Fluid supply structure

Abstract

This technology provides a method to suppress changes in the physical properties of multiple fluids supplied to a target object before supply, and to contribute to making each fluid more readily reactive in the target object after supply. [Solution] The nozzle comprises a tubular first discharge nozzle 32 having a first discharge port 3a for discharging a first fluid toward the object to be supplied S, and a tubular second discharge nozzle 42 having a second discharge port 4a for discharging a second fluid toward the object to be supplied S, and having a larger diameter than the first discharge nozzle 32. The first discharge port 3a and the second discharge port 4a are positioned facing the object to be supplied S, and the second discharge nozzle 42 is coaxially positioned on the outer circumference of the first discharge nozzle 32, thereby integrating the first discharge nozzle 32 and the second discharge nozzle 42 into a double-pipe structure, forming a nozzle unit U3. The open end faces 3b of the first discharge port 3a and the open end faces 4b of the second discharge port 4a are flush with each other.

Description

Technical Field

[0001] The present invention relates to a technology that can contribute to a fluid supply structure for supplying a plurality of fluids having different physical properties (such as liquid composition, components, concentration, etc.).

Background Art

[0002] There is a technology for supplying a plurality of fluids having different physical properties (such as liquid composition, components, concentration, etc.) to a supply target object, and performing desired processing or treatment on the supply target object by utilizing the reaction caused by the mixing of the respective fluids.

[0003] For example, in the medical field, there is known an instrument for spraying and supplying a affected part (that is, a supply target object) while mixing two types of liquids having different liquid compositions (liquids stored and preserved so as not to mix (react) with each other). According to such an instrument, it is supposed that a reaction product (adhesion prevention material or biological tissue material) generated by the reaction of the two types of liquids can be formed by coating the affected part (for example, claims 1 and 2 of Patent Document 8).

[0004] In addition, a method of introducing two types of fluids into a mixing device such as a dynamic mixer or a static mixer and mixing them (for example, Patent Documents 9 and 10), and a method of discharging the two types of fluids so as to intersect in a free space and mixing them while forming a spiral flow (for example, Patent Document 11) are also known.

[0005] Thus, technologies that utilize the reaction by mixing a plurality of fluids have also begun to be studied in other fields, for example, in the field of ozone water obtained by dissolving ozone gas in a solvent.

[0006] In recent years, ozone has attracted attention due to its strong oxidizing power, and in addition to being used in the cleaning field, decontamination field, disinfection field, etc., attempts have been made to use it in various fields. As an example in the cleaning field, there is a mode of using it in a cleaning process of a substrate (such as a semiconductor wafer) applied to various electric devices (for example, Patent Documents 1 to 7, Non-Patent Documents 1 to 3).

[0007] In the case of ozonated water obtained by dissolving ozone gas in a solvent, it is preferable to supply it to the object to be supplied while maintaining the desired ozone concentration. For example, in Patent Document 4, it is disclosed that by supplying two types of fluids, namely hot water and pressurized ozonated water (i.e., both stored and kept so as not to mix with each other until immediately before supply) to the object to be supplied (a substrate in Patent Document 4) while mixing them, it is easier to maintain the ozone concentration of the ozonated water until immediately before the two are mixed, and the mixing raises the temperature of the ozonated water (i.e., raises the temperature due to the reaction between the two), making it easier to exert the desired oxidizing power. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2002-261068 [Patent Document 2] Patent No. 4444557 [Patent Document 3] Japanese Patent Publication No. 2009-297588 [Patent Document 4] Japanese Patent Publication No. 2021-034672 [Patent Document 5] Patent No. 5332052 [Patent Document 6] Patent No. 7186751 [Patent Document 7] Japanese Patent Publication No. 2008-311257 [Patent Document 8] Japanese Patent Publication No. 2006-95098 [Patent Document 9] Patent No. 5652213 [Patent Document 10] Japanese Patent Publication No. 2011-121038 [Patent Document 11] Patent No. 5164790 [Non-patent literature]

[0009] [Non-Patent Document 1] T. Miura et al, “Novel plasmaless photoresist removal method in gas phase at room temperature”, ECS Transactions, Volume 19, Issue 3, pp. 423 (2009). [Non-Patent Document 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). [Non-Patent Document 3] Ozone Handbook (Revised 2nd Edition), Japan Ozone Association [Overview of the project] [Problems that the invention aims to solve]

[0010] In methods such as those described in Patent Document 8, where multiple fluids are simply mixed and supplied to the object to be supplied, if, for example, the reaction time for mixing each fluid is relatively short, the time available to utilize the reaction after the fluid has been supplied (reached) the object to be supplied becomes limited. This may make it difficult to perform the desired processing or treatment.

[0011] Furthermore, if, for example, one of the multiple fluids is ozonated water, the following challenges arise. First, as mentioned above, simply dissolving ozone gas in a solvent makes it difficult to obtain high-concentration ozonated water. For example, one could consider dissolving ozone gas in a solvent under pressure, but this method is prone to rapid self-decomposition of ozone, which may make it difficult to maintain practical safety.

[0012] Also, when simply mixing warm water and ozone water in a pressurized state as in Patent Document 4 and supplying it to the object to be supplied, the ozone water decompresses while rapidly rising in temperature (for example, returning to the normal pressure state), and it becomes easy to degas (foam). The ozone water thus degassed may have a reduced ozone concentration and may not be able to exhibit the desired oxidizing power.

[0013] That is, the ozone water in the pressurized state as described above returns to the normal pressure state before being supplied to the object to be supplied (before reaching), and its physical properties change greatly. Therefore, even if it is supplied to the object to be supplied together with warm water, there is a possibility that the reaction between the ozone water and the warm water cannot be effectively utilized.

[0014] Therefore, in a method of supplying a plurality of fluids to an object to be supplied, it is desirable to suppress changes in physical properties in each fluid until it is supplied to the object to be supplied (for example, suppress changes in pressure, temperature, etc. in the case of ozone water), and further make it easier for each fluid to react sufficiently in the object to be supplied after the supply.

[0015] The present invention has been made in view of the above circumstances, and provides a technology that can contribute to suppressing changes in the physical properties of a plurality of fluids to be supplied to an object to be supplied until before the supply, and making it easier for each fluid after the supply to react sufficiently in the object to be supplied.

Means for Solving the Problems

[0016] The fluid supply structure according to this invention can contribute to solving the above problems. In a first aspect of the fluid supply structure, it includes a tubular first discharge nozzle having a first discharge port for discharging a first fluid toward an object to be supplied, and a tubular second discharge nozzle having a second discharge port for discharging a second fluid toward the object to be supplied and having a larger diameter than the first discharge nozzle.

[0017] And, with the first discharge port and the second discharge port facing the object to be supplied, the second discharge nozzle is coaxially positioned on the outer peripheral side of the first discharge nozzle, so that the first discharge nozzle and the second discharge nozzle form a double-tube structure and are integrated, and the opening end surfaces of the first discharge port and the second discharge port are flush with each other.

[0018] In the first aspect, the temperature-raisable liquid may be introduced from the outer peripheral side of the second discharge nozzle to the inner peripheral wall surface side of the second discharge nozzle along a direction intersecting the axial direction of the second discharge nozzle.

[0019] Further, a spiral groove extending in the S winding direction or the Z winding direction with respect to the axial direction of the second discharge nozzle may be provided on the inner peripheral wall surface of the second discharge nozzle.

[0020] Further, a second fluid inlet for introducing the second fluid from the outer peripheral side of the second discharge nozzle to the inner peripheral wall surface side of the second discharge nozzle is provided on the inner peripheral wall surface of the second discharge nozzle, and the second fluid inlet may be in a shape opening toward one side or the other side in the circumferential direction of the inner peripheral wall surface of the second discharge nozzle.

[0021] Further, a tapered surface with a tapered shape whose diameter decreases as it approaches the second discharge port is formed on the inner peripheral wall surface of the second discharge nozzle on the second discharge port side, and the second fluid inlet may be located on the tapered surface.

[0022] Further, a gas introduction portion for introducing gas from the outer peripheral side of the second discharge nozzle to the inner peripheral wall surface side of the second discharge nozzle may be provided on the second discharge nozzle.

[0023] Further, the outer peripheral wall surface of the first discharge nozzle may be subjected to a water-repellent treatment.

[0024] Furthermore, the device may also include a support portion that rotatably supports the object to be supplied, wherein the support portion rotates the object to be supplied in a direction opposite to the swirling flow direction of the second fluid flowing through the second discharge nozzle.

[0025] The second embodiment comprises a tubular first discharge nozzle having a first discharge port for discharging a first fluid toward an object to be supplied, and a tubular second discharge nozzle having a second discharge port for discharging a second fluid toward the object to be supplied.

[0026] Furthermore, the first discharge port and the second discharge port are positioned facing the object to be supplied, the first discharge nozzle and the second discharge nozzle are bundled together and integrated, and the open end faces of the first discharge port and the second discharge port are flush with each other.

[0027] In the second embodiment, a plurality of the second discharge nozzles may be arranged circumferentially with respect to the outer peripheral wall surface of the first discharge nozzle. In this case (and in the first embodiment), the inner peripheral wall surface of the first discharge nozzle on the first discharge port side may be characterized by having a tapered shape that narrows in diameter as it approaches the first discharge port.

[0028] Furthermore, in the first and second embodiments, the first fluid may be ozonated water, and the second fluid may be a miscible liquid that is miscible with the ozonated water. Furthermore, the first discharge nozzle may be made of a material containing a fluororesin. Furthermore, the first discharge nozzle may be characterized by having a hollow space between the inner and outer circumferential wall surfaces, and the hollow space being in a vacuum state.

[0029] When ozonated water is used as the first fluid and a miscible liquid that is miscible with the ozonated water is used as the second fluid, the configuration for supplying the ozonated water and the miscible liquid may be configured as follows.

[0030] In other words, the system comprises an ozone water generating unit that receives ozone gas and a solvent capable of dissolving the ozone gas into a gas-liquid mixer to generate ozonated water; an ozonated water supply unit that discharges the ozonated water through a first discharge nozzle; and a miscible liquid supply unit that discharges a miscible liquid having miscibility with the ozonated water through a second discharge nozzle.

[0031] The gas-liquid mixer comprises a solvent flow passage through which the solvent flows, and an ozone gas introduction passage connected to the solvent flow passage for introducing the ozone gas into the solvent flow passage, and is designed to receive the ozone gas at an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less.

[0032] Furthermore, the miscible liquid supply unit is capable of discharging the miscible liquid at a higher temperature than the ozonated water discharged from the ozonated water supply unit, and the ozonated water supply unit and the miscible liquid supply unit can discharge both the ozonated water and the miscible liquid together or alternately, enabling mixing of the two in the object to be supplied.

[0033] The miscible liquid supply unit may be characterized by discharging the miscible liquid at a temperature of 40°C or higher. It may also be characterized by further comprising a support unit that rotatably supports the object to be supplied. [Effects of the Invention]

[0034] As described above, the present invention can help to suppress changes in the physical properties of multiple fluids supplied to an object before supply, and to facilitate sufficient reaction of each fluid in the object after supply. [Brief explanation of the drawing]

[0035] [Figure 1] A schematic diagram illustrating an example configuration of an ozone water supply device according to the embodiment. [Figure 2] A schematic diagram illustrating the regions R1 to R3 formed on the object S to be supplied. [Figure 3] A schematic diagram illustrating the discharge configuration according to Example 1. [Figure 4] A schematic diagram illustrating the regions R1 to R3 formed on the object S to be supplied by the discharge configuration of Example 1. [Figure 5] A schematic diagram illustrating the discharge configuration according to Example 2. [Figure 6] A schematic diagram illustrating an example of showerhead H (viewed from the showerhead supply surface H11). [Figure 7] A schematic diagram illustrating another example of showerhead H (viewed from the showerhead supply surface H12). [Figure 8] A schematic diagram illustrating the discharge configuration according to Example 3. [Figure 9] A schematic diagram illustrating the discharge configuration according to Example 4. [Figure 10] A schematic diagram illustrating the discharge configuration according to Example 5 (a schematic diagram showing a cross-section along the radial direction of the discharge nozzles 32 and 42). [Figure 11] A schematic diagram illustrating the discharge configuration according to Example 6. [Figure 12] A schematic diagram illustrating the discharge configuration according to Example 6 (a schematic diagram showing a cross-section along the axial direction of the discharge nozzles 32 and 42). [Figure 13] A schematic diagram illustrating the discharge configuration according to Example 6 (a schematic diagram showing a radial cross-section of the discharge nozzles 32 and 42). [Figure 14] A schematic diagram illustrating the discharge configuration according to Example 9. [Figure 15] A schematic diagram illustrating the discharge configuration according to Example 9 (a schematic diagram showing a cross-section along the axial direction of the discharge nozzles 32 and 42). [Modes for carrying out the invention]

[0036] The fluid supply structure of the embodiment of the present invention is completely different from methods such as supplying multiple fluids to the object to be supplied while mixing them, as in Patent Document 8, or from configurations such as supplying hot water and pressurized ozonated water to the object to be supplied, as in Patent Document 4.

[0037] In other words, this embodiment includes a tubular first discharge nozzle (discharge nozzle 32 in the later embodiment) having a first discharge port for discharging a first fluid toward the object to be supplied, and a tubular second discharge nozzle (discharge nozzle 42 in the later embodiment) having a second discharge port for discharging a second fluid toward the object to be supplied. Furthermore, the first and second discharge ports are positioned facing the object to be supplied, and both the first and second discharge nozzles are bundled together to form a single unit, or they are arranged coaxially to form a double-pipe structure and are integrated. The opening end faces of the first and second discharge ports are flush with each other.

[0038] With this fluid supply structure, the first and second fluids supplied to the object to be supplied do not mix with each other while flowing through the first and second discharge nozzles, respectively, and changes in their physical properties can be suppressed until before supply.

[0039] Furthermore, both the first and second discharge nozzles are bundled together to form a single unit, or they are arranged coaxially to form a double-pipe structure and thus integrated, resulting in them being located close to (or adjacent to) each other. Therefore, the first and second fluids discharged from the first and second discharge nozzles may be more easily mixed with each other when supplied to the object to be supplied. In other words, each fluid may be more likely to react sufficiently with the object to be supplied.

[0040] When ozonated water is used as the first fluid and a miscible liquid that is miscible with the ozonated water is used as the second fluid, the configuration for supplying the ozonated water and the miscible liquid can be configured as follows.

[0041] First, the ozonated water supply configuration is such that ozonated water is generated by receiving ozone gas and a solvent capable of dissolving the ozone gas (hereinafter simply referred to as "solvent" as appropriate) into a gas-liquid mixer, and then the ozonated water is discharged and supplied to the target object to which the ozonated water is supplied. The gas-liquid mixer receives ozone gas at an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less.

[0042] Furthermore, the configuration for supplying the miscible liquid is such that a miscible liquid (hereinafter simply referred to as "miscible liquid") that is miscible with ozonated water is discharged at a temperature higher than the discharged ozonated water (hereinafter simply referred to as "temperature that can be increased") to the discharged side of the object to be supplied (hereinafter simply referred to as "discharged side"), which is the side from which the ozonated water is discharged.The configuration is such that both the ozonated water and the miscible liquid at the temperature that can be increased (hereinafter simply referred to as "temperature that can be increased") are discharged together or alternately, thereby enabling mixing of the two at the discharged side.

[0043] With this configuration, since the system receives high-concentration ozone gas with a sufficiently reduced ozone partial pressure to produce ozonated water, it is possible to sufficiently suppress the rapid self-decomposition reaction in the ozone gas, thereby maintaining practical safety. Furthermore, the ozone gas received as described above becomes more easily soluble in the solvent in the gas-liquid mixer, making it possible to safely produce high-concentration (e.g., 100 ppm or more) ozonated water.

[0044] Furthermore, when supplying ozonated water to the object to be supplied (the discharge side), it is not necessary to pressurize the ozonated water as in Patent Document 4, and degassing of the ozonated water can be suppressed. Therefore, compared to the configuration in Patent Document 4, the attenuation of the ozone concentration in the ozonated water can be sufficiently suppressed.

[0045] Furthermore, the ozonated water discharged to the discharge side of the object being supplied (the ozonated water remaining on the discharge side) mixes with the heat-reducing liquid and is heated, making it easier to exert the desired oxidizing power. This makes it possible to obtain the desired effect (e.g., cleaning effect, decontamination effect, disinfection effect, etc.) according to the object being supplied.

[0046] The fluid supply structure of this embodiment may be configured such that, as described above, both the first discharge nozzle and the second discharge nozzle are integrated, and the opening end faces of the first and second discharge ports are flush. Furthermore, when ozonated water and a heat-reducing liquid are used as the first and second fluids, as described above, ozonated water produced by receiving high-concentration ozone gas in a state where the ozone partial pressure has been sufficiently reduced is used, and the configuration may be such that the ozonated water discharged to the object to be supplied can be mixed with the heat-reducing liquid to raise its temperature. In other words, it is possible to appropriately apply common technical knowledge from various fields (for example, the fluid supply field, the ozone field, the cleaning field, the decontamination field, the disinfection field, etc.) and modify the design as needed by referring to prior art documents, etc., as an example thereof.

[0047] In the embodiments described later, detailed explanations are omitted as appropriate, for example, by referring to the same reference numerals and terms for similar content. Also, in the figures, the white arrows depict the discharge state of ozonated water, and the black arrows depict the discharge state of miscible liquid at the temperature that can be heated.

[0048] ≪Reference≫ For example, with conventional ozone generators (ozonizers), the ozone gas that can be produced is at a low concentration (for example, ozone concentration of 20% by volume or less), and often contains a large amount of gas other than ozone (for example, oxygen, etc.) (hereinafter referred to as non-ozone components). Even with such low-concentration ozone gas, it is difficult to produce high-concentration ozonated water, and the resulting water will contain a large amount of dissolved non-ozone components.

[0049] Furthermore, when ozonated water is produced by dissolving low-concentration ozone gas in a solvent under high pressure, it contains not only ozone but also non-ozone components in a supersaturated state. When such ozonated water is released into the atmosphere, the non-ozone components make it easy for the water to degas (for example, by generating bubbles and scattering into the atmosphere), and the ozone components also become easily dispersed, making it impossible to maintain the high-concentration state of the ozonated water.

[0050] In recent years, it has become possible to produce high-concentration ozone gas (for example, ozone concentration of 50% by volume or more) by concentrating ozone gas generated by ozonizers, etc., using methods such as adsorption concentration (a method utilizing surface adsorption of silica gel, etc.) or cooling concentration.

[0051] For example, Meidensha's cooling and concentration-type ozone gas generator (product name: Pure Ozone Generator) can produce extremely high concentrations of ozone gas (over 90% by volume) with an ozone concentration close to approximately 100% by volume, and has also achieved practical safety by obtaining international safety standard SEMI-S2 certification.

[0052] However, as mentioned above, even with concentrated ozone gas, it is necessary to maintain a reduced pressure state to prevent rapid self-decomposition reactions. Therefore, it is difficult to apply this to a configuration in which the ozone gas is received into a gas-liquid mixer under high pressure to produce ozonated water.

[0053] On the other hand, in this embodiment, as in the ozone water generation unit 2 described later, the ozone gas is received into the gas-liquid mixer under reduced pressure (ozone partial pressure of 30 kPa (abs) or less). Therefore, even extremely high-concentration ozone gas, which has been concentrated as described above, can be used safely, and it becomes quite possible to produce ozonated water of the desired high concentration.

[0054] As a specific example, if the ozone gas received in a gas-liquid mixer has an ozone concentration of 90% by volume or more and an oxygen concentration of 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).

[0055] Furthermore, in the case of ozone gas with an ozone concentration of 50% by volume 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 a reduced pressure of 60 kPa (abs) or less (i.e., a partial ozone pressure of 30 kPa (abs) or less).

[0056] Examples <Main components of the supply device 1 according to the example> Figure 1 is a schematic diagram illustrating the configuration of an ozone water supply device 1 according to an embodiment. This device 1 mainly comprises an ozone water generation unit 2 that receives ozone gas and a solvent in a gas-liquid mixer 21 to generate ozone water, an ozone water supply unit 3 that discharges and supplies the ozone water to the object to be supplied S, and a miscible liquid supply unit 4 that receives a miscible liquid and discharges and supplies a heat-adjustable liquid to the object to be supplied S.

[0057] This device 1 can be operated by, for example, a control unit (not shown) which appropriately controls the ozone water generation unit 2, the ozone water supply unit 3, the miscible liquid supply unit 4, etc. An example of a control unit is one which appropriately acquires the state of the ozone water generation unit 2, the ozone water supply unit 3, the miscible liquid supply unit 4, etc. (for example, the temperature, flow rate, pressure, etc. of the solvent, ozone water, and miscible liquid, respectively; hereinafter simply referred to as the device state as appropriate), and controls the device state, or controls the discharge of ozone water and heatable liquid respectively (for example, controlling to discharge ozone water and heatable liquid together or alternately, as described later).

[0058] Various configurations can be applied to the solvent and ozonated water flow paths within the ozonated water generation unit 2 (for example, the flow paths indicated by arrows Y1 and Y2), the ozonated water flow paths within the ozonated water supply unit 3 (not shown), and the miscible liquid flow paths within the miscible liquid supply unit 4 (not shown). One example is a configuration using various types of piping. However, the ozonated water flow paths within the ozonated water supply unit 3 and the miscible liquid flow paths within the miscible liquid supply unit 4 are configured independently of each other (i.e., they are not connected to each other).

[0059] In each of the aforementioned flow paths, in addition to applying piping as described above, temperature control units (e.g., heaters and coolers) 22, 31, 41, etc., as shown in Figure 1, or various flow path equipment (e.g., on-off valves, pumps, storage tanks, measuring instruments, etc.) may be provided. If impurities (in the case of metal piping, impurities such as metal ions generated by the dissolution of the inner surface of the piping) may be mixed into each of the aforementioned flow paths, it is preferable to configure the system to suppress such mixing. For example, the temperature control units 22, 31, 41 may be installed on the outer surface of each flow path (e.g., the outer surface of the piping) and configured to indirectly control the temperature of the inner surface of the flow path. Furthermore, when using metal piping, it is preferable to use piping whose inner surface is coated with Teflon® or the like.

[0060] In the apparatus 1 shown in Figure 1, ozonated water is generated by the ozonated water generation unit 2 (ozonated water generation process), and the discharged side S1 of the object to be supplied is positioned in the direction of discharge of ozonated water by the ozonated water supply unit 3 and the direction of discharge of the heat-upable liquid by the miscible liquid supply unit 4. The apparatus is used to discharge both the ozonated water and the heat-upable liquid together or alternately (ozonated water supply process, miscible liquid supply process, described later).

[0061] As a result, as shown in Figure 2, for example, the discharge side S1 of the object to be supplied is formed with three regions: a region R1 where ozonated water exists, a region R2 where the heat-uptable liquid exists, and a region R3 where regions R1 and R2 overlap. That is, when the ozonated water in region R1 and the heat-uptable liquid in region R2 are mixed in region R3, the ozonated water in region R3 (and its periphery) absorbs heat from the heat-uptable liquid and becomes hotter. The heated ozonated water then has increased oxidizing power.

[0062] As described above, heated ozonated water may generate OH radicals through ozonolysis. Although these OH radicals have relatively high activity, their lifetime is shorter than that of ozone, and they tend to disappear immediately after generation (due to their low selectivity of reactivity, they react with surrounding substances immediately after generation and disappear). However, as shown in Figure 2, OH radicals generated at the discharge side S1 have a higher probability of effectively acting on the discharge side S1 before they disappear.

[0063] Therefore, the ozonated water at the discharge side S1 is prone to an increase in reaction rate constant (for example, by several orders of magnitude) due to the generation of OH radicals, and thus retains sufficient oxidizing power even when diluted with a heat-adjustable liquid.

[0064] <Example configuration of ozone water generation unit 2> The ozonated water generation unit 2 shown in Figure 1 is configured to generate high-concentration (e.g., 100 ppm or more) ozonated water by receiving ozone gas at an ozone concentration of 50 volume% or more and an ozone partial pressure of 30 kPa (abs) or less while receiving a solvent in the gas-liquid mixer 21. Furthermore, the generated ozonated water can be supplied to the subsequent ozonated water supply unit 3 (for example, as shown by arrow Y1).

[0065] The gas-liquid mixer 21 can be, for example, an ejector, aspirator, or jet pump, but is not limited to these, and various configurations can be applied. In other words, the gas-liquid mixer 21 can have a configuration that includes a solvent flow passage (not shown) through which the received solvent flows, and an ozone gas introduction passage (not shown) connected to the solvent flow passage for introducing the received ozone gas into the solvent flow passage.

[0066] In a gas-liquid mixer 21 configured as described above, which has a solvent flow path and an ozone gas introduction path, a suction pressure is generated in the ozone gas introduction path according to Bernoulli's theorem, depending on the flow rate (flow velocity) of the solvent flowing through the solvent flow path. In addition, vapor is generated in the ozone gas introduction path according to the saturated vapor pressure of the solvent. For example, if the solvent is raw water, it will have properties equivalent to water (saturated vapor pressure properties and water vapor pressure properties).

[0067] Based on these solvent properties and the pressure at which the gas-liquid mixer 21 receives ozone gas (hereinafter referred to as the receiving pressure), it is possible to determine a range of solvent temperatures (hereinafter referred to as the aspirable range) in which the vapor pressure in the ozone gas introduction path of the gas-liquid mixer 21 is lower than the receiving pressure. This aspirable range is preferably set appropriately (for example, set to 25°C or lower as described in paragraph

[0023] of Japanese Patent Publication No. 4296393) taking into consideration the general solubility characteristics of gases in solvents (solubility tends to increase as the solvent temperature decreases). Therefore, if the solvent temperature is outside the aspirable range, for example, the solvent temperature can be adjusted in advance before receiving the solvent in the gas-liquid mixer 21 (for example, by a temperature adjustment unit not shown), or the temperature adjustment unit 22 can be operated to adjust the solvent temperature.

[0068] Before the ozonated water generated by the gas-liquid mixer 21 is supplied to the subsequent ozonated water supply unit 3, a concentration-adjusting gas to stabilize the ozone concentration may be added, or the ozonated water may be circulated within the ozonated water generation unit 2 (for example, circulating in a way that feeds back to the upstream side of the gas-liquid mixer 21 as shown by arrow Y2) or temporarily stored. When increasing the concentration using a concentration-adjusting gas, for example, the ozonated water may be acidified by adding carbon dioxide or the like.

[0069] Any solvent capable of dissolving ozone gas can be used, such as raw water, pure water, or ultrapure water. Furthermore, if necessary, the purity of the solvent can be increased using a pure water production device (not shown in the diagram).

[0070] Ozone gas can be generated using various ozone gas generators, and when received in the gas-liquid mixer 21, the ozone concentration must be 50% by volume or higher and the ozone partial pressure 30 kPa (abs) or lower. One example of an ozone gas generator is the ozone gas generator manufactured by Meidensha (product name: Pure Ozone Generator).

[0071] With this type of ozone water generator 2, it is possible to safely produce ozone water with a high concentration of 100 ppm or more (for example, 300-400 ppm).

[0072] <Example configuration of ozone water supply unit 3> The ozone water supply unit 3 shown in Figure 1 is configured to discharge ozone water introduced from the ozone water generation unit 2 from the discharge unit 30. However, the discharge configuration only needs to be such that it can be discharged and supplied to the discharge side S1 of the object to be supplied S, and various configurations can be applied. As an example, as shown in Examples 1 to 9 described later, a configuration in which the water is discharged through a discharge nozzle 32 or the discharge port 33 of a shower head H can be used.

[0073] Furthermore, the ozonated water in the ozonated water supply unit 3 may be temperature-controlled (for example, cooled by the temperature control unit 31) to maintain the ozone concentration before being discharged to the object S to be supplied, and may also be temporarily stored in the ozonated water supply unit 3.

[0074] The temperature of the ozonated water discharged to the object S should be within a range that does not cause solidification and can be heated by the heat-raising liquid, and can be set appropriately according to the heat-raising liquid.

[0075] Furthermore, the flow path through which ozonated water flows can be constructed using various materials (e.g., metal materials, resin materials, etc.). A preferred example is the use of materials with low thermal conductivity or resistance to ozone. Specifically, in the discharge nozzle 32 described later, a material containing fluororesin (e.g., polytetrafluoroethylene) (e.g., a material with polytetrafluoroethylene as the main component) can be used.

[0076] <Example of configuration of the miscible liquid supply unit 4> The miscible liquid supply unit 4 shown in Figure 1 is configured to receive a miscible liquid and discharge a heat-upable liquid from the discharge unit 40. However, the discharge configuration only needs to be such that it can be discharged and supplied to the discharge side S1 of the object to be supplied S, and various configurations can be applied. As an example, as shown in Examples 1 to 9 described later, a configuration in which the liquid is discharged through a discharge nozzle 42 or a discharge port 43 of a shower head H can be used.

[0077] Furthermore, the miscible liquid in the miscible liquid supply unit 4 may be heated to a temperature that can be increased before being discharged to the discharge side S1 of the object to be supplied (before it reaches the discharge side S1) (for example, by heating with the temperature adjustment unit 41). However, if the miscible liquid is already at a temperature that can be increased when it is received in the miscible liquid supply unit 4, it may be discharged as is. Alternatively, it may be temporarily stored in the ozonated water supply unit 3.

[0078] Any miscible liquid that is miscible with ozonated water can be used as appropriate. Examples include raw water, pure water, ultrapure water, ion-exchanged water, basic aqueous solutions, and acidic aqueous solutions. However, while organic solvents such as lower alcohols are miscible with ozonated water, it is possible that the CC bonds of the organic solvent may be broken by the ozone. Therefore, if there is a possibility of any effect on the supplied substance S, it is undesirable. Tap water can also be used, but if necessary (for example, depending on the type of supplied substance S), it is preferable to increase the purity of the water using a pure water production device (not shown in the figure) before application.

[0079] The maximum temperature at which a miscible liquid can be heated can be set as appropriate. For example, if the ozonated water is at room temperature (e.g., 5°C to 35°C), the maximum temperature can be set to a temperature higher than room temperature (e.g., 40°C or higher). By setting the maximum temperature in this way, the thermal energy of the miscible liquid (heatable liquid) can be transferred to the ozonated water, thereby promoting the generation of OH radicals. Furthermore, if the miscible liquid is raw water, pure water, ultrapure water, or ion-exchanged water, the upper limit of the maximum temperature can be set to 100°C.

[0080] <An example of the object S to be supplied> The object to be supplied S can be positioned in the direction of discharge of ozonated water by the ozonated water supply unit 3 and the direction of discharge of the heat-reducing liquid by the miscible liquid supply unit 4, and it is sufficient that it can exert the oxidizing power of ozonated water to obtain the desired effect, and various embodiments can be applied. Examples include various substrates that can be cleaned, such as those shown in Patent Documents 1-7, Non-Patent Documents 1-3, Japanese Patent Publication No. 2017-173461, and Japanese Patent Publication No. 2017-123402 (e.g., semiconductor substrates, glass substrates); chemical agents, biological agents, nuclear power plants, etc., that can be decontaminated, such as those shown in Japanese Patent Publication No. 2019-181182 and Japanese Patent Publication No. 2019-66226; and various containers (e.g., beverage containers) and medical devices (e.g., endoscopes), etc., that can be disinfected, such as those shown in Japanese Patent Publication No. 2017-186022, Japanese Patent Publication No. 2017-148703, and Japanese Patent Publication No. 2016-119942. Other examples include facilities and vehicles in areas where infectious diseases originating from birds and animals have occurred, and steel materials that require pickling with hydrochloric acid, sulfuric acid, etc.

[0081] As a specific example, when the target object S is various substrates that can be cleaned, the apparatus 1 can be appropriately applied to clean the substrate as needed for each of the various processing steps (photolithography, etching, ion implantation, CMP, etc.). This ensures that the substrate surface is cleaned so that no unwanted substances such as particles or organic matter remain on the substrate surface.

[0082] Furthermore, if the object to be supplied S is porous, the ozonated water and heat-up liquid discharged from the device 1 will not only be present on the surface of the discharged side S1, but may also be present on the surface of micropores and other structures formed on the interior side of the object to be supplied S. In other words, regions R1 to R3 as shown in Figure 2 will be formed on the surface of these micropores and other structures, and the desired effect will be obtained due to the oxidizing power of the ozonated water.

[0083] <Other> The discharge direction, discharge flow rate (flow velocity), discharge force, etc., of the ozonated water discharged by the ozonated water supply unit 3 and the heat-reducing liquid discharged by the miscible liquid supply unit 4 can be set as appropriate. For example, the discharge directions of the ozonated water and the heat-reducing liquid may not simply be set perpendicular to the object to be supplied S (vertically upward or downward in the figures), as shown in Figures 3, 5, and 8 below, but may be set in a direction inclined at a predetermined angle with respect to the object to be supplied S.

[0084] Furthermore, from the viewpoint of optimizing the mixing efficiency of ozonated water and the heat-reducing liquid, and consequently the OH radical generation efficiency, it is preferable that the angles of the discharge directions of the ozonated water and the heat-reducing liquid relative to the object S to be supplied (hereinafter, these will be simply referred to as the ozonated water discharge angle and the heat-reducing liquid discharge angle, respectively) be made changeable as needed. For example, the apparatus 1 may be equipped with an angle adjustment function that allows the ozonated water discharge angle and the heat-reducing liquid discharge angle to be changed.

[0085] The discharge flow rate and discharge force of the ozonated water and the heat-generating liquid are set appropriately according to the positional relationship between the device 1 and the object S to be supplied, but it is preferable to set the discharge flow rate and discharge force of the ozonated water appropriately within a range that prevents degassing of the ozonated water after discharge.

[0086] Furthermore, when both ozonated water and a heat-adjustable liquid are to be discharged, the discharge of the heat-adjustable liquid is to be started first, and then, after a predetermined time has elapsed (for example, several seconds to tens of seconds), the discharge of the ozonated water is to be started. In this case, for example, similar to the discharge configuration of Example 1 shown in Verification Examples 1 and 2 below, the discharge side S1 of the object to be supplied S can be preheated with the heat-adjustable liquid (heated before the discharge of ozonated water is started), which makes it easier for OH radicals to be generated and an enhanced oxidation effect can be obtained, potentially allowing for the exertion of a higher oxidizing power.

[0087] Furthermore, the object to be supplied S may be appropriately supported via the support portion 6, as shown in Examples 1 to 3 described later, or it may be appropriately contained within the container 5.

[0088] <Example 1> Figures 3 and 4 show Embodiment 1 and illustrate an example of a discharge configuration using tubular discharge nozzles 32 and 42. In Figure 3, the discharge nozzle 32 is positioned vertically above the container 5 capable of containing the object to be supplied S, and is positioned to penetrate the container 5 in an inward and outward direction. One end of the discharge nozzle 32 is connected to the discharge section 30 of the ozone water supply unit 3, thereby enabling the ozone water from the ozone water supply unit 3 to be discharged vertically downward into the container 5.

[0089] The discharge nozzle 42 is positioned vertically above the container 5 at a predetermined distance from the discharge nozzle 32, and is positioned to penetrate the container 5 in an inward-outward direction. One end of the discharge nozzle 42 is connected to the discharge section 40 of the miscible liquid supply unit 4, thereby enabling the heating-capable liquid from the miscible liquid supply unit 4 to be discharged vertically downward into the container 5.

[0090] The object to be supplied, S, shown in Figures 3 and 4, is in the shape of a flat plate, and a coating layer S1a corresponding to the discharge side S1 is provided on one end side in the thickness direction (the side facing the discharge nozzles 32 and 42). The object to be supplied, S, is rotatably supported by a support part 6 in a position where the coating layer S1a faces the discharge nozzles 32 and 42.

[0091] In the case of the support unit 6 in Figure 3, it is composed of a support base 61 that supports the object to be supplied S, and a rotating shaft 62 that extends vertically downward from the center of the support base 61 and rotates the support base 61. In the support base 61, it is preferable to have a configuration that can support the object to be supplied S so that it does not shift position when the support base 61 is rotated, and one example of such a configuration is one in which it is supported by a vacuum chuck.

[0092] According to the discharge configuration of this embodiment 1, by performing both the ozonated water supply step, in which ozonated water is discharged via the discharge nozzle 32, and the miscible liquid supply step, in which a heat-upable liquid is discharged via the discharge nozzle 42, together or alternately, regions R1 to R3 similar to those in Figure 2 are formed on the coating layer S1a of the object to be supplied, as shown in Figure 4, for example.

[0093] Furthermore, while both the ozonated water supply process and the miscible liquid supply process are being performed together or alternately as described above, a rotation process may be performed in which the object to be supplied S is rotated by the support part 6. By appropriately performing this rotation process, the ozonated water and the heat-reducing liquid discharged in the ozonated water supply process and the miscible liquid supply process are more likely to spread and distribute along the surface of the coating layer S1a due to the centrifugal force of the rotation, and regions R1 to R3 are also more likely to expand. As a result, the oxidizing power of the ozonated water is more likely to be exerted broadly and evenly on the coating layer S1a.

[0094] Furthermore, when both the ozonated water supply process and the miscible liquid supply process are performed alternately, the rotation process may be performed while one of the processes is stopped and the other is switched to (i.e., while both processes are stopped). In this case, the ozonated water and the heat-reducing liquid are more likely to spread and distribute along the surface of the coating layer S1a each time they are discharged, potentially making it easier for region R3 to expand further. This may make it easier for the oxidizing power of the ozonated water to be exerted more broadly and evenly on the coating layer S1a.

[0095] When the discharge of both ozonated water and the heat-generating liquid is stopped, and the support unit 6 continues to rotate the object to be supplied S, the ozonated water and heat-generating liquid remaining on the coating layer S1a will be removed by the centrifugal force of the rotation and discharged, for example, through the discharge unit 51 provided on the container 5.

[0096] A specific example is a case where the ozonated water supply process and the miscible liquid supply process are performed alternately, and the cycle consisting of the ozonated water supply process, the miscible liquid supply process, and a rotation process performed while both the ozonated water supply process and the miscible liquid supply process are stopped is repeated. By repeating such a cycle, it is possible to efficiently and evenly exert the oxidizing power of the ozonated water.

[0097] Since the ozonated water discharged from the discharge unit 51 decomposes over time, even if it is released into the natural environment, the burden on that natural environment can be sufficiently suppressed (for example, significantly suppressed compared to cases where sulfuric acid or chemical solutions are used).

[0098] <Example 2> Figures 5 to 7 show Example 2, illustrating an example of a discharge configuration when using a shower head H. In Figure 5, the shower head H is located vertically above the container 5. This shower head H has multiple ozonated water outlets 33 and multiple miscible liquid outlets 43 on the shower head supply surface H1, which is the side of the shower head H facing the object to be supplied S.

[0099] Furthermore, on the outside of the container 5 of the shower head H, there are connecting parts (fittings, etc.) 34 and 44 that can be connected to the discharge parts 30 and 40, respectively. Connecting part 34 communicates with the discharge port 33 via an ozone water channel (not shown) inside the shower head H, and connecting part 44 communicates with the discharge port 43 via a heat-reducing liquid channel (not shown) inside the shower head H. However, the ozone water channel and the heat-reducing liquid channel are configured independently of each other (i.e., they are not connected to each other). This configuration allows ozone water and heat-reducing liquid to be discharged, respectively, through the discharge ports 33 and 43.

[0100] The shape of the showerhead supply surface H1 and the outlets 33 and 43 are not particularly limited and can be set as appropriate.

[0101] For example, the showerhead supply surface H1 is made larger than the surface in the coating layer S1a that faces the showerhead supply surface H1 (hereinafter simply referred to as the discharged side facing surface), making it easier to discharge ozonated water or a heat-sensitive liquid over the entire surface of the discharged side facing surface.

[0102] As a specific example, if the shape of the surface facing the discharge side is circular, it can be made circular, as shown in Figure 6 for the showerhead supply surface H11, and multiple discharge ports 33, 43 can be provided at dispersed positions on the showerhead supply surface H11. When each discharge port 33, 43 is provided at dispersed positions, various configurations can be applied. In the case of Figure 6, multiple discharge ports 33 are provided so as to be dispersed on the showerhead supply surface H11, and discharge ports 43 are provided at the four sides of each discharge port 33.

[0103] Furthermore, even if the shower head supply surface H12 extends in a strip-like shape, as shown in Figure 7, if the multiple discharge ports 33, 43 are arranged alternately at predetermined intervals in the direction of extension (linearly along the shower head supply surface H12), it is possible to discharge ozonated water and heat-reducing liquid over the entire surface facing the discharge side by appropriately performing the ozonated water supply process, the miscible liquid supply process, and the rotation process, similar to Example 1.

[0104] The shapes of the discharge ports 33 and 43 can be set as appropriate, and examples include circular, rectangular, elliptical, or slit-shaped ports. In Figures 6 and 7, the discharge ports 33 and 43 are depicted with different shapes for convenience (discharge port 33 is depicted as circular, and discharge port 43 as rectangular), but they may be the same shape.

[0105] According to this embodiment 2, in addition to achieving the same effects as in embodiment 1, the following can be said: It becomes easier to discharge and distribute ozonated water and heat-upable liquid over the entire surface facing the discharge side. As a result, a region R3 is more easily formed over the entire surface facing the discharge side, which may make it easier for the oxidizing power of the ozonated water to be exerted evenly and fully.

[0106] <Example 3> Figure 8 shows Example 3, illustrating an example of a discharge configuration when a pair of shower heads Ha and Hb are used. In the shower heads Ha and Hb shown in Figure 8, they are positioned on the vertical upper and lower sides of the container 5, respectively, facing each other with the object to be supplied S in between, in the same configuration as shower head H in Example 2.

[0107] In the case of the object to be supplied S shown in Figure 8, coating layers S1a and S1b corresponding to the discharge side portion S1 are provided on one end side and the other end side in the thickness direction, respectively. Furthermore, the support portion 6 that supports the object to be supplied S has a holding portion 63 that holds the outer peripheral edge of the object to be supplied S, and is configured to rotatably support the object to be supplied S in a position where the coating layers S1a and S1b face the shower heads Ha and Hb, respectively.

[0108] Specific examples of the holding portion 63 include a configuration in which the outer peripheral edge of a flat object to be supplied S is gripped in the thickness direction of the object to be supplied S, and a configuration in which a plurality of claw portions arranged on the radially outer side of the object to be supplied S are pressed radially inward against the outer peripheral edge of the object to be supplied S while holding it (for example, a configuration in which an edge grip is used for holding).

[0109] According to this embodiment 3, in addition to achieving the same effects as in embodiments 1 and 2, the following can be said. That is, since ozonated water and a heat-reducing liquid can be discharged together (together or alternately) to each discharged side S1 on both the side surfaces of the object to be supplied S, it is possible to improve work efficiency (shortening of work time, etc.).

[0110] <Example 4> Figure 9 shows Embodiment 4, illustrating an example of a discharge configuration using a nozzle unit U1 that integrates discharge nozzles 32 and 42.

[0111] The nozzle unit U1 shown in Figure 9 has a configuration in which the discharge nozzles 32 and 42 are bundled together and integrated, with the discharge ports 3a and 4a of each nozzle facing the object to be supplied S (in the case of Figure 9, the coating layer S1a). In addition, the opening end faces 3b and 4b of each discharge port 3a and 4a are flush with each other.

[0112] An insulating material or the like may be appropriately interposed between the discharge nozzles 32 and 42 to prevent heat transfer between them, which makes it easier to suppress the temperature rise of the ozonated water flowing through the discharge nozzle 32.

[0113] For example, as shown in Example 5 described later, if the outer peripheral walls 3c and 4c of both discharge nozzles 32 and 42 are cylindrical, the contact surface between them becomes linear, and the contact area becomes sufficiently small. As a result, only a small amount of heat is transferred from the heat-enhancing liquid circulating in discharge nozzle 42 to the ozonated water circulating in discharge nozzle 32, and it is possible that the temperature rise of the ozonated water can be sufficiently suppressed even without using insulating materials such as those mentioned above.

[0114] The discharge configuration using the nozzle unit U1 of this embodiment 4 provides the same effects as in embodiment 1, in addition to the following: Since the discharge nozzles 32 and 42 of the nozzle unit U1 are bundled together and integrated, they are located in close proximity (or adjacent) to each other. Therefore, the ozonated water and heat-sensitive liquid discharged from the discharge nozzles 32 and 42 may be more easily mixed (blended) with each other when supplied to the object S to be supplied.

[0115] For example, if regions R1 to R3 similar to those shown in Figure 4 are formed, it is conceivable that region R3 will be more easily expanded. In other words, the oxidizing power of ozonated water may be more easily exerted over a wider and more uniform area at the discharge side S1 of the object being supplied S.

[0116] <Example 5> Figure 10 shows Embodiment 5, illustrating an example of a discharge configuration using a nozzle unit U2 in which multiple discharge nozzles 42 are provided on the outer peripheral wall surface 3c of a discharge nozzle 32 and integrated together.

[0117] The nozzle unit U2 shown in Figure 10 has multiple (nine in Figure 10) discharge nozzles 42 arranged along the circumferential direction of the outer peripheral wall surface 3c of the discharge nozzle 32.

[0118] In the discharge nozzle 32, for example, as shown in Figure 10, a hollow section 3e may be provided between the outer peripheral wall surface 3c and the inner peripheral wall surface 3d, and the hollow section 3e may be configured to be in a vacuum state. This hollow section 3e makes it easier to prevent heat transfer between the discharge nozzles 32 and 42, and makes it easier to suppress the temperature rise of the ozonated water flowing inside the discharge nozzle 32.

[0119] The discharge configuration using the nozzle unit U2 of this embodiment 5 provides the same effects as in embodiment 4, in addition to the following: With the nozzle unit U2, a region R2 containing a heat-up liquid is formed in an annular shape (annular along the surface of the discharge side S1) on the discharge side S1 of the object to be supplied, and a region R1 containing ozonated water is formed on the inner circumference of this annular region R2. As a result, regions R1 and R2 overlap evenly, making it easier to form region R3, and it is thought that this region R3 can be expanded more easily.

[0120] Therefore, when the ozonated water and heat-up liquid discharged from the discharge nozzles 32 and 42 are supplied to the discharge side S1 of the object to be supplied, they may be more easily mixed, and the oxidizing power of the ozonated water may be more easily exerted over a wider and more uniform area.

[0121] <Example 6> Figures 11 to 13 show Embodiment 6, illustrating an example of a discharge configuration using a nozzle unit U3 in which discharge nozzles 32 and 42 are arranged coaxially to form a double-pipe structure and integrated.

[0122] The nozzle unit U3 shown in Figures 11 to 13 has a double-pipe structure, in which the discharge nozzle 42 has a larger diameter than the discharge nozzle 32, and the discharge nozzle 42 is positioned coaxially on the outer circumference of the discharge nozzle 32.

[0123] In the discharge nozzle 32, for example, as shown in Figure 12, the inner circumferential wall surface 3d on the discharge port 3a side may be made into a tapered shape that narrows in diameter as it approaches the discharge port 3a. In the case of the discharge nozzle 32 shown in Figure 12, both the outer circumferential wall surface 3c and the inner circumferential wall surface 3d are tapered shapes that narrow in diameter as they approach the discharge port 3a (in the case of Figure 12, they have tapered surfaces 3f and 3g, respectively). With such a tapered shape of discharge nozzle 32, a Venturi effect can be obtained, for example, the flow velocity of the ozonated water discharged from the discharge nozzle 32 tends to increase, and a swirling flow (for example, a swirling flow like the dotted arrow in Figure 12) tends to be generated in the ozonated water near the discharge port 3a.

[0124] Furthermore, similar to Example 5, the discharge nozzle 32 may be configured such that, for example as shown in Figure 13, a hollow portion 3e is provided between the outer peripheral wall surface 3c and the inner peripheral wall surface 3d, and the hollow portion 3e is kept in a vacuum state. This hollow portion 3e makes it easier to prevent heat transfer between the discharge nozzles 32 and 42, and makes it easier to suppress the temperature rise of the ozonated water flowing through the discharge nozzle 32.

[0125] The discharge configuration using nozzle unit U3 of this embodiment 6 provides the same effects as in embodiments 4 and 5, and also offers the following advantages. Specifically, since nozzle unit U3 has a configuration in which the discharge nozzle 32 is housed on the inner circumference side of the discharge nozzle 42, it may be easier to miniaturize and simplify it compared to nozzle units U1 and U2.

[0126] Furthermore, on the discharge side S1 of the object to be supplied, a region R2 containing a heat-up liquid is formed in an annular shape (annular along the surface of the discharge side S1), similar to Example 5, and a region R1 containing ozonated water is formed on the inner circumference side of this annular region R2. Here, as shown in Figure 12, if the discharge port 3a side of the inner circumferential wall surface 3d of the discharge nozzle 32 is tapered, it is conceivable that a region R3 where regions R1 and R2 overlap will be more easily formed, and that this region R3 will be more easily expanded.

[0127] Therefore, when the ozonated water and heat-up liquid discharged from the discharge nozzles 32 and 42 are supplied to the discharge side S1 of the object to be supplied, they may be more easily mixed, and the oxidizing power of the ozonated water may be more easily exerted more broadly and evenly.

[0128] <Example 7> This embodiment 7 describes an example of design modification in a discharge configuration using the nozzle unit U3.

[0129] The nozzle unit U3 can, for example, appropriately design and modify the discharge nozzles 32 and 42 to control the flow of a heat-raising liquid introduced into and circulating within the discharge nozzle 42 so that it moves toward the discharge port 4a while swirling along the inner circumferential wall surface 4d.

[0130] One example of a configuration that causes the heat-upable liquid to swirl (hereinafter simply referred to as a swirling configuration) is a configuration in which the heat-upable liquid is introduced from the outer circumference of the discharge nozzle 42 to the inner circumferential wall surface 4d of the discharge nozzle 42 along a direction that intersects the axial direction of the discharge nozzle 42 (the vertical direction shown in Figures 11 and 12) (for example, a direction that is perpendicular (intersecting in three dimensions) to the axis of the discharge nozzle 42 in a different plane). By introducing the heat-upable liquid along a direction that intersects the axial direction of the discharge nozzle 42 in this way, the introduced heat-upable liquid is encouraged to swirl along the inner circumferential wall surface 4d and move toward the discharge port 4a.

[0131] Another example of a swirling configuration is when a fluid inlet (for example, a fluid inlet 4h in Figures 14 and 15 described later) is provided on the inner circumferential wall surface 4d of the discharge nozzle 42 for introducing a heat-up liquid (introduced from the outer circumferential side of the discharge nozzle 42 to the inner circumferential wall surface 4d side of the discharge nozzle 42), and the fluid inlet is shaped to open toward one or the other side in the circumferential direction of the inner circumferential wall surface 4d.

[0132] With a discharge nozzle 42 having such a fluid inlet, the heat-up liquid introduced from the fluid inlet is encouraged to swirl in the direction of the opening of the fluid inlet within the circumferential direction of the inner circumferential wall surface 4d, and moves toward the discharge port 4a.

[0133] Furthermore, multiple fluid inlets may be provided on the inner circumferential wall surface 4d of the discharge nozzle 42, and they can be applied selectively as appropriate. For example, both a fluid inlet opening toward one side in the circumferential direction of the inner circumferential wall surface 4d (hereinafter simply referred to as a one-sided fluid inlet) and a fluid inlet opening toward the other side in the circumferential direction (hereinafter simply referred to as a other-sided fluid inlet) can be provided. By selectively applying either of these one-sided or other-sided fluid inlets, the direction in which the heating-capable liquid is promoted can be appropriately set.

[0134] Another example of a swirling configuration is to provide a helical groove (for example, a groove like the rifling of a gun barrel; not shown) on the inner circumferential wall surface 4d of the discharge nozzle 42, extending in an S-winding direction or a Z-winding direction with respect to the axial direction of the discharge nozzle 42 (up and down direction as shown in Figures 11 and 12). With a discharge nozzle 42 having such a helical groove, the heat-raising liquid introduced into the discharge nozzle 42 is encouraged to swirl along the helical groove as it moves toward the discharge port 4a.

[0135] The specific examples of the spiral configurations described above may be combined and applied as appropriate, potentially yielding desired synergistic effects. For example, when a spiral groove is provided on the inner circumferential wall surface 4d, a heat-upable liquid can be introduced from the outer circumferential side of the discharge nozzle 42 to the inner circumferential wall surface 4d of the discharge nozzle 42, along the direction of extension of the spiral groove. Furthermore, when a fluid inlet and a spiral groove are provided together on the inner circumferential wall surface 4d, the fluid inlet can be shaped to open toward the direction of extension of the spiral groove.

[0136] As in this embodiment 7, the discharge configuration using a nozzle unit U3 with a swirling configuration provides the same effects as in embodiment 6, and also offers the following advantages. Specifically, the ozonated water and the heat-sensitive liquid discharged from the discharge ports 3a and 4a, respectively, and reaching the discharged side S1 (for example, the coating layer S1a), flow in a dispersed manner along the surface of the discharged side S1 from the point of arrival. However, a swirling flow is more likely to occur in the case of the heat-sensitive liquid.

[0137] In other words, the ozonated water and the heat-generating liquid intersect at the discharge side surface S1 with different velocity vectors. This makes it easier for region R3, where regions R1 and R2 overlap, to form, and for this region R3 to expand further. Furthermore, turbulence is more likely to occur in region R3.

[0138] Therefore, when the ozonated water and heat-up liquid discharged from the discharge nozzles 32 and 42 are supplied to the discharge side S1 of the object to be supplied, they may be more easily mixed, and the oxidizing power of the ozonated water may be more easily exerted more broadly and evenly.

[0139] Furthermore, in the region R3 where turbulence occurs, the shear stress on the surface of the discharged side S1 tends to increase. Therefore, if the purpose is to clean the object S being supplied, for example, an improvement in the cleaning effect can be expected.

[0140] In the rotation process in which the object to be supplied S is rotated by the support part 6, if the object to be supplied S is rotated in the same direction as the swirling flow of the heat-generating liquid, it is conceivable that centrifugal force due to the rotation will be more easily generated in the heat-generating liquid, and regions R2 and R3 will be more easily expanded.

[0141] On the other hand, if the object to be supplied S is rotated in the opposite direction to the swirling flow of the heat-up liquid, the relative velocity of the heat-up liquid on the surface of the discharge side S1 increases, turbulence in region R3 is more likely to occur, and the shear stress on the surface of the discharge side S1 is more likely to increase.

[0142] Furthermore, in the case where both a one-sided fluid inlet and a other-sided fluid inlet are provided on the inner circumferential wall surface 4d of the discharge nozzle 42, the rotation direction of the object to be supplied S and the swirling flow of the heat-generating liquid can be set to be in the same direction or opposite directions by selectively applying the two inlets, without having to switch the rotation direction of the object to be supplied S by the support part 6.

[0143] <Example 8> This embodiment 8 describes another example of design modification in a discharge configuration using the nozzle unit U3.

[0144] In the case of a discharge configuration using a nozzle unit U3 having a swirling configuration as in Example 7, the heat-enhancing liquid flowing through the discharge nozzle 42 while swirling tends to be subjected to a centrifugal force acting radially outward on the discharge nozzle 42 due to the swirling flow. In this case, the heat-enhancing liquid inside the discharge nozzle 42 tends to flow away from the outer peripheral wall surface 3c of the discharge nozzle 32, and a gap (hereinafter simply referred to as the nozzle internal gap) is easily formed between it and the outer peripheral wall surface 3c.

[0145] The shape and ease of formation of the void inside the nozzle vary depending on the flow rate and swirling angle of the heat-generating liquid inside the discharge nozzle 42, but for example, introducing gas into the discharge nozzle 42 may make it easier for the void inside the nozzle to form.

[0146] One example of a configuration that facilitates the formation of a void within the nozzle (hereinafter simply referred to as a void-forming configuration) is to provide the discharge nozzle 42 with a gas introduction section (for example, a gas introduction section 4i in Figures 14 and 15 described later) that introduces gas into the discharge nozzle 42 (introducing it from the outer circumference side of the discharge nozzle 42 to the inner circumferential wall surface 4d side of the discharge nozzle 42).

[0147] The gas introduced from the gas inlet should be one that does not affect the object S to be supplied (e.g., contamination) or the ozonated water or the heat-generating liquid (e.g., effects due to chemical reactions). Examples include using an inert gas (e.g., nitrogen gas, carbon dioxide gas) or outside air.

[0148] Furthermore, the gas introduction section can be configured in a way that allows gas to be introduced into the discharge nozzle 42. One example is a configuration in which it opens into the inner circumferential wall surface 4d of the discharge nozzle 42. In addition, if a fluid inlet is provided on the inner circumferential wall surface 4d of the discharge nozzle 42, the fluid inlet and the gas introduction section may be integrated into a single configuration.

[0149] For example, by providing a gas-liquid mixer (similar to the gas-liquid mixer 21, for example) that integrates a fluid inlet and a gas inlet in the discharge nozzle 42, the gas can be dissolved in a heat-sensitive liquid and introduced into the discharge nozzle 42 together with the heat-sensitive liquid (introduced in a gas-liquid two-phase flow state).

[0150] Furthermore, if it is desirable to avoid contact of air bubbles with the target object S as much as possible, it is preferable to provide a separate fluid inlet and gas inlet to suppress the dissolution of gas into the heat-generating liquid.

[0151] Another example of a void-forming configuration is to give the outer peripheral wall surface 3c of the discharge nozzle 32 a water-repellent finish. This water-repellent finish only needs to be applied in a way that does not affect the object S being supplied, or the ozonated water or the heat-reducing liquid. For example, a fine uneven structure (for example, a structure with protrusions of a few μm) can be formed on the outer peripheral wall surface 3c to produce a lotus effect (the so-called lotus leaf effect).

[0152] As in this embodiment 8, the discharge configuration using a nozzle unit U3 having a void-forming structure provides the same effects as in embodiments 6 and 7, in addition to the following: The heat-enhancing liquid introduced into the discharge nozzle 42 can be circulated so as to move away from the outer peripheral wall surface 3c of the discharge nozzle 32. This makes it easier to form a void inside the nozzle between the heat-enhancing liquid and the outer peripheral wall surface 3c, and makes it easier to suppress the transfer of heat from the heat-enhancing liquid circulating inside the discharge nozzle 42 to the ozonated water circulating inside the discharge nozzle 32.

[0153] Furthermore, when a gas is dissolved in a heat-adjustable liquid, resulting in a gas-liquid two-phase flow state, turbulence in region R3 becomes more likely to occur, and the shear stress on the discharge side surface S1 becomes more likely to increase.

[0154] <Example 9> Figures 14 and 15 show Example 9, illustrating an example of a discharge configuration using a nozzle unit U4 that facilitates the formation of the swirling configuration of Example 7 and the gap-forming configuration of Example 8.

[0155] In the nozzle unit U4 shown in Figures 14 and 15, the inner circumferential wall surface 4d of the discharge nozzle 42 has a tapered surface 4g on the discharge port 4a side, which narrows in diameter as it approaches the discharge port 4a. In the case of the discharge nozzle 42 shown in Figures 14 and 15, a fluid inlet 4h and a gas inlet 4i are provided separately on the tapered surface 4g.

[0156] In the discharge configuration using the nozzle unit U4 of this embodiment 9, in addition to achieving the same effects as in embodiments 6 to 8, the following can be said. That is, the heat-upable liquid introduced into the discharge nozzle 42 becomes easier to swirl along the tapered surface 4g, and this swirling flow tends to make it easier for centrifugal force to act radially outward on the discharge nozzle 42.

[0157] In this case, the heat-enhancing liquid in the discharge nozzle 42 tends to flow away from the outer peripheral wall surface 3c of the discharge nozzle 32. Then, as shown in Figure 15, for example, it moves towards the discharge port 4a while swirling to form a fluid layer 4j along the tapered surface 4g and is discharged. This makes it easier for an internal void to form between the heat-enhancing liquid (fluid layer 4j) and the outer peripheral wall surface 3c.

[0158] Here, if the dimensional difference t1 between the radial dimension of the discharge port 3a and the radial dimension of the discharge port 4a is greater than the layer thickness t2 near the discharge port 4a in the fluid layer 4j, a gap will be formed between the fluid layer 4j and the discharge port 3a (the gap indicated by the reference numeral 4k in Figure 15).

[0159] If such a gap is formed, the gas in the void inside the nozzle will be discharged from the discharge port 4a together with the heat-generating liquid (discharged in a gas-liquid two-phase flow state). Therefore, if it is desirable to avoid contact of gas bubbles with the target object S as much as possible, it is preferable to increase the flow rate of the heat-generating liquid introduced into the discharge nozzle 42, for example, and set it appropriately so that the layer thickness t2 is greater than the dimensional difference t1.

[0160] In this case, the fluid layer 4j comes into contact with the vicinity of the discharge port 4a of the discharge nozzle 32, but the contact area is extremely small. That is, the amount of heat transferred from the fluid layer 4j (heat-boosting liquid) to the ozonated water flowing inside the discharge nozzle 32 is extremely small, and the temperature of the ozonated water can be sufficiently suppressed to prevent it from rising.

[0161] <<Verification Example 1>> In this Verification Example 1, the oxidizing power of ozonated water on the target object S was verified by applying the discharge configuration of Example 1 (hereinafter simply referred to as the Example 1 discharge configuration) in the apparatus 1. As for the verification conditions, a 20 mm x 20 mm rectangular chip obtained by cutting a commercially available semiconductor wafer was used as the target object S. The rectangular chip had a 2 μm thick coating layer S1a made of novolac resin-based photoresist formed on one end in the thickness direction (post-baked) and was then supported on the support base 61 of the support unit 6 (not rotated). In the ozonated water generation unit 2, ozonated water with an ozone concentration of approximately 300 ppm was produced by receiving ozone gas (ozone concentration 90 vol%, ozone partial pressure 10 kPa (abs)) generated by an ozone gas generator (product name Pure Ozone Generator) manufactured by Meidensha, and no concentration adjustment gas was added.

[0162] The discharge nozzle 32 was set so that the discharge direction of the ozonated water is located in the center of the coating layer S1a and the ozonated water discharge angle is approximately 90°. The discharge nozzle 42 was set so that the discharge direction of the heat-enhancing liquid is located on one diagonal side of the coating layer S1a (positioned so that the heat-enhancing liquid after discharge flows from one diagonal side to the other side of the coating layer S1a) and the heat-enhancing liquid discharge angle is approximately 10°.

[0163] Then, for the coating layer S1a of the rectangular tip, first, a heat-enhancing liquid with a temperature of 80°C was discharged from the discharge nozzle 42 at a flow rate of 300 cc / min. After 30 seconds, ozonated water with a temperature of 4°C was discharged from the discharge nozzle 32 at a flow rate of 300 cc / min, and the surface state of the coating layer S1a was observed. As a result, it was observed that within one minute of the start of ozonated water discharge (for example, after several tens of seconds), the central part of the coating layer S1a (for example, the area around region R3 as shown in Figure 4) began to peel off and was removed, and the removal rate was observed to be 3.5 μm / min.

[0164] On the other hand, in the comparative example discharge configuration (hereinafter simply referred to as the comparative example discharge configuration), ozonated water at a temperature of 80°C was discharged from the discharge nozzle 32 at a flow rate of 300 cc / min onto the coating layer S1a of the rectangular tip, and the surface condition of the coating layer S1a was observed. A few minutes after the start of ozonated water discharge, the central part of the coating layer S1a began to peel off and was removed, with a removal rate of 0.7 μm / min.

[0165] Therefore, based on the observation results of the discharge configuration in Example 1 and the comparative example discharge configuration, the following can be said. First, the ozonated water in the comparative example discharge configuration was at a high temperature (80°C) before discharge, and it can be seen that the ozone concentration had already decreased (e.g., halved) by the time of discharge, which resulted in a lower removal rate.

[0166] On the other hand, in the discharge configuration of Example 1, the ozonated water is diluted by mixing with the heat-enhancing liquid in the coating layer S1a, and the ozone concentration is reduced, similar to the ozonated water in the comparative example discharge configuration. Therefore, from the viewpoint of ozonated water concentration, it could be expected that the removal rate would be similar to that of the ozonated water in the comparative example discharge configuration. However, the actual observation results showed a good removal rate. This suggests that in the case of the ozonated water in the discharge configuration of Example 1, the heat of the heat-enhancing liquid is absorbed in the coating layer S1a to raise the temperature (for example, to about 50°C), and the reaction rate constant increases due to the generation of OH radicals. In other words, it was confirmed that the ozonated water in the discharge configuration of Example 1 obtains a sufficient amount of accelerated oxidation effect due to OH radicals in the coating layer S1a, thereby exhibiting high oxidizing power.

[0167] ≪Verification Example 2≫ In this Verification Example 2, first, a KrF laser photoresist is applied to one end of the rectangular chip used in Verification Example 1 in the thickness direction to form a coating layer S1a with a thickness of 0.5 μm. Then, ion species (phosphorus) are implanted into the surface of the coating layer S1a (acceleration voltage 150 kV, implantation volume 5 × 10⁻¹⁰). 14 pieces / cm 2 A hardened layer was formed on the surface side of the coating layer S1a by ion implantation.

[0168] Then, under the same verification conditions as in Verification Example 1, a heat-enhancing liquid with a temperature of 80°C was first discharged from the discharge nozzle 42 at a flow rate of 300 cc / min onto the coating layer S1a (hardened layer side) of the rectangular tip. After 30 seconds, ozonated water with a temperature of 4°C was discharged from the discharge nozzle 32 at a flow rate of 300 cc / min, and the surface state of the coating layer S1a was observed. As a result, similar to Verification Example 1, within 1 minute of the start of ozonated water discharge (for example, after several tens of seconds), the central part of the coating layer S1a (for example, the area around region R3 as shown in Figure 4) began to peel off and was removed, with a removal rate of 0.5 μm / min.

[0169] Similarly, using the comparative example discharge configuration, ozonated water at a temperature of 80°C was simply discharged from the discharge nozzle 32 at a flow rate of 300cc / min onto the coating layer S1a of the rectangular tip, and the surface condition of the coating layer S1a was observed. Even after several minutes (10 minutes) had elapsed since the start of ozonated water discharge, no peeling of the coating layer S1a occurred.

[0170] Therefore, it was confirmed that, with the ozonated water in the discharge configuration of Example 1, even if a hardened layer is formed on the surface side of the coating layer S1a, a sufficient amount of OH radicals promote oxidation effect can be obtained in the coating layer S1a, and high oxidizing power can be exhibited.

[0171] Although the present invention has been described in detail only with respect to the specific examples described above, it will be obvious to those skilled in the art that a wide variety of modifications are possible within the scope of the technical concept of the present invention, and it is natural that such modifications fall within the scope of the claims.

[0172] For example, the elements in Examples 1 to 9 may be combined as appropriate, and the design can also be modified by applying the contents disclosed in prior art documents as appropriate, making it possible to achieve the same effects as in Examples 1 to 9.

[0173] Furthermore, in the case of the object to be supplied S shown in Figures 3, 5, and 8, it is supported in a position extending horizontally within the container 5, but it is not limited to this, and it may be supported in various positions. For example, the object to be supplied S may be supported in a position extending vertically within the container 5. In this case, the device 1 may be appropriately redesigned so that the discharge direction of the discharge nozzles 32 and 42 and the discharge direction of the shower heads H, Ha, and Hb are horizontal (i.e., the discharged side S1 is positioned in the respective discharge direction of the ozonated water and the heat-upable liquid). [Explanation of Symbols]

[0174] 1…Ozone water supply device 2…Ozone water generation unit 21... Gas-liquid mixer 3…Ozone water supply unit 30,40...Discharge part 32, 42… Discharge nozzles (1st discharge nozzle, 2nd discharge nozzle) 3a, 4a...Discharge port (1st discharge port, 2nd discharge port) 33,43…Discharge port 4…Miscible liquid supply section 4h... Fluid inlet 4i...Gas inlet 5…Container 6...Support part U1~U4...Nozzle Unit H, Ha, Hb... shower head H1, H11, H12... Shower head supply surface S…Object to be supplied S1...Discharged side part S1a, S1b...covering layer R1~R3…area

Claims

1. A tubular first discharge nozzle having a first discharge port for discharging a first fluid toward an object to be supplied, A tubular second discharge nozzle having a larger diameter than the first discharge nozzle, having a second discharge port for discharging the second fluid toward the object to be supplied, Equipped with, With the first and second discharge ports facing the object to be supplied, the second discharge nozzle is coaxially positioned on the outer circumference of the first discharge nozzle, thereby integrating the first and second discharge nozzles into a double-pipe structure. A fluid supply structure characterized in that the opening end surface of the first discharge port and the opening end surface of the second discharge port are flush with each other.

2. The fluid supply structure according to claim 1, characterized in that the heat-increasing liquid is introduced to the second discharge nozzle from the outer circumference side to the inner circumferential wall side of the second discharge nozzle along a direction intersecting the axial direction of the second discharge nozzle.

3. The fluid supply structure according to claim 1, characterized in that the inner circumferential wall surface of the second discharge nozzle is provided with a helical groove extending in the S-winding direction or the Z-winding direction with respect to the axial direction of the second discharge nozzle.

4. The inner circumferential wall surface of the second discharge nozzle is provided with a second fluid inlet for introducing the second fluid from the outer circumferential side of the second discharge nozzle to the inner circumferential wall surface side of the second discharge nozzle. The fluid supply structure according to claim 1, characterized in that the second fluid inlet is shaped to open toward one or the other side in the circumferential direction of the inner circumferential wall surface of the second discharge nozzle.

5. The inner circumferential wall surface of the second discharge nozzle has a tapered shape that narrows as it approaches the second discharge port. The fluid supply structure according to claim 4, characterized in that the second fluid inlet is located on the tapered surface.

6. The fluid supply structure according to any one of claims 1 to 5, characterized in that the second discharge nozzle is provided with a gas introduction section for introducing gas from the outer circumference side of the second discharge nozzle to the inner circumferential wall surface side of the second discharge nozzle.

7. The fluid supply structure according to any one of claims 1 to 5, characterized in that the outer peripheral wall surface of the first discharge nozzle is treated with a water-repellent coating.

8. The system further includes a support portion that rotatably supports the object to be supplied, The fluid supply structure according to any one of claims 1 to 5, characterized in that the support portion rotates the object to be supplied in a direction opposite to the swirling flow direction of the second fluid flowing through the second discharge nozzle.

9. A tubular first discharge nozzle having a first discharge port for discharging a first fluid toward an object to be supplied, A tubular second discharge nozzle having a second discharge port for discharging the second fluid toward the object to be supplied, Equipped with, The first discharge port and the second discharge port are positioned facing the object to be supplied, and the first discharge nozzle and the second discharge nozzle are bundled together and integrated. A fluid supply structure characterized in that the opening end surface of the first discharge port and the opening end surface of the second discharge port are flush with each other.

10. The fluid supply structure according to claim 9, characterized in that a plurality of the second discharge nozzles are arranged in a circumferential direction with respect to the outer peripheral wall surface of the first discharge nozzle.

11. The fluid supply structure according to any one of claims 1 to 5 and 10, characterized in that the inner circumferential wall surface of the first discharge nozzle on the side of the first discharge port has a tapered shape that narrows in diameter as it approaches the first discharge port.

12. The fluid supply structure according to any one of claims 1 to 5 and 10, characterized in that the first fluid is ozonated water and the second fluid is a miscible liquid that is miscible with the ozonated water.

13. The fluid supply structure according to claim 12, characterized in that the first discharge nozzle is made of a material containing a fluororesin.

14. The fluid supply structure according to claim 12, characterized in that a hollow portion is provided between the inner circumferential wall surface and the outer circumferential wall surface of the first discharge nozzle, and the hollow portion is in a vacuum state.

15. An ozone water generating unit that receives ozone gas and a solvent capable of dissolving the ozone gas into a gas-liquid mixer to generate ozonated water, An ozone water supply unit that discharges the ozone water through the first discharge nozzle, A miscible liquid supply unit that dispenses a miscible liquid having miscibility with the ozonated water through the second discharge nozzle, Equipped with, The gas-liquid mixer includes a solvent flow passage through which the solvent flows, An ozone gas introduction path is provided connected to the solvent flow path and introduces the ozone gas into the solvent flow path, It is equipped to receive the ozone gas at an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less. The aforementioned miscible liquid supply unit is The miscible liquid can be discharged at a higher temperature than the ozonated water discharged from the ozonated water supply unit. The fluid supply structure according to claim 12, characterized in that the ozone water supply unit and the miscible liquid supply unit discharge both the ozone water and the miscible liquid together or alternately, and the two can be mixed with the object to be supplied.

16. The fluid supply structure according to claim 15, characterized in that the miscible liquid supply unit discharges the miscible liquid at a temperature of 40°C or higher.

17. The fluid supply structure according to claim 15, further comprising a support portion for rotatably supporting the object to be supplied.

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