JP2000037671A - Method of and apparatus for treating surface of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase a treating speed by using high concentration ozone efficiently by making a structure at least from an ozone supply port to an object to be treated sealable so that no gas/liquid interface exists between the ozone solution supply port and the object. SOLUTION: A high concentration ozone aqueous solution produced by an ozone aqueous solution generator 4 is supplied from an ozone solution supply port 5 to a reaction treatment tray 1 of about 1 m2 cross-sectional area and 0.05 m depth, and a silicon substrate 3 coated with a photoresist film 2 is placed in the liquid of the tray 1. A plate-shaped lid 7 is fitted to the tray 1, and the solution in the tray 1 is sealed. The supplied ozone solution is discharged from an ozone discharge opening 8. In this way, in a process in which the high concentration ozone solution is brought into contact with an object to be treated, since no gas/liquid interface exists between the supply port 5 and the object, the release of the dissolved ozone into a gas phase can be prevented, and the dissolved ozone can efficiently be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of a semiconductor, such as an ultra-large scale integrated circuit (ultra-large scale integrated circuit), which requires miniaturization and ultra-cleaning, or a liquid crystal substrate, which requires ultra-cleaning. At this time, using a solution of high concentration ozone dissolved in the substrate, peeling of the photoresist film, removal of surface fine particles, removal of metal contaminants, formation of insulating oxide film, wettability and adhesion of substrate surface The present invention relates to a method and an apparatus for treating a surface of a substrate for improvement.

[0002]

2. Description of the Related Art Conventionally, there have been the following methods for performing a surface treatment on a substrate.

A. First Conventional Example As disclosed in Japanese Patent Application Laid-Open No. 9-22867, the photoresist is completely removed by a stripping tank for stripping the photoresist with a stripper and a water tank for washing with pure water containing ozone. There are those that improve the yield. In order to oxidize and remove the organic thin film residue slightly remaining on the substrate when the resist is peeled off, ozone water is used in a cleaning tank in the subsequent stage.

As shown in FIG. 10, a tank 52 for circulating a stripping solution 51 is separately provided in a stripping tank 50, and a sensor 53 for measuring a stripping solution concentration is installed in the tank 52. When the concentration is reduced, the sensor 53
The new stripping solution of the stripping solution is introduced into the tank 52 from the new solution supply device 54 on the basis of the signal. By supplying this new stripping solution, the stripping solution in the tank 52 always keeps the set concentration, and the stripping solution kept at this set concentration is supplied to the stripping tank 50.
Supplied to As a result, the substrate 55 coated with the photoresist film is vertically immersed in the stripping tank 50, and the photoresist film is removed by the stripping solution sprayed from the submerged spray nozzle 56 that can move in parallel. Further, in order to oxidize and remove a small amount of the organic thin film residue remaining when the resist is stripped, the substrate 55 is washed with pure water containing ozone in a cleaning tank 57.
Is washed with water.

[0005] According to Conventional Example 1, the dissolving power of the dissolving liquid for the photoresist film is maintained, and the amount of the stripping liquid used can be reduced. Further, the yield of removing the photoresist film can be improved by washing the organic thin film remaining on the substrate surface after peeling with pure water containing ozone.

B. Second conventional example As disclosed in Japanese Patent Application Laid-Open No. 8-181137, an organic substance removing step of removing organic substances attached to a substrate by supplying ultrapure water containing ozone to the substrate, and an organic substance produced in the organic substance removing step. A process of etching an oxide film to be formed with hydrofluoric acid, followed by an oxide film forming process of forming an oxide film by contacting with ultrapure water containing ozone. There is something that forms.

All of the organic substance removing step, the etching step, and the oxide film forming step are sequentially performed in a closed vessel 101 shown in FIG.

While nitrogen gas is introduced from the inert gas inlet 102 in FIG. 11, pure water is supplied to the rotating wafer 103 from the chemical solution supply nozzle 104, and the wafer is rotated to uniformly wet the wafer surface.

Subsequently, with the wafer 103 rotated,
2 ppm of ozone-added ultrapure water is supplied from the nozzle 104 to oxidize organic substances on the wafer surface and form an oxide film on the wafer surface. Then, the ozone water is stopped and the wafer is washed with pure water.

Next, with the wafer 103 rotated,
A hydrofluoric acid aqueous solution is supplied from the nozzle 104 to etch the oxide film generated in the organic substance removing step. After completion of the etching, the hydrofluoric acid solution is stopped and the substrate is washed with pure water.

Next, the nozzle 1 is attached to the rotated wafer 103.
Ozone-added ultrapure water is supplied from 04 to form a 0.6 nm oxide film on the wafer surface. Finally, the wafer 103
Dry by rotating.

According to Conventional Example 2, for example, the characteristics of an oxide film on a silicon wafer can be greatly improved, so that a higher performance and highly integrated device can be realized.

[0013]

The first and second prior arts have the following problems.

(1) In order to improve the processing speed, it is conceivable to increase the ozone concentration in the aqueous solution. However, in the conventional example, the reaction processing vessel is released to the gas phase, and the interface between the ozone solution and the gas phase exists, so that ozone is released into the gas phase, and the dissolved ozone cannot be used effectively. .

(2) Ozone has a property of being hardly soluble in water, so that a large amount of ozone gas is required when producing high-concentration ozone water.

The present invention has been made in consideration of such problems, and it is intended to improve the processing speed by effectively using high-concentration ozone and to reduce the amount of ozone gas required for ozone water production. An object of the present invention is to provide a method and an apparatus for effectively using a high-concentration ozone solution that can be reused.

[0017]

According to a first aspect of the present invention, in the process of contacting a substrate with a high-concentration ozone solution, a gas-liquid interface is provided between the ozone solution supply port and the object to be processed. It is characterized in that at least the part from the ozone supply port to the object to be treated is sealed so as not to exist.

In a second aspect of the present invention, in the process of bringing a high-concentration ozone solution into contact with an object to be processed, ozone is present in a gas phase.

According to a third aspect of the present invention, in the process of contacting an object to be treated with a high-concentration ozone solution, a lid is provided on an upper portion of the reaction vessel, and the reaction vessel is filled with the solution. It is characterized by.

According to a fourth aspect of the present invention, in the process of contacting an object to be treated with a high-concentration ozone solution, an ozone solution spray nozzle having a shape similar to the shape of the object is used. It is characterized in that the dissolved ozone is brought into contact with the object before the ozone reaches the gas-liquid interface.

According to a fifth aspect of the present invention, in the process of bringing a high-concentration ozone solution into contact with an object to be processed, an ozone gas generated by an ozone generator is introduced into a gas phase portion in a reaction processing vessel. This suppresses the release of dissolved ozone into the gas phase.

According to a sixth aspect of the present invention, in the process of bringing a high-concentration ozone solution into contact with an object to be processed, ozone gas discharged from an ozone solution production process is introduced into a gas phase portion in a reaction processing vessel. By doing so, the discharge of dissolved ozone into the gas phase is suppressed.

According to a seventh aspect of the present invention, in the process of contacting a substrate with a high-concentration ozone solution, acetone, acetic acid or a mixed solution thereof is used as a solvent for dissolving ozone. .

Further, in the substrate surface treatment method according to the present invention, in the process of contacting an object to be treated with a high-concentration ozone solution, ozone is present in the gas phase and the pressure of the supplied ozone gas is higher than atmospheric pressure. It is characterized by being.

Further, the substrate surface treatment apparatus according to the ninth aspect is used in a process of bringing a high-concentration ozone solution into contact with an object to be treated, and comprises a reaction vessel, an ozone solution supply port connected to the reaction vessel, and An ozone outlet, and an ozone water producing apparatus for supplying an ozone solution to the reaction processing container from the supply port, so that there is no gas-liquid interface between the ozone solution supply port and the object to be processed. The reaction processing container is characterized by being filled with an ozone solution.

The substrate surface treatment apparatus according to the tenth aspect is used in a process for bringing a high-concentration ozone solution into contact with an object to be processed, and comprises a reaction vessel, an ozone solution supply port connected to the reaction vessel, and An ozone outlet and an ozone water producing apparatus for supplying an ozone solution to the reaction vessel from the supply port, supplying the ozone solution while leaving a gas phase in the reaction vessel, It is characterized in that ozone is supplied into the gas phase.

The substrate surface treatment apparatus according to the eleventh aspect is used in a process for bringing a high-concentration ozone solution into contact with an object to be processed, and includes a reaction processing container, a sample table that makes the object to be processed rotatable, An ozone solution supply port connected to the reaction processing vessel facing the workpiece, an ozone discharge port connected to the reaction processing vessel, and an ozone solution supplied to the reaction processing vessel from the ozone solution supply port. And an ozone solution injection nozzle having a shape similar to the shape of the object to be treated is detachably connected to the ozone solution supply port in proximity to the object to be treated, and the ozone supply port Characterized in that dissolved ozone from the substrate is brought into contact with the object to be processed before forming a gas-liquid interface.

The substrate surface treatment apparatus according to the twelfth aspect is used in a process of bringing a high-concentration ozone solution into contact with an object to be processed, and comprises a reaction vessel, an ozone solution supply port connected to the reaction vessel, A gas supply port and an ozone discharge port, an ozone water producing apparatus that supplies an ozone solution to the reaction processing container from the ozone solution supply port, and an ozone generator for suppressing release of dissolved ozone into a gas phase. It is characterized by consisting of.

The substrate surface treatment apparatus according to the thirteenth aspect is used in a process of bringing a high-concentration ozone solution into contact with an object to be treated, and comprises a reaction vessel, an ozone solution supply port connected to the reaction vessel, A gas supply port and an ozone discharge port, and an ozone water production device for supplying an ozone solution from the ozone solution supply port to the reaction processing vessel, wherein the ozone water production device is connected to the gas supply port by a connecting pipe. The ozone gas discharged from the ozone water producing apparatus is introduced from the gas supply port to a gas phase portion in the reaction processing vessel.

[0030]

Embodiments of the present invention will be described below in detail.

Embodiment 1 FIG. 1 is a schematic view of an experimental apparatus for explaining Embodiment 1 of the present invention, and FIG. 2 is a schematic view of a substrate surface treatment apparatus showing Embodiment 1 of the present invention.

In the present embodiment, a high-concentration ozone solution is supplied into the reaction processing vessel, and the ozone concentration in the solution is measured. In FIG. 1, reference numeral 1a denotes a reaction treatment tray which is a reaction treatment container, 4 denotes an ozone water production device, 5 denotes an ozone solution supply port for guiding the ozone water produced by the ozone water production device 4 to the reaction treatment tray 1a, 6 is an overflow gutter. In FIG. 2, since the reaction processing tray 1b has a structure capable of sealing the solution, the ozone water generated by the ozone water production device 4 is supplied from the ozone solution supply port 5 without a gas-liquid interface. Reference numeral 8 denotes an ozone outlet. By eliminating the gas-liquid interface, the processing method described in claim 1 is performed. By comparing the case with the gas-liquid interface and the case without the gas-liquid interface, the effectiveness of the processing method according to claim 1 is shown.

FIG. 3 shows the ozone concentration in the solution produced by the ozone producing apparatus, the ozone concentration in the case of FIG. 1, and the ozone concentration in the case of FIG.

As shown in FIG. 3, when there is an interface between the high-concentration ozone solution and the gas phase and there is no ozone in the gas phase, the dissolved ozone is partially released into the gas phase, A decrease in ozone concentration in the solution is observed. In contrast,
If the reaction vessel is filled with a high-concentration ozone solution and there is no gas-liquid interface between the ozone solution supply port and the object to be immersed, ozone in the solution is not released into the gas phase. No decrease in the concentration was observed, indicating that the dissolved ozone could be used effectively.

Embodiment 2 A high-concentration ozone solution was supplied into a reaction processing container while the object to be processed was immersed in the reaction processing container, and the ozone concentration in the solution near the processing substrate was measured. The treatment method described in claim 2 is performed by causing ozone to exist in the gas phase. By comparing the case where ozone gas is present in the gas phase with the case where ozone is not present in the gas phase, the effectiveness of the treatment method according to claim 2 is shown.

FIG. 4 shows the results of measuring the ozone concentration when ozone is present in the gas phase and when ozone is not present in the gas phase.

There is an interface between the highly concentrated ozone solution and the gas phase,
When no ozone was present in the gas phase, the dissolved ozone was partially released into the gas phase, and a decrease in the ozone concentration in the solution was observed. On the other hand, when a high-concentration ozone solution is supplied into the reaction processing vessel, and ozone is supplied into the gas phase in the reaction processing vessel, and ozone is present in the gas phase in the reaction processing vessel, Since ozone in a solution is hardly released into the gas phase, a decrease in concentration is suppressed, and dissolved ozone can be effectively used.

Third Embodiment FIGS. 5 and 6 are schematic views of an experimental apparatus showing a third embodiment of the present invention. In any case, the purpose is to remove the photoresist film 2 applied on the silicon substrate 3 which is the object to be processed.

In FIG. 5, high-concentration ozone water generated by the ozone water production device 4 is supplied from the ozone solution supply port 5 to the reaction treatment tray 1 (cross-sectional area: 1 m ² , depth: 0.05 m).
A silicon substrate 3 on which a photoresist film 2 is applied is placed in a liquid of a reaction processing tray 1. The supplied ozone water is discharged from the overflow gutter 6.

In FIG. 6, high-concentration ozone water generated by the ozone water producing apparatus 4 is supplied from the ozone solution supply port 5 to the reaction treatment tray 1 (cross-sectional area: 1 m ² , depth: 0.05 m).
A silicon substrate 3 on which a photoresist film 2 is applied is placed in a liquid of a reaction processing tray 1. The reaction processing tray 1 is provided with a flat lid 7 to seal the solution in the reaction processing tray 1. The supplied ozone water is discharged from the ozone outlet 8.

By using the substrate surface treating apparatus having the structure shown in FIG. 6, the surface treating method of claim 3 is carried out. Further, by comparing the results of the apparatus of FIG. 5, the effect of the invention according to claim 3 becomes clear.

As a processing substrate, an 8-inch silicon wafer coated with a 6 μm resist was used. Ozone water flow rate is 200 mL / min, ozone water concentration is 10, 2
It was varied between 0 and 50 ppm.

The resist peeling speed was calculated by measuring the thickness of the resist.

The results are shown in Table 1. By installing the lid, an effect of about 1.5 to 2 times as the peeling speed was observed.

[0045]

[Table 1]

Fourth Embodiment In the third embodiment, it has been found that the use of acetone, acetic acid, a mixed solution thereof, or the like in addition to water as a solvent for dissolving ozone has a high resist stripping effect. This is considered to be because the ozone concentration in the solution increased due to the higher solubility of ozone in acetone and acetic acid than in water.

Fifth Embodiment By replacing the lid 7 in the third embodiment with an oil film having a low solubility in an ozone solution, for example, an oil film such as silicon oil, the resist stripping speed is improved. When an experiment similar to that of the third embodiment was performed by covering with an oil film having a thickness of 1 to 2 mm, an effect 1.4 to 2 times that of the case without the oil film was obtained.

Sixth Embodiment FIG. 7 is a schematic diagram showing a sixth embodiment of the present invention. The purpose is to form a clean oxide film on a silicon substrate.

In FIG. 7, ozone water generated by the ozone water producing device 14 is introduced into a reaction tank main body 10 as a reaction processing vessel from a supply port 15. An 8-inch silicon substrate 12 is set on a sample table 13 having a rotating mechanism. The solution after the reaction is discharged from the waste liquid outlet 16 and the gas after the reaction is discharged from the outlet 17. Gas can be supplied from the gas supply port 18 as needed.

The silicon substrate 12 is set on the sample table 13 while introducing nitrogen gas from the gas supply port 18. 3 cc of ultrapure water was supplied from the supply port 20, and the sample stage 13 was rotated at 500 rpm to wet the surface.

At a substrate rotation speed of 3000 rpm, the supply port 15
High-concentration ozone water (20 ppm) from 300cc / mi
n for 1 minute to remove organic contaminants on the surface, followed by cleaning with pure water.

Subsequently, at a substrate rotation speed of 3000 rpm, a 30% aqueous solution of 0.5% hydrofluoric acid was supplied from the supply port 21 to 30 cc / m 2.
After supplying the solution for 2 minutes in, the oxide film on the surface was etched and washed with pure water.

Next, an ozone solution injection nozzle 19 having a structure similar to the shape of the substrate 12 is connected to the supply port 15, and 20 ppm of ozone water is supplied from the nozzle 19 at 400 cc / min at a substrate rotation speed of 3000 rpm. The solution is supplied for 30 seconds so that the dissolved ozone is brought into contact with the object before reaching the gas-liquid interface, thereby forming an oxide film on the substrate surface. The distance between the nozzle 19 and the substrate 12 is 0.5 to 1.0 mm.

The substrate surface treatment method according to the fourth aspect is performed by using the substrate surface treatment apparatus having the structure shown in FIG. Further, the effect of the present invention becomes clear by comparison with the case where the ozone solution injection nozzle 19 is removed.

Table 2 shows the result of measurement of the oxide film 30 seconds after the ozone water treatment. The thickness of the oxide film was increased 1.3 to 1.5 times by the ozone solution spray nozzle 19.

As in the fourth embodiment, as the solvent for dissolving ozone, acetone, acetic acid, or a mixed solution thereof having low reactivity with ozone can be used in addition to water.

[0057]

[Table 2]

Seventh Embodiment The seventh embodiment aims at forming a clean oxide film on a silicon substrate.

In FIG. 8, reference numeral 30 denotes a reaction port main body, and a supply port 35 for supplying ozone water generated by the ozone water production apparatus 34.
Introduce from. On a sample stage 33 having a rotating mechanism,
An 8-inch silicon substrate 32 is set. The solution after the reaction is discharged from the waste liquid outlet 36 and the gas after the reaction is discharged from the outlet 37. Gas can be supplied from the gas supply port 38 as needed.

The silicon substrate 32 is set on the sample table 33 while introducing nitrogen gas from the gas supply port 38. 3 cc of ultrapure water was supplied from the supply port 40, and the sample stage 33 was rotated at 500 rpm to wet the surface.

At a substrate rotation speed of 3000 rpm, the supply port 35
High-concentration ozone water (20 ppm) from 300cc / mi
n for 1 minute to remove organic contaminants on the surface, and then washed with pure water.

Subsequently, at a substrate rotation speed of 3000 rpm, 300 cc /
min for 2 minutes to etch the oxide film on the surface,
It was washed with pure water.

Next, 50 to 300 g / Nm produced by the ozone generator 42 at a substrate rotation speed of 3000 rpm.
While supplying the ozone gas ³ from the gas supply port 38, 20 ppm ozone water was supplied from the supply port 35 at 400 cc / mi.
n for 30 seconds to form an oxide film on the substrate surface.

The substrate surface treatment method according to the fifth aspect is performed by using the substrate surface treatment apparatus having the structure shown in FIG. Further, the effect of the present invention becomes clear by comparison with the case where nitrogen gas is supplied from the gas supply port 38 instead of ozone gas.

Table 3 shows the results of measurement of the oxide film 30 seconds after the ozone water treatment. Ozone gas supply increased the thickness of the oxide film by 1.4 to 1.6 times.

As in Embodiment 4, as the solvent for dissolving ozone, acetone, acetic acid, a mixed solution thereof, or the like can be used in addition to water.

[0067]

[Table 3]

Eighth Embodiment In the seventh embodiment, even when a high-pressure ozone gas is supplied from the gas supply port 38 instead of supplying a normal-pressure high-concentration ozone gas, the thickness of the oxide film increases. By supplying an ozone gas concentration of 20 to ³⁰ g / Nm ³ from the gas supply port 38 at a pressure of 2 atm or more, the thickness of the oxide film is 1.3 to 1.6 times that in the case where nitrogen gas is supplied. became. The higher the supply gas pressure, the more effective,
Considering the safety of the device, it can be said that 2 to 5 atmospheres is suitable.

Embodiment 9 In Embodiment 7, as the ozone gas supplied from the gas supply port 38, as shown in FIG. 9, the ozone water producing apparatus 34 and the gas supply port 38 are connected by a connecting pipe 43, and the ozone water is supplied. The substrate surface treatment method according to claim 6 is performed by using ozone gas discharged from the manufacturing apparatus 34.

From the supply port 35, 20 ppm ozone water
In order to suppress the release of dissolved ozone into the gaseous phase in parallel with the process of forming an oxide film on the substrate surface, 50 g / Ozone gas of Nm ³ or more is connected to the connecting pipe 43.
Through the ozone supply port 38 to the gaseous phase portion in the reaction processing vessel 30. As compared with the case where nitrogen was supplied from the gas supply port 38, an oxide film having a thickness of 1.2 to 1.6 times was formed.

[0071]

As described above, according to the first aspect of the present invention, in the process of bringing a high-concentration ozone solution into contact with an object to be processed, the process until the high-concentration ozone solution comes into contact with the object through a supply port. Since the gas-liquid interface is eliminated in between, the release of dissolved ozone into the gas phase can be prevented, and the dissolved ozone can be effectively used in the process using the high-concentration ozone solution. Since it has a strong oxidizing effect, the photoresist stripping and oxide film forming processes can be performed quickly and efficiently.

According to the second aspect of the present invention, in the process of contacting a high-concentration ozone solution with an object to be processed, ozone is present in the gas phase, so that dissolved ozone is released into the gas phase. Ozone dissolved in a process using a high-concentration ozone solution can be effectively used.

According to the third aspect of the present invention, in the process of bringing the high-concentration ozone solution into contact with the object to be treated, a lid is provided on the upper portion of the reaction processing container and the container is sealed. By filling with ozone, release of dissolved ozone into the gas phase can be prevented, and dissolved ozone can be effectively used in a process using a high-concentration ozone solution.

According to the fourth aspect of the present invention, the dissolved ozone is brought into contact with the object before the dissolved ozone reaches the gas-liquid interface by using the ozone solution injection nozzle having a shape similar to the shape of the object. Therefore, the release of dissolved ozone into the gas phase can be prevented, and the dissolved ozone can be effectively used in a process using a high-concentration ozone solution.

According to the fifth aspect of the present invention, the release of dissolved ozone into the gas phase is suppressed by introducing the ozone gas generated by the ozone generator into the gas phase in the reaction vessel. Further, the release of dissolved ozone into the gas phase can be prevented, and the dissolved ozone can be effectively used in a process using a high-concentration ozone solution.

According to the sixth aspect of the invention, the ozone gas discharged from the ozone solution production process is introduced into the gas phase in the reaction processing vessel, thereby suppressing the release of dissolved ozone into the gas phase. Therefore, the release of dissolved ozone into the gas phase can be prevented, and the dissolved ozone can be effectively used in a process using a high-concentration ozone solution. This also allows not only effective use of the high-concentration ozone solution but also effective use of the ozone gas discharged from the production of the ozone solution.

According to the seventh aspect of the present invention, in the process of bringing a high-concentration ozone solution into contact with an object, acetone, acetic acid or a mixed solution thereof having an ozone solubility of about 10 times that of water is used. The use of ozone as a solvent dissolves, especially in an organic washing process, the use of acetone having a high lipophilic property as compared with the use of water having a low lipophilic property as the solvent, thereby improving the cleaning effect of the ozone solution. It can be significantly improved.

According to the invention of claim 8, in the process of bringing the high-concentration ozone solution into contact with the object, ozone is present in the gas phase and the pressure of the supplied ozone gas is higher than atmospheric pressure. Therefore, by introducing high-pressure ozone gas, the release of dissolved ozone into the gas phase can be suppressed, and the thickness of the oxide film can be increased.

Further, according to the ninth to thirteenth aspects of the present invention, it is possible to prevent the dissolved ozone from being released into the gas phase, so that the dissolved ozone can be effectively used in a process using a high-concentration ozone solution. .

[Brief description of the drawings]

FIG. 1 is a schematic view of an experimental apparatus for explaining a first embodiment of the present invention.

FIG. 2 is a schematic diagram of a substrate surface treatment apparatus according to the first embodiment of the present invention.

3 is a diagram showing an ozone concentration in a solution generated by an ozone producing apparatus, an ozone concentration in the case of FIG. 1, and an ozone concentration in a case of FIG.

FIG. 4 is a diagram showing the results of measuring the ozone concentration when ozone is present in the gas phase and when ozone is not present in the gas phase.

FIG. 5 is a schematic diagram of an experimental apparatus for explaining Embodiments 3, 4, and 5 of the present invention.

FIG. 6 is a schematic diagram of a substrate surface treatment apparatus showing Embodiments 3, 4, and 5 of the present invention.

FIG. 7 is a schematic view of a substrate surface treatment apparatus according to a sixth embodiment of the present invention.

FIG. 8 is a schematic diagram of a substrate surface treatment apparatus showing Embodiments 7 and 8 of the present invention.

FIG. 9 is a schematic view of a substrate surface treatment apparatus according to a ninth embodiment of the present invention.

FIG. 10 is a schematic view of an apparatus showing a first conventional example.

FIG. 11 is a schematic view of an apparatus showing a second conventional example.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 reaction tray, 2 photoresist film, 3 silicon substrate, 4 ozone water production equipment, 5 ozone solution supply port, 6 overflow gutter, 7 lid, 8 ozone outlet, 10 reaction tank body, 12 silicon substrate, 13 sample stand , 14 ozone water production equipment, 15 ozone solution supply port, 16 solution discharge port, 17 gas discharge port, 18 gas supply port, 19 ozone solution injection nozzle, 20 pure water supply port, 21 hydrofluoric acid supply port, 30 reactions Tank body, 32
Silicon substrate, 33 sample stand, 34 ozone water production equipment, 35 ozone solution supply port, 36 solution discharge port, 3
7 gas outlet, 38 gas supply port, 40 pure water supply port,
41 hydrofluoric acid supply port, 42 ozone generator, 43
Connecting pipe, 50 stripping tank, 51 stripper, 52 tank,
53 sensor, 54 new liquid supply device, 55 substrate, 5
6 submerged injection nozzle, 57 cleaning tank, 101 closed tank,
102 inert gas inlet, 103 wafer 104
Chemical supply nozzle.

 ────────────────────────────────────────────────── ─── Continued on front page (72) Inventor Makoto Miyamoto 2-3-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Mitsubishi Electric Corporation (reference) 3B116 AA01 AB34 BB22 BB89 CD42 3B201 AA02 AA03 AB34 BB02 BB03 BB04 BB05 BB22 BB32 BB93 BB96 CD33 5F046 MA02 MA10 5F058 BA20 BC02 BE03 BF29 BF58 BF63 BF65 BJ01

Claims (13)

[Claims] In a process of bringing a high-concentration ozone solution into contact with an object to be processed, at least a portion from the ozone supply port to the object to be processed is prevented so that a gas-liquid interface does not exist between the ozone solution supply port and the object to be processed. A substrate surface treatment method characterized by having a structure capable of being sealed. 2. A substrate surface treatment method in which ozone is present in a gas phase in a process of bringing a high-concentration ozone solution into contact with an object to be processed. 3. A lid is provided on an upper portion of the reaction processing container,
The method according to claim 1, wherein the substrate is sealed. 4. The method according to claim 1, wherein the dissolved ozone is brought into contact with the object before the dissolved ozone reaches the gas-liquid interface by using an ozone solution injection nozzle having a shape similar to the shape of the object. Item 4. The method for treating a surface of a substrate according to Item 1. 5. The substrate surface treatment method according to claim 2, wherein the ozone gas generated by the ozone generator is introduced into a gas phase portion in the reaction processing vessel to suppress the release of dissolved ozone into the gas phase. 6. The substrate surface treatment method according to claim 2, wherein the ozone gas discharged from the ozone solution production process is introduced into a gas phase portion in the reaction processing vessel to suppress the release of dissolved ozone into the gas phase. . 7. A substrate surface treatment method, wherein acetone, acetic acid, or a mixed solution thereof is used as a solvent for dissolving ozone in a process of contacting a high-concentration ozone solution with an object to be processed. 8. The substrate surface treatment method according to claim 2, wherein the pressure of the supplied ozone gas is higher than the atmospheric pressure. 9. A reaction treatment container, which is used in a process of contacting a high-concentration ozone solution with an object to be treated, an ozone solution supply port and an ozone discharge port connected to the reaction treatment container, An ozone water producing apparatus for supplying an ozone solution to the processing container, wherein the reaction processing container is filled with an ozone solution so that a gas-liquid interface does not exist between the ozone solution supply port and the object to be processed. A substrate surface treatment apparatus characterized in that: 10. A reaction processing vessel, which is used in a process of contacting a high-concentration ozone solution with an object to be processed, an ozone solution supply port and an ozone discharge port connected to the reaction processing vessel, and An ozone water producing apparatus for supplying an ozone solution to the processing vessel, wherein the ozone solution is supplied while leaving the gas phase in the reaction processing vessel, and ozone is supplied in the gas phase in the reaction processing vessel. A substrate surface treatment apparatus characterized by the above-mentioned. 11. A reaction processing container, a sample stage that allows the object to be rotated freely, and a reaction table that is used in a process of bringing a high-concentration ozone solution into contact with the object to be processed, An ozone solution supply port connected to a container, an ozone discharge port connected to the reaction processing container, and an ozone water producing apparatus for supplying an ozone solution to the reaction processing container from the ozone solution supply port. An ozone solution injection nozzle having a shape similar to the shape of the processing object is detachably connected to the ozone solution supply port in proximity to the processing object, and dissolved ozone from the ozone supply port forms a gas-liquid interface. A substrate surface treatment apparatus characterized by being brought into contact with an object to be processed before. 12. An ozone solution supply port, a gas supply port, an ozone outlet, and an ozone solution supply port, which are used in a process of bringing a high-concentration ozone solution into contact with an object to be processed, and are connected to the reaction processing vessel. A substrate surface treatment apparatus comprising: an ozone water producing apparatus for supplying an ozone solution to the reaction processing container from a solution supply port; and an ozone generator for suppressing release of dissolved ozone into a gas phase. . 13. A reaction processing container, which is used in a process of bringing a high-concentration ozone solution into contact with an object to be processed, an ozone solution supply port, a gas supply port, and an ozone discharge port connected to the reaction processing container. An ozone water producing apparatus for supplying an ozone solution from the solution supply port to the reaction processing vessel, wherein the ozone water producing apparatus is connected to a gas supply port by a connecting pipe, and the ozone gas discharged from the ozone water producing apparatus Is introduced from the gas supply port to a gas phase portion in the reaction processing vessel.