JP2001110772A - Substrate treatment method and substrate treater - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate treatment method having high treatment capacity, and a processor. SOLUTION: This is a method of washing a wafer W, and here the liquid film 31 of pure water is made on the surface of the wafer W, while the liquid film 32 of ozone water is created by dissolving ozone gas 20 in the liquid film 31 of pure water, and the resist film 30 made on the surface of the wafer W is removed. A washer 1 can execute such a washing method suitably.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate.

[0002]

2. Description of the Related Art For example, a semiconductor wafer (hereinafter, "wafer")
That. In the photolithography process of (1), a process of applying a resist to the wafer, exposing the pattern, and then developing the wafer is performed. After that, the resist is removed from the wafer.

[0003] When removing the resist, a cleaning device is used. In this cleaning device, SPM (H ₂ SO ₄
The wafer is immersed in a cleaning bath filled with a chemical solution called “/ H ₂ O ₂ mixed solution” to remove the resist. On the other hand, today, it is demanded to remove the resist using ozone water, which is easy to treat with a waste liquid, without using a chemical solution from the viewpoint of environmental protection. In this case, the wafer is immersed in a cleaning tank filled with ozone water, and the resist is oxidized by oxygen atom radicals in the ozone water to be decomposed into carbon dioxide, water and the like.

[0004]

SUMMARY OF THE INVENTION However, usually,
Ozone water is generated by bubbling and dissolving high-concentration ozone gas in pure water, and then this ozone water is filled in the cleaning tank, during which time the ozone in the liquid disappears and the ozone water disappears. In some cases, the concentration decreased. Since the cleaning ability of ozone water is affected by the level of ozone concentration, the cleaning ability is low with low-concentration ozone water, and the resist cannot be sufficiently removed in some cases. In addition, since the reaction between ozone and the resist is very fast, when the wafer is immersed in ozone water, the supply of ozone to the resist surface becomes insufficient, and a high reaction rate cannot be obtained.

Accordingly, it is an object of the present invention to provide a substrate processing method and a substrate processing apparatus capable of obtaining a high processing capability.

[0006]

In order to solve the above-mentioned problems, the invention according to claim 1 is a method for processing a substrate,
There is provided a substrate processing method, comprising: a step of forming a liquid film of a solvent on a surface of a substrate; and a step of processing a substrate by dissolving a processing gas in the liquid film of the solvent.

According to the substrate processing method of the first aspect,
Since the process gas is dissolved in the liquid film of the solvent while the liquid film of the solvent is formed on the surface of the substrate, the liquid film of the solvent can be transformed into a liquid film of the liquid capable of processing the substrate. Such a liquid film of the liquid is generated immediately before the processing, so that the concentration does not decrease and the processing ability is high. Therefore, effective processing can be performed on the substrate. The processing gas includes, for example, ozone gas, chlorine gas, fluorine gas, hydrogen gas, ozone gas having various reactive species (radicals, ions), chlorine gas, fluorine gas, hydrogen gas and the like.

According to a second aspect of the present invention, there is provided a method of processing a substrate, comprising the steps of: pressurizing an atmosphere around the substrate; forming a liquid film of a solvent on the surface of the substrate; Dissolving gas to process the substrate.

According to the substrate processing method of the second aspect,
While forming the liquid film of the solvent on the surface of the substrate, the processing gas is dissolved in the liquid film of the solvent. Further, the surrounding atmosphere of the substrate is pressurized to, for example, 196 kPa. Then, the amount of the processing gas dissolved in the liquid film of the solvent can be increased, and the processing capacity can be further improved.

[0010] In the substrate processing method according to any one of the first and second aspects, the step of forming the liquid film of the solvent on the surface of the substrate may include supplying the vapor of the solvent to the surface of the substrate. It is preferable to perform it. According to this method, the vapor of the solvent is supplied to the surface of the substrate, so that a thin liquid film of the solvent can be formed on the surface of the substrate. In this case, if the solvent liquid film is formed by condensing the vapor of the solvent on the surface of the substrate as described in claim 4, a thin liquid film of the solvent can be easily formed. Will be able to The condensation may be performed by adjusting the temperature of the substrate to a temperature lower than the dew point of the solvent. Then, when the solvent vapor is supplied to the substrate, the solvent vapor can be easily condensed on the surface of the substrate. If the thickness of the solvent liquid film is thin, the solvent liquid film can be transformed into a high-concentration processable liquid liquid film, and the processing can be performed quickly.

According to a sixth aspect of the present invention, there is provided a method for processing a substrate, comprising the steps of adjusting the substrate to a predetermined temperature, and supplying the solvent vapor to the surface of the substrate after adjusting the substrate to the predetermined temperature. And condensing the solvent vapor on the surface of the substrate to form a liquid film of the solvent, and dissolving the processing gas in the liquid film of the solvent to process the substrate.
A substrate processing method is provided.

According to a sixth aspect of the present invention, in the same manner as in the first to fourth aspects, the substrate is processed using the vapor of the solvent and the processing gas. Here, the predetermined temperature is set to a temperature lower than the dew point temperature of the solvent and at which the processing is optimally performed.
If the temperature difference between the dew point temperature of the solvent and the substrate temperature is wide, the vapor of the solvent is excessively condensed, and a large amount of droplets adhere to the surface of the substrate. In such a case, a liquid film of a thick solvent is formed on the substrate, which causes a reduction in processing capability. However, after adjusting the temperature of the substrate to a predetermined temperature, the solvent vapor is supplied to the surface of the substrate, so that the solvent vapor can be appropriately condensed, and a thin liquid film of the solvent can be formed without fail. A reduction in processing capacity can be prevented.

According to a seventh aspect of the present invention, there is provided a method of processing a substrate, comprising: a step of adjusting the substrate to a predetermined temperature; a step of pressurizing an atmosphere around the substrate; Supplying a vapor of the solvent to the surface of the substrate; condensing the vapor of the solvent on the surface of the substrate to form a liquid film of the solvent; and dissolving the processing gas in the liquid film of the solvent to process the substrate. And a method for treating a substrate.

According to a seventh aspect of the present invention, in the same manner as in the first to fourth aspects, the substrate is processed using the vapor of the solvent and the processing gas. Here, after adjusting the substrate to a predetermined temperature,
Since not only the vapor of the solvent is supplied to the surface of the substrate but also the surrounding atmosphere of the substrate is pressurized, a higher processing capacity than that of the sixth aspect can be obtained.

In the substrate processing method according to any one of claims 1 to 7, the processing gas is supplied to the surface of the substrate before the step of supplying the vapor of the solvent to the surface of the substrate. It is preferable to provide a step of performing According to this method, when a liquid film of the solvent is formed on the surface of the substrate, the processing gas can be immediately dissolved in the liquid film of the solvent, and the processing can be performed quickly.

In the step of adjusting the temperature of the substrate to a predetermined temperature, a temperature-adjusted air flow may be supplied to the surface of the substrate. According to this method, the substrate can be immediately adjusted to a predetermined temperature, and the processing can be performed quickly. Note that air, an inert gas (for example, N ₂ gas), a processing gas, or the like is preferably used for the airflow.

According to a tenth aspect of the present invention, there is provided an apparatus for processing a substrate, comprising: a processing container for processing the substrate;
A substrate processing apparatus is provided, comprising: a solvent vapor supply unit for supplying a solvent vapor to a substrate in the processing container; and a processing gas supply unit for supplying a processing gas to the processing container. .

According to the substrate processing apparatus of the present invention, the solvent vapor is supplied to the processing vessel containing the substrate by the solvent vapor supply means. On the other hand, the processing gas is supplied from the processing gas supply means into the processing container. Thus, the vapor of the solvent and the processing gas are supplied by individual means.

An invention according to claim 11 is an apparatus for processing a substrate, comprising a processing container in which the substrate is processed.
Solvent vapor supply means for supplying a solvent vapor to the substrate in the processing vessel, processing gas supply means for supplying a processing gas into the processing vessel, exhaust means for exhausting an atmosphere in the processing vessel, There is provided a substrate processing apparatus provided with an exhaust amount adjusting mechanism for adjusting an exhaust amount of an exhaust unit.

According to the substrate processing apparatus of the eleventh aspect, similarly to the tenth aspect, the vapor of the solvent and the processing gas are separately supplied. Further, the exhaust amount of the exhaust unit is reduced by the exhaust amount adjusting mechanism, and the inside of the processing container is set to a predetermined pressurized atmosphere.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the accompanying drawings based on a cleaning apparatus configured to collectively clean, for example, 25 wafers. This cleaning apparatus uses an ozone gas to process a wafer W
FIG. 1 is a sectional explanatory view of a cleaning apparatus 1 according to an embodiment of the present invention.

As shown in FIG. 1, the cleaning apparatus 1 includes a processing container 2 for cleaning a wafer W. The processing container 2 includes a container main body 3 having a size enough to store 25 wafers W, and a lid 4 for opening and closing the upper opening of the container main body 3. When the lid 4 closes the upper opening of the container body 3 as in the illustrated example, the gap between the lid 4 and the container body 3 is sealed by a sealing member 5 such as an O-ring. Then, the atmosphere in the container body 3 is prevented from leaking outside.

In the container main body 3, three parallel holding members 6a, 6b, 6c for holding the wafer W are provided in a horizontal posture. As shown in FIG. 2, these holding members 6a, 6b,
In each of the grooves 6c, 25 grooves 7 for holding the lower portion of the periphery of the wafer W are formed at equal intervals. Therefore, the container body 3
Has a configuration in which 25 wafers W can be stored in a state of being arranged at equal intervals.

As shown in FIG. 1, a heater 8 is mounted on the inner wall of the upper part of the container body 3 so as to surround the held wafer W. Heater 8 is C
It is connected to PU9. The amount of heat generated by the heater 8 is adjusted by an operation signal from the CPU 9, and the temperature of the wafer W stored in the processing container 2 and the atmosphere around the wafer W are set to a predetermined temperature.

On the other hand, a steam supply means 11 for supplying steam 10 into the processing vessel 2 is provided at the bottom of the vessel body 3. The steam supply means 11 includes a heating plate 12 fixed to the inner wall at the bottom of the container body 3, a heater 13 attached to the lower surface of the heating plate 12, and a pure water supply circuit for dropping pure water onto the upper surface of the heating plate 12. 14. Heater 13 is CP
Connected to U9. The amount of heat generated by the heater 13 is adjusted by an operation signal from the CPU 9. In the pure water supply circuit 14, the inlet is connected to the pure water supply source 15, and the outlet is opened above the hot plate 12. Also,
A flow controller 16 is provided in the pure water supply circuit 14. The flow controller 16 is connected to the CPU 9. Flow controller 1 according to an operation signal from CPU 9
6, the flow rate of pure water in the pure water supply circuit 14 is adjusted. Therefore, if pure water is dropped from the pure water supply circuit 14 onto the hot plate 12 heated by the heater 13 that has generated heat, the pure water is vaporized and steam 10 is generated. It is configured to be filled with steam 10. The pure water that could not be vaporized is supplied to the drain circuit 17 connected to the inner wall at the bottom of the container body 3.
Is drained through.

The cover 4 has an ozone gas 20 in the processing vessel 2.
Is connected to an ozone gas supply circuit 21 for supplying the gas. An inlet of the ozone gas supply circuit 21 is connected to an ozone gas supply source 22, and the ozone gas supply circuit 21 is provided with a flow controller 23 and a UV lamp 24. This flow controller 23 is connected to the CPU 9. The flow rate controller 23 is controlled by an operation signal from the CPU 9 to adjust the flow rate of the ozone gas 20 in the ozone gas supply circuit 21. The UV lamp 24 irradiates the ozone gas 20 passing through the ozone gas supply circuit 21 with ultraviolet rays to activate ozone. Further, an exhaust circuit 25 for exhausting the atmosphere in the processing container 2 is connected to the lid 4.

In the cleaning device 1, the water vapor 10 is condensed to form a liquid film of pure water on the surface of the wafer W. In this case, C
The PU 9 transmits an operation signal to the heater 13 to transmit the water vapor 10.
While the amount of heat generated by the heater 13 is adjusted to the extent that the water vapor can be sufficiently generated, an operation signal is also transmitted to the heater 8 to adjust the temperature of the wafer W to a temperature lower than the temperature of the water vapor 10. By controlling the temperature difference from the temperature, the water vapor 10 is optimally condensed on the surface of the wafer W. Further, the ozone gas 20 is dissolved in the liquid film of pure water formed on the surface of the wafer W to generate a liquid film of ozone water, thereby performing a process using ozone. In this case, CP
U9 sends an operation signal to the flow controller 16 to adjust the amount of generated water vapor 10 to adjust the thickness of the pure water liquid film, and also sends an operation signal to the flow controller 23 to send pure water. The flow rate of the ozone gas 20 is adjusted so as to match the thickness of the liquid film.
Is prevented from dissolving, and the ozone gas 20 can be optimally and reliably dissolved into the pure water liquid film.

[0028] Other, N ₂ of drying by discharging or pure water discharge nozzle 26 for rinsing by discharging pure water to the surface of the wafer W, N ₂ gas on the surface of the wafer W (the inert gas)
An ejection nozzle 27 is provided.

Next, the cleaning apparatus 1 constructed as described above is used.
The cleaning method according to the embodiment of the present invention, which is performed in the embodiment, will be described. As shown in FIG. 3, a resist film 30 is formed on the surface of the wafer W. As shown in FIG. 1, such 25 wafers W are stored in the processing container 2.
The thickness of the resist film 30 is, for example, 1200 nm.

Next, the heater 13 is heated to, for example, 120 ° C., and pure water is dropped from the pure water supply circuit 14 to the hot plate 12 to generate steam 10 at 120 ° C. and supply the steam 10 into the processing vessel 2. . On the other hand, the ozone gas supply circuit 21
From, for example, ozone at 192 g / m ³ (normal)
Ozone gas 2 having about [9 vol% (volume percentage)]
0 is supplied into the processing container 2. Thus, steam 10
And ozone gas 20 are supplied by individual means.

The heater 8 generates heat to adjust the temperature of the wafer W to a predetermined temperature. This predetermined temperature is applied to steam 1
The temperature is set to a temperature lower than the dew point temperature of 0 and at which processing using ozone is optimally performed. Here, the wafer W
Is adjusted to a temperature lower than the dew point temperature of the water vapor 10, so when the water vapor 10 is supplied, the water vapor 10 is condensed on the surface of the wafer W to form a liquid film of pure water as shown in FIG. 31 can be formed. This pure water liquid film 31
Is dissolved in the ozone gas 20.

At this time, the ozone gas 2
0 is dissolved to form a liquid film of ozone water on the surface of the wafer W, and a large amount of oxygen atom radicals are generated in the liquid film. Oxygen atom radicals generated on the surface of the wafer W immediately cause an oxidation reaction without disappearing, decompose the resist into carboxylic acid, carbon dioxide, water, etc., and as shown in FIG. The resist film 30 is sufficiently oxidized and decomposed by 32 to be converted to water-soluble, and can be easily removed by rinsing with pure water thereafter.

As described above, according to the cleaning method, the ozone gas 20 is dissolved in the pure water liquid film 31 while the pure water liquid film 31 is formed on the surface of the wafer W. 31 can be transformed into a liquid film 32 of ozone water from which the resist film 30 can be removed. Since the liquid film 32 of such ozone water is generated on the wafer W and immediately before the reaction, the ozone concentration does not decrease with the passage of time, and the processing ability is high. Therefore, an effective treatment using ozone can be performed on the wafer W.

Moreover, since the water vapor 10 is supplied to the surface of the wafer W adjusted to a temperature lower than the dew point temperature of the water vapor 10, the water vapor 10 can be easily condensed on the surface of the wafer W, and the surface of the wafer W can be easily condensed. A liquid film 31 of pure water having a small thickness can be easily formed. If the film thickness is thin,
The liquid film 31 of pure water can be transformed into a liquid film 32 of high-concentration ozone water, and processing using ozone can be performed quickly. Further, new ozone gas 20 is supplied from the ozone gas supply circuit 21 to continuously dissolve the liquid film. Therefore, the ozone lost by the reaction can be supplemented, new ozone can be quickly and sufficiently supplied to the resist film 30 through the thin liquid film, and a high reaction rate can be maintained. The liquid films such as the pure water liquid film 31 and the ozone water liquid film 32 are preferably thin enough not to form water droplets. Also,
Since the temperature of the wafer W is adjusted to a temperature lower than the dew point temperature of the water vapor 10 within a range where the oxidation reaction can be actively performed, the processing using ozone can be promoted.

[0035] Then, pure water was from the discharge nozzle 26 discharges the pure water rinse the resist film dissolve in water from the wafer W (rinsing), by discharging the N ₂ gas (inert gas) from the N ₂ discharge nozzle 27 After removing (drying) the droplets from the wafer W, the wafer W is carried out of the cleaning apparatus 1. Note that the rinsing and drying may not be performed by the cleaning apparatus 1, but may be carried out from the cleaning apparatus 1 after removing the resist film 30 and carried into a cleaning apparatus or drying apparatus dedicated to rinsing.

Thus, according to the cleaning method according to the embodiment of the present invention, the ozone water liquid film 32 having a high processing capability is formed on the surface of the wafer W immediately before the cleaning.
Can be effectively treated using ozone. As a result, the resist film 30 can be sufficiently removed. Further, the cleaning apparatus 1 according to the embodiment of the present invention can suitably perform the above-described cleaning method.

Although an example of the embodiment of the present invention has been described, the present invention is not limited to this example but can take various forms. For example, a small amount of catalyst gas may be supplied into the processing vessel to promote the generation of oxygen atom radicals in the liquid film so that the oxidation reaction can be more actively performed. In this case, the catalyst gas includes NOx gas and the like.

Also, the case where steam is generated inside the apparatus by providing steam supply means in the processing vessel has been described. However, steam is generated outside the cleaning apparatus and this steam is supplied into the processing vessel. Is also good. In such a configuration, since there is no need to provide a steam supply means in the processing container, the size of the cleaning device can be reduced accordingly.

In the cleaning device 1, the exhaust circuit 25
However, in the present invention, the flow rate controller 42 is provided in the exhaust circuit 41 to freely adjust the pressure in the processing chamber 2 as in the cleaning device 40 shown in FIG. good. The flow controller 42 is connected to the CPU 9. Further, a pressure sensor 43 is provided in the processing container 2, and a detection signal from the pressure sensor 43 is sent to the CPU 9. The CPU 9 controls the flow rate controller 42 based on the detection signal to reduce the exhaust amount of the exhaust circuit 41. On the other hand, the ozone gas supply source 22
The supply pressure of ozone gas is set to 196 kPa. For this reason, the inside of the processing container 2 can be set and maintained at, for example, 196 kPa as a predetermined pressurized atmosphere. In FIGS. 1 and 6, components having substantially the same functions and configurations are denoted by the same reference numerals, and redundant description will be omitted.

A steam supply circuit 44 for supplying steam 10 is connected to a lower portion of the processing vessel 2. A flow rate controller 45 is provided in the steam supply circuit 44, and the steam supply circuit 4
4 is connected to a steam supply 46. The steam supply source 46 includes a steam generation container 47, a pure water supply source 48, a pure water supply circuit 49, a hot plate 50, a heater 51, and a drainage circuit 52.
have. Also, the CPU 9 has a flow controller 45.
Are connected to adjust the supply amount of the steam 10.

[0041] the _{N 2} discharge nozzle 27 connects the _{N 2} supply circuit 60 for supplying _{N 2} gas. This N ₂ supply circuit 60 is branched into two. At one branch destination, N ₂
N ₂ supply source 61 filled with gas, flow controller 6
2 and a predetermined temperature, for example, 150
A hot N ₂ supply source 63 filled with N ₂ gas heated to ° C. and a flow controller 64 are provided. The CPU
By 9 controls the flow controller 62, 64, _{N 2}
The gas supplied to the discharge nozzle 27 is N ₂ gas or hot N
It is configured to appropriately switch to _two gases. In addition, a drain circuit 65 is connected to the lower part of the processing container 2.

Next, the cleaning device 4 configured as described above is used.
The cleaning method performed at 0 will be described. First, the wafer W at normal temperature (23 ° C.) is stored in the processing container 2. Then,
The heater 8 is heated to, for example, 115 ° C. to adjust the wafer W to a predetermined temperature. On the other hand, the ozone gas 20 is supplied from the ozone gas supply circuit 21 into the processing chamber 2 at a supply pressure of 196 kPa. At this time, for example, hot N ₂ gas at 150 ° C. is discharged from the N ₂ discharge nozzle 27 onto the surface of the wafer W. Then, the temperature of the wafer W can be immediately raised to a predetermined temperature.

After adjusting the temperature of the wafer W to a predetermined temperature, the supply of the hot N ₂ gas is stopped, and the steam 10 is introduced into the processing vessel 20 through the steam supply circuit 44 and supplied to the surface of the wafer W. On the other hand, the flow rate controller 42 of the exhaust circuit 41 is throttled to reduce the amount of exhaust, and
A pressurized atmosphere of kPa is set. In such a processing container 20, the concentration of the ozone gas 20 is increased.

Here, on the surface of the wafer W, water vapor 10
Is condensed to form a liquid film 31 of pure water.
Since the ozone gas 20 is supplied and filled in the processing container 2 in advance, the ozone gas 20 can be immediately dissolved in the pure water liquid film 31 to form the ozone water liquid film 32. The ozone-water liquid film 32 formed on the surface of the wafer W in this way allows the processing using ozone to be performed quickly.

Further, if the water vapor 10 is supplied while the wafer W is in the normal temperature state, the temperature difference between the dew point temperature of the water vapor 10 and the wafer temperature is wide, so that the water vapor 10 is excessively condensed, and a large amount of water vapor is condensed. Water droplets adhere to the surface of the wafer W. In this case, a thick pure water liquid film 31 is formed on the wafer W, which causes a reduction in processing capability. However, as described above, after the temperature of the wafer W is raised to a predetermined temperature, the water vapor 10 is supplied to the surface of the wafer W, so that the water vapor 10 can be appropriately condensed, and pure water having a small film thickness can be reliably formed. The liquid film 31 can be formed to prevent a decrease in processing capacity. Moreover, the atmosphere around the wafer W is set to 19
Since the pressure is increased to 6 kPa, the amount of the ozone gas 20 dissolved in the pure water liquid film 31 can be increased. An extremely high concentration ozone water liquid film 32 can be formed on the wafer W. Therefore, the processing capacity can be further improved.

After removing the resist film 30, the processing container 2
The wafer W is carried out from the inside, and then is sequentially transported to a cleaning device or a drying device dedicated to rinsing to perform rinsing cleaning and drying. On the other hand, in the processing container 2, the supply of the steam 10 and the ozone gas 20 is stopped. The droplets of the processing chamber 2 was drained by draining circuit 65, dissipate the flow controller 42 to fully open, N ₂ performs N ₂ purged by the discharge nozzle 27, expelling ozone gas 20 and steam 10 from the processing chamber 2 To dry the internal atmosphere. Then, the next normal-temperature wafer W is stored in the processing container 2. Here, if the normal temperature wafer W is stored in the processing container 2 in a state where the water vapor 10 remains, a large amount of water droplets adhere to the surface of the wafer W as described above. However, since the processing chamber 2 and the steam supply source 46 are separately provided and the atmosphere in the processing chamber 2 can be easily replaced, the surface of the wafer W is dried until the steam is introduced after the temperature of the wafer is increased. Can be maintained.

According to this cleaning method, the time for raising the temperature of the wafer is reduced by using hot N ₂ gas,
Since the ozone gas 20 is supplied before supplying 0, the generation time of the liquid film 32 of the ozone water is also shortened, so that the processing using ozone can be performed quickly and the throughput can be improved. Further, the ambient atmosphere of the wafer W is pressurized to improve the solubility of ozone in the pure water liquid film 30.
The removal efficiency of the resist film is increased, and a more effective treatment using ozone can be performed.

According to the cleaning device 40, since the steam 10 is supplied into the processing vessel 2 through the steam supply circuit 44, the amount of water in the processing vessel 2 can be easily adjusted, and the internal atmosphere can be dried. Can be. Further, since the heater 51 generates heat in the water vapor supply source 46, the heater 5
1 does not affect the wafer W in the processing chamber 2.
Therefore, the wafer W is not overheated and the wafer temperature does not rise more than necessary. As a result, for example, it is possible to prevent a situation in which the wafer temperature exceeds the dew point temperature of the water vapor 10, the water vapor hardly condenses, the liquid film of the pure water is not formed, and the processing using ozone cannot be performed.
A flow controller may be provided not only in the cleaning device 40 but also in the exhaust circuit 25 of the cleaning device 1 so as to pressurize the atmosphere around the wafer W in the processing chamber 2.

Although the case where the resist film is removed using ozone gas has been described, another film may be removed using ozone gas. For example, an organic film (BARC: bottom anti-reflective coating) that is applied under the resist film to increase the resolution can also be removed. Furthermore, various kinds of deposits attached to the surface of the wafer may be removed by using a processing gas other than the ozone gas.

For example, a chlorine (Cl ₂ ) gas is supplied to transform a pure water liquid film into a hydrochloric acid (HCl) liquid film to generate chlorine atom radicals in the liquid film.
Particles can be removed. Further, it is also possible to supply hydrogen (H ₂ ) gas to generate hydrogen atom radicals in a liquid film of pure water, thereby removing metal deposits and particles from the wafer. Also, a fluorine (F ₂ ) gas is supplied to transform a pure water liquid film into a hydrofluoric acid (HF) liquid film to generate fluorine atom radicals in the liquid film, thereby removing a natural oxide film and particles from the wafer. It is possible to

Further, an excitation reaction may be caused in the processing gas in advance to have radicals. That is, ozone gas having an oxygen atom radical, chlorine gas having a chlorine atom radical, hydrogen gas having a hydrogen atom radical,
By supplying a fluorine gas having a fluorine atom radical to generate a larger amount of radical, cleaning can be promoted.

The present invention can be applied not only to the case where the substrate is cleaned but also to the case where a predetermined processing liquid is applied to the surface of the substrate. Further, the present invention can be applied not only to a batch-type process for processing a plurality of substrates at once, but also to a single-wafer-type process for processing substrates one by one. The substrate is not limited to the wafer W,
A CD substrate, a CD substrate, a printed substrate, a ceramic substrate, or the like may be used.

[0053]

EXAMPLE Next, an example of the present invention was performed. First, an organic material film (BARC) was processed, and the relationship between the ozone concentration in the ozone gas and the removal rate of the organic material film was examined. FIG. 7 shows the result. In FIG. 7, the horizontal axis represents the ozone concentration [g / m
³ (normal)], and the vertical axis represents the removal rate [nm /
s]. As can be understood from FIG. 7, the removal rate increases as the ozone concentration increases.

Next, a treatment using ozone was performed in a state where the inside of the treatment container was pressurized, and the treatment ability was examined. In this process, the pressure in the processing vessel was set to 196 kPa
In addition, the ozone concentration in the ozone gas was set to about 162 g / m ³ (n
normal) [7.6 vol% (volume percentage)], the processing time is set to 3 minutes (min), and the initial film thickness of the organic film is set to 67.4 nm. Further, the boiling point of pure water rises in the processing vessel in a pressurized atmosphere. Therefore, the temperature of pure water and, consequently, the temperature of steam are raised to 80 ° C, 90 ° C.
C., 100.degree. C., 110.degree. C., and 120.degree. C. were set, and organic substance removal characteristics in each case were examined.
FIG. 8 shows the result.

In FIG. 8, the horizontal axis represents the wafer temperature [° C.]
The vertical axis indicates the thickness [nm] of the organic film after the treatment. Graph line a in FIG. 8 is when the temperature of pure water is 80 ° C., graph line b in FIG. 7 is when the temperature of pure water is 90 ° C., and graph line c in FIG. When the temperature of the pure water is 100 ° C., the graph line d in FIG.
The middle graph line e shows the organic substance removal characteristics when the temperature of the pure water is 120 ° C., respectively.

As can be understood from the graph lines a to e in FIG. 8, the higher the temperature of pure water, the better the organic substance removal characteristics as a whole. This suggests that the higher the temperature, the faster the reaction rate and the more active the process using ozone. In graph lines b, d, and e, the removal amount of the organic film increases as the wafer temperature increases. When the wafer temperature approaches the temperature of the water vapor and the temperature difference is reduced, the water vapor is appropriately condensed and a liquid film of pure water having a small thickness is optimally formed. It is considered that the thinner the film thickness, the more reliably the ozone gas is dissolved into the liquid film of the pure water without stopping only at the upper side of the pure water, and the more preferable the organic substance removal is. In addition, it is considered that the liquid film of the high-concentration ozone water was formed, and the removal rate was increased as described with reference to FIG. On the other hand, the removal amount decreases at about 80 ° C. on the graph line b, about 90 ° C. on the graph line d, and about 100 ° C. on the graph line e. It is considered that when the wafer temperature is too close to the temperature of water vapor, it becomes difficult to form a liquid film of pure water, and it is considered that the processing using ozone cannot be promoted.

Further, the processing was performed by setting the temperature of pure water to 90 ° C. without pressurizing the atmosphere around the wafer W. The result is shown at point f in FIG. On the other hand, the conditions such as the wafer temperature and the heating temperature of pure water were not changed, and
When performing the processing by 96KPa, the result is moved to a point b ₁ in the graph line b. Comparing these points f and point b _1, towards the point b ₁ is the removal amount of the organic substance film is more than doubled. Thus, it can be confirmed that pressurizing the atmosphere around the wafer obtains higher processing performance.

[0058]

According to the first to ninth aspects of the present invention, a liquid film of a liquid having a high processing ability is formed on the surface of the substrate immediately before the processing, so that the substrate can be effectively processed. Can be. As a result, deposits such as organic deposits, metal deposits, particles, and natural oxide films can be sufficiently removed from the substrate.

In particular, according to the second aspect, the processing capacity is further improved, and according to the sixth aspect, a liquid film of a solvent having a small film thickness can be reliably formed to prevent a reduction in the processing capacity. .
According to claim 7, both effects of claims 2 and 6 can be obtained.

According to the third aspect, a thin liquid film of the solvent can be formed on the surface of the substrate, and according to the fourth and fifth aspects, the liquid film of the solvent can be easily formed. Become. Therefore, the processing can be performed quickly.

According to the eighth aspect, the processing gas can be immediately dissolved in the liquid film of the solvent, and according to the ninth aspect, the substrate can be immediately adjusted to a predetermined temperature.
Therefore, the processing can be performed quickly, and the throughput can be improved.

The substrate processing apparatus according to the tenth aspect can suitably implement the substrate processing method according to the first and sixth aspects. The substrate processing apparatus according to the eleventh aspect is capable of suitably performing the substrate processing method according to the second and seventh aspects.

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view of a cleaning apparatus according to an embodiment of the present invention.

FIG. 2 is a perspective view of a holding member.

FIG. 3 is a first process explanatory view illustrating a process performed by the cleaning method according to the embodiment of the present invention;

FIG. 4 is a second process explanatory view illustrating a process performed by the cleaning method according to the embodiment of the present invention.

FIG. 5 is a third step explanatory view illustrating steps performed in the cleaning method according to the embodiment of the present invention;

FIG. 6 is an explanatory sectional view of a cleaning apparatus according to another embodiment different from the cleaning apparatus of FIG. 1;

FIG. 7 is a graph showing a relationship between an ozone concentration and a removal rate in an example.

FIG. 8 is a graph showing organic matter removal characteristics when a process using ozone is performed in a state where the atmosphere around the wafer is pressurized.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cleaning apparatus 2 Processing container 8 Heater 10 Water vapor 11 Water vapor supply means 20 Ozone gas 21 Ozone gas supply circuit W Wafer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Miyasaka, 650 Mitsuzawa, Hosaka-cho, Nirasaki, Yamanashi Prefecture Tokyo Electron Kyushu Co., Ltd. Process Development Center (72) Inventor Shusuke Tsutsumi 3-6-Akasaka, Minato-ku, Tokyo No. Tokyo Electron Co., Ltd. (72) Inventor Tadashi Iino 650 Mitsuzawa, Hosaka-cho, Nirasaki City, Yamanashi Prefecture Tokyo Electron Kyushu Co., Ltd. Process Development Center F-term (reference) 2H096 AA25 JA04 LA02 LA03 5F046 MA01 MA02

Claims (11)

[Claims] 1. A method of processing a substrate, comprising: a step of forming a liquid film of a solvent on a surface of the substrate; and a step of processing a substrate by dissolving a processing gas in the liquid film of the solvent. Characteristic, substrate processing method. 2. A method for processing a substrate, comprising: a step of pressurizing an atmosphere around the substrate; a step of forming a liquid film of a solvent on the surface of the substrate; and a step of dissolving a processing gas in the liquid film of the solvent. And a step of processing the substrate. 3. The substrate processing method according to claim 1, wherein the step of forming the liquid film of the solvent on the surface of the substrate is performed by supplying a vapor of the solvent to the surface of the substrate. . 4. The substrate according to claim 1, wherein the step of forming a liquid film of the solvent on the surface of the substrate is performed by condensing a vapor of the solvent on the surface of the substrate. Processing method. 5. The method according to claim 1, wherein said substrate is adjusted to a temperature lower than a dew point temperature of said solvent.
Or the substrate processing method according to 4. 6. A method of processing a substrate, the method comprising: adjusting a substrate to a predetermined temperature; adjusting the substrate to a predetermined temperature; and then supplying a solvent vapor to a surface of the substrate; Condensing the vapor on the surface of the substrate to form a liquid film of a solvent, and dissolving a processing gas in the liquid film of the solvent to process the substrate. 7. A method for treating a substrate, comprising: adjusting a substrate to a predetermined temperature; pressing an ambient atmosphere around the substrate; adjusting the substrate to a predetermined temperature; Supplying a vapor of the solvent, and condensing the vapor of the solvent on the surface of the substrate to form a liquid film of the solvent, and dissolving the processing gas in the liquid film of the solvent to process the substrate. Characteristic, substrate processing method. 8. The method according to claim 1, further comprising a step of supplying the processing gas to the surface of the substrate before the step of supplying the vapor of the solvent to the surface of the substrate. ,
8. The substrate processing apparatus according to 5, 6, or 7. 9. The substrate processing method according to claim 6, wherein, in the step of adjusting the temperature of the substrate to a predetermined temperature, an airflow whose temperature has been adjusted is supplied to the surface of the substrate. 10. An apparatus for processing a substrate, comprising: a processing container in which the processing of the substrate is performed; and solvent vapor supply means for supplying a solvent vapor to the substrate in the processing container;
A processing gas supply unit for supplying a processing gas into the processing container. 11. An apparatus for processing a substrate, comprising: a processing container in which the processing of the substrate is performed; and a solvent vapor supply means for supplying a solvent vapor to the substrate in the processing container;
A processing gas supply unit that supplies a processing gas into the processing container; an exhaust unit that exhausts an atmosphere in the processing container; and an exhaust amount adjustment mechanism that adjusts an exhaust amount of the exhaust unit. Substrate processing equipment.