hinder the operation of drawing the chemical solution from the chemical solution tank 56 by the pump 53.

  The catalyst unit 21, the mixing unit 52, the chemical liquid tank 56, the piping and piping components for connecting them are accommodated in the inert gas seal chamber 221, and the piping between the inert gas seal chamber 221 and the processing chamber 2 is treated. A double structure having an inner pipe through which the liquid flows and an outer pipe surrounding the inner pipe was adopted.

  Nitrogen gas was supplied at 5 kPa from the branch pipe of the inert gas supply pipe 77 into the space between the inner pipe and the outer pipe and inside the inert gas seal chamber 221. In addition, for supplying nitrogen gas to the inert gas seal chamber 221, an inert gas supply pipe 77 connected to the chemical liquid tank 56 is used. However, another inert gas supply pipe may be prepared. The supply pressure of nitrogen gas may be different between the chamber 221 and the chemical liquid tank 56. Since the purpose of supplying nitrogen gas to the inert gas seal chamber 221 and the chemical liquid tank 56 is to prevent oxygen and the like from diffusing into the processing liquid, the gas may be managed not by the gas supply pressure but by the gas supply flow rate.

  As the liquid (dilution water) to be mixed with the ammonia water in the mixing unit 52, the ultrapure water described in the item [Raw Water] and the excess water described in the item [Processed Water to be Evaluated] are described. Hydrogen oxide-removed water, hydrogen-dissolved water, and water from which oxygen and hydrogen peroxide were removed were used.

The diluted ammonia water obtained by mixing so that the concentration of ammonia water after mixing is 0.19 mg NH ₃ / L (25% NH ₃ is diluted approximately 1366 times) has a conductivity of 2.0 μS / cm and a pH of This water quality is preferably 8.9, since an antistatic effect can be obtained without adding carbonic acid to the dilution water.

  The flow rate of the diluted ammonia water passing through the mixing unit 52 is controlled to 2.1 L / min. Among them, 200 mL / min of diluted ammonia water is continuously added to the dissolved oxygen concentration meter 220, the conductivity meter 219, and the pH meter 218. Then, 1.5 L / min of diluted ammonia water was supplied to the processing chamber 2.

  The results (increase in sheet resistance) are shown in Table 4 below.

  Table 4 shows the following. When the dilution water is hydrogen water, corrosion of copper and molybdenum cannot be completely suppressed. Corrosion is not suppressed only by removing dissolved oxygen from ultrapure water.

  However, when ammonia water diluted with water obtained by removing dissolved oxygen and hydrogen peroxide from the above ultrapure water and adding hydrogen at a predetermined concentration or more is used for substrate treatment in a low oxygen atmosphere, copper and The corrosion of molybdenum could be completely suppressed.

W ... Substrate 1 ... Substrate processing apparatus 1a ... Processing liquid inlet 2 of substrate processing apparatus 1 ... Processing chamber 3 ... Spin chuck 4, 4a ... Processing liquid nozzle 5 ... Control Unit 6 ... clamping member 7 ... chuck rotation drive mechanism 8 ... spin base 9 ... subsystem 9a of ultrapure water production apparatus ... ultrapure water (liquid to be treated) circulation of subsystem 9 Piping 9b ... Outlet from ultrapure water (liquid to be treated) circulation pipe of subsystem 9 10 ... Main piping 10a ... Branching point 11 ... Blocking plate 18 ... Gas valve 19 ... Nozzle Arm 20 ... support shaft 21 ... catalyst unit 22 ... membrane separation unit 23 ... drain pipe 24 ... drain valve 27 ... treatment liquid supply pipe 28 ... treatment liquid valve 31 ...・ Support shaft 32 ... peripheral wall 33 ... flat plate 34 · -Substrate facing surface 39 ... Gas supply pipe 41 ... Gas flow rate adjustment valve 51 ... Chemical solution preparation unit 52 ... Mixing unit 53 ... First chemical solution supply pipe 54 ... Chemical solution valve 55- .. Chemical liquid flow rate adjusting valve 56 ... Chemical liquid tank 57 ... Pump 75 ... Second chemical liquid supply pipe 76 ... Chemical liquid valve 77 ... Inert gas supply pipe 78 ... Inert gas valve 79 ... Chemical liquid flow rate adjustment valve 81 ... Chemical liquid preparation unit 82 ... Chemical liquid dilution tank 83 ... Diluted chemical liquid supply pipe 84 ... Diluted chemical liquid valve 85 ... Second treatment liquid supply pipe 86・ Processing liquid valve 87 ... Processing liquid flow rate adjustment valve 90 ... Processing liquid supply pipe 91 ... Processing liquid valve 100 ... Piping 101 ... Inner piping 102 ... Outer piping 103 ... Non Active gas valve 104 ... Inert gas supply pipe 105 ... exhaust valve 106 ... inert gas exhaust pipe 201 ... treatment tank 202 ... overflow section 203 ... treatment liquid nozzle 204 ... discharge port 205 ... Resistivity meter 206, 207 ... Drain pipe 208 ... Drain valve 209 ... Lid member 210 ... Level sensor 211 ... Exhaust gas valve 212 ... Exhaust gas pipe 213 ... Treatment liquid valve 214 ··························································································································································· Active gas inlet 223 ... Inert gas outlet 224 ... Transparent tank

Claims (32)

A substrate processing method for disposing a substrate in a processing chamber of a substrate processing apparatus and processing the substrate,
Placing a platinum group metal catalyst in the vicinity of the processing chamber or in the processing chamber,
Filling the processing chamber in which the substrate is disposed with an inert gas;
A hydrogen-dissolved liquid obtained by passing a hydrogen-dissolved liquid obtained by adding hydrogen to the liquid to be processed through the platinum group metal catalyst is supplied into the processing chamber filled with the inert gas, A substrate processing method, wherein the substrate is processed with a dissolution processing solution. Filling the processing chamber with the inert gas so that the oxygen gas concentration in the processing chamber is 2% or less;
Adding the hydrogen to the liquid to be treated so that the dissolved hydrogen concentration in the hydrogen solution is 8 μg / L or more,
The hydrogen solution is passed through the platinum group metal catalyst so that the dissolved oxygen concentration in the hydrogen solution is 2 μg / L or less and the hydrogen peroxide concentration is 2 μg / L or less. 2. The substrate processing method according to 1.   3. The substrate processing method according to claim 1, wherein the hydrogen-dissolving processing solution is supplied into the processing chamber and discharged toward the substrate disposed in the processing chamber.   A blocking member having a substrate facing surface facing the substrate is provided in the processing chamber, and when the processing chamber in which the substrate is disposed is filled with an inert gas, the surface of the substrate is blocked in the processing chamber. The substrate processing method according to claim 3, wherein the substrate-facing surface of the member is opposed, and the inert gas is supplied to a space between the blocking member and the substrate.   2. The substrate is processed by installing a processing tank in the processing chamber, supplying the hydrogen-dissolved processing solution into the processing tank, and disposing the substrate in the processing tank. Alternatively, the substrate processing method according to claim 2.   The substrate processing method according to claim 1, wherein an outer side of a pipe for supplying the hydrogen-dissolved processing solution into the processing chamber is surrounded with an inert gas.   Preparing a diluted chemical solution by mixing the hydrogen-dissolved processing solution with a chemical solution, supplying the diluted chemical solution into the processing chamber filled with the inert gas, and processing the substrate with the diluted chemical solution. The substrate processing method according to claim 1.   The substrate processing method according to claim 7, wherein the hydrogen-dissolving treatment liquid and the chemical solution are mixed in a pipe that supplies the hydrogen-dissolving treatment liquid into the processing chamber.   Supplying the chemical solution to the tank, supplying an inert gas into the tank, pumping out the chemical solution from the tank, and injecting it into the hydrogen-dissolving treatment solution in the pipe; The substrate processing method according to claim 8, wherein mixing is performed.   The chemical solution and the hydrogen-dissolved processing solution are supplied to a tank and mixed, and a diluted chemical solution obtained by diluting the hydrogen-dissolving processing solution with the chemical solution is pumped out of the tank and supplied into the processing chamber. 7. The substrate processing method according to any one of 1 to 6.   The substrate processing method according to claim 10, comprising supplying an inert gas into the tank.   The substrate processing method according to claim 8, wherein an outer side of a pipe for supplying the diluted chemical solution into the processing chamber is surrounded by an inert gas.   The substrate processing method according to claim 1, wherein the platinum group metal catalyst is a palladium catalyst.   13. The substrate processing method according to claim 1, wherein the platinum group metal catalyst is a palladium catalyst supported on a monolithic organic porous anion exchanger.   15. The substrate according to claim 1, wherein the substrate to be treated with the hydrogen-dissolving treatment solution is a substrate on which a single element or a compound of at least one of copper, molybdenum, and tungsten is exposed. The substrate processing method according to item.   The substrate processing method according to claim 1, wherein the liquid to be processed is ultrapure water. A processing chamber in which a substrate is disposed and a substrate processing liquid for processing the substrate is supplied;
An inert gas filling mechanism for filling the processing chamber in which the substrate is disposed with an inert gas;
A catalyst unit that is installed in the vicinity of the processing chamber or inside the processing chamber and is filled with a platinum group metal catalyst that passes through a hydrogen solution obtained by adding hydrogen to the liquid to be processed; and
A substrate processing apparatus, wherein a hydrogen-dissolved processing solution obtained by passing the hydrogen-dissolved solution through the platinum group metal catalyst is supplied into the processing chamber as the substrate processing solution. The dissolved hydrogen concentration of the hydrogen solution is 8 μg / L or more,
The inert gas filling mechanism fills the processing chamber with the inert gas so that the oxygen gas concentration in the processing chamber is 2% or less,
The substrate processing apparatus according to claim 17, wherein the catalyst unit has a dissolved oxygen concentration of 2 μg / L or less and a hydrogen peroxide concentration of 2 μg / L or less with respect to the hydrogen-dissolving treatment liquid.   The processing chamber is provided with at least a substrate holding mechanism for holding the substrate and a processing liquid nozzle for supplying the substrate processing liquid to the substrate held by the substrate holding mechanism. Item 19. The substrate processing apparatus according to Item 17 or Item 18. A blocking member having a substrate facing surface facing the substrate held by the substrate holding mechanism;
The processing liquid nozzle and the inert gas filling mechanism are provided in the blocking member, and the substrate processing liquid and the inert gas held by the substrate holding mechanism, and the substrate facing surface of the blocking member, The substrate processing apparatus according to claim 19, wherein the substrate processing apparatus is configured to be capable of being supplied in between.   19. The processing chamber is provided with a processing tank in which at least the substrate is disposed, and a processing liquid nozzle for supplying the substrate processing liquid into the processing tank. 2. The substrate processing apparatus according to 1. The pipe for supplying the substrate processing liquid into the processing chamber includes an inner pipe through which the substrate processing liquid flows, and an outer pipe surrounding the inner pipe,
The substrate processing apparatus according to claim 17, further comprising means for supplying an inert gas between the inner pipe and the outer pipe.   The apparatus further comprises a chemical preparation unit that prepares a diluted chemical by injecting a chemical into a pipe for supplying the substrate processing liquid into the processing chamber, and mixing the chemical and the substrate processing liquid in the pipe. The substrate processing apparatus according to any one of claims 17 to 22.   24. The substrate processing apparatus according to claim 23, further comprising a chemical solution tank for storing the chemical solution, and means for supplying an inert gas into the chemical solution tank.   A chemical solution dilution tank is provided for diluting the substrate processing solution with the chemical solution by supplying the chemical solution and the substrate processing solution, and a diluted chemical solution obtained by diluting the substrate processing solution with the chemical solution is provided in the processing chamber. The substrate processing apparatus according to claim 17, wherein the substrate processing apparatus is supplied to the substrate processing apparatus.   26. The substrate processing apparatus according to claim 25, further comprising means for supplying an inert gas into the chemical solution dilution tank. The piping for supplying the diluted chemical solution into the processing chamber includes an inner pipe through which the diluted chemical solution flows, and an outer pipe surrounding the inner pipe,
27. The substrate processing apparatus according to claim 25, further comprising means for supplying an inert gas between the inner pipe and the outer pipe.   The substrate processing apparatus according to any one of claims 17 to 27, wherein the platinum group metal catalyst is a palladium catalyst.   28. The substrate processing apparatus according to claim 17, wherein the platinum group metal catalyst is a palladium catalyst supported on a monolithic organic porous anion exchanger.   30. The substrate according to any one of claims 17 to 29, wherein the substrate to be treated with the hydrogen-dissolving treatment solution is a substrate on which a single element or a compound of at least one of copper, molybdenum, and tungsten is exposed. The substrate processing apparatus according to item.   31. The substrate processing apparatus according to claim 17, wherein the liquid to be processed is ultrapure water.   32. A catalyst unit installed near or inside a processing chamber of the substrate processing apparatus according to any one of claims 17 to 31 and filled with a platinum group metal catalyst, A catalyst unit that supplies a hydrogen-dissolved processing solution obtained by passing through the platinum group metal catalyst into the processing chamber as a substrate processing solution.

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