Ozone water supply device and supply method

Abstract

This ozone water supply device (1) is provided with: an ozone water generation unit (2) for generating ozone water by receiving an ozone gas having an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less and a solvent in a gas-liquid mixer (21); an ozone water supply unit (3) that discharges and supplies the ozone water to an object (S) to be supplied; and a miscible liquid supply unit (4) that receives a miscible liquid that is miscible with the ozone water, and that discharges and supplies a heatable liquid to an object (S) to be supplied. The ozone water and the mixed liquid are simultaneously or alternately discharged, and the ozone water and the mixed liquid are mixed at the discharged side part (S1).

Description

Technical Field

[0001] This invention relates to technology that can contribute to ozone water supply devices and supply methods. Background Technology

[0002] In recent years, ozone has attracted attention due to its strong oxidizing power. In addition to its use in cleaning, decontamination, and sterilization, it has been explored for various other applications. As an example in the cleaning field, it can be used in cleaning processes for substrates (semiconductor wafers, etc.) used in various electrical equipment (e.g., Patent Documents 1-7, Non-Patent Documents 1-3).

[0003] In ozonated water obtained by dissolving ozone gas in a solvent, it is preferable to supply it to the object being supplied while maintaining the desired ozone concentration. For example, in Patent Document 4, it is disclosed that by supplying both hot water and pressurized ozonated water to the object being supplied (a substrate in Patent Document 4), the ozone concentration of the ozonated water is easily maintained during the period just before the two are about to mix, and the mixing of the ozonated water raises its temperature, making it easier to exert the desired oxidizing power.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2002-261068

[0007] Patent Document 2: Japanese Patent No. 4444557

[0008] Patent Document 3: Japanese Patent Application Publication No. 2009-297588

[0009] Patent Document 4: Japanese Patent Application Publication No. 2021-034672

[0010] Patent Document 5: Japanese Patent No. 5332052

[0011] Patent Document 6: Japanese Patent No. 7186751

[0012] Patent Document 7: Japanese Patent Application Publication No. 2008-311257

[0013] Non-patent literature

[0014] Non-patent literature 1: T. Miura et al., “Novel plasmaless photoresist removal method ingas phase at room temperature”, ECS Journal, Vol. 19, No. 3, pp. 423 (2009).

[0015] Non-patent literature 2: T. Miura et al., “Production and Detection of OH Species by a Highly Concentrated Ozone Gas for Thin Film Processing”, ACSIN-12 & ICSPM21 (2013).

[0016] Non-Patent Document 3: Ozone Handbook (Revised Second Edition) Japan Ozone Association Summary of the Invention

[0017] In the method described above, which simply dissolves ozone gas in a solvent, it is difficult to obtain high-concentration ozone water. For example, a method of dissolving ozone gas in a solvent under pressure could also be considered, but this method is prone to causing a rapid self-decomposition reaction of ozone, which may make it difficult to maintain practical safety.

[0018] Furthermore, when only hot water and pressurized ozone water are supplied to the object as in Patent Document 4, the ozone water is easily degassed (foamed) as it rapidly heats up and depressurizes (e.g., returns to normal pressure). This degassed ozone water has a lower ozone concentration and may not exert the desired oxidizing power.

[0019] The present invention was made in view of the above circumstances, and its object is to provide a technology that can help to easily and safely generate high concentrations of ozone water, suppress the ozone concentration decay of the generated ozone water, and easily exert the desired oxidizing power.

[0020] The ozone water supply device and method of the present invention can help solve the above-mentioned problems. In one embodiment of the supply device, it includes: an ozone water generating unit that receives ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer to generate ozone water; an ozone water supply unit that discharges the ozone water; and a mixed liquid supply unit that discharges a mixed liquid that is miscible with the ozone water.

[0021] The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path for introducing ozone gas into the solvent flow path. The gas-liquid mixer receives the ozone gas with an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less.

[0022] The feature is that, when an object to which ozone water is supplied is arranged in the discharge direction of the ozone water discharged from the ozone water supply unit, the mixed liquid supply unit can discharge the mixed liquid to the side of the object to which the ozone water is discharged, i.e., the discharge side, at a temperature higher than that of the ozone water discharged from the ozone water supply unit. By simultaneously or alternately discharging the ozone water and the mixed liquid through the ozone water supply unit and the mixed liquid supply unit, the two can be mixed on the discharge side.

[0023] One method of supplying ozone water includes: an ozone water generation step in which ozone gas and a solvent capable of dissolving the ozone gas are received in a gas-liquid mixer to generate ozone water; an ozone water supply step in which the ozone water is discharged; and a mixed liquid supply step in which a mixed liquid that is miscible with the ozone water is discharged.

[0024] The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path for introducing ozone gas into the solvent flow path. The gas-liquid mixer receives the ozone gas with an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less.

[0025] In the mixed liquid supply process, the ozone water is characterized in that, when an object to which the ozone water is supplied is arranged in the discharge direction of the ozone water discharged through the ozone water supply process, the mixed liquid is discharged to the side of the object to which the ozone water is discharged, i.e., the discharge side, at a temperature higher than that of the ozone water discharged through the ozone water supply process. By simultaneously or alternately performing the ozone water supply process and the mixed liquid supply process, both the ozone water and the mixed liquid are mixed at the discharge side.

[0026] As described above, according to the present invention, it is possible to easily and safely generate high concentrations of ozone water, suppress the ozone concentration decay of the generated ozone water, and easily obtain the desired oxidizing power. Attached Figure Description

[0027] Figure 1 This is a schematic structural diagram illustrating an example of the ozone water supply device used to explain the embodiments.

[0028] Figure 2 It is a schematic diagram used to illustrate the structure of regions R1 to R3 formed on the supplied object S.

[0029] Figure 3 This is a schematic structural diagram illustrating the discharge structure of Example 1.

[0030] Figure 4 This is a schematic structural diagram illustrating the regions R1 to R3 formed on the supplied object S by the discharge structure of Example 1.

[0031] Figure 5 This is a schematic structural diagram illustrating the discharge structure of Example 2.

[0032] Figure 6 This is a schematic structural diagram illustrating an example of a spray head H (a diagram facing the spray head supply surface H11).

[0033] Figure 7 This is a schematic structural diagram illustrating another example of the spray head H (a diagram facing the spray head supply surface H12).

[0034] Figure 8 This is a schematic structural diagram illustrating the discharge structure of Example 2. Detailed Implementation

[0035] The ozone water supply device and supply method of the present invention are completely different from the structure shown in Patent Document 4, which only supplies hot water and pressurized ozone water to the object to be supplied.

[0036] That is, in this embodiment, ozone water is generated by receiving ozone gas and a solvent capable of dissolving the ozone gas (hereinafter appropriately referred to as solvent) in a gas-liquid mixer, and the ozone water can be discharged to a target object that is the target of the ozone water supply. The gas-liquid mixer receives ozone gas with an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less.

[0037] Furthermore, the system is configured to discharge a mixed liquid (hereinafter referred to as the mixed liquid) that is miscible with ozone water to the side of the object to which the ozone water was discharged, i.e., the discharge side (hereinafter referred to as the discharge side), at a temperature higher than that of the discharged ozone water (hereinafter appropriately referred to as the heatable temperature). Moreover, the system is configured to mix the ozone water and the heatable liquid (hereinafter appropriately referred to as the heatable liquid) at the discharge side by discharging them simultaneously (together) or alternately.

[0038] With this structure, since it generates ozone water by accepting high-concentration ozone gas in a state where the ozone partial pressure is sufficiently reduced, it is possible to effectively suppress and prevent rapid self-decomposition reactions in the ozone gas, thus maintaining practical safety. Furthermore, the ozone gas accepted as described above readily dissolves in solvents in a gas-liquid mixer, enabling the safe generation of high-concentration (e.g., 100 ppm or higher) ozone water.

[0039] Furthermore, when supplying ozone water to the object being supplied (the discharge side), it is not necessary to pressurize the ozone water as in Patent Document 4, thus suppressing the degassing of the ozone water. Therefore, compared to the structure in Patent Document 4, the ozone concentration decay of the ozone water can be sufficiently suppressed.

[0040] Furthermore, the ozone water discharged to the discharge side of the object being supplied (the ozone water remaining on the discharge side) mixes with the heatable liquid and heats up, easily exerting the desired oxidizing power. Thus, the desired effect (e.g., cleaning effect, stain removal effect, sterilization effect, etc.) corresponding to the object being supplied can be obtained.

[0041] The ozone water supply device and method of this embodiment utilize ozone water generated from high-concentration ozone gas in a state where the ozone partial pressure is sufficiently reduced, as described above. Any structure capable of mixing the ozone water discharged to the object being supplied with a heatable liquid to raise its temperature is acceptable. That is, technical knowledge from various fields (e.g., ozone, cleaning, stain removal, sterilization, etc.) can be appropriately applied, and design modifications can be made as needed, referring to existing technical documents, etc. Examples of such modifications will be given later.

[0042] It should be noted that in the embodiments described later, detailed descriptions will be appropriately omitted, for example, by referring to the same reference numerals for the same content. Additionally, in the figures, hollow arrows depict the discharge state of ozone water, while solid arrows depict the discharge state of a mixed liquid that can be heated.

[0043] "refer to"

[0044] For example, in the case of conventional ozone gas generating devices (ozone generators), the ozone gas that can be generated is at a low concentration (e.g., ozone concentration less than 20% by volume), and sometimes contains a large amount of gas formed by components other than ozone (e.g., oxygen, etc.) (hereinafter appropriately referred to as non-ozone components). Even when using such low-concentration ozone gas, it is difficult to generate high-concentration ozonated water, as a large amount of non-ozone components will dissolve.

[0045] Furthermore, ozone water, which is produced by dissolving low-concentration ozone gas in a solvent under high pressure to achieve a high concentration, also contains non-ozone components dissolved in a supersaturated state, in addition to the ozone component. When such ozone water is released into the atmosphere, the non-ozone components easily degas (e.g., by forming bubbles and dispersing into the atmosphere), and the ozone component also easily disperses. Therefore, it is impossible to maintain a high concentration of ozone water.

[0046] In recent years, ozone gas generated by ozone generators and the like has been concentrated by methods such as adsorption concentration (using surface adsorption methods such as silica gel) or cooling concentration, thereby generating ozone gas with high concentrations (e.g., ozone concentration of 50% or more by volume).

[0047] For example, the ozone gas generating device (trade name: Pure Ozone Generator) manufactured by Meidensha, which uses a cooling and concentration method, can also generate ozone gas with an ozone concentration close to about 100% by volume (ozone concentration of 90% by volume or more), and has obtained international safety standard SEMI-S2 certification, thus achieving practical safety.

[0048] However, even in the concentrated ozone gas as described above, it is necessary to maintain a depressurized state to avoid a rapid self-decomposition reaction. Therefore, it is difficult to apply to a structure that accepts the ozone gas in a gas-liquid mixer under high pressure to generate ozone water.

[0049] On the other hand, in this embodiment, as in the ozone water generation unit 2 described later, since the structure accepts ozone gas in the gas-liquid mixer under reduced pressure (ozone partial pressure below 30 kPa (abs)), it is also possible to safely utilize the extremely high concentration of ozone gas concentrated as described above to fully generate the desired high concentration of ozone water.

[0050] As a specific example, when the ozone concentration of the ozone gas received in the gas-liquid mixer is 90% or more by volume and the oxygen concentration is less than 10% by volume, the ozone gas can be safely maintained by reducing the total pressure of the ozone gas to 30 kPa (abs) or less (i.e., the ozone partial pressure to 30 kPa (abs) or less).

[0051] In addition, in the case of ozone gas with an ozone concentration of 50% or more and an oxygen concentration of less than 50% by volume, the ozone gas can be safely maintained by reducing the total pressure of the ozone gas to 60 kPa (abs) or less (i.e., the ozone partial pressure to 30 kPa (abs) or less).

[0052] Example

[0053] <Main Structure of Supply Device 1 in the Embodiment>

[0054] Figure 1 This is a schematic structural diagram illustrating the structure of the ozone water supply device 1 used to explain the embodiment. The device 1 includes, as its main components: an ozone water generating unit 2, which receives ozone gas and a solvent in a gas-liquid mixer 21 to generate ozone water; an ozone water supply unit 3, which supplies the ozone water to a target substance S; and a mixed liquid supply unit 4, which receives a mixed liquid and supplies a heatable liquid to the target substance S.

[0055] The device 1 can, for example, be operated by a control unit (not shown) that appropriately controls the ozone water generating unit 2, the ozone water supply unit 3, and the mixed liquid supply unit 4. As an example of the control unit, it can be configured to appropriately obtain the state of the ozone water generating unit 2, the ozone water supply unit 3, and the mixed liquid supply unit 4 (for example, the respective temperature, flow rate, pressure, etc. of the solvent, ozone water, and mixed liquid; hereinafter, it is appropriately referred to as the device state), control the device state, or control the discharge of the ozone water and the heatable liquid (for example, controlling the simultaneous or alternating discharge of ozone water and the heatable liquid as described later).

[0056] The solvent in the ozone water generating unit 2, the flow path of the ozone water (e.g., the flow paths indicated by arrows Y1 and Y2), the flow path of the ozone water in the ozone water supply unit 3 (not shown), and the flow path of the mixed liquid in the mixed liquid supply unit 4 (not shown) can be configured in various ways. For example, configurations using various piping can be employed. However, the flow paths of the ozone water in the ozone water supply unit 3 and the flow paths of the mixed liquid in the mixed liquid supply unit 4 are independent structures (i.e., structures that are not interconnected).

[0057] In the flow paths described above, in addition to using piping as mentioned, other methods may also be used, for example, as shown in the example below. Figure 1 Temperature regulating units (e.g., heaters, coolers) 22, 31, 41, etc., are provided, or various flow path devices (e.g., on / off valves, pumps, storage tanks, measuring instruments, etc.) are provided. It should be noted that when impurities (such as metal ions generated from the dissolution of the inner circumferential surface of the pipe in the case of metal piping) may be introduced into the aforementioned flow paths, it is preferable to configure the system to suppress this introduction. For example, temperature regulating units 22, 31, and 41 can be configured to be located on the outer circumference of each flow path (e.g., the outer circumference of the pipe), allowing for indirect temperature regulation of the inner circumference of that flow path. Furthermore, in the case of metal piping, piping with an inner circumferential surface coated with Teflon (registered trademark) or similar materials can be used.

[0058] exist Figure 1In the device 1, ozone water is generated by the ozone water generating unit 2 (ozone water generating process), and when the discharge side S1 of the supplied object S is located in the discharge direction of ozone water being discharged by the ozone water supply unit 3 and the discharge direction of heatable liquid being discharged by the mixed liquid supply unit 4, both the ozone water and the heatable liquid are discharged simultaneously or alternately (performing the ozone water supply process and the mixed liquid supply process described later).

[0059] Therefore, for example Figure 2 As shown, on the discharge side S1 of the supplied object S, a region R1 containing ozone water, a region R2 containing a heatable liquid, and a region R3 where regions R1 and R2 overlap are formed. That is, by mixing the ozone water from region R1 and the heatable liquid from region R2 in region R3, the ozone water present in region R3 (and the periphery of region R3) absorbs heat from the heatable liquid and becomes heated. Moreover, the oxidizing power of the heated ozone water is increased.

[0060] As mentioned above, ozonated water, when heated, sometimes generates OH radicals through ozone decomposition. While these OH radicals have relatively high reactivity, their lifetime is shorter than that of ozone, and therefore they tend to disappear immediately after generation (due to their low selectivity, they react with surrounding substances and disappear immediately after generation). However, if... Figure 2 As shown, the OH free radicals generated on the discharged side S1 are more likely to act effectively on the discharged side S1 before they disappear.

[0061] Therefore, the ozone water discharged from side S1 has a reaction rate constant that tends to increase (e.g., by numerical level) due to the generation of OH free radicals, and thus has sufficient oxidizing power even when diluted with a heatable liquid.

[0062] <Structural Example of Ozone Water Generation Unit 2>

[0063] Figure 1 The ozone water generating unit 2 shown is structured as follows: Ozone gas with an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less is received in a gas-liquid mixer 21 while a solvent is being received, and the ozone gas is dissolved in the solvent to generate high-concentration (e.g., 100 ppm or more) ozone water. Furthermore, it is designed to allow the generated ozone water to be discharged to the subsequent ozone water supply unit 3 (e.g., discharged as indicated by arrow Y1).

[0064] Examples of gas-liquid mixers 21 include injectors, aspirators, and jet pumps, but they are not limited to these and can be applied in various ways. That is, the gas-liquid mixer 21 can be any structure that has a solvent flow path (not shown) for the flow of the accepted solvent and an ozone gas inlet path (not shown) connected to the solvent flow path and introducing the accepted ozone gas into the solvent flow path.

[0065] According to the gas-liquid mixer 21 with a structure having a solvent flow path and an ozone gas inlet path, in the ozone gas inlet path, an attraction pressure based on Bernoulli's theorem is generated according to the flow rate (velocity) of the solvent flowing in the solvent flow path. Additionally, in the ozone gas inlet path, vapor corresponding to the saturated vapor pressure of the solvent is generated. For example, when the solvent is water, it has various characteristics equivalent to water (saturated vapor pressure characteristics, water vapor pressure characteristics).

[0066] Based on the various properties of such solvents and the pressure at which ozone gas is received by the gas-liquid mixer 21 (hereinafter appropriately referred to as the receiving pressure), a range of solvent temperatures (hereinafter appropriately referred to as the attractable range) in which the vapor pressure of the ozone gas inlet path of the gas-liquid mixer 21 is lower than the receiving pressure can be derived. This attractable range is preferably appropriately set taking into account the general solubility characteristics of the gas relative to the solvent (the tendency for solubility to increase as the solvent temperature decreases) (for example, set to 25°C or below as in paragraph

[0023] of Japanese Patent No. 4296393). Therefore, if the solvent temperature deviates from the attractable range, for example, the solvent temperature can be pre-adjusted in the stage before the solvent is received by the gas-liquid mixer 21 (for example, by adjusting it by a temperature adjustment unit not shown), or the solvent temperature can be adjusted by operating the temperature adjustment unit 22.

[0067] Before the ozone water generated by the gas-liquid mixer 21 is discharged to the downstream ozone water supply unit 3, a concentration-regulating gas to stabilize the ozone concentration can be added, or it can be circulated within the ozone water generation unit 2 (for example, circulated upstream of the gas-liquid mixer 21 as shown by arrow Y2) or temporarily stored. In cases where a high concentration is achieved through the concentration-regulating gas, for example, adding carbon dioxide gas to the ozone water to acidify it can be used.

[0068] As for solvents, any solvent capable of dissolving ozone gas can be appropriately used. Examples include raw water, pure water, and ultrapure water. Additionally, depending on the need, the purity of the solvent can be increased using a pure water manufacturing device (not shown).

[0069] Ozone gas can be generated by various ozone gas generating devices, provided that the ozone concentration is 50% by volume or more and the ozone partial pressure is 30 kPa (abs) or less when received by the gas-liquid mixer 21. As an example of an ozone gas generating device, an ozone gas generating device manufactured by Meidensha (trade name: Pure Ozone Generator) can be cited.

[0070] According to this ozone water generating unit 2, ozone water with a high concentration of 100 ppm or more (e.g., 300 to 400 ppm) can be safely generated.

[0071] <Structural Example of Ozone Water Supply Unit 3>

[0072] Figure 1 The ozone water supply unit 3 shown is configured to discharge ozone water introduced from the ozone water generation unit 2 through the discharge unit 30. However, in this discharge structure, any structure that can discharge the ozone water to the discharge side S1 of the object to be supplied S is acceptable, and various methods can be applied. As an example, as shown in Embodiments 1 to 3 described later, a structure that discharges the ozone water through the discharge nozzle 32 and the discharge port 33 of the spray head H can be cited.

[0073] In addition, the ozone water in the ozone water supply unit 3 can be temperature-controlled (e.g., cooled by the temperature control unit 31) to maintain the ozone concentration before being discharged to the target object S, or it can be temporarily stored in the ozone water supply unit 3.

[0074] The temperature of the ozone water discharged to the object S can be set appropriately based on the temperature of the heatable liquid, as long as it is within a range that will not become solidified and can be heated by the heatable liquid.

[0075] <Structural Example of Mixed Liquid Supply Unit 4>

[0076] Figure 1 The mixed liquid supply section 4 shown is configured to accept the mixed liquid and discharge the heatable liquid from the discharge section 40. However, in this discharge structure, any structure that can discharge the liquid to the discharge side S1 of the object to be supplied S is acceptable, and various methods can be applied. As an example, as shown in Embodiments 1 to 3 described later, a structure that discharges the liquid via the discharge nozzle 42 and the discharge port 43 of the spray head H can be cited.

[0077] Furthermore, for the mixed liquid in the mixed liquid supply unit 4, it is possible to adjust the temperature (e.g., by heating it with the temperature adjustment unit 41) to a temperature that can be heated before it is discharged to the discharge side S1 of the object being supplied S. However, if the temperature that can be heated has already been reached when the mixed liquid is received in the mixed liquid supply unit 4, it can be discharged directly. Alternatively, it can be temporarily stored in the ozone water supply unit 3.

[0078] Any liquid that is miscible with ozone water can be appropriately used. Examples include raw water, pure water, ultrapure water, ion-exchanged water, alkaline aqueous solutions, and acidic aqueous solutions. However, while organic solvents such as lower alcohols are miscible with ozone water, they are not preferred because ozone can break the C-C bonds of these solvents, potentially affecting the supplied substance S. Tap water can also be used, but it is preferable to improve its purity using a pure water production device (not shown) as needed (e.g., depending on the type of supplied substance S).

[0079] The scalable temperature of the mixed liquid can be appropriately set. For example, when the ozone water is at room temperature (e.g., 5°C to 35°C), the scalable temperature can be set to a temperature higher than room temperature (e.g., above 40°C). By setting the scalable temperature in this way, the heat energy of the mixed liquid (the scalable liquid) can be transferred to the ozone water, resulting in the promotion of OH free radical generation. Furthermore, when the mixed liquid is raw water, pure water, ultrapure water, or ion-exchanged water, the upper limit of the scalable temperature can be set to 100°C.

[0080] <An example of the supplied object S>

[0081] The object S to be supplied can be located in the discharge direction of ozone water discharged through ozone water supply unit 3 and the discharge direction of heatable liquid discharged through mixed liquid supply unit 4, and can exert the oxidizing power of ozone water to obtain the desired effect. Various methods can be applied. As examples, various substrates (e.g., semiconductor substrates, glass substrates) that can be cleaned, as shown in Patent Documents 1-7, Non-Patent Documents 1-3, Japanese Patent Application Publication Nos. 2017-173461 and 2017-123402; chemical reagents, biological reagents, nuclear energy equipment, etc. that can be decontaminated, as shown in Japanese Patent Application Publication Nos. 2019-181182 and 2019-66226; and various containers (e.g., beverage containers) and medical devices (e.g., endoscopes) that can be sterilized, as shown in Japanese Patent Application Publication Nos. 2017-186022, 2017-148703, and 2016-119942. Furthermore, examples include facilities in areas where infectious diseases from birds and animals occur, vehicles, and steel that requires pickling with hydrochloric acid, sulfuric acid, etc.

[0082] As a specific example, when various substrates that can be cleaned are provided as the object S, it is possible to use the apparatus 1 appropriately for cleaning in each of the various processing steps of the substrate (photolithography, etching, ion implantation, CMP, etc.). This allows the substrate surface to be cleaned so that no unwanted substances such as particles or organic matter remain on the substrate surface.

[0083] Furthermore, when the object being supplied, S, is porous, the ozone water and heatable liquid discharged from the device 1 may exist not only on the surface of the discharged side S1, but also on the surface of the micropores formed inside the object being supplied, S. That is, they may also form on the surface of these micropores. Figure 1 The regions R1 to R3 shown can achieve the desired effect based on the oxidizing power of ozone water.

[0084] <Other>

[0085] For the ozone water discharged through the ozone water supply unit 3 and the heatable liquid discharged through the mixed liquid supply unit 4, their discharge direction, discharge flow rate (velocity), discharge force, etc., can be appropriately set. For example, the discharge directions of the ozone water and the heatable liquid may not be as described later. Figure 3 , Figure 5 , Figure 8 Instead of simply setting the direction to be orthogonal to the object S being supplied (in the figure, the upper or lower side in the vertical direction), it is set to the direction that is inclined at a specified angle to the object S being supplied.

[0086] Furthermore, based on the viewpoint of optimizing the mixing efficiency of ozone water and the heatable liquid to thereby optimize the generation efficiency of OH free radicals, the angles of ozone water and the heatable liquid relative to the supplied object S in their respective discharge directions (hereinafter, appropriately referred to as ozone water discharge angle and heatable liquid discharge angle, respectively) are preferably adaptable and can be changed flexibly. For example, in device 1, an angle adjustment function unit that can change the ozone water discharge angle and the heatable liquid discharge angle separately can be provided.

[0087] The discharge flow rate and discharge force of ozone water and heatable liquid can be appropriately set according to the positional relationship between the device 1 and the object S to be supplied, but the discharge flow rate and discharge force of ozone water are preferably set within a range that will not cause degassing of ozone water after discharge.

[0088] Furthermore, when both ozone water and the heatable liquid are set to discharge state, it can be exemplified that after a predetermined time (e.g., several seconds to tens of seconds) has elapsed since the discharge of the heatable liquid begins, the discharge of ozone water then begins. In this case, similar to the discharge structure of Example 1 shown in Verification Examples 1 and 2 described later, since the discharged side S1 of the supplied object S can be preheated by the heatable liquid (heating is performed before the discharge of ozone water begins), OH free radicals are easily generated, resulting in an oxidation-promoting effect. Therefore, it is possible to exert a higher oxidizing power.

[0089] In addition, the object S to be supplied can be properly supported by the support part 6 as shown in Embodiments 1 to 3 described later, or it can be properly housed in the container 5.

[0090] <Example 1>

[0091] Figure 3 , Figure 4 Example 1 illustrates an example of a discharge structure using tubular discharge nozzles 32 and 42. Figure 3 In this container, the discharge nozzle 32 is positioned above the container 5 in the vertical direction, penetrating the container 5 in the inward and outward directions. The discharge nozzle 32 is configured such that one end of the discharge nozzle 32 is connected to the discharge section 30 of the ozone water supply section 3, thereby allowing the ozone water from the ozone water supply section 3 to be discharged downward in the vertical direction relative to the inside of the container 5.

[0092] The discharge nozzle 42 is positioned at a predetermined distance from the discharge nozzle 32 on the vertical side above the container 5, with the nozzle penetrating the container 5 in the inward and outward directions. The discharge nozzle 42 is configured such that one end of the discharge nozzle 42 is connected to the discharge section 40 of the mixed liquid supply section 4, thereby enabling the discharge of the heatable liquid from the mixed liquid supply section 4 to the vertically downward side relative to the inside of the container 5.

[0093] Figure 3 , Figure 4 The object to be supplied, S, is flat and has a covering layer S1a on one side in the thickness direction (the side facing the discharge nozzles 32 and 42), which corresponds to the discharge side S1. The object to be supplied, S, is supported by the support 6 in a position where the covering layer S1a faces the discharge nozzles 32 and 42, allowing it to rotate freely.

[0094] exist Figure 3 In the case of the support portion 6, it consists of a support platform 61 that supports the object to be supplied S and a rotating shaft 62 that extends vertically downward from the center of the support platform 61 and rotates the support platform 61. For the support platform 61, it is preferable to have a structure that can support the object to be supplied S without causing positional displacement when the support platform 61 is rotated. As an example, a structure that supports the object by means of a vacuum suction cup can be given.

[0095] According to the discharge structure of this embodiment 1, by simultaneously or alternately performing the ozone water discharge process of discharging ozone water through the discharge nozzle 32 and the mixed liquid discharge process of discharging the heatable liquid through the discharge nozzle 42, for example... Figure 4 As shown, a layer S1a is formed on the covering layer of the supplied object S, and... Figure 2 The same region R1 to R3.

[0096] It should be noted that during the simultaneous or alternating ozone water discharge process and the mixed liquid discharge process as described above, a rotation process in which the supplied object S is rotated by the support 6 can also be performed. By properly executing this rotation process, the ozone water and the heatable liquid discharged through the ozone water discharge process and the mixed liquid discharge process are easily distributed along the surface of the covering layer S1a under the action of the centrifugal force of the rotation, and regions R1 to R3 are also easily expanded. As a result, the oxidizing power of the ozone water can be widely and evenly exerted on the covering layer S1a.

[0097] Furthermore, when alternating between the ozone water discharge process and the mixed liquid discharge process, a rotation process can be performed during the period when one of the processes is stopped and the other is switched on (i.e., during the period when both are stopped). In this case, the ozone water and the heatable liquid tend to expand and distribute along the surface of the covering layer S1a each time they are discharged, and region R3 may expand more easily. As a result, the oxidizing power of the ozone water may be more easily and evenly exerted in the covering layer S1a.

[0098] With the discharge of both ozone water and the heatable liquid stopped, while the object S being supplied continues to rotate via the support 6, the ozone water and heatable liquid remaining in the covering layer S1a are removed by the centrifugal force of the rotation, for example, by being discharged via the discharge section 51 provided in the container 5.

[0099] As a specific example, when alternating between the ozone water discharge process and the mixed liquid discharge process, a cycle consisting of repeatedly performing the ozone water supply process, the mixed liquid supply process, and a rotation process performed while both the ozone water supply process and the mixed liquid supply process are stopped can be cited. By repeatedly performing such a cycle, it is possible to easily, efficiently, and evenly exert the oxidizing power of ozone water.

[0100] Since the ozone water discharged from the discharge section 51 decomposes over time, even when released into the natural environment, the load on the natural environment can be sufficiently suppressed (for example, compared to the case of using sulfuric acid or pharmaceutical solutions).

[0101] <Example 2>

[0102] Figures 5-7 Example 2 illustrates an example of the discharge structure using spray head H. Figure 5 In the container 5, a spray head H is provided on the upper side in the vertical direction. On the side of the spray head H facing the object S being supplied, i.e., the spray head supply surface H1, multiple ozone water outlets 33 and multiple mixed liquid outlets 43 are respectively provided.

[0103] Furthermore, on the outside of the container 5 in the spray head H, there are connecting parts (connectors, etc.) 34 and 44 that can be connected to the discharge parts 30 and 40 respectively. The connecting part 34 is connected to the discharge outlet 33 via the ozone water flow path (not shown) inside the spray head H, and the connecting part 44 is connected to the discharge outlet 43 via the heatable liquid flow path (not shown) inside the spray head H. However, the ozone water flow path and the heatable liquid flow path are independent structures (i.e., they are not connected to each other). Thus, the structure allows ozone water and heatable liquid to be discharged through the discharge outlets 33 and 43 respectively.

[0104] There are no particular restrictions on the shape of the spray head supply surface H1, the outlet 33, 43, etc., and they can be set appropriately.

[0105] For example, regarding the spray head supply surface H1, it can be exemplified that it is formed in a shape larger than the surface of the covering layer S1a facing the spray head supply surface H1 (hereinafter appropriately referred to as the discharge side facing surface), so that ozone water and heatable liquid can be easily discharged throughout the entire area of ​​the discharge side facing surface.

[0106] As a specific example, when the shape of the opposing sides of the discharged parts is circular, examples such as... Figure 6 The spray head supply surface H11 shown is circular, and multiple outlets 33 and 43 are arranged in dispersed positions relative to this spray head supply surface H11. Various methods can be applied when the outlets 33 and 43 are arranged in dispersed positions. Figure 6 In the case of a spray head supply surface H11, a plurality of outlets 33 are provided in a dispersed manner, and outlets 43 are provided at the four sides of each outlet 33.

[0107] It should be noted that, for example, Figure 7 As shown in the spray head supply surface H12, even if the spray head supply surface H12 is in the shape of a strip, as long as the multiple outlets 33 and 43 are arranged alternately at predetermined intervals in the extending direction (in a straight line along the spray head supply surface H12), ozone water and heatable liquid can be fully discharged in the entire area of ​​the opposite side of the discharged portion by properly performing the ozone water discharge process, the mixed liquid discharge process, and the rotation process in the same way as in Example 1.

[0108] The shapes of the outlets 33 and 43 can be appropriately set; for example, they could be circular, rectangular, elliptical, or slit-shaped. It should be noted that for... Figure 6 , Figure 7 For ease of explanation, the outlets 33 and 43 are depicted with different shapes (outlet 33 is depicted as a circle and outlet 43 is depicted as a rectangle), but they can also be the same shape.

[0109] According to this embodiment 2, in addition to achieving the same effects as in embodiment 1, it can also be said to achieve the following effects: It facilitates the discharge and distribution of ozone water and a heat-generating liquid across the entire area of ​​the discharge side facing each other. Therefore, region R3 is easily formed relative to the entire area of ​​the discharge side facing each other, making it possible to easily and evenly exert the oxidizing power of the ozone water.

[0110] <Example 3>

[0111] Figure 8 Example 3 illustrates an example of a discharge structure using a pair of spray heads, Ha and Hb. Figure 8 The spray heads Ha and Hb shown are arranged in the same manner as spray head H in Example 2, facing each other in the vertical direction above and below the container 5, respectively, with the object being supplied S between them.

[0112] exist Figure 8 In the case of the object to be supplied, a covering layer S1a and S1b, corresponding to the discharge side S1, are respectively provided on one end side and the other end side in the thickness direction. In addition, the support part 6 supporting the object to be supplied S has a holding part 63 that holds the outer periphery of the object to be supplied S, so that the object to be supplied S can be supported in a rotatable manner with the covering layers S1a and S1b facing the spray heads Ha and Hb respectively.

[0113] As a specific example of the holding part 63, a structure that holds the outer peripheral edge of the flat object S in the thickness direction of the object S being supplied, and a structure that holds a plurality of claws disposed on the radially outer side of the object S relative to the outer peripheral edge of the object S while pressing them toward the radially inner side (for example, a structure that uses so-called edge clamps for holding).

[0114] According to this embodiment 3, in addition to achieving the same effects as in embodiments 1 and 2, it can also be said to achieve the following effects. That is, since ozone water and heatable liquid can be appropriately discharged (discharged simultaneously or alternately) to each discharge side S1 of one end side and the other end side of the supplied object S, it is possible to improve work efficiency (shorten work time, etc.).

[0115] Verification Example 1

[0116] In this verification example 1, the oxidizing power of ozone water on the supplied object S was verified in apparatus 1 based on the discharge structure of Example 1 (hereinafter appropriately referred to as the discharge structure of Example 1). As verification conditions, a 20mm × 20mm square chip obtained by cutting a commercially available semiconductor wafer was used as the supplied object S. In addition, after forming a 2μm thick cover layer S1a (after baking) of a phenolic varnish resin-based photoresist on one end of the square chip in the thickness direction, it was supported by the support platform 61 of the support part 6 (in a non-rotating state). In addition, in the ozone water generation part 2, ozone water with an ozone concentration of about 300ppm was generated by receiving ozone gas (ozone concentration 90% by volume, ozone partial pressure 10kPa (abs)) generated by an ozone gas generation device (trade name: pure ozone generator) manufactured by Meidensha, without adding concentration adjustment gas.

[0117] The discharge nozzle 32 is configured such that the ozone water discharge direction is located in the center of the cover layer S1a, and the ozone water discharge angle is approximately 90°. The discharge nozzle 42 is configured such that the heatable liquid discharge direction is located on one side of the cover layer S1a in the diagonal direction (the discharged heatable liquid flows from one side of the cover layer S1a in the diagonal direction to the other side), and the heatable liquid discharge angle is approximately 10°.

[0118] Then, for the cover layer S1a of the square chip, firstly, a heatable liquid at 80°C was discharged from the discharge nozzle 42 at a flow rate of 300 cc / min. Then, after 30 seconds, ozone water at 4°C was discharged from the discharge nozzle 32 at a flow rate of 300 cc / min, and the surface state of the cover layer S1a was observed. As a result, it was observed that within one minute of the start of ozone water discharge (e.g., after several tens of seconds), the surface near the center of the cover layer S1a (e.g., ...) showed improved surface condition. Figure 4 The area near R3 (as shown in the figure) begins to peel off and is removed at a rate of 3.5 μm / min.

[0119] On the other hand, as a comparative example of the discharge structure (hereinafter appropriately referred to as the comparative example discharge structure), for the cover layer S1a of the square chip, only ozone water at a temperature of 80°C was discharged from the discharge nozzle 32 at a flow rate of 300cc / min, and the surface state of the cover layer S1a was observed. The result was that after several minutes from the start of the discharge of ozone water, the cover layer S1a began to peel off near the center and was removed at a removal rate of 0.7μm / min.

[0120] Therefore, based on the observations of the discharge structure in Example 1 and the comparative example discharge structure, the following can be concluded. First, the ozone water in the comparative example discharge structure was at a high temperature (80°C) before discharge, and the ozone concentration had already decreased (e.g., halved) at the time of discharge, indicating that the removal rate was reduced.

[0121] On the other hand, the ozone water in the discharge structure of Example 1 was diluted by mixing with the heatable liquid in the cover layer S1a, resulting in a decrease in ozone concentration similar to that in the ozone water in the discharge structure of the comparative example. Therefore, based on the viewpoint of ozone water concentration, a removal rate similar to that in the ozone water discharge structure of the comparative example could be expected, but the actual observed results showed a good removal rate. This shows that in the case of the ozone water in the discharge structure of Example 1, the cover layer S1a absorbs heat from the heatable liquid and is heated (e.g., heated to about 50°C), and the reaction rate constant increases due to the generation of OH free radicals. That is, it can be confirmed that the ozone water in the discharge structure of Example 1 can obtain an oxidation-promoting effect from a sufficient amount of OH free radicals in the cover layer S1a, thereby exhibiting high oxidizing power.

[0122] Verification Example 2

[0123] In this verification example 2, firstly, for the square chip used in verification example 1, a 0.5 μm thick capping layer S1a was formed by coating one end of the capping layer S1a with a KrF laser photoresist in the thickness direction. Then, ion implantation was performed on the surface of the capping layer S1a (with an accelerating voltage of 150 kV and an implantation depth of 5 × 10⁻⁶ kJ / m³). 14 pcs / cm 2 Ion implantation (phosphorus) is used to form a hardened layer on the surface side of the capping layer S1a.

[0124] Then, under the same verification conditions as in Verification Example 1, for the cover layer S1a (hardened layer side) of the square chip, firstly, a heatable liquid at 80°C was discharged from the discharge nozzle 42 at a flow rate of 300 cc / min. Then, after 30 seconds, ozone water at 4°C was discharged from the discharge nozzle 32 at a flow rate of 300 cc / min, and the surface state of the cover layer S1a was observed. The result was the same as in Verification Example 1: within one minute of the start of ozone water discharge (e.g., after several tens of seconds), the surface near the center of the cover layer S1a (e.g., near the center) showed improved surface condition. Figure 4 The area near R3 (as shown in the figure) begins to peel off and is removed at a rate of 0.5 μm / min.

[0125] Similarly, using the comparative example discharge structure, for the cover layer S1a of the square chip, only ozone water at a temperature of 80°C was discharged from the discharge nozzle 32 at a flow rate of 300cc / min, and the surface state of the cover layer S1a was observed. However, even after several minutes (after 10 minutes) from the start of the ozone water discharge, no peeling of the cover layer S1a occurred.

[0126] Therefore, it can be confirmed that, even when a hardened layer is formed on the surface side of the covering layer S1a, the ozone water discharged in the structure according to Example 1 can still achieve an oxidation-promoting effect from a sufficient amount of OH free radicals and exert a high oxidizing power.

[0127] The above description only details specific examples. However, it is obvious to those skilled in the art that various modifications can be made within the scope of the technical concept of the present invention, and such modifications naturally fall within the scope of the claims.

[0128] For example, in Figure 3 , Figure 5 , Figure 8 In the case of the supplied object S shown, it is configured to be supported in a horizontally extending position within the container 5, but it is not limited to this and can be supported in various positions. For example, the supplied object S can be supported in a vertically extending position within the container 5. In this case, the device 1 can be appropriately modified by making the discharge directions of the discharge nozzles 32 and 42 and the discharge directions of the spray heads H, Ha, and Hb horizontal (i.e., so that the discharged side S1 is located in the discharge directions of ozone water and the heatable liquid).

Claims

1. An ozone water supply device, characterized in that, The supply device includes: An ozone water generating unit, wherein the ozone water generating unit receives ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer to generate ozone water; Ozone water supply unit, wherein the ozone water supply unit discharges the ozone water; and A miscible liquid supply unit discharges a miscible liquid that is miscible with the ozone water. The gas-liquid mixer includes: Solvent flow path, wherein the solvent flow path supplies the solvent; and An ozone gas inlet path is provided, which is connected to the solvent flow path to introduce ozone gas into the solvent flow path. The gas-liquid mixer accepts the ozone gas at an ozone concentration of 50% or more by volume and an ozone partial pressure of 30 kPa (abs) or less. When an object to which ozone water is supplied is positioned in the discharge direction of the ozone water supplied by the ozone water supply unit, the mixed liquid supply unit can discharge the mixed liquid at a temperature higher than that of the ozone water discharged from the ozone water supply unit to the side of the object to which the ozone water is discharged, i.e., the discharge side. The ozone water supply section and the mixed liquid supply section discharge the ozone water and the mixed liquid simultaneously or alternately, thereby enabling the two to mix on the discharged side.

2. The ozone water supply device as described in claim 1, characterized in that, The mixed liquid supply unit discharges the mixed liquid at a temperature above 40°C.

3. The ozone water supply device as described in claim 1, characterized in that, The supply device also includes a spray head, which is provided with a plurality of ozone water outlets that discharge ozone water through the ozone water supply section and mixed liquid outlets that discharge mixed liquid through the mixed liquid supply section.

4. The ozone water supply device as described in claim 1, characterized in that, The supply device also includes a pair of spray heads, each of which has multiple ozone water outlets for discharging ozone water through the ozone water supply unit and multiple mixed liquid outlets for discharging the mixed liquid through the mixed liquid supply unit. The pair of spray heads are positioned facing each other across the object being supplied.

5. The ozone water supply device as described in claim 1, characterized in that, The supply device also includes a support portion that supports the object being supplied so that it can rotate freely.

6. A method for supplying ozone water, characterized in that, The supply method has the following characteristics: The ozone water generation process involves receiving ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer to generate ozone water. An ozone water supply process, wherein the ozone water is discharged during the ozone water supply process; and The mixed liquid supply process involves discharging a mixed liquid that is miscible with the ozone water. The gas-liquid mixer includes: Solvent flow path, wherein the solvent flow path supplies the solvent; and An ozone gas inlet path is provided, which is connected to the solvent flow path to introduce ozone gas into the solvent flow path. The gas-liquid mixer accepts the ozone gas at an ozone concentration of 50% or more by volume and an ozone partial pressure of 30 kPa (abs) or less. In the mixed liquid supply process, when an object to which ozone water is supplied is positioned in the discharge direction of the ozone water discharged through the ozone water supply process, the mixed liquid is discharged into the object to which the ozone water is discharged, i.e., the discharge side, at a temperature higher than that of the ozone water discharged through the ozone water supply process. By simultaneously or alternately performing the ozone water supply process and the mixed liquid supply process, both the ozone water and the mixed liquid are mixed on the discharged side.

7. The method for supplying ozone water as described in claim 6, characterized in that, The mixed liquid supply process discharges the mixed liquid at a temperature above 40°C.

8. The method for supplying ozone water as described in claim 6, characterized in that, The supply method uses a spray head, which is provided with multiple ozone water outlets for discharging ozone water through the ozone water supply process and multiple mixed liquid outlets for discharging the mixed liquid through the mixed liquid supply process.

9. The method for supplying ozone water as described in claim 6, characterized in that, The supply method uses a pair of spray heads, each of which has multiple ozone water outlets for discharging ozone water through the ozone water supply process and multiple mixed liquid outlets for discharging the mixed liquid through the mixed liquid supply process. The pair of spray heads are positioned facing each other across the object being supplied.

10. The method for supplying ozone water as described in claim 6, characterized in that, The supplied object is supported so that it can rotate freely.

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