JP2003086557A - Substrate treatment method and apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of feeding a substrate with ozonized water of high ozone concentration produced by an ozonized water producer which prevents ozone in the ozonized water from being decomposed due to static electricity during sending of the ozonized water to a processor via a feed pipe from the producer. SOLUTION: A processor 10 is fed with ozonized water 18 via a feed pipe 16 made of synthetic resin having corrosion resistance to the ozonized water from a storage tank 20 and supplies the ozonized water to a substrate W to treat it. In this process, the ozonized water is sent to the processor, when carbon dioxide is dissolved in the ozonized water, to lower its resistivity to 1 MΩ.cm or less.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a semiconductor wafer,
The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate by supplying ozone water to a substrate such as a glass substrate for a flat panel display (FPD).

[0002]

2. Description of the Related Art In the manufacturing process of semiconductor devices, FPDs, etc., for example, ozone water in which pure water is dissolved is carried while supporting a substrate in a horizontal posture or an inclined posture by a plurality of conveying rollers while conveying ozone water. A process of supplying to the substrate from a nozzle to remove organic substances adhering to the surface of the substrate for cleaning, or peeling the resist film formed on the surface of the substrate is performed. In a substrate processing apparatus that performs such a process, ozone water, for example, has a dissolution membrane module inserted in the middle of a pipe that connects a pure water supply source and a nozzle, and the pure water flows through the dissolution membrane module. At the same time, it is generated by supplying ozone gas to the dissolution membrane module and dissolving the ozone gas in pure water flowing in the dissolution membrane module. The ozone water generated in this manner is a synthetic resin material having corrosion resistance to ozone water, for example, FEP (Fluorinated ethyrene propyren).
e), and is supplied to the nozzle through a liquid supply pipe formed of a fluororesin material such as PFA (Perfluoroalkoxy fluoroplastics).

[0003]

As described above, the liquid supply pipe connecting the dissolution membrane module and the nozzle is formed of a fluororesin so as not to be corroded by ozone water. It is an electrical insulator. For this reason,
When the ozone water flows in the liquid sending pipe, static electricity is generated due to friction between the inner wall surface of the pipe and the ozone water, and the liquid sending pipe is charged. The present inventor has found that a part of ozone in ozone water is decomposed by static electricity on the liquid supply pipe. As a result, while the ozone water generated in the dissolution membrane module is sent to the nozzle through the liquid supply pipe, the concentration of ozone in the ozone water decreases, and the ozone water with the decreased ozone concentration is discharged from the nozzle to the substrate. Therefore, there is a problem that the substrate is not sufficiently processed.

The present invention has been made in view of the above circumstances, and while the ozone water generated in the ozone water generating section is supplied to the processing section through the liquid supply pipe, it is generated by static electricity. To provide a substrate processing method capable of preventing decomposition of ozone in ozone water, supplying ozone water having a high ozone concentration to the substrate, and sufficiently processing the substrate, and preferably implementing the method. An object of the present invention is to provide a substrate processing apparatus capable of performing the above.

[0005]

The invention according to claim 1 is
The ozone water generated in the ozone water generation unit is sent to the processing unit through a liquid sending pipe formed of a synthetic resin material having corrosion resistance to ozone water, and the processing unit supplies the ozone water to the substrate to supply the substrate. In the method for treating a substrate, the ozone water whose carbon dioxide gas is dissolved and whose specific resistance value is 1 MΩ · cm or less is fed to the treatment section.

According to the second aspect of the present invention, the ozone water produced in the ozone water producing section is fed to the treating section through a liquid delivery pipe formed of a synthetic resin material having corrosion resistance to the ozone water, and the treating section is treated. In a substrate processing method of supplying ozone water to a substrate in a part to process the substrate, static electricity carried by the liquid sending pipe is removed by flowing ozone water in the liquid sending pipe.

According to the third aspect of the present invention, the ozone water generated in the ozone water generating section is fed to the processing section through a liquid feeding pipe formed of a synthetic resin material having a corrosion resistance to the ozone water for treatment. In a substrate processing method of supplying ozone water to a substrate at a portion to treat the substrate, the ozone water having a specific resistance value of 1 MΩ · cm or less due to dissolution of carbon dioxide gas is sent to the treatment portion, and It is characterized in that static electricity caused by the liquid supply pipe is removed by flowing ozone water in the liquid supply pipe.

According to a fourth aspect of the present invention, in the substrate processing method according to the first or third aspect, ozone gas and carbon dioxide gas are dissolved in pure water in the ozone water generating section,
It is characterized in that ozone water in which carbon dioxide gas is dissolved is prepared.

According to a fifth aspect of the present invention, a processing section for supplying ozone water to the substrate to process the substrate, an ozone water generating section for dissolving ozone gas in pure water to generate ozone water, and ozone. In the substrate processing apparatus, which is formed of a synthetic resin material having corrosion resistance to water, and has a liquid supply pipe for supplying the ozone water generated by the ozone water generation unit to the processing unit, the ozone water generation A carbon dioxide gas dissolving means for dissolving carbon dioxide gas in pure water or ozone water to make the specific resistance value of the ozone water to be fed to the processing portion 1 MΩ · cm or less is provided in the middle of the section or the liquid supply pipe. It is characterized by that.

According to a sixth aspect of the present invention, a processing section for supplying ozone water to the substrate to process the substrate, an ozone water generating section for dissolving ozone gas in pure water to generate ozone water, and ozone. In the substrate processing apparatus, which is formed of a synthetic resin material having corrosion resistance to water, and a liquid supply pipe for supplying the ozone water generated in the ozone water generation unit to the processing unit, the liquid supply pipe In addition, it is characterized in that a static elimination means for removing static electricity caused by the liquid supply pipe by flowing ozone water in the liquid supply pipe is provided.

According to a seventh aspect of the present invention, a processing section for supplying ozone water to the substrate to process the substrate, an ozone water generating section for dissolving ozone gas in pure water to generate ozone water, and ozone. In the substrate processing apparatus, which is formed of a synthetic resin material having corrosion resistance to water, and has a liquid supply pipe for supplying the ozone water generated by the ozone water generation unit to the processing unit, the ozone water generation A carbon dioxide gas dissolving means for dissolving carbon dioxide gas in pure water or ozone water to make the specific resistance value of the ozone water to be fed to the treatment section 1 MΩ · cm or less is provided in the middle part or in the liquid supply pipe. At the same time, the liquid delivery pipe is provided with a static eliminator for removing static electricity caused by the ozone water flowing in the liquid delivery pipe.

The invention according to claim 8 is the substrate processing apparatus according to claim 5 or 7, wherein the carbon dioxide gas dissolving means is provided in the ozone water producing section, and ozone gas is added to pure water in the ozone water producing section. And carbon dioxide gas are dissolved to prepare ozone water in which carbon dioxide gas is dissolved.

According to a ninth aspect of the present invention, in the substrate processing apparatus according to the sixth or seventh aspect, the static elimination means is:
It is characterized in that it is provided with a covering pipe formed of a conductive material and covering the outer surface side of the liquid sending pipe, and a conducting wire electrically connected to the covering pipe and grounding the covering pipe.

According to a tenth aspect of the present invention, in the substrate processing apparatus according to any one of the fifth to ninth aspects, the ozone water producing section has a tank for storing ozone water and corrosion resistance to ozone water. A circulation pipe that is formed of a synthetic resin material and is disposed outside the tank to circulate ozone water between the inside of the tank and the tank, and the inside of the circulation pipe is filled with ozone water. It is characterized in that a circulation pipe static elimination means for removing static electricity caused by the flow of the circulation pipe is provided.

According to an eleventh aspect of the present invention, in the substrate processing apparatus according to the tenth aspect, the circulation pipe static eliminator is
It is characterized in that it is provided with a coating pipe which is made of a conductive material and covers the outer surface side of the circulation pipe, and a conductive wire which is electrically connected to the coating pipe and grounds the coating pipe.

According to the substrate processing method of the first aspect of the present invention, carbon dioxide gas is dissolved in the ozone water supplied to the processing section through the liquid supply pipe, and the specific resistance value of the ozone water is 1 MΩ.
Since it is less than or equal to cm, generation of static electricity due to friction between the inner wall surface of the pipe and ozone water due to the flow of ozone water in the liquid supply pipe formed of a synthetic resin material can be suppressed. Therefore, the influence of static electricity on the liquid supply pipe is reduced, and the decomposition of ozone in ozone water is prevented. Therefore, ozone water having a high ozone concentration can be supplied to the substrate.

According to the substrate processing method of the second aspect of the present invention, the ozone water flows in the liquid sending pipe formed of the synthetic resin material, whereby static electricity is generated by friction between the inner wall surface of the pipe and the ozone water. Even if the pipe is charged, its static electricity is removed, so that it is possible to prevent the ozone in the ozone water from being decomposed by the static electricity on the liquid supply pipe. Therefore, ozone water having a high ozone concentration can be supplied to the substrate.

According to the substrate processing method of the third aspect of the present invention, carbon dioxide gas is dissolved in the ozone water supplied to the processing section through the liquid supply pipe, and the specific resistance value of the ozone water is 1 MΩ.
Since it is less than or equal to cm, generation of static electricity due to friction between the inner wall surface of the pipe and ozone water due to the flow of ozone water in the liquid supply pipe formed of a synthetic resin material can be suppressed. Further, even if the liquid supply pipe is charged, static electricity is removed from the liquid supply pipe. Therefore, it is possible to prevent the ozone in the ozone water from being decomposed by the static electricity of the liquid supply pipe. Therefore, ozone water having a high ozone concentration can be supplied to the substrate.

In the substrate processing method of the invention according to claim 4,
Since the ozone water in which carbon dioxide gas is dissolved is prepared in the ozone water generating unit, generation of static electricity can be suppressed over the entire flow path from the ozone water generating unit to the processing unit.

In the substrate processing apparatus of the fifth aspect of the present invention, carbon dioxide gas is dissolved in pure water or ozone water by the carbon dioxide gas dissolving means, and ozone water having a specific resistance value of 1 MΩ · cm or less is sent. Since the liquid is supplied to the processing unit through the liquid pipe, it is possible to suppress the generation of static electricity due to the friction between the inner wall surface of the pipe and the ozone water that accompanies the flow of ozone water in the liquid pipe formed of the synthetic resin material. Therefore, the influence of static electricity on the liquid supply pipe is reduced, and the decomposition of ozone in ozone water is prevented. Therefore, ozone water having a high ozone concentration can be supplied to the substrate in the processing section.

In the substrate processing apparatus according to the sixth aspect of the present invention, the ozone water generated in the ozone water generating unit flows in the liquid supply pipe formed of the synthetic resin material, so that the inner wall surface of the pipe and the ozone water are Even if static electricity is generated by friction with the liquid sending pipe and the static charge is removed by the static eliminating means, it is possible to prevent ozone in the ozone water from being decomposed by the static electricity carried by the liquid sending pipe. Therefore, ozone water having a high ozone concentration can be supplied to the substrate in the processing section.

In the substrate processing apparatus of the seventh aspect of the present invention, carbon dioxide gas is dissolved in pure water or ozone water by the carbon dioxide gas dissolving means, and ozone water having a specific resistance value of 1 MΩ · cm or less is sent. Since the liquid is supplied to the processing unit through the liquid pipe, it is possible to suppress the generation of static electricity due to the friction between the inner wall surface of the pipe and the ozone water that accompanies the flow of ozone water in the liquid pipe formed of the synthetic resin material. Further, even if the liquid supply pipe is charged, the static electricity is removed by the static elimination means. Therefore, it is possible to prevent the ozone in the ozone water from being decomposed by the static electricity of the liquid supply pipe. Therefore, ozone water having a high ozone concentration can be supplied to the substrate in the processing section.

In the substrate processing apparatus of the invention according to claim 8,
In the ozone water generation unit, the carbon dioxide gas is dissolved in the pure water by the carbon dioxide gas dissolution means in the pure water, and the ozone water in which the carbon dioxide gas is dissolved is prepared, so that the entire flow path from the ozone water generation unit to the treatment unit is completed. Generation of static electricity is suppressed.

In the substrate processing apparatus of the invention according to claim 9,
The static electricity generated in the liquid supply pipe flows to a conductive coating pipe that covers the outer surface side of the liquid supply pipe, and is removed through a grounding wire that is electrically connected to the coating pipe.

In the substrate processing apparatus according to the tenth aspect of the present invention, in the ozone water producing section, the ozone water is circulated between the inside of the tank and the inside of the circulation pipe, and inside the circulation pipe formed of the synthetic resin material. Even if static electricity is generated due to friction between the inner wall surface of the pipe and ozone water by flowing through the circulation pipe, the static electricity is removed by the static electricity elimination means of the circulation pipe. The ozone is prevented from being decomposed.
Therefore, the efficiency of ozone water generation in the ozone water generation unit is increased, the ozone water generation time for the ozone water concentration to reach a predetermined high concentration is shortened, and the ozone concentration reached is further increased. Then, it becomes possible to feed the ozone water having a high ozone concentration from the ozone water generating unit to the processing unit through the liquid feeding pipe.

In the substrate processing apparatus according to the eleventh aspect of the present invention, the static electricity generated in the circulation pipe flows to the conductive coating pipe that covers the outer surface side of the circulation pipe, is electrically connected to the coating pipe, and is grounded. Is removed through the lead wire.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a diagram schematically showing an example of a schematic configuration of a substrate processing apparatus used for carrying out the substrate processing method according to the present invention. The substrate processing apparatus includes a processing unit 10 that processes the substrate W while transporting the substrate W while supporting the substrate W in a horizontal posture or an inclined posture by a plurality of transport rollers (not shown).

The processing unit 10 has a shower nozzle 12 above the substrate W conveyed by a plurality of conveying rollers and jetting and supplying ozone water in which ozone is dissolved in pure water to the upper surface of the substrate W. It is arranged. Further, a recovery pan 14 for recovering the ozone water supplied from the shower nozzle 12 to the substrate W and flowing down from the substrate W is disposed below the processing unit 10.

A liquid supply pipe 16 is connected to the shower nozzle 12, and the liquid supply pipe 16 is connected to a liquid storage tank 20 in which ozone water 18 is stored. The liquid supply pipe 16 is formed of a synthetic resin material having corrosion resistance to ozone water, for example, a fluorinated resin material such as FEP or PFA. A liquid feed pump 22 is provided in the liquid feed pipe 16.
And a filter 24 is provided so as to be interposed.

The liquid storage tank 20 has a closed structure, and an ozone gas exhaust pipe 28 having an opening / closing valve 26 inserted therein so as to communicate with a space above the liquid surface of the ozone water 18 stored therein. Is attached. Inside the liquid storage tank 20,
The on-off valve 26 performs exhaust adjustment so that the space above the liquid surface of the ozone water 18 is filled with ozone gas and is maintained at a positive pressure, for example, a positive pressure of 580 Pa to 980 Pa. in this way,
By maintaining the space above the liquid surface of the ozone water 18 in the liquid storage tank 20 at a positive pressure, deozone from the ozone water 18 is suppressed and ozone gas is easily dissolved in the ozone water 18. In addition, inside the liquid storage tank 20, ozone water 18
For cooling, for example, to a temperature of 15 ° C. to 20 ° C., for example, a spiral chiller pipe 30 through which cooling water flows is provided so as to be immersed in the ozone water 18 in the liquid storage tank 20. ing. By cooling the ozone water in this manner, the solubility of ozone gas in pure water increases. Further, inside the liquid storage tank 20, one end of a carbon dioxide gas supply pipe 32, which is connected to a carbon dioxide gas supply source in a flow path, is inserted, and its gas outlet is arranged near the inner bottom of the liquid storage tank 20. There is. And the carbon dioxide supply pipe 32
The carbon dioxide gas can be dissolved in the ozone water 18 by blowing the carbon dioxide gas into the ozone water 18 in the liquid storage tank 20 from the gas discharge port.

The liquid storage tank 2 is provided outside the liquid storage tank 20.
A liquid circulation pipe 34 having both ends connected to the outflow port and the inflow port formed in the shape of 0 is provided. The liquid circulation pipe 34 is formed of a synthetic resin material having corrosion resistance to ozone water, for example, a fluorinated resin material such as FEP or PFA. A liquid circulation pump 36 is provided so as to be interposed in the liquid circulation pipe 34. By operating the liquid circulation pump 36, the liquid circulation pipe 36 is connected between the inside of the liquid storage tank 20 and the liquid circulation pipe 34 outside thereof. Ozone water 18 circulates between them.

An ejector 38 is provided on the downstream side of the liquid circulation pump 36 in the liquid circulation pipe 34.
The ejector 38 has a liquid passage, the inlet and the outlet of which are connected to the liquid circulation pipe 34, and a part of which is narrowly formed,
Further, it has a structure in which a gas passage is formed, one end of which is connected to the ozone gas supply pipe 40 which is connected to the ozone gas supply source in a flow path, and the other end of which is connected to a narrow portion of the liquid passage. The ozone water, which is pressurized by the liquid circulation pump 36 and flows into the liquid passage of the ejector 38 from the liquid circulation pipe 34, is increased in flow velocity when passing through the narrow portion of the liquid passage to be a jet flow. The ozone gas in the gas passage is caught and sucked into the liquid passage, and the sucked ozone gas is dissolved in the ozone water. In this way, the concentration of ozone water is increased when the ozone water passes through the ejector 38.

In the substrate processing apparatus having the above structure,
The ozone water 18 stored in the liquid storage tank 20 is circulated between the inside of the liquid storage tank 20 and the liquid circulation pipe 34, and the ozone water is supplied to the ejector 38 inserted in the liquid circulation pipe 34. Ozone is dissolved in the ozone water as it passes. Therefore, the concentration of ozone in the ozone water stored in the liquid storage tank 20 is kept high at a predetermined concentration.
Further, carbon dioxide gas is dissolved in the ozone water 18 by blowing carbon dioxide gas into the ozone water 18 in the liquid storage tank 20 from the gas discharge port of the carbon dioxide gas supply pipe 32. At this time, the amount of dissolved carbon dioxide gas is such that the specific resistance value of the ozone water 18 becomes 1 MΩ · cm or less. As described above, the ozone water 18 in which the predetermined ozone concentration is maintained and the carbon dioxide gas is dissolved is supplied from the storage tank 20 to the liquid delivery pipe 16
Is fed to the shower nozzle 12 of the processing section 10 through
It is supplied to the substrate W from the shower nozzle 12.

Since the liquid supply pipe 16 is made of a fluorinated resin material and is an electrical insulator as described above, when ozone water flows in the liquid supply pipe 16, the inner wall surface of the pipe and the ozone are discharged. Liquid transfer pipe 1 due to static electricity generated by friction with water
6 becomes charged. When the liquid sending pipe 16 is charged, the liquid sending pipe 1
Part of the ozone in the ozone water flowing in 6 may be decomposed by static electricity. In this case, the liquid storage tank 20
And the processing unit 10 are arranged close to each other, and the liquid delivery pipe 1
If the length of 6 is shortened, it is possible to reduce the influence due to the electrification of the liquid supply pipe 16, but installing the liquid storage tank 20 near the processing unit 10 is effective in terms of space and maintenance work. Often impossible.

In this apparatus, ozone water 18 having a specific resistance value of 1 MΩ · cm or less is prepared by dissolving carbon dioxide gas in a liquid storage tank 20, and the ozone water is passed through a liquid supply pipe 16. The data is sent to the processing unit 10.
In this way, since the specific resistance value of the ozone water flowing in the liquid delivery pipe 16 is adjusted to 1 MΩ · cm or less, generation of static electricity due to friction between the inner wall surface of the pipe and the ozone water can be suppressed. Therefore, even if the length of the liquid supply pipe 16 becomes long,
It is possible to suppress the influence of the charging of the liquid supply pipe 16 to a small extent, and it is possible to supply ozone water having a high ozone concentration to the processing unit 10 and supply it to the substrate W from the shower nozzle 12. As a result, processing such as cleaning the substrate W with ozone water is always sufficiently performed.

Table 1 shows the results of experimental examples conducted to investigate the relationship between the specific resistance value of ozone water and the decrease in ozone concentration of ozone water. In the experiment, the ozone water was generated from the ozone water generating unit (storage tank), and the length of 10 m was φ6 / 8F.
It was carried out by a method of comparing the ozone concentration in the ozone water generation part with the ozone concentration in the ozone water discharge part when the ozone water was fed to the treatment part through the EP tube (liquid feed pipe). Portable electrical conductivity meter CM-2 is used to measure the resistivity of ozone water.
Ozone water concentration meter EL-500 (manufactured by EBARA CORPORATION) is used to measure the concentration of ozone water using 1P (manufactured by Toa Denpa Kogyo).
2 units were used. The specific resistance value of pure water in which ozone gas was dissolved was 13.7 MΩ · cm. In addition, as a result of measuring the charge amount of the FEP tube during the feeding of the ozone water with the static electricity meter SFM-775 (manufactured by Harada Sangyo), the specific resistance value of the ozone water is 2.3 MΩ · cm, 1.3 M.
Ω · cm, 0.27 MΩ · cm and 0.11 MΩ · c
m is -0.96 kV, -0.53 respectively
It was kV, -0.44kV and -0.34kV.

[0038]

[Table 1]

It is preferable that the ozone concentration at the time of generating the ozone water and the ozone concentration at the time of discharging the ozone water are the same, but at a liquid feeding distance of 10 m, a decrease in the concentration of 1 ppm or less is acceptable. . From the results shown in Table 1, if the specific resistance value of ozone water is 1 MΩ · cm or less, the decrease in ozone concentration can be tolerated.

In addition, in the configuration of the apparatus shown in FIG.
Instead of providing the carbon dioxide gas supply pipe 32 in the liquid storage tank 20, the liquid supply pipe 16 is provided with a static eliminator that removes static electricity caused by the ozone water flowing in the liquid supply pipe 16 and causing the liquid supply pipe 16 to have static electricity. A substrate processing apparatus can be configured. As the static eliminating means, for example, as shown in FIG. 2, the outer surface side of the liquid supply pipe 16 is covered with a coating pipe 42 formed of a conductive material, for example, a conductive resin material in which a conductive material layer is provided on a fluororesin material. A structure in which the conductor 44 is covered and the conductor 44 is electrically connected to the sheath 42 and the conductor 44 is grounded is adopted. In the apparatus having such a configuration, the static electricity generated in the liquid supply pipe 16 flows to the coating pipe 42 that covers the outer surface side of the liquid supply pipe 16, passes from the coating pipe 42 through the lead wire 44, and is, for example, factory equipment. Is removed by flowing to the ground line provided as.

Further, in the configuration of the apparatus shown in FIG. 1, the carbon dioxide gas supply pipe 32 may be provided in the liquid storage tank 20 and the discharging pipe 16 may be provided with a destaticizing means to form a substrate processing apparatus.

A static eliminating means for removing static electricity on the liquid circulation pipe 34 by flowing ozone water through the liquid circulation pipe 34 to the liquid circulation pipe 34 attached to the liquid storage tank 20, for example, It is also possible to cover the outer surface side of the liquid circulation pipe 34 with a coating pipe formed of a conductive resin material, electrically connect the conducting wire to the coating pipe, and provide a neutralizing means having a configuration in which the conducting wire is grounded. Good. In the apparatus having such a configuration, the static electricity generated in the liquid circulation pipe 34 during the circulation of the ozone water flows to the coating pipe that covers the outer surface side of the liquid circulation pipe 34, passes from the coating pipe through the lead wire, and, for example, , Flows to the ground wire provided as factory equipment and is removed.

Next, FIG. 3 is a schematic view schematically showing another structural example of the substrate processing apparatus used for carrying out the substrate processing method according to the present invention. In this apparatus, in order to dissolve ozone gas in pure water and carbon dioxide gas in ozone water, the dissolution membrane module 46,
48 are installed. Dissolved film module 46, 48
Although the detailed structure is not shown in the figure, it has a double pipe structure and is provided with an inner pipe made of a material that allows only gas to pass through without passing liquid.

One end of the inner tube of the first dissolution membrane module 46 is connected in communication with a pure water supply pipe 52 in which a pure water supply source is connected in a flow path and a liquid feed pump 50 is inserted. The other end of the inner pipe is connected to one end of the inner pipe of the second dissolution membrane module 48 via a connecting pipe 54. An ozone gas supply pipe 56 is connected to the outer tube of the first dissolution membrane module 46 in order to supply the ozone gas into the space formed between the outer tube and the inner tube. It is connected. Further, the other end of the inner pipe of the second dissolved film module 48 is connected to a liquid delivery pipe 58 that is connected to the shower nozzle 12 of the processing unit 10 by a flow path. The outer tube of the second dissolution membrane module 48 is a carbon dioxide gas supply pipe that is connected to a carbon dioxide gas source in a flow path to supply carbon dioxide gas into a space formed between the outer tube and the inner tube. 60 are connected for communication.

In the apparatus having the above structure, the first
Pure water is caused to flow in the inner tube of the dissolution membrane module 46 and ozone gas is caused to flow in the space between the inner tube and the outer tube, so that the ozone gas flowing on the outer surface side of the inner tube has a difference in gas partial pressure. At this point, ozone water permeates through the wall surface of the inner pipe to the inner surface side of the inner pipe, and ozone gas is dissolved in pure water flowing in the inner pipe to generate ozone water. In addition, the second dissolved film module 4
Ozone water is caused to flow into the inner pipe of No. 8 and carbon dioxide is caused to flow into the space between the inner pipe and the outer pipe, so that the carbon dioxide gas flowing on the outer surface side of the inner pipe is It penetrates through the wall surface of the pipe to the inner surface side of the inner pipe, and carbon dioxide gas dissolves in the ozone water flowing in the inner pipe, and the carbon dioxide gas dissolves to generate ozone water with a specific resistance value of 1 MΩ · cm or less. It The ozone water passes through the liquid sending pipe 58 and the processing unit 10
To the shower nozzle 12 of the
Is supplied to the substrate W, and the substrate W is treated with ozone water. Since the specific resistance value of the ozone water flowing in the liquid delivery pipe 58 is adjusted to 1 MΩ · cm or less, the same action as described above suppresses the generation of static electricity due to the friction between the inner wall surface of the pipe and the ozone water. The same effect as above can be obtained.

In the apparatus shown in FIG. 3, a dissolution membrane module 46 for dissolving ozone gas in pure water to generate ozone water is installed on the upstream side, and carbon dioxide gas is dissolved in ozone water on the downstream side. Although the dissolution membrane module 48 is installed, a dissolution membrane module that dissolves carbon dioxide gas in pure water to make the specific resistance value 1 MΩ · cm or less is installed on the upstream side, and the carbon dioxide gas is on the downstream side. You may make it install the melt | dissolution film | membrane module which melt | dissolves ozone gas in the melt | dissolved pure water and produces | generates ozone water.

Further, in the configuration of the apparatus shown in FIG.
Dissolved film module 4 that dissolves carbon dioxide in ozone water
8 is not provided, the other end of the inner tube of the dissolution membrane module 46 is directly connected to the liquid sending pipe 58 that is connected to the shower nozzle 12 of the processing unit 10 by a flow path, and the liquid sending pipe 58 is provided.
Further, the substrate processing apparatus can be configured by providing a static eliminator having a configuration as shown in FIG. 2 that removes static electricity carried by the liquid sending pipe 58 by flowing ozone water in the liquid sending pipe 58. . Further, the dissolution membrane module 48 for dissolving carbon dioxide gas in ozone water may be provided, and the liquid delivery pipe 58 may be provided with a destaticizing means to configure the substrate processing apparatus. Further, in the configuration of the apparatus shown in FIG. 1, a carbon dioxide gas supply pipe 32 is not provided in the liquid storage tank 20, but a dissolution film for dissolving carbon dioxide gas in ozone water as shown in FIG. The module 48 may be installed.

[0048]

According to the substrate processing method of each of the first to third aspects of the present invention, ozone water having a high ozone concentration can be supplied to the substrate, and therefore the substrate can be sufficiently processed. .

In the substrate processing method of the invention according to claim 4,
It is possible to suppress the generation of static electricity, reduce the influence of static electricity, and prevent the decomposition of ozone in the ozone water over the entire flow path from the ozone water generating unit to the processing unit.

When the substrate processing apparatus according to each of the fifth to seventh aspects of the present invention is used, ozone water having a high ozone concentration can be supplied to the substrate, and therefore the substrate can be sufficiently processed.

In the substrate processing apparatus of the invention according to claim 8,
It is possible to suppress the generation of static electricity, reduce the influence of static electricity, and prevent the decomposition of ozone in the ozone water over the entire flow path from the ozone water generating unit to the processing unit.

In the substrate processing apparatus of the invention according to claim 9,
The static electricity generated in the liquid supply pipe is surely removed through the coating pipe and the conducting wire.

In the substrate processing apparatus according to the tenth aspect of the present invention, the ozone water having a high ozone concentration is supplied from the ozone water generating section,
It can be delivered to the processing unit through a liquid delivery pipe.

In the substrate processing apparatus according to the eleventh aspect of the present invention, static electricity generated in the circulation pipe is surely removed through the coating pipe and the conducting wire.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing an example of a schematic configuration of a substrate processing apparatus used for carrying out a substrate processing method according to the present invention.

FIG. 2 is an enlarged cross-sectional view showing an example of the configuration of a static eliminator that removes static electricity from the liquid delivery pipe.

FIG. 3 is a schematic diagram schematically showing another configuration example of the substrate processing apparatus used for carrying out the substrate processing method according to the present invention.

[Explanation of symbols]

10 Processing unit 12 shower nozzle 16,58 Liquid supply piping 18 Ozone water 20 Liquid storage tank 22,50 liquid feed pump 32, 60 Carbon dioxide gas supply pipe 34 Liquid circulation piping 36 liquid circulation pump 38 ejector 40, 56 ozone gas supply pipe 42 cladding 44 conductor 46, 48 Dissolved membrane module 52 Pure water supply pipe 54 Communication piping W board

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/78 C02F 1/78 F term (reference) 3B201 AA02 AA03 AB13 BB03 BB22 BB89 BB93 BB98 4D050 BD04 BD08 4D075 BB78X CA47 DA06 DB11 DC22 DC24 EA06 EB60 4F042 AA07 BA21 CA01 CB02 CB08 CB19

Claims (11)

[Claims] 1. The ozone water generated in the ozone water generating section is sent to the processing section through a liquid supply pipe formed of a synthetic resin material having corrosion resistance to the ozone water, and the ozone water is supplied to the substrate in the processing section. In the substrate processing method of processing the substrate by supplying to the processing unit, carbon dioxide gas is dissolved and ozone water having a specific resistance value of 1 MΩ · cm or less is fed to the processing unit. 2. The ozone water generated in the ozone water generating section is sent to the processing section through a liquid supply pipe formed of a synthetic resin material having corrosion resistance to the ozone water, and the ozone water is supplied to the substrate in the processing section. A substrate processing method for supplying a liquid to a substrate to process a substrate, wherein static electricity carried by the liquid feeding pipe is removed by flowing ozone water in the liquid feeding pipe. 3. The ozone water generated in the ozone water generating section is sent to the processing section through a liquid supply pipe formed of a synthetic resin material having corrosion resistance to ozone water, and the ozone water is supplied to the substrate in the processing section. In the substrate processing method for supplying a substrate to the substrate, the carbon dioxide gas is dissolved to supply ozone water having a specific resistance value of 1 MΩ · cm or less to the processing unit, and ozone is supplied in the liquid supply pipe. A method for treating a substrate, characterized in that static electricity caused by a liquid supply pipe is removed by flowing water. 4. The substrate processing method according to claim 1 or 3, wherein ozone gas and carbon dioxide gas are dissolved in pure water in the ozone water generation unit to prepare ozone water in which carbon dioxide gas is dissolved. A characteristic substrate processing method. 5. A processing unit for supplying ozone water to a substrate to process the substrate, an ozone water generation unit for generating ozone water by dissolving ozone gas in pure water, and a synthesis having corrosion resistance to ozone water. A substrate processing apparatus comprising: a liquid supply pipe formed of a resin material, for supplying ozone water generated by the ozone water generation unit to the processing unit, wherein the ozone water generation unit or the liquid supply pipe A carbon dioxide gas dissolving means for dissolving carbon dioxide gas in pure water or ozone water to make the specific resistance value of the ozone water fed to the processing section 1 MΩ · cm or less is provided in the middle of Substrate processing equipment. 6. A processing unit for supplying ozone water to a substrate to process the substrate, an ozone water generation unit for generating ozone water by dissolving ozone gas in pure water, and a synthesis having corrosion resistance to ozone water. A substrate processing apparatus comprising: a liquid supply pipe formed of a resin material, for supplying ozone water generated by the ozone water generating unit to the processing unit, wherein the liquid supply pipe has the liquid supply pipe. A substrate processing apparatus, characterized in that it is provided with a static eliminator for removing static electricity caused by a liquid supply pipe caused by ozone water flowing inside. 7. A processing unit for supplying ozone water to a substrate to process the substrate, an ozone water generating unit for dissolving ozone gas in pure water to generate ozone water, and a synthesis having corrosion resistance to ozone water. A substrate processing apparatus comprising: a liquid supply pipe formed of a resin material, for supplying ozone water generated by the ozone water generation unit to the processing unit, wherein the ozone water generation unit or the liquid supply pipe In the middle of the process, a carbon dioxide gas dissolving means for dissolving carbon dioxide gas in pure water or ozone water to make the specific resistance value of the ozone water sent to the treatment section 1 MΩ · cm or less is provided, and the liquid sending pipe 1. A substrate processing apparatus, further comprising a static eliminator for removing static electricity caused by ozone water flowing through the liquid sending pipe. 8. The substrate processing apparatus according to claim 5, wherein the ozone water generating unit is provided with the carbon dioxide gas dissolving means, and the ozone water generating unit dissolves ozone gas and carbon dioxide gas in pure water. The substrate processing apparatus is characterized in that ozone water in which carbon dioxide gas is dissolved is prepared. 9. The substrate processing apparatus according to claim 6 or 7, wherein the static elimination means is formed of a conductive material and covers the outer surface side of the liquid supply pipe, and the coating pipe is electrically connected. And a conductor wire that is connected to the grounding wire to ground the cladding tube. 10. The substrate processing apparatus according to claim 5, wherein the ozone water generation unit stores a tank for storing ozone water,
A circulation pipe, which is formed of a synthetic resin material having corrosion resistance to ozone water, is arranged outside the tank to circulate ozone water between the inside and the tank, and the circulation pipe is provided with a circulation pipe. A substrate processing apparatus, comprising: a circulation pipe static eliminator for removing static electricity on the circulation pipe caused by ozone water flowing through the pipe. 11. The substrate processing apparatus according to claim 10, wherein the circulation pipe static elimination means coats an outer surface side of the circulation pipe formed of a conductive material, and electrically coats the coating pipe. A conductor that is connected to ground the cladding
A substrate processing apparatus comprising: