JP2006116542A - Method and apparatus for treating substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To significantly improve cleaning power and a film removing capability by enhancing the activity of a cleaning liquid and a treating liquid. <P>SOLUTION: A cleaning liquid S supplied to a substrate W is irradiated with ultraviolet rays from a UV irradiation part 31. In this case, the cleaning liquid S containing ozone is brought to an excited state, by the ultraviolet rays irradiation, as represented by "O<SB>3</SB>→ O(<SP>3</SP>p)+O<SB>2</SB>", whereby oxygen radicals can be provided by low energy. Thus, oxygen radicals can easily be generated, the activity of the cleaning liquid S can be enhanced, and the cleaning power can be significantly improved. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention supplies a cleaning solution to a semiconductor substrate, a glass substrate for a liquid crystal display, a glass substrate for a photomask, a substrate for an optical disk (hereinafter simply referred to as a substrate), and performs a cleaning process or forms a coating film. In particular, the present invention relates to a cleaning process and a film removal process performed by supplying a liquid in which ozone is dissolved.

  The conventional scrub cleaning is a typical physical cleaning that can remove particles adhering to the surface of a semiconductor substrate without using a chemical solution. There are two methods for separating particles from the substrate surface: the brush scrub method, in which the brush is in direct contact with the substrate surface rotating at high speed, and a high-pressure jet nozzle that jets ultrapure water at a high pressure. "Jet scrub method" that jets pure water, "Ultrasonic scrub method" that supplies ultrasonic vibration to the substrate by supplying ultra pure water with ultrasonic waves to the substrate surface, and a combination of these Method ”.

  In recent years, it has been pointed out that organic substances adhere to a substrate left in a clean room atmosphere, which causes a reduction in the electrical breakdown voltage of the insulating film. Further, the adhesion of organic substances can reduce the “wetting property” of the substrate and can be a factor that impedes the cleaning effect. Furthermore, some of these organic substances may be hydrolyzed during the cleaning process and remain as particles on the substrate surface. However, these organic substances can be removed relatively easily with a mixture of sulfuric acid and hydrogen peroxide solution, but from the viewpoint of wastewater treatment work and environmental problems associated with the large consumption of acid, acid and alkali are not used as much as possible. There is a need for cleaning methods.

  One technique for solving these problems is to remove organic substances by irradiating ultraviolet rays in the atmosphere. The ultraviolet rays irradiated by this method use a bright line (185 nm) emitted from a low-pressure mercury lamp in which a low-pressure mercury vapor is sealed in a high-purity quartz glass tube, or a bright line (172 nm) emitted from an excimer lamp.

However, each lamp described above has the following restrictions on use.
That is, the low-pressure mercury lamp takes a long time from when the power is turned on until it can be used. This low-pressure mercury lamp is expensive because it uses high-purity quartz, and if the replacement frequency increases, the cost of maintenance will increase.

  In addition, the excimer lamp mentioned above has a short time from when the power is turned on to when it can be used, so it can be lit and used only when necessary, reducing lamp replacement frequency and reducing maintenance costs. On the other hand, since the apparatus including the excimer lamp is very expensive, there are advantages and disadvantages in terms of cost.

  In addition, both lamps irradiate ultraviolet rays in the atmosphere, but both involve generation of a large amount of ozone. Therefore, safety measures for ventilation and prevention of leakage of the processing chamber are necessary. In both cases, when ultraviolet rays are irradiated in the atmosphere, the ultraviolet rays are almost absorbed by the oxygen present in the air before reaching the vicinity of the substrate surface, so the distance between the substrate surface and the lamp needs to be as small as possible. is there. In particular, the excimer lamp having an ultraviolet wavelength of 172 nm has a large absorption, and in order to obtain a sufficient effect, it is necessary to bring the lamp close to a distance of about 2 to 3 mm from the substrate surface. In addition, although the low-pressure mercury lamp is not as large as the excimer lamp, it is necessary to dispose the lamp at a distance of about 30 mm from the substrate surface.

  Thus, in order to obtain the effect of removing organic substances by ultraviolet rays, it is necessary to bring the lamp closer to the substrate surface. However, in the case of using the lamp as an auxiliary means for the cleaning process using the cleaning liquid, due to the space such as the brush and the cleaning liquid supply nozzle. Irradiation must be performed at a certain distance from the substrate. Therefore, in order to achieve both the above-described absorption problems, the ultraviolet irradiation chamber and the cleaning chamber must be formed separately, and an extra space is required.

  Therefore, the use of a cleaning liquid (so-called ozone water) in which ozone gas is dissolved in pure water as an object that can be processed in the same chamber is attracting attention. This ozone water is said to have a higher cleaning effect as the dissolved concentration of ozone is higher.

However, such a conventional example has the following problems.
That is, as described above, in order to increase the cleaning effect, it is necessary to increase the dissolution concentration of ozone. However, the existing dissolution method has a limit of dissolving about 10 to 20 ppm in pure water at most. The inventors used ozone water having such a dissolved concentration and performed cleaning treatment on various organic substances to investigate the effect, but could not obtain a sufficient cleaning effect.

  Specifically, a substrate on which HMDS (hexamethyldisilazane) was intentionally applied under reduced pressure was used as a test sample, and the degree of cleaning was determined by measuring the contact angle of the substrate surface after the cleaning process. The applied HMDS is a typical substance of organic substances adhering to the substrate in a clean room, and has a property that the contact angle with water sensitively affects as the amount of adhesion increases, so it is suitable as an index for organic substance removal. . FIG. 7 is a graph showing the relationship between the liquid deposition time and the contact angle when the above-mentioned ozone water is supplied to the test sample. For comparison, the substrate surface is irradiated with only 172 nm ultraviolet rays with an excimer lamp. The relationship between the irradiation time and the contact angle is also shown.

  As is clear from this graph, ozone water having the above-mentioned dissolved concentration cannot obtain a sufficient cleaning effect, and is considerably inferior to cleaning processing using only an excimer lamp. This level of cleaning effect can be used only for batch-type cleaning processing, in which a plurality of substrates are processed at the same time, so that the processing time per substrate can be set longer. In the single wafer cleaning process as the substrate diameter increases, it is actually required to shorten the cleaning time required for one substrate. However, as shown in FIG. There is a problem that sufficient cleaning cannot be performed in such a short time.

  In addition to the cleaning process, there is a problem that the film removal ability cannot be sufficiently obtained in the same manner as described above even in the process of removing the photoresist film by supplying ozone water to the substrate coated with the photoresist film. .

  The present invention has been made in view of such circumstances, and a substrate processing method and apparatus capable of greatly improving the cleaning ability and the film removal ability by increasing the activity of the cleaning liquid and the processing liquid. The purpose is to provide.

In order to achieve such an object, the present invention has the following configuration.
That is, the invention according to claim 1 is a substrate processing method in which a cleaning liquid is supplied to a substrate to perform a cleaning process, and a cleaning liquid obtained by dissolving ozone in pure water is rotated from a nozzle having a discharge port facing the substrate. And a step of irradiating the cleaning solution supplied to the substrate with ultraviolet light having a wavelength in the range of 242.4 to 300 nm.

  [Action / Effect] It has been known for a long time that a cleaning solution in which ozone is dissolved has a cleaning effect. However, the cleaning effect is obtained by immersing the entire substrate in ozone water stored in a cleaning tank. It has been. However, because single-wafer processing, which is performed one by one as the substrate becomes larger, requires a shorter processing time, in order to be usable in single-wafer processing, it has a higher cleaning ability than batch processing. Is required. However, since the present ozone water is generated by directly dissolving ozone gas in pure water or using electrolytic water on the anode side (so-called anode water) generated by electrolysis, the concentration of ozone dissolved in the cleaning liquid Is at most about 10 ppm. In the future, even if ozone dissolution technology advances and the concentration dramatically increases, the filters and piping materials that supply it must have sufficient ozone resistance. Therefore, the inventors have invented a method of supplying a cleaning liquid having a minimum ozone dissolution concentration to the substrate and enhancing the cleaning effect by auxiliary means.

In the reaction in the air, if organic substances attached to the substrate are removed only by ozone, cleaning is insufficient, and it is considered necessary that oxygen radicals contribute to the reaction. Even in the reaction in the cleaning solution, the reaction of oxygen radicals remains the dominant factor. Referring to the process of generating oxygen radicals, first, the oxygen molecules in accordance with the wavelength of light taking excited state as follows. In order to obtain an oxygen radical (O ⁽³ p)) requires high energy To do.

hν
O ² → O ( ³ p) + O ( ³ p) λ <242.4nm (5.16eV)
O ² → O ( ³ p) + O ( ¹ D) λ <175.0 nm (7.08 eV)
O ² → O ( ³ p) + O ( ¹ S) λ <133.2 nm (9.30 eV)

On the other hand, in the case of ozone, the following excited state is taken. In this case, oxygen radicals can be obtained with low energy.
O ₃ → O ( ³ p) + O ₂ λ <300.0nm (4.13eV)

  Therefore, if a cleaning solution in which ozone is dissolved at a low concentration is supplied to the substrate and irradiated with ultraviolet rays (λ = 1 to 400 nm), oxygen radicals can be easily generated and the activity of the cleaning solution can be increased. it can.

  In addition, since oxygen molecules take an excited state as described above depending on the wavelength of light, high energy is required to obtain oxygen radicals. Energy can also generate oxygen radicals. In other words, when ultraviolet rays in the wavelength region of 242.4 nm <λ <300.0 nm are irradiated in the atmosphere, oxygen is not decomposed, but organic substances attached to the substrate are oxidized by oxygen radicals excited by ozone decomposition, and water and carbonate Become gas. Therefore, if the cleaning liquid in which ozone is dissolved is irradiated with ultraviolet rays in the above wavelength region, ozone is easily decomposed into oxygen radicals, and the activity of the cleaning liquid can be increased.

  In addition, from the graph of FIG. 8 showing the transmittance of ultraviolet rays of λ = 254 nm in various aqueous solutions, the ultraviolet rays having wavelengths in the vicinity of the ultraviolet rays are hardly transmitted and absorbed through air or distilled water. Further, since the cleaning liquid deposited on the substrate surface is about 1 mm, the ultraviolet rays having a wavelength in this region are hardly absorbed except for ozone. Furthermore, ozone is not generated at all by the decomposition of oxygen even when irradiated with ultraviolet rays in the above wavelength range in the atmosphere.

  Although it is possible to generate oxygen radicals by irradiating ultraviolet rays having a wavelength of 242.4 nm or less as described above, it is structurally expensive and has a long distance from the substrate surface due to absorption. While it is necessary to generate ultraviolet rays using a quartz low-pressure mercury lamp or excimer lamp, which cannot be set, ultraviolet rays in the above-mentioned wavelength range can be generated by a low-cost ozone-less low-pressure mercury lamp. is there. The reason why this lamp is inexpensive is that quartz having a purity lower than that of the lamp tube material for generating ozone can be used.

  As is apparent from the above description, according to the method invention of claim 1, if the cleaning liquid in which ozone is dissolved is irradiated with ultraviolet rays, oxygen radicals can be easily generated to increase the activity of the cleaning liquid. Therefore, even with low-concentration ozone water, the cleaning ability can be greatly improved, and it can be applied to single-wafer cleaning processing accompanying an increase in diameter. Moreover, since the ozone dissolution concentration of the cleaning liquid supplied to the substrate can be kept low, it is not necessary to provide sufficient ozone resistance to the filter or piping material that supplies the cleaning liquid.

  In addition, since ultraviolet rays having a wavelength in the range of 242.4 to 300 nm are hardly absorbed by pure water or air, the distance between the ultraviolet irradiation means and the substrate surface can be set large. Therefore, a cleaning brush or the like can be used together with ultraviolet irradiation, and the treatment can be performed in the same chamber. In addition, since ozone is not generated at all, consideration for ventilation and the like can be reduced, and it can be generated by a low-cost ozone-less low-pressure mercury lamp.

  Further, the invention described in claim 2 is a supporting means for supporting and rotating the substrate, and a cleaning liquid supplying means for supplying a cleaning liquid prepared by dissolving ozone to the substrate from a nozzle having discharge holes directed to the substrate. And ultraviolet irradiation means for irradiating the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm, and supplying the cleaning liquid from the cleaning liquid supply means to the rotated substrate supported by the support means The cleaning liquid supplied to the substrate is irradiated with ultraviolet rays from the ultraviolet irradiation means during the cleaning process.

  [Operation and Effect] According to the invention described in claim 2, the invention described in claim 1 can be suitably implemented.

  The invention described in claim 3 is a substrate processing method in which a processing liquid is supplied to a substrate coated with a coating film to remove the coating film, and a dissolved processing liquid obtained by dissolving ozone in pure water. And a step of irradiating the processing liquid supplied to the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm. It is characterized by having.

  [Operation / Effect] According to the invention described in claim 3, a treatment liquid in which ozone is dissolved at a low concentration is supplied to a substrate coated with a coating film such as a photoresist liquid, and the wavelength is 242. Irradiation with ultraviolet rays in the range of 4 to 300 nm makes it possible to easily generate oxygen radicals and increase the activity of the treatment liquid.

  The invention according to claim 4 supplies the substrate to the substrate with a support means for supporting and rotating the substrate, and a treatment liquid obtained by dissolving ozone in pure water from a nozzle having a discharge hole facing the substrate. A treatment liquid supply means for irradiating the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm, and the treatment liquid is supported by the support means and rotated on the substrate. During the coating removal process performed by supplying the treatment liquid from the supply means, the treatment liquid supplied to the substrate is irradiated with ultraviolet rays from the ultraviolet irradiation means.

  [Operation and Effect] According to the invention described in claim 4, the invention described in claim 3 can be suitably implemented.

  In the present invention, it is preferable that the step of irradiating the ultraviolet rays is performed in the atmosphere.

  In the present invention, it is preferable that the ultraviolet irradiation means irradiates ultraviolet rays in the atmosphere.

  In the present invention, it is preferable that the ultraviolet irradiation means includes an ozone-less UV lamp and a reflector that irradiates the substrate with ultraviolet rays from the ozone-less UV lamp.

  In the present invention, it is preferable that the processing liquid supply means directs the discharge hole of the nozzle toward the rotation center of the substrate during supply.

  According to the present invention, if the cleaning liquid in which ozone is dissolved is irradiated with ultraviolet rays, oxygen radicals can be easily generated to increase the activity of the cleaning liquid. Therefore, even with low-concentration ozone water, the cleaning ability can be greatly improved, and it can be applied to single-wafer cleaning processing accompanying an increase in diameter. Moreover, since the ozone dissolution concentration of the cleaning liquid supplied to the substrate can be kept low, it is not necessary to provide sufficient ozone resistance to the filter or piping material that supplies the cleaning liquid. In addition, since ultraviolet rays having a wavelength in the range of 242.4 to 300 nm are hardly absorbed by pure water or air, the distance between the ultraviolet irradiation means and the substrate surface can be set large. Therefore, a cleaning brush or the like can be used together with ultraviolet irradiation, and the treatment can be performed in the same chamber. In addition, since ozone is not generated at all, consideration for ventilation and the like can be reduced, and it can be generated by a low-cost ozone-less low-pressure mercury lamp.

  FIG. 1 is a block diagram illustrating a schematic configuration of the substrate processing apparatus according to the first embodiment.

  A disc-shaped spin chuck 1 having six support pins 1a formed in a columnar shape is rotatively driven by an electric motor 5 via a rotating shaft 3 connected to the bottom surface. Yes. By this rotational drive, the substrate W whose peripheral portion is in contact with and supported by the support pins 1a is rotated around the rotation center P in a horizontal plane. Around the spin chuck 1, a splash prevention cup 9 is provided for preventing the cleaning liquid S discharged from the ultrasonic nozzle 7 from splashing. The scattering prevention cup 9 is indicated by an arrow in the drawing when an uncleaned substrate W is placed on the spin chuck 1 or when a transport means (not shown) receives the cleaned substrate W from the spin chuck 1. Thus, it is configured to move up and down with respect to the spin chuck 1. In addition, said spin chuck 1, the rotating shaft 3, and the electric motor 5 are equivalent to the support means in this invention.

  The nozzle 7 is supported by the support arm 11 in an inclined posture with the discharge hole directed toward the rotation center P, and as shown by an arrow in the figure, the nozzle 7 is moved up and down / oscillated together with the support arm 11. ing. The position to be swung is a cleaning position located above the substrate W and a standby position separated to the side of the substrate W and the anti-scattering cup 9. A piping 15 is connected to the body, and ozone water in which ozone is dissolved in pure water is supplied as a cleaning liquid from an ozone water supply device 21 connected via a control valve 19 that is controlled to open and close by a controller 17. Is done. The ozone dissolution concentration of the cleaning liquid is a low concentration of about 10 ppm. When this cleaning liquid is supplied to the nozzle 7, ultrasonic vibration (for example, 1.5 MHz) is applied by the oscillator 7a. A high frequency voltage corresponding to the natural frequency is applied from the ultrasonic vibration power source 23 to the oscillator 7a. The nozzle 7, the pipe 15, the control valve 19, and the ozone water supply device 21 correspond to the cleaning liquid supply means of the present invention.

  A UV irradiation unit 31 (ultraviolet irradiation means) for irradiating ultraviolet rays toward the substrate W is movably provided at an irradiation position above the scattering prevention cup 9. The UV irradiation unit 31 is configured to be movable between an irradiation position shown in the figure and a standby position (not shown) separated to the side of the scattering prevention cup 9. The UV irradiation unit 31 is configured by attaching a plurality of ozoneless UV lamps 33 to a reflection plate 35 for irradiating ultraviolet rays toward the substrate W side. To emit. The ultraviolet ray irradiated from the ozoneless UV lamp 33 is preferably in the wavelength region of 242.4 nm <λ <300.0 nm so that oxygen radicals can be generated from ozone with low energy, but here, as an example, the wavelength of λ = 254 nm An ozone-less UV lamp 33 is used.

  The electric motor 5, the drive mechanism 13, the control valve 19, the ozone water supply device 21, the ultrasonic vibration power source 23, and the ozone-less UV lamp power source 37 described above are centrally controlled by the controller 17. It is like that.

  Next, processing performed by the substrate processing apparatus configured as described above will be described with reference to FIGS.

<Cleaning process>
First, the anti-scattering cup 9 is lowered with respect to the spin chuck 1 and the substrate W is placed on the spin chuck 1. Then, the scattering prevention cup 9 is raised, the nozzle 7 is moved to the cleaning position, the UV irradiation unit 31 is moved to the irradiation position above the substrate W, and the substrate W starts to be irradiated with ultraviolet rays. Next, while rotating the substrate W at a low speed at a constant speed, the cleaning liquid S is supplied from the nozzle 7 to the substrate W, and the cleaning liquid S is deposited on the upper surface of the substrate W (FIG. 2).

At this time, the cleaning liquid S containing ozone takes an excited state such as “O ₃ → O ( ³ p) + O ₂ ” by being irradiated with ultraviolet rays, and can obtain oxygen radicals with low energy. Therefore, oxygen radicals can be easily generated, the activity of the cleaning liquid can be increased, and the cleaning ability can be greatly improved. Also, positive and negative ions are generated in the atmosphere in the vicinity of the substrate W.

  Further, as shown in FIG. 8, the ultraviolet rays having this wavelength pass through water and air well and are hardly absorbed, so that the interval between the UV irradiation unit 31 and the substrate W surface can be set large. Therefore, it is not necessary to place the ultraviolet irradiation means close to the substrate as in the conventional example, the nozzle 7 can be used simultaneously with the ultraviolet irradiation, the processing can be performed in the same processing section, and the cleaning process can be performed efficiently. . Further, since ozone is not generated at all, consideration for ventilation and the like can be reduced, and it can be generated by a low-cost ozone-less UV lamp. Therefore, the configuration of the apparatus can be simplified and the apparatus cost can be suppressed.

<Drying process>
After performing the cleaning process for holding the liquid accumulated state for a certain period of time as described above, the discharge of the cleaning liquid is stopped and the nozzle 7 is moved to the standby position. At the same time, the substrate W is rotated at a high speed so that the accumulated cleaning liquid S is scattered around the substrate W, and the substrate W is shaken and dried (FIG. 3).

  By the way, when the cleaning liquid is supplied to the substrate W during the cleaning process, the substrate W is charged (mainly charged to the negative electrode) due to the high specific resistance of the cleaning liquid. Also in this drying process, the substrate W is charged by rotational driving. This charging phenomenon generally has a monotonous increase in the amount of charge as the cleaning time increases (see FIG. 9), and depending on the processing time, the element formed on the surface of the substrate W may be destroyed. . Even if the element does not break down, particles removed from the surface of the substrate W by the previous cleaning process may be attracted and reattached by electrostatic force. Therefore, by continuing the irradiation of ultraviolet rays even during the drying process, positive and negative ions are generated in the atmosphere near the substrate W, and the charged substrate W can be neutralized. As a result, inconveniences such as element destruction and reattachment can be avoided.

  Depending on the type of substrate W and the stage of the process, charging may be acceptable, and if the amount of redeposition falls within an acceptable level, ultraviolet irradiation may be stopped during the drying process. Good. Further, the ultraviolet irradiation may be performed for a certain time instead of the entire cleaning process.

  Further, it is not essential to apply ultrasonic vibration to the cleaning liquid, and the cleaning liquid may be simply supplied from the nozzle.

FIG. 4 is a block diagram illustrating a schematic configuration of the substrate processing apparatus according to the second embodiment.
In the first embodiment, the substrate processing apparatus for cleaning the substrate has been described as an example. However, in this embodiment, a substrate coated with a photoresist film, which is an example of a coating film, is processed to form a film. A substrate processing apparatus for removing the substrate will be described as an example. Note that the same components as those in the first embodiment described above are denoted by the same reference numerals, and detailed description thereof is omitted.

  Ozone water in which ozone is dissolved in pure water is supplied as a treatment liquid to the pipe 15 connected to the nozzle 7 from an ozone water supply device 21 connected via a control valve 19 controlled to open and close by the controller 17. The Further, a mixing valve 43 for mixing a predetermined amount of ammonia into the pipe 15 from the ammonia supply device 41 is disposed on the downstream side of the on-off valve 19. The ozone water to which ammonia is added is ultrasonically vibrated. Is applied to the substrate W with the photoresist film F applied on the surface thereof as a processing liquid E from the nozzle 7. Although ammonia is added to ozone water here, other bases may be added.

  Next, the removal process of the photoresist film by the substrate processing apparatus configured as described above will be described with reference to FIGS.

<Cleaning process>
First, after placing the substrate W on which the photoresist film F is deposited on the spin chuck 1, the nozzle 7 is moved to the cleaning position, and the UV irradiation unit 31 is moved above the substrate W to irradiate ultraviolet rays. Start. Then, while rotating the substrate W at a low speed, the processing liquid E is supplied from the nozzle 7 to the substrate W, and the processing liquid E is deposited on the upper surface of the substrate W (FIG. 5).

  At this time, as the treatment liquid E containing ozone is irradiated with ultraviolet rays, oxygen radicals can be obtained with low energy as described above. Therefore, oxygen radicals can be easily generated, the activity of the treatment liquid can be increased, and the ability to remove the photoresist film F can be greatly improved.

  Since the ultraviolet rays of the irradiating wavelength penetrates water and air well and are hardly absorbed, the nozzle 7 can be used simultaneously with the irradiation of the ultraviolet rays, so that the processing can be performed in the same processing section, and the cleaning process is performed efficiently. As in the case of the apparatus of the first embodiment described above, it can be generated by a low-cost ozone-less UV lamp. .

In this apparatus, since the thing which added ammonia which is a base to ozone water as the process liquid E is employ | adopted, there exist the following effects further.
That is, the pH of the treatment liquid can be controlled by adding ammonia, which is a base, to ozone water. In general, particles such as photoresist film F and alumina peeled from the substrate W are easily charged to the positive electrode, and the surface potential of the substrate W tends to be negative. Although it adheres to the substrate W surface, the photoresist film F and the like peeled off by the addition of ammonia can be charged to the same negative electrode as the substrate W. Accordingly, it is possible to prevent the photoresist film F and the like peeled off by generating a repulsive force between them and reattaching to the substrate W by electrostatic force.

<Drying process>
As described above, after performing the coating removal process for holding the state where the processing liquid E is accumulated for a certain period of time, the supply of the processing liquid E is stopped and the nozzle 7 is moved to the standby position. At the same time, by rotating the substrate W at a high speed, the processing liquid E containing the dissolved photoresist film F is scattered around and the substrate W is shaken and dried (FIG. 6).

  The substrate W is charged due to the high specific resistance of the cleaning liquid E during the cleaning process or due to the rotational drive during the drying process. By continuing the irradiation of ultraviolet rays during the drying process, the substrate W It is possible to neutralize the charged substrate W by generating positive and negative ions in the atmosphere in the vicinity of the substrate, and avoid problems such as element destruction and reattachment.

  In the apparatus of Example 2, ammonia as a base is added to the treatment liquid in which ozone water is dissolved. However, even if a surfactant is added instead of ammonia, reattachment can be prevented. In the above apparatus, ammonia is mixed with ozone water by the mixing valve 43, but ozone water to which ammonia is added is generated in advance and supplied from the ozone water supply apparatus 21 without being mixed in the middle. You may make it do.

  Further, ammonia may be added to the ozone water in the cleaning substrate processing apparatus of Example 1 described above. In the substrate processing apparatus for film removal of Example 2, ozone water to which ammonia is not added is added. Needless to say, the processing may be performed by using them.

1 is a block diagram illustrating a schematic configuration of a substrate processing apparatus according to a first embodiment. It is a figure with which it uses for operation | movement description of a washing | cleaning process. It is a figure where it uses for operation | movement description of a drying process. FIG. 6 is a block diagram illustrating a schematic configuration of a substrate processing apparatus according to a second embodiment. It is a figure where it uses for operation | movement description of the removal process of a photoresist film. It is a figure where it uses for operation | movement description of a drying process. It is a graph which shows the relationship between UV irradiation time / ozone water accumulation time, and a contact angle. It is a graph which shows the transmittance | permeability of the ultraviolet-ray in a various medium. It is a graph which shows the relationship between the pure water supply time and the charge amount of a board | substrate.

Explanation of symbols

W ... Substrate S ... Cleaning solution E ... Processing solution F ... Photoresist coating 1 ... Spin chuck 3 ... Rotating shaft 5 ... Electric motor 7 ... Nozzle 15 ... Piping 17 ... Controller 19 ... Control valve 21 ... Ozone water supply device 31 ... UV irradiation Part 33 ... Ozone-less UV lamp 41 ... Ammonia supply device 43 ... Mixing valve

Claims (8)

In a substrate processing method of supplying a cleaning liquid to a substrate and performing a cleaning process,
Supplying a cleaning solution obtained by dissolving ozone in pure water to a rotating substrate from a nozzle having a discharge port facing the substrate;
Irradiating the cleaning liquid supplied to the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm to the cleaning solution in which ozone is dissolved;
A substrate processing method comprising: A support means for supporting and rotating the substrate;
Cleaning liquid supply means for supplying a cleaning liquid obtained by dissolving ozone to the substrate from a nozzle having discharge holes directed to the substrate;
An ultraviolet irradiation means for irradiating the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm,
The cleaning liquid supplied to the substrate is irradiated with ultraviolet rays from the ultraviolet irradiation means during a cleaning process performed by supplying the cleaning liquid from the cleaning liquid supply means to the substrate supported and rotated by the support means. Substrate processing apparatus. In a substrate processing method for supplying a processing liquid to a substrate coated with a coating film and performing a coating removal process,
Supplying a dissolved processing liquid obtained by dissolving ozone in pure water to a rotating substrate from a nozzle having discharge holes directed to the substrate;
Irradiating the processing liquid supplied to the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm. A support means for supporting and rotating the substrate;
A treatment liquid supply means for supplying a treatment liquid obtained by dissolving ozone in pure water to the substrate from a nozzle having discharge holes directed to the substrate;
An ultraviolet irradiation means for irradiating the substrate with ultraviolet rays having a wavelength in the range of 242.4 to 300 nm,
During the coating removal process performed by supplying the processing liquid from the processing liquid supply means to the substrate supported and rotated by the supporting means, the processing liquid supplied to the substrate is irradiated with ultraviolet rays from the ultraviolet irradiation means. A substrate processing apparatus, characterized in that: In the substrate processing method of Claim 1 or 3,
The substrate processing method characterized in that the step of irradiating with ultraviolet rays is performed in the atmosphere. The substrate processing apparatus according to claim 2 or 4,
The substrate processing apparatus, wherein the ultraviolet irradiation means irradiates ultraviolet rays in the atmosphere. The substrate processing apparatus according to any one of claims 2, 4, and 6,
The ultraviolet ray irradiating means includes an ozoneless UV lamp and a reflection plate for irradiating ultraviolet rays from the ozoneless UV lamp to the substrate side. The substrate processing apparatus according to any one of claims 2, 4, 6, and 7,
The substrate processing apparatus, wherein the processing liquid supply means directs the nozzle discharge hole toward the center of rotation of the substrate during supply.

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