JP2007266636A - Substrate treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate treatment device which can obtain high processing capacity. <P>SOLUTION: This substrate treatment device 1 is provided with a processing container 2 which accommodates a substrate W and processes the substrate inside, a heater 20 which heats the substrate W accommodated in the processing container 2, a water vapor feeding means 5 which feeds water vapor into the processing container 2, an ozone gas feeding means 7 which feeds ozone gas into the processing container 2, and an N<SB>2</SB>gas feeding means 9 which feeds N<SB>2</SB>gas into the processing container 2. Further, the device is provided with an exhaust pipe 23 which exhausts the inside of the processing container 2, a flow rate controller 71 provided in the exhaust pipe 23, and a control unit 21 which controls the flow rate controller 71 so as to pressurize the inside of the processing container 2. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  For example, in a photolithography process of a semiconductor wafer (hereinafter referred to as “wafer”), a resist is applied to the wafer, a pattern is exposed, and then a development process is performed. Thereafter, the resist is removed from the wafer.

In removing the resist, a processing apparatus is used. In this processing apparatus, the wafer is immersed in a cleaning tank filled with a chemical solution called SPM (mixed solution of H ₂ SO ₄ / H ₂ O ₂ ). Remove the resist. On the other hand, today, from the viewpoint of environmental conservation, there is a demand for resist removal using ozone water that is easy to dispose of without using chemicals. 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 and water.

  However, ozone water is usually generated by bubbling high-concentration ozone gas into pure water and dissolved, and then the ozone water is filled in the cleaning tank. In some cases, the ozone concentration decreased. The cleaning ability of ozone water is affected by the high and low ozone concentration, so the cleaning ability is low with low concentration ozone water, and resist removal may not be performed sufficiently. Also, a high temperature is required for the reaction between ozone and the resist. In order to generate high-temperature ozone water, for example, ozone may be bubbled into pure water at 80 ° C. However, pure water at high temperature has low gas solubility, so high concentration ozone water could not be generated and high reaction rate could not be obtained.

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

In order to solve the above-described problems, according to the present invention, a processing container for storing a substrate and processing the substrate therein, a heater for heating the substrate stored in the processing container, and a water vapor in the processing container are provided. a steam supply means for supplying, and ozone gas supply means for supplying ozone gas into the processing chamber, and N ₂ gas supply means for supplying a N ₂ gas into the processing chamber, and an exhaust pipe for exhausting the processing chamber There is provided a substrate processing apparatus comprising: a flow rate controller provided in the exhaust pipe; and a control unit that controls the flow rate controller so as to pressurize the inside of the processing container.
The heater may be controlled by the control unit so as to adjust the substrate stored in the processing container to a temperature higher than the dew point temperature of water vapor and lower than the temperature of water vapor.
A pressure sensor for detecting the pressure in the processing container may be provided, and the flow controller may be controlled by the control unit based on detection of the pressure sensor.
In this application, the following inventions are also disclosed.
A method of processing a substrate, the step of storing a substrate having an organic film formed on the surface thereof in a processing vessel, the step of supplying water vapor and ozone gas into the processing vessel, and the surface of the substrate with water A step of generating a hydroxyl radical in which molecules and ozone molecules are mixed, a step of changing the organic film to water-soluble by the hydroxyl radical, and a step of washing away the water-modified film. A substrate processing method is provided.
In the process of supplying water vapor and ozone gas into the processing container, the inside of the processing container may be pressurized.
The pressurization in the processing container may be performed by controlling a flow rate controller provided in an exhaust pipe of the processing container.
The flow controller may be controlled by a control unit based on the pressure in the processing container.
In the step of supplying water vapor and ozone gas into the processing container, the temperature of the substrate may be adjusted to a temperature higher than the dew point temperature of the water vapor and lower than the temperature of the water vapor.
A step of adjusting the substrate to a predetermined temperature may be included before the step of supplying water vapor into the processing container.
Before the step of supplying water vapor and ozone gas into the processing container, ozone gas may be supplied into the processing container.

The present invention also discloses the following inventions.
A method of processing a substrate, comprising: supplying a solvent vapor to the substrate; supplying a processing gas to the substrate; and processing the substrate with a reactant generated by a reaction between the solvent vapor and the processing gas. Disclosed is a substrate processing method.
In this substrate processing method, for example, water vapor is appropriately used as the solvent vapor, and ozone gas or the like is appropriately used as the processing gas. According to this substrate processing method, the vapor of the solvent is supplied to the substrate, the processing gas is supplied to the substrate, and the reaction material (atom, molecule, radical, etc.) generated by the reaction between the vapor of the solvent and the processing gas is used. Process. Since such a reactive substance is generated in the processing chamber and is immediately used for processing without disappearing, it exhibits a high processing capacity. Therefore, for example, when a resist film is formed on the surface of the substrate, the resist film can be suitably transformed into a water-soluble film by the hydroxyl radical generated by the reaction between water vapor and ozone gas.

  Also, a method of processing a substrate, the step of pressurizing the ambient atmosphere of the substrate, the step of supplying a vapor of the solvent to the substrate, the step of supplying a processing gas to the substrate, the vapor of the solvent and the processing gas, And a step of treating the substrate with a reactive substance generated by the reaction described above.

  According to this substrate processing method, the substrate is similarly processed by the reactant generated by the reaction between the solvent vapor and the processing gas. In addition, the ambient atmosphere of the substrate is pressurized. Then, it becomes possible to process a substrate in a higher temperature atmosphere. The higher the temperature, the higher the reaction rate, because the generation of reactants and the reaction by the reactants are more active.

  In these substrate processing methods, it is preferable to form a mixed layer in which solvent molecules and gas molecules are mixed on the surface of the substrate. According to such a configuration, a mixed layer in which solvent molecules and gas molecules are mixed is formed on the surface of the substrate, so that the reactant can be generated in the mixed layer to process the substrate. As described above, if, for example, water vapor is used as the solvent vapor and ozone gas is used as the processing gas, a mixed layer in which water molecules and ozone molecules are mixed can be formed. Further, while the solvent molecule layer is formed on the surface of the substrate, the mixed layer may be formed by mixing gas molecules in the solvent molecule layer. In this case, since the layer of solvent molecules is transformed into a mixed layer capable of processing the substrate immediately before processing, high processing capability can be obtained. Furthermore, if the ambient atmosphere of the substrate is pressurized, the amount of gas molecules mixed with the solvent molecule layer can be increased, so that the processing capability can be further improved.

  The substrate is preferably adjusted to a temperature higher than the dew point temperature of the solvent and lower than the temperature of the solvent vapor. By doing so, the solvent vapor is not condensed on the surface of the substrate to form droplets or a liquid film, and a high-density layer of solvent molecules can be easily formed on the surface of the substrate. For example, the reaction material generated in the mixed layer of solvent molecules and gas molecules reacts more quickly with the processing target on the surface of the substrate than the reaction material generated by dissolving the processing gas in the solvent liquid film. can do. In addition, gas molecules are appropriately mixed in a layer of high-density solvent molecules to react actively, and a large amount of reactants may be generated in a mixed layer in which high-density solvent molecules and gas molecules are mixed. it can. Therefore, processing can be performed quickly. Further, even if the substrate temperature or the ambient temperature of the substrate is increased, the amount of gas molecules mixed with the solvent molecule layer does not decrease so much, and the processing in a high temperature atmosphere is possible.

  A step of adjusting the substrate to a predetermined temperature may be provided before the step of supplying the solvent vapor to the substrate. According to such a configuration, the predetermined temperature is set to a temperature higher than the dew point temperature of the solvent and lower than the temperature of the solvent vapor within a temperature range where the treatment is optimally performed. When gas molecules are mixed in the solvent molecule layer, if the temperature difference between the dew point temperature of the solvent and the substrate temperature is wide, a low density solvent molecule layer is formed on the surface of the substrate. If this happens, the amount of reactant generated will be reduced, leading to a reduction in processing capacity. However, since the solvent vapor is supplied to the substrate after the substrate is adjusted to a predetermined temperature, a high-density layer of solvent molecules can be formed reliably, and a large amount of reactants are generated, resulting in a decrease in processing capacity. Can be prevented.

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

  It is preferable to perform a step of supplying a processing gas to the substrate before the step of supplying the solvent vapor to the substrate. According to such a method, if a processing gas is supplied to the substrate in advance, when a high-density layer of solvent molecules is formed on the surface of the substrate, the gas molecules are immediately mixed in the solvent molecule layer to react the reactants. And can be processed quickly.

  An apparatus for processing a substrate, a processing container for processing a substrate, a solvent vapor supply means for supplying a vapor of a solvent into the processing container, and a processing gas for supplying a processing gas into the processing container Disclosed is a substrate processing apparatus comprising supply means, holding means for holding a substrate in the processing container, and dry gas supply means for supplying a dry gas to the holding means.

  According to this substrate processing apparatus, the substrate is held by the holding means in the processing container. A solvent vapor is supplied into such a processing container by a solvent vapor supply means. On the other hand, the processing gas is supplied from the processing gas supply means into the processing container. In this way, the solvent vapor and the process gas are supplied by separate means. This substrate processing apparatus can suitably carry out the disclosed substrate processing method.

  Further, for example, when the solvent vapor condenses on the holding means, or when the substrate after the treatment with the reactive substance is moved to the next washing treatment tank by the holding means, for example, droplets may adhere to the holding means. . If the substrate is held by such a holding means, solvent droplets or washing solution droplets also adhere to the surface of the substrate. Here, the reactant generated in the mixed layer in which the solvent molecules and the gas molecules are mixed adheres to the surface of the substrate, for example, than the reactant generated by dissolving the processing gas in the solvent droplets. It can react immediately with the processing object. Therefore, the drying gas is supplied from the drying gas supply means to the holding means, and the holding means is dried to remove the solvent droplets. Therefore, it is possible to prevent the processing gas from being dissolved in the solvent droplets, and the processing can be suitably performed. Similarly, the washing liquid droplets can be removed.

  The substrate processing apparatus preferably includes an exhaust unit that exhausts the atmosphere in the processing container and an exhaust amount adjustment mechanism that adjusts an exhaust amount of the exhaust unit.

  According to such a configuration, the exhaust amount of the exhaust means is reduced by the exhaust amount adjusting mechanism to create a predetermined pressurized atmosphere in the processing container. This substrate processing apparatus can suitably carry out the disclosed substrate processing method.

  An apparatus for processing a substrate, the first processing chamber for storing the substrate, the second processing chamber for storing the substrate disposed adjacent to the first processing chamber, and the first processing chamber. A solvent vapor supply means for supplying a solvent vapor into the chamber; a process gas supply means for supplying a process gas into the first process chamber; a process liquid supply means for supplying a process liquid into the second process chamber; A moving means for moving the substrate between the first processing chamber and the second processing chamber; and a dry gas supply means for supplying a dry gas to the moving means in the first processing chamber. Disclosed is a substrate processing apparatus.

  According to this substrate processing apparatus, the substrate is first stored in the first processing chamber. In the first processing chamber, the solvent vapor is supplied by the solvent vapor supply means, and the processing gas is supplied by the processing gas supply means. This substrate processing apparatus can suitably carry out the disclosed substrate processing method. Further, the substrate can be moved by the moving means and stored in the second processing chamber, and the processing liquid can be supplied by the processing liquid supply means to liquid-treat the substrate.

  In addition, droplets adhere to the moving means in the second processing chamber, but since the drying gas is supplied from the drying gas supply means, the droplets can be removed from the moving means. For this reason, it is possible to prevent the droplets from adhering to the surface of the substrate from the moving means and the processing gas from being dissolved in the droplets. Therefore, processing can be performed favorably.

  The substrate processing apparatus preferably includes an exhaust unit that exhausts the atmosphere in the processing container and an exhaust amount adjustment mechanism that adjusts an exhaust amount of the exhaust unit.

  According to such a configuration, the exhaust amount adjusting mechanism restricts the exhaust amount of the exhaust means to create a predetermined pressurized atmosphere in the first processing chamber. This substrate processing apparatus can suitably carry out the disclosed substrate processing method.

  According to the present invention, the reactive substance (hydroxyl radical) generated immediately before the processing is immediately utilized for the processing without disappearing, so that a high processing capacity can be obtained and the substrate can be effectively processed. it can. Further, compared with the case where the substrate is processed by dissolving the processing gas in the solvent droplets, processing in a high temperature atmosphere is possible. As a result, for example, organic deposits can be sufficiently removed from the substrate.

  The processing capacity can be further improved. Further, the substrate can be processed by generating a reactive substance (hydroxyl radical) in a mixed layer in which solvent molecules (water molecules) and gas molecules (ozone molecules) are mixed.

  The solvent vapor (water vapor) is not condensed on the surface of the substrate to form droplets. In addition, a layer of high-density solvent molecules (water molecules) can be easily formed on the surface of the substrate. For this reason, solvent molecules (water molecules) and gas molecules (ozone molecules) can be actively reacted in the mixed layer to generate a large amount of reactants (hydroxyl radicals). Therefore, processing can be performed quickly. Furthermore, in the solvent molecule (water molecule) layer, the amount of mixed gas molecules (ozone molecules) does not decrease much even when the substrate temperature and the ambient temperature around the substrate are increased. Under a higher temperature atmosphere, generation of a reactive substance (hydroxyl radical) and promotion of reaction by the reactive substance can be achieved. A layer of solvent molecules (water molecules) with a high density can be reliably formed, and a reduction in processing capacity can be prevented. The temperature raising time of the substrate can be shortened. Gas molecules (ozone molecules) can be immediately mixed in the solvent molecule (water molecule) layer to generate reactants (hydroxyl radicals), and processing can be performed quickly.

  Hereinafter, a preferred embodiment of the present invention will be described based on a processing apparatus 1 configured to process, for example, 50 wafers W in a lump with reference to the accompanying drawings. The processing apparatus 1 removes the resist from the wafer W using ozone gas. FIG. 1 is a cross-sectional explanatory view of the processing apparatus 1.

As shown in FIG. 1, the processing apparatus 1 includes a processing container 2 for processing a wafer W, a wafer guide 3 as a holding means for holding the wafer W in the processing container 2, and a water vapor 4 in the processing container 2. Water vapor supply means 5 as solvent vapor supply means for supplying gas, ozone gas supply means 7 as process gas supply means for supplying ozone (O ₃ ) gas 6 into the processing container 2, and hot N ₂ gas ( N ₂ gas supply means 9 as dry gas supply means for supplying (dry gas) 8.

  The processing container 2 is roughly divided into, for example, a container main body 10 having a size capable of sufficiently storing 50 wafers W, and a container cover 11 that opens and closes the upper surface opening of the container main body 10. When the container cover 11 closes the upper surface opening of the container body 10 as in the illustrated example, the gap between the container cover 11 and the container body 10 is sealed with a lip type O-ring 13. The atmosphere of the ozone processing chamber 15 formed in the processing container 2 is configured not to leak outside.

  A lamp heater mechanism 20 is installed on the outer peripheral surface (upper surface) of the container cover 11. The lamp heater mechanism 20 is connected to the control unit 21 and generates heat when supplied with power from the control unit 21. By adjusting the amount of power supplied by the controller 21, the amount of heat generated by the lamp heater mechanism 20 is controlled, and the wafer W and the ambient atmosphere of the wafer W are heated to a predetermined temperature.

  In the processing container 2, exhaust boxes 22, 22 are provided for taking in the atmosphere of the ozone processing chamber 15 and exhausting it outside. An exhaust pipe 23 leading to the factory exhaust system is connected to the exhaust boxes 22 and 22.

  As shown in FIG. 2, the wafer guide 3 includes a guide portion 25 and four parallel holding members 26a, 26b, 26c, and 26d fixed to the guide portion 25 in a horizontal posture. In each of the holding members 26a to 26d, 50 grooves 27 for holding the lower peripheral edge of the wafer W are formed at equal intervals. Accordingly, the wafer guide 3 is configured to hold 50 wafers W arranged at equal intervals.

  The water vapor supply means 5 is provided at the bottom of the container body 10. The steam supply means 5 includes a hot plate 30 fixed to the inner wall at the bottom of the container body 10, a heater 31 attached to the lower surface of the hot plate 30, and pure water supply for dropping pure water on the upper surface of the hot plate 30. Circuit 32. The heater 31 is connected to the control unit 21. The amount of heat generated by the heater 31 is controlled by power supply from the control unit 21. The inlet side of the pure water supply circuit 32 is connected to a pure water supply source 33. The outlet side of the pure water supply circuit 32 opens above the hot plate 30. The pure water supply circuit 32 is provided with an on-off valve 35 and a flow rate controller 36. The on-off valve 35 and the flow rate controller 36 are connected to the control unit 21. In accordance with an operation signal from the control unit 21, the opening / closing of the on-off valve 35 is controlled to determine whether or not pure water is allowed to flow. The configuration is adjusted. Accordingly, when pure water is dropped from the pure water supply circuit 32 onto the hot plate 30 heated by the heater 31 that has generated heat, the pure water is vaporized and the water vapor 4 is generated. Can be supplied. The pure water that could not be vaporized is drained through a drain pipe 37 connected to the inner wall at the bottom of the container body 10.

  The ozone gas supply means 7 includes an ozone gas supply source 40 that generates and supplies ozone gas 6, an ozone gas supply circuit 41 that supplies ozone gas 6 from the ozone gas generation source 40, and ozone gas 6 from the ozone gas supply circuit 41 in the processing container 2. And an ozone gas nozzle 42 to be discharged. The ozone gas supply circuit 41 is provided with an opening / closing valve 43, a flow rate controller 44, and a UV lamp 45. The on-off valve 43 and the flow rate controller 44 are connected to the control unit 21. According to an operation signal from the control unit 21, the opening / closing of the on-off valve 43 is controlled to determine whether or not to flow the ozone gas 6, and the flow rate controller 44 is controlled to adjust the flow rate of the ozone gas 6 in the ozone gas supply circuit 41. It has become. The UV lamp 45 irradiates the ozone gas 6 passing through the ozone gas supply circuit 41 with ultraviolet rays and activates ozone.

N ₂ gas supply unit 9, _{N 2} gas, and _{N 2} gas supply circuit 50 for supplying the hot _{N 2} gas, _{N 2} gas supplied from _{N 2} gas supply circuit 50, N for discharging hot _{N 2} gas 8 ₂ gas nozzles 51 and 51 are provided. The inlet side of the N ₂ gas supply circuit 50 is connected to an N ₂ gas supply source (not shown). The N ₂ gas supply circuit 50 is provided with an on-off valve 52 and a heater 53 for heating the N ₂ gas. The on-off valve 52 and the heater 53 are connected to the control unit 21. Accordingly, the opening the closing valve 52 by the control unit 21, if operating the heater 53 to heat the supplied example room temperature N ₂ gas from the N ₂ gas supply source, the hot N ₂ from each N ₂ gas nozzle 51 The gas 8 can be discharged. At this time, if the wafer hand 3 is blown directly, the wafer hand 3 can be quickly dried.

In the processing apparatus 1, a water molecule layer (H ₂ O molecular layer) is formed as a solvent molecule layer. In this case, the control unit 21 supplies power to the heater 31 to adjust the heat generation amount of the heater 31 to such an extent that the water vapor 4 can be generated sufficiently, while also supplying power to the lamp heater mechanism 20 to transfer the wafer W to the dew point of the water vapor 4. The temperature is adjusted to be higher than the temperature, and a temperature difference between the wafer W and the dew point temperature of the water vapor 4 is appropriately controlled to form a high-density water molecule layer on the surface of the wafer W. Further, ozone molecules are mixed with the water molecule layer formed on the surface of the wafer W to form a mixed layer in which high-density water molecules and ozone molecules are mixed, thereby performing treatment using ozone. In this case, the control unit 21 controls the flow rate controller 36 to adjust the generation amount of the water vapor 4 to adjust the degree of formation of the water molecule layer, while transmitting an operation signal to the flow rate controller 44 to The flow rate of the ozone gas 6 is adjusted so as to match the degree of formation of the molecular layer, so that ozone molecules can be appropriately mixed with the water molecule layer without excess or deficiency.

In addition, a pure water discharge nozzle 55 that discharges pure water onto the wafer W to perform rinse cleaning is provided. Further, if hot N ₂ gas 8 is discharged from the N ₂ gas nozzles 51, 51 to the wafer W, the wafer W can be dried.

  Next, processing performed in the processing apparatus 1 configured as described above will be described. In the processing apparatus 1, the water vapor 4 is supplied to the wafer W, the ozone gas 6 is supplied to the wafer W, and the wafer W is processed by the hydroxyl radical generated by the reaction between the water vapor 4 and the ozone gas 6. That is, first, a resist film 60 is formed on the surface of the wafer W as shown in FIG. As shown in FIG. 1, 50 such wafers W are stored in the processing container 2. Note that the thickness of the resist film 60 is, for example, 1200 nm.

Next, the heater 31 generates heat, for example, at 120 ° C., and pure water is dropped from the pure water supply circuit 32 onto the hot plate 30 to generate 120 ° C. water vapor 4 and supply it into the processing vessel 2. On the other hand, ozone gas 6 having, for example, about 192 g / m ³ (normal) [9 vol% (volume percentage)] of ozone is supplied from the ozone gas supply circuit 41 and discharged into the processing container 2 by the ozone gas nozzle 42. Thus, the water vapor 4 and the ozone gas 6 are supplied by separate means.

In addition, the lamp heater mechanism 20 is heated to adjust the temperature of the wafer W to a predetermined temperature. This predetermined temperature is set to a temperature higher than the dew point temperature of the water vapor 4 and lower than the temperature of the water vapor 4 within a temperature range in which the treatment using ozone is optimally performed. Here, since the temperature of the wafer W is adjusted to a temperature higher than the dew point temperature of the water vapor 4, when the water vapor 4 is supplied, the water vapor 4 is not condensed as shown in FIG. A layer of high-density water molecules (H ₂ O molecule) 61 can be easily formed on the surface of the wafer W without forming a liquid film of pure water.

Ozone molecules (O ₃ molecule) 62 are mixed with the layer of water molecules 61, and a mixed layer in which water molecules 61 and ozone molecules 62 are mixed is formed on the surface of the wafer W. In this mixed layer, water molecules 61 and ozone molecules 62 react with each other, and a large amount of reactive substances such as oxygen atom radicals (O. Oxygen radical) and hydroxyl radicals (OH. Hydroxy radical) are generated on the surface of the wafer W. . The hydroxyl radical generated on the surface of the wafer W does not disappear but immediately causes an oxidation reaction, decomposes the resist into carboxylic acid, carbon dioxide, water, etc., and sufficiently oxidizes the resist film 60 as shown in FIG. Decomposition and change into a water-soluble film 60a. The water-soluble film 60a can be easily removed by subsequent rinsing with pure water.

  As described above, according to such a processing method, a layer of high-density water molecules 61 is formed on the surface of the wafer W, while ozone molecules 62 are mixed with the layer of high-density water molecules 61. For this reason, the layer of the water molecules 61 can be transformed into a mixed layer in which the water molecules 61 and the ozone molecules 62 are mixed, from which the resist film 60 can be removed. This mixed layer is generated on the wafer W and immediately before the reaction, does not cause a decrease in ozone concentration over time, has a hydroxyl radical, and extinguishes the hydroxyl radical immediately after it is generated in the processing container 2. Since it can be used almost for processing, it has a high processing capacity. Therefore, the process using ozone can be effectively performed on the wafer W. For example, a removal rate (Removal Rate) that is 1.5 times or more that of the prior art can be obtained.

  In addition, since the water vapor 4 is supplied to the wafer W adjusted to a temperature higher than the dew point temperature of the water vapor 4 and lower than the temperature of the water vapor 4, the water vapor 4 is condensed on the surface of the wafer W to form a liquid film of pure water. Will not form. The hydroxyl radical generated in the mixed layer in which water molecules 61 and ozone molecules 62 are mixed is more likely to be the resist film 60 on the surface of the wafer W than the hydroxyl radical generated by dissolving the ozone gas 6 in the pure water liquid film. Can react immediately.

  In addition, a layer of high-density water molecules 61 can be easily formed. The ozone molecules 62 are appropriately mixed in the layer of the high-density water molecules 61 to actively react, and a large amount of hydroxyl radicals are generated in the mixed layer in which the high-density water molecules 61 and the ozone molecules 62 are mixed. be able to. Furthermore, in the pure water liquid film, the solubility decreases as the liquid temperature increases, and the ozone gas 6 becomes difficult to dissolve, whereas in the water molecule 61 layer, the wafer temperature and the ambient temperature of the wafer W are high. Even so, the mixing amount of the ozone molecules 62 does not decrease so much. For this reason, it is possible to perform treatment using ozone in a high temperature atmosphere as compared with the case of performing treatment using ozone by dissolving the ozone gas 6 in a liquid film of pure water. The higher the temperature, the more active the generation of hydroxyl radicals and the reaction by hydroxyl radicals. Therefore, a high reaction rate can be obtained, and treatment using ozone can be performed quickly.

  Further, new ozone gas 6 is supplied from the ozone gas supply circuit 41, and the molecular layer is continuously mixed. For this reason, ozone and hydroxyl radicals that have disappeared due to the reaction can be supplemented, and new ozone and hydroxyl radicals can be quickly and sufficiently supplied to the resist film 60 through the molecular layer. Therefore, a high reaction rate can be maintained. It should be noted that the water molecule layer, the mixed layer, and the like should have a density that does not form water droplets. Further, since the wafer W is adjusted to a temperature higher than the dew point temperature of the water vapor 4 within a range in which the oxidation reaction can be actively performed, it is possible to promote the treatment using ozone.

Thereafter, pure water was from the discharge nozzle 55 discharges the pure water washing away resist that water-soluble from the wafer W (rinse), the wafer W from the N ₂ gas nozzle 51 to eject N ₂ gas (inert gas) After removing the droplets (drying), the wafer W is unloaded from the processing apparatus 1. Rinse cleaning and drying may not be performed by the processing apparatus 1, but may be performed by removing the resist film 60 and then carrying it out from the processing apparatus 1 and carrying it into a rinsing dedicated processing apparatus or drying apparatus. On the other hand, the next new 50 wafers W are loaded into the processing apparatus 1 and subsequently processed using ozone.

Here, during processing, when the water vapor 4 is condensed on the wafer guide 3 and water droplets adhere thereto, or the wafer W after processing using ozone is moved to, for example, a processing apparatus dedicated to the next rinse by the wafer guide 3. In some cases, water droplets may adhere to the wafer hand 3. When the wafer W that has not been processed is held on the wafer guide 3, water droplets also adhere to the surface of the wafer W. As described above, hydroxyl radicals generated by the reaction are formed on the surface of the wafer W by forming a mixed layer in which water molecules 61 and ozone molecules 62 are mixed rather than dissolving ozone gas 6 in a pure water liquid film. Can react with the resist film 60 immediately. Therefore, the hot N ₂ gas 8 is supplied from the N ₂ gas supply means 9 to the wafer hand 3 until the next new 50 wafers W are loaded, and the wafer hand 3 is dried. As a result, it is possible to prevent the water droplets from being removed from the wafer hand 3 and prevent the ozone gas 6 from being dissolved in the water droplets, and the treatment using ozone can be suitably performed continuously.

  Thus, according to such a processing method, immediately before the processing, a mixed layer in which high-density water molecules 61 and ozone molecules 62 are mixed is generated on the surface of the wafer W, and the hydroxyl radicals generated in the mixed layer are extinguished. In fact, since it can be used for almost all processing, the wafer W can be effectively processed using ozone. In addition, the reaction between water molecules 61 and ozone molecules 62 can be actively performed in a high-temperature atmosphere to promote the generation of hydroxyl radicals and the reaction due to hydroxyl radicals, thereby performing treatment using ozone. As a result, the resist film 60 can be sufficiently removed. Moreover, the processing apparatus 1 can implement suitably the above processing method.

  During the treatment using ozone in the embodiment of the present invention, various reactions are performed in addition to mixing the ozone molecules 62 with the water molecule 61 layer. For example, the steam 4 and the ozone gas 6 are collided and mixed in the processing container 2 to generate a mixed gas. In this mixed gas, a large amount of hydroxyl radicals liberated by thermal decomposition or collision are generated. When the mixed gas comes into contact with the wafer W, the hydroxyl radical undergoes an oxidation reaction, and the resist is converted into carboxylic acid, carbon dioxide, water, or the like, similar to the mixed layer in which the water molecules 61 and the ozone molecules 62 are mixed. Decompose. In this way, a large amount of hydroxyl radicals are generated in the mixed gas immediately before contact with the wafer W, and directly reacted with the resist film 60 without erasing the hydroxyl radicals, so that high processing capability can be obtained.

  Next, the processing apparatus 70 according to the embodiment of the present invention will be described with reference to FIG. In the processing apparatus 1, the exhaust pipe 23 is exhausted as it is, but the processing apparatus 70 shown in FIG. 5 has a configuration in which a flow controller 71 is provided in the exhaust pipe 23 to freely adjust the pressure in the processing container 2. It has become. The flow controller 71 is connected to the control unit 21. A pressure sensor 72 is attached to the processing container 2. The pressure in the processing container 2 detected by the pressure sensor 72 is input to the control unit 21. The control unit 21 controls the flow rate controller 71 based on the pressure detected by the pressure sensor 72 to restrict the exhaust amount of the exhaust pipe 23. On the other hand, the ozone gas supply source 40 sets the supply pressure of the ozone gas 6 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 FIG. 1 and FIG. 5, constituent elements having substantially the same function and configuration are denoted by the same reference numerals, and redundant description is omitted.

  Further, the processing apparatus 70 is configured to generate water vapor 4 outside the processing container 2 and introduce the water vapor 4 into the processing container 2. That is, the water vapor supply means 75 includes a water vapor supply source 76 that generates and supplies water vapor 4, a water vapor supply circuit 77 that supplies the water vapor 4 from the water vapor supply source 76, and the water vapor 4 from the water vapor supply circuit 77. 2 is provided with a water vapor nozzle 78 for discharging into the gas tank 2. The water vapor supply source 76 includes a hot plate, a heater, and the like. The water vapor supply circuit 77 is provided with an on-off valve 79 and a flow rate controller 80. The on-off valve 79 and the flow rate controller 80 are connected to the control unit 21, and the supply amount of the water vapor 4 can be controlled by the control unit 21. In such a configuration, it is not necessary to provide the water vapor supply means in the processing container 2, and accordingly, the processing apparatus can be reduced in size.

  In addition, the bottom opening of the processing container 2 is closed by the container bottom 81. A gap between the processing container 2 and the container bottom 81 is sealed with a gasket 82. A drainage pipe 83 is connected to the container bottom 81, and an opening / closing valve 84 is interposed in the drainage pipe 83.

Next, a processing method performed by the processing device 70 configured as described above will be described. First, a normal temperature (23 ° C.) wafer W is stored in the processing container 2. Next, the lamp heater mechanism 20 generates heat to, for example, 115 ° C. to adjust the wafer W to a predetermined temperature. On the other hand, the ozone gas supply means 7 supplies the ozone gas 6 into the processing container 2 at a supply pressure of 196 kPa. At this time, hot N ₂ gas 8 of, eg, 150 ° C. is supplied to the wafer W by the N ₂ gas supply means 9. Then, the wafer W can be immediately heated to a predetermined temperature.

After adjusting the wafer W to a predetermined temperature, the supply of the hot N ₂ gas 8 is stopped, and the water vapor 4 is supplied into the processing container 2 by the water vapor supply means 75. On the other hand, the control unit 21 restricts the flow rate controller 71 of the exhaust pipe 23 to lower the exhaust amount, and the inside of the processing container 2 is made a pressurized atmosphere of 196 kPa. In such a processing container 2, the concentration of the ozone gas 6 is increased.

  Here, on the surface of the wafer W, as shown in FIG. 4, a layer of high-density water molecules 61 is formed. However, the ozone gas 6 is supplied and filled in the processing container 2 in advance. Therefore, ozone molecules 62 are immediately mixed with the water molecule 61 layer to form a mixed layer, and a large amount of hydroxyl radicals can be generated in the mixed layer. In this way, treatment using ozone can be rapidly performed by the hydroxyl radicals in the mixed layer.

  Further, if the water vapor 4 is supplied while the wafer W is in a normal temperature state, the temperature difference between the dew point temperature of the water vapor 4 and the wafer temperature is widened, so the water vapor 4 is condensed and a large amount of water droplets adhere to the surface of the wafer W. Resulting in. As a result, a pure water liquid film having a large film thickness is formed on the wafer W, resulting in a decrease in processing capability. However, since the water vapor 4 is supplied to the wafer W after the temperature of the wafer W is raised to a predetermined temperature as described above, a high-density layer of water molecules 61 can be reliably formed, resulting in a decrease in processing capability. Can be prevented. Moreover, since the atmosphere around the wafer W is pressurized to 196 kPa, the amount of hydroxyl radicals generated can be increased by increasing the amount of ozone molecules 62 mixed with the water molecule 61 layer. Furthermore, it becomes possible to perform the uta treatment using ozone in a higher temperature atmosphere. Therefore, the processing capacity can be further improved.

After the resist film 60 is transformed into a water-soluble film 60a, the wafer W is unloaded from the processing container 2, and then sequentially transported to a rinsing-only processing apparatus and a drying apparatus for rinsing and drying. On the other hand, in the processing container 2, the supply of the water vapor 4 and the ozone gas 6 is stopped. The droplets of the processing chamber 2 was drained by drain pipe 83, the cause the flow controller 71 is fully opened, performs N ₂ purged by N ₂ gas supply unit 9, the water vapor 4 and ozone gas 6 from the processing chamber 2 Drive out and dry the internal atmosphere. Further, as described above, the wafer guide 3 is also dried to remove the droplets. Then, the next normal temperature wafer W is stored in the processing container 2. Here, if the wafer W at room temperature is stored in the processing container 2 with the water vapor 4 remaining, a large amount of water droplets are formed on the surface of the wafer W in the same manner as when water droplets are attached to the wafer guide 3. It will stick to. However, since the processing container 2 and the water vapor supply source 76 are provided separately and the atmosphere in the processing container 2 can be easily replaced, even if a new wafer W is carried into the processing container 2, this wafer Water droplets can be prevented from adhering to the surface of W, and the surface of the wafer W can be kept dry until the water vapor 4 is introduced into the processing container 2.

According to such a processing method, the hot N ₂ gas 8 is used to shorten the heating time of the wafer W, and the ozone gas 6 is supplied before the water vapor 4 is supplied to generate the hydroxyl groups in the mixed layer and the mixed layer. Since the time is also shortened, treatment using ozone can be performed quickly and throughput can be improved. Further, the ambient atmosphere of the wafer W is pressurized to improve the mixing amount of the ozone molecules 62 with respect to the water molecule 61 layer and to enable processing in a higher temperature atmosphere, so the removal efficiency of the resist film 60 is increased. , More effective treatment using ozone can be performed.

  According to such a processing apparatus 70, since the water vapor 4 is supplied into the processing container 2 through the water vapor supply circuit 77, the amount of water in the processing container 2 can be easily adjusted, and the internal atmosphere can be dried. Further, the thermal influence of the heater provided in the water vapor supply source 76 does not reach the wafer W in the processing container 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 becomes too high and the water molecules 61 are hardly adsorbed on the surface of the wafer W, so that the water molecule layer is not formed and treatment using ozone cannot be performed. . Similarly to the processing apparatus 1, the wafer guide 3 can be dried to remove water droplets, and the ozone gas 6 can be prevented from being dissolved in the water droplets. Note that the flow controller 71 may be provided not only in the processing apparatus 70 but also in the drain pipe 23 of the processing apparatus 1 to pressurize the ambient atmosphere of the wafer W in the processing container 2.

  Next, the processing device 90 will be described with reference to FIG. A processing apparatus 70 shown in FIG. 6 includes the processing container 2, a cleaning tank 91, and a passage portion 92 provided between the processing container 2 and the cleaning tank 91, and uses ozone processing and rinsing processing. It is comprised so that it can perform.

In the ozone processing chamber 15 (first processing chamber) formed in the processing container 2, the ozone gas 6 is supplied by the ozone gas supply means 7, the water vapor 4 is supplied by the water vapor supply means 75, and the N ₂ gas supply means 9. The N ₂ gas and the hot N ₂ gas 8 are supplied. The bottom opening of the processing container 2 is not closed and communicates with an opening / closing position 121 formed in the passage 92.

  The cleaning tank 91 surrounds an inner tank 94 that forms a rinse treatment chamber (second processing chamber) 93, a middle tank 95 that surrounds the opening of the inner tank 94, and an opening of the middle tank 95. And an attached outer tub 96.

  The rinse treatment chamber 93 is supplied with pure water (DIW) as a treatment liquid by a pure water supply means 96 as a treatment liquid supply means. The pure water supply means 96 includes a pure water supply circuit 100 that supplies pure water, and pure water nozzles 111 and 111 that discharge the pure water supplied from the pure water supply circuit 100 into the rinse treatment chamber 93. . The inlet side of the pure water supply circuit 100 is connected to a pure water supply source (not shown). The pure water supply circuit 100 is provided with an on-off valve 112 and a flow rate controller 113. The on-off valve 112 and the flow rate controller 113 are controlled by the control unit 21.

  In the inner tank 94, the upper surface opening portion communicates with an opening / closing position 121 formed in the passage portion 92. A drainage pipe 115 for draining pure water in the rinse treatment chamber 93 is connected to the center of the bottom of the inner tank 94. An open / close valve 116 is interposed in the drainage pipe 115. The middle tank 95 is configured to receive pure water that has overflowed from the upper end of the inner tank 94 and to flow it to an overflow pipe 117 connected to the bottom. An opening / closing valve 118 is interposed in the overflow pipe 117. In the outer tub 96, pure water is always stored and an annular seal plate 119 is provided. The upper end of the seal plate 119 is in close contact with the bottom surface of the passage portion 92. For this reason, the outer tub 96 has a water sealing function using pure water so that the liquid atmosphere in the cleaning tub 91 is not leaked to the outside.

  The passage portion 92 is provided with a shutter 120 that opens and closes between the ozone treatment chamber 15 and the rinse treatment chamber 93. The shutter 120 is configured to be movable in a vertical direction (Z direction in FIG. 6) and a horizontal direction (X direction in FIG. 6) by a drive mechanism (not shown). Further, the passage portion 92 is roughly divided into the above-described opening / closing position 121 and a standby position 122 for waiting the shutter 120. Accordingly, if the shutter 120 is moved to the open / close position 121 by the drive mechanism, the indoor atmosphere of the ozone treatment chamber 15 and the indoor atmosphere of the rinse treatment chamber 93 can be blocked, while the shutter 120 is moved to the standby position 122. The indoor atmosphere of the ozone treatment chamber 15 and the indoor atmosphere of the rinse treatment chamber 93 can be communicated with each other.

An N ₂ nozzle 123 for discharging N ₂ gas is embedded in the bottom wall portion 92a on one side (right side in FIG. 6) of the passage portion 92, and an N ₂ nozzle 123 is embedded in the bottom wall portion 92a on the other side. . If these N ₂ nozzles 123 discharge N ₂ gas, an air curtain is formed above the rinse treatment chamber 93. The shutter 120 and the air curtain can prevent the atmosphere in the ozone treatment chamber 15 from diffusing into the rinse treatment chamber 93 and the liquid atmosphere in the rinse treatment chamber 93 from flowing into the ozone treatment chamber 15.

  A drainage unit 125 is provided at the bottom of the passage unit 92 on the standby position 122 side. A drainage pipe 126 is connected to the drainage part 125. On-off valve 127 is interposed in drainage pipe 126. Further, when the shutter 120 is closed, even if the liquid atmosphere in the cleaning tank 91 is condensed on the bottom surface of the shutter 120 and the liquid droplets adhere to the bottom surface of the shutter 120, the liquid droplets are discharged from the passage 92. The liquid is discharged to the outside through a passage (not shown). Further, even when the shutter 120 is opened with the liquid droplets attached, the liquid droplets dropped by their own weight from the bottom surface of the shutter 120 during the standby are discharged through the liquid discharge part 125 and the liquid discharge pipe 126.

  The wafer guide 128 is configured to be movable up and down by an elevating mechanism (not shown). For this reason, the wafer W can be moved between the ozone processing chamber 15 and the rinsing processing chamber 93 arranged above and below. The wafer W indicated by the solid line in FIG. 6 shows the storage state in the ozone processing chamber 15 by the raised wafer guide 128, and the wafer W indicated by the two-dot chain line W ′ in FIG. The storage state in the rinse treatment chamber 93 is shown. The processing apparatus 90 is configured to switch the processing chamber for storing the wafer W between the ozone processing chamber 15 and the rinsing processing chamber 93 by moving the wafer guide 128 up and down. The processing device 90 is configured to consistently perform processing using ozone and rinsing processing in a sealed interior.

  A box 130 for storing the processing container 2 and the cleaning tank 91 is provided. In the box 130, the drainage pipes 115, 117, 126 and the drainage passage are introduced, and the outlet sides thereof are opened. A drain circuit 131 is connected to the bottom of the box 130, and the drain circuit 131 communicates with a factory drain system. An open / close valve 132 is interposed in the drain circuit 131. If the on-off valve 132 is opened, the pure water flowing in the drainage pipes 115, 117, 126 is drained to the factory drainage system via the box 130 and the drainage circuit 131. An exhaust circuit 133 for exhausting is connected to the box 130. For this reason, the box 130 can exhaust the atmosphere around the processing container 2 and the cleaning tank 91. For example, when the container cover 11 is opened and the wafer W is loaded and unloaded, the indoor atmosphere of the ozone processing chamber 15 and It is possible to prevent the liquid atmosphere in the rinse treatment chamber 93 from diffusing outside.

Next, a processing method performed by the processing device 90 configured as described above will be described with reference to a flowchart shown in FIG. The container cover 11 is opened, and for example, 50 wafers W on which the resist film 60 is formed are stored in the processing container 2 and carried into the apparatus (S1). Thereafter, the container cover 11 is closed (S2). Further, the shutter 120 is closed and N ₂ gas is discharged from the N ₂ nozzle 123 to form an air curtain, thereby blocking the indoor atmosphere in the ozone treatment chamber 15 and the indoor atmosphere in the rinse treatment chamber 93.

  Next, processing using ozone is performed in the ozone processing chamber 15 (S3). That is, the wafer W is heated to a predetermined temperature by the lamp heater mechanism 20 or the like. Water vapor 4 is supplied into the ozone treatment chamber 15 by the water vapor supply means 75, and a layer of water molecules 61 is formed on the surface of the wafer W. Further, ozone gas 6 is supplied by the ozone gas supply means 7, and ozone molecules 62 are mixed in the water molecule 61 layer. Similar to the processing apparatuses 1 and 70, a large amount of hydroxyl radicals are generated, and the resist film 60 is sufficiently oxidized and decomposed to be water-soluble.

  The supply of the water vapor 4 and the ozone gas 6 is stopped, and the treatment using ozone is finished. Thereafter, rinsing (rinsing) is performed in the rinsing chamber 93 (S4). That is, pure water is supplied into the rinsing chamber 93 in advance by the pure water nozzles 111, 111 of the pure water supply means 96. When filled with pure water, the shutter 120 is opened. Here, the wafer W is quickly stored in the rinse processing chamber 93 in a state where the wafer guide 128 is lowered and confined in the processing apparatus 90. For this reason, the wafer W can be immersed in pure water in a short time and can be shifted to the rinsing process without having an opportunity to come into contact with the outside air. Here, as described above, since the resist film 60 is altered to the water-soluble film 60 a, the resist can be easily removed from the wafer W in the rinse treatment chamber 93.

After the rinsing process, the wafer guide 128 is raised and the wafer W is moved into the ozone processing chamber 15. Then, the container cover 11 is opened (S5), and the wafer W is taken out from the processing container 2 and unloaded from the processing apparatus 90 (S6). When the container cover 11 is opened, the ambient atmosphere of the processing container 2 and the cleaning tank 91 is exhausted by the box 130 to prevent the indoor atmosphere of the ozone processing chamber 15 and the rinsing processing chamber 93 from diffusing to the surroundings. . Further, in preparation for 50 wafers W to be processed next, N ₂ gas supply means 9 supplies normal temperature N ₂ gas into the ozone processing chamber 15 to perform N ₂ purge, and the atmosphere in the ozone processing chamber 15 is changed. Replacement or hot N ₂ gas is supplied to the wafer guide 128 to remove the droplets.

The wafer W unloaded from the processing apparatus 90 is transferred to another processing apparatus. In this other processing apparatus, for example, a chemical solution process, a final rinse process, and a dry process are performed in a processing container, and a rinse process is performed in a cleaning tank. Examples of the chemical treatment include SC1 treatment (ammonia treatment) for removing particles and organic impurities from the surface of the wafer W by supplying ammonia (NH ₄ OH) vapor and water vapor, for example. In this manner, in another processing apparatus, after SC1 processing in the processing container, rinsing processing is performed in the cleaning tank, and finally, final rinsing processing and drying processing are performed in the processing container. Of course, it is also possible to separately provide chemical processing, rinsing processing, final rinsing processing, and drying processing, and sequentially transfer the wafers W to these devices.

  According to this processing apparatus 90, the process using ozone and the rinsing process can be performed consistently, and the apparatus can be miniaturized. Further, since the wafer W is not unloaded from the apparatus until the rinse process is finished after the process using ozone is started, the wafer W is prevented from coming into contact with the outside air after the process using ozone. be able to. For this reason, a natural oxide film is formed on the surface of the wafer W, or the film 60a that has become water-soluble by treatment using ozone can be prevented from being hardened and denatured insoluble due to contact with the outside air. . Various reactants generated on the surface of the wafer W by the treatment using ozone can be prevented from changing into different forms due to contact with the outside air. For example, it is possible to prevent a change to contamination or the like. For this reason, the rinsing process can be suitably performed. Furthermore, the wafer W can be moved up and down quickly, and the rinsing process can be performed immediately after the process using ozone, thereby improving the throughput. Further, similarly to the processing apparatuses 1 and 70, the wafer guide 128 can be dried to remove water droplets.

  In the processing apparatus 90, the case where the ozone processing chamber 15 and the rinsing processing chamber 93 are vertically arranged has been described. However, the ozone processing chamber 15 and the rinsing processing chamber 93 may be arranged side by side. Even with this arrangement, treatment using ozone and rinsing treatment can be performed consistently, and contact with outside air can be prevented and throughput can be improved.

  Next, the processing device 140 will be described with reference to FIG. In the processing apparatus 140 shown in FIG. 8, the flow rate controller 71 is provided in the exhaust pipe 23 and the pressure sensor 72 is attached to the processing container 2, similarly to the processing apparatus 70 according to the embodiment of the present invention. The control unit 21 controls the flow rate controller 71 based on the pressure detected by the pressure sensor 72 to restrict the exhaust amount of the exhaust pipe 23.

  According to the processing apparatus 140, since the inside of the ozone processing chamber 15 can be in a pressurized atmosphere, the amount of ozone molecules 62 mixed with the water molecule 61 layer can be increased and more similar to the processing apparatus 70. Since processing in a high temperature atmosphere is possible, the processing capacity can be further improved. Further, similarly to the processing apparatuses 1, 70, 90, the wafer guide 128 can be dried to remove water droplets.

  Although an example of the embodiment of the present invention has been described, the present invention is not limited to this example and can take various forms. For example, the catalyst gas may be supplied in a very small amount into the processing container 2 to promote the generation of hydroxyl radicals so that the oxidation reaction can be performed more actively. In this case, NOx gas etc. are mentioned as catalyst gas.

  Further, although the case where the resist film 60 is removed using the ozone gas 6 has been described, other films may be removed using the ozone gas 6. For example, an organic film (BARC: bottom anti-reflective coating) that is applied under the resist film 60 to increase the resolution can be removed. Furthermore, various deposits adhered on the wafer may be removed using a processing gas other than the ozone gas 6.

For example, chlorine (Cl ₂ ) gas is supplied, the water molecule 61 layer is transformed into a hydrochloric acid (HCl) molecule layer (mixed layer in which water molecules and chlorine molecules are mixed) to generate chlorine atom radicals, It is possible to remove metal deposits and particles from the surface of the wafer W. It is also possible to remove hydrogen deposits and particles from the surface of the wafer W by supplying hydrogen (H ₂ ) gas and generating hydrogen atom radicals in the water molecule 61 layer. Also, fluorine (F ₂ ) gas is supplied, and the water molecule 61 layer is transformed into, for example, a hydrofluoric acid (HF) molecule layer (a mixed layer in which water molecules and fluorine molecules are mixed) to generate fluorine atom radicals. Thus, the natural oxide film and particles can be removed from the surface of the wafer W.

  Furthermore, an excitation reaction may be caused in advance in the processing gas to have radicals. That is, ozone gas having oxygen atom radicals, chlorine gas having chlorine atom radicals, hydrogen gas having hydrogen atom radicals, fluorine gas having fluorine atom radicals are supplied to generate a larger amount of radicals to promote the treatment. You can also.

  The present invention can be applied not only to batch processing for processing a plurality of substrates in a batch, but also to single wafer processing for processing substrates one by one. Further, the substrate is not limited to the wafer W, but may be an LCD substrate, a CD substrate, a printed substrate, a ceramic substrate, or the like.

Next, an example of the present invention was performed. First, the treatment target was an organic film (BARC), and the relationship between the ozone concentration in ozone gas and the removal rate was examined. The result is shown in FIG. In FIG. 9, the horizontal axis is the ozone concentration [g / m ³ (normal)], and the vertical axis is the removal rate [nm / s]. As can be understood from FIG. 9, the removal rate increases as the ozone concentration increases.

Next, the removal rate when processing using ozone is performed in a state in which the ambient atmosphere of the wafer is pressurized and the case where chemical processing is performed using conventional SPM (mixed solution of H ₂ SO ₄ / H ₂ O ₂ ). The removal rates are compared, and the results are shown in FIG. Resist films and organic films were used for the treatment. In this case, the atmosphere around the wafer is pressurized to 196 kPa, the wafer is heated to 110 ° C., and water vapor heated to 120 ° C. is supplied to the wafer. The bar graphs g and i show the removal rate when processing using ozone is performed in a state where the ambient atmosphere of the wafer is pressurized, and the bar graphs h and j show the removal rate when chemical processing by SPM is performed. ing. When the resist film is processed using ozone in a state where the ambient atmosphere of the wafer is pressurized, the removal rate of 20 [nm / s] can be obtained as shown by the bar graph g in FIG. When the chemical solution treatment is performed, the removal rate can be about 9.5 [nm / s] as shown by the bar graph h in FIG. Further, when the organic film is processed using ozone in a state where the ambient atmosphere of the wafer is pressurized, the removal rate is about 0.2 [nm / s] as shown by the bar graph i in FIG. When the chemical solution treatment by SPM is performed, the removal rate can be about 0.05 [nm / s] as shown by the bar graph j in FIG. Thus, it can be confirmed from FIG. 10 that a higher removal rate is obtained by performing treatment using ozone in a state where the ambient atmosphere of the wafer is pressurized.

It is sectional explanatory drawing of a processing apparatus. It is a perspective view of a wafer guide. It is a 1st process explanatory view for explaining processing performed with a processing device of Drawing 1. FIG. 6 is a second process explanatory diagram for explaining a process performed by the processing apparatus of FIG. 1. It is a section explanatory view of a processing device concerning an embodiment of the invention. It is sectional explanatory drawing of a processing apparatus. It is a flowchart for demonstrating the process performed with the processing apparatus of FIG. It is sectional explanatory drawing of a processing apparatus. In the Example of this invention, it is a graph which shows the relationship between ozone concentration and removal rate. In the Example of this invention, it is a graph which compares and shows the removal rate at the time of performing the process using ozone in the state which pressurized the ambient atmosphere of the wafer, and the removal rate at the time of performing the chemical | medical solution process by SPM.

Explanation of symbols

1 processor 2 treatment container 3 wafer guide 4 steam 5 steam supply means 6 ozone gas 7 ozone gas supply means 8 hot _{N 2} gas 9 N ₂ gas supply unit W wafer

Claims (3)

A processing container for storing the substrate and processing the substrate therein;
A heater for heating the substrate stored in the processing container;
Water vapor supply means for supplying water vapor into the processing vessel;
Ozone gas supply means for supplying ozone gas into the processing vessel;
And N ₂ gas supply means for supplying a N ₂ gas into the processing chamber,
An exhaust pipe for exhausting the inside of the processing vessel, a flow rate controller provided in the exhaust pipe,
And a control unit that controls the flow rate controller so as to pressurize the inside of the processing container.   The heater is controlled by the control unit so as to adjust a substrate stored in the processing container to a temperature higher than a dew point temperature of water vapor and lower than a temperature of water vapor. Item 2. The substrate processing apparatus according to Item 1. A pressure sensor for detecting the pressure in the processing vessel;
The substrate processing apparatus according to claim 1, wherein the flow controller is controlled by the control unit based on detection of the pressure sensor.

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