JP4623307B2 - Electrolytic cell and sulfuric acid recycle type cleaning system using the electrolytic cell - Google Patents

Description

  The present invention provides an electrolytic cell that causes an electrolysis reaction by energizing while passing an electrolytic solution between a plurality of electrodes, and effectively uses an electrolytic solution containing a large amount of active ingredients obtained by the reaction; The present invention relates to a sulfuric acid recycle type cleaning system in which sulfuric acid is electrolyzed using an electrolytic cell and persulfuric acid produced is used for cleaning.

Concentrated sulfuric acid and hydrogen peroxide mixed solution (SPM) or solution in which ozone is blown into concentrated sulfuric acid in the process of peeling and cleaning resist residue, fine particles, metal and natural oxide film in wafer cleaning technology in VLSI manufacturing process (SOM) is frequently used. It has been found that persulfuric acid formed by oxidation of sulfuric acid by hydrogen peroxide or ozone is useful for cleaning. SPM requires replenishment of hydrogen peroxide water to compensate for the decrease in persulfuric acid decomposition. Since it is diluted with water in hydrogen peroxide water, it is difficult to maintain the liquid composition constant, and the liquid is discarded and renewed every predetermined time or every specified number of treatment batches. For this reason, there is a problem that a large amount of chemicals must be stored. On the other hand, the liquid does not dilute in one SOM, and the liquid renewal cycle can be generally longer than that of SPM. However, the generation efficiency of persulfuric acid by ozone is low, and the cleaning effect is slightly inferior to SPM. In these methods, the concentration of persulfuric acid produced has a limit, which has led to the limit of the cleaning effect.
The inventors of the present invention have invented a technique for continuously supplying persulfuric acid having a high cleaning effect continuously and in a large amount. That is, we developed a cleaning system that recycles sulfuric acid by continuously producing persulfuric acid by electrolytic treatment of sulfuric acid solution.

In the cleaning system, it is desirable to use a diamond electrode from the viewpoint of durability, and in order to further reduce the size of the apparatus, it is desired to use an electrolytic cell in which an electrolytic reaction apparatus for performing an electrolytic treatment is downsized. An electrolysis cell using a conductive diamond electrode has been proposed in the past (for example, Patent Document 1), and the electrodes are arranged to face each other, and an electrolysis reaction is performed by passing the electrolyte through the gap while passing through the electrode. Can be generated. Furthermore, in order to increase the electrolysis efficiency, it is desired to use an electrolysis cell using many electrode plates.
As the structure of the electrolytic cell, for example, a pair of electrode plates made of diamond or the like, which are provided with windows on a pair of opposing wall surfaces of a container and joined with a conductive paste on a contact surface with a conductive plate connected to a DC power source, are used. A plurality of electrode plates are arranged between the electrodes in multiple layers so that the distance between the electrode plates is kept by an insulating material by about 1 to 10 mm, and the electrolyte is passed between the electrodes. Possible structures are conceivable. When direct current electricity is supplied from the outer surface of the outermost electrode plate through the current supply plate, the electrode plate provided in the middle acts as a bipolar electrode.
Special table 2004-525765 gazette

Conventionally, since the flow rate was not large, such as the generation of electrolyzed water, as an application of the electrolysis apparatus, the pressure in the electrolytic cell is about 0.1 MPa at most. However, the production efficiency of the product is very important in semiconductor manufacturing, and the amount flowing into the electrolytic cell is very large, so that the pressure in the electrolytic cell can reach 0.4 MPa at the maximum. However, the conventional electrolytic cell as described above can be attached to the contact surface between the electrode plate and the current plate with a conductive paste and then attached to the electrode cell window with a sealing material sandwiched between them. Therefore, the pressure is limited by the diameter and thickness of the electrode plate, and a large pressure cannot be applied. Further, when the pressure increases due to an operation error, there is a problem that the electrode plate is easily cracked during operation.
In particular, among the diamond electrodes, the self-standing electrode that has been removed after laminating the diamond film on the substrate is weaker than the metal electrode and is not flexible and brittle. It will crack. If only the periphery of the electrode is fixed and the central part is not supported, the larger the size and the thinner the plate, the more likely it is to break.
Therefore, the conventional electrolytic cell does not have sufficient pressure resistance, and there is a possibility that the electrode may be damaged in a use state where the inflow pressure of the electrolytic solution is large. In particular, when a diamond electrode is used as an electrode, the electrode itself is expensive, so that the replacement cost when the electrode is damaged is very expensive compared to other electrodes. In addition, when a chemical substance that is dangerous in handling, such as high-concentration sulfuric acid, is used as the electrolytic solution, there is a risk that the electrolytic solution leaks due to breakage of the electrode. Above all, there is a problem that throughput due to electrode breakage is lowered.

  The present invention has been made against the background of the above circumstances, and by providing an electrolytic cell with higher pressure resistance than the conventional type, electrode breakage is prevented, electrode replacement costs are reduced, and there is a risk of electrolyte leakage. It is an object of the present invention to provide an electrolytic cell capable of avoiding and improving throughput and a sulfuric acid recycle type cleaning system using the electrolytic cell.

That is, among the electrolytic cells of the present invention, the invention according to claim 1 has a plurality of layers of conductive diamond electrodes and insulating spacers interposed between the electrodes, and is compressed and fixed from outside the electrodes at both ends. An electrode unit, and a pair of energizers respectively connected to the electrodes at both ends of the electrode unit ,
The spacer has a thickness equal to the distance between the electrodes, is parallel to each other with an interval between them, and has a plurality of electrode support portions that are connected to each other at both ends, and a plurality of the electrode support portions that penetrate between the electrode support portions in the thickness direction. An electrolyte solution passage portion, and an electrolyte solution introduction port and an electrolyte solution delivery port that are provided in the spacer and communicate with each electrolyte solution passage portion through connection portions at both ends of the electrode support portion, respectively. To do.

According to the first aspect of the invention, since the plurality of electrodes are compressed and fixed via the spacers, the electrode area can be sufficiently increased, and the strength of the electrode unit is increased by the compressive force from the outside. To prevent electrode breakage and electrolyte leakage as much as possible.
Even a conductive diamond that is relatively brittle as an electrode of an electrolytic cell having excellent pressure resistance can prevent the electrode from being damaged, thereby reducing the replacement cost and improving the throughput. In the case of a thin and self-supporting diamond electrode, the strength is further fragile, so that the higher effect of the present invention can be obtained.
In addition, the electrode support portion supports the adjacent electrodes and can maintain high strength, and the electrolyte solution can be smoothly passed through the electrolyte solution introduction port and the electrolyte solution delivery port corresponding to each electrolyte solution passage portion. The On the other hand, the electrolytic solution introduced into the electrolytic solution introduction port is brought into contact with the adjacent electrode surface while passing through the electrolytic solution passage part, and an electrolytic reaction occurs, and thereafter, the electrolytic solution is sent out of the electrolytic cell from the electrolytic solution delivery port. The
In addition, each electrolyte solution passage part, and the electrolyte solution introduction port and the electrolyte solution delivery port correspond one-to-one, and the electrolyte solution introduction port and the electrolyte solution delivery port correspond to a plurality of electrolyte solution passage parts. It may be.

  According to a second aspect of the present invention, there is provided the electrolysis cell according to the first aspect, wherein the electrode unit is sandwiched and compressed and fixed by a current-carrying member from outside the electrodes at both ends.

  According to the second aspect of the present invention, it is possible to reliably fix the electrode unit in a state in which good electrical conductivity is maintained and to improve the pressure resistance, and to reduce the electrical contact resistance between the electrode and the electrical conductor. it can.

  According to a third aspect of the present invention, there is provided the electrolysis cell according to the second aspect, wherein a plate-like conductive material made of conductive fibers is sandwiched between the current-carrying body and the electrodes at both ends. And

  According to the third aspect of the present invention, the compressive fixing force is widely transmitted to the electrode surface by the elastic force of the plate-like conductive material, and the electrical connection between the energization body and the electrode is ensured, and the electrode unit and the energization The electrical resistance between the body can be drastically reduced. For example, just pressing the electrode plates and the current-carrying planes with a surface pressure of about 0.4 MPa reduces the contact area by touching only the top of the surface roughness, but by placing a soft metal fiber in the middle, contact It is expected that the area will increase.

According to a fourth aspect of the present invention, there is provided the electrolytic cell according to any one of the first to third aspects, wherein the electrolytic solution passing portion is in a flowing direction from the electrolytic solution introduction port to the electrolytic solution delivery port. It is characterized by extending along.

According to the fourth aspect of the present invention, electrolysis is performed while the electrolyte solution is smoothly passed through the electrolytic solution passing portion from the electrolyte solution introduction port to the electrolyte solution delivery port.

According to a fifth aspect of the present invention, there is provided the electrolytic cell according to any one of the first to fourth aspects, wherein the spacer is installed in a direction in which the electrolytic solution delivery port faces upward, and the gas in the electrolytic unit is an electrolytic cell. It is characterized by a structure that can be pulled out.

According to the fifth aspect of the present invention, gas such as hydrogen gas by-produced by electrolysis is easily discharged to the outside of the electrolytic cell through the electrolytic solution delivery port as the electrolytic solution is delivered. This prevents the product gas from staying in the electrolysis unit and causing an increase in internal pressure and a decrease in electrolysis efficiency.

The invention of an electrolysis cell according to claim 6 is the invention according to any one of claims 1 to 5 , wherein the electrode unit is pressed to the outside by an elastic force on the outside of one or both ends of the electrode unit. 1 elastic member is provided.

According to the sixth aspect of the present invention, the first elastic member always applies an inward elastic force to the electrode unit to increase the strength of the electrode unit, and the electrode is deformed over time or temporarily. In this case, a stable compression / fixing force can be applied by the elastic force. In addition, when a stress that deforms the electrode to the outside is applied, the electrode is supported and an excessive load is applied to the electrode to avoid damage.

According to a seventh aspect of the present invention, there is provided the electrolysis cell according to the sixth aspect , wherein the electrode unit is provided with a second elastic member that presses the electrode unit inward by elastic force on the outer periphery, The second elastic member is fixed by receiving a pressing force from the second elastic member and receiving a pressing force by the first elastic member on the inner peripheral side.

According to the seventh aspect of the invention, the compressive force can be balanced by receiving the pressing force from the outer peripheral side by the second elastic member and receiving the pressing force by the first elastic member on the inner peripheral side. It is possible to ensure a uniform strength as much as possible in the surface direction by applying a compression fixing force over a wide range of the electrode surface.

The invention of the electrolytic cell according to claim 8 is characterized in that, in the invention according to any one of claims 1 to 7 , it is used for sulfuric acid electrolysis.

In the invention according to claim 8 , the sulfuric acid electrolyte can be safely electrolytically reacted by an electrolytic cell having sufficient strength.

The invention of the sulfuric acid recycling type cleaning system using the electrolytic cell according to claim 9 comprises a cleaning device for cleaning a material to be cleaned using a persulfuric acid solution as a cleaning liquid, and the electrolytic cell of the present invention, and by an electrolytic reaction in the electrolytic cell. The persulfuric acid solution is circulated between an electrolysis reaction device that generates persulfate ions from sulfate ions contained in the cleaning waste liquid of the material to be cleaned to regenerate the persulfuric acid solution, and the cleaning device and the electrolysis reaction device. And a circulation line.

According to the sulfuric acid recycle type cleaning system according to claim 9, a sufficient amount of solution can be subjected to cleaning while performing an electrolytic reaction using an electrolytic cell having excellent pressure resistance, and efficient processing can be performed. become. And the risk which a sulfuric acid recycle type washing system has can be reduced. That is, the risk of damage to the diamond electrode during operation is reduced, and problems such as a decrease in throughput due to electrode breakage, replacement of expensive diamond electrodes, and risk of leakage of high-temperature concentrated sulfuric acid are solved.

The sulfuric acid recycle type cleaning system of the present invention can be used in the process of cleaning and peeling off contaminants attached to a substrate such as a silicon wafer in the semiconductor industry with a high concentration sulfuric acid solution as described above. Persulfuric acid solution can be produced on-site by electrolytic reactor in the temperature range from 10 ℃ to 90 ℃ in order to improve resist stripping and oxidation effect by omitting pretreatment process such as ashing process. Therefore, it is applied to a cleaning system that does not require the addition of chemicals such as hydrogen peroxide and ozone from the outside.
An outline of this cleaning system will be described below. 1) Electrolytic reaction device for producing persulfuric acid solution from high concentration sulfuric acid solution 2) Cleaning device for cleaning electronic material substrate such as silicon wafer, glass substrate for liquid crystal, photomask substrate 3) Pump for circulating high concentration sulfuric acid solution And, if desired, 4) a heat exchanger that recovers the heat of the feed liquid from the electrolytic reactor and the return liquid from the washing tank, and 5) gas-liquid separation at the outlet of the electrolytic reactor And a catalyst processing apparatus for burning hydrogen.

The concentration of sulfuric acid used as a cleaning solution greatly affects the persulfuric acid production efficiency by electrolysis and the resist removal effect. When the sulfuric acid concentration is about 4 to 7M, the persulfuric acid production efficiency by electrolysis is improved, but the resist peeling and dissolving effect is lowered. Therefore, the inventors repeated various experiments and found that a sulfuric acid concentration in the range of 8 to 18M was appropriate.
In the electrolytic reaction apparatus, a high-concentration sulfuric acid solution is electrolyzed to produce persulfuric acid that improves the cleaning effect. Since the persulfuric acid production efficiency is higher as the solution temperature is lower, the electrolysis temperature when producing persulfuric acid is 10 to 90 ° C., preferably 40 to 80 ° C. When a platinum electrode is used as the anode material as an electrode material in such an electrolytic reaction apparatus, persulfuric acid cannot be produced efficiently, and platinum is eluted. Thus, it has been reported that persulfuric acid is produced from sulfuric acid using a conductive diamond electrode when the current density is about 0.2 A / cm ² (Ch. Cominellis et al., Electrochemical and Solid-State). Letters, Vol. 3 (2) 77-79 (2000), Special Table 2003-511555). In the case of an electrode having a diamond thin film supported on a metal substrate or the like, there is a problem in that the diamond film peels off and the action effect may disappear in a short period of time, so the substrate is removed after being deposited on the substrate. A free standing conductive diamond electrode is desirable. In addition, the conductive diamond thin film is obtained by doping a predetermined amount of boron or nitrogen at the time of synthesis to impart conductivity, and generally boron doped. If the doping amount is too small, technical significance does not occur. If the doping amount is too large, the doping effect is saturated. Therefore, a doping amount in the range of 50 to 20,000 ppm with respect to the carbon amount of the diamond thin film is suitable. .
The electrolytic treatment in the electrolytic reactor is performed by contacting the electrode surface with a current density of 10 to 100,000 A / m ² , contacting the sulfuric acid solution in a direction parallel to the electrode surface, and a liquid flow rate of 1 to 10,000 m / h. It is desirable.

The cleaning apparatus may be either a single wafer type or a batch type. However, in the cleaning apparatus, a soluble TOC is generated in the cleaning liquid along with the separation and dissolution of contaminants such as resist when the electronic substrate is cleaned. At this time, since it is necessary to efficiently remove the TOC of the cleaning liquid and prevent the organic substance from reattaching to the electronic substrate material, the persulfuric acid production rate in the electrolytic reaction apparatus with respect to the TOC production rate (g / L / hr) The electrolysis conditions are preferably set so that (g / L / hr) is 10 to 500 times.
The higher the temperature, the higher the effect of removing organic substances such as resist, and generally the cleaning is often performed at 100 to 150 ° C. Therefore, in the present invention, it is desirable to exchange heat between the feed liquid from the electrolytic reaction apparatus to the cleaning apparatus and the return liquid from the cleaning apparatus to the electrolytic reaction apparatus. The gas discharged from the electrolytic reaction apparatus is due to electrolysis of water contained in the solution, and hydrogen is generated from the cathode and oxygen is generated from the anode. Since these flow in the pipe in a mixed state, they ignite or explode due to static electricity generated in the solution and the pipe. In the present invention, air or nitrogen is supplied in the middle of the piping immediately after the electrolytic cell so as to be below the explosion limit of hydrogen, and a gas-liquid separator for separating the electrolytic solution and the diluted gas is provided. Pass the liquid. The dilution gas is released into the atmosphere through a mist separator or processed with a catalytic combustion apparatus.

As described above, according to the electrolysis cell of the present invention, the electrode unit having a plurality of layers of conductive diamond electrodes and spacers interposed between the electrodes, and compressed and fixed from outside the electrodes at both ends, A pair of current-carrying members respectively connected to the electrodes at both ends of the electrode unit, the spacer having the same thickness as the inter-electrode distance, arranged in parallel with a distance from each other, and both ends connected to each other A plurality of electrode support portions, a plurality of electrolyte solution passage portions that are provided between the electrode support portions and penetrated in the thickness direction, and are provided in the spacer, and each electrolyte solution passage portion is connected to the both ends of the electrode support portions. Electrode solution inlet port and electrolyte solution outlet port that communicate with each part improve the pressure resistance of the electrode unit using conductive diamond electrodes, and efficiently pass the electrolyte solution with sufficient pressure and flow rate Electrolysis It is possible to respond. Further, the improvement of the pressure resistance prevents the conductive diamond electrode from being damaged as much as possible, and there is an effect that an increase in electrode replacement cost and a decrease in throughput due to the replacement can be avoided. Even in an electrolytic cell using a thin and brittle self-supporting diamond electrode, a large flow rate of the electrolytic solution can be processed.

Moreover, according to the sulfuric acid recycle type cleaning system using the electrolytic cell of the present invention, the cleaning apparatus for cleaning a material to be cleaned using a persulfuric acid solution as a cleaning liquid and the electrolytic cell according to any one of claims 1 to 8 are provided. An electrolytic reaction device that generates persulfate ions from sulfate ions contained in the cleaning waste liquid of the material to be cleaned by electrolytic reaction in the electrolytic cell to regenerate the persulfuric acid solution, and between the cleaning device and the electrolytic reaction device, Since it comprises a circulation line for circulating the persulfuric acid solution, it is possible to efficiently electrolyze a high-concentration sulfuric acid solution and generate persulfuric acid over a long period of time. In addition, contaminants, mainly organic substances, attached to a substrate such as a semiconductor wafer can be effectively removed by using this as a cleaning liquid.
In particular, in the semiconductor industry, it is suitable for the process of cleaning and removing contaminants adhering to a substrate such as a silicon wafer with a high-concentration sulfuric acid solution. In order to enhance the effect, a persulfuric acid solution is produced on-site by the electrolysis cell in a temperature range of 10 ° C. to 90 ° C., and a chemical solution such as hydrogen peroxide or ozone is not required from the outside by repeatedly using the sulfuric acid solution. A cleaning system can be constructed.

Below, one Embodiment of the electrolysis cell of this invention is described. First, the electrode unit 1 will be described with reference to FIGS.
A plurality of square diamond electrodes 2... 2 are prepared as electrodes constituting the electrolysis unit 1. The diamond electrode 2 is manufactured by forming a diamond thin film on a substrate and doping boron in a range of preferably 50 to 20,000 ppm with respect to the carbon content of the diamond thin film. After the formation, the substrate is removed to make a self-supporting type.

  Further, a spacer 3 made of a material (for example, made of polytetrafluoroethylene) having the same outer shape as the diamond electrode 2 and having insulating properties and corrosion resistance is prepared. The spacer 3 has a narrow portion having a thickness corresponding to the gap between the electrodes, both ends in the width direction, and a gap that is equally spaced therefrom, and a total of five in parallel along the vertical direction. These constitute electrode support portions 301. Moreover, between each electrode support part 301 and 301 is penetrated in the thickness direction except for the upper and lower end parts, and electrolyte solution liquid passing parts 302. The width and interval of the electrode support portion 301 can be set as appropriate. However, since the interval between the electrode support portions 301 and 301 is the width of the electrolyte solution passing portion 302, the required liquid contact area with the electrode and the electrode It is necessary to determine in consideration of the support force by the support portion 301. The lower part of the electrolyte solution passing part 302 has the same thickness as the electrode support part 301, and a through hole is formed in the center part thereof so as to communicate with the electrolyte solution passing part 302 from the lower end. The electrolyte inlet 302a is constituted by the holes.

In addition, a partition piece 303 having a thickness that is a fraction of the thickness of the electrode support portion 301 is formed along the center of the thickness direction in the upper part of the electrolyte solution passage portion 302. Each side space constitutes an electrolyte outlet 302b. The partition piece 303 is unnecessary if only the function of the electrolyte solution delivery port is considered, but the shape retaining property of the spacer 3 is ensured by connecting the electrode support portions.
The electrolytic solution introduction port 302a has a relatively small cross-sectional area, thereby increasing the internal pressure of the electrolytic solution reaching the electrolytic solution introduction port 302a, and from each electrolytic solution introduction port 302a to each electrolytic solution passage part 302. It is set so that the amount of electrolyte solution to reach the same.
The spacers 3... 3 are arranged between the diamond electrodes 2 and 2 so that the electrolyte introduction port 302a is located below and the electrolyte delivery port 302b is located above. To do.

Next, assembly of the electrode unit 1 to the electrolytic cell 100 will be described with reference to FIGS.
The diamond electrode 2 at both ends of the electrode unit 1, and the copper alloy plate current-carrying bodies 4, 4 sandwiched between the two sides are formed in a similar shape to the diamond electrode 2 and are formed in a small square shape. The spring storage recesses 4a... 4a for storing one end of the pressure spring as the first elastic member of the invention are formed except for the central portion at the positions of 3 rows × 3 columns at equal intervals. The current-carrying rod 5 is fixed by screwing. The current-carrying rod 5 and an external power source (not shown) are assumed to use plug-in connectors that can be easily attached and detached.

  In addition, between the diamond electrode 2 at the both ends of the electrode unit 1 and the above-described electric conductor 4, a plate-like conductive material 6 made of sintered copper conductive fibers having the same outer shape as the electric conductor 4 is sandwiched. It is. The plate-like conductive material 6 has elasticity also in the thickness direction. As described above, the electrode used the square material as it was as the electrode plate, and the current-carrying member and the conductive fiber spacer were also square. This produces the following advantages. (A) The electrolysis area is 1.273 times wider than when a round material having a square side as a diameter is used. (B) Since the body to be described later is manufactured in a round shape and the gap between the rectangular electrodes can be used as a liquid inlet / outlet header, the production cost of the electrolysis cell is reduced.

  Ring-shaped covers 7 made of polytetrafluoroethylene and having quadrangular holes in which the conductors 4 can be accommodated without substantial gaps are disposed on the outer peripheral sides of the pair of conductors 4, 4. A cover reinforcing plate 8 having substantially the same contour shape as the cover 7 is screwed to the outside of the cover. The cover 7 is a floating type between a body 11 and a flange 15 to be described later so as to follow the thickness of the electrode unit 1. Since the electrode 2 and the spacer 3 are slightly different in dimensions depending on the lot to be made and the number of times of assembling and reassembling, a means capable of moving (moving) in the structure for pressing against the electrode becomes indispensable. .

  An O-ring 10 is disposed along the inner contour of the diamond electrode 2 between the inner surface of the cover 7 and the outer surface of the diamond electrode 2 at both ends of the electrode unit 1 to prevent electrolyte leakage. Yes. Further, a ring-shaped polytetrafluoroethylene body 11 covering the cover reinforcing plates 8 and 8 on both sides and projecting further outward is provided on the outer peripheral side of the cover 7 and the cover reinforcing plate 8 on both sides. An O-ring 14 is also disposed between the outer peripheral surface of the cover 7 and the inner peripheral surface of the body 11 to prevent leakage of the electrolytic solution. The O-ring groove in which the O-ring that seals the electrode is disposed is preferably a dovetail groove type in which the O-ring does not fall even if the O-ring groove faces downward.

The body 11 is formed between the covers 7 on both sides with an annular protrusion 12 that protrudes inward with a thickness substantially the same as that of the electrode unit 1 and slightly smaller than the thickness of the electrode unit 1. The annular protrusion 12 has a height that reaches slightly inward than the electrode unit 1 is inscribed, and the electrode unit housing groove 12a... 12a is cut out along the axial direction. When the electrolysis cell is assembled, the electrode unit 1 can be set in accordance with the electrode unit housing groove 12a, and alignment can be performed easily and reliably.
Further, at the position facing the body 11 in the radial direction, the electrolyte solution introduction hole 13a is formed so as to penetrate the inner and outer periphery on the side where the electrolyte solution introduction port 302a of the spacer is located, and the electrolyte solution delivery port 302b of the spacer is formed. The electrolyte solution delivery hole 13b is formed on the side where it is located so as to penetrate the inner and outer circumferences. As a result, the electrolyte introduction side header space 14a is secured between the annular protrusion 12 and the electrode unit 1 on the electrolyte introduction hole 13a side, and the annular projection 12 and the electrode unit 1 are located on the electrolyte delivery hole 13b side. An electrolyte solution delivery side header space 14b is secured between them.

Further, flanges 15 and 15 having a diameter larger than that of the body 11 are disposed outside the cover reinforcing plate 8 and the body 11 in the axial direction, and both flanges 15 and 15 are disposed in the circumferential direction on the outer periphery side of the body 11. The stud bolt 17, the coil spring 21, and the nut 18 are fastened and fixed at the same interval. The body 11 and the flanges 15, 15 have a slight gap when assembled, and the coil spring 21 is tightened between the nut 18 and the outer surface of the flange 15 in an elastically compressed state. In addition, an elastic force acts on the inside as the second elastic member, and an inward pressing force is applied to the electrode unit 1 via the flange 15, the cover reinforcing plate 8, and the cover 7. Thereby, the electrode unit 1 described above is compressed and fixed by the floating cover reinforcing plate 8 and the cover 7. The compressive force is transmitted from the diamond electrodes 2 at both ends to the electrode support portion 301 in the inner spacer 3 and further sequentially transmitted to the inner diamond electrode 2. Thereby, each diamond electrode 2 is supported by each electrode support portion 301 of each spacer 3. In this embodiment, the coil springs 21 and 21 are provided on one flange 15 side. However, the coil springs 15 and 15 may be provided on the flanges 15 and 15 side in the same manner. .
In addition, a through hole is formed in the center portion of the flanges 15 and 15 and the above-described current-carrying rod 5 is inserted therethrough.

  In addition, coil springs 22... 22 are interposed between the current-carrying members and the flanges 15 and 15 as first elastic members in a compressed state corresponding to the spring housing recesses 4 a. As a result, the elastic force of the coil spring 22 is transmitted to the electrode unit 1 through the energizing body 4, and compression and fixing are performed on the inner peripheral side of the electrode unit 1. Similarly to the above, this compressive force is sequentially transmitted from the diamond electrodes 2 at both ends to the inner diamond electrode 2 through the electrode support portions 301 of the spacers, and each diamond electrode 2 is supported by the electrode support portions 301 more firmly. become. As described above, the electrode unit 1 is applied with a good balance between the compressive force from the outer peripheral side and the compressive force from the inner peripheral side, and exhibits good pressure resistance. Further, the current-carrying body 4 is pressed against the electrode 2 side by the compressive force to reduce the contact resistance, and the electrode 2 and the conductor 4 are efficiently brought into surface contact with each other by the elastic force of the plate-like conductive material 6 interposed therebetween. To further reduce the contact resistance. The electrolysis cell 100 of this invention is comprised by the above.

Next, the operation of the electrolytic cell 100 will be described.
One of the current-carrying rods 5 and 5 is a positive electrode and the other is a negative electrode, and a power source (not shown) is connected and energized, and the electrolytic solution is fed into the electrolytic solution introduction hole 13a. In this case, the electrolytic cell 100 is preferably arranged with the electrolyte solution delivery port 302b side upward.
Then, the electrolytic solution flows into the electrolytic solution introduction side header space 14a. At this time, the electrolyte solution introduction port 302a provided in the spacer 3 is formed with a sufficiently small (relatively small) cross-sectional area as compared with the electrolyte solution delivery port 302b, and the electrolyte solution introduction side header space 14a. The internal pressure increases. As a result, the electrolyte flows into the electrolyte solution inlets 302a... 302a of each spacer 3 at substantially the same flow rate. The electrolyte solution that has passed through the electrolyte solution inlet 302 a then flows into each electrolyte solution passage portion 302 and is passed along the electrolyte solution passage portion 302.

  The electrode unit 1 is energized by the energizing rods 5 and 5 as described above, and the applied voltage is transmitted to the diamond electrodes 2 and 2 at both ends of the electrode unit 1 through the energizing body 4 and the energizing plate 6. By applying this voltage, the diamond electrodes 2... 2 on the inside are polarized, and anodes and cathodes appear at predetermined intervals. As a result, the electrolytic solution passing through the electrolytic solution passing portion 302 undergoes an electrolytic reaction when energized. For example, when a sulfuric acid solution is passed as an electrolytic solution, sulfate ions in the electrolytic solution are oxidized to generate persulfate ions. The electrolytic solution in which the electrolytic reaction has occurred passes through the electrolytic solution delivery part 302b through the electrolytic solution delivery port 302b, reaches the electrolytic solution delivery side header space 14b, and is delivered to the outside of the electrolytic cell 100 through the electrolytic solution delivery hole 13b. . The electrolyte solution delivery port 302b is formed with a sufficiently large (relatively large) cross-sectional area as compared with the electrolyte solution introduction port 302a, so that the electrolyte solution is quickly delivered and generated along with the electrolytic reaction. By-product gas such as hydrogen is smoothly extracted together with the electrolyte.

  In the electrolytic cell 100, each diamond electrode 2 ... 2 receives a stable compressive fixing force over the entire surface, and has high strength. In addition, even when the electrolyte pressure fluctuates and a deforming force is generated in the diamond electrode 2, minute deformation of the electrode is allowed with the compressive force applied, and the electrode can be more reliably prevented from being damaged. There is almost no work and a good throughput can be obtained.

Next, an embodiment of a sulfuric acid recycle type cleaning system using the electrolytic cell will be described with reference to FIG.
An electrolytic reaction apparatus is connected to a cleaning tank 101 corresponding to the cleaning apparatus of the present invention by a return pipe 102 and a feed pipe 104. The electrolytic reaction apparatus is configured by connecting two electrolytic cells 100 and 100 in parallel and connecting a DC power source 108 to each electrode so that the electrolytic cells 100 and 100 are in series.

  The return pipe 102 and the feed pipe 104 each have at least an inner surface made of tetrafluoroethylene, and a liquid feed pump 105 for feeding a persulfuric acid solution is interposed in the return pipe 102. The return pipe 102, the feed pipe 104, and the liquid feed pump 105 constitute the circulation line of the present invention. In addition, a heat exchanger 110 is interposed between the return pipe 102 and the feed pipe 104 as heat exchange means, and the solution flowing through the return pipe 102 and the solution flowing through the feed pipe 104 are exchanged by the heat exchanger 110. Can exchange heat with each other. Note that at least the inner surface of the flow path (not shown) in the heat exchanger 110 is made of tetrafluoroethylene. As described above, the flow path of the return pipe 102, the feed pipe 104, and the heat exchanger 110 is made of tetrafluoroethylene or the like that is resistant to persulfuric acid, so that wear due to persulfuric acid can be avoided.

  The cleaning tank 101 is provided with an ultrapure water supply line 111 for supplying ultrapure water, and further includes a heater 112 for heating the stored solution. In addition, a gas-liquid separator 130 including a mist separator is interposed in the feed pipe 104 at the outlet of the electrolysis cells 100, 100, and the separated gas is supplied to the catalytic combustion device 131 to remove hydrogen from the system. It is configured not to discharge.

Next, the operation of the sulfuric acid recycling type cleaning system will be described.
For example, a high-concentration sulfuric acid solution adjusted at a ratio of 40 L of 97% concentrated sulfuric acid and 10 L of ultrapure water is placed in the washing tank 101 and heated and maintained at 130 ° C. by the heater 112. This is sent to the electrolytic cells 100 and 100 through the return pipe 102 by the liquid feed pump 105. At this time, it is desirable to set the output of the liquid feed pump 105 so that the linear flow rate of the electrolysis cells 100 and 100 is 1 to 10,000 m / hr. In addition, in energization in electrolysis cells 100 and 100, it is desirable to control energization so that the current density on the diamond electrode surface may be 10 to 100,000 A / m ² .

When the electrolysis cells 100 and 100 are energized, the sulfate ions in the solution undergo an oxidation reaction to generate persulfate ions, and the persulfate solution 120 is regenerated. The persulfuric acid solution 120 is fed to the cleaning tank 101 through the feed pipe 104, and a high-concentration persulfuric acid solution 120 is obtained in the cleaning tank 101. At this time, the solution is separated from gas such as hydrogen generated by electrolysis through the mist separator 130. The separated gas is burned by the catalytic combustion device 131, and safe exhaust gas is discharged out of the system.
In the washing tank 101, although the persulfate ion concentration gradually decreases due to self-decomposition, the solution circulates between the electrolytic reactor and is electrolyzed in the electrolytic cells 100, 100 to generate persulfate ions. Sulfate ion concentration is maintained. In this embodiment, the process of producing persulfuric acid from sulfuric acid at the time of start-up has been described. However, as the present invention, persulfuric acid may be prepared from the beginning. However, in terms of producing persulfuric acid on-site, it is advantageous to produce persulfuric acid using an electrolytic cell.

  The semiconductor wafer 140, which is a material to be cleaned, is accommodated in the cleaning tank 101, and cleaning is started. Then, in the cleaning tank 101, contaminants on the semiconductor wafer 140 and the like are effectively peeled and removed and transferred into the persulfuric acid solution 120. Contaminants that have migrated into the solution are decomposed by the high oxidizing action of persulfate ions.

Further, when the persulfuric acid solution 120 moves between the washing tank 101 and the electrolytic reaction apparatus through the return pipe 102 and the feed pipe 104, the solution sent from the washing tank 101 to the electrolytic reaction apparatus, and the electrolytic reaction apparatus from the washing tank Heat exchange is performed with the solution sent to 101 in the heat exchanger 110. The solution sent from the cleaning tank 101 is heated to about 130 ° C. so as to be suitable for cleaning. On the other hand, the solution sent from the electrolytic reaction apparatus has a temperature of about 40 ° C. suitable for electrolysis. As a result of the heat exchange of these solutions, the solution moving through the return pipe 102 is lowered to a temperature close to 40 ° C., while the solution moving through the feed pipe 104 is heated to a temperature close to 130 ° C. The solution that is heat-exchanged by the heat exchanger 110 and moves through the return pipe 102 is then gradually cooled by natural cooling to a temperature of about 40 ° C. suitable for the electrolytic reaction. If it is desired to reliably lower the temperature, a cooling means for forcibly cooling the electrolysis cell 100 by water cooling or air cooling may be provided. The persulfuric acid solution 120 that is heat-exchanged by the heat exchanger 110 and moves through the feed pipe 104 is sent to the cleaning tank 101 and mixed with the persulfuric acid solution 107 remaining in the cleaning tank 101. When the temperature of the persulfuric acid solution 120 in the cleaning tank 101 decreases, the temperature can be raised to an optimum temperature for cleaning by heating with the heater 112. As described above, the solution is cooled when being sent from the washing tank 101 to the electrolytic reaction apparatus, and after being electrolyzed, it is heated when being returned from the electrolytic reaction apparatus to the washing tank 101. Since the amount of heat to be cooled and the amount of heat to be heated in this one cycle are substantially equal, a high-efficiency heat exchanger 110 is incorporated, and heat energy is applied from the outside for the amount of heat radiation, so that the temperature of the solution can be efficiently obtained. Adjustments can be made.
By cleaning the semiconductor wafer 140 with the sulfuric acid recycling type cleaning system, it is effective to regenerate the persulfuric acid solution by repeatedly using the persulfuric acid solution without the need for the addition of hydrogen peroxide or ozone. Washing can be continued.

Next, a modified example of the electrolytic cell will be described with reference to FIG.
In the above-described embodiment, the internal pressure immediately before the electrolytic solution introduction port is increased by sufficiently reducing the electrolytic solution introduction port in the spacer so that the equivalent electrolytic solution flows into each spacer. This is because when introducing the electrolyte into the electrode unit, it is easier for the electrolyte to flow into the center in the width direction of the spacer, and it is difficult for the electrolyte to flow into the end side, thereby avoiding a difference in the amount of flow.

  Other measures can be taken to achieve this goal. That is, as shown in FIG. 7A, the electrolyte cross-sectional area of the electrolyte introduction port 310a located on the center side is reduced, and the cross-sectional area of the electrolyte introduction port 311a on the end side is increased. A difference in flow rate due to a difference in position in the width direction can be reduced. In addition to this, as shown in FIG. 7B, the number of electrolyte introduction ports 320a corresponding to the electrolyte solution introduction portions close to the center is small, and the number of electrolyte solution introduction ports of each electrolyte solution introduction portion is small. The number of electrolyte solution inlets 321a corresponding to the liquid passage portion may be increased.

Also, in one electrolyte solution passage part 302, on the electrolyte solution inlet side, a difference in flow rate and liquid passage linear velocity occurs depending on the distance in the width direction of the inlet port. That is, the flow rate and the liquid passage speed are relatively large at a position close to the electrolyte introduction port, and the flow volume and the liquid passage speed are reduced as the position is farther from the end. In order to avoid this, as shown in FIG. 7 (c), a plurality of electrolyte introduction ports are provided in the width direction for one electrolyte solution passage part 302, and the introduction of the electrolyte located at the center of the introduction port is provided. By reducing the cross-sectional area of the channel as the port 330a and increasing the cross-sectional area of the electrolyte inflow port 331a at the end, the difference in flow rate due to the difference in the position in the width direction can be reduced. In these cases, it is also possible to combine the flow rate adjustments between the plurality of electrolyte solution passing portions.
In addition to the holes provided on the inner side in the thickness direction of the spacer, the electrolyte solution inlet may be provided in a slit shape at both ends in contact with the electrode.

[Example 1]
Examples of the present invention will be described below in comparison with comparative examples.
A high-concentration sulfuric acid solution prepared at a ratio of 97 L concentrated sulfuric acid 40 L and ultrapure water 10 L was prepared and maintained at 40 ° C. In the electrolytic cell of the present invention, two tanks in which ten conductive diamond electrodes boron-doped on a Si substrate having a diameter of 15 cm and a thickness of 1 mm were incorporated were arranged in parallel. Effective anode area for electrolysis is 30dm ^2, by setting the current density 30A / dm ^2, and electrolysis of sulfuric acid solution at 40 ° C.. The voltage applied to 10 electrodes was 35V.

[Comparative Example 1]
An electrolytic test was conducted in the same manner as in Example 1 except that an electrolytic cell having an electric current plate and an electrode plate bonded with a conductive paste was used. The voltage applied to 10 electrodes was 40 V, and the energy consumption increased by about 14%.

[Example 2]
A high-concentration sulfuric acid solution prepared at a ratio of 97 L of 97% concentrated sulfuric acid and 10 L of ultrapure water was prepared in a washing tank and heated to 130 ° C. In the electrolytic cell of the present invention, two tanks in which ten conductive diamond electrodes boron-doped on a Si substrate having a diameter of 15 cm and a thickness of 1 mm were incorporated were arranged in parallel. Effective anode area for electrolysis is 30dm ^2, by setting the current density 30A / dm ^2, and electrolysis at 40 ° C.. When the outlet water of the electrolytic reactor was sampled, it was confirmed that the persulfuric acid production rate was 3 g / l / hr. In the cleaning tank, a 5-inch silicon wafer with a resist was immersed for 50 minutes / cycle with an immersion cycle of 10 minutes, and the resist was dissolved (TOC generation rate was 0.03 g / l / hr). This solution was circulated at a flow rate of 10 l / min between the washing tank and the electrolytic reaction apparatus with a liquid feed pump. When the silicon wafer with the resist was immersed, the solution in the cleaning tank was colored brown and the TOC concentration was 30 mg / l. However, the solution in the cleaning tank became colorless and transparent after 10 minutes of circulation treatment. The concentration was below the detection limit. Such wafer cleaning was continued for 8 hours (2,400 wafers were cleaned), but the resist stripping effect of the high-concentration sulfuric acid solution was good, and the TOC concentration was below the detection limit. Therefore, it continued for another 32 hours (9,600 cleaning wafers, 12,000 total processing wafers), but the resist stripping effect of the high-concentration sulfuric acid solution was good, and the TOC concentration was below the detection limit. It was.

[Comparative Example 2]
The wafer was cleaned in the same manner as in Example 1 except that an electrolysis cell having a structure in which the current plate and the electrode plate were fixed with a conductive paste without pressing the current plate against the conductive diamond electrode plate with a compression spring was used. did. After 4 hours of stable operation, the electrode plate cracked and the sulfuric acid solution leaked from the electrolytic cell. For this reason, the cleaning operation was stopped.

  Although the present invention has been described based on the above embodiments and examples, the present invention is not limited to the above description, and can naturally be modified without departing from the scope of the present invention. It is.

It is a disassembled perspective view of the electrode unit in the electrolysis cell of one embodiment of the present invention. Similarly, it is an enlarged view showing a spacer. Similarly, it is the disassembled perspective view which abbreviate | omitted a part of electrolysis cell. Similarly, it is the front view which omitted a part of electrolysis cell. It is the VV sectional view taken on the line of FIG. It is a schematic block diagram of the sulfuric acid recycle type cleaning system of the present invention. It is a figure which shows the example of a change of the spacer of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrode unit 2 Diamond electrode 3 Spacer 301 Electrode support part 302 Electrolyte solution flow part 302a Electrolyte solution introduction port 302b Electrolyte solution delivery port 4 Electric current body 6 Plate-shaped electrically conductive material 7 Cover 8 Cover reinforcement board 11 Body 12 Annular protrusion 12a Electrode Unit storage groove 13a Electrolyte introduction hole 13b Electrolyte delivery hole 14a Electrolyte introduction side header space 14b Electrolyte delivery side header space 100 Electrolytic cell 101 Cleaning tank 102 Return pipe 104 Feed pipe 105 Feed pump 108 DC power supply 110 Heat exchanger 120 persulfuric acid solution

Claims (9)

A plurality of conductive diamond electrodes and insulating spacers interposed between the electrodes, and electrode units compressed and fixed from outside the electrodes at both ends, and connected to the electrodes at both ends of the electrode units, respectively A pair of electrical conductors ,
The spacer has a thickness equal to the distance between the electrodes, is parallel to each other with an interval between them, and has a plurality of electrode support portions that are connected to each other at both ends, and a plurality of the electrode support portions that penetrate between the electrode support portions in the thickness direction. An electrolyte solution passage portion, and an electrolyte solution introduction port and an electrolyte solution delivery port that are provided in the spacer and communicate with each electrolyte solution passage portion through connection portions at both ends of the electrode support portion, respectively. Electrolytic cell. The electrode unit, electrolysis cell 請 Motomeko 1 wherein you characterized by being compressed fixed pinching by energizing member from the electrode outside of said end.   3. The electrolysis cell according to claim 2, wherein a plate-like conductive material made of conductive fibers is sandwiched between the current-carrying body and the electrodes at both ends. The electrolytic cell according to claim 1, wherein the liquid passing part extends along a liquid passing direction from the electrolytic solution introduction port to an electrolytic solution delivery port. The electrolysis cell according to any one of claims 1 to 4, wherein the spacer is installed in a direction in which the electrolyte solution delivery port faces upward, and gas in the electrolysis unit escapes outside the electrolysis cell. 6. The first elastic member according to claim 1, wherein a first elastic member that presses the electrode inward by elastic force is provided outside the electrode at one end or both ends of the electrode unit. Electrolytic cell. The electrode unit is provided with a second elastic member that presses the electrode unit inward by elastic force on the outer periphery, receives a pressing force from the outer periphery on the second elastic member, and on the inner periphery the first The electrolysis cell according to claim 6, wherein the electrolysis cell is fixed by receiving a pressing force by one elastic member. The electrolytic cell according to claim 1 , wherein the electrolytic cell is used for sulfuric acid electrolysis . A cleaning apparatus for cleaning a material to be cleaned using a persulfuric acid solution as a cleaning liquid, and an electrolytic cell according to any one of claims 1 to 8, wherein sulfuric acid contained in the cleaning waste liquid of the material to be cleaned by an electrolytic reaction in the electrolytic cell Electrolysis comprising: an electrolytic reaction device that generates persulfate ions from ions to regenerate a persulfate solution; and a circulation line that circulates the persulfate solution between the cleaning device and the electrolytic reaction device. A sulfuric acid recycling cleaning system using a cell.

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