JP2002261068A - Device and method for substrate treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device and method for substrate treatment capable of reducing a processing time by improving the efficiency of treatment while keeping activating energy. SOLUTION: The substrate processor for treating the surface of a substrate S with ozone water Lo is provided with a pressurizing treatment chamber 1 having pressure atmosphere kept inside of it, and an ozone water nozzle 5 for feeding ozone water generated in the pressurized gaseous ozone atmosphere to the surface of the substrate S housed in the chamber 1. Then, the ozone water Lo generated in the pressurized gaseous ozone atmosphere from the nozzle 5 is supplied to the surface of the substrate S held in the pressure atmosphere in the chamber 1 to treat the surface of the substrate S. In this case, the ozone water Lo to be supplied from the nozzle 5 is solution obtained by dissolving ozone into the pure water by high density under a pressurized condition and is pressurized by pressure equal to or lower than that in the chamber 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate processing apparatus and a substrate processing method, and more particularly, to a method for applying ozone water to a semiconductor substrate, a glass substrate of a liquid crystal display, a glass substrate for a photomask, a substrate for an optical disk, and the like. The present invention relates to a substrate processing apparatus and a substrate processing method for performing a used process.

[0002]

2. Description of the Related Art In a semiconductor device manufacturing process, particles (fine particles) adhering to a semiconductor substrate (a so-called wafer), metal contamination, organic matter contamination, etc. in the manufacturing process accompanying the miniaturization and high integration of semiconductor devices. However, it has greatly affected the yield and characteristics of devices. For example, the adhesion of particles causes an oxide film breakdown voltage defect and a wiring short circuit, and metal contamination and organic substance contamination cause an oxide film breakdown voltage defect and a junction leak defect.

However, the manufacturing process of a semiconductor device is as follows.
Since most of them are sources of particles, metal impurities, and organic contaminants, it is necessary to keep the front and back surfaces of the semiconductor substrate clean throughout the entire manufacturing process in order to improve device yield and its characteristics. .
Therefore, in each manufacturing process, a semiconductor substrate cleaning step is appropriately performed.

In the manufacturing process of a semiconductor device,
In processes such as lithography, etching, and ion implantation, a resist which is an organic film is used. After each process, a process of removing and removing the resist from the semiconductor substrate is performed.

In recent years, in the above-mentioned cleaning step and peeling / removing step, wet processing has become the mainstream from the viewpoint of increasing the diameter of semiconductor substrates and reducing costs.

[0006] In such wet processing of a semiconductor substrate, chemicals such as aqueous ammonia, hydrochloric acid, sulfuric acid, and hydrogen peroxide, chemicals obtained by mixing these, and aqueous solutions thereof are used as processing liquids. For example, sulfuric acid and hydrogen peroxide solution are mixed in a stock solution, and the mixed solution (hereinafter, referred to as a sulfuric acid peroxide solution) is used for cleaning for removing organic substances and for stripping and removing an organic film (resist). 80 ° C ~
A method of treating at a high temperature of 150 ° C., a method of treating with fuming nitric acid, and a method of treating at a high temperature of about 80 ° C. using an organic stripper mixed with an amine or the like are performed.

However, the above-described processing method has the following problems. For example, treatment using sulfuric acid-hydrogen peroxide
The operability is poor because it is a high-temperature treatment using a high-concentration chemical solution. Furthermore, in addition to the cost of the chemical itself, the cost of waste liquid treatment also increases, which is a factor that increases the running cost. This is the same as the treatment using the highly reactive fuming nitric acid and the treatment using the organic stripping liquid which is a high-temperature process.

Therefore, ozone-dissolved water (hereinafter referred to as ozone water) obtained by dissolving ozone gas in pure water is used as a processing liquid for cleaning for removing organic substances and for removing and removing an organic film (resist). It is becoming.
In the wet treatment using ozone water, the ozone water itself is relatively inexpensive, and the cost of waste liquid treatment is not required because ozone in the ozone water is naturally decomposed. In addition, this treatment method is not limited to the removal of organic substances, and can be widely applied to a cleaning treatment for removing metal contaminants and a case where an oxide film is formed on a substrate surface by using the oxidizing power of ozone. is there.

In the substrate processing using ozone water, for the purpose of shortening the processing time, when dissolving ozone in pure water, the pressure of the ozone gas is increased to increase the ozone concentration, and the temperature is further lowered. The ozone concentration is secured by keeping the solubility of ozone high.

[0010]

However, in such a method, the ozone water is not supplied when the ozone water is supplied onto the substrate, that is, when the ozone water is supplied from the supply nozzle of the ozone water onto the substrate. It is discharged from the pressurized state of the nozzle to the atmospheric pressure. For this reason, the ozone gas in the ozone water is gasified (defoamed) by the pressure change, and the ozone concentration of the ozone water supplied onto the substrate decreases. In particular, this phenomenon is more likely to occur as the ozone concentration in the ozone water is higher. Therefore, the processing efficiency cannot be increased as expected.

For the purpose of preventing this, a method and an apparatus for processing a substrate in a processing tank having no gas-liquid interface are disclosed in JP-A-2000-37671. However, in such a method, since the liquid needs to be sealed, the sealing configuration of the processing tank becomes complicated. Furthermore, it is difficult to mix ozone with the reaction accelerator at the reaction action point, that is, near the substrate surface.

Further, low-temperature ozone water has low activation energy in a chemical reaction (oxidative decomposition reaction),
Low removal power for resist film and contaminants. Therefore, it cannot be removed depending on the type of the resist film,
There is a problem that a resist film damaged or deteriorated due to being used as a mask during dry etching or high-concentration ion implantation cannot be removed, that is, the processing ability is poor.

Therefore, according to the present invention, high-concentration ozone water can be supplied to the substrate surface without lowering the temperature, whereby the processing time can be shortened while maintaining the processing capability of ozone water. It is an object to provide a substrate processing apparatus and a substrate processing method.

[0014]

According to the present invention, there is provided a substrate processing apparatus for processing a surface of a substrate with ozone water, the apparatus comprising: A processing chamber and an ozone water nozzle for supplying ozone water generated in a pressurized ozone gas atmosphere to a surface of a substrate housed in the pressure processing chamber are provided.

In the substrate processing apparatus having such a configuration, the pressurized processing chamber in which the substrates are accommodated is set to the pressurized atmosphere, so that the substrate held in the pressurized atmosphere is pressed from the ozone water nozzle to the pressurized ozone gas atmosphere. By being generated, ozone water maintained at a high concentration is supplied. For this reason, the ozone water is supplied onto the substrate while maintaining the pressurized state, and the ozone water in which the solubility of ozone is maintained, that is, the ozone water maintained at a high concentration is supplied onto the substrate. .

The present invention is also a substrate processing method for treating the surface of a substrate with ozone water, wherein ozone water generated in a pressurized ozone gas atmosphere is supplied to the surface of the substrate held in a pressurized atmosphere. It is characterized in that the surface of the substrate is treated.

In the substrate processing method having such a configuration, the ozone water generated in the pressurized ozone gas atmosphere is supplied to the surface of the substrate held in the pressurized atmosphere, so that the ozone water is maintained in a pressurized state. Is maintained on the substrate, that is, while the solubility of ozone is maintained.
Therefore, ozone water whose ozone concentration has been increased by pressurization is supplied to the surface of the substrate while maintaining the ozone concentration.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a substrate processing apparatus and a substrate processing method according to the present invention will be described in detail based on embodiments. Note that the substrate processing apparatus and the substrate processing method of the present invention remove a resist film formed on a substrate such as a semiconductor substrate or a liquid crystal substrate in a manufacturing process of a semiconductor device, a liquid crystal display device, and other substrate products. And a substrate processing apparatus and a substrate processing method for removing metal contaminants and organic contaminants adhering to the surface of the substrate, and for forming an oxide film on the surface of the substrate. In the following embodiments, the present invention will be described by taking as an example a case where a resist film on a semiconductor substrate (substrate) is removed.

(First Embodiment) FIG. 1 is a schematic configuration diagram showing an example of a substrate processing apparatus according to a first embodiment. The substrate processing apparatus shown in FIG. 1 includes a pressure processing chamber 1, and has a configuration in which a rotary cleaning device is sealed in the pressure processing chamber 1.

The pressure processing chamber 1 has an opening / closing part not shown here, and the substrate S can be freely taken in and out of the opening / closing part. A pressurizing pipe 11 is connected to the pressurizing processing chamber 1, and the inside of the pressurizing processing chamber 1 is configured to be pressurized to a predetermined pressure by pressurizing gas from the pressurizing pipe 11. ing. This pressurizing pipe 11 is provided with an on-off valve 12.

A chuck 2 for fixing and holding the substrate S is arranged in the pressure processing chamber 1. The chuck 2 includes, for example, a support member (edge clamp ring) 3 for holding down the edge of the substrate S and fixing the substrate S, and a surface Sa which is a processing surface of the substrate S.
And its back surface Sb can be fixed in a non-contact state. Thereby, the back surface Sb of the substrate S can also be cleaned. However, when it is not necessary to consider the back surface cleaning of the substrate S, the chuck 2 may be of any type, such as a vacuum chuck type or a guide pin type using centrifugal force.

The chuck 2 is a so-called spin chuck, which is provided at the tip of a rotating shaft 4 which is rotated by the power of a motor or the like (not shown). Is horizontally rotatable. In consideration of the hermetically sealed state in the pressure processing chamber 1, it is preferable that the rotation drive mechanism of the rotating shaft 4 is disposed inside the pressure processing chamber 1.

Above the chuck 2, a supply end of an ozone water nozzle 5 drawn from outside the pressure processing chamber 1 and a supply end of a pure water nozzle (not shown) are arranged. Ozone water Lo or pure water is supplied onto the surface Sa of the substrate S fixed to the chuck 2. The ozone water nozzle 5 and the pure water nozzle are provided with a supply pump 51 for discharging ozone water Lo and pure water onto the substrate S from each supply end. The supply pump 51 may be disposed outside the pressure processing chamber 1 as illustrated, or may be disposed inside the pressure processing chamber 1.

The ozone water nozzle 5 has a supply pump 5
The ozone water generating means 52 is connected via 1. The ozone water generating means 52 generates ozone water Lo in which the solubility of ozone (O ₃ ) is increased by pressurizing the ozone gas atmosphere.

The chuck 2 for holding the substrate S is disposed in the pressurized processing chamber 1 while being installed in the cup-shaped processing chamber 6, and the ozone water Lo supplied on the substrate S is provided. And the hydrogen peroxide solution Lh is prevented from scattering into the pressure processing chamber 1 due to the centrifugal force caused by the rotation of the substrate S. A waste liquid pipe 61 drawn out of the pressurized processing chamber 1 is connected to the bottom surface of the processing chamber 6, and the waste liquid pipe 61 is provided with an on-off valve 62. Further, an exhaust pipe 64 drawn out of the pressurized processing chamber 1 is connected to the processing chamber 6, and the exhaust pipe 64 is also provided with an on-off valve 65. The on-off valves 62 and 65 are provided as, for example, pressure regulating valves, and the inside of the pressurization processing chamber 1 is made to have a predetermined pressure by introducing pressurized gas from the on-off valves 62 and 65 and the pressurizing pipe 11. It is kept in a pressurized atmosphere.

Next, a substrate processing method according to a first embodiment using such a substrate processing apparatus will be described.

First, ozone water Lo pressurized to a predetermined pressure P ₀ by the ozone water generation means 52 is generated. The ozone water Lo is preferably a saturated solution obtained by dissolving ozone (O ₃ ) in pure water in a saturated state under the predetermined pressure P ₀ . The temperature of the ozone water Lo is set to an optimum value in accordance with other conditions. However, in order to secure the activation energy of the ozone water Lo, it is preferable that the temperature is maintained at about room temperature. 200
It is assumed to be about ppm.

Then, the substrate S whose surface is covered with a resist film (not shown) is carried into the pressure processing chamber 1, and the substrate S is chucked with the processing surface (surface) Sa facing upward. To be held. The resist formed on the surface Sa of the substrate S may or may not be uniform in film thickness, and may be patterned.

Next, the opening and closing part of the pressure processing chamber 1 is closed to make the inside hermetically sealed, a pressurized gas is supplied from the pressure pipe 11 into the pressure processing chamber 1, and the inside of the pressure processing chamber 1 is kept at a predetermined pressure. pressurized to pressure P ₁ of. At this time, the pressure P ₁ of the pressure treatment chamber 1 is preferably at the ozone water generating unit 52 with the generated ozone water Lo (ozone atmosphere) in the applied pressure P ₀ or more. As the pressurized gas supplied from the pressurizing pipe 11, for example, compressed air, an inert gas such as nitrogen gas (N ₂ ) or argon gas (Ar), or ozone (O ₃ ) is used. . In particular, when dissolution into ozone water Lo is expected from the atmosphere in the pressure processing chamber 1, it is preferable to use ozone (O ₃ ) as the pressurized gas.

In the above state, the rotating shaft 4 is operated to rotate the substrate S at a predetermined number of revolutions, and from the supply end of the ozone water nozzle 5 provided near the center of rotation of the substrate S, the surface of the substrate S Ozone water Lo generated in a pressurized ozone gas atmosphere is supplied onto the rotation center. Thereby, the surface S of the substrate S
The ozone water Lo is spread over the entirety a, and the ozone water Lo is caused to flow toward the periphery of the substrate S, and the resist film on the surface of the substrate S is oxidized and removed by the ozone water Lo.

After the resist film on the surface of the substrate S is oxidized and decomposed by the supply of the ozone water Lo as described above, and the resist film is removed from the surface of the substrate S, the supply of the ozone water Lo is stopped. If the purpose is to remove metal contaminants and organic contaminants on the surface of the substrate S, supply of the ozone water Lo is stopped after a sufficient time has passed for the ozone water Lo to remove these contaminants. I decided to. Also,
When the purpose is to form an oxide film, the supply of the ozone water Lo is stopped when the oxide film having a predetermined thickness is formed.

Next, if necessary, pure water is supplied from the tip of a pure water nozzle (not shown) to the center of rotation of the surface of the substrate S for rinsing. Dry S. Thereafter, the rotation of the substrate S is stopped, and a series of steps is completed. The ozone water Lo supplied to the surface of the substrate S is shaken off from the periphery of the substrate S to the outside by the centrifugal force due to the rotation of the substrate S, and is discharged from the waste liquid pipe 61 connected to the bottom surface of the processing chamber 6. You.

According to the substrate processing method using the substrate processing apparatus described above, the ozone water Lo generated in the pressurized ozone gas atmosphere is applied to the surface of the substrate S held in the pressurized atmosphere of the pressurized processing chamber 1. Supplied to Therefore, ozone water Lo
Is kept pressurized, that is, ozone (O
The solution is supplied onto the substrate S in a state where the solubility of ₃ ) is maintained. That is, the ozone water Lo whose ozone concentration is increased by pressurization is converted into ozone (O ₃ ) by defoaming.
The ozone is supplied to the surface of the substrate S while maintaining the ozone concentration without decreasing the concentration.

Therefore, it is possible to cause more ozone to act on the substrate S without lowering the temperature of the ozone water, that is, without lowering the activation energy of the ozone water. As a result, it is possible to improve the processing efficiency and shorten the processing time while maintaining the processing ability for organic substances and the like that are difficult to remove such as a deteriorated resist.

In the above embodiment, when the pressure P ₁ in the pressurized processing chamber 1 is equal to or higher than the pressure P ₀ applied to the ozone water Lo generated by the ozone water generation means 52, the ozone water nozzle 5 Defoaming from the supplied ozone water Lo can be reliably prevented. However, when the supply pump 51 is not provided in the ozone water supply nozzle 5, the pressure P ₁ in the pressure processing chamber 1 is smaller than the pressure P ₀ applied to the ozone water Lo in the ozone generation means 52. And pressurized to the highest possible pressure. Thus, defoaming from the ozone water Lo supplied from the ozone water nozzle 5 can be further reduced.

(Second Embodiment) FIG. 2 is a schematic configuration diagram showing an example of a substrate processing apparatus according to a second embodiment. In the substrate processing apparatus shown in this figure, a hydrogen peroxide water nozzle 7 is provided in the processing apparatus of the first embodiment described with reference to FIG. The hydrogen peroxide water nozzle 7 is a processing liquid nozzle described in the claims.

The hydrogen peroxide water nozzle 7 is connected to the chuck 2
A hydrogen peroxide solution Lh (a processing liquid shown in the claims) is supplied onto the substrate S fixed to the substrate S, and is provided so as to be movable in the radial direction from the rotation center of the substrate S to the periphery. However, since the inside of the pressurized processing chamber 1 in which the chuck 2 is disposed is maintained in a pressurized state, a moving mechanism (not shown) for moving the hydrogen peroxide nozzle 7 is pressurized. It is preferable to be arranged in the processing chamber 1.

Next, a substrate processing method according to a second embodiment using such a substrate processing apparatus will be described.

[0039] First, as in the first embodiment, the pressure state inside a predetermined pressure P ₁ accommodating the substrate S to pressure treatment chamber 1, to rotate the substrate S at a predetermined rotational speed. Next, ozone water Lo is supplied onto the rotation center of the surface of the substrate S from the supply end of the ozone water nozzle 5 provided near the rotation center of the substrate S. Thus, the ozone water Lo is spread over the entire surface of the substrate S, and the ozone water Lo is caused to flow toward the periphery of the substrate S. The ozone water Lo is generated in a pressurized ozone gas atmosphere, as in the first embodiment, so that the solubility of ozone (O ₃ ) is increased.

As described above, the supply of the hydrogen peroxide solution Lh from the supply end of the hydrogen peroxide solution nozzle 7 is started in a state where the ozone water Lo is supplied to the surface Sa of the rotated substrate S.

Then, the supply end of the hydrogen peroxide water nozzle 7 is moved at a predetermined speed from near the rotation center of the substrate S to the periphery. Thus, the initial mixing position of the ozone water Lo and the hydrogen peroxide solution Lh is scanned over the entire surface Sa of the rotated substrate S. Here, the initial mixing position is a point at which the hydrogen peroxide solution Lh is supplied to the ozone water Lo supplied to the surface of the substrate S. Further, the moving speed of the hydrogen peroxide water nozzle 7 does not need to be constant. For example, by decreasing the speed closer to the peripheral edge of the substrate S, the supply amount of the processing liquid to each part of the rotated substrate S is kept constant. I do.

At this time, the hydrogen peroxide solution Lh is supplied to the substrate S at an initial mixing position with the ozone water Lo within a range where the amount of hydrogen peroxide does not exceed 1.5 mol per mol of ozone.
The concentration and the supply amount (flow rate) from the hydrogen peroxide nozzle 7 are set so as to be supplied to the surface Sa. For example, the supply flow rate of ozone water Lo and hydrogen peroxide water L
When the supply flow rate of the hydrogen peroxide is set to be the same as that of the ozone water Lo, the molar concentration of hydrogen peroxide in the hydrogen peroxide solution Lh is 1.5 times or less the molar concentration of ozone in the ozone water Lo. By setting the concentration of the hydrogen oxide water Lh,
Adjust the concentration of ozone and hydrogen peroxide at the mixing location.

By the supply of the ozone water Lo and the hydrogen peroxide solution Lh as described above, the resist film on the surface of the substrate S is oxidized and decomposed, and after the resist film is removed from the surface of the substrate S, the ozone water Lo and the hydrogen peroxide are removed. The supply of water Lh is stopped. In the case where the above series of processes is aimed at removing organic pollutants, after a sufficient time has passed for the organic pollutants on the substrate S to be removed by the ozone water Lo, the ozone water Lo and the hydrogen peroxide are removed. The supply of the water Lh is stopped. Hereinafter, a series of steps is completed in the same manner as in the first embodiment.

According to the substrate processing method described above, the substrate
On the surface of S, the ozone water Lo and the hydrogen peroxide solution Lh
By scanning the mixing position, the entire surface of the substrate is
OH radical (OH^*) Is quickly generated and the substrate
OH radicals (OH^*)
Can be used. In other words, such a substrate processing method
In the method, as shown in the following reaction formula (1), ozone
Ozone in water Lo (O _Three) For hydrogen peroxide solution Lh
Hydrogen peroxide (H_TwoO_Two) Acts to break down organic matter
OH radical (OH^*) Quickly
Will be generated.

[0045]

Embedded image

For comparison, the following series of reaction formula (2) shows the decomposition of ozone in water. As shown in the reaction formula (2), it can be seen that ozone (O ₃ ) is decomposed in a chain reaction with the OH ₂ radical (OH ₂ ^* ) as an initiator. However, this reaction is not so fast.

Embedded image

On the other hand, as shown in the above reaction formula (1),
When hydrogen peroxide (H ₂ O ₂ ) is added to ozone water Lo,
Decomposition of hydrogen peroxide (H ₂ O ₂ ) causes OH ₂ ions (O ₂
H ₂ ⁻ ) is supplied, so that the OH ₂ ion (O
The decomposition of ozone (O ₃ ) is accelerated by H ₂ ⁻ ), and the generation rate of OH radical (OH ^* ) is increased as compared with the reaction formula (2).

In this case, particularly, the ozone water Lo and the hydrogen peroxide water Lh are mixed on the surface Sa of the substrate S, which is a point of use, by separately providing the ozone water nozzle 5 and the hydrogen peroxide water nozzle 7. It has a configuration. For this reason,
An OH radical (OH ^* ) having a very short life is quickly generated on the substrate S, so that the OH radical (OH ^* ) can effectively act on the surface of the substrate. As a result, in the substrate processing using the ozone water Lo, the removal efficiency of the organic substance such as the resist can be further improved and the processing time can be reduced as compared with the first embodiment. In addition, since it is not necessary to lower the temperature of the ozone water Lo, the activation energy of the OH radical (OH ^* ), which is an active species, can be maintained, and the ability to remove the altered resist can be maintained.

Further, by moving at least one of the ozone water nozzle 5 and the hydrogen peroxide water nozzle 7 from the center of rotation of the substrate S to the periphery, the mixing position of the ozone water Lo and the hydrogen peroxide water Lh is changed. The scanning was performed over the entire surface Sa of the substrate S. Therefore, the surface Sa entire area of the substrate S, and quickly produce OH radicals (OH ^*), it is possible to effectively act the OH radicals (OH ^*) to the surface Sa entire area of the substrate S. As a result, it is possible to improve the resist removal efficiency over the entire surface Sa of the substrate S.

Here, FIG. 3 shows that ozone water Lo
The supplied ozone (O_Three) And hydrogen peroxide solution Lh
Hydrogen (H_TwoO_Two) And ratio (mol
Ratio) and the resist removal rate. This group
As shown in the rough, ozone (O _Three) Peracid per mole
Hydrogen (H_TwoO_Two) Is present in a range of 1.5 mol or less.
Ozone (O_Three) Resist removal than the case alone
It can be seen that the rate increases. Therefore, this range
Ozone water Lo is provided on the surface Sa of the substrate S so as to be secured.
And hydrogen peroxide solution Lh to supply the resist.
It is possible to improve the removal efficiency without fail.
You.

From this graph, it can be seen that ozone (O ₃ ) 1
Hydrogen peroxide on the molar (H ₂ O ₂₎ 0.05 moles to 0.
By setting the ratio to 37 mol, the removal rate of the resist can be increased 1.5 times as compared with the case of using only ozone water. For this reason, it is preferable to supply the ozone water Lo and the hydrogen peroxide water Lh so as to have such a ratio at the initial mixing position. Further, it can be seen that the resist removal efficiency is highest when the ratio of hydrogen peroxide (H ₂ O ₂ ) is about 0.2 mol per 1 mol of ozone (O ₃ ). For this reason, it is most preferable to supply the ozone water Lo and the hydrogen peroxide solution Lh so as to have such a ratio at the initial mixing position. The same applies to not only the removal of the resist but also the cleaning for removing other organic contaminants.

In the second embodiment, the supply end of the hydrogen peroxide solution nozzle 7 is movable, but at least one of the ozone water nozzle 5 and the hydrogen peroxide solution nozzle 7 The same effect can be obtained as long as it is movable from the rotation center of S to the periphery. However, when one of the nozzles is fixed, the nozzle to be fixed is arranged near the center of rotation of the substrate S (that is, on the extension of the rotation axis 4), so that the ozone water Lo and the hydrogen peroxide Ensure that the water Lh is supplied.

In this embodiment, the hydrogen peroxide solution Lh is supplied to the ozone water Lo supplied on the substrate S, so that OH radicals (OH ^* ) are generated at a position closer to the surface of the substrate S. can do. As a result, the OH radicals (O
H ^* ). Therefore, when only one of the nozzles is movable, the ozone water nozzle 5
Is preferably arranged at the rotation center of the substrate S.

(Third Embodiment) FIG. 4 is a schematic diagram showing an example of a substrate processing apparatus according to a third embodiment. The substrate processing apparatus of the third embodiment shown in this figure is a modified example of the substrate processing apparatus of the second embodiment described with reference to FIG. The configuration of the supply end with the water nozzle 7 ′, the ozone water nozzle 5 ′ and the hydrogen peroxide water nozzle 7 ′ are fixed, and the other configuration is the same.

That is, at least one of the supply end 5a of the ozone water nozzle 5 'and the supply end 7a of the hydrogen peroxide water nozzle 7' of the third embodiment shown in FIG. It has a discharge port extending over the length of the radius of the substrate S, and is arranged from the center of rotation of the substrate S to the periphery.

For example, as shown in the figure, both the supply end 5a of the ozone water nozzle 5 'and the supply end 7a of the hydrogen peroxide water nozzle 7' are the discharge ports arranged from the rotation center of the substrate S to the periphery. May be provided. Further, the supply end 5a of the ozone water nozzle 5 'is fixedly disposed only near the rotation center of the substrate S (that is, on the extension of the rotation shaft 4), and the supply end 7a of the hydrogen peroxide water nozzle 7' is rotated. They may be arranged from the center to the periphery, or vice versa. However, when only the tip of one of the nozzles has a discharge port of such a shape, the tip of the other nozzle is positioned at the rotation center of the substrate S (that is, on the extension of the rotation axis 4).
By fixing in the vicinity, the ozone water Lo and the hydrogen peroxide water Lh are reliably supplied to the entire surface of the substrate S.

From the viewpoint of more quickly supplying the hydrogen peroxide solution Lh to the ozone water Lo supplied to the surface Sa of the substrate S, the supply end 5a of the ozone water nozzle 5 'and the hydrogen peroxide solution nozzle 7 'Both supply ends 7a
It is preferable to have a discharge port arranged from the rotation center to the periphery. In this case, in particular, as shown in the plan view of FIG.
It is preferable to arrange the supply ends 5a and 7a closer to each other.

At this time, the supply ends 5a, 7a of the ozone water nozzle 5 'and the supply end 7a of the hydrogen peroxide water nozzle 7' are arranged in the rotation direction of the substrate S shown by the arrow in the figure.
It is preferable to arrange a so that the hydrogen peroxide solution Lh is supplied to the ozone water Lo.

FIG. 6 is a plan view showing the opening shape of the processing liquid discharge port of the supply ends 5a and 71. As shown in FIG. 6A, the supply ends 5a and 71 may have a configuration in which a plurality of discharge ports A are arranged. Further, as shown in FIG. 6 (2), the supply ends 5a and 7a may be provided with a discharge port B having one continuous opening shape. Here, the supply end 5a of the ozone water nozzle 5 'and the supply end 7a of the hydrogen peroxide water nozzle 7' need not have the same configuration.

Next, a substrate processing method according to a third embodiment using such a substrate processing apparatus will be described.

[0061] First, as in the first embodiment, the pressure state inside a predetermined pressure P ₁ accommodating the substrate S to pressure treatment chamber 1, to rotate the substrate S at a predetermined rotational speed. Next, ozone water Lo is supplied onto the rotation center of the surface of the substrate S from the supply end 5a of the ozone water nozzle 5 'provided near the rotation center of the substrate S. Thereby, the ozone water L is applied to the entire surface of the substrate S.
and the ozone water L toward the periphery of the substrate S.
Flow o. It is assumed that the ozone water Lo is generated in a pressurized ozone gas atmosphere to increase the solubility of ozone (O ₃ ) as in the first embodiment.

As described above, the supply of the hydrogen peroxide solution Lh from the supply end 7a of the hydrogen peroxide solution nozzle 7 'is started while the ozone water Lo is supplied to the surface Sa of the rotated substrate S. . Thereby, the hydrogen peroxide solution Lh is simultaneously supplied from the rotation center of the substrate S to the periphery, and the range from the rotation center to the periphery is changed to the ozone water Lo and the hydrogen peroxide solution L.
h. Then, the mixing position is scanned over the entire surface Sa of the substrate S by the rotation of the substrate S.

At this time, the concentration and the supply amount of the hydrogen peroxide solution Lh are set in the same manner as in the second embodiment.

With the supply of the ozone water Lo and the hydrogen peroxide solution Lh as described above, the resist film on the surface of the substrate S is oxidized and decomposed, and the resist film is removed from the surface of the substrate S. A series of steps are completed in the same manner as described above.

In the substrate processing method described above, the ozone water L is applied to the surface of the substrate S as in the second embodiment.
o and the hydrogen peroxide solution Lh are mixed. Therefore, the second
As in the embodiment, on the surface Sa of the substrate S, OH radicals (OH ^* ) having an extremely short life are quickly generated,
OH radicals (OH ^* ) can be made to effectively act on the surface Sa of the substrate S, so that the removal efficiency can be further improved and the processing time can be reduced as compared with the first embodiment. Become.

As in the second embodiment, the initial mixing position of the ozone water Lo and the hydrogen peroxide solution Lh is scanned over the entire surface Sa of the substrate S, so that the surface Sa of the substrate S is scanned.
It is possible to uniformly improve the resist removal efficiency over the entire region.

In particular, in the substrate processing method of the third embodiment, the supply end 5a of the ozone water nozzle 5 'and the supply end 7a of the hydrogen peroxide water nozzle 7' are arranged from the center of rotation of the substrate 1 to the periphery. As a result, the mixing position of the ozone water Lo and the hydrogen peroxide solution Lh is scanned over the entire surface Sa of the substrate S by the rotation of the substrate S. For this reason, the initial mixing position is wider than in the first embodiment, and the removal efficiency of the processing resist can be further improved and the processing time can be reduced as compared with the second example. Moreover, the nozzle 5 ',
There is no need to provide a moving mechanism 7 ', and the configuration of the substrate processing apparatus can be simplified.

In the first, second and third embodiments, the substrate S is
The case in which the substrate processing apparatus that holds the back surface Sb of the substrate with a space therebetween is used has been described. However, when the back surface Sb of the substrate S is disposed in close contact with the chuck 2,
For example, a heating mechanism such as a heater may be provided internally, and the substrate S may be heated by the heating mechanism. In this case, the ozone water Lo and the hydrogen peroxide solution Lh are supplied to the heated substrate S by the procedure of each of the above-described embodiments.

As a result, the ozone water Lo supplied onto the substrate S is indirectly heated by the substrate S, so that the chemical activity of ozone in the ozone water Lo increases. Therefore, the activation energy of the oxidative decomposition reaction by the ozone water Lo is increased, and the ability to remove the resist film (or contaminants) can be enhanced. Moreover, since the ozone water Lo is heated on the surface of the substrate S, the temperature of the ozone water Lo is maintained at a low temperature until immediately before the ozone water Lo is supplied onto the substrate S.
On top of it. Therefore, reactive molecules (ie, ozone) involved in the oxidative decomposition reaction are formed on the surface of the substrate S
Can be supplied in large amounts, and the resist film can be efficiently removed. As a result, for example, even a deteriorated resist film can be quickly removed with a sufficient removing power.

(Fourth Embodiment) FIG. 7 is a schematic diagram showing an example of a substrate processing apparatus according to a fourth embodiment. The substrate processing apparatus shown in this figure includes the same pressure processing chamber 1 as the substrate processing apparatus of the first embodiment described with reference to FIG.
In the pressure processing chamber 1, a batch-type cleaning device is sealed. In the following, the same components as those of the substrate processing apparatus of the first embodiment will be described with the same reference numerals.

That is, the pressure processing chamber 1 is the same pressure processing chamber 1 as described in the first embodiment,
Is provided. A waste liquid pipe 61 provided with an open / close valve 62 is connected to the bottom surface of the pressurized processing chamber 1, and an exhaust pipe 64 provided with an open / close valve 65 is connected to the upper surface. Opening / closing valves 62 and 65 provided in the waste liquid pipe 61 and the exhaust pipe 64 can be opened and closed and the internal pressure can be adjusted. By introducing the pressurized gas, the inside of the pressurized processing chamber 1 is maintained at a predetermined pressurized atmosphere.

The processing chamber 1 is provided with a processing tank 8 for accommodating the substrate S, and the bottom of the processing tank 8 is supplied with an ozone water nozzle 5 drawn from outside the pressure processing chamber 1. An end and a supply end of a pure water nozzle (not shown) are connected to the processing tank 8 so that ozone water Lo and pure water are supplied into the processing tank 8. The ozone water nozzle 5 is provided with a supply pump 51 and an ozone water generation unit 52 similar to the ozone water nozzle of the first embodiment. Further, a drain pipe 81 drawn out of the pressurized processing chamber 1 is connected to the processing tank 8.
2 are provided.

Next, a substrate processing method according to a fourth embodiment using such a substrate processing apparatus will be described.

First, the ozone water generating means 52
As in the first embodiment, ozone water L in which the concentration of ozone gas generated in an ozone gas atmosphere pressurized to a predetermined pressure P ₀ is saturated.
Generate o.

A substrate S whose surface is covered with a resist film (not shown) is housed in a processing tank 8 of the pressure processing chamber 1.
The opening / closing part of the pressure processing chamber 1 is closed to make the inside hermetically sealed.
Then, pressurize the pressurized gas pressure treatment chamber 1 is supplied from the pressure pipe 11 to pressurize the pressure treatment chamber 1 to a predetermined pressure P ₁ of the same as the first embodiment. The pressurized gas used at this time is the first
This is the same as the embodiment.

Next, ozone water Lo generated in a pressurized ozone gas atmosphere is supplied into the processing tank 8 from the supply end of the ozone water nozzle 5. Thus, the processing tank 8 is filled with the ozone water Lo, and the substrate S is immersed in the ozone water Lo to oxidatively remove the resist film on the surface of the substrate S. At this time, the ozone water L
o, the ozone water Lo overflowing from the processing tank 8 is discharged from the waste liquid pipe 61.

After the resist film on the surface of the substrate S is oxidized and decomposed by the supply of the ozone water Lo as described above, the supply of the ozone water Lo is stopped after the resist film is removed from the surface of the substrate S. If the purpose is to remove metal contaminants and organic contaminants on the surface of the substrate S, supply of the ozone water Lo is stopped after a sufficient time has passed for the ozone water Lo to remove these contaminants. I decided to. Also,
When the purpose is to form an oxide film, the supply of the ozone water Lo is stopped when the oxide film having a predetermined thickness is formed.

Next, after the ozone water Lo in the processing tank 8 is discharged from the drain pipe 81, if necessary, pure water is supplied into the processing tank 8 to perform rinsing. The substrate 1 is unloaded from the inside and dried to complete a series of steps.

In the substrate processing method using the substrate processing apparatus described above, similarly to the first embodiment, the ozone water Lo generated in the pressurized ozone gas atmosphere is supplied to the pressurized processing chamber 1.
Is supplied to the surface of the substrate S held in the pressurized atmosphere, so that more ozone can act on the substrate S. As a result, it is possible to improve the processing efficiency and shorten the processing time while maintaining the processing ability for organic substances and the like that are difficult to remove such as a deteriorated resist.

In each of the above embodiments, the substrate S
The case where the supply of the ozone water Lo and the hydrogen peroxide water Lh to the top is continuously performed has been described. However, the supply of these treatment liquids may be continuous or intermittent, and when performed intermittently, ozone water Lo or hydrogen peroxide water Lh is applied to the portion in contact with the surface of the substrate S. The flow of the ozone water Lo and the hydrogen peroxide water Lh in this portion can be secured without stagnation. For this reason, it becomes possible to supply fresh ozone water Lo and hydrogen peroxide water Lh to the surface of the substrate S, and the supply of the resist film is more quickly performed as compared with the case where these are continuously supplied. Removal can be performed.

[0081]

As described above, according to the substrate processing apparatus and the substrate processing method of the present invention, ozone water generated in a pressurized ozone gas atmosphere is supplied onto a substrate held in a pressurized atmosphere. High-concentration ozone water generated in a pressurized ozone gas atmosphere can be supplied onto a substrate while maintaining the ozone concentration. For this reason, without lowering the temperature of the ozone water, that is, without lowering the activation energy of the ozone water, more ozone is allowed to act on the substrate, and the deteriorated resist and the like are difficult to remove organic substances and the like. Thus, it is possible to improve the processing efficiency and shorten the processing time while maintaining the processing capability.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a substrate processing apparatus according to a first embodiment.

FIG. 2 is a configuration diagram of a substrate processing apparatus used in a substrate processing method according to a second embodiment.

FIG. 3 is a diagram showing a relationship between a ratio of hydrogen peroxide to ozone and a resist removal rate.

FIG. 4 is a configuration diagram of a substrate processing apparatus used in a substrate processing method according to a third embodiment.

FIG. 5 is a plan view illustrating a more preferable example of a substrate processing apparatus according to a third embodiment.

FIG. 6 is a plan view illustrating a shape of a discharge port of a processing liquid in a substrate processing apparatus according to a third embodiment.

FIG. 7 is a configuration diagram of a substrate processing apparatus according to a fourth embodiment.

[Explanation of symbols]

1 ... Pressure processing chamber, 2 ... Chuck (spin chuck),
5, 5 'ozone water nozzle, 7, 7' hydrogen peroxide water nozzle, 8 treatment tank, Lh hydrogen peroxide water, Lo ozone water, S substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B08B 3/10 B08B 3/10 Z

Claims (13)

[Claims] 1. A substrate processing apparatus for processing a substrate surface with ozone water, comprising: a pressure processing chamber in which the inside is maintained in a pressurized atmosphere; An ozone water nozzle for supplying ozone water generated in a pressurized ozone gas atmosphere to the substrate processing apparatus. 2. The substrate processing apparatus according to claim 1, wherein a processing tank for storing a substrate is provided in the pressurized processing chamber, and the ozone water nozzle supplies the ozone water into the processing tank. A substrate processing apparatus characterized by the above-mentioned. 3. The substrate processing apparatus according to claim 1, wherein a spin chuck for rotating and holding the substrate is provided in the pressure processing chamber, and the ozone water nozzle is provided on the substrate held by the spin chuck. A substrate processing apparatus for supplying the ozone water. 4. The substrate processing apparatus according to claim 3, wherein a heating means for heating the substrate is provided in the spin chuck. 5. The substrate processing apparatus according to claim 3, wherein a processing liquid nozzle for supplying a processing liquid containing hydrogen peroxide is provided on the substrate held by the spin chuck. . 6. The substrate processing apparatus according to claim 5, wherein at least one of the ozone water nozzle and the processing liquid nozzle has a supply end extending from a rotation center of the substrate held on the spin chuck to a periphery thereof. A substrate processing apparatus characterized in that a substrate is scanned. 7. The substrate processing apparatus according to claim 5, wherein at least one of the ozone water nozzle and the processing liquid nozzle has a discharge port extending from a rotation center of the substrate held on the spin chuck to a peripheral edge. A substrate processing apparatus characterized by the above-mentioned. 8. A substrate processing method for treating the surface of a substrate with ozone water, comprising: supplying ozone water generated in a pressurized ozone gas atmosphere to the surface of the substrate held in a pressurized atmosphere; A substrate processing method, comprising: treating a surface of a substrate. 9. The substrate processing method according to claim 8, wherein the ozone water is pressurized at a pressure equal to or lower than a pressure in a pressurized atmosphere in which the substrate is stored. 10. The substrate processing method according to claim 8, wherein the ozone water is supplied onto a substrate heated under the pressurized atmosphere. 11. The substrate processing method according to claim 8, wherein a processing liquid containing hydrogen peroxide together with the ozone water is supplied to a surface of the substrate held in the pressurized atmosphere, and A substrate processing method comprising mixing the ozone water and a processing liquid. 12. The substrate processing method according to claim 11, wherein the supply position of at least one of the ozone water and the processing liquid is set from a rotation center of the substrate with respect to the substrate surface rotated while being kept substantially horizontal. A substrate processing method, wherein an initial mixing position of the ozone water and the processing liquid is scanned over the entire surface of the substrate by scanning over the periphery. 13. The substrate processing method according to claim 11, wherein at least one of the ozone water and the processing liquid is applied to the periphery of the substrate from the center of rotation of the substrate to the periphery thereof. Wherein the initial mixing position of the ozone water and the processing liquid is scanned over the entire surface of the substrate.