JP2006218351A - Ozonolysis method, ozonolysis apparatus and treatment apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ozonolysis method capable of easily and certainly decomposing ozone by a simple method, an ozonolysis apparatus and a treatment apparatus capable of reducing a concentration of ozone in a waste liquid. <P>SOLUTION: The ozonolysis apparatus 1 is provided with a body part 2 provided with an inlet port 21 and an outlet port 22; and a plurality of filter members 3 provided so as to partition a space in the body part 2 to the inlet port 21 side and the outlet port 22 side. The respective filter members 3 are constituted of a support 31 permeable with a gas; and a catalyst 32 carried on a surface of the support 31. In the ozonolysis apparatus 1, ozone is decomposed by bringing ozone into contact with a hydrogen ion on a surface of the catalyst 32. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ozonolysis method, an ozonolysis apparatus, and a processing apparatus.

In recent years, cleaning, resist stripping, and the like in a semiconductor manufacturing process have been performed using the strong oxidizing power of ozone (see, for example, Patent Document 1).
By the way, since ozone is a gas toxic to the human body, it is necessary to decompose unreacted ozone by some method after these treatments.
As a method of decomposing ozone, there is a method of contacting with a chemical solution such as an alkaline aqueous solution in which hydrogen sulfide or metal sulfide is dissolved (see, for example, Patent Document 2).
However, in this method, there is a problem that the cost of the chemical solution is high and the cost is high, and that the chemical solution itself is toxic to the human body.

JP 2000-1000068 A Japanese Patent Laid-Open No. 8-281064

  An object of the present invention is to provide an ozonolysis method, an ozonolysis apparatus, and a treatment apparatus capable of reducing the ozone concentration in the effluent, which can easily and reliably decompose ozone by a simple method.

Such an object is achieved by the present invention described below.
The ozonolysis method of the present invention is characterized in that the ozone is decomposed by bringing ozone and hydrogen ions into contact with each other on the surface of the catalyst.
Thereby, ozone can be decomposed | disassembled easily and reliably by a simple method.
In the ozonolysis method of the present invention, the catalyst is preferably composed mainly of a noble metal and / or a transition metal oxide.
Such a catalyst is excellent in ozone resolution.

In the ozonolysis method of the present invention, the noble metal is preferably Au, Ag, Cu, Ir, Ta, Ti, W, Pt, Pd, Rh, Ru, or an alloy containing at least one of them.
These are particularly excellent in ozone resolution.
In the ozonolysis method of the present invention, the transition metal oxide is selected from the group consisting of Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Cu, W, Ta, Ti, Ir, and Mo. It is preferable that the oxide contains at least one selected.
These are particularly excellent in ozone resolution.

In the ozonolysis method of the present invention, it is preferable that the ozone decomposition is performed in a state where the catalyst is heated.
Thereby, decomposition | disassembly of ozone can be performed more rapidly.
In the ozonolysis method of the present invention, the hydrogen ions are preferably generated by decomposing a reducing agent supplied to the catalyst on the surface of the catalyst.
Thereby, since the decomposition of the reducing agent into hydrogen ions and the decomposition of ozone can be performed on the same catalyst, it is possible to reduce the size of the apparatus when it is made into an apparatus. There is.

In the ozonolysis method of the present invention, it is preferable that the ozone and the reducing agent are supplied to the catalyst in a mixed state.
Thereby, since ozone and a reducing agent are supplied to the catalyst in a premixed state, contact between ozone and hydrogen ions occurs more reliably and uniformly, and as a result, ozone is decomposed more efficiently.
In the ozonolysis method of the present invention, it is preferable that the reducing agent is mainly composed of hydrogen gas or methanol.
A reducing agent mainly composed of hydrogen gas or methanol is preferable because it is relatively easy to decompose at a low temperature and easily generate hydrogen ions.

In the ozonolysis method of the present invention, the hydrogen ions are preferably generated by decomposing a reducing agent supplied to a second catalyst different from the catalyst on the surface of the second catalyst.
Since the decomposition of the reducing agent and the decomposition of ozone are performed on different catalysts, these decomposition reactions can be performed more efficiently and reliably without competing. Thereby, the decomposition efficiency of ozone increases more.

In the ozonolysis method of the present invention, it is preferable that the second catalyst is mainly composed of a noble metal and / or a transition metal oxide.
Such a second catalyst is excellent in reducing agent resolution.
In the ozonolysis method of the present invention, the noble metal is preferably Pt, Au, or an alloy containing at least one of these.
These are particularly excellent in reducing agent resolution.
In the ozonolysis method of the present invention, the transition metal oxide is selected from the group consisting of Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Cu, W, Ta, Ti, Ir, and Mo. It is preferable that the oxide contains at least one selected.
These are particularly excellent in reducing agent resolution.
In the ozonolysis method of the present invention, the hydrogen ions generated on the surface of the second catalyst pass through an electrolyte membrane through which the hydrogen ions provided between the catalyst and the second catalyst can pass. The catalyst is preferably supplied to the catalyst.
Thereby, the produced | generated hydrogen ion can be used for the decomposition reaction of ozone without waste.

The ozonolysis apparatus of the present invention has a main body part and a catalyst accommodated in the main body part,
The ozone is decomposed by bringing ozone and hydrogen ions into contact with each other on the surface of the catalyst.
Thereby, an ozone decomposing apparatus capable of easily and reliably decomposing ozone by a simple method is obtained.

In the ozonolysis apparatus of the present invention, the ozonolysis apparatus has a second catalyst housed in the main body, different from the catalyst,
It is preferable that the hydrogen ions are generated by decomposing the reducing agent supplied into the main body on the surface of the second catalyst.
Since the decomposition of the reducing agent and the decomposition of ozone are performed on different catalysts, these decomposition reactions can be performed more efficiently and reliably without competing. Thereby, the decomposition efficiency of ozone increases more.

In the ozonolysis apparatus of the present invention, an electrolyte membrane through which the hydrogen ions can pass is provided between the catalyst and the second catalyst.
It is preferable that the hydrogen ions generated on the surface of the second catalyst are supplied to the catalyst via the electrolyte membrane.
Thereby, the produced | generated hydrogen ion can be used for the decomposition reaction of ozone without waste.

The treatment apparatus of the present invention uses a treatment agent containing ozone to treat a surface of a member to be treated,
An ozonolysis apparatus of the present invention connected to the processing unit,
The waste discharged from the processing unit is supplied to the ozone decomposing apparatus, and the ozone contained in the exhaust is decomposed.
Thereby, a highly safe processing apparatus is obtained.

The treatment apparatus of the present invention further comprises an ozone generator that generates ozone by electrolysis of water,
While supplying the processing agent containing the ozone produced | generated with this ozone production | generation apparatus to the said process part, it is preferable to supply the hydrogen gas which arises in the case of the electrolysis of the said water to the said ozone decomposition apparatus.
Thereby, it is not necessary to separately provide an apparatus for processing hydrogen gas, and therefore the entire processing apparatus can be reduced in size and the running cost of the processing apparatus can be reduced.
The treatment apparatus of the present invention preferably uses electricity generated when decomposing the ozone in the ozone decomposing apparatus as a part of electric power required for driving each part.
Thereby, reduction of the processing cost (running cost of a processing apparatus) of a to-be-processed member can be aimed at.

Hereinafter, an ozonolysis method, an ozonolysis apparatus, and a processing apparatus of the present invention will be described based on the illustrated preferred embodiments.
FIG. 1 is a schematic view showing an embodiment of the processing apparatus of the present invention.
The processing apparatus 10 of the present invention is an apparatus that performs processing (for example, removal of organic substances) on the surface of an object to be processed (member to be processed) S using a processing agent containing ozone.

A processing apparatus 10 illustrated in FIG. 1 includes a processing chamber (processing unit) 100 that performs processing of an object to be processed S, an ozone supply device 200 that supplies ozone to the processing chamber 100, and a water vapor supply that supplies water vapor to the processing chamber 100. Device 300.
The processing chamber 100 can be hermetically sealed. In the lower part of the processing chamber 100, a heating means 120 configured by, for example, a hot plate is provided in order to heat the inside of the processing chamber 100 to a predetermined temperature.

In the processing chamber 100, for example, by decomposing an object to be processed S in an atmosphere (processing agent) of a mixed gas containing at least water vapor and ozone, decomposition of an organic substance (for example, a resist layer) attached to the object to be processed S is performed. -Removal is performed.
The processing chamber 100 and the ozone supply device 200 are connected via an ozone supply pipe 210. The ozone supply device 200 is a device for supplying ozone to the processing chamber 100 at a desired flow rate and pressure.

The ozone supply device 200 may be, for example, a cylinder containing ozone, but in the present embodiment, the ozone supply device 200 includes an ozone generation device that generates (generates) ozone by electrolysis of water.
Further, the ozone supply device 200 is provided with a supply pipe for supplying a gas (gas) containing hydrogen gas (reducing agent) generated together with ozone to electrolyze water to the ozone decomposition device 1 described later. One end of 220 is connected. The other end of the supply pipe 220 is connected in the middle of the exhaust pipe 520.

The processing chamber 100 and the water vapor supply device 300 are connected via a water vapor supply pipe 310. The water vapor supply device 300 can be hermetically sealed.
The water vapor supply device 300 contains water such as pure water, ultrapure water, ion exchange water, distilled water, and RO water. The water vapor supply device 300 includes a heating means (not shown) that heats the water stored therein to, for example, about 95 to 130 ° C.

A gas supply device 400 is connected to the processing chamber 100 via a gas supply pipe 410. In the illustrated configuration, the gas supply pipe 410 includes branch pipes 420 a and 420 b that branch in the processing chamber 100.
Further, a mist trap device 500 is connected to the processing chamber 100 through an exhaust pipe 510, and the ozonolysis apparatus 1 of the present invention is connected to the mist trap apparatus 500 through an exhaust pipe 520.

Using such a processing apparatus 10, for example, the surface of the object to be processed S can be processed as follows.
First, the object to be processed S is stored in the cassette 110, and the cassette 110 is set in the processing chamber 100 in this state.
Next, while supplying an inert gas (for example, nitrogen gas) heated to about 100 to 200 ° C., for example, from the gas supply device 400 through the gas supply pipe 410 into the processing chamber 100, The exhaust pipe 510 is evacuated to replace the inside of the processing chamber 100 with an inert gas atmosphere.

At substantially the same time, the heating means 120 of the processing chamber 100 is operated to set the temperature of the processing chamber 100 to a predetermined temperature.
After the temperature of the object to be processed S is stabilized at a predetermined temperature (substantially the same as the temperature in the processing chamber 100), water vapor is supplied from the water vapor supply device 300 into the processing chamber 100 through the water vapor supply pipe 310.
At almost the same time, ozone is supplied into the processing chamber 100 from the ozone supply device 200 via the ozone supply pipe 210.

Next, the exhaust pipe 510 is closed, and the inside of the processing chamber 100 is pressurized to, for example, about 50 to 200 kpa. The temperature, pressure and flow rate of water vapor, the flow rate and pressure of ozone, etc. are appropriately set according to the purpose of processing.
For example, when the processing purpose is removal of the resist layer, the following conditions are preferably set.
That is, the temperature in the processing chamber 100 is preferably about 95 to 140 ° C.

Moreover, it is preferable that the atmosphere (processing agent) of the processing chamber 100 includes at least water vapor and ozone, and the volume ratio of water vapor to water (water vapor / ozone) is, for example, about 1 to 4.
Furthermore, the temperature in the processing chamber 100 is preferably set higher as the volume ratio of water vapor to ozone (water vapor / ozone) increases. Specifically, the volume ratio (water vapor / ozone) is increased by 0.1. Every time, it is preferable to raise the temperature in the processing chamber 100 by, for example, about 1 to 3 ° C.

As a method for heating the processing chamber 100, as described above, in addition to the method using the heating means 120 for heating the entire processing chamber 100 to a predetermined temperature, for example, a heated gas is supplied from the gas supply device 400. Or a method of heating the object to be processed S using radiant heat of an infrared irradiation apparatus (not shown), and one or more of these methods can be used in combination.
When the processing of the object to be processed S is completed, the temperature of the object to be processed S is decreased to, for example, about 40 ° C., and then an ozone water cleaning tank (not shown) or a rinsing tank (not shown) from the inside of the processing tank 100. ), And after subjecting the object to be processed S to a cleaning process, it is dried.

On the other hand, the gas (exhaust gas) in the processing chamber 100 is discharged to the mist trap device 500 through the exhaust pipe 510, where the mist in the exhaust gas (exhaust discharged from the processing chamber 100) is removed.
Further, the exhaust gas processed by the mist trap device 500 is mixed with a gas containing hydrogen gas supplied through the supply pipe 220, and this mixed gas is sent to the ozone decomposition apparatus 1 through the exhaust pipe 520. .
And in the ozone decomposition | disassembly apparatus 1, the ozone contained in mixed gas (exhaust gas) is decomposed | disassembled.
In addition, a valve 530 is provided at a connection portion between the exhaust pipe 520 and the supply pipe 220 so that a mixing ratio between the exhaust gas and the gas containing hydrogen gas can be adjusted.

Next, the ozonolysis apparatus 1 of the present invention will be described in detail.
<First Embodiment>
First, a first embodiment of the ozonolysis apparatus of the present invention will be described.
FIG. 2 is a longitudinal sectional view showing a first embodiment of the ozonolysis apparatus of the present invention.
The ozonolysis apparatus 1 shown in FIG. 2 includes a main body 2 having an inflow port 21 and an outflow port 22, and a space in the main body 2, the inflow port 21 side (upstream side) and the outflow port 22 side (downstream side). And a plurality (three in this embodiment) of filter members 3 provided so as to be partitioned into each other.

An exhaust pipe 520 is connected to the inflow port 21, while a discharge pipe 540 is connected to the outflow port 22.
Each filter member 3 includes a support 31 through which gas or liquid (fluid) can pass, and a catalyst 32 supported on the surface of the support 31.
The support 31 only needs to allow fluid to pass smoothly, and the shape (form) thereof is not particularly limited, and examples thereof include a porous shape, a mesh shape, and a honeycomb shape.
Examples of the constituent material of the support 31 include carbon, alumina, silica, and the like, and one or more of these can be used in combination.
In addition, in each filter member 3, you may make it use the support body 31 of a different shape, respectively.

The catalyst 32 has a function of promoting the decomposition of ozone. In the present embodiment, when exhaust gas and a gas containing hydrogen gas are supplied as mixed gas into the ozonolysis apparatus 1 (that is, the catalyst 32), first, on the surface of the catalyst 32 (on the catalyst 32), the catalyst By the action of 32, the hydrogen gas is decomposed into hydrogen ions as shown in the following formula (1).
Further, when ozone and hydrogen ions come into contact with each other on the surface of the catalyst 32, as shown in the following formula (2), ozone is decomposed into oxygen and water, and from oxygen to the following formula (3). As shown, water is produced.

H ₂ → 2H ⁺ + 2e ⁻ (1)
O ₃ + 2H ⁺ + 2e ⁻ → O ₂ + H ₂ O (2)
1 / 2O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O (3)
At this time, the generated water is discharged to the outside of the ozonolysis apparatus 1 from the discharge pipe 540 connected to the outlet 22 as gas (water vapor) or liquid.

The catalyst 32 may be a substance having a catalytic action (catalytic ability), and an organic or inorganic catalyst can be used. In particular, a substance mainly composed of a noble metal and / or a transition metal oxide is used. Is preferred. Such a catalyst 32 is excellent in ozone resolution.
As the noble metal, Au, Ag, Cu, Ir, Ta, Ti, W, Pt, Pd, Rh, Ru, or an alloy containing at least one of them is preferable. These are particularly excellent in ozone resolution.
Examples of the transition metal oxide include Au, Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Mo, Re, W, Ta, Nb, V, Hf, Zr, and Ti. An oxide containing at least one selected from the group consisting of Ir, Cu, and Al, among these, among them, Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, An oxide containing at least one selected from the group consisting of Cu, W, Ta, Ti, Ir and Mo is preferable. These are also particularly excellent in ozone resolution.

The shape of the catalyst 32 is preferably granular (particularly spherical) as shown in the figure. Thereby, a contact area with ozone and hydrogen gas (reducing agent) can be increased, and ozone can be decomposed more efficiently.
In this case, the average particle diameter of the catalyst 32 is preferably about 1 nm to 1000 μm, and more preferably about 5 nm to 500 nm. Thereby, the contact area with ozone or hydrogen gas can be made sufficiently large.

The amount of the catalyst 32 carried on the support 31 is preferably in the range of about 1 mg to 1000 mg / cm ^2, more preferably about 50mg~300mg / cm ^2.
The shape of the catalyst 32 is not limited to a granular shape, and may be, for example, a lump or the like, and the entire filter member 3 may be configured (formed) with the catalyst 32.
Moreover, as shown in FIG. 2, the ozonolysis apparatus 1 has a heating means 9 for heating the filter member 3 (catalyst 32). The heating means 9 heats the catalyst 32 when decomposing ozone. By performing the decomposition of ozone while the catalyst 32 is heated, the decomposition of ozone can be performed more quickly and reliably.

Such a heating means 9 can be comprised by a heater, an infrared irradiation means, a high frequency provision means, etc., for example.
In the present embodiment, the hydrogen gas is decomposed into hydrogen ions and ozone is decomposed on the same catalyst 32. For this reason, there exists an advantage that size reduction of the ozonolysis apparatus 1 can be achieved.

Further, ozone and hydrogen gas are supplied into the ozone decomposition apparatus 1 (catalyst 32) in a state where they are mixed in advance. For this reason, contact between ozone and hydrogen ions (hydrogen gas) occurs more reliably and uniformly, and as a result, ozone is decomposed more efficiently.
Moreover, since hydrogen gas generated as a by-product when ozone is generated is used as a reducing agent when decomposing ozone, it is not necessary to separately provide an apparatus for treating (decomposing or removing) hydrogen gas. For this reason, the entire processing apparatus 1 can be reduced in size, and the running cost of the processing apparatus 1 can be reduced.

In addition, when the discharge | emission discharged | emitted from the process chamber 100 is a liquid, this liquid discharge | emission (drainage) can be supplied to the ozone decomposition apparatus 1 as it is. In this case, the waste liquid and the gas containing hydrogen gas are mixed in the exhaust pipe 520, and ozone and hydrogen gas are supplied to the ozone decomposition apparatus 1 as a liquid containing them.
In addition, even when the emission is a gas, a gas emission (exhaust gas) or a gas containing hydrogen gas is dissolved in an appropriate solvent (for example, water) to obtain a liquid containing ozone and hydrogen gas. The ozone decomposing apparatus 1 may be supplied.
Moreover, you may make it introduce | transduce into the ozonolysis apparatus 1 (supply) separately, without mixing discharge material (exhaust gas, waste liquid) and hydrogen gas. In this case, the supply pipe 220 is directly connected to the main body 2 of the ozonolysis apparatus 1.

In this embodiment, hydrogen gas is used as the reducing agent. Instead of hydrogen gas, for example, alcohols such as methanol and ethanol, ethers such as dimethyl ether, and the like can be used. As the agent, those mainly composed of hydrogen gas or methanol are suitable. A reducing agent mainly composed of hydrogen gas or methanol is preferable because it is relatively easy to decompose at a low temperature and easily generate hydrogen ions.
In the processing apparatus 10 shown in FIG. 1, when a gas other than hydrogen gas is used as the reducing agent, for example, the supply pipe 220 is omitted, and the reducing agent supply means is, for example, the main body 2 of the ozone decomposition apparatus 1. Alternatively, it is connected in the middle of the exhaust pipe 520 or the like.

Second Embodiment
Next, a second embodiment of the ozonolysis apparatus of the present invention will be described.
Hereinafter, the ozonolysis apparatus of the second embodiment will be described with a focus on the differences from the ozonolysis apparatus of the first embodiment, and the description of the same matters will be omitted.
FIG. 3 is a longitudinal sectional view showing a second embodiment of the ozonolysis apparatus of the present invention.

The ozonolysis apparatus 1 shown in FIG. 3 includes a main body 2 including inflow ports 21a and 21b and outflow ports 22a and 22b, an electrolyte membrane 4 provided in the main body 2, and a hydrogen ion generation unit 5. And an ozonolysis unit 6.
An exhaust pipe 520 is connected to the inlet 21a, and a supply pipe 220 is connected to the inlet 21b. On the other hand, a discharge pipe 540 is connected to the outlets 22a and 22b.

The electrolyte membrane 4 is a membrane through which hydrogen ions (protons) can pass, and is made of, for example, an organic polymer material film that functions as a proton (H ⁺ ) conductor.
Examples of the constituent material of the organic polymer material film include ion exchange resins such as perfluoroalkyl sulfonic acid resins, carboxylic acid fluorine resins, polytetrafluoroethylene, and the like.

Among these, as a polymer material film composed mainly of a perfluoroalkylsulfonic acid resin, for example, Nafion (manufactured by DuPont), Flemion (manufactured by Asahi Glass Co., Ltd.) or the like can be used.
The electrolyte membrane (solid electrolyte membrane) 4 partially protrudes from both sides of the hydrogen ion generation unit 5 and the ozone decomposition unit 6. That is, the plane area of the electrolyte membrane 4 is set larger than the plane areas of the hydrogen ion generation unit 5 and the ozone decomposition unit 6.

The portion of the electrolyte membrane 4 that protrudes from the hydrogen ion generation unit 5 and the ozonolysis unit 6 is sandwiched between the first frame 2a and the second frame 2b that constitute the main body 2, and thereby the electrolyte A joined body 7 of the membrane 4, the hydrogen ion generation unit 5, and the ozone decomposition unit 6 is fixed to the main body unit 2.
On one surface side of the electrolyte membrane 4, a hydrogen ion generator 5 is provided in contact with the electrolyte membrane 4. The hydrogen ion generator 5 includes a catalyst layer 52 on the electrolyte membrane 4 side and a substrate 51 that supports the catalyst layer 52.

The substrate 51 has a function as a diffusion layer for diffusing a reducing agent or a gas (for example, water vapor or carbon dioxide) generated by the decomposition of the reducing agent as described above.
The substrate 51 is made of, for example, a porous material having conductivity such as carbon paper, a mesh-like metal foam made of steel wool, aluminum (Al), or sponge titanium. It is preferably composed of a porous metal material or the like. Thereby, the function as a collector can be provided to the substrate 51.

The catalyst layer 52 is a layer containing a catalyst (second catalyst) that promotes the decomposition of a reducing agent (for example, hydrogen gas or methanol) in the hydrogen ion generator 5, and is a conductive powder such as carbon powder. And a second catalyst is supported on a base material containing a resin such as a perfluoroalkylsulfonic acid resin.
The second catalyst may be a substance having a catalytic action (catalytic ability), and an organic or inorganic catalyst can be used. In particular, the second catalyst is mainly composed of a noble metal and / or a transition metal oxide. Is preferably used. Such a second catalyst is excellent in reducing agent resolution.

Examples of the noble metal include Pt, Pd, Rh, Ru, Ir, Ag, Au, and alloys containing at least one of these, among which Pt, Au, or any of them An alloy containing at least one is preferable. These are particularly excellent in reducing agent resolution.
Examples of the transition metal oxide include Au, Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Mo, Re, W, Ta, Nb, V, Hf, Zr, and Ti. An oxide containing at least one selected from the group consisting of Ir, Cu, and Al, among these, among them, Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, An oxide containing at least one selected from the group consisting of Cu, W, Ta, Ti, Ir and Mo is preferable. These are also particularly excellent in reducing agent resolution.

The shape of the second catalyst is also preferably granular (particularly spherical). Thereby, a contact area with a reducing agent can be increased and a hydrogen ion can be produced | generated more efficiently.
In this case, the average particle diameter of the second catalyst is preferably about 1 nm to 1000 μm, and more preferably about 5 nm to 500 nm. Thereby, a contact area with a reducing agent can be made large enough.
The amount of the second catalyst carried on the catalyst layer 52 is preferably in the range of about 1 mg to 1000 mg / cm ^2, more preferably about 50mg~300mg / cm ^2.

On the other surface side of the electrolyte membrane 4 (on the side opposite to the hydrogen ion generating portion 5), an ozone decomposing portion 6 is provided in contact with the electrolyte membrane 4. The ozonolysis unit 6 is composed of a catalyst layer 62 on the electrolyte membrane 4 side and a substrate 61 that supports the catalyst layer 62.
The substrate 61 has a function as a diffusion layer that diffuses, for example, ozone or a gas (for example, water vapor or oxygen gas) generated by the decomposition of ozone.
The substrate 61 can be the same as the substrate 51.

The catalyst layer 62 is a layer containing a catalyst that promotes ozone decomposition in the ozone decomposition section 6. The catalyst layer 62 carries a catalyst similar to the catalyst 32 of the first embodiment.
The amount of catalyst supported on the catalyst layer 62 is preferably in the range of about 1 mg to 1000 mg / cm ^2, more preferably about 50mg~300mg / cm ^2.
Such a hydrogen ion production | generation part 5 and the ozone decomposition | disassembly part 6 are each joined to the different surface of the electrolyte membrane 4, and the joined body 7 is comprised by integrating as shown in FIG. This bonding can be performed by a method such as hot pressing or bonding with an adhesive.

A first frame 2 a is provided on the opposite side of the ozone decomposition section 6 from the electrolyte membrane 4.
In the first frame 2a, a plurality of grooves 23a are formed in stripes on the surface of the ozone decomposition section 6 side. The inflow port 21a and the outflow port 22a communicate with the groove 23a. Thereby, the exhaust gas (exhaust gas) discharged from the processing chamber 100 is supplied to the ozone decomposition unit 6 through the inlet 21a and the groove 23a, and the gas generated by the decomposition of ozone contained in the exhaust gas is It is discharged out of the ozonolysis apparatus 1 from the ozonolysis part 6 through the groove 23a and the outlet 22a.

A second frame 2b is provided on the opposite side of the hydrogen ion generator 5 from the electrolyte membrane 4.
In the second frame 2b, a plurality of grooves 23b are formed in a stripe shape on the surface on the hydrogen ion generator 5 side. In the present embodiment, each groove 23b is provided substantially parallel to each groove 23a formed in the first frame 2a. However, these grooves 23a and 23b are provided so as to be substantially orthogonal to each other. It may be.
An inflow port 21b and an outflow port 22b communicate with the groove 23b. Thereby, the reducing agent is supplied to the hydrogen ion generation unit 5 through the inlet 21b and the groove 23b, and the gas generated by the decomposition of the reducing agent is transferred to the hydrogen ion generation unit through the groove 23b and the outlet 22b. 5 is discharged out of the ozonolysis apparatus 1.

  As a constituent material of the main body 2 (the first frame 2a, the second frame 2b), for example, a carbon material such as carbon, nickel (Ni), aluminum (Al), or at least one of these materials Alloys, metal materials such as stainless steel, ceramic materials such as alumina, and the like can be used alone or in combination of two or more thereof.

Moreover, in the ozonolysis apparatus 1 of this embodiment, as shown in FIG. 3, the external circuit 8 is connected to the board | substrate 51 of the hydrogen ion production | generation part 5 and the board | substrate 61 of the ozonolysis part 6, respectively via wiring. Has been.
In the ozonolysis apparatus 1 of the present embodiment, when a reducing agent (hydrogen gas) is supplied to the hydrogen ion generation unit 5, the above formula (I) is applied to the surface of the catalyst (second catalyst) carried on the catalyst layer 52. ) To generate hydrogen ions and electrons.

The generated hydrogen ions move (are supplied) to the ozonolysis section 6 via the electrolyte membrane 4 and the electrons via the external circuit 8.
On the other hand, when the effluent discharged from the processing chamber 100 is supplied to the ozone decomposition unit 6, the ozone in the effluent and the hydrogen moved from the hydrogen ion generation unit 5 on the surface of the catalyst supported on the catalyst layer 62. Ions and electrons react as shown in the above formulas (2) and (3) to produce water (water vapor).
The generated water is discharged to the outside of the ozonolysis apparatus 1.

Thus, in this embodiment, since the decomposition of the reducing agent and the decomposition of ozone are performed on different catalysts, these decomposition reactions can be performed more efficiently and reliably without competing. Thereby, the decomposition efficiency of ozone increases more.
In addition, since the electrolyte membrane is arranged between different catalysts, the generated hydrogen ions can be used for ozone decomposition without waste.

  In this embodiment, electrons generated when decomposing ozone can be taken out as electricity to the external circuit 8. And in the processing apparatus 10 provided with this ozonolysis apparatus 1, the electricity generated in the ozonolysis apparatus 1 can be used as a part of electric power necessary for the operation of each part (for example, the ozone supply apparatus 200, the heating means 120, etc.) It has become. Thereby, reduction of the processing cost of the to-be-processed object S (running cost of the processing apparatus 10) can be aimed at.

The electricity generated in the ozonolysis apparatus 1 may be supplied to each part of the processing apparatus 10 as it is, or a storage battery is provided in the external circuit 8 to store the power, and then supplied to the processing apparatus 10. Also good.
Also in the second embodiment, similarly to the first embodiment, a heating means for heating the catalyst supported on the catalyst layer 52 and / or the catalyst supported on the catalyst layer 62 can be provided. Thereby, ozone contained in the used processing liquid can be decomposed more efficiently.

<Third Embodiment>
Next, a third embodiment of the ozonolysis apparatus of the present invention will be described.
Hereinafter, the ozonolysis apparatus of the third embodiment will be described with a focus on the differences from the ozonolysis of the first and second embodiments, and description of similar matters will be omitted.
FIG. 4 is a longitudinal sectional view showing a third embodiment of the ozonolysis apparatus of the present invention.
In the ozonolysis apparatus 1 shown in FIG. 4, a plurality (three in this embodiment) of joined bodies 7 are provided in the main body 2. This makes it possible to decompose ozone more efficiently.

The preferred embodiments of the ozonolysis method, ozonolysis apparatus and treatment apparatus of the present invention have been described above, but the present invention is not limited to this.
For example, the structure of each part of the ozonolysis apparatus and the processing apparatus of the present invention can be replaced with any structure that can exhibit the same function.
Further, the present invention may be a combination of any two or more configurations (features) of the above-described embodiments.

Next, specific examples of the present invention will be described.
1. Production of ozonolysis apparatus (Example 1)
The ozonolysis apparatus shown in FIG. 2 was manufactured.
The specifications of each part are as shown below.
・ Main body
Constituent material: Stainless steel Filter
Number of installations: 3 ・ Support
Constituent material: Alumina
Shape: Honeycomb shape
Average thickness: 5mm
·catalyst
Constituent material: Pt (precious metal)
Shape: Granular
Average particle size: 500 nm
Amount supported: 300 mg / cm ²
Temperature: 80 ° C
(Example 2)
An ozonolysis apparatus was produced in the same manner as in Example 1 except that the constituent material of the catalyst was changed to Cr ₂ O ₃ (transition metal oxide).

(Example 3)
The ozonolysis apparatus shown in FIG. 3 was manufactured.
The specifications of each part are as shown below.
・ Main body
Constituent materials: stainless steel, joined body, electrolyte membrane
Composition material: Nafion (DuPont)
Average thickness: 1mm
・ Hydrogen ion generator ・ Substrate
Constituent material: Carbon
Shape: Porous
Average thickness: 0.5mm
・ Catalyst layer
Average thickness: 0.1mm
·Base material
Composition: Contains carbon powder and perfluoroalkylsulfonic acid resin ・ Catalyst
Constituent material: Pt-Ru alloy (noble metal)
Shape: Granular
Average particle size: 500 nm
Amount supported: 100 mg / cm ²
・ Ozone decomposition part ・ Substrate
Constituent material: Carbon
Shape: Porous
Average thickness: 0.5mm
・ Catalyst layer
Average thickness: 0.1mm
·Base material
Composition: Contains carbon powder and perfluoroalkylsulfonic acid resin ・ Catalyst
Constituent material: Pt (precious metal)
Shape: Granular
Average particle size: 500 nm
Amount supported: 100 mg / cm ²
Temperature: 80 ° C
Example 4
The ozonolysis was performed in the same manner as in Example 3 except that the constituent material of the catalyst of the hydrogen ion generating portion was changed to PtO (transition metal oxide) and the constituent material of the catalyst of the ozonolysis portion was changed to Pd (noble metal). The device was manufactured.

(Comparative Example 1)
An ozonolysis apparatus was produced in the same manner as in Example 1 except that the constituent material of the support for the filter member was replaced with polyimide, and catalyst loading was omitted.
(Comparative Example 2)
An ozonolysis apparatus was produced in the same manner as in Example 3 except that the catalyst loading was omitted in the ozonolysis section.

2. Evaluation Ozone decomposition was performed by supplying ozone water having an ozone concentration of 10 ppm and hydrogen water having a hydrogen gas concentration of 4 ppm to the ozone decomposing apparatus of each Example and each Comparative Example.
In the ozonolysis apparatuses of Examples 1 and 2 and Comparative Example 1, a mixed liquid of ozone water and hydrogen water was supplied at a flow rate of 1 L / min.
Moreover, ozone water and hydrogen water were separately supplied to the ozonolysis apparatuses of Examples 3 and 4 and Comparative Example 2 at a flow rate of 1 L / min.
And the ozone concentration in the waste liquid of the ozonolysis apparatus of each Example and each comparative example was measured, respectively.

As a result, the ozone concentration in the waste liquid collected from the ozonolysis apparatus of each example was clearly lower than the ozone concentration in the waste liquid collected from the ozonolysis apparatus of each comparative example.
In particular, the ozone concentration in the waste liquid recovered from the ozonolysis apparatuses of Examples 3 and 4 showed a low value.

Further, in each of the ozonolysis apparatuses of each example, ozone could be decomposed in the same manner as described above even when a methanol aqueous solution was used instead of hydrogen water.
In addition, an ozone treatment apparatus was manufactured in the same manner as in the above examples, except that the constituent materials of the catalyst were changed, and evaluation was performed in the same manner as described above.
Moreover, when the ozone treatment apparatus shown in FIG. 4 was manufactured and evaluated in the same manner as described above, the same result as described above was obtained.

It is the schematic which shows embodiment of the processing apparatus of this invention. It is a longitudinal cross-sectional view which shows 1st Embodiment of the ozonolysis apparatus of this invention. It is a longitudinal cross-sectional view which shows 2nd Embodiment of the ozonolysis apparatus of this invention. It is a longitudinal cross-sectional view which shows 3rd Embodiment of the ozonolysis apparatus of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Ozone decomposition apparatus 2 ... Main-body part 2a ... 1st frame 2b ... 2nd frame 21, 21a, 21b ... Inlet 22, 22a, 22b ... Outlet 23a, 23b ... Groove 3 ... Filter member 31 ... Support 32 ... Catalyst 4 ... Electrolyte membrane 5 ... Hydrogen ion generating part 51 ... Substrate 52 ... Catalyst layer 6 ... Ozone decomposition part 61 ... Substrate 62 ... Catalyst Layer 7... Bonded body 8... External circuit 9... Heating means 10... Processing apparatus 100... Processing chamber 110 ... Cassette 120 ... Heating means 200 ... Ozone supply apparatus 210 ... Ozone supply pipe 220. Supply pipe 300 ... Steam supply apparatus 310 ... Steam supply pipe 400 ... Gas supply apparatus 410 ... Gas supply pipe 420a, 420b ... Branch pipe 500 ... Mist trap apparatus 510 ... An exhaust pipe 520 ...... exhaust pipe 530 ...... valve 540 ...... discharge pipe S ...... workpiece

Claims (19)

  An ozone decomposing method comprising decomposing the ozone by bringing ozone and hydrogen ions into contact with each other on the surface of the catalyst.   The ozonolysis method according to claim 1, wherein the catalyst is mainly composed of a noble metal and / or a transition metal oxide.   The ozonolysis method according to claim 2, wherein the noble metal is Au, Ag, Cu, Ir, Ta, Ti, W, Pt, Pd, Rh, Ru, or an alloy containing at least one of them.   The transition metal oxide includes at least one selected from the group consisting of Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Cu, W, Ta, Ti, Ir, and Mo. The ozonolysis method according to claim 2, which is an oxide.   The ozone decomposing method according to any one of claims 1 to 4, wherein the ozone decomposing is performed in a state where the catalyst is heated.   The ozone decomposing method according to any one of claims 1 to 5, wherein the hydrogen ions are generated by decomposing a reducing agent supplied to the catalyst on the surface of the catalyst.   The ozonolysis method according to claim 6, wherein the ozone and the reducing agent are supplied to the catalyst in a mixed state.   The ozonolysis method according to claim 6 or 7, wherein the reducing agent is mainly composed of hydrogen gas or methanol.   The ozone according to any one of claims 1 to 5, wherein the hydrogen ions are generated by decomposing a reducing agent supplied to a second catalyst different from the catalyst on the surface of the second catalyst. Disassembly method.   The ozonolysis method according to claim 9, wherein the second catalyst is mainly composed of a noble metal and / or a transition metal oxide.   The ozonolysis method according to claim 10, wherein the noble metal is Pt, Au, or an alloy containing at least one of them.   The transition metal oxide includes at least one selected from the group consisting of Ag, Pt, Pd, Ni, Co, Rh, Ru, Fe, Mn, Cr, Cu, W, Ta, Ti, Ir, and Mo. The ozonolysis method according to claim 2, which is an oxide.   The hydrogen ions generated on the surface of the second catalyst are supplied to the catalyst through an electrolyte membrane through which the hydrogen ions provided between the catalyst and the second catalyst can pass. Item 13. The ozonolysis method according to any one of Items 9 to 12. A main body, and a catalyst housed in the main body,
An ozone decomposing apparatus for decomposing the ozone by bringing ozone and hydrogen ions into contact with each other on the surface of the catalyst. A second catalyst housed in the main body and different from the catalyst;
The ozone decomposing apparatus according to claim 14, wherein the hydrogen ion is generated by decomposing a reducing agent supplied into the main body on the surface of the second catalyst. An electrolyte membrane through which the hydrogen ions can pass between the catalyst and the second catalyst;
The ozonolysis apparatus according to claim 14 or 15, wherein the hydrogen ions generated on the surface of the second catalyst are supplied to the catalyst via the electrolyte membrane. Using a processing agent containing ozone, a processing unit for processing the surface of the member to be processed,
The ozonolysis apparatus according to any one of claims 14 to 16 connected to the processing unit,
The processing apparatus characterized in that the exhaust discharged from the processing section is supplied to the ozone decomposing apparatus to decompose the ozone contained in the exhaust. Furthermore, it is equipped with an ozone generator that generates ozone by electrolysis of water,
The processing apparatus of Claim 17 which supplies the processing agent containing the ozone produced | generated with this ozone production | generation apparatus to the said process part, and supplies the hydrogen gas produced in the case of the electrolysis of the said water to the said ozone decomposition apparatus.   The processing apparatus according to claim 17 or 18, wherein the processing apparatus uses electricity generated when decomposing the ozone in the ozone decomposing apparatus as a part of electric power required for driving each part.

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