JP4536711B2 - Substrate processing equipment - Google Patents

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 development 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, it is desired to remove the resist using ozone water that can be easily treated with a waste liquid without using a chemical solution. 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, normally, 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 this time, ozone in the liquid disappears. In some cases, the ozone 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 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, ozone may be bubbled into pure water at 80 ° C., for example. However, since pure water at high temperature has low gas solubility, high-concentration ozone water could not be generated, and a 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, an ozone processing chamber for storing a substrate and processing the substrate therein, a heater for heating the substrate stored in the ozone processing chamber, and the ozone processing chamber Water vapor supply means for supplying water vapor; ozone gas supply means for supplying ozone gas into the ozone treatment chamber; a rinse treatment chamber for rinsing the substrate after being treated in the ozone treatment chamber; the ozone treatment chamber; a wafer guide for moving substrates between the rinsing chamber, and N ₂ gas supply means for supplying a N ₂ gas into the ozone processing chamber, and an exhaust pipe for exhausting the ozone treatment chamber, provided in the exhaust pipe A flow controller, and a controller for controlling the flow controller so as to pressurize the ozone treatment chamber, and the N ₂ gas supply means supplies N ₂ gas. Then, the ozone processing chamber is pressurized under the control of the flow rate controller by the control unit , water vapor and ozone gas are supplied to the pressurized ozone processing chamber, substrate processing is performed, and processing is performed in the ozone processing chamber. A substrate processing apparatus is provided, wherein the substrate after being moved is moved to the rinse processing chamber by the wafer guide.
In this case, a pressure sensor for detecting the pressure in the ozone processing chamber may be provided, and the flow controller may be controlled by the control unit based on the detection of the pressure sensor.
The heater may be controlled to adjust the substrate stored in the ozone treatment chamber to a temperature higher than the dew point temperature of water vapor and lower than the temperature of water vapor.

In this application, the following inventions are also disclosed.
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. The substrate processing method characterized by having a process is disclosed.
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, a substrate is supplied by a reactant (atom, molecule, radical, etc.) generated by a reaction between the solvent vapor and the processing gas. Process. Since such a reactive substance is generated in the processing chamber and immediately utilized for processing without disappearing, it exhibits high processing capability. Therefore, for example, when a resist film is formed on the surface of the substrate, the resist film can be suitably altered to a water-soluble film by hydroxyl radicals 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 solvent vapor to the substrate, the step of supplying a processing gas to the substrate, the solvent vapor and the processing gas, And a step of processing the substrate with a reactive substance generated by the reaction described above.

  According to this substrate processing method, similarly, the substrate is processed with the reactant generated by the reaction between the solvent vapor and the processing gas. Further, the atmosphere around 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 can be obtained because the generation of the reaction material and the reaction by the reaction material are actively performed.

  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.

  It is preferable to adjust the substrate to a temperature higher than the dew point temperature of the solvent and lower than the temperature of the solvent vapor. Then, 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, a reaction material generated in a mixed layer of solvent molecules and gas molecules reacts more quickly with a processing target on the surface of the substrate than a reaction material generated by dissolving a processing gas in a 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 can 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 when the substrate temperature or the temperature of the ambient atmosphere around the substrate is increased, the amount of gas molecules mixed with the solvent molecule layer does not decrease so much, and 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 that is higher than the dew point temperature of the solvent and lower than the temperature of the vapor of the solvent 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. As a result, the amount of reactants generated is 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 reliably formed, 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-adjusted 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 (eg, N 2 gas), a processing gas, or the like is preferably used for the airflow.

  It is preferable to perform a step of supplying a processing gas to the substrate before the step of supplying a vapor of the solvent 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 and the reactant is mixed. And can be processed quickly.

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

  According to this substrate processing apparatus, the substrate is held by the holding means in the processing container. In such a processing container, the solvent vapor is supplied 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. 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 in the holding unit, or when the substrate after the treatment with the reactant is moved to the next water washing treatment tank by the holding unit, for example, droplets may adhere to the holding unit. . When the substrate is held by such a holding means, droplets of the solvent and the washing liquid will 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. 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 unit configured to move the substrate between the first processing chamber and the second processing chamber; and a drying gas supply unit configured to supply a drying gas to the moving unit 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 a situation in which the droplets adhere to the surface of the substrate from the moving means and the processing gas is 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 processing is immediately utilized for processing without annihilation, so that high processing capability can be obtained and effective processing can be performed on the substrate. it can. Further, as compared with the case where a substrate is processed by dissolving a processing gas in a solvent droplet, 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 gas molecules (ozone molecules) mixed does not decrease so much even if the substrate temperature or the temperature of the ambient atmosphere around the substrate increases. Under a higher temperature atmosphere, generation of a reactive substance (hydroxyl radical) and promotion of the 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 the treatment 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 an explanatory cross-sectional view of a processing apparatus 1 according to the first embodiment of the present invention.

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 unit for holding the wafer W in the processing container 2, and water vapor 4 in the processing container 2. Water vapor supply means 5 as a solvent vapor supply means for supplying gas, ozone gas supply means 7 as a 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 that hold 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 water vapor 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 opening / closing 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 to flow pure water, and the flow rate of the pure water in the pure water supply circuit 32 is controlled by controlling the opening of the flow controller 36. 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 on-off 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 opening / closing valve 43 is controlled to determine whether or not the ozone gas 6 is allowed to flow, 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 to activate ozone.

The N ₂ gas supply means 9 discharges N ₂ gas and hot N ₂ gas 8 supplied from the N ₂ gas supply circuit 50 that supplies N ₂ gas and hot N ₂ gas, and N ₂ gas supply circuit 50. 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 opening / closing 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 Fukikakere directly to the wafer guide 3, it is possible to quickly dry the wafer guide 3.

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 and adjusts the heat generation amount of the heater 31 to such an extent that the water vapor 4 can be sufficiently generated, 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 a 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 by 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 water vapor 4 at 120 ° C. 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.

Further, 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 where 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 (OH · hydroxy radicals) and hydroxyl radicals (OH · hydroxy radicals) 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. This water-soluble film 60a can be easily removed by subsequent rinsing with pure water.

  As described above, according to the processing method, the layer of the high-density water molecules 61 is formed on the surface of the wafer W, while the ozone molecules 62 are mixed with the layer of the high-density water molecules 61. For this reason, the layer of the water molecule 61 can be transformed into a mixed layer in which the water molecule 61 and the ozone molecule 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 being generated in the processing container 2. Since it can be used for almost all processing, the processing capability is high. 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.

  Moreover, 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. Resist film 60 on the surface of wafer W has hydroxyl radicals generated in a mixed layer in which water molecules 61 and ozone molecules 62 are mixed rather than hydroxyl radicals generated by dissolving ozone gas 6 in a pure water liquid film. Can react immediately.

  In addition, a high-density water molecule 61 layer can be easily formed. The ozone molecule 62 is appropriately mixed in the layer of the high-density water molecules 61 to react actively, 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. Further, in the liquid film of pure water, 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 temperature of the wafer and the ambient atmosphere 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 actively 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 compensated, 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, or the like may 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 is discharged from the pure water discharge nozzle 55 to wash away the water-soluble resist from the wafer W (rinse cleaning), and N2 gas (inert gas) is discharged from the N2 gas nozzles 51 and 51 to drop droplets from the wafer W. After being removed (dried), the wafer W is unloaded from the processing apparatus 1. Rinse cleaning and drying may be performed without being performed by the processing apparatus 1, for example, after the resist film 60 is removed and carried out from the processing apparatus 1 and carried into a processing apparatus or drying apparatus dedicated to rinsing. 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 the processing using ozone is moved to, for example, a processing apparatus dedicated to the next rinsing by the wafer guide 3. If, likely that water droplets adhere to the wafer guide 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, the hydroxyl radical generated by the reaction is formed on the surface of the wafer W by forming a mixed layer in which the water molecules 61 and the ozone molecules 62 are mixed rather than dissolving the ozone gas 6 in the liquid film of pure water. Can react with the resist film 60 immediately. Therefore, until the loading of a new 50 wafers W of the next, supplying the hot N2 gas 8 from the N2 gas supply unit 9 to the wafer guide 3 to dry the wafer guide 3. As a result, it is possible to prevent the ozone gas 6 from being dissolved in the water droplets by removing the water droplets from the wafer guide 3, and the treatment using ozone can be suitably performed continuously.

  Thus, according to the processing method according to the first embodiment of the present invention, 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 immediately before the processing. Since the hydroxyl radicals generated in the layer can be used for the treatment almost without annihilation, the wafer W can be effectively treated using ozone. Moreover, the reaction of the water molecule 61 and the ozone molecule 62 can be actively performed in a high temperature atmosphere to promote the generation of hydroxyl radicals and the reaction due to the hydroxyl radicals, thereby performing treatment using ozone. As a result, the resist film 60 can be sufficiently removed. Moreover, the processing apparatus 1 concerning embodiment of this invention can implement suitably the above processing method.

  In addition, during the process using ozone in the embodiment of the present invention, various reactions are performed in addition to mixing the ozone molecules 62 in the water molecule 61 layer. For example, the water vapor 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, a processing apparatus 70 according to the second embodiment 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 downsized accordingly.

  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 150 ° C., for example, 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 reduce 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 in advance into the processing container 2 to be filled. Therefore, the ozone molecule 62 is 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 quickly performed by the hydroxyl radical in the mixed layer.

Further, if the water vapor 4 is supplied while the wafer W is in the normal temperature state, the temperature difference between the dew point temperature of the water vapor 4 and the wafer temperature is widened. Resulting in. As a result, a liquid film of pure water having a large film thickness is formed on the wafer W, leading to a reduction 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 capacity. Can be prevented. In addition, 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, we are possible to perform processing using ozone in the higher temperature atmosphere. Therefore, the processing capability 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 transferred to a processing apparatus and a drying apparatus dedicated to rinsing to perform rinse cleaning 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, it 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 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 adhere to the wafer guide 3. It will stick to. However, since the processing container 2 and the water vapor supply source 76 can be 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 a hydroxyl group 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 that the removal efficiency of the resist film 60 is increased. Thus, it is possible to carry out a more effective treatment using ozone.

  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 where the wafer temperature becomes too high and the water molecules 61 are not easily adsorbed on the surface of the wafer W, the water molecule layer is not formed, and the 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 so as to pressurize the ambient atmosphere of the wafer W in the processing container 2.

Next, a processing apparatus 90 according to the third embodiment will be described with reference to FIG. The processing apparatus 90 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 and a rinsing process. 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 open / close position 121 formed in the passage 92.

  The cleaning tank 91 surrounds the inner tank 94 that forms the rinse treatment chamber (second processing chamber) 93, the middle tank 95 that surrounds the opening of the inner tank 94, and the 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 pure water supplied from the pure water supply circuit 100 into the rinsing chamber 93. Yes. 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 through an overflow pipe 117 connected to the bottom. An open / close 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 driven by mechanism (not shown), and is freely configured move vertically and horizontally. 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. Therefore, if the shutter 120 is moved to the open / close position 121 by the driving 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.

The 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 the 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 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 shown by the solid line in FIG. 6 shows the accommodation state in the ozone processing chamber 15 by the raised wafer guide 128, and the wafer W shown 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, and 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 and 126 is drained to the factory drainage system via the box 130 and drainage circuit 131. An exhaust circuit 133 that performs exhaust is connected to the box 130. For this reason, the box 130 can exhaust the ambient atmosphere of 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, with the wafer guide 128 lowered and confined in the processing apparatus 90, the wafer W is quickly accommodated in the rinse processing chamber 93. 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, N2 gas at normal temperature is supplied into the ozone processing chamber 15 by the N2 gas supply means 9 and N2 purge is performed to replace the atmosphere in the ozone processing chamber 15. Alternatively, 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, chemical treatment, final rinsing, and drying are performed in a processing container, and rinsing 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. Thus, in another processing apparatus, after performing 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 provide separate apparatuses for performing the chemical treatment, the rinsing process, the final rinsing process, and the drying process, and sequentially transfer the wafers W to these apparatuses.

  According to this processing apparatus 90, the process using ozone and the rinse process can be performed consistently, and the apparatus can be downsized. Further, since the wafer W is not unloaded from the apparatus until the rinse process is completed 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 to become insoluble due to contact with outside air, for example. . 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 external air contact. For example, it is possible to prevent a change to contamination or the like. For this reason, a rinse process can be performed suitably. 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 arranged up and down has been described. However, the ozone processing chamber 15 and the rinsing processing chamber 93 may be arranged in a horizontal row. Even with such an 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, a processing apparatus 140 according to the fourth embodiment 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 second embodiment. 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, Since processing in a high temperature atmosphere is possible, the processing capacity can be further improved. Further, similarly to the processing apparatuses 1, 70, and 90, the wafer guide 128 can be dried to remove water droplets.

  Although an example of an 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 small amount into the processing vessel 2 to promote the generation of hydroxyl radicals so that the oxidation reaction can be performed more actively. In this case, examples of the catalyst gas include NOx 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, by supplying chlorine (Cl ₂ ) gas, 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 to generate 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. In other words, supply ozone gas having oxygen atom radicals, chlorine gas having chlorine atom radicals, hydrogen gas having hydrogen atom radicals, fluorine gas having fluorine atom radicals, and generate a larger amount of radicals to promote 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, and 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 the ozone gas and the removal rate was examined. The result is shown in FIG. In FIG. 9, the horizontal axis represents ozone concentration [g / m3 (normal)], and the vertical axis represents 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 where 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. A resist film and an organic material film were used as treatment targets. 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, a removal rate of 20 [nm / s] can be obtained as shown by a 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 can be obtained by performing treatment using ozone in a state where the ambient atmosphere of the wafer is pressurized.

It is a section explanatory view of the processing device concerning a 1st embodiment of the present invention. 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 sectional explanatory drawing of the processing apparatus concerning the 2nd Embodiment of this invention. It is sectional explanatory drawing of the processing apparatus concerning the 3rd Embodiment of this invention. It is a flowchart for demonstrating the process performed with the processing apparatus of FIG. It is sectional explanatory drawing of the processing apparatus concerning the 4th Embodiment of this invention. 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)

An ozone processing chamber for storing the substrate and processing the substrate inside;
A heater for heating a substrate housed in the ozone treatment chamber;
Water vapor supply means for supplying water vapor into the ozone treatment chamber;
Ozone gas supply means for supplying ozone gas into the ozone treatment chamber;
A rinse treatment chamber for rinsing the substrate after being treated in the ozone treatment chamber;
A wafer guide for moving a substrate between the ozone treatment chamber and the rinse treatment chamber;
And N ₂ gas supply means for supplying a N ₂ gas into the ozone processing chamber,
An exhaust pipe for exhausting the ozone treatment chamber;
A flow controller provided in the exhaust pipe;
A controller that controls the flow rate controller so as to pressurize the ozone treatment chamber ,
The N ₂ gas supply means supplies N ₂ gas, and then pressurizes the ozone treatment chamber under the control of the flow rate controller by the control unit ,
Water vapor and ozone gas are supplied into the ozone treatment chamber after being pressurized, and substrate treatment is performed.
The substrate processing apparatus, wherein the substrate after being processed in the ozone processing chamber is moved to the rinse processing chamber by the wafer guide. A pressure sensor for detecting the pressure in the ozone treatment chamber;
  The substrate processing apparatus according to claim 1, wherein the flow controller is controlled by the controller based on detection of the pressure sensor. The said heater is controlled so that the board | substrate accommodated in the said ozone treatment chamber may be adjusted to the temperature higher than the dew point temperature of water vapor | steam, and lower than the temperature of water vapor | steam, It is characterized by the above-mentioned. 2. The substrate processing apparatus according to 1.