JP2006013143A - Apparatus and method for wet treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wet treatment apparatus and a wet treatment method for inexpensively and efficiently removing an organic thin film and contaminants on the surface of a substrate from the substrate without electrically destroying the substrate, and by reducing a burden exerted on the environment. <P>SOLUTION: The wet treatment device generates a solvent 18 containing radicals by applying voltage to a positive electrode and a negative electrode arranged in the solvent under the presence of a catalyst 25 for increasing the ionic product of the solvent, and separates and cleans the organic thin film and contaminants on the surface of the substrate 10 by bringing a solvent 18 containing the radicals into contact with the substrate 10. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wet processing apparatus and a wet processing method for removing organic thin films and contaminants from a substrate.

  In a lithography process in a semiconductor and liquid crystal substrate manufacturing process, an organic thin film such as an organic resist film is generally used as a patterning mask. The organic thin film and the contaminants derived from the organic matter constituting the organic thin film must be peeled off when the semiconductor patterning is completed. As a method for removing the organic thin film, a removal method using a mixed solution of sulfuric acid and hydrogen peroxide (Sulfuric-Acid Hydrogen-Peroxide Mixture, hereinafter referred to as SPM) heated to 100 ° C. or higher, or using an organic solvent. There is a way to handle it.

  However, in these methods, the cost of chemicals such as SPM and organic solvent to be used, the cost of processing equipment for waste liquid containing acids and organic substances, the cost of processing equipment for by-products such as organic volatile components and acid gas generated in the processing equipment, There are costs for operating the processing equipment, and costs for treating the waste liquid generated secondary by the treatment of the waste liquid and by-products. In recent years, mother substrates such as semiconductor wafers and liquid crystal panels have been increased in size, and large substrates with one side exceeding 1 m are used. Therefore, the generation amount of chemicals and waste liquids used in the organic thin film peeling process is small. Increasingly, the environmental load associated with this is becoming a problem.

  In order to reduce the environmental load, instead of these methods, an organic thin film peeling method using an oxidative decomposition action of an organic substance by a hydroxyl radical has been studied. As a method for generating a hydroxyl radical, a method of irradiating ultraviolet light to ozone water, a method of irradiating hydrogen peroxide water to ultraviolet light, a method of applying ultrasonic waves to pure water, etc. are generally used. It is used for decomposing organic substances in sewage and cleaning substrates. However, the hydroxyl radicals produced by these methods are at low concentrations.

  A typical conventional technique for solving this problem is described in Patent Document 1. In Patent Document 1, an anode that is a workpiece and a cathode that is opposed to the anode at a predetermined interval are disposed in ultrapure water, and the anode that is the workpiece and the cathode are disposed between the anode and the cathode. By disposing ultra-pure water dissociation and having a water-permeable catalyst member, and applying a voltage between the anode and cathode, which are workpieces, to form a flow of ultra-pure water in the catalyst member , By decomposing water molecules in ultrapure water into hydrogen ions and hydroxide ions, and supplying the generated hydroxide ions to the surface of the workpiece, by chemical elution reaction or oxidation reaction with hydroxide ions It is described that the workpiece removal processing or oxide film formation processing is performed. In this method, an anode that is a workpiece and an opposing cathode are immersed in ultrapure water via a water-permeable catalyst, and a voltage is applied between the workpiece and the cathode to Decomposes water molecules into hydrogen ions and hydroxide ions. At this time, the catalyst promotes dissociation of ultrapure water. With this method, studies are being made on cleaning treatment of metals such as silicon, iron, and aluminum, and semiconductor manufacturing.

JP 2001-64799 A

  In Patent Document 1, the generated hydroxide ions supply electrons to the surface of the workpiece, which is an electrode, and the hydroxide ions change into hydroxyl radicals. Therefore, compared with the method using ozone etc., the hydroxyl radical of high concentration 5-10 times is produced | generated.

  However, in the technique described in Patent Document 1, since one side of the electrode, which is a hydroxide ion generating means, is an object to be processed, it is useful when the object to be cleaned is a metal. When this technique is used for a panel, there is a problem that an object to be processed is electrically destroyed.

  Also, in the manufacturing process of semiconductors and liquid crystal panels, the substrate is not necessarily a conductor or semiconductor, and the organic resist film formed on the substrate and the deposits derived from the organic resist film are usually insulators. It was difficult to apply the technique described in 1.

  An object of the present invention is to provide a wet processing apparatus and a wet processing method capable of removing an organic thin film, contaminants, and the like from a substrate without electrically destroying the substrate.

  In the course of research for solving the above problems, the present inventor applied a voltage to an electrode pair including an anode electrode and a cathode electrode in the presence of a catalyst that increases the ionic product of the solvent, The present invention was completed by finding that a solvent containing a high concentration of radicals can be generated without being electrically destroyed.

The present invention is a wet processing apparatus for stripping and cleaning an organic thin film and contaminants on the surface of an object to be processed using a solvent containing radicals,
A radical solvent that includes an electrode pair including an anode electrode and a cathode electrode, and an ion product increasing unit that is disposed between the electrode pair and the object to be processed and increases an ion product of the solvent, and generates a solvent containing radicals. Generating means;
It is a wet processing apparatus characterized by including a radical solvent flow means for flowing a solvent containing the radical.

  According to the present invention, in the presence of the means for increasing the ion product, a voltage is applied to the electrode pair to generate a solvent containing a high concentration radical, and the solvent containing the high concentration radical is made to flow by the radical solvent flow means. Thus, the organic thin film and the contaminants on the surface of the object to be processed can be removed by bringing the object into contact with the object to be processed without electrically destroying the object to be processed.

In the present invention, the solvent is pure water,
The radical is a hydroxyl radical.

  According to the present invention, by using pure water as a solvent, a hydroxyl radical is generated, and the organic thin film and the pollutant derived from the organic matter are decomposed into carbon dioxide and water by the hydroxyl radical, thereby realizing a clean environment. be able to. Therefore, it is suitable in fields requiring precision cleaning such as liquid crystal panels and semiconductor manufacturing processes. Also, costs for chemicals such as SPM and organic solvents, costs for treatment of waste liquids containing acids and organic substances, costs for treatment of by-products such as organic volatile components and acid gases generated in the treatment equipment, and operation of these treatment facilities It is possible to suppress the cost of the waste liquid and the expense for treating the waste liquid generated secondary by the treatment of the waste liquid and the by-products.

  In the present invention, the radical solvent flow means causes the solvent containing radicals to flow in the vicinity of the electrode in a fluid state capable of giving the contaminant a peeling force exceeding the adhesion force of the contaminant attached to the object to be processed. It is characterized by that.

  According to the present invention, the solvent in which radicals have not disappeared is allowed to flow in the vicinity of the electrode pair in a state having a peeling force that exceeds the adhesion force of contaminants attached to the object to be processed, so that the solvent adheres to the object to be processed. Contaminants can be removed more effectively.

The present invention provides the ion product increasing means,
It is a nonwoven fabric having ion exchange capacity.

  According to the present invention, the ion exchange resin has a high ion product increasing effect, and the contact area between the solvent and the catalyst is increased by using a non-woven fabric including the ion exchange resin, so that a higher ion product increasing effect can be obtained. Can do.

The present invention includes a step of applying a voltage to an anode electrode and a cathode electrode disposed in a solvent in the presence of a catalyst means for increasing the ionic product of the solvent to generate a solvent containing radicals;
And a step of bringing the solvent containing radicals into contact with an object to be processed.

  According to the present invention, since the anode electrode and the cathode electrode are arranged in the solvent, a solvent containing radicals can be generated without electrically destroying the object to be processed. Furthermore, the presence of a catalyst that increases the ionic product of the solvent makes it possible to produce a solvent containing a high concentration of radicals. Then, by bringing a solvent containing a high concentration of radicals into contact with the object to be processed, the organic thin film such as an organic resist film on the surface of the object to be processed and contaminants derived from the organic substance are peeled and removed without destroying the substrate. Can do.

  According to the present invention, an organic thin film such as an organic resist film on the surface of an object to be processed and an organic material can be obtained by bringing a solvent containing a high concentration of radicals into contact with the object to be processed without electrically destroying the object to be processed. The originating contaminant can be peeled off. A radical solvent generating means for generating a solvent containing radicals, comprising an electrode pair including an anode electrode and a cathode electrode and an ion product increasing means for increasing the ion product of the solvent; and a radical solvent flow for flowing the radical solvent. And a wet processing apparatus capable of realizing the above-described wet processing method is provided by arranging the ion product increasing means between the electrode pair and the object to be processed.

  According to the present invention, a clean environment can be realized. Therefore, it is suitable in fields requiring precision cleaning such as liquid crystal panels and semiconductor manufacturing processes. In addition, it is possible to reduce the cost of processing chemicals and waste liquids required for peeling and removing.

According to the present invention, it is possible to effectively remove organic-derived contaminants adhering to an object to be processed.
According to the present invention, a high ion product increasing effect can be obtained.

  According to the present invention, by bringing a solvent containing a high concentration of radicals into contact with an object to be processed, organic thin films such as an organic resist film on the surface of the object to be processed and pollutants derived from organic substances can be obtained without destroying the substrate. It can be peeled off.

  FIG. 1 is a cross-sectional view schematically showing the entire configuration of a wet processing apparatus 1 according to an embodiment of the present invention.

  A wet processing apparatus 1 according to an embodiment of the present invention includes a radical solvent generating unit that generates a solvent containing radicals, including an ion product increasing unit that increases an ion product of an electrode pair including a positive electrode and a negative electrode and a solvent. And a radical solvent flow means for flowing a solvent containing radicals. The ion product increasing means is disposed between the electrode pair and the object to be processed.

  As an object to be processed by the wet process, for example, a wet process can be preferably performed on a semiconductor substrate such as a silicon wafer and a substrate 10 such as a liquid crystal substrate.

  Although it does not specifically limit as a solvent, For example, a pure water, hydrogen peroxide solution, etc. can be used preferably. If pure water is used as a solvent, environmental treatment is reduced because no special treatment is required for wastewater and exhaust, compared to conventional methods using SPM and organic solvents, as well as methods using ozone. This is preferable because the cost required for processing costs can be reduced. In addition, pure water containing inevitable impurities may be used as the pure water. However, if there are many ionic species in the pure water, the deterioration of the ion product increasing catalyst 25 is accelerated, so that ultrapure water is used from the viewpoint of maintainability. Further preferred.

  FIG. 2 is a cross-sectional view schematically showing a configuration in the vicinity of the electrolytic radical generating head 27, the catalyst 25, and the substrate 10 in the wet processing apparatus 1 according to the embodiment of the present invention. An electrolytic radical generation head 27 is configured by arranging a plurality of radical generation anodes 21 which are anode electrodes for generating radicals and radical generation cathodes 22 which are cathode electrodes with an insulating layer 26 spaced from each other. The electrolytic radical generating head 27 is disposed opposite to the substrate 10 as the object to be processed, and the catalyst 25 is provided with a function of increasing the ion product of pure water in the gap formed by the electrolytic radical generating head 27 and the substrate 10. Place.

  Pure water is supplied into the gap, and a voltage is applied to the radical generating anode 21 and the radical generating cathode 22 by the power supply device 19 to generate radicals. The generated radicals react with the organic substance to be cleaned 24 such as an organic resist film formed on the base material 23 in the vicinity of the electrode, and decompose and wash and remove the organic substance to be cleaned 24.

  The radical solvent generating means is a means for generating a solvent containing radicals, for example, an electrolytic radical generating head 27 configured to include an electrode pair including an anode electrode 21 and a cathode electrode 22, and an ion product of the solvent. It can comprise by including the ion product increase catalyst 25 which increases.

  FIG. 3 is a front view schematically showing the configuration of the electrolytic radical generating head 27. In this electrolytic radical generating head 27, an electrolytic radical generating anode 21 which is an anode electrode and an electrolytic radical generating cathode 22 which is a cathode electrode are used as a pair of electrodes, and the electrode pairs are uniformly distributed with a constant interval. It is configured to include. The arrangement of the electrolytic radical generating anode 21 and the electrolytic radical generating cathode 21 is not particularly limited, but it is preferable that the electrolytic radical generating anode 21 and the electrolytic radical generating cathode 22 are alternately arranged on the lattice points. Further, the shapes of the electrolytic radical generating anode 21 and the electrolytic radical generating cathode 22 are not particularly limited, and examples thereof include a circle, an ellipse, a rectangle such as a square, and a rectangle.

  The material constituting the radical generating anode 21 and the radical generating cathode 22 is not particularly limited, but preferably has a high electrical conductivity, is hardly subject to modification by the hydroxyl radical 17 and is electrochemically stable, such as glassy carbon. Carbon materials such as gold, platinum, nickel and palladium can be used. Among these, platinum, nickel, palladium, and the like can be more preferably used because the production efficiency of the hydroxyl radical 17 can be improved by the catalytic effect thereof.

  The material other than the electrode of the electrolytic radical generating head 27 is preferably formed of a material that is not oxidized and deteriorated by the hydroxyl radical 17. Examples of such materials that are not oxidized and deteriorated by the hydroxyl radical 17 include polytetrafluoroethylene (PTFE), polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ) And other Teflon (registered trademark) resins.

  The ion product increasing means increases the ion product of the solvent and is not particularly limited. For example, a non-woven fabric having ion exchange ability can be preferably used. Although it does not specifically limit as a material which has ion exchange ability, For example, ion exchange resin, such as an ion exchange membrane which has a strong acidic cation exchange group, has a high ion product increase effect, and is preferable. When a non-woven fabric is formed using an ion exchange resin, the contact area between pure water and the ion exchange resin is increased, and a high ion product increasing effect can be obtained.

  As for the arrangement of the ion product increasing means, it is preferable to arrange an ion product increasing catalyst 25 as an ion product increasing means between the electrolytic radical generating head 27 and the substrate 10. More preferably, the ion product increasing catalyst 25 and the electrolytic radical generating head 27 are arranged in the vicinity of the substrate 10. The method for fixing the ion product increasing catalyst 25 is not particularly limited. For example, the ion product increasing catalyst 25 is fixed to the surface of the electrolytic radical generating head 27 and rotated accompanying the electrolytic radical generating head 27. In addition, it is preferable that the ion product increasing catalyst 25 is fixed to another member and fixed without being attached to the electrolytic radical generating head 27. The intervals between the electrolytic radical generating head 27, the ion product increasing catalyst 25, and the substrate 10 are preferably reduced because the hydroxyl radicals 17 disappear in a short time in water. For example, when each interval is 0.1 mm and the thickness of the ion product increasing catalyst 25 is 0.5 mm, the hydroxyl radicals 17 are well carried to the substrate, and the organic matter 24 to be cleaned such as organic thin films and organic matter-derived contaminants is removed. It can be peeled and removed efficiently.

  The radical solvent flow means is means for flowing a solvent containing radicals. For example, the substrate table 32, a substrate table rotating device that rotationally drives the substrate table 32, and a substrate holding for holding the substrate 10 on the substrate table 32. It can be preferably realized by including the means and an electrolytic radical generating head rotating device that rotationally drives the electrolytic radical generating head 27. Examples of the substrate holding means include a vacuum chuck and a mechanical chuck. The electrolytic radical generating head rotating device can be realized by including a bearing 36 and an electrolytic radical generating head rotating drive motor 37, for example. The substrate table rotating device can be realized, for example, by including a bearing 36 and a substrate table rotation drive motor 38.

  The wet treatment apparatus 1 of the present embodiment can include a solvent supply means 34 for supplying a solvent to the treatment tank 33, a waste water treatment means, and a control means.

  The control means 39 can control the solvent supply means 34 and the waste water treatment means. The control means 39 controls the solvent supply means 34 and the drainage means 35 so that pure water is always supplied and the processing liquid 18 is discarded to the drainage line. According to the control means 39, the flow rate of the processing liquid 18 can be adjusted.

  The solvent supply means 34 supplies the solvent to the processing tank 33, and can be configured by including, for example, a pure water supply line and a pure water feed pump that sends pure water to the pure water supply line. . Furthermore, the above-described configuration may include a distillation apparatus or an ion exchange apparatus for producing pure water, and a raw water supply line for supplying raw water to the distillation apparatus or the ion exchange apparatus.

  The drainage means 35 is, for example, a liquid feed pump for feeding a treatment liquid 18 containing products and residues generated by wet treatment from organic thin films such as organic resist films and pollutants derived from organic matter to a drainage line. And a drainage line.

  Further, the control means 39 can control the electrolytic radical generating head rotating device and the substrate table rotating device. By rotating at least one of the electrolytic radical generating head 27 and the substrate 10 held on the substrate table 32, the solvent containing radicals can be flowed with respect to the substrate 10. Furthermore, preferably, the electrolytic radical generating head 27 and the substrate 10 can be rotated in opposite directions to increase the flow of the solvent containing radicals.

  Although the rotation direction of the electrolytic radical generation head 27 and the rotation direction of the substrate 10 are not particularly limited, the electrolytic radical generation head 27 is shown in FIG. The substrate 10 is rotated in the direction A, and the substrate 10 is rotated by the substrate table rotating device in the direction B opposite to the direction A of rotation of the electrolytic radical generating head 27. The flow of the liquid 18 can be increased. In addition, the electrolytic radical generating head 27 may be rotated in the rotation direction opposite to the A rotation direction. In this case, rotating the substrate table 32 in the rotation direction opposite to the B rotation direction causes the flow of the processing liquid 18. It is preferable from the point of enlargement. Thus, by rotating the electrolytic radical generating head 27 and the substrate 10 to increase the flow of the treatment liquid 18 on the surface of the substrate 10, the hydroxyl radicals 17 can be quickly supplied onto the substrate 10, and further wet The effect of quickly removing products generated by the treatment, organic thin films such as an organic resist film, residues of contaminants derived from organic substances, and the like is enhanced.

  In the present embodiment, one control unit 39 controls the power supply device 19, the electrolytic radical generation head rotation drive motor 37, the substrate table rotation drive motor 38, the pure water supply unit 34, and the drainage unit 35. You may control using a control means.

  The mechanism by which the hydroxyl radical 17 is generated in the anode electrode and the cathode electrode will be described in detail with reference to FIGS.

  FIG. 4 is a cross-sectional view schematically showing a mechanism in which the hydroxyl radical 17 is generated by the radical generating cathode 22, the ion product increasing catalyst 25, and pure water.

  On the radical generation cathode 22 which is a cathode electrode, the oxygen molecules 14 contained in the treatment liquid 18 receive electrons 13 in the vicinity of the radical generation cathode 22 and change to superoxide anion radicals 15. Furthermore, a large amount of hydroxyl ions 11 and hydrogen ions 12 are generated in pure water by the effect of the ion product increasing catalyst 25 and the electric field formed by the radical generation cathode 22 and the radical generation anode 21. The superoxide anion radical 15 is reduced by the hydrogen ions 12 to generate hydrogen peroxide 16. The hydrogen peroxide 16 further receives electrons 13 from the radical generation cathode 22 to generate hydroxyl ions 11 and hydroxyl radicals 17.

  FIG. 5 is a cross-sectional view schematically showing a mechanism in which the hydroxyl radical 17 is generated by the radical generating anode 21, the ion product increasing catalyst 25, and pure water.

  A hydroxyl radical generation mechanism on the radical generation anode 21 which is an anode electrode will be described. The hydroxyl ions 11 produced in a large amount in pure water by the action of the electric field formed by the radical producing cathode 22 and the radical producing anode 21 and the ion product increasing catalyst 25 are oxidized on the radical producing anode, and the hydroxyl radical 17 is converted into the hydroxyl radical 17. Generated.

  In the wet treatment method of the present invention, in the presence of catalyst means for increasing the ionic product of a solvent, a voltage containing a radical is generated by applying a voltage to an anode electrode and a cathode electrode arranged in the solvent, and this radical is removed. In this method, the organic thin film on the surface of the object to be processed and the pollutants derived from the organic substance are peeled and cleaned by bringing the solvent to be in contact with the object to be processed.

  In the wet processing method of the present invention, an organic thin film such as an organic resist film is formed on a part of or the entire surface, and a substrate such as a semiconductor substrate and a liquid crystal substrate to which contaminants derived from organic substances constituting the organic thin film are attached. It becomes a processing target.

  FIG. 6 is a flowchart showing a wet processing method according to an embodiment of the present invention. Wet processing is started from step A0. In step A1, a voltage is applied to the anode electrode and the cathode electrode. In step A2, a solvent containing radicals is generated by the electric field and the ion product increasing catalyst. In step A3, the organic thin film and the contaminant derived from the organic substance are peeled and removed by bringing a solvent containing radicals into contact with the object to be processed. In step A4, the wet process is finished.

  According to the method of the present invention, first, in the presence of a catalyst means for increasing the ionic product of a solvent, a voltage is applied to the anode electrode and the cathode electrode arranged in the solvent to generate a solvent containing radicals.

  Specific examples of the solvent used in the method of the present invention include pure water and hydrogen peroxide solution. Since pure water is used as a solvent, it does not require special treatment for waste water and exhaust gas as compared with conventional methods using SPM and organic solvents, as well as methods using ozone. This can reduce the cost required for processing costs. As the pure water, pure water containing inevitable impurities may be used. However, if there are many ionic species, an ion exchange resin is used for the catalyst, which causes a problem of rapid deterioration. Therefore, ultrapure water is preferable from the viewpoint of maintainability.

  The temperature of the pure water is not particularly limited, but it is preferably used at 80 ° C. or lower from the viewpoint of suppressing the decrease in the lifetime of the hydroxyl radical 17. Furthermore, it is preferable to use at normal temperature from the viewpoint of cost.

  The ion product increasing means for increasing the ion product of a solvent such as pure water is not particularly limited as long as it can increase the ion product of the solvent. For example, a non-woven fabric having ion exchange capacity is preferably used. be able to. Although it does not specifically limit as a material which has ion exchange ability, For example, ion exchange resin, such as an ion exchange membrane which has a strong acidic cation exchange group, has a high ion product increase effect, and is preferable. When a non-woven fabric is formed using an ion exchange resin, the contact area between pure water and the ion exchange resin is increased, and a high ion product increasing effect can be obtained.

The concentration of the hydroxyl radical 17 effective for peeling and removing the organic thin film and contaminants depends on the applied electric field strength and current value and the flow rate of pure water between the electrode head and the substrate. For example, when the electric field strength is 1 × 10 ⁴ V / m, the current value is 20 A, and the pure water flow rate is 1 L / min, the effective concentration of the hydroxyl radical 17 is 0.01 mol / L.

  A solvent containing radicals can be generated by applying a voltage to the radical generation anode 21 that is an anode electrode and the radical generation cathode 22 that is a cathode electrode arranged in the solvent. The voltage applied to the radical generation anode 21 and the radical generation cathode 22 can be appropriately selected from a wide range, but is more preferably 0.1 V or more and 5 V or less. This is because when the voltage exceeds 5 volts, side reactions on the electrode increase.

  Next, the organic thin film on the surface of the object to be processed 10 and the contaminant derived from the organic substance are peeled and washed by bringing the solvent containing radicals into contact with the object to be processed 10.

  As a method of bringing the solvent containing radicals into contact with the object to be processed 10, for example, there is a method of bringing a solvent containing radicals into contact with the object to be processed. An organic thin film such as an organic resist film and an organic substance to be cleaned 24 are obtained by flowing a solvent containing the hydroxyl radical 17 generated at the radical generating cathode 22 and the radical generating anode 21 and bringing it into contact with the surface of the substrate 10 that is the object to be processed. Decompose and remove.

  The hydroxyl radical 17 has a high oxidation-reduction potential, and has a sufficiently high oxidizing ability to break and oxidize strong bonds such as covalent bonds between carbons in hydrocarbons that occupy most of organic thin film and organic-derived contaminants. Have. These organic substances are decomposed into water and carbon dioxide by the hydroxyl radical 17. Therefore, by bringing the hydroxyl radical 17 into flow and bringing it into contact with the surface of the substrate 10 that is the object to be processed, the organic thin film such as the organic resist film and the organic substance 24 to be cleaned are decomposed into water and carbon dioxide. The environment can be realized.

  FIG. 7 is a front view showing an electrolytic radical generating head 27 according to another embodiment. The electrolytic radical generating head 27 is configured by alternately arranging rod-shaped electrolytic radical generating anodes 21 and electrolytic radical generating cathodes 22. According to this electrode arrangement, since the width of the insulating layer 26 between the electrodes is uniform and the electrode arrangement is simple, it can be easily manufactured. The width of the electrodes and the width of the insulating layer between the electrodes are not particularly limited, but both are preferably about 0.5 mm because uniform wet processing can be performed.

  FIG. 8 is a front view showing an electrolytic radical generating head 27 according to still another embodiment. The electrolytically purified radical generating head 27 is configured by arranging an electrolytic radical generating anode 21 and an electrolytic radical generating cathode 22 symmetrically with respect to a point. The shapes of the electric field radical generating anode 21 and the electric field radical generating cathode 22 are not particularly limited. For example, it is preferable that the shape is an isosceles triangle and the adjacent electrodes are electrodes having different poles. According to this electrode arrangement, since it is point-symmetric, the same conditions can be obtained over the entire surface of the substrate 10 with respect to the flow of the processing liquid 18 and the rotation of the electric field radical generating head 27, so that uniform processing is possible. In FIG. 7, the insulating layer 26 between the electrodes is indicated by a black line between the radical generating anode electrode 21 and the radical generating negative electrode 22. Since the insulating layer 26 between the electrodes has the same width over the entire electrode surface, a uniform electric field can be formed.

It is sectional drawing which shows typically the structure of the wet processing apparatus 1 which is embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing an enlarged configuration of the vicinity of the electrolytic radical generating head 27, the catalyst 25, and the substrate 10 in the wet processing apparatus 1 according to the embodiment of the present invention. 3 is a front view schematically showing a configuration of an electrolytic radical generation head 27. FIG. It is sectional drawing which shows typically the mechanism in which the hydroxyl radical 17 generate | occur | produces with the radical production | generation cathode 22, the ion product increase catalyst 25, and a pure water. It is sectional drawing which shows typically the mechanism in which the hydroxyl radical 17 generate | occur | produces with the radical production | generation anode 21, the ion product increase catalyst 25, and a pure water. It is a flowchart which shows the wet processing method which is embodiment of this invention. It is a front view which shows the electrolytic radical production | generation head 27 of other embodiment. It is a front view which shows the electrolytic radical production | generation head 27 of other embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wet processing apparatus 10 Substrate 11 Hydroxyl ion 12 Hydrogen ion 13 Electron 14 Oxygen molecule 15 Superoxide anion radical 16 Hydrogen peroxide 17 Hydroxyl radical 18 Treatment liquid 19 Power supply device 21 Radical generation anode 22 Radical generation cathode 23 Base material 24 Resist and resist Cleaning organic matter 25 Ion product increasing catalyst 26 Insulating layer 27 Electrolytic radical generating head 31 Electrolytic radical generating head rotating shaft 32 Substrate table 33 Treatment tank 34 Pure water supply means 35 Draining means 36 Bearing 37 Electrolytic radical generating head rotation drive motor 38 Substrate table rotation Drive motor 39 Control means A Electrolytic radical generation head rotation direction B Substrate rotation direction

Claims (5)

A wet processing apparatus that peels and cleans an organic thin film and contaminants on the surface of an object to be processed using a solvent containing radicals,
A radical solvent that includes an electrode pair including an anode electrode and a cathode electrode, and an ion product increasing unit that is disposed between the electrode pair and the object to be processed and increases an ion product of the solvent, and generates a solvent containing radicals. Generating means;
A wet processing apparatus comprising: a radical solvent flowing means for causing the solvent containing radicals to flow. The solvent is pure water;
The wet processing apparatus according to claim 1, wherein the radical is a hydroxyl radical.   The radical solvent flow means causes the solvent containing radicals to flow in the vicinity of the electrode in a fluid state capable of giving the contaminant a peeling force exceeding the adhesion force of the contaminant attached to the object to be processed. The wet processing apparatus according to claim 1 or 2. The ion product increasing means includes
The wet processing apparatus according to any one of claims 1 to 3, wherein the wet processing apparatus is a nonwoven fabric having ion exchange capacity. Generating a solvent containing radicals by applying a voltage to an anode electrode and a cathode electrode disposed in the solvent in the presence of a catalyst means for increasing the ionic product of the solvent;
And a step of bringing a solvent containing radicals into contact with an object to be processed. A wet processing method for peeling and cleaning an organic thin film and a contaminant on a substrate surface.

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