WO2014208794A1

WO2014208794A1 - Apparatus for generating electrolyzed water, used in semiconductor process

Info

Publication number: WO2014208794A1
Application number: PCT/KR2013/005736
Authority: WO
Inventors: 안종호
Original assignee: 솔브레인나노텍 주식회사
Priority date: 2013-06-27
Filing date: 2013-06-27
Publication date: 2014-12-31

Abstract

The present invention relates to an apparatus for generating electrolyzed water, used in a semiconductor process such as semiconductor substrate cleaning and the like, wherein cleaning power is improved by having desired dissolved hydrogen, dissolved oxygen and OPR in electrolyzed water according to an increase in the hydraulic pressure of electrolyzed water, and the deterioration of electrolysis efficiency due to the increase in hydraulic pressure can be simultaneously prevented by allowing constant current to flow through the structure of an electrolytic bath.

Description

Electrolyzed Water Generator for Semiconductor Process

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyzed water generating device used in semiconductor processes such as semiconductor substrate cleaning. As the water pressure of the electrolyzer is improved, the electrolyzed water has the desired dissolved hydrogen, dissolved oxygen, and OPR to improve cleaning power and The present invention relates to an electrolytic water generating device capable of preventing a decrease in electrolytic efficiency due to improvement in water pressure by allowing a constant current to flow based on the structure.

Generally, in the process of manufacturing a semiconductor device, a display device, or the like, cleaning of the surface of the substrate is required, in order to remove particles (particulates), which are contaminants on the substrate, and to highly clean the surface of the substrate. In the manufacturing process of semiconductor devices such as microprocessors, memories, CCDs, and flat panel display devices such as TFT liquid crystals, circuit patterns with submicron dimensions on substrate surfaces such as silicon (Si), silicon oxide (SiO ₂ ), and glass Formation and thin film formation are performed, and it is a very important subject to reduce the trace amount of contamination of this substrate surface in each process of manufacture. In particular, contamination by microparticles (particles), such as silica particles, alumina particles, and organic particles, lowers the yield of the device. Therefore, it is necessary to minimize the contamination before entering the next step. Decontamination is generally performed by cleaning the substrate surface with a cleaning liquid. Electrolytic water such as alkaline water is frequently used to remove particle contamination. The electrolyzed water electrolyzes pure water to generate alkaline or acidic water. Pure water is composed of ions of H + and OH-, and when electrolyzed, alkaline ions are generated at the negative electrode (-) and acidic ions at the positive electrode (+). . When water is electrolyzed, it is oxidized and reduced. At this time, the potential value is expressed as ORP (Oxidation Reduction Potential). The ORP may be referred to as a reference value for determining whether water is oxidized water or reduced water. If the ORP value is a positive value, it is an oxidized water. If the ORP value is a negative value, it is a reduced water. Conventionally, although not shown in the drawings, to produce electrolytic water, the cathode and anode chambers in which the electrolytic cell is divided into ion permeable diaphragms are charged, and the cathode and anode electrodes are charged and current is flowed between the two electrodes with pure water in the electrolyte chamber. When it is inserted, the diaphragm is interposed and electrolyzed, and the pH value of the water in the cathode chamber is increased to alkaline water and the pH value of water in the anode chamber is lowered to form acidic water. In this conventional device, the anode and the cathode are each made of one sheet. In this case, since the amount of current is different at the upper and lower ends of the electrolyzer due to the difference in the pressure generated at the upper and lower ends of the electrolyzer, the portion of the high water pressure flows less, and the portion of the low water pressure flows much current. In other words, the current in the electrolytic cell is inversely related to the water pressure. Therefore, the lower end of the electrolytic cell has a low electrolytic efficiency, and the upper end has a high electrolytic efficiency, but may be overelectrolyzed. In other words, even in the electrolyzed water generated due to the difference in electrolytic efficiency, constant pH and OPR cannot be expected. Thus, there is a problem that non-uniform cleaning occurs in the cleaning of the substrate.

1 shows a conventional electrolytic cell 1 (Korean Patent Registration No. 0229584), the structure of which is the same as the above-mentioned electrolytic cell, except that ions are selectively flowed to efficiently flow alkaline or acidic water. An example in which the ion exchange membrane 2 is formed on both surfaces of the partition wall 3 is shown as a configuration for producing. However, this technique is a type in which the ion exchange membrane 2 is bonded to the partition 3 and the contact resistance (Rc) due to the generation of the interface between the ion exchange membrane and the barrier and the contact resistance (Rc) due to the generation of the interface between the ion exchange membrane and the barrier rib. The resistance will increase. This increase in resistance eventually has a problem of lowering the conduction efficiency.

Accordingly, the present invention is to solve the above-described problems, it is possible to generate an electrolytic water that can ensure the uniformity of the semiconductor cleaning process by the electrolytic water having a constant pH, OPR so that a constant current is induced regardless of the water pressure To provide a device.

Electrolytic water generating device used in the semiconductor process according to the problem to be solved by the present invention is a plurality of anode electrodes formed in series with a multi-stage electrode in a form separated from each other in a vertical direction from the bottom of the electrolytic cell, a plurality of multi-step electrode formed in series A plurality of cathode electrodes formed as multi-stage electrodes in series so as to be separated from each other in a vertical direction from a lower part of an electrolytic cell at positions corresponding to the two anode electrodes, an anode electrode at an end of the plurality of anode electrodes, and the plurality of cathode electrodes It is formed and includes an external power source for applying a voltage to the cathode electrode of the other end, the anode electrode and the cathode electrode which is not connected to the external power source is characterized in that connected to each other by a wire. That is, a plurality of cathode electrodes are formed in series at a predetermined interval in a vertical direction from the lower part of the electrolytic cell, and a plurality of anode electrodes are formed in series at a predetermined interval so as to face the plurality of cathode electrodes. It is formed to apply a DC voltage to the anode electrode at one end of the two anode electrodes and the cathode electrode at the other end of the plurality of cathode electrodes, so that a constant current flows at all times without being affected by the water pressure due to the height difference in the electrolytic cell. As a result, the electrolytic efficiency is improved, and a constant pH and redox potential (OPR) are obtained.

The semiconductor process is a cleaning process in the semiconductor or LED process, including deposition (CVD), diffusion (Diffusion), exposure (Expose), development (Develop), etching (Etch), polishing (CMP) In the scrubbing process, the process includes MEGASONIC, Brushing, and Jet. In addition, the semiconductor process refers to a process including FPD Cleaning, LCD Cleaning, Photo Mask Cleaning.

In addition, the electrolyzer is configured with an inlet line at the bottom thereof is connected to the filter unit, the discharge line is connected to the top by the flow control valve to control the water pressure in the electrolyzer by adjusting the flow rate of the electrolyzed water discharged from the electrolyzer (higher) Therefore, the present invention is characterized by improving the dissolved hydrogen concentration (DH) and OPR of the electrolyzed water to improve the cleaning power of the electrolyzed water. Accordingly, the decrease in the electrolytic efficiency due to the high pressure of the electrolytic cell is constant even if a high dissolved hydrogen concentration (DH) and OPR are obtained by improving the water pressure by allowing a constant current to flow up and down by the structure of the above-mentioned electrolyzer. The current flows to prevent the reduction of the overall electrolytic efficiency.

As described above, the electrolyzed water generating device used in the semiconductor process according to the present invention improves the dissolved hydrogen concentration and OPR value by improving the pressure of the electrolyzer, thereby improving the cleaning power and allowing a constant current to flow through each electrode. By doing so, there is an advantage to improve the electrolytic efficiency.

In addition, the electrolyzed water generating device used in the semiconductor process according to the present invention has an advantage of reducing power loss due to the reduction in interfacial resistance, since it does not constitute a separate ion exchange membrane.

1 is a schematic view showing an electrolytic water generating device according to the prior art, Figure 2 is a schematic view showing an electrolytic cell which is one configuration of the electrolytic water generating device used in the semiconductor process according to the present invention, Figure 3 is a state diagram of the use of the present invention, 4A and 4B are schematic views showing an embodiment of an electrolytic cell which is one configuration of the present invention.

The electrolytic water generating apparatus used in the semiconductor process of the present invention corresponds to a plurality of anode electrodes formed of multi-stage electrodes in series, separated from each other in a vertical direction from the bottom of the electrolyzer, and a plurality of anode electrodes formed of multi-stage electrodes in series, respectively. A plurality of cathode electrodes formed of multi-stage electrodes in series so as to be separated from each other in a vertical direction from a lower part of the electrolytic cell, an anode electrode at one end of the plurality of anode electrodes, and a cathode electrode at another end of the plurality of cathode electrodes It is formed and includes an external power source for applying a voltage to, characterized in that the anode electrode and the cathode electrode which is not connected to the external power source is connected to each other by a wire. That is, a plurality of cathode electrodes are formed in series at a predetermined interval in a vertical direction from the lower part of the electrolytic cell, and a plurality of anode electrodes are formed in series at a predetermined interval so as to face the plurality of cathode electrodes. It is formed to apply a DC voltage to the anode electrode at one end of the two anode electrodes and the cathode electrode at the other end of the plurality of cathode electrodes, so that a constant current flows at all times without being affected by the water pressure due to the height difference in the electrolytic cell. As a result, the electrolytic efficiency is improved, and a constant pH and redox potential (OPR) are obtained.

Hereinafter will be described in more detail with reference to the accompanying drawings an embodiment of the present invention.

Figure 2 is a schematic diagram showing an electrolytic cell which is one configuration of the electrolytic water generating apparatus used in the semiconductor process according to the present invention, Figure 3 is a state diagram of the present invention, Figures 4a and 4b is an implementation of the electrolytic cell of one configuration of the present invention A schematic diagram showing an example.

The present invention is characterized by maintaining a constant pH, OPR in the electrolyzed water discharged from the electrolytic cell by improving the electrolytic efficiency by using a multi-stage electrode electrically connected in series in the electrolytic cell. In particular, the present invention improves cleaning power by discharging electrolyzed water having a high dissolved hydrogen concentration and OPR as the water pressure of the electrolyzer is increased, and the conductivity reduction by the high water pressure of the electrolyzer is multi-stage electrically connected in the above-mentioned electrolyzer. The use of the electrode is characterized by improving the electrolytic efficiency.

The electrolytic water generating device used in the semiconductor process of the present invention includes an electrolytic cell 110 as shown in FIG. The alkali water generating chamber 120, the acidic water generating chamber 130, the respective alkaline water generating chambers 120, and the acidic water generating chamber 130 are partitioned into the partition wall 160 by the ion exchange resin inside the electrolytic cell 110. ) And a cathode electrode configured in a plurality of partition walls 124 for partitioning up and down into a plurality of chambers (C1, C2, etc., A1, A2, etc.) and the chambers (C1, C2, etc., A1, A2, etc.) 140), the anode pole 150 is characterized by. Here, in the case of the alkaline water generating chamber 120 and the acidic water generating chamber 130 in which pure water flows in the electrolytic cell 110, it is appropriate to increase the water pressure by narrowing the chamber interval. Increasing the water pressure in this way increases the dissolved hydrogen concentration (DH), OPR, and the like of the electrolyzed water, thereby improving the washing power. Preferably, the inlet water pressure of the pure water in the electrolyzer 110 is appropriately 0.1 to 0.5 MPa, and the electrolyzed water discharge water pressure in the electrolyzer 110 is appropriately adjusted to 0.2 MPa or less. When configuring the electrolytic cell 110 to increase the water pressure there is a problem that the conductivity of the current is lowered according to the high water pressure. To this end, in the present invention, as shown in FIG. 2, a voltage is applied to the lowermost cathode electrode 140 and the uppermost anode electrode 150, and the chamber is different between the anode electrode 150 and the cathode electrode 140. As it is connected to each other, the electrodes in each chamber are to be electrically connected in series. By doing so, the current is formed differently according to the up and down water pressure of the electrolytic cell, so that the electrolytic efficiency is lowered or the non-uniformity is improved.

The cathode electrode 140 and the anode electrode 150 are configured such that a platinum group metal such as platinum or iridium, a platinum group metal of platinum or iridium, or a mixture thereof is plated on a titanium or stainless steel material. As the electrode material of the cathode electrode 140 and the anode electrode 150, a material that is difficult to be oxidized such as titanium is selected in order to facilitate electron transfer and easily oxidize between both electrodes by electrolysis. It is preferable to plate platinum, iridium, or the like. Moreover, since the polarity of a power supply may be changed, it is preferable to apply the same plating to all the said positive electrodes.

In the present invention, as shown in Figure 2, the alkaline water generating chamber 120 and the acidic water generating chamber 130 are respectively divided into four chambers (C1, C2, C3, C4, A1, A2, A3, A4), respectively. An example in which four cathode electrodes 140 and four anode electrodes 150 are provided in a chamber of the present invention is shown. Of course, the number of such chambers and electrodes can be configured selectively.

That is, in the embodiment shown in FIG. 2, the cathode electrode 140 and the anode electrode 150 are disposed in the respective chambers, and the anode electrode 150 of the lowermost chamber A1 and the chamber C2 thereon are disposed. The cathode electrode 140 of the structure is electrically connected to the anode electrode 150 of the lower chamber and the cathode electrode 140 of the upper chamber electrically connected, and the lowermost chamber (C1) and the uppermost chamber (A4) finally Apply a DC voltage. When forming the electrode of the multi-step as described above, it is possible to obtain the effect of increasing the electrode area. As described above, when the area of the electrode is increased, an effect of controlling the dissociation reaction of water in the partition wall 160 may be obtained and the electrolytic efficiency may be increased. In particular, the lower chambers C1 and A1 have high water pressure but the current is constant, and the upper chambers C4 and A4 have low water pressure, but the current is constant so that the overall electrolytic efficiency is high and constant. That is, a potential difference occurs in each electrode due to a resistance difference due to water pressure. For example, when a voltage of 100 V is formed in an electrode part located in the lowermost chambers C1 and A1 of the electrolytic cell 110, the upper end is about 20 The voltage difference is generated in such a way that a voltage of 80V, which is reduced by%, and a voltage of 60V, which is reduced by 20%, is generated at the upper end thereof, so that a constant current flow is always generated in each electrode. As a result, a constant current flows at all times without being affected by the pressure difference due to the height difference in the electrolytic cell 110, thereby improving the electrolytic efficiency and maintaining the pH of the electrolyzed water and the constant of OPR. It is easy to obtain the electrolyzed water.

The partition wall 160 is formed of an ion exchange resin, and prevents the mixing of the alkali water and the acid water generated in the alkaline water generating chamber 120, the acidic water generating chamber 130, and increases the efficiency of the current The material is a well-known material, and the description is abbreviate | omitted.

In the present invention, the ion exchange membrane 170 is formed on both surfaces of the partition wall 160, that is, the surfaces exposed to the alkali water generating chamber 120 and the acidic water generating chamber 130, respectively. The ion exchange membrane 170 may selectively constitute an anion exchange membrane 171 or a cation exchange membrane 172.

In particular, in the present invention, as shown in FIGS. 4A and 4B, the anion coating layer 181 having an anion exchange group on both surfaces of the partition wall 160, that is, the surface exposed to the alkali water generating chamber 120 and the acidic water generating chamber 130, respectively. Or an ion exchange unit 180 composed of a cation coating layer 182 having a cation exchange group.

Here, the anion coating layer 181 is characterized by having an anion exchange group, the cation coating layer 182 is characterized by having a cation exchange group. The anion coating layer 181 and the cation coating layer 182 is formed by dissolving a resin having an anion exchange group and a cation exchange group, respectively, in an organic solvent and applying this solution to both sides of the partition wall 160. The anion exchange group may be a primary amine group, a secondary amine group, a tertiary amine group, a quaternary ammonium group, a polyethyleneimine group or a phosphonium group, and the cation exchange group may be a sulfonic acid group, a phosphoric acid group or a carboxylic acid group. Can be. Thus, the ion exchange unit 180 is formed on both sides of the partition wall 160 to induce only the selected ions to the alkaline water generating chamber 120 and the acidic water generating chamber 130, and the ion exchange membrane itself according to the configuration of a separate ion exchange membrane. It is possible to prevent a decrease in conduction efficiency due to an increase in the resistance of the entire system due to the ion transfer resistance and the contact resistance (Rc) due to the generation of the interface between the ion exchange membrane and the partition wall.

Meanwhile, in the present invention, an embodiment of the anion coating layer 181 and the cation coating layer 182 is presented, and the anion coating layer 181 and the cation coating layer 182 are poorly soluble in the organic solvent, the polymer binder and the organic solvent, respectively. The example which consists of ion selective resin powder is shown. Here, the ion-selective resin powder is poorly soluble in the organic solvent and is present in the anion coating layer 181 and the cation coating layer 182 by the mixture of the polymer binder and the organic solvent, but is not exposed in the form of particles. will be. That is, since the ion-selective resin powder is present in the form of particles, the reaction area with the ions can be increased, thereby increasing the reaction efficiency with the ions.

In particular, the ion-selective resin powder is characterized in that it is poorly soluble in the organic solvent, the ion-selective resin powder is to be poorly soluble in the organic solvent by using a crosslinked. Here, poor solubility is defined as solubility of 6 wt% or less.

As the ion-selective resin powder, it is appropriate to use a polymer resin powder having a cation exchange group or a polymer resin powder having an anion exchange group. The cation exchange group and the anion exchange group are as described above.

In the ion-selective resin powder, the polymer resin is not limited, but is cross-linked and insoluble in an organic solvent, such as poly (styrene-divinylbenzene), polystyrene, polyisulfone, polyamide, polyester, polyimide, poly Any one or a mixture of two or more selected from ether, polyethylene and polytetrafluoroethylene can be used.

In addition, the polymer binder may use one or two or more of a nonionic polymer, a polymer having a cation exchange group, and a polymer having an anion exchange group. As the nonionic polymer, although not limited thereto, one or two or more mixtures selected from the group consisting of polyisulfone, polysulfone, polyvinylidenedifluoride, polyacrylonitrile, and cellulose acetate may be used. .

In addition, the organic solvent is determined by the type of the polymer binder, and all the organic solvents in which the selected polymer binder is dissolved are possible. It is reasonable to use one or more mixtures selected from the group consisting of carbonates.

It is reasonable that the anion coating layer 181 and the cation coating layer 182 having the above-described configuration are blended with 20 to 200 parts by weight of the polymeric binder and 50 to 600 parts by weight of the organic solvent based on 100 parts by weight of the ion-selective resin powder.

3 is a schematic view showing a state of use of the electrolytic water generating device 100 of the present invention. Electrolytic water generating device 100 of the present invention is connected to the electrolytic cell 110, the front end of the electrolytic cell 110 by the filter unit 10 and the inlet line 20, the discharge water discharged from the electrolytic cell 110 flow rate The discharge valve 60 is configured with a control valve 61 is configured, the discharge line 60 is characterized in that the storage line 30 and the discharge line 40 is connected by a three-way valve (50).

First, inflow water is introduced into the filter unit 10, and pure water is discharged into the inflow line 20, and pure water flows into the electrolytic cell 110. The inlet line 20 communicates with the

pure water inlets

121 and 131 formed at the lower end of the electrolytic cell 110 and the electrolyte solution inlet 161 so that pure water through the filter unit 10 flows into the electrolytic cell 110. To make it possible. Here, the line connected to the electrolyte solution inlet 161 of the inlet line 20 is connected through the electrolyte solution reservoir 60 and the opening / closing valve 61 as shown in FIG. 3. That is, the electrolyte solution is mixed from the electrolyte solution reservoir 60 to the pure water flowing into the inlet line 20 so that the electrolyte solution flows into the partition wall 160 through the electrolyte solution inlet 161. The pure water introduced in this way allows the alkali water generation chamber 120 to generate alkali water in the electrolytic cell 110 and the acid water generation in the acid water generation chamber 130, and the alkali water formed at the top of the electrolytic cell 110. The electrolytic water is discharged through the outlet 122, the electrolyte solution outlet 162, and the acidic water outlet 132, and the alkaline water outlet 122, the electrolyte solution outlet 162, and the acidic water outlet 132 are discharge lines 60. Is connected to. In particular, in the present invention, it is appropriate to configure the flow rate control valve 61 in the discharge line 60 to control the water pressure of the electrolytic cell 10. By operating the flow control valve 61 to adjust the water pressure in the alkaline water generating chamber 120 and the acidic water generating chamber 130, an appropriate dissolved oxygen, dissolved hydrogen, OPR can be obtained to the discharged alkaline or acidic water. To make it possible.

The discharge line 60 is connected to the storage line 30 and the discharge line 40 by a three-way valve (50). That is, the alkaline or acidic water may be flowed to the storage line 30 or the discharge line 40 through the control of the three-way valve 50 according to the use. For example, when the alkaline water is stored in the storage tank 31 and used in the semiconductor process, only the alkaline water flows into the storage tank 31 by turning on the three-way valve 50-1 of the storage line 30 communicating with the alkaline water outlet 122. The remaining three-way valves 50-2 and 3 are turned off so that the treated water from the electrolyte solution outlet 162 mixed with the acid water, the dregs, the wastes, etc. is allowed to flow to the discharge line 40, as shown in the drawing. There is no bar but can be circulated to the filter unit 10 or discarded.

In this way, the alkali or acidic water selectively stored in the storage tank 31 is used in the semiconductor process, especially in the manufacture of semiconductor devices or in the manufacture of liquid crystals. In the manufacture of a semiconductor device, pure water is guided through the filter unit 10, and electrolytic water obtained by electrolyzing such pure water through the electrolytic cell 110 is used to clean a semiconductor substrate such as silicon or to coat the surface of the semiconductor substrate. Will be polished. Pure water is water of high purity having a resistivity of about 5 to 18, in which most impurities such as ions, fine particles, microorganisms, and organic substances are removed. By electrolyzing these waters, acidic water having strong oxidative properties and alkaline water having strong reducing properties are produced. For example, in the case of using a polishing apparatus used for manufacturing a semiconductor device, in order to perform polishing using alkaline water, only the storage line 30 which interworks with the alkaline water generating chamber 120 is opened, and the alkaline water is polished to the polishing apparatus of the polishing apparatus. To supply. In this case, the acidic water generated in the acidic water generating chamber 130 is unnecessary and disposed of through the discharge line 40. In addition, in order to polish using acidic water, only the storage line 30 interlocked with the acidic water generating chamber 130 is opened to supply acidic water to the polishing pad. In this case, the electrolyte solution supplied to the partition wall 160 is to electrolyze an electrolyte solution such as HCl, HNO ₃ , NH ₄ Cl, NH ₄ F, NH ₄ OH, and the like to generate electrolytic water having an arbitrary pH.

Meanwhile, the present invention provides an embodiment for discharging strong acidic water or strong alkaline water by selectively configuring the ion exchange unit 180 as shown in FIGS. 4A and 4B.

First, the example shown in FIG. 4A is an example of discharging strong acidic water, applying an anion coating layer 181 on both sides of the partition wall 160, and introducing an electrolyte solution into the electrolyte solution inlet 161 communicating with the partition wall 160. Pure water is introduced into the

pure water inlets

121 and 131 of the alkaline water generating chamber 120 and the acidic water generating chamber 130. Here, the electrolyte solution is shown as an example using a solution in which NH ₄ OH dissolved in pure water. Among the electrolyzed water introduced into the partition wall 160, hydroxide ions OH ⁻ flow into the acidic water generation chamber 130 by electric force, and the hydroxide ions OH ^{− in the} alkali water generation chamber 120 also generate acidic water. Move to chamber 130. In addition, water (H ₂ O), as illustrated is Figure electrolysis hydroxide ions (OH ^-) shifts to the acidic water generating chamber 130. Therefore, the acid number generation chamber 130 hydroxyl ion (OH ^-) is be a lot to generate a gangsanseongsu. The partition wall 160 is an anion of hydroxide ion (OH ^-) to the function of this so as to easily flow to the acid to create the chamber 130.

Meanwhile, in FIG. 4B, a cation coating layer 182 is applied to both surfaces of the partition wall 160, an electrolyte solution is introduced into the electrolyte solution inlet 161 communicating with the partition wall 160, and the alkaline water generating chamber 120 and acidic water are provided. Pure water is introduced into the

pure water inlets

121 and 131 of the production chamber 130. Ammonium ions (NH 4 +) in the electrolyte solution introduced into the partition wall 160 flows to the alkaline water generating chamber 120 by electric force, and the ammonium ions (NH 4 +) of the acidic water generating chamber 130 are also alkali water generating chambers ( Go to 130). In addition, as shown, water (H ₂ O) is also electrolyzed to move the hydrogen ions (H +) to the alkaline water generating chamber (120). Therefore, in the alkali water generating chamber 120, hydrogen ions (H +) are increased to generate strong alkaline water. In this case, the partition wall 160 serves to easily flow hydrogen ions (H +), which are cations, into the alkaline water generating chamber 120.

The present invention by the configuration and operation as described above is to generate the electrolytic water required in the semiconductor process, that is, the process for cleaning the semiconductor substrate. For example, a roll-shaped brush for cleaning a semiconductor substrate and the electrolytic cell 110 are connected by the storage line 30 to supply electrolytic water, that is, acidic water and alkaline water to the brush.

The present invention will be described based on the following experimental examples.

Experimental Example 1

In Experimental Example 1, when the input pressure of the electrolyzer was adjusted to 0.2 MPa and the output pressure to 0.05 MPa, and when NH ₄ OH 50 ppm and 100 ppm were diluted in pure water and pure water by the electrolyte solution inlet 161 communicating with the partition wall 160, respectively. OPR and dissolved hydrogen concentration were measured, and the results are shown in Table 1 below.

Table 1

	electric current	Electrolyzer Input Pressure	Electrolyzer Output Pressure	pH	ORP	Dissolved hydrogen
Ultrapure water	10 [A]	0.2 Mpa	0.05 Mpa	7.5	-500 mV	700 ppb
Ultrapure Water + NH ₄ OH (50 ppm)	10 [A]	0.2 Mpa	0.05 Mpa	9.5	-650 mV	850 ppb
Ultrapure Water + NH ₄ OH (100 ppm)	10 [A]	0.2 Mpa	0.05 Mpa	10.5	-780 mV	1500 ppb

As shown in Table 1, when the electrolyte solution in which the NH ₄ OH is diluted into the pure water is introduced into the electrolyte solution inlet 161 communicating with the partition wall 160, the electrolytic water (functional water) having high dissolved hydrogen concentration is generated. It can be seen that. Also, it can be seen that OPR and electrolytic water (functional water) having a high dissolved hydrogen concentration are produced when 100 ppm is diluted than when 50 ppm of NH ₄ OH is diluted with pure water.

-. Experimental Example 2

Experimental Example 2 adjusted the input pressure of the electrolyzer to 0.1 MPa and the output pressure to 0.05 MPa, and diluted NH ₄ OH 50 ppm and 100 ppm in pure water and pure water with the electrolyte solution inlet 161 communicating with the partition wall 160, respectively. OPR and dissolved hydrogen concentration were measured and the results are shown in Table 2 below.

TABLE 2

	electric current	Electrolyzer Input Pressure	Electrolyzer Output Pressure	pH	ORP	Dissolved hydrogen
Ultrapure water	10 [A]	0.1 Mpa	0.05 Mpa	7.5	-350 mV	400 ppb
Ultrapure Water + NH ₄ OH (50 ppm)	10 [A]	0.1 Mpa	0.05 Mpa	9.5	-550 mV	600 ppb
Ultrapure Water + NH ₄ OH (100 ppm)	10 [A]	0.1 Mpa	0.05 Mpa	10.5	-670 mV	1100 ppb

As shown in Table 2, when the electrolyte solution in which the NH ₄ OH is diluted into pure water is introduced into the electrolyte solution inlet 161 communicating with the partition 160, OPR and electrolytic water (functional water) having a high dissolved hydrogen concentration are generated. It can be seen that. In particular, in the present experimental example, as a result of lowering the input pressure by 0.1 MPa than the experimental example 1, it can be seen that electrolytic water (functional water) having low OPR and dissolved hydrogen concentration in each example was produced.

-. Experimental Example 3

Experimental Example 3 adjusted the input pressure of the electrolyzer to 0.1 MPa and the output pressure to 0.01 MPa, and diluted NH ₄ OH 50 ppm and 100 ppm in pure water and pure water with the electrolyte solution inlet 161 communicating with the partition wall 160, respectively. OPR and dissolved hydrogen concentration were measured and the results are shown in Table 3 below.

TABLE 3

	electric current	Electrolyzer Input Pressure	Electrolyzer Output Pressure	pH	ORP	Dissolved hydrogen
Ultrapure water	10 [A]	0.1 Mpa	0.01 Mpa	7.5	-230 mV	250 ppb
Ultrapure Water + NH ₄ OH (50 ppm)	10 [A]	0.1 Mpa	0.01 Mpa	9.5	-420 mV	410 ppb
Ultrapure Water + NH ₄ OH (100 ppm)	10 [A]	0.1 Mpa	0.01 Mpa	10.5	-550 mV	550 ppb

As shown in Table 3, when the electrolyte solution in which the NH ₄ OH is diluted into the pure water is introduced into the electrolyte solution inlet 161 communicating with the partition wall 160, the electrolytic water (functional water) having a high dissolved hydrogen concentration is generated. It can be seen that. In particular, in the present experimental example, as a result of lowering the output pressure by 0.04 MPa than Experimental Example 2, it can be seen that electrolytic water (functional water) having low OPR and dissolved hydrogen concentration in each example was produced.

As shown in the above experimental examples, electrolytic water having high OPR and dissolved hydrogen concentrations was generated in an electrolyte solution diluted to 100 ppm of NH ₄ OH than 50 ppm of NH ₄ OH than pure water. In the case of 0.2 MPa, electrolyzed water with OPR and dissolved hydrogen concentration higher than 0.1 MPa, output pressure 0.05 MPa, and 0.01 MPa was found.

Those skilled in the art will appreciate that various changes and modifications can be made without departing from the spirit of the present invention. Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification but should be defined by the claims.

Claims

An electrolyzer including an electrolyzer, wherein the electrolyzer comprises an anode and a cathode to discharge acidic or alkaline water.
The method of claim 1,

The electrolyzers are separated from each other in a vertical direction from the bottom with a plurality of anode poles formed in multi-step electrodes in series, and a plurality of anode poles formed in series with the multi-step electrodes, respectively, at positions corresponding to each other in a vertical direction from the bottom. And a plurality of cathode poles formed of a multi-level electrode in series in a separated form, an anode pole at one end of the plurality of anode poles, and an external power source for applying a voltage to the cathode pole at the other end of the plurality of cathode poles. And an anode pole and a cathode pole not connected to the external power source are connected to each other by an electrically connected wire.
The method of claim 2,

In the electrolytic cell, the electrolyzed water generating device used in the semiconductor process, characterized in that the partition wall formed by the ion exchange resin is configured to partition between the plurality of anode and cathode electrodes.
The method of claim 3, wherein

Ion exchange membrane is formed on both sides of the partition wall, the ion exchange membrane is used in the semiconductor process, characterized in that consisting of an anion exchange membrane or a cation exchange membrane.
The method of claim 3, wherein

An ion exchange part is coated on both sides of the partition wall, wherein the ion exchange part comprises an anion coating layer having an anion exchange group or a cation coating layer having a cation exchange group.
The method of claim 5,

The anion coating layer or the cation coating layer,

The organic solvent, the polymer binder and the organic solvent, characterized in that it consists of poorly soluble ion-selective resin powder, wherein the ion-selective resin powder is cross-linked, it is a polymer resin having a cation exchange group or a polymer resin having an anion exchange group Electrolyzed water generating device used in the semiconductor process.
The method of claim 2,

The electrolyzer is an electrolytic water generating device used in a semiconductor process, characterized in that the inlet line is formed at the lower end is connected to the filter unit, the discharge line is formed at the upper end, the flow control valve is configured in the discharge line.
The method of claim 7, wherein

The discharge line is an electrolytic water generating device used in a semiconductor process, characterized in that the storage line and the discharge line is connected by a three-way valve.