JP7115139B2 - OH radical treatment device and OH radical treatment method - Google Patents

Description

The present disclosure relates to an OH radical treatment device and an OH radical treatment method.

Conventionally, OH radicals have been widely used for sterilization, deodorization, bleaching, or cleaning of objects to be treated. For example, Patent Document 1 discloses a sterilization apparatus that supplies ozone and hydrogen peroxide gas into a chamber containing an object to be treated to generate OH radicals to sterilize the object to be treated.

JP 2016-154835 A

Although many techniques for measuring OH radicals in aqueous solutions have been reported, techniques for detecting OH radicals in the gas phase such as in the chamber have not yet been developed.

In view of such problems, an object of the present disclosure is to provide an OH radical treatment apparatus and an OH radical treatment method capable of detecting OH radicals in the gas phase.

In order to solve the above problems, an OH radical treatment apparatus according to an aspect of the present disclosure includes a chamber, a decompression pump connected to the chamber, a controller for decompressing the inside of the chamber to a first pressure below atmospheric pressure, A radical supply unit for supplying OH radicals or precursors of OH radicals into a depressurized chamber, and OH radicals or precursors of OH radicals are supplied into the chamber by the radical supply unit, After the inside of the chamber is at or above a second pressure higher than the first pressure, an OH radical detection probe having an aromatic carboxylic acid, a polar aprotic organic solvent, and a polar protic organic solvent is combined with the gas inside the chamber. a switching unit that changes from a non-contact state of non-contact to a contact state of contact with the gas in the chamber;
Prepare.

Further, the switching unit may bring the OH radical detection probe in the contact state into the non- contact state, and the control unit may reduce the pressure in the chamber after bringing the OH radical detection probe into the non-contact state by the switching unit.

Also, the second pressure may be a predetermined pressure equal to or higher than the atmospheric pressure.

Further, the switching unit is provided in the chamber, has an opening, and includes a storage container for storing the OH radical detection probe, a probe supply unit capable of supplying the OH radical detection probe to the storage container, and a storage container. and a probe discharge unit capable of discharging the OH radical detection probe from.

In addition, the probe supply section includes a storage section that stores the OH radical detection probe, and a supply pipe that has a supply port that faces the opening of the storage container or communicates with the storage vessel and is connected to the storage section. Alternatively, the probe outlet may include an outlet pipe connected to an outlet provided in the container.

Alternatively, the switching unit may include a container provided in the chamber, having an opening, and containing the OH radical detection probe, and a lid provided to seal the opening of the container. good.

The switching unit includes a container provided in the chamber, having an opening, and containing the OH radical detection probe, an opening provided in the chamber through which the container can pass, and an opening/closing door for opening and closing the opening. , may be provided.

Further, the switching unit is provided in the chamber, has an opening, and includes a storage container that stores the OH radical detection probe, a cylinder that can store the OH radical detection probe, a piston that can reciprocate within the cylinder, A supply pipe communicating with the cylinder and having a supply port may be provided.

Also, the radical supply unit may supply one or both of ozone and hydrogen peroxide gas and water vapor into the chamber.

In order to solve the above problems, an OH radical treatment method according to an aspect of the present disclosure includes steps of reducing the pressure in the chamber to a first pressure, and supplying OH radicals or precursors of OH radicals into the chamber. setting the inside of the chamber to a second pressure higher than the first pressure; contacting the OH radical detection probe with a gas in the chamber.

The present disclosure makes it possible to detect OH radicals in the gas phase.

It is a figure explaining an OH radical treatment apparatus. It is a figure explaining an OH radical measuring device. 1 is a flow chart showing the flow of an OH radical treatment method according to an embodiment; FIG. 4 is a diagram showing pressure fluctuations in the chamber; FIG. 5A is a first diagram illustrating the switching unit of the first modified example. FIG. 5B is a second diagram illustrating the switching unit of the first modified example. FIG. 6A is a first diagram illustrating a switching unit of the second modification. FIG. 6B is a second diagram illustrating the switching unit of the second modification. FIG. 7A is a first diagram illustrating a switching section of the third modification. FIG. 7B is a second diagram illustrating the switching unit of the third modification.

An embodiment of the present disclosure will be described in detail below with reference to the accompanying drawings. The dimensions, materials, and other specific numerical values shown in such embodiments are merely examples for facilitating understanding, and do not limit the present disclosure unless otherwise specified. In the present specification and drawings, elements having substantially the same function and configuration are given the same reference numerals to omit redundant description, and elements that are not directly related to the present disclosure are omitted from the drawings. do.

[OH radical treatment device 100]
FIG. 1 is a diagram illustrating an OH radical treatment apparatus 100. FIG. In FIG. 1, lines indicating signals from the central control unit 160 and lines indicating signals from the switching control unit 250 are omitted for easy understanding. Moreover, in FIG. 1, the OH radical detection probe 102 is indicated by cross hatching.

As shown in FIG. 1, the OH radical treatment apparatus 100 includes a chamber 110, a decompression pump 120, a radical supply section 130, a discharge section 140, a pressure recovery section 150, a central control section 160, and a switching section 200. including.

Chamber 110 is a sealable container. The chamber 110 is provided with an opening/closing door 112 . The opening/closing door 112 communicates or blocks the internal space of the chamber 110 with the outside. The object W to be processed is stored in the chamber 110 or taken out from the chamber 110 through the opening/closing door 112 .

A vacuum pump 120 is connected to the chamber 110 via a pipe 122 . The decompression pump 120 reduces the pressure inside the chamber 110 . That is, the suction side of decompression pump 120 is connected to chamber 110 . An on-off valve 124 is provided in the pipe 122 .

Radical supply unit 130 supplies ozone, hydrogen peroxide gas, and water vapor into chamber 110 . In this embodiment, the radical supplier 130 includes a hydrogen peroxide supplier 132 and an ozone supplier 134 .

The hydrogen peroxide supply unit 132 includes a pipe 132a, a pump 132b, and an on-off valve 132c. A pipe 132a connects the supply source of mixed gas containing hydrogen peroxide gas and water vapor to the chamber 110 . The mixed gas may contain nitrogen (inert gas) or oxygen. The pump 132b is provided in the pipe 132a. The pump 132b is connected to the mixed gas supply source on the suction side and connected to the chamber 110 on the discharge side. Pump 132b supplies the mixed gas to chamber 110 . The on-off valve 132c is provided between the pump 132b and the chamber 110 in the pipe 132a. The hydrogen peroxide supply unit 132 can change the supply amount of the hydrogen peroxide gas or the mixing ratio of the hydrogen peroxide gas and water vapor, and supplies the mixed gas with the optimum composition for the sterilization/sterilization conditions to the chamber 110. do.

The ozone supply unit 134 includes a pipe 134a, a pump 134b, and an on-off valve 134c. The pipe 134a connects the supply source of ozone or a mixed gas containing ozone (for example, an ozonizer, a mixed gas supply source of ozone and oxygen gas) and the chamber 110 . The pump 134b is provided in the pipe 134a. The pump 134b is connected to the ozone supply source on the suction side and connected to the chamber 110 on the discharge side. Pump 134 b supplies ozone to chamber 110 . The on-off valve 134c is provided between the pump 134b and the chamber 110 in the pipe 134a. The ozone supply unit 134 can change the supply amount of ozone or a mixed gas containing ozone (generally, ozone and oxygen gas), and supplies the gas with the optimum composition for the sterilization/sterilization conditions to the chamber 110. do.

Radical supply unit 130 supplies ozone, hydrogen peroxide gas, and water vapor into chamber 110 , thereby supplying OH radicals, precursors of OH radicals, or compounds of OH radicals into chamber 110 . . The configuration including the radical supply unit 130 can supply OH radicals having a sterilization/sterilization effect into the chamber 110 . Therefore, it is possible to improve the sterilization/sterilization efficiency of the workpiece W in the chamber 110 .

The exhaust part 140 exhausts the gas inside the chamber 110 to the outside of the chamber 110 . The discharge unit 140 includes a discharge pipe 140a, an on-off valve 140b, a drain recovery unit 142, an exhaust pipe 142a, an on-off valve 142b, a waste liquid pipe 142c, an on-off valve 142d, a pressure reducing pump 144, and a deozonizer (ozonolysis). catalyst) 146.

The discharge pipe 140 a connects the chamber 110 and the drain recovery section (gas-liquid separator) 142 . The on-off valve 140b is provided on the discharge pipe 140a. The drain recovery part 142 separates liquid components from the gas exhausted from the chamber 110 .

The exhaust pipe 142 a connects the upper portion of the drain recovery portion 142 and the suction side of the decompression pump 144 . The decompression pump 144 exhausts the gas stored in the drain recovery section 142 to the outside. The deozonizer 146 is provided between the drain recovery section 142 and the decompression pump 144 in the exhaust pipe 142a. The deozonizer 146 decomposes ozone contained in the gas passing through the exhaust pipe 142a. The on-off valve 142b is provided between the drain recovery section 142 and the deozonizer 146 in the exhaust pipe 142a.

The waste liquid pipe 142c is connected to the lower portion of the drain recovery section 142. As shown in FIG. The waste liquid pipe 142c is provided with an on-off valve 142d.

Pressure recovery unit 150 includes a suction pipe 152 , a filter 154 and an on-off valve 156 . A suction tube 152 is connected to the chamber 110 . Filter 154 is, for example, a HEPA (High Efficiency Particulate Air) filter. A filter 154 is provided in the intake pipe 152 . An on-off valve 156 is provided between the chamber 110 and the filter 154 in the intake pipe 152 .

The central control unit 160 (control unit) is composed of a semiconductor integrated circuit including a CPU (central processing unit). In order to control the switching control unit 250 and the like, the central control unit 160 reads programs, parameters, and the like for operating the CPU itself from the ROM. The central control unit 160 manages and controls the entire OH radical processing apparatus 100 in cooperation with RAM as a work area and other electronic circuits.

In this embodiment, the central control unit 160 drives and controls the decompression pumps 120 and 144, the pumps 132b and 134b, and the deozonizer 146. The central control unit 160 also controls the opening and closing of the on-off valves 124 , 132 c , 134 c , 140 b , 142 b , 142 d and 156 .

The switching section 200 includes a container 210 , a probe supply section 220 , a probe discharge section 230 , a pressure sensor 240 and a switching control section 250 . A container 210 is provided within the chamber 110 . The storage container 210 is a container having an opening. A discharge port 214 is formed in the bottom surface of the container 210 . The containing container 210 contains the OH radical detection probe 102 . The OH radical detection probe 102 will be described in detail below.

[OH radical detection probe 102]
The OH radical detection probe 102 according to the present embodiment comprises an aromatic carboxylic acid or a derivative of an aromatic carboxylic acid (hereinafter collectively referred to as “aromatic carboxylic acids”), a polar aprotic organic solvent, and a polar and a protic organic solvent. By including the polar protic organic solvent in the OH radical detection probe 102, the aromatic carboxylic acids and OH radicals can be reacted, and the OH radicals can be detected.

A conventional OH radical detection probe for measuring OH radicals in a liquid phase is an aqueous solution using water as a solvent for dissolving terephthalic acid. For this reason, when the measurement of OH radicals in the gas phase, especially in water vapor (or in the humidified gas phase with high humidity) is attempted with conventional OH radical detection probes, precursors of OH radicals dissolved in the aqueous solution The OH radicals generated from the reaction preferentially react with terephthalic acid, and cannot be distinguished from the reaction with OH radicals in the gas phase. Therefore, conventional OH radical detection probes have the problem that they cannot selectively and quantitatively detect OH radicals in the gas phase.

On the other hand, in the OH radical detection probe 102 according to the present embodiment, an anhydrous solvent comprising a polar aprotic organic solvent is used as the main solvent, whereby OH radicals are generated by dissolving OH radical precursors in the liquid phase. (OH radicals do not occur without moisture (Shigeki Nakayama et al., Generation of OH radicals and applied technology, NTS, pp.191-217 (2008), J.A.Roth, D.E.Sullivan: Kinetics of ozone decomposition in water : Kinetic study, Ind.Eng.Chem.Res.,26, pp.39-43 (1987), Takayuki Morioka et al. , No.11, pp.28-40 (1994))). Therefore, in the OH radical detection probe 102 according to the present embodiment, OH radicals generated from precursors of OH radicals dissolved in a liquid phase such as a water solvent (aqueous solution) react with aromatic carboxylic acids. You can avoid a messy situation.

Moreover, when OH radicals and aromatic carboxylic acids react, protons (H ⁺ ) are generated. Therefore, if only a polar aprotic organic solvent is used as the organic solvent for dissolving the aromatic carboxylic acids, the protons will not be accepted, and the reaction between the OH radical and the aromatic carboxylic acids will not proceed.

Therefore, the OH radical detection probe 102 according to the present embodiment can accept protons generated by the reaction by providing a polar protic organic solvent as a sub-solvent. As a result, the reaction between OH radicals and aromatic carboxylic acids can be advanced to generate hydroxyl forms of aromatic carboxylic acids, and as a result, OH radicals in the gas phase can be detected. In particular, the OH radical detection probe 102 of this embodiment can detect OH radicals in water vapor or in a humidified gas phase with high humidity. Here, the gas phase is a concept that includes not only a phase in which only gas exists, but also a gas in which liquid (for example, liquid water) is included. The gas containing liquid is a gas containing mist, a gas containing a layer of liquid (for example, a gas containing multiple layers of water molecules), or a gas in which liquid is dispersed (aerosol).

Further, aromatic carboxylic acids constituting the OH radical detection probe 102 according to the present embodiment include phthalic acid (o-phthalic acid, m-phthalic acid, p-phthalic acid (terephthalic acid)), phthalic acid derivatives (for example, , dimethyl terephthalate), benzoic acid, derivatives of benzoic acid (e.g., hydroxybenzoic acid (2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid), and substituents on the benzene ring selected from the group of compounds having a carboxyl group or a carbonyl group bonded through (e.g., coumarin (abbreviated as Cou), coumarin-3-carboxylic acid (abbreviated as CCA), phenylalanine) The aromatic carboxylic acid is preferably one or more selected from the group consisting of terephthalic acid, salicylic acid, 4-hydroxybenzoic acid, coumarin, and phenylalanine, and the OH radical detection probe 102 The aromatic carboxylic acid constituting is preferably terephthalic acid, which is inexpensive and readily available.In addition, the above aromatic carboxylic acids other than terephthalic acid react specifically (selectively) with OH radicals, like terephthalic acid. Therefore, instead of or in addition to terephthalic acid, the OH radical detection probe 102 may contain the above aromatic carboxylic acids other than terephthalic acid.

Polar aprotic organic solvents constituting the OH radical detection probe 102 according to the present embodiment include, for example, N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetone, acetonitrile, dimethylsulfoxide (DMSO ), dioxane, chloroform, ethylene dichloride, and methylene chloride. The polar aprotic organic solvent is a polar organic solvent that does not donate protons. Therefore, by including a polar aprotic organic solvent instead of water in the OH radical detection probe 102, it is possible to stop the reaction in which the precursor of OH radicals in the liquid becomes OH radicals. In addition, the polar aprotic organic solvent can easily dissolve aromatic carboxylic acids and the like. In other words, the polar aprotic organic solvent should be able to dissolve the aromatic carboxylic acid in the liquid (http://www.st.rim.or.jp/~shw/MSDS/20034250.pdf). In addition, the polar aprotic organic solvent preferably has a relatively high dielectric constant, such as one or more selected from the group of DMF, DMSO, and acetonitrile.

…反応式（１）
反応式（１）は、テレフタル酸 ＋ ＯＨラジカル → ２－ヒドロキシテレフタル酸（ＨＴＡ） ＋ プロトン で表すこともできる。
なお、極性プロトン性有機溶媒は、相対的に比誘電率が大きいものが好ましい。 Further, the polar protic organic solvent constituting the OH radical detection probe 102 according to this embodiment includes methanol, ethanol, 1-propanol, 2-propanol (isopropanol), acetic acid, ethyl acetate, formic acid, 1-butanol, and isobutyl alcohol. , ethylene glycol, and methanediol. The polar protic organic solvent is a polar organic solvent that donates protons. Therefore, by including a polar protic organic solvent in the OH radical detection probe 102, it becomes possible for the OH radical detection probe 102 to receive protons generated by the reaction. Then, the reaction shown in the following reaction formula (1) proceeds. In other words, the OH radical detection probe is made to contain a polar protic organic solvent in order to advance the reaction formula (1).

... reaction formula (1)
Reaction formula (1) can also be represented by terephthalic acid + OH radical → 2-hydroxyterephthalic acid (HTA) + proton.
The polar protic organic solvent preferably has a relatively high dielectric constant.

By the way, in order to improve the OH radical detection sensitivity of the OH radical detection probe 102, it is conceivable to increase the concentration of aromatic carboxylic acids in the OH radical detection probe 102. FIG.

However, the wavelength of fluorescence emitted from the hydroxy form of aromatic carboxylic acids is close to the wavelength of fluorescence emitted from aromatic carboxylic acids. Specifically, the wavelength of fluorescence emitted from HTA, which is a hydroxy derivative of an aromatic carboxylic acid, has a peak at or near 425 nm, and the wavelength of fluorescence emitted from terephthalic acid, which is an aromatic carboxylic acid, is 340 nm. , or there is a peak around 340 nm. Therefore, when the concentration of terephthalic acid in the OH radical detection probe 102 is increased, the width of the peak indicating the intensity of fluorescence generated from unreacted terephthalic acid increases and the base of the peak broadens. Then, the peak indicating the intensity of fluorescence generated from HTA in the OH radical detection probe 102 is buried in the peak of unreacted terephthalic acid. Therefore, even if the concentration of the aromatic carboxylic acid in the OH radical detection probe 102 is increased, there is a problem that the fluorescence intensity generated from HTA cannot be measured accurately or the fluorescence generated from HTA cannot be measured.

In general, a molecule in an electronically excited state has an electric dipole moment different from that in the electronic ground state. Thus, in polar solvents, reorientation of the solvent molecules can occur while in the excited state so as to stabilize the dipole moment of the excited molecule. As a result, the excited state is relatively stabilized, and it is observed that the fluorescence spectrum shifts to longer wavelengths and the fluorescence lifetime becomes longer. Therefore, the wavelength peak of the fluorescence generated from the HTA in the OH radical detection probe 102 is shifted to 425 nm or a predetermined wavelength longer than 425 nm. Similarly, the peak wavelength of fluorescence generated from terephthalic acid in the OH radical detection probe 102 is 340 nm or is shifted to the long wavelength side from 340 nm by a predetermined wavelength.

Therefore, in the OH radical detection probe 102 of this embodiment, the content of the polar protic organic solvent may be higher than that of the polar aprotic organic solvent.

By making the content of the polar protic organic solvent higher than that of the polar aprotic organic solvent, the polarizability of the OH radical detection probe 102 can be enhanced with the polar protic organic solvent. This makes it possible to increase the reaction conversion rate between the OH radical and the aromatic carboxylic acid, and as a result, increase the production amount of the hydroxy form of the aromatic carboxylic acid. Therefore, it is possible to increase the fluorescence intensity of the hydroxy form of the aromatic carboxylic acid without increasing the amount of the aromatic carboxylic acid. Therefore, the OH radical detection probe 102 can improve the detection sensitivity of the hydroxy form (OH radical) of aromatic carboxylic acids.

If the content of the polar protic organic solvent exceeds 16 times the content of the polar aprotic organic solvent, the solubility of the aromatic carboxylic acids will decrease. Thus, the OH radical detection probe 102 contains more than 1 to 16 times more polar protic organic solvent than polar aprotic organic solvent. The OH radical detection probe 102 preferably contains more than 1 to 8 times as much polar protic organic solvent as the polar aprotic organic solvent. As a result, the fluorescence intensity of the hydroxy form of the aromatic carboxylic acid can be increased while maintaining the solubility of the aromatic carboxylic acid.

Further, the aromatic carboxylic acid in the solvent (polar aprotic organic solvent and polar protic organic solvent) in the OH radical detection probe 102 is, for example, 0.02 mmol/L (0.02 mM=0.02 mol/m ³ ) The aromatic carboxylic acid concentration is preferably 0.2 mmol/L or more and 2 mmol/L or less, preferably 20 mmol/L or more (20 mM=20 mol/m ³ ) or less.

Also, the polar protic organic solvent contained in the OH radical detection probe 102 is any one or more of methanol, ethanol, and propanol. The polar protic organic solvent contained in the OH radical detection probe 102 is a monohydric alcohol in which the number of carbon atoms in the hydrocarbon portion with an OH group (hydroxy group) is reduced (that is, the polarization (dielectric constant) is increased). Thus, a strongly polarized protic polar organic solvent can be obtained. This makes it possible to increase the fluorescence intensity of the hydroxy form of the aromatic carboxylic acid. In the polar protic organic solvent, the degree of polarization is indicated by the dielectric constant (relative dielectric constant), and the greater the dielectric constant, the greater the polarization.

Also, the polar protic organic solvent contained in the OH radical detection probe 102 is preferably propanol (1-propanol, 2-propanol), more preferably ethanol, and most preferably methanol. The higher the volume ratio of OH groups (hydroxy groups) in the total atoms constituting the polar protic organic solvent, the stronger the polarization and thus the stronger the polar solvent. Therefore, it is possible to increase the fluorescence intensity of the hydroxy form of the aromatic carboxylic acid while maintaining the solubility of the aromatic carboxylic acid.

The probe supply section 220 includes a storage section 222 , a supply pipe 224 and a first on-off valve 226 . The storage part 222 stores the OH radical detection probe 102 . Reservoir 222 is provided outside chamber 110 . The supply pipe 224 has a supply port 224 a on one end side and is connected to the reservoir 222 on the other end. The supply pipe 224 is provided in the chamber 110 so that the supply port 224 a faces the opening 212 of the container 210 . That is, supply tube 224 passes through chamber 110 . A first on-off valve 226 is provided in the supply pipe 224 . The first on-off valve 226 is provided outside the chamber 110 .

The probe discharge section 230 includes a discharge pipe 232 , a measured liquid storage section 234 and a second on-off valve 236 . The discharge pipe 232 connects the discharge port 214 provided in the container 210 and the measured liquid reservoir 234 . The measurement liquid storage part 234 stores the OH radical detection probe 102 discharged from the storage container 210 . A measurement liquid reservoir 234 is provided outside the chamber 110 . That is, exhaust pipe 232 passes through chamber 110 . A second on-off valve 236 is provided between the discharge port 214 and the measured liquid reservoir 234 in the discharge pipe 232 . A second on-off valve 236 is provided outside the chamber 110 .

The concentration of OH radicals in the OH radical detection probe 102 stored in the measurement liquid storage part 234 is measured by the OH radical measurement device 300 described later.

Pressure sensor 240 detects the pressure within chamber 110 .

The switching control unit 250 is composed of a semiconductor integrated circuit including a CPU (Central Processing Unit). The switching control unit 250 reads programs, parameters, and the like for operating the CPU itself from the ROM. The switching control section 250 manages and controls the entire switching section 200 in cooperation with a RAM as a work area and other electronic circuits. In this embodiment, the switching control unit 250 controls opening and closing of the first on-off valve 226 and the second on-off valve 236 based on the detection value of the pressure sensor 240 .

[OH radical measuring device 300]
FIG. 2 is a diagram for explaining the OH radical measuring device 300. As shown in FIG. In FIG. 2, solid-line arrows indicate the flow of light, and dashed-line arrows indicate the flow of signals.

As shown in FIG. 2, the OH radical measurement device 300 includes an irradiation section 310, a measurement section 320, and a measurement control section 330. As shown in FIG.

The irradiation unit 310 irradiates the OH radical detection probe 102 taken out from the measurement liquid reservoir 234 (after being brought into contact with the gas in the chamber 110) with ultraviolet rays (for example, ultraviolet rays with a wavelength of 310 nm). The measurement unit 320 emits fluorescence from the OH radical detection probe 102 when the irradiation unit 310 irradiates ultraviolet rays (for example, hydroxyterephthalic acid (hereinafter referred to as “HTA”) which is a hydroxy derivative of aromatic carboxylic acids). The intensity of fluorescence at a wavelength of 425 nm) is measured.

The measurement control section 330 is composed of a semiconductor integrated circuit including a CPU (Central Processing Unit). The measurement control unit 330 reads programs, parameters, and the like for operating the CPU itself from the ROM. The measurement control unit 330 manages and controls the entire OH radical measurement device 300 in cooperation with a RAM as a work area and other electronic circuits. In this embodiment, the measurement control section 330 functions as a concentration derivation section 332 .

The concentration derivation unit 332 derives the concentration of OH radicals in the gas inside the chamber 110 based on the fluorescence intensity measured by the measurement unit 320 .

For example, when terephthalic acid is employed as the aromatic carboxylic acid constituting the OH radical detection probe 102, when OH radicals in the gas phase bind to the OH radical detection probe 102, the reaction shown in the reaction formula (1) proceeds. .

Thus, in this case, terephthalic acid reacts with OH radicals to produce 2-hydroxyterephthalic acid (HTA) and protons. Therefore, when the irradiation unit 310 irradiates the OH radical detection probe 102 with ultraviolet rays, the HTA emits fluorescence. Measurement unit 320 measures the intensity of fluorescence generated from HTA (fluorescence intensity), and the concentration of HTA, that is, the concentration of OH radicals in the gas phase (in the gas in chamber 110), is determined from the fluorescence intensity. can be calculated.

Therefore, it is possible to prepare a plurality of HTA standard solutions having different concentrations, irradiate each solution with ultraviolet rays, measure the fluorescence intensity, and prepare a calibration curve of the HTA fluorescence intensity. Therefore, the concentration derivation unit 332 can derive the concentration of OH radicals based on the fluorescence intensity measured by the measurement unit 320 and the calibration curve.

[OH radical treatment method]
Next, an OH radical treatment method using the OH radical treatment apparatus 100 will be described. FIG. 3 is a flow chart showing the flow of the OH radical treatment method according to this embodiment. FIG. 4 is a diagram showing pressure fluctuations in chamber 110. As shown in FIG.

As shown in FIG. 3, the OH radical treatment method includes a storage step S110, a first pressure reduction step S120, a first supply step S130, a second supply step S140, a discharge step S150, a second pressure reduction step S160, a pressure recovery step S170, An extraction step S180 is included. In the initial state, the opening/closing door 112 is open, and the decompression pumps 120, 144 and the pumps 132b, 134b are stopped. In the initial state, the on-off valves 124, 132c, 134c, 140b, 142b, 142d, the first on-off valve 226 and the second on-off valve 236 are closed, and the on-off valve 156 is open. Each step will be described in detail below.

[Accommodation step S110]
In the accommodation step S110, an actuator (not shown) accommodates the workpiece W inside the chamber 110 from the outside. After the workpiece W is completely housed in the chamber 110 , the actuator closes the opening/closing door 112 . Also, the central control unit 160 closes the on-off valve 156 . The chamber 110 is thereby sealed. As shown in FIG. 4, in the accommodation step S110 (time T0 to time T1 in FIG. 4), the inside of the chamber 110 is maintained at the second pressure P2. Here, the second pressure P2 is the atmospheric pressure.

[First decompression step S120]
In the first decompression step S120, the central control unit 160 opens the on-off valve 124 and drives the decompression pump 120. As shown in FIG. As shown in FIG. 4, in the first pressure reduction step S120 (from time T1 to time T2 in FIG. 4), the pressure inside the chamber 110 is reduced from the second pressure P2 to the first pressure P1. Note that the first pressure P1 is a predetermined pressure that is less than the atmospheric pressure.

[First supply step S130]
In the first supply step S<b>130 , first, the central control unit 160 closes the on-off valve 124 and stops the decompression pump 120 . Subsequently, the central control unit 160 opens the on-off valves 132c and 134c to drive the pumps 132b and 134b. A sterilizing gas containing hydrogen peroxide gas, water vapor, and ozone is thereby supplied into the chamber 110 . Then, the object W to be processed is sterilized by the sterilizing gas. As shown in FIG. 4, in the first supply step S130 (from time T2 to time T3 in FIG. 4), the pressure inside the chamber 110 is raised from the first pressure P1 to the second pressure P2.

The central control unit 160 then opens the on-off valve 140 b and the on-off valve 142 b to drive the deozonizer 146 . In addition, the central control unit 160 drives the decompression pump 144 based on the detection value of the pressure sensor 240 so that the inside of the chamber 110 is maintained at the second pressure P2. The on-off valve 142 d is appropriately opened according to the degree of storage of the waste liquid in the drain recovery section 142 .

[Second supply step S140]
In the second supply step S140, first, the switching control unit 250 determines whether the pressure (detection value) inside the chamber 110 detected by the pressure sensor 240 is equal to or higher than the second pressure P2. When the switching control unit 250 determines that the pressure is not equal to or higher than the second pressure P2, it waits until the detected value becomes equal to or higher than the second pressure P2. When the switching control unit 250 determines that the pressure is equal to or higher than the second pressure P2, the switching control unit 250 opens the first on-off valve 226 (time T3 in FIG. 4). Thereby, the OH radical detection probe 102 is supplied to the container 210 . That is, the probe supply unit 220 brings the OH radical detection probe 102 into contact with the gas inside the chamber 110 through the opening 212 of the container 210 . Note that the switching control unit 250 closes the first on-off valve 226 when a predetermined amount of the OH radical detection probe 102 is supplied to the container 210 .

[Ejection step S150]
In the discharge step S150, first, the switching control unit 250 determines whether or not a predetermined time has passed since the first on-off valve 226 was opened. The predetermined time is less than the sterilization time of the object W to be processed (time from time T3 to time T4 in FIG. 4). If the switching control unit 250 determines that the predetermined time has not passed, it waits until the predetermined time has passed. When the switching control unit 250 determines that the predetermined time has passed, the switching control unit 250 opens the second on-off valve 236 . Then, the OH radical detection probe 102 housed in the housing container 210 is discharged by its own weight into the measurement liquid reservoir 234 via the discharge port 214 and the discharge pipe 232 . In other words, the probe discharger 230 switches the OH radical detection probe 102 from the above contact state to a non-contact state in which the OH radical detection probe 102 is not in contact with the gas inside the chamber 110 . Then, the concentration of OH radicals in the OH radical detection probe 102 discharged to the measurement liquid reservoir 234 is measured by the OH radical measurement device 300 . Further, when the discharge of the OH radical detection probe 102 from the storage container 210 to the measurement liquid reservoir 234 is completed, the switching control section 250 closes the second on-off valve 236 .

[Second decompression step S160]
In the second decompression step S160, first, the central control unit 160 determines whether or not the sterilization time has elapsed. When it is determined that the sterilization time has elapsed, the central control unit 160 closes the on-off valves 132c and 134c and stops the pumps 132b and 134b. This stops the supply of sterilizing gas into the chamber 110 . Then, as shown in FIG. 4, the pressure inside the chamber 110 is reduced from the second pressure P2 to the first pressure P1 in the second pressure reduction step S160 (time T4 to time T5 in FIG. 4).

[Restore pressure step S170]
In the pressure recovery step S170, first, the central control unit 160 closes the on-off valves 140b and 142b, and stops the decompression pump 144 and the deozonizer 146. FIG. The central control unit 160 then opens the on-off valve 156 . Then, outside air is supplied into the chamber 110 through the filter 154 and the suction pipe 152 . Therefore, as shown in FIG. 4, the pressure inside the chamber 110 is restored from the first pressure P1 to the second pressure P2 in the pressure restoration step S170 (time T5 to time T6 in FIG. 4).

[Extraction step S180]
In the take-out step S180 (from time T6 to time T7 in FIG. 4), the actuator opens the opening/closing door 112 and takes out the workpiece W from the chamber 110 to the outside. Thus, the object W to be treated is sterilized.

In addition, in the OH radical treatment method, the inside of the chamber 110 may be appropriately purged with a gas that does not contain OH radicals.

As described above, in the OH radical treatment apparatus 100 and the OH radical treatment method using the apparatus according to the present embodiment, the OH radical detection probe 102 is detected only after the second pressure P2, which is higher than the first pressure P1, becomes equal to or higher than the second pressure P2. are exposed to the gas in chamber 110 . Therefore, evaporation of the liquid from the OH radical detection probe 102 can be suppressed as compared with the case where the OH radical detection probe 102 is exposed to the gas in the chamber 110 even at the first pressure P1. As a result, the composition of the OH radical detection probe 102 can be maintained, and the concentration of OH radicals can be measured with high accuracy using the OH radical detection probe 102 .

Also, in the switching unit 200 , the first on-off valve 226 and the second on-off valve 236 are provided outside the chamber 110 . That is, the first on-off valve 226 and the second on-off valve 236 are placed under atmospheric pressure. Therefore, it is possible to switch the OH radical detection probe 102 between the contact state and the non-contact state without providing a special sealing mechanism or the like.

[First modification]
FIG. 5A is a first diagram illustrating the switching unit 400 of the first modified example. FIG. 5B is a second diagram illustrating the switching unit 400 of the first modified example. In addition, in FIGS. 5A and 5B, the flow of signals is indicated by dashed arrows. 5A and 5B, the OH radical detection probe 102 is indicated by cross hatching.

As shown in FIGS. 5A and 5B , switching section 400 includes container 210 , lid section 410 , pressure sensor 240 , and switching control section 450 . Components that are substantially the same as those of the switching unit 200 are denoted by the same reference numerals, and descriptions thereof are omitted.

The lid portion 410 is provided so as to be able to seal the opening portion 212 of the container 210 .

In the first modification, switching control unit 450 drives an actuator (not shown) based on the detection value of pressure sensor 240 to open and close lid unit 410 .

Specifically, in the accommodation step S110, while the open/close door 112 of the chamber 110 is open, the switching control unit 450 drives the actuator to move the container 210 and the lid 410 into the chamber 110. contain. At this time, as shown in FIG. 5A, the opening 212 of the storage container 210 is sealed with the lid 410 .

When switching control unit 450 determines that the pressure (detection value) in chamber 110 detected by pressure sensor 240 is equal to or higher than second pressure P2, switching control unit 450 drives the actuator to the open position shown in FIG. 5B. The lid part 410 is moved. Then, the opening 212 is unsealed, and the OH radical detection probe 102 comes into contact with the gas inside the chamber 110 (contact state).

In addition, when a predetermined time has elapsed since lid portion 410 was moved to the open position, switching control portion 450 drives the actuator to move lid portion 410 to the closed position shown in FIG. 5A. Then, the opening 212 is sealed, and the OH radical detection probe 102 is out of contact with the gas inside the chamber 110 (non-contact state).

Then, in the removal step S180, switching control unit 450 drives the actuator to remove container 210 and lid 410 from chamber 110 to the outside while opening/closing door 112 of chamber 110 is open.

As described above, the switching unit 400 according to the first modification switches the OH radical detection probe 102 to the chamber 110 only after the pressure reaches the second pressure P2 or higher by a simple operation such as opening and closing the lid 410. can be exposed to gases inside.

[Second modification]
FIG. 6A is a first diagram illustrating the switching unit 500 of the second modification. FIG. 6B is a second diagram illustrating the switching unit 500 of the second modification. In FIGS. 6A and 6B, lines indicating signals from the switching control unit 550 to the on-off valves 522a and 526a are omitted for easy understanding. Also, the OH radical detection probe 102 in FIGS. 6A and 6B is indicated by cross hatching.

As shown in FIGS. 6A and 6B, switching section 500 includes auxiliary chamber 510 , purge mechanism 520 , pressure sensor 240 , and switching control section 550 . Components that are substantially the same as those of the switching unit 200 are denoted by the same reference numerals, and descriptions thereof are omitted.

In a second variation, chamber 110 includes opening 114a and opening/closing door 114b. The opening 114a has a size through which the storage container 210 can pass, but through which the workpiece W cannot pass. The opening/closing door 114b opens and closes the opening 114a.

Auxiliary chamber 510 is provided to communicate with chamber 110 through opening 114a. Auxiliary chamber 510 is a closed container. The auxiliary chamber 510 is provided with an opening/closing door 512 . The opening/closing door 512 communicates or blocks the internal space of the auxiliary chamber 510 with the outside.

Purge mechanism 520 purges auxiliary chamber 510 . The purge mechanism 520 includes a supply pipe 522, a pump 524, an on-off valve 522a, an exhaust pipe 526, and an on-off valve 526a. Supply pipe 522 connects a supply of purge gas (eg, nitrogen) and auxiliary chamber 510 . A pump 524 is provided in the supply pipe 522 . The pump 524 is connected to the purge gas supply source on the suction side and connected to the auxiliary chamber 510 on the discharge side. Pump 524 supplies purge gas to auxiliary chamber 510 . An on-off valve 522 a is provided between the pump 524 and the auxiliary chamber 510 in the supply pipe 522 . The exhaust pipe 526 is a pipe connected to the auxiliary chamber 510 and open to the atmosphere at its end. The on-off valve 526 a is provided in the exhaust pipe 526 .

In the second modification, switching control unit 550 drives an actuator (not shown) based on the detection value of pressure sensor 240 to open/close doors 114 b and 512 . In addition, the switching control unit 550 controls the opening and closing of the on-off valves 522 a and 526 a and controls the driving of the pump 524 .

More specifically, the switching control unit 550 drives the actuator to open the open/close door 512 to move the storage container 210 containing the OH radical detection probe 102 to the auxiliary chamber 510 before the second supply step S140 is started. accommodate within. Then, the switching control unit 550 drives the actuator to close the open/close door 512 . Subsequently, the switching control unit 550 opens the on-off valves 522 a and 526 a to drive the pump 524 . As a result, the interior of the auxiliary chamber 510 is replaced with the purge gas. In addition, the inside of the auxiliary chamber 510 is maintained at the second pressure P2 or less.

When switching control unit 550 determines that the pressure (detection value) in chamber 110 detected by pressure sensor 240 is equal to or higher than second pressure P2, switching control unit 550 drives the actuator to the open position shown in FIG. 6B. The opening/closing door 114b is moved. The switching control unit 550 then drives the actuator to move the container 210 from the auxiliary chamber 510 into the chamber 110 . Then, the OH radical detection probe 102 comes into contact with the gas inside the chamber 110 (contact state).

Further, the switching control unit 550 drives the actuator to move the storage container 210 from the chamber 110 into the auxiliary chamber 510 after a predetermined time has elapsed since the open/close door 114b was moved to the open position. Then, the switching control unit 550 moves the open/close door 114b to the closed position shown in FIG. 6A. Then, the OH radical detection probe 102 is out of contact with the gas inside the chamber 110 (non-contact state).

Then, the switching control unit 550 stops the pump 524 and closes the on-off valves 522a and 526a. Further, the switching control unit 550 drives the actuator to open the open/close door 512 and take out the storage container 210 from the auxiliary chamber 510 to the outside.

As described above, the switching unit 500 according to the second modification includes the auxiliary chamber 510 and the purge mechanism 520. FIG. As a result, it is possible to prevent outside air from entering the chamber 110 and sterilization gas from flowing out of the chamber 110 .

[Third Modification]
FIG. 7A is a first diagram illustrating a switching section 600 of the third modification. FIG. 7B is a second diagram illustrating the switching section 600 of the third modification. In addition, in FIGS. 7A and 7B, the flow of signals is indicated by dashed arrows. 7A and 7B, the OH radical detection probe 102 is indicated by cross hatching.

As shown in FIGS. 7A and 7B , switching unit 600 includes container 210 , syringe 610 , pressure sensor 240 , and switching control unit 650 . Components that are substantially the same as those of the switching unit 200 are denoted by the same reference numerals, and descriptions thereof are omitted.

In a third variant, the chamber 110 is provided with a septum 116 . The septum 116 is composed of an elastic member such as elastomer or rubber.

Syringe 610 includes cylinder 612, piston 614, and needle tube 616 (supply tube). Cylinder 612 is a cylindrical container. Cylinder 612 can accommodate OH radical detection probe 102 . Piston 614 is cylindrical in shape. Piston 614 is provided in cylinder 612 so as to be able to reciprocate. The outer diameter of piston 614 is slightly smaller than the inner diameter of cylinder 612 . A needle tube 616 is communicated with the cylinder 612 . The needle tube 616 has a supply port 616a.

A container 210 is disposed within the chamber 110 . In the third modification, container 210 is provided at a position where supply port 616 a faces opening 212 of container 210 when needle tube 616 is inserted into chamber 110 through septum 116 .

In the third modification, switching control unit 650 drives an actuator (not shown) based on the value detected by pressure sensor 240 to insert/remove syringe 610 into/from chamber 110 (septum 116), or move piston 614 into/from cylinder 612. Move back and forth inside.

Specifically, when switching control unit 650 determines that the pressure (detection value) in chamber 110 detected by pressure sensor 240 is equal to or higher than second pressure P2, switching control unit 650 drives the actuator to cause cylinder 612 to An OH radical detection probe 102 is accommodated. Switch control unit 650 then drives the actuator to insert needle tube 616 of syringe 610 into chamber 110 via septum 116 . Subsequently, the switching control unit 650 moves the piston 614 to move the OH radical detection probe 102 from the cylinder 612 to the container 210 as shown in FIG. 7A. Then, the OH radical detection probe 102 is accommodated in the container 210, and the OH radical detection probe 102 comes into contact with the gas inside the chamber 110 (contact state).

Further, when a predetermined time has passed since the OH radical detection probe 102 was accommodated in the container 210, the switching control unit 650 moves the piston 614 to move the probe 102 from the container 210 into the cylinder 612 as shown in FIG. 7B. OH radical detection probe 102 is moved. Then, the OH radical detection probe 102 is out of contact with the gas inside the chamber 110 (non-contact state).

Switch control unit 650 then drives the actuator to pull needle tube 616 of syringe 610 out of septum 116 .

That is, the syringe 610 of the third modified example includes a probe supply unit that is provided to supply the OH radical detection probe 102 to the container 210 and a probe discharge unit that is provided to discharge the OH radical detection probe 102 from the container 210. functions as a department.

As described above, the switching unit 600 according to the third modification includes the syringe 610 . As a result, the OH radical detection probe 102 can be exposed to the gas in the chamber 110 only after the pressure reaches the second pressure P2 or higher by a simple operation such as inserting and removing the syringe 610 .

Although the embodiments have been described above with reference to the accompanying drawings, it goes without saying that the present disclosure is not limited to such embodiments. It is obvious that a person skilled in the art can conceive of various modifications or modifications within the scope of the claims, and they are naturally within the technical scope.

For example, in the above embodiments and modifications, the switching units 200, 400, 500, and 600 switch the OH radical detection probe 102 between the contact state and the non-contact state. However, if the pressure in the chamber 110 is not reduced after reaching the second pressure P2 (for example, if the opening/closing door 112 is opened or the inside of the chamber 110 is purged), the switching units 200, 400, 500, and 600 , the OH radical detection probe 102 only needs to be in a contact state.

Further, in the above-described embodiment and modifications, the case where the second pressure P2 is the atmospheric pressure has been described as an example. However, the second pressure P2 may be a pressure above atmospheric pressure. In any case, the second pressure P2 should be higher than the first pressure P1. As a result, evaporation of the liquid from the OH radical detection probe 102 can be suppressed compared to the case where the OH radical detection probe 102 is exposed to the gas in the chamber 110 even at the first pressure P1.

Further, in the above embodiment, the case where the reservoir 222 is provided outside the chamber 110 has been described as an example. However, reservoir 222 may be provided within chamber 110 .

Further, in the above-described embodiment, the configuration in which the supply port 224 a of the supply pipe 224 faces the opening 212 of the container 210 has been described as an example. However, the OH radical detection probe 102 may be supplied to the container 210 via the supply pipe 224, and the supply port 224a may communicate with the container 210.

Further, in the above embodiment, the configuration in which the OH radical detection probe 102 is discharged by its own weight into the measurement liquid reservoir 234 has been described as an example. However, probe exhaust 230 may comprise a pump. In this case, the pump discharges the OH radical detection probe 102 from the storage container 210 to the measurement liquid reservoir 234 .

Further, in the second depressurizing step S160 of the above embodiment, the case where the inside of the chamber 110 is depressurized from the second pressure P2 to the first pressure P1 has been described as an example. However, in the second decompression step S160, the chamber 110 may be decompressed, and the decompression pressure is not limited.

Further, in the first modified example, the configuration in which the lid portion 410 moves within the chamber 110 has been described as an example. However, lid 410 may move between chamber 110 and outside chamber 110 .

Further, in the second modified example, the configuration in which the switching unit 500 includes the purge mechanism 520 has been described as an example. However, the purge mechanism 520 is not an essential component. Also, the configuration in which the switching unit 500 includes the auxiliary chamber 510 has been described as an example. However, auxiliary chamber 510 is not an essential feature. The switching unit 500 may include at least the opening 114a and the opening/closing door 114b.

In the above embodiment, the case where the probe supply section 220 includes the storage section 222 and the supply pipe 224, and the probe discharge section 230 includes the discharge pipe 232 and the measured liquid storage section 234 is taken as an example. explained. However, the configuration of the probe supply unit is not limited as long as it can supply the OH radical detection probe 102 to the container 210 . Similarly, the configuration of the probe ejection section is not limited as long as it can eject the OH radical detection probe 102 from the container 210 . For example, the probe supply section may be composed of the syringe 610 described above, and the probe discharge section 230 may include the discharge tube 232 and the measurement liquid storage section 234 . Further, the probe supply section 220 may include the storage section 222, the supply pipe 224, and the first on-off valve 226, and the probe discharge section may be configured by the syringe 610 described above.

Further, in the above-described embodiment and modifications, the case where the radical supply unit 130 supplies the sterilization gas containing ozone, hydrogen peroxide gas, and water vapor to the chamber 110 has been described as an example. However, the radical supply unit 130 may supply one or both of ozone and hydrogen peroxide gas and water vapor into the chamber 110 . Also, the radical supply unit 130 may supply one or both of ozone and hydrogen peroxide gas to the chamber 110 . Further, the radical supply unit 130 may supply one or both of oxygen radicals and nitrogen oxides and water (water vapor) into the chamber 110 . Also, the radical supply unit 130 may supply one or both of oxygen radicals and nitrogen oxides into the chamber 110 . Further, a mechanism for irradiating ultraviolet (UV) rays into the chamber 110 may be provided, and the radical supply unit 130 may supply either one or both of hydrogen peroxide gas and ozone. Alternatively, the chamber 110 may contain titanium oxide, and the radical supply unit 130 may supply ozone. Thereby, OH radicals can be supplied to the chamber 110 .

Further, in the above-described embodiment and modifications, the switching units 200, 400, 500, and 600 have been described with the configuration including the switching control units 250, 450, 550, and 650 as an example. However, the switching control units 250, 450, 550, 650 are not essential components.

Further, in the above embodiment and modifications, the case where the OH radical treatment apparatus 100 sterilizes the object W to be treated has been described as an example. However, the OH radical treatment apparatus 100 may deodorize, bleach, or clean the object W to be treated.

Further, in the above-described embodiment and modifications, the configuration including an aromatic carboxylic acid as an OH radical detection probe that generates a fluorescent compound upon reaction with OH radicals has been described as an example. However, the OH radical detection probe may comprise chemicals that produce fluorescent compounds other than aromatic carboxylic acids.

Also, in the above embodiments and modifications, the case where the OH radical detection probe contains only an aromatic carboxylic acid, a polar aprotic organic solvent, and a polar protic organic solvent has been described as an example. However, the OH radical detection probe need not contain water and may contain other solvents.

Further, in the above embodiment, the case where the OH radical measurement device 300 includes the irradiation section 310, the measurement section 320, and the measurement control section 330 has been described as an example. However, the OH radical measurement device 300 detects the concentration of the reaction product (hydroxy form of aromatic carboxylic acid) between the aromatic carboxylic acid and the OH radical in the OH radical detection probe 102, and the gas in the chamber 110 The configuration is not limited as long as the concentration of OH radicals can be converted. The OH radical measurement device 300 is, for example, a gas chromatograph (GC), a liquid chromatograph (LC), a mass spectrometer (MS), a gas chromatograph mass spectrometer (GC-MS, GC-MS/MS), a liquid chromatograph mass Any one or any two or more of an analysis device (LC-MS, LC-MS/MS) and an infrared spectrometer (IR) may be used.

INDUSTRIAL APPLICABILITY The present disclosure can be used for an OH radical treatment device and an OH radical treatment method.

100 OH radical processing device 110 chamber 114a opening 114b open/close door 120 decompression pump 130 radical supply unit 160 central control unit (control unit)
200 Switching part 210 Storage container 212 Opening 214 Discharge port 220 Probe supply part 222 Storage part 224 Supply pipe 230 Probe discharge part 232 Discharge pipe 400 Switching part 410 Lid part 500 Switching part 600 Switching part 612 Cylinder 614 Piston 616 Needle tube (supply tube )

Claims (10)

a chamber;
a vacuum pump connected to the chamber;
a controller for reducing the pressure in the chamber to a first pressure below atmospheric pressure;
a radical supply unit that supplies OH radicals or precursors of the OH radicals into the decompressed chamber;
The OH radicals or the precursors of the OH radicals are supplied into the chamber by the radical supply unit, and after the inside of the chamber reaches a second pressure higher than the first pressure or higher, the aromatic carboxylic acid, a polar aprotic organic solvent, and an OH radical detection probe having a polar protic organic solvent , from a non-contact state in which the gas in the chamber is out of contact with the gas in the chamber. a switching unit for setting a state;
OH radical treatment device. The switching unit changes the OH radical detection probe in the contact state to the non- contact state,
2. The OH radical treatment apparatus according to claim 1, wherein the control unit reduces the pressure in the chamber after bringing the OH radical detection probe into the non-contact state by the switching unit. 3. The OH radical treatment apparatus according to claim 1, wherein said second pressure is a predetermined pressure equal to or higher than atmospheric pressure. The switching unit is
a container provided in the chamber, having an opening, and containing the OH radical detection probe;
a probe supply unit capable of supplying the OH radical detection probe to the container;
a probe discharge unit capable of discharging the OH radical detection probe from the storage container;
The OH radical treatment device according to any one of claims 1 to 3, comprising: The probe supply unit is
a reservoir for storing the OH radical detection probe;
a supply pipe facing an opening of the storage container or having a supply port communicating with the storage container and connected to the reservoir;
with
5. The OH radical treatment apparatus according to claim 4, wherein the probe discharge part has a discharge pipe connected to a discharge port provided in the container. The switching unit is
a container provided in the chamber, having an opening, and containing the OH radical detection probe;
a lid portion provided so as to be able to seal the opening portion of the container;
The OH radical treatment device according to any one of claims 1 to 3, comprising: The switching unit is
a container provided in the chamber, having an opening, and containing the OH radical detection probe;
an opening provided in the chamber through which the container can pass;
an opening/closing door that opens and closes the opening;
The OH radical treatment device according to any one of claims 1 to 3, comprising: The switching unit is
a container provided in the chamber, having an opening, and containing the OH radical detection probe;
a cylinder capable of accommodating the OH radical detection probe;
a piston reciprocatingly movable within the cylinder;
a supply pipe communicating with the cylinder and having a supply port;
The OH radical treatment device according to any one of claims 1 to 3, comprising: 9. The OH radical treatment apparatus according to any one of claims 1 to 8, wherein the radical supply unit supplies one or both of ozone and hydrogen peroxide gas and water vapor into the chamber. reducing the pressure in the chamber to a first pressure;
a step of supplying OH radicals or precursors of the OH radicals into the chamber and setting the inside of the chamber to a second pressure higher than the first pressure;
A step of contacting an OH radical detection probe having an aromatic carboxylic acid, a polar aprotic organic solvent, and a polar protic organic solvent with the gas in the chamber after the pressure in the chamber is equal to or higher than the second pressure. When,
OH radical treatment method comprising.

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