TW201536692A - Apparatus for supplying hydroxyl radical-containing water and method for supplying hydroxyl radical-containing water - Google Patents

Abstract

Provided are an apparatus for supplying hydroxyl radical-containing water and a method for supplying hydroxyl radical-containing water capable of supplying hydroxyl radical with higher concentration to a point of use through varying the length of a pipe for supplying radical water, in which, the apparatus for supplying hydroxyl radical-containing water comprises an ozone-containing water supply path 3 for supplying the ozone-containing water resulted by dissolving ozone and additive for suppressing the decomposition of ozone into the pure water, a generating means 4 disposed upon the supply path 3 for generating hydroxyl radical-containing water by adding ozonolysis catalyst solution onto the ozone-containing water, and a hydroxyl radical-containing water supply path 5 for delivering and supplying the generated hydroxyl radical-containing water onto the point of use, wherein a pipe length variable means 6 capable of substantially changing the length of the pipe of the hydroxyl radical-containing water supply path 5 is comprised.

Description

Hydroxyl radical-containing water supply device and hydroxyl radical-containing water supply method

The present invention relates to a hydroxyl radical-containing water supply device and a hydroxyl group-containing radical water supply method, and is a technique suitable for supplying a hydroxyl group-containing radical water having a desired concentration in a semiconductor cleaning process or the like.

The AOP (advanced oxidation process) is a method in which a physicochemical treatment method such as ozone, hydrogen peroxide, or the like is used to decompose a catalytic liquid or ultraviolet rays. An active radical species having a strong oxidizing power such as a hydroxyl radical, and the object is treated. This oxidation-promoting treatment is not only used for water treatment, but also used in semiconductor cleaning processes in recent years.

For example, Patent Document 1 listed below proposes a cleaning method in which hydrogen peroxide water is added to an ozone water monomer and ultrasonic waves are applied, thereby generating hydroxyl radicals. In this method, although the ozone concentration can be detected by a dissolved ozone concentration detector and fed back to the ozone generating device, the measurement of the radical concentration is not performed.

Further, Patent Document 2 listed below proposes a method for adjusting a content generated by a radical generating means in accordance with a measurement result of a hydroxyl radical concentration in a hydroxyl radical supply device used in a semiconductor cleaning process or the like. The free radical concentration of hydroxyl radical water.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-325902

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-75449

However, since such a method of measuring and adjusting the radical concentration in-line only has a problem that the generated hydroxyl radical cannot be efficiently utilized in the semiconductor cleaning process, there is still room for improvement. . that is, After review by the inventors of the present invention, it was confirmed that although the reaction between the dissolved ozone and the hydrogen peroxide water can be completely mixed in an instant, the radical concentration can become a maximum value in an instant, but actually undergoes peroxidation. The effect of the amount of hydrogen water added or the state of mixing, and the subsequent diffusion state is delayed by the rate limit, and the maximum radical concentration is delayed by several seconds when mixed with hydrogen peroxide water. Therefore, it has been confirmed that when the time until the use point determined by the supply rate of the treatment liquid and the length of the pipe is fixed, the radical water of the maximum radical concentration cannot be utilized. The situation will increase.

Accordingly, it is an object of the present invention to provide a hydroxyl group-containing radical water supply device and a hydroxyl group-containing radical water supply capable of changing a length of a pipe for supplying radical water to supply a higher concentration of hydroxyl radicals to a point of use. method.

In addition, free radical water is synonymous with hydroxyl radical-containing water, meaning pure water containing hydroxyl radicals, but in addition to hydroxyl radicals, it may also contain superoxide radicals (peroxides) and peroxyl radicals (superoxide). Hydroperoxyl radical), water-soluble free radicals such as hydrotrioxy radicals.

The above object is achieved by the present invention described below.

That is, the hydroxyl group-containing radical water supply device of the present invention Provided is a supply path containing ozone water, which is an ozone-containing water obtained by dissolving ozone and an additive for suppressing decomposition of ozone in pure water; and a means for generating is provided in the supply path and containing ozone Water is added to the ozonolysis catalyst to form hydroxyl-containing radical water; the supply path of the hydroxyl-containing radical water is to transfer and supply the generated hydroxyl-containing radical water to the point of use; and the pipe length variable means The length of the piping of the supply path of the hydroxyl group-containing radical water can be substantially changed.

According to the hydroxyl group-containing radical water supply device of the present invention, the ozone-containing water can be supplied to the ozone-decomposing catalyst liquid by the means for generating the supply path of the ozone-containing water to generate the hydroxyl group-containing radical water. At this time, since the ozone-containing water contains an additive substance for suppressing decomposition of ozone, the concentration of the generated hydroxyl radical can be maintained for a longer period of time.

After review by the inventors of the present invention, it was confirmed that although the reaction between the dissolved ozone and the ozonolysis catalyst liquid can be completely mixed in an instant, the radical concentration can become a maximum value in an instant, but actually it is mixed. The effect of the state, and the subsequent diffusion state is rate limited, as shown in Figure 2, the maximum radical concentration is delayed by a few seconds when mixed with the ozonolysis catalyst. Further, since the reaction rate or the mixed state of the ozone-decomposing ozone differs depending on the concentration of the ozone-decomposing catalyst liquid to be mixed, it is from the injection point of the ozonolysis catalyst liquid until the maximum radical concentration is reached. The time will vary depending on the concentration of the ozone decomposition catalyst solution injected.

In the present invention, since a pipe length variable means capable of substantially changing the length of the pipe of the supply path of the hydroxyl group-containing radical water is provided, a higher concentration of hydroxyl radicals can be supplied to the point of use. As a result, it is possible to provide a hydroxyl group-containing radical water supply device which can change the length of the pipe for supplying radical water and supply a higher concentration of hydroxyl radicals to the point of use.

In the above, preferably, the concentration measuring means is provided in the supply path of the hydroxyl group-containing radical water to measure the concentration of the hydroxyl group-containing radical water in the supply path of the hydroxyl group-containing radical water; and control The means adjusts the above-described production means in such a manner that the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means is such that the concentration of the hydroxyl group-containing radical water is close to a set value. Since the concentration of the hydroxyl group-containing radical water can be linearly measured by the concentration measuring means provided in the supply path of the hydroxyl group-containing radical water, the hydroxyl group-containing radical water can be produced at a more stable concentration by the control means. A higher concentration of hydroxyl radicals is supplied to the point of use.

Further, it is preferable that the control means operates the piping in accordance with the concentration of the hydroxyl group-containing radical water required for the treatment and the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means. The variable length means and the aforementioned means of generating. It is particularly preferable that the control means is a hydroxyl group measured according to the concentration measuring means in accordance with a predetermined flow rate in accordance with a predetermined flow rate of the hydroxyl group-containing radical water required for the treatment. The concentration of radical water operates the aforementioned means of production. According to this configuration, the pipe length of the supply path of the hydroxyl group-containing radical water is changed in accordance with the required concentration of the hydroxyl group-containing radical water and the concentration of the hydroxyl group-containing radical water, and the flow rate of the ozone decomposition catalyst liquid is controlled. A higher concentration of hydroxyl radicals is supplied to the point of use.

It is preferable that the additive substance is at least one or more additive substances selected from the group consisting of a water-soluble organic substance, a mineral acid, a salt of the inorganic acid, and hydrazine. These substances are capable of suppressing the decomposition of ozone and maintaining the concentration of the generated hydroxyl radicals for a longer period of time. Therefore, a higher concentration of hydroxyl radicals can be supplied to the point of use.

Preferably, the pipe length variable means includes a valve mechanism capable of changing a mixing position for adding an ozone decomposition catalyst liquid to the hydroxyl group-containing radical water. According to such a valve mechanism, the length of the pipe containing the supply path of the hydroxyl radical water can be substantially changed by opening and closing of the valve.

On the other hand, the hydroxyl group-containing radical water supply method of the present invention is an ozone-containing water obtained by dissolving ozone and an additive substance for suppressing decomposition of ozone in pure water, by adding ozone to the ozone-containing water. The means for generating the decomposition catalyst liquid transfers and supplies the generated hydroxyl group-containing radical water to the point of use while generating the hydroxyl group-containing radical water; wherein the pipe length variable means can be substantially changed by the length of the pipe of the supply path The aforementioned hydroxyl group-containing radical water is supplied.

According to the hydroxyl group-containing radical water supply method of the present invention, by the above-mentioned action, it is possible to provide a hydroxyl group free to supply a higher concentration of hydroxyl radicals to a point of use by changing the length of a pipe for supplying radical water. Base water supply method.

Preferably, in the above, the following control is performed: the concentration of the hydroxyl group-containing radical water is measured by a concentration measuring means, and the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means is used to make the hydroxyl group-containing radical The generation means is adjusted in such a manner that the concentration of water is close to the set value. Since the concentration of the hydroxyl group-containing radical water can be linearly measured by the concentration measuring means, the generation means can be adjusted accordingly, and the hydroxyl group-containing radical water can be produced at a more stable concentration while supplying a higher concentration of hydroxyl radicals. To the point of use.

In addition, it is preferred to perform the following control: concentration measurement means Measuring the concentration of the hydroxyl group-containing radical water, and operating the pipe length variable means according to the concentration of the hydroxyl group-containing radical water required for the treatment and the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means Means of generation. It is particularly preferable to carry out the following control: in view of the concentration of the hydroxyl group-containing radical water required for the treatment, the above-described piping length variable means is operated in advance with a predetermined process, and the hydroxyl group-containing radical measured by the above-mentioned concentration measuring means is used. The concentration of water operates the aforementioned means of production. According to this configuration, the pipe length of the supply path of the hydroxyl group-containing radical water is changed in accordance with the required concentration of the hydroxyl group-containing radical water and the concentration of the hydroxyl group-containing radical water, and the flow rate of the ozone decomposition catalyst liquid is controlled. A higher concentration of hydroxyl radicals is supplied to the point of use.

Further, it is preferable that the additive substance is at least one or more additive substances selected from the group consisting of a water-soluble organic substance, a mineral acid, a salt of the inorganic acid, and hydrazine. These substances are capable of suppressing the decomposition of ozone and maintaining the concentration of the generated hydroxyl radicals for a longer period of time. Therefore, a higher concentration of hydroxyl radicals can be supplied to the point of use.

Preferably, the pipe length variable means includes a valve mechanism capable of changing a mixing position for adding an ozone decomposition catalyst liquid to the hydroxyl group-containing radical water. With such a valve mechanism, the hydroxyl-containing radical water can be substantially changed by the opening and closing of the valve. The length of the piping of the supply path.

1‧‧‧Ozone water generation means

1a‧‧‧Oxygen cylinder

1b‧‧Ozone generator

1c‧‧Ozone dissolver

1d‧‧‧Ozone Decomposer

2‧‧‧Addition of substances

2a‧‧‧Adding material tank

2b, 3b, 4b‧‧ ‧ pumps

3‧‧‧Supply route (supply path containing ozone water)

3a‧‧‧lots containing ozone water

3c, 4c‧‧‧ supply manifold

4‧‧‧Generation means (method of generating hydroxyl radical-containing water)

4a‧‧‧Ozone decomposition catalyst tank

5‧‧‧Supply route (supply path containing hydroxyl radical water)

6‧‧‧Variable length of piping

6a‧‧‧Valve header

6b‧‧‧Tubular components

7‧‧‧Concentration measurement method (measurement method for concentration of hydroxyl radical-containing water)

Unit 7a‧‧

8‧‧‧Control means

G1 to G4‧‧‧ flowmeter

M1, M2‧‧‧ Mixer

P1‧‧‧ piping

P1‧‧‧measuring point

T1 to t4‧‧‧ time

V1 to V9,

V11 to V13‧‧‧ valve

V10‧‧‧ flow control valve

V14‧‧‧pressure adjustment valve

V20‧‧‧ valve mechanism

F1 to F4‧‧‧ filter

Fig. 1 is a schematic configuration diagram conceptually showing an example of a hydroxyl group-containing radical water supply device of the present invention.

Fig. 2 is a view for explaining the effect of the action of the hydroxyl group-containing radical water supply device of the present invention.

Fig. 3 is a view showing the configuration of an apparatus of an example of the hydroxyl group-containing radical water supply device of the present invention.

Fig. 4 is a perspective view showing an example of a main part of a hydroxyl group-containing radical water supply device of the present invention.

Fig. 5 is a perspective view showing another example of the main part of the hydroxyl group-containing radical water supply device of the present invention.

Fig. 1 is a schematic configuration diagram conceptually showing an example of a hydroxyl group-containing radical water supply device of the present invention. As shown in Fig. 1, the apparatus of the present invention includes an ozone-containing water supply path 3 (hereinafter also referred to simply as "supply path 3"), and is supplied with ozone and dissolved substances for suppressing decomposition of ozone. Ozone-containing water obtained in pure water; a production means 4 is provided in the supply path 3, and an ozone decomposing catalyst liquid is added to the ozone-containing water to form a hydroxyl radical-containing water (hereinafter also referred to as "free radicals" The case of water); and the supply path of free radical water 5 (hereinafter also referred to as the abbreviation) In the case of "supply path 5", the generated radical water is transferred and supplied to the point of use.

The ozone-containing water supply path 3 is for supplying an ozone-containing water containing an additive substance, and the ozone-containing water system can add an additive substance to the ozone water generated by the ozone water generating means 1 by, for example, the additive substance mixing means 2. And generated.

In the apparatus of the present invention, the supply path 5 for the radical water is provided with a pipe length varying means 6 for substantially changing the length of the pipe of the supply path 5 of the radical water. In the example of the drawings, the pipe length varying means 6 is provided at the upstream end of the radical water supply path 5, but the pipe length varying means 6 may be provided at the intermediate position or the downstream side of the supply path 5. .

Further, in the present invention, the concentration measuring means 7 for measuring the concentration of the radical water may be provided in the supply path 5 of the radical water. In the example of the drawings, the concentration measuring means 7 is provided on the downstream side of the pipe length varying means 6, but the concentration measuring means 7 may be provided on the upstream side of the pipe length varying means 6.

Hereinafter, the hydroxyl group-containing radical water supply device of the present invention will be described more specifically with reference to Fig. 3 .

The ozone water generating means 1 of the present embodiment includes an oxygen cylinder 1a for supplying oxygen, an ozone generator 1b for generating ozone by supplied oxygen, and an ozone dissolver 1c for dissolving ozone from pure Pure water supplied by the water supply device.

Pure water is water that has been removed from impurities, and usually has an electrical resistivity of 15 MΩ ‧ cm or more. From the viewpoint of using a radical water as a cleaning liquid for a member such as an electronic component, a semiconductor, or a liquid crystal related member (hereinafter referred to as an electronic member), it is preferable to use ultrapure water having an electrical resistivity of 17 MΩ·cm or more. . Further, the electrical resistivity can be measured using a commercially available specific resistivity meter.

The ozone generator 1b can be a known ozone generator such as an ozonizer, and is a device that is connected to the oxygen cylinder 1a and generates ozone from the oxygen supplied from the oxygen cylinder 1a. The ozone generator 1b can be exemplified by, for example, a general-purpose water-cooled ozone generator and a silent discharge ozone generator, and Sumitomo Precision Industries, REGAL JOINT CO., LTD., ECO-DESING CERTIFICATION CO., LTD. etc. are sold.

The ozone dissolver 1c can be filled with a solvent (for example, pure water), and is internally supplied with ozone generated by the ozone generator 1b, whereby ozone can be dissolved.

Usually, the ozone is dissolved in a form of, for example, 1 ppm to 400 ppm, preferably 1 ppm to 100 ppm, relative to the concentration of pure water. The concentration of the ozone can be measured by, for example, an absorbance photometer "WATERLYZER (trade name)" (manufactured by Nippon Kurosu Kagaku Co., Ltd.), an in-line type dissolved ozone monitor (manufactured by Nippon Ebara Industrial Co., Ltd.), or the like.

The ozone decomposer 1d is a device for decomposing ozone contained in the gas discharged from the ozone dissolver 1c and discharging the gas. For example, the ozone decomposer 1d can be exemplified by a thermal decomposition type using a high-temperature heater, an adsorption type using activated carbon or the like. Valves V1 to V4 are valves used to perform the starting and stopping of the various devices. Further, the ozone-containing water supply path 3 before the addition of the additive is provided with a filter F1 for filtering and removing particles or the like.

The additive material mixing means 2 in the present embodiment includes an additive tank 2a for storing an additive, a pump 2b for supplying an additive, and a filter F2 for filtering fine particles. And removed. In the present embodiment, the additive substance is added to the ozone-containing water supply path 3 via the valve V6, but the additive substance may be circulated through the additive substance tank 2a via the valve V5. The valve V7 is a flow rate adjusting valve for automatically adjusting the amount of addition according to the result of the flow meter G1 for measuring the liquid supply flow rate, whereby an additive substance can be appropriately added. In addition, the valve V7 may also be a flow regulating valve that adjusts the amount of addition by hand. In this case, it may also be a diaphragm pump or a bellows pump according to the result of the flow meter G1. The stroke control of the pump 2b or the number of discharges per unit time can be controlled in the case of a rotary pump (centrifugal pump) based on an inverter or the like.

The order in which the ozone and the additive are dissolved in the pure water is not particularly limited as long as the two components are added to the same system. In the present embodiment, (1) is added to pure water in the order of ozone and an additive, and may be dissolved in pure water in the order of (2) added substances and ozone. Dissolved, or may be (3) simultaneously adding ozone and added substances to pure water and dissolving them. In particular, from the viewpoint of high concentration of ozone and autolysis, the above procedure (1) is preferably employed.

The ozone-containing water supply path 3 after the addition of the added substance is provided with a mixer M1 for stirring the ozone-containing water, a tank 3a for the ozone water to store the ozone-containing water, and a pump 3b for the pump 3b. The ozone-containing water is circulated; a supply header 3c is provided for distributing the ozone-containing water to each point of use; and a circulation path is used to circulate the ozone-containing water via the valve V9. At this time, the valve V9 may be an automatic valve for setting the pressure of the supply header 3c to be fixed. In addition, filters can be inserted into the circulation system.

Further, in order to maintain the concentration of the ozone and the additive, the waste liquid can be discharged from the ozone-containing water tank 3a via the valve V8. A flow regulating valve V10 is provided in each of the supply paths that have been distributed from the supply header 3c, and the flow regulating valve V10 is used to automatically follow the result of the flow meter G2 that measures the flow rate thereof. Adjust the flow. In addition, the flow regulating valve V10 may also be a manual flow regulating valve for finely adjusting the flow rate. In this case, the pressure control of the valve V9 may be performed, and the pressure supplied to the header 3c may be fixed, and the pump 3b. The stroke control, the number of discharges per unit time, or the rotation speed control based on an inverter or the like.

The additive substance is at least one or more additive substances selected from the group consisting of a water-soluble organic substance, an inorganic acid, a salt of the above-mentioned inorganic acid, and hydrazine.

As the water-soluble organic substance, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol can be exemplified. And alcohols such as t-butanol, acetone, acetic acid, formic acid, citric acid, and the like.

In the water-soluble organic substance, from the viewpoint of use as a cleaning liquid for an electronic member or the like of the radical water, it is preferred to use a lower boiling point, and examples thereof include n-propanol, isopropanol, and n-butanol. , isobutanol, tert-butanol, and the like. The most preferred water soluble organic material is isopropanol.

The inorganic acid or the salt of the above inorganic acid may, for example, be hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite, hydrogensulfite or hydrogen. Fluoric acid. Among them, carbonic acid is preferred because it can be volatilized as a carbonic acid gas after use of the radical water.

In the present embodiment, the generation means 4 for generating radical water is an example in which an ozone decomposition catalyst liquid is added to the ozone-containing water in the ozone-containing water supply path 3. In the present invention, an aqueous solution of an ozone decomposing catalyst can be used for the ozonolysis catalyst liquid, and an ozone decomposing catalyst can be exemplified by ammonia, hydrogen peroxide, or other alkali-based compound. When these ozonolysis catalyst liquids are added to the ozone-containing water, the ozone is decomposed to generate OH radicals.

The generation means 4 includes an ozone decomposition catalyst liquid tank 4a for storing ozone decomposing catalyst liquid, a pump 4b for supplying ozone decomposition catalyst liquid, and a filter F3 for filtering the particles. Remove. In the present embodiment, the ozone decomposing catalyst liquid is constantly circulated through the pressure regulating valve V14, and the supply path 3 for supplying the ozone-containing water to be supplied to each use point is added via the valve V12 and the supply header 4c. Ozone decomposes the catalyst fluid.

A valve V13 is provided on the downstream side of the pump 4b as a flow rate adjusting valve for automatically adjusting the supply flow rate based on the result of the flow meter G4 for measuring the flow rate, whereby the circulation flow rate of the ozone decomposition catalyst liquid is maintained constant. At this time, the valve V13 may be manually operated, and the pressure supplied to the header 4c may be fixed by the pressure regulating valve V14. Further, a valve V11 is provided as a flow regulating valve for automatically adjusting the supply flow rate based on the result of the flow meter G3 for measuring the flow rate in each of the paths for supplying the respective use points, thereby adding the ozone decomposing catalyst at a predetermined flow rate. liquid. In addition, valve V11 can also be used to fine tune In the case of the flow rate regulating valve of the flow rate, in this case, the pressure of the supply manifold 4c may be fixed, and the pressure control by the pressure regulating valve V14, the stroke control of the pump 4b, and the unit time may be performed. The number of discharges is controlled, or the rotation speed is controlled based on an inverter or the like.

In the case where a water-soluble organic substance is used as the above-mentioned additive substance, that is, when an ozone decomposing catalyst such as ozone or hydrogen peroxide or an aqueous organic substance is present in water, it is considered that a hydroxyl radical is generated based on the reaction formula shown below.

First, a hydroxyl radical is generated from ozone and hydrogen peroxide (Formula 1). Although hydroxyl radicals are rapidly eliminated due to their short life, in the presence of water-soluble organic substances, hydroxyl radicals initiate a chain reaction with water-soluble organic substances (Formula 2).

Further, a hydroxyl radical (formula 3) is produced by the organic radical (R‧) generated by the chain reaction and hydrogen peroxide.

Reaction formula:

The formation of hydroxyl radicals by the reaction of ozone with hydrogen peroxide (Formula 1):

O ₃ +H ₂ O ₂ → OH‧+HO ₂ ‧+O ₂

O ₃ +HO ₂ ^- → OH‧+O ₂ ^- ‧+O ₂

The chain reaction of organic matter (Formula 2):

RH+OH‧ → R‧+H ₂ O

R‧+O ₂ → RO ₂ ‧

RO ₂ ‧+RH → ROOH+R‧

RO ₂ ‧+HO ₂ ‧ → RO‧+O ₂ +OH‧

The decomposition of hydrogen peroxide is generated for (Formula 3):

H ₂ O ₂ +R‧ → HOR+OH‧

On the other hand, in the case where ozone, hydrogen peroxide, and carbonic acid are present in water, it is considered that a hydroxyl radical is generated according to the reaction formula shown below.

First, a hydroxyl radical is generated from ozone and hydrogen peroxide (Formula 4). Although hydroxyl radicals are rapidly eliminated due to their short lifetime, in the presence of carbonic acid, hydroxyl radicals initiate a chain reaction with carbonic acid (Formula 5).

Further, a peroxyl radical (HO ₂ ‧) generated by the reaction of carbonic acid with hydrogen peroxide and ozone generate a hydroxyl radical (formula 6).

Reaction formula:

The formation of hydroxyl radicals by the reaction of ozone with hydrogen peroxide (Formula 4):

O ₃ +H ₂ O ₂ → OH‧+HO ₂ ‧+O ₂

O ₃ +HO ₂ ^- → OH‧+O ₂ ^- ‧+O ₂

The chain reaction of carbonic acid (Equation 5):

CO ₃ ^2- +OH‧ → CO ₃ ^- ‧+OH ^-

CO ₃ ^- ‧+OH‧ → CO ₂ +HO ₂ ^-

O ₃ +HO ₂ ^- → OH‧O ₂ ^- ‧+O ₂

The formation of hydroxyl radicals generated by the reaction of carbonic acid and hydrogen peroxide with hydroxyl radicals (formula 6):

CO ₃ ^2- +OH‧ → CO ₃ ^- ‧+OH ^-

CO ₃ ^- ‧+H ₂ O ₂ → HCO ₃ ^- +HO ₂ ‧

O ₂ ^- ‧+O ₃ → O ₃ ^- ‧+O ₂

O ₃ ^- ‧+H ₂ O → OH‧+O ₂ +OH ^-

In the formation of free radical water, the ozone decomposing catalyst such as ozone and hydrogen peroxide and the weight of the additive are preferably used to form ozone: ozone decomposition catalyst: additive substance = 10 to 40: 10 to 40: 1 to 4 The method of dissolving is more preferably dissolved in the form of ozone: ozonolysis catalyst: added substance = 10 to 20:10 to 20:1 to 2. By dissolving ozone (ozone decomposition catalyst): added substance = 10 to 40:10 to 40:1 to 4 by ozone, ozone decomposition catalyst, and added substance weight ratio, the hydroxyl radical concentration can be set to be more High concentration.

The pipe length variable means 6 has a structure which can substantially change the pipe length of the supply path 5 of the radical water. As shown in Figure 4, it is better to match The tube length variable means 6 has a valve mechanism V20 which is capable of changing a mixing position for adding an ozone decomposition catalyst liquid to radical water.

The pipe length changing means 6 has a structure in which a plurality of U-shaped pipes P1 are connected to a valve header 6a having a valve mechanism V20 composed of a plurality of on-off valves, and all of the U-shaped pipes P1 are via Each of the on-off valves is connected to communicate, and the other ports of any one of the on-off valves are opened, whereby the mixed ozone decomposition catalyst liquid can be added at this position. At this time, the ozone decomposing catalyst liquid flows into the valve header 6a, and is added to the supply path 3 containing the ozone water through the opening and closing valve in the valve opening state in the valve header 6a. Thereby, radical water is generated, and the path located on the downstream side of the addition position becomes the supply path 5 of the radical water. Further, the length of the supply path 5 of the radical water can be changed by opening one of the on-off valves of each of the on-off valves.

In the present embodiment, in order to supply radical water to a plurality of use points, the pipe length varying means 6 is provided in the same number as the number of use points. Each of the supply paths 5 is provided with a mixer M2 for stirring the radical water and a filter F4 for filtering and removing impurities and the like.

After review by the inventors of the present invention, it was confirmed that although the reaction between the dissolved ozone and the ozonolysis catalyst liquid can be completely mixed in an instant, the radical concentration can become a maximum value in an instant, but actually it is mixed. The effect of the state, and the subsequent diffusion state is rate limited, As shown in Fig. 2, the maximum radical concentration is delayed by several seconds when mixed with the ozonolysis catalyst. Further, since the reaction rate or the mixed state of the dissolved ozone is different depending on the concentration of the ozone decomposition catalyst liquid to be mixed, the time from the injection point of the ozone decomposition catalyst liquid to the maximum radical concentration is It will vary depending on the concentration of the ozone decomposition catalyst solution injected.

Therefore, as shown in FIG. 2, for example, in the case where the concentration of the ozone decomposing catalyst is high, in the period from the injection of the ozonolysis catalyst liquid to the time t1, the radical water is supplied to the point of use. In the manner, the pipe length variable means 6 substantially changes the pipe length of the radical water supply path 5, that is, the supply can be performed at the maximum radical concentration. In the same manner, if the length of the pipe of the supply path 5 is substantially changed by the pipe length variable means 6 by supplying the radical water to the point of use at time t2, t3, and t4 in response to the concentration of the ozone decomposing catalyst, The concentration of the ozonolysis catalyst can be supplied at the maximum radical concentration.

In the present invention, it is preferable to provide a concentration measuring means 7 for measuring the concentration of the hydroxyl group-containing radical water in the supply path 5 of the radical water. The concentration measuring means 7 is means for measuring the concentration of the hydroxyl group-containing radical water in the supply path 5 of the radical water. In the present invention, it is preferred that the concentration measuring means 7 optically detect the concentration of the hydroxyl radical. By optically detecting the concentration, concentration measurement and concentration control can be performed linearly with higher responsiveness.

The concentration measuring means 7 includes, for example, measuring means for measuring light absorption characteristics of a wavelength region including a sampled wavelength of 195 nm to 400 nm; and calculation means for absorbing light according to hydroxyl radicals in a wavelength region including a wavelength of 195 nm to 400 nm. The coefficient determines the concentration of the hydroxyl radical from the measured light absorption characteristics.

The measuring means is, for example, a light source that generates probe light, a cell 7a that emits probe light, a beam splitter that splits the probe light emitted from the unit 7a, and a detector. The intensity of the specific wavelength light that has been split is detected.

The calculation means includes, for example, a digital oscilloscope connected to a detector, and a personal computer (PC: Personal Computer) connected to a digital oscilloscope. In addition, a delay time generator may be provided, and the timing control signal may also be transmitted to the digital oscilloscope, and the timing control signal is used to control the time gate between the integral operation and the integral operation of the integrator. time interval.

Although the absorption coefficient of a hydroxyl radical can be used as a literature value, it can also be determined as follows. Preferably, for example, the ozone-containing aqueous solution is irradiated with excitation light, and after the change in the light absorption characteristics immediately after the irradiation is included in a wavelength region including the wavelength of 195 nm to 205 nm, a known absorption coefficient such as ozone and hydrogen peroxide is used as an initial value. Determine the absorption coefficient based on the two components and After the optimum value of the concentration-time distribution, the initial value of the absorption coefficient of the third component is obtained from the difference between the absorbance distribution calculated from the optimum value and the measured absorbance distribution, and respectively obtained The three components are based on the optimum values of the light absorption coefficient and the concentration-time distribution, thereby obtaining the light absorption coefficient of the above-mentioned oxidation-promoting active species.

In order to determine the concentration of hydroxyl radicals from the measured absorbance characteristics based on the absorbance coefficient of such hydroxyl radicals, the absorbance, the molar absorbance coefficient, and the absorbance according to Lambert-Beer Law can be used. The light path length of the unit is used to determine the concentration. Further, the concentration of the oxidation-promoting species can be determined from the absorbance at a complex wavelength, the Mohr absorbance coefficient at a complex wavelength of each component, and the optical path length of the unit by a simultaneous multicomponent determination method. Therefore, the light absorption characteristics can be measured linearly, and the concentration of the oxidation-promoting active species as a result of the calculation can be immediately displayed on the screen or output.

In the present invention, it is preferable to provide a control means 8 for controlling the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means 7 so that the concentration of the hydroxyl group-containing radical water is close to the set value. The generation means 4 is adjusted. In the present embodiment, the control means 8 transmits a signal for changing the flow rate setting value to the valve V11 for automatically adjusting the flow rate of the ozone decomposition catalyst liquid supplied through the supply header 4c, thereby adjusting and generating the signal. Means 4.

For example, when the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means 7 is lower than the set value, the control means 8 transmits a signal for increasing the set value of the flow rate to the valve V11, whereby the The measured concentration is close to the set value. For such control, well-known proportional control, integral control, differential control, and control (PID (Proportional-Integral-Derivative) control) can be used.

Further, the pipe length variable means 6 may be operated by the control means 8 in such a manner as to approach the concentration of the desired hydroxyl radical in response to the concentration of the hydroxyl radical required at the point of use. For example, in the case where the concentration of the ozone decomposition catalyst liquid is high due to the high concentration of the hydroxyl radicals required, the radical length change means 6 is substantially changed by supplying the radical water to the use point at time t1. The length of the piping of the radical water supply path 5, that is, the maximum radical concentration can be supplied. In the same manner, the length of the pipe of the supply path 5 is substantially changed by the pipe length variable means 6 by supplying the radical water to the point of use at the time t2, t3, and t4 in response to the concentration of the hydroxyl radical required. The maximum radical concentration can be supplied regardless of the concentration of the desired hydroxyl radical.

On the other hand, the hydroxyl group-containing radical water supply method of the present invention is characterized in that ozone-containing water obtained by dissolving ozone and an additive substance for suppressing decomposition of ozone in pure water is supplied to the above-mentioned Ozone-depleting ozone-decomposing catalyst liquid The means 4 transfers and supplies the generated radical water to the point of use while generating radical water, and the radical water is supplied via the pipe length varying means 6 which substantially changes the length of the pipe of the supply path 5.

As described above, the hydroxyl group-containing radical water supply method of the present invention can be suitably carried out by the apparatus of the present invention. A preferred embodiment of the hydroxyl radical-containing water supply method of the present invention is as described for the apparatus of the present invention.

In the case where the radical water is used as the cleaning liquid, the organic matter-removable material is not particularly limited, but it is preferably, for example, a semiconductor wafer, a device, a liquid crystal substrate, or the like, which needs to be carefully cleaned in advance. Precision parts. The free radical water system does not affect the environment, the human body, and the body to be cleaned, and can effectively remove organic matter. Specific examples of the precision component include an electronic component such as a germanium wafer, a printed circuit board, a glass substrate, a liquid crystal substrate, a magnetic disk substrate, a compound semiconductor substrate, and the like; and an electronic component manufacturing apparatus and a cleaning apparatus Various components in the filter, such as a filter for filtration, a filter cover for filtration, a pipe, a wafer carrier, a washing tank, a pump, and the like.

Although it is not clear that the detailed mechanism of the removal efficiency of the organic substance can be obtained by the radical water, it is considered to be based on the following actions/mechanisms to exert the removal efficiency of the organic substance. Hydroxyl radicals have strong oxidation and Sterilization. Therefore, the hydroxyl radical system functions to neutralize the electric charge of the organic substance and to release the neutralized organic substance from the surface of the object to be washed, and it is difficult to adhere again. For example, in the case of organic matter, it is converted into water and carbon dioxide by oxidative decomposition; in the case of metal, electrons are taken from the metal to be ionized, and electrons are dissolved in the cleaning liquid.

When the radical water is used as the cleaning liquid, the method of applying the radical water to the object to be washed is not particularly limited, and for example, it may be a dipping method for immersing the object to be washed in free radical water, or It may also be a spray method for spraying free radical water on the object to be washed by a sprayer.

The contact time between the radical water and the object to be washed may be specified, and may be appropriately set in accordance with the degree of contamination of the object to be washed, the application method of the radical water, and the required degree of washing.

(Other embodiments)

(1) In the above-described embodiment, an example in which the concentration of the hydroxyl radical or the concentration of the ozone-decomposing catalyst liquid is used to operate the pipe length in advance is described. However, in the present invention, it is also possible to carry out the control by means of control means. Control: The variable length of the pipe is operated according to the concentration of the hydroxyl radical-containing water measured by the concentration measuring means.

In the case where the concentration of the hydroxyl radical in the measurement point p1 shown in FIG. 2 is lowered, when the radical water of the maximum radical concentration is to be supplied at the point of use, It takes a long time to reach the supply. In the present embodiment, in this case, the piping of the supply path 5 for radically lengthening the radical water can be substantially lengthened by the pipe length varying means 6 in accordance with the concentration of the radical water measured by the concentration measuring means 7. The operation of the length, whereby the free radical water of the maximum radical concentration is supplied at the point of use.

In addition, the concentration of the ozone decomposing catalyst when the ozone decomposing catalyst liquid is added to the ozone-containing water or the amount of the ozonolysis catalyst liquid to be added may be controlled by the control means 8 by the control means 8. For example, in the case of the apparatus shown in Fig. 3, the pipe length varying means 6 can be operated by the control means 8 in accordance with the measurement result of the flow meter G3.

(2) In the above-described embodiment, the example in which the pipe length variable means 6 shown in Fig. 4 is used has been described. However, in the present invention, the pipe length of the supply path of the hydroxyl group-containing radical water can be substantially changed. , the variable length of the pipe can be used in any configuration.

For example, as shown in FIG. 5, the pipe length changing means includes a valve header 6a, a supply path 3 for ozone water, a supply path 5 for radical water, and a supply of an ozone decomposition catalyst liquid. The path is connected and has a flow path groove for causing the ozone to decompose the catalyst liquid and a central flow path for flowing the ozone-containing water; and the tubular member 6b is water-tightly inserted into the central flow of the valve header 6a The path has a plurality of openings formed at a spiral position around the periphery.

The tubular member 6b is rotated by using a rotary actuator or the like while flowing the ozone-containing water inside the tubular member 6b, whereby the position of the opening of the flow path groove opening is in the longitudinal direction of the tubular member 6b. The change is such that the position at which the mixed ozone decomposition catalyst liquid is added can be changed, and the length of the piping of the supply path 5 of the radical water can be substantially changed.

The other pipe length variable means 6 may be a means for not changing the position at which the mixed ozone decomposition catalyst liquid is added, and for example, a flexible pipe having a bellows shape and a flexible pipe may be used. The means for changing the length of the flexible pipe, and the pipe having the inner pipe tightly inserted into the outer pipe and being retractable, and the actuator for changing the length of the retractable pipe Means, etc.

Such a pipe length varying means 6 may be provided at any position of the radical water supply path 5. For example, such a pipe length variable means 6 can be provided on the downstream side of the concentration measuring means of the hydroxyl radical.

(3) In the above-described embodiment, an example is described in which the means for generating the hydroxyl group-containing radical water and the means for changing the length of the pipe are controlled by the control means. However, the ozone water generating means or the addition may be further controlled by the control means. Material mixing means.

(4) In the above-described embodiment, the concentration measuring means for determining the concentration of the hydroxyl radical from the measured light absorption characteristic based on the absorption coefficient of the hydroxyl radical in the wavelength region containing the specific wavelength has been described. For example, the following concentration measuring means may be used: the tail on the high wavelength side of the absorption peak of the absorption band of water (n→σ* migration absorption band of water molecules) appearing in the far ultraviolet region ( The tailing portion (for example, 170 nm to 210 nm) measures the absorption of far ultraviolet rays, thereby measuring the concentration of hydroxyl radicals.

(industry availability)

The hydroxyl group-containing radical water producing apparatus and manufacturing method of the present invention can be used in many processes in semiconductor and display manufacturing, and in general manufacturing processes and the like. For example, a resist removal process on a glass substrate such as a mask for semiconductors, various resist removal processes for a FPD (Flat Panel Display) process, and a front process of a semiconductor substrate. Various resist removal and organic contamination removal in the crystal process, various resist removal steps in the wiring process of the semiconductor substrate, and organic matter removal, organic removal processes on other substrates, other organic removal processes, various substrates It is used in hydrophilization processes, other hydrophilization processes, and the like. Moreover, it can be used in the field of sterilization washing of foods, decomposition treatment of environmental pollutants, and the like.

1‧‧‧Ozone water generation means

2‧‧‧Addition of substances

3‧‧‧Supply route (supply path containing ozone water)

4‧‧‧Generation means (method of generating hydroxyl radical-containing water)

5‧‧‧Supply route (supply path containing hydroxyl radical water)

6‧‧‧Variable length of piping

7‧‧‧Concentration measurement method (concentration measurement of hydroxyl radical-containing water) segment)

Claims (8)

A hydroxyl-containing radical water supply device is provided with a supply path for ozone-containing water, and is an ozone-containing water obtained by dissolving ozone and an additive substance for suppressing decomposition of ozone in pure water; Adding an ozonolysis catalyst liquid to the ozone-containing water to form a hydroxyl group-containing radical water in the supply path; and supplying a hydroxyl group-containing radical water to the supply path for transferring the generated hydroxyl group-containing radical water to the use The point and the pipe length variable means are capable of substantially changing the length of the pipe of the supply path of the hydroxyl group-containing radical water. The hydroxyl group-containing radical water supply device according to claim 1, wherein the concentration measuring means is provided in the supply path of the hydroxyl group-containing radical water to measure the supply path of the hydroxyl group-containing radical water. The concentration of the hydroxyl radical water; and the control means adjust the concentration means by adjusting the concentration of the hydroxyl group-containing radical water measured by the concentration measuring means so that the concentration of the hydroxyl group-containing radical water is close to a set value. The hydroxyl group-containing radical water supply device according to claim 2, wherein the control means is based on a concentration of the hydroxyl group-containing radical water required for the treatment and a concentration of the hydroxyl group-containing radical water measured by the concentration measuring means. The pipe length varying means and the above-described generating means are operated. The hydroxyl radical-containing water supply device according to any one of claims 1 to 3, wherein the pipe length variable means has a valve mechanism, the valve mechanism The mixing position for adding the ozonolysis catalyst liquid to the hydroxyl group-containing radical water can be changed. A method for supplying a hydroxyl radical-containing water, which is an ozone-containing water obtained by dissolving ozone and an additive substance for suppressing decomposition of ozone in pure water, by adding an ozone decomposition catalyst to the ozone-containing water. The liquid generating means generates and supplies the hydroxyl group-containing radical water to the point of use while generating the hydroxyl group-containing radical water, and supplies it via a pipe length variable means capable of substantially changing the length of the pipe of the supply path. The aforementioned hydroxyl group-containing radical water. The hydroxyl group-containing radical water supply method according to claim 5, wherein the control is performed by measuring a concentration of the hydroxyl group-containing radical water by a concentration measuring means, and measuring a hydroxyl group-containing radical according to the concentration measuring means. The concentration of water is adjusted in such a manner that the concentration of the hydroxyl group-containing radical water is close to a set value. The hydroxyl group-containing radical water supply method according to claim 6, wherein the concentration of the hydroxyl group-containing radical water is measured by a concentration measuring means, and the concentration of the hydroxyl group-containing radical water required for the treatment is The concentration of the hydroxyl group-containing radical water measured by the concentration measuring means is operated by the means for varying the length of the pipe and the generating means. The hydroxyl group-containing radical water supply method according to any one of claims 5 to 7, wherein the pipe length variable means has a valve mechanism which can be changed to add the hydroxyl group-containing radical water. Ozone decomposes the mixing position of the catalyst liquid.