JP2010103190A - Substrate processing apparatus and method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate processing apparatus and method capable of efficiently removing resist residues on the surface of a substrate by using a sulphuric acid while using a hydrogen peroxide solution which is unstable at a high temperature. <P>SOLUTION: The substrate processing apparatus for processing a substrate in a processing container 5 using a first processing liquid containing a sulphuric acid and a second processing liquid containing a hydrogen peroxide solution includes: a processing tank 10 for storing the first processing liquid in a state that the temperature is higher than a normal temperature; a substrate moving up-down mechanism 31 for moving up and down the substrate between the processing tank 10 and the processing container 5; and a mist supply means 40 for supplying the mist of the second processing liquid to near the liquid surface of the first processing liquid of the substrate in picking up the substrate from the processing tank 10 by the substrate moving up-down mechanism 31 or immersing the substrate into the processing tank 10. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a substrate processing apparatus and a substrate processing method for processing a substrate using sulfuric acid and hydrogen peroxide solution, and more particularly to a substrate processing apparatus and a substrate processing method capable of efficiently removing a resist residue on a substrate surface.

Conventionally, a method of cleaning a substrate such as a semiconductor wafer (hereinafter also referred to as a wafer) using a mixed solution of sulfuric acid and hydrogen peroxide as a cleaning solution is known. Specifically, the resist adhering to the wafer is sufficiently decomposed by caloic acid (H ₂ SO ₅ , also called peroxo acid) generated by mixing sulfuric acid and hydrogen peroxide solution. Cleaning is performed (this principle will be described later).

  A substrate processing apparatus for processing a substrate using a mixed solution of sulfuric acid and hydrogen peroxide will be described with reference to FIG. FIG. 12 is a schematic configuration diagram showing a configuration of a general substrate processing apparatus.

As shown in FIG. 12, a general substrate processing apparatus includes an inner tank 110 in which a wafer is to be accommodated for cleaning, and an external liquid that is provided around the inner tank 110 and into which overflowed liquid flows from the inner tank 110. And a tank 112. A return pipe 114 for returning the liquid in the outer tank 112 to the inner tank 110 is provided. The return pipe 114 heats the liquid passing through the return pipe 114, a return pump 116 for sending the liquid in the outer tank 112 to the inner tank 110, a damper 118 for reducing vibration of the return pipe 114 itself, and the like. A heater 120 and a filter 122 for filtering the liquid passing through the return pipe 114 are interposed in series. The substrate processing apparatus includes a sulfuric acid storage tank 124 that stores sulfuric acid (H ₂ SO ₄ ) and a hydrogen peroxide solution storage tank 130 that stores hydrogen peroxide (H ₂ O ₂ ), The sulfuric acid supply pipe 128 and the hydrogen peroxide solution supply pipe 134 supply sulfuric acid and hydrogen peroxide solution into the inner tank 110, respectively. The supply of each chemical solution is adjusted by a sulfuric acid supply valve 126 and a hydrogen peroxide solution supply valve 132, respectively.

  Next, a method for producing a mixed solution using such a substrate processing apparatus will be described below. In the initial state, the inner tank 110 and the outer tank 112 are empty.

  First, in a state where the return pump 116 and the heater 120 are turned off, the sulfuric acid supply valve 126 and the hydrogen peroxide solution supply valve 132 are opened, and sulfuric acid and hydrogen peroxide solution are supplied from the sulfuric acid storage tank 124 and the hydrogen peroxide solution storage tank 130. Are simultaneously supplied into the inner tank 110. Here, the supply amount of sulfuric acid is, for example, 25 liter / min, the supply amount of hydrogen peroxide water is, for example, 5 liter / min, and the ratio of supply amount of sulfuric acid and hydrogen peroxide solution is, for example, 5: 1. The reason for sufficiently increasing the supply amount of sulfuric acid relative to the hydrogen peroxide solution will be described later. The supply of sulfuric acid and hydrogen peroxide water is continued until the inner tank 110 is full and the liquid overflows to the outer tank 112.

  The sulfuric acid and the hydrogen peroxide solution are supplied to the inner tank 110, whereby the sulfuric acid and the hydrogen peroxide solution are mixed.

  Here, there are two types of mixing of sulfuric acid and hydrogen peroxide solution.

  First, as the first pattern, the following chemical reactions can be mentioned.

H ₂ SO ₄ + H ₂ O ₂ → H ₂ SO ₄ + H ₂ O + O ^* Formula (1)
The reaction according to the formula (1) generates active oxygen (O ^* ). This active oxygen is a strong oxidant.

  On the other hand, the following chemical reaction is mentioned as a 2nd pattern.

H ₂ SO ₄ + H ₂ O ₂ → H ₂ SO ₅ + H ₂ O (2)
Caroic acid (also referred to as peroxo acid, H ₂ SO ₅ ) is generated by the reaction according to the formula (2). Although this caloic acid is also a strong oxidizing agent like active oxygen, caroic acid is more effective than active oxygen in decomposing organic substances such as a resist adhering to the wafer. That is, by mixing sulfuric acid and hydrogen peroxide water to generate caloic acid, the resist attached to the wafer can be sufficiently removed.

  Here, a graph with the horizontal axis representing the ratio (molar ratio) of sulfuric acid to the hydrogen peroxide solution and the vertical axis representing the production rate of caroic acid is shown in FIG. As shown in FIG. 13, the larger the ratio (molar ratio) of sulfuric acid to the hydrogen peroxide solution, the higher the generation rate of caloic acid and the more sufficiently the resist attached to the wafer can be removed. For this reason, the ratio of the amount of sulfuric acid and hydrogen peroxide solution supplied to the inner tank 110 is set to 5: 1, for example.

  When the supply of sulfuric acid and hydrogen peroxide solution to the inner tank 110 is completed, the return pump 116 is operated next, and the liquid in the outer tank 112 is returned to the inner tank 110 through the return pipe 114. Further, the liquid overflows from the inner tank 110 to the outer tank 112. In this way, the liquid is circulated in the combined unit of the inner tank 110 and the outer tank 112. Here, the heater 120 also operates simultaneously, and the liquid passing through the return pipe 114 is heated. As a result, the temperature of the liquid in the inner tank 110 rises to a temperature suitable for wafer cleaning (for example, 100 to 150 ° C.).

  After the return pump 116 and the heater 120 are operated until the temperature of the liquid in the inner tank 110 reaches a certain temperature, the return pump 116 and the heater 120 are turned off again. Thereafter, a plurality of wafers are immersed in the inner tank 110 at the same time, and a mixture of sulfuric acid and hydrogen peroxide solution, more specifically, a mixture of sulfuric acid and hydrogen peroxide solution is used to generate the wafers. The resist adhering to is decomposed and the resist is removed. In this way, a series of wafer cleaning steps are completed.

Patent Document 1 and Patent Document 2 describe a substrate processing apparatus or a substrate processing method using sulfuric acid and hydrogen peroxide solution for sufficiently generating carolic acid effective for removing a resist from a substrate as described above. An example is disclosed.
JP 2000-164550 A JP 2008-041794 A

  However, when performing the substrate processing for removing the resist residue on the substrate surface using the above-described sulfuric acid and hydrogen peroxide solution as a processing solution, there are the following problems.

  When substrate processing is performed using sulfuric acid, the cleaning power increases as the temperature of sulfuric acid increases. Therefore, the temperature of sulfuric acid and hydrogen peroxide solution in the processing layer is a temperature suitable for wafer cleaning (for example, 100 to 100). However, if the hydrogen peroxide solution is kept at a high temperature (for example, 100 ° C. or higher), the hydrogen peroxide solution decomposes due to the following chemical reaction. Cannot be stably mixed with sulfuric acid, active oxygen or caroic acid cannot be stably generated, and the detergency is reduced.

2H ₂ O ₂ → 2H ₂ O + O ₂ Formula (3)
Furthermore, when the temperature of sulfuric acid and hydrogen peroxide solution is maintained at a temperature suitable for wafer cleaning (for example, 100 to 150 ° C.), the concentration of hydrogen peroxide solution is decomposed by the reaction of formula (3) and the concentration decreases. Therefore, there is a problem that the hydrogen peroxide solution cannot be supplied at a predetermined concentration.

  The present invention has been made in view of the above points, and a substrate processing apparatus capable of efficiently removing a resist residue on a substrate surface using sulfuric acid while using an unstable hydrogen peroxide solution at a high temperature, and It is to provide a substrate processing method.

  In order to solve the above-described problems, the present invention is characterized by the following measures.

  1st invention is a substrate processing apparatus which processes a board | substrate using the 1st process liquid containing a sulfuric acid, and the 2nd process liquid containing a hydrogen-peroxide solution, Comprising: Said 1st process liquid is high temperature from normal temperature A processing tank that is stored in the above state, a processing container that is disposed above the processing tank and that processes the substrate using the first processing liquid and the second processing liquid, the processing tank, and the processing container, A substrate raising / lowering mechanism for raising / lowering the substrate between the first and second substrates stored in the processing tank of the substrate when the substrate is lifted from the processing tank by the substrate raising / lowering mechanism or immersed in the processing tank. A mist supply means for supplying a mist of the second processing liquid is provided near the liquid surface of the processing liquid.

  In the present invention, immersing the substrate in the first processing liquid does not only mean that the entire substrate is submerged below the liquid surface of the first processing liquid, but part of the substrate is the first. It also means that the other part of the substrate is submerged below the liquid level of the first processing liquid while being exposed above the liquid level of the processing liquid. Therefore, immersing the substrate in the first processing liquid also means that the substrate is pulled down with a part of the substrate submerged below the liquid surface of the first processing liquid.

  According to a second aspect of the present invention, in the substrate processing apparatus according to the first aspect of the present invention, the outer tank that receives the first processing liquid overflowed from the processing tank, the first processing liquid is recovered from the outer tank, and again And a processing liquid circulating means for supplying the processing tank.

  According to a third aspect of the present invention, in the substrate processing apparatus according to the second aspect, the mist supply means is in the vicinity of the liquid surface of the first processing liquid stored in the processing tank inside the processing container. It is provided.

  According to a fourth aspect of the present invention, in the substrate processing apparatus according to the third aspect of the present invention, the substrate processing apparatus includes an inert gas supply unit that is provided inside the processing container and supplies an inert gas into the processing container.

  According to a fifth invention, in the substrate processing apparatus according to the fourth invention, the inert gas supply means is provided above the mist supply means.

  A sixth invention is a substrate processing method for processing a substrate using a first processing solution containing sulfuric acid and a second processing solution containing hydrogen peroxide, wherein the substrate is held at a temperature higher than room temperature. A liquid film of the first processing liquid held at a temperature higher than normal temperature is formed on the substrate by being immersed in the first processing liquid or pulled up from the first processing liquid held at a temperature higher than normal temperature. And a mist supply step of supplying a mist of the second processing liquid in the vicinity of the liquid surface of the first processing liquid on the substrate.

  A seventh invention is characterized in that, in the substrate processing method according to the sixth invention, an inert gas is supplied into a processing vessel for processing the substrate in an airtight manner.

  An eighth invention is characterized in that, in the substrate processing method according to the seventh invention, the inert gas is supplied from above from a mist supply part for supplying a mist of the second processing liquid.

  According to the present invention, the resist residue on the substrate surface can be efficiently removed using sulfuric acid while using an unstable hydrogen peroxide solution at a high temperature.

Next, the best mode for carrying out the present invention will be described with reference to the drawings.
(First embodiment)
A substrate processing apparatus and a substrate processing method according to a first embodiment of the present invention will be described with reference to FIGS.

  First, the substrate processing apparatus according to the present embodiment will be described with reference to FIGS. 1 and 2.

  FIG. 1 is a schematic cross-sectional view schematically showing the configuration of the substrate processing apparatus according to the present embodiment. FIG. 2 is a perspective view schematically showing the configuration of the substrate processing apparatus of the substrate processing apparatus according to the present embodiment.

  The substrate processing apparatus according to the present embodiment includes a processing container 5 for performing a substrate processing for processing a substrate using a first processing liquid 1 and a second processing liquid containing sulfuric acid in an airtight manner, and a first processing liquid. , A processing tank 10 that stores water at a temperature higher than normal temperature, an outer tank 11 that is connected to the upper end opening of the processing tank 10 and receives the first processing liquid 1 containing sulfuric acid overflowed from the processing tank 10, and a processing tank 10, a predetermined number of, for example, 50 semiconductor wafers W (hereinafter referred to as “wafers”) to be processed are held in a state where they are arranged at appropriate intervals, for example, a wafer boat 30 and a rapid supply into the processing tank 10. The first processing liquid storage tank 20 for storing the first processing liquid 1 and the steam for supplying the second processing liquid containing hydrogen peroxide to the wafer W in the processing tank 10 in the state of steam or mist・ Mist supply means A gas / mist supply nozzle 40, a supply nozzle 28 for supplying the first processing liquid 1 in the first processing liquid storage tank 20 into the processing tank 10, and a bottom of the processing tank 10 are disposed on the wafer W. A supply means for supplying the first treatment liquid 1, for example, a jet nozzle 42 is provided.

  In this embodiment, an example in which sulfuric acid is used as the first processing liquid and hydrogen peroxide water is used as the second processing liquid will be described. However, the first treatment liquid is not particularly limited as long as it contains sulfuric acid, and the second treatment liquid is not particularly limited as long as it contains hydrogen peroxide water.

  Moreover, the steam / mist supply means and the steam / mist supply nozzle in the embodiment and the modification of the present invention correspond to the mist supply means in the present invention. That is, the mist supply means in the present invention includes means for supplying the mist of the second processing liquid or a nozzle for supplying the mist of the second processing liquid.

  The processing vessel 5 is disposed above the processing tank 10 and has a side wall 5a formed by extending a side wall opposite to the side of the outer tank 11 connected to the upper end opening of the processing tank 10, and an upper end opening of the side wall 5a. The opening part 5b is provided so as to expand outward so that the opening cross-sectional area of the processing container is increased, and the upper lid 5c is placed on the opening part 5b and is hermetically locked. Therefore, the lower side of the side wall 5a of the processing container 5 is integrally connected to the side wall opposite to the side connected to the upper end opening of the processing tank 10 of the outer tank 11.

  The processing container 5, the processing tank 10, and the outer tank 11 are made of a material having a high corrosion resistance and chemical resistance, such as quartz. Further, a drainage port 10 a is provided at the bottom of the processing tank 10, and a drain pipe 13 is connected to the drainage port 10 a via a drain valve 12. In addition, a mesh 17 is laid on the upper part of the drainage port 10a, and the mesh 17 can collect dust and the like in the chemical solution discharged from the treatment tank 10. In addition, the 1st process liquid extraction pipe | tube 18 is connected to the upper side of the process tank 10, for example, the position of 20-40 mm from the upper end of the process tank 10, The ratio connected to this 1st process liquid extraction pipe | tube 18 is connected. The resistivity detector 19 is configured to measure the specific resistance value of the first treatment liquid 1 in the treatment tank 10.

  Further, a drainage port 11 a is provided at the bottom of the outer tub 11, and a circulation pipe 43 is connected to the drainage port 11 a and the jet nozzle 42. A pump 44, a damper 45, and a filter 46 are interposed in the circulation line 43 in order from the drainage port 11 a side. A pure water supply source 48 is connected between the filter 46 and the jet nozzle 42 via a switching valve 47. Further, a drain pipe 52 is connected between the drain port 11 a and the pump 44 via a switching valve 51, and a first processing liquid supply source 49 a is connected via a switching valve 49, A drain pipe 54 is branched from the switching valve 47 through a drain valve 53. The circulation pipe 43, the pump 44, the damper 45, and the filter 46 correspond to the processing liquid circulation means in the present invention.

  In this case, as shown in FIG. 2, the jet nozzles 42 are formed at appropriate intervals in the longitudinal direction of pipe-shaped nozzle bodies 42a disposed on both lower sides of the wafers W held by the wafer boat 30. The structure is provided with a number of nozzle holes 42b.

  As described above, by providing a circulation piping system between the jet nozzle 42 and the drain port 11a of the outer tub 11, the first treatment liquid supplied from the first processing liquid supply source 49a to the processing tub 10 by the pump 44 is provided. The first processing liquid is overflowed from the processing tank 10 and received by the outer tank 11, the first processing liquid is recovered from the outer tank 11, the recovered first processing liquid is reusably regenerated, and the regenerated first The particles, metal ions, oxide film, etc. adhering to the surface of the wafer W can be removed while the processing liquid is circulated through the circulation pipe 43 and supplied again from the jet nozzle 42 to the wafer W. Further, after draining the first processing liquid, the switching valve 47 is switched to spray the pure water supplied from the pure water supply source 48 onto the wafer W from the jet nozzle 42 to remove the chemical liquid adhering to the wafer W. be able to. In this case, the pure water overflowed from the treatment tank 10 is discharged through the drain pipe 52.

  On the other hand, as shown in FIG. 1, the first processing liquid tank 20 is provided with an outside air inlet 22 for supplying the first processing liquid 1 to the processing tank 10 at the upper end of the sealed tank body 21. ing. In addition, an overflow pipe 23 for maintaining a constant amount of the first processing liquid 1 in the tank is disposed in the tank body 21, and the first processing liquid is disposed in the vicinity of the outside of the tank body 21. An upper limit sensor 24a, a lower limit sensor 24b, and an appropriate amount sensor 24c for detecting an upper limit, a lower limit, and an appropriate amount of the liquid level of the liquid 1 are disposed, and a predetermined amount of the first processing liquid 1 is always stored in the tank by these sensors. It is like that. In this case, the capacity of the first treatment liquid 1 in the tank needs to be at least a single amount rapidly supplied into the processing tank 10, for example, 35 liters (l) or more, preferably a rapid supply amount for two times. For example, it is better to accommodate 70 liters (l). In addition, a heater 25 having a heater wire inserted through a quartz tube, for example, is disposed at the bottom of the tank body 21 so that the first treatment liquid 1 in the tank can be heated to a predetermined temperature, for example, 150 to 170 ° C. It has become.

  A supply port (not shown) provided at the bottom of the tank body 21 of the first processing liquid tank 20 configured as described above and a supply nozzle 28 are connected via a supply pipe 26, and the supply pipe The first processing liquid 1 in the first processing liquid tank 20 is supplied from the supply nozzle 28 to the outer tank 11 in the processing tank 10 by opening and closing the supply valve 27 interposed in the pipe 26. .

  On the other hand, the steam / mist supply nozzle 40 is connected to a hydrogen peroxide solution supply pipe 26a provided with an on-off valve 29, and is disposed above both opposing sides of the processing tank 10, as shown in FIGS. Each steam / mist supply nozzle 40 is formed with a plurality of steam / mist supply nozzle holes 40b at appropriate intervals inside the processing tank below the pipe-shaped nozzle body 40a.

  As shown in FIG. 2, the wafer boat 30 is a pair of bolts 32a fixed to a mounting member 32 connected to a substrate lifting mechanism 31 disposed outside the processing tank 10 (only one is shown in the drawing). An inverted T-shaped support member 33, a single center holding rod 34 installed at the lower end of the center between the support members 33, and 2 installed on the left and right side ends between the support members 33 in parallel with each other. The side holding rod 35 of the book is configured to move up and down in the processing container 5 by driving the substrate lifting mechanism 31 and to lift the substrate between the processing tank 10 and the processing container 5. Yes. Further, as will be described later, when the substrate is lifted from the processing tank 10 by the substrate lifting mechanism 31 or immersed in the processing tank 10, the vapor / mist supply nozzle 40 is stored in the substrate processing tank 10. The vapor or mist of the second treatment liquid is supplied near the liquid surface of the treatment liquid. In this case, the central holding bar 34 and the side holding bar 35 are each provided with a plurality of, for example, 50 holding grooves 34a and 35a at appropriate intervals in the longitudinal direction. These holding bars 34 and 35 are made of a material excellent in corrosion resistance, heat resistance and strength resistance, for example, polyether ether ketone (PEEK) or quartz member.

  An inert gas supply nozzle 50 for supplying an inert gas containing nitrogen gas into the processing container 5 is provided inside the processing container 5 and above the steam / mist supply nozzle 40. As with the steam / mist supply nozzle 40, the inert gas supply nozzle 50 is provided with a number of inert gas supply nozzle holes 50b at appropriate intervals inside the processing tank below the pipe-shaped nozzle body 50a. Do it. The inert gas supply nozzle 50 corresponds to the inert gas supply means of the present invention.

  The reaction gas generated by the reaction between the high-temperature sulfuric acid liquid film and the hydrogen peroxide solution is enclosed in a processing vessel 5 provided to be airtight and exhausted from an exhaust pipe (not shown).

  Next, a substrate processing method using the substrate processing apparatus of this embodiment will be described with reference to FIGS.

  FIG. 3 is a flowchart for explaining the procedure of each step of the substrate processing method according to the present embodiment. 4A to 4C are diagrams for explaining the substrate processing method according to the present embodiment, and are schematic cross-sectional views schematically showing the inside of the processing container in each step. The state in the processing container when or after each of the steps S11 to S18 in FIG. 3 corresponds to the schematic cross-sectional views of FIGS. 4A (a) to 4C (h). FIG. 5 is a diagram for explaining the substrate processing method according to the present embodiment, in the vicinity of the surface of the first cleaning liquid stored in the substrate processing tank to be pulled up, It is a figure which shows typically a mode that mist is supplied.

  As shown in FIG. 3, the substrate processing method according to the present embodiment includes a preparation process, a liquid film formation process, a vapor / mist supply process, and an end process. The preparation step includes steps S11 and S12, the liquid film formation step includes steps S13 to S15, the steam / mist supply step includes step S16, and the end step includes step S17. And step S18.

  Note that the steam / mist supply step in the present embodiment corresponds to the mist supply step in the present invention. That is, the mist supply step in the present invention includes a step of supplying the mist of the second processing liquid.

  First, a preparation process including steps S11 and S12 is performed.

  First, step S11 is performed. Step S <b> 11 is a step of preparing for carrying a wafer into the processing container. FIG. 4A (a) is a schematic cross-sectional view schematically showing the inside of the processing container when the step S11 is performed.

  In step S11, as shown in FIG. 4A (a), the wafer boat 30 is accommodated in the processing container 5 without holding the substrate (wafer) W. The treatment tank 10 is supplied with a first treatment liquid 1 containing a sulfuric acid cleaning liquid kept at a high temperature. An inert gas is supplied from the inert gas supply nozzle 50.

  Specifically, the first processing liquid 1 overflows from the processing tank 10, and the first processing liquid 1 overflowed by driving the pump 44 of the circulation pipe 43 is transferred from the jet nozzle 42 to the inside of the processing tank 10. Injected and supplied.

  Next, step S12 is performed. Step S12 is a step of opening the upper lid of the processing container and holding the substrate on the wafer boat. FIG. 4A (b) is a schematic cross-sectional view schematically showing the inside of the processing container when the step S12 is performed.

  The supply of the inert gas from the inert gas supply nozzle is stopped, the upper lid 5c of the processing container 5 is opened, the wafer boat 30 is lifted using the substrate lifting mechanism 31, and a plurality of sheets conveyed by a wafer chuck (not shown), for example 50 wafers W are received by the wafer boat 30, and the wafer boat 30 is lowered again into the processing container 5, and the upper lid 5 c of the processing container 5 is closed and sealed.

  Next, a liquid film forming process including steps S13 and S15 and a steam / mist supply process including step S16 are performed.

  First, step S13 is performed. Step S13 is a step of immersing the substrate in a first treatment liquid containing sulfuric acid kept at a high temperature. FIG. 4A (c) is a schematic cross-sectional view schematically showing the inside of the processing container when the step S13 is performed.

  The substrate (wafer) W is immersed in the processing bath 10 and waits for the temperature of the substrate to rise to the same temperature as the first processing liquid 1 containing sulfuric acid kept at a high temperature. Specifically, it waits for about 20 seconds.

  At the same time, nitrogen gas is supplied from the inert gas supply nozzle 50. Nitrogen gas is a buffer that controls the atmosphere, and controls the distribution of hydrogen peroxide water vapor or mist to supply the vapor or mist of hydrogen peroxide water to a portion in contact with or near the liquid surface of the substrate cleaning liquid. In addition to functioning as a gas, it also functions as a replacement gas when the inside of the processing vessel 5 is replaced in the end step described later. That is, steam or mist containing sulfuric acid generated when hydrogen peroxide water vapor or mist is supplied to sulfuric acid contained in a liquid film formed on the substrate (wafer) surface or sulfuric acid stored in the treatment tank 10 is treated. When the inside of the container 5 is prevented, or when the substrate (wafer) is discharged from the processing container 5, the atmosphere containing sulfuric acid in the processing container 5 is replaced with an inert gas atmosphere, This is to prevent the atmosphere containing sulfuric acid from leaking out of the processing container 5.

  Nitrogen gas corresponds to the inert gas in the present invention, but is not particularly limited, and various other inert gases such as He, Ar, and Xe can be used.

  Next, step S14 is performed. Step S14 is a step of starting supply of the vapor or mist of the second treatment liquid containing the hydrogen peroxide solution toward the vicinity of the liquid surface of the sulfuric acid cleaning liquid. FIG. 4B (d) is a schematic cross-sectional view schematically showing the inside of the processing container after the step S14 is performed.

  Note that the second treatment liquid can be supplied in a state of either steam or mist, or in a state where steam and mist are mixed. Hereinafter, in the present embodiment, the case of supplying in the state of mist will be described, and the case of supplying in the state of steam will be described in the modification of the first embodiment.

  The on-off valve 29 is opened, and the hydrogen peroxide solution supplied from the hydrogen peroxide solution supply pipe 26 a is supplied as a mist from the vapor / mist supply nozzle 40 toward the wafer W. Further, it may be supplied as a mist containing steam through a steam generator (not shown) provided in the middle, and similarly, supplied as a mist having a temperature adjusted through a temperature regulator (not shown) provided in the middle. Good. The temperature of the mist is not particularly limited as long as the temperature of the liquid film of the first treatment liquid containing sulfuric acid formed on the surface of the substrate does not fall below a predetermined temperature, as will be described later. For example, it can be set to 70 ° C. or higher and 100 ° C. or lower.

  Next, step S15 and step S16 are performed simultaneously. A step S15 forms a liquid film of the sulfuric acid cleaning liquid held at a high temperature on both surfaces of the substrate by pulling up the substrate immersed in the sulfuric acid cleaning liquid held at a high temperature. Step S16 is a step of supplying hydrogen peroxide mist to the portion of the substrate that is pulled up in contact with the surface of the sulfuric acid cleaning liquid or in the vicinity of the liquid surface. FIG. 4B (e) and FIG. 4B (f) are schematic cross-sectional views schematically showing the state of the processing container during and after the step S15 and step S16 are performed simultaneously. .

  Specifically, the substrate lift mechanism 31 is used to slowly pull the wafer boat 30 upward, thereby pulling up the substrate from the sulfuric acid cleaning liquid in a state where a liquid film of the sulfuric acid cleaning liquid held at a high temperature is formed on both surfaces of the substrate. At the same time, a mist of hydrogen peroxide is supplied to the portion of the substrate that is brought into contact with the surface of the sulfuric acid cleaning solution, that is, near the interface between the sulfuric acid cleaning solution and the substrate.

  The pulling speed for pulling up the substrate is such that the temperature of the substrate is almost equal to the temperature of the processing liquid stored in the processing tank when the supply speed at which the mist of hydrogen peroxide solution is supplied from the shower supply nozzle is a certain value. Although not particularly limited, it may be 10 to 50 mm / sec.

  Here, referring to FIG. 5, when supplying a mist of hydrogen peroxide solution toward the liquid surface of the sulfuric acid cleaning solution, that is, the vicinity of the interface between the sulfuric acid cleaning solution and the substrate, the resist residue on the substrate surface is removed. The function and effect will be described.

  Referring to FIG. 5, a liquid film is formed on both surfaces of the wafer W pulled up from the sulfuric acid cleaning liquid. Since the wafer W is gradually pulled up from the sulfuric acid cleaning liquid held at a high temperature and not held at a high temperature above the liquid surface of the sulfuric acid cleaning liquid, the temperature of the wafer W pulled up is a portion in contact with the liquid surface of the sulfuric acid cleaning liquid. Then, the temperature is equal to the temperature of the sulfuric acid cleaning solution, and the temperature is lower than the temperature of the sulfuric acid cleaning solution as the portion is farther upward from the liquid surface.

  When a substrate on which a liquid film having such a temperature distribution along the vertical direction is pulled up from the sulfuric acid cleaning liquid, a mist of hydrogen peroxide solution is supplied near the surface of the sulfuric acid cleaning liquid. Since the portion of the sulfuric acid cleaning liquid in contact with the liquid surface or the vicinity of the liquid surface is maintained at a high temperature, the sulfuric acid of the liquid film formed on the substrate surface and maintained at a high temperature and the mist of the supplied hydrogen peroxide solution react. The mist of high-temperature hydrogen peroxide water causes a chemical reaction represented by the following formula (4) and dissociates to generate active oxygen.

_{H 2 O 2 → H 2 O} + O * ··· formula (4)
The active oxygen generated in this manner reacts with sulfuric acid to cause, for example, a chemical reaction represented by the following formula (5) to generate caroic acid.

H ₂ SO ₄ + O ^* → H ₂ SO ₅ Formula (5)
Here, in order to promote the chemical reaction of the above formulas (4) and (5), it is desirable to keep the temperature as high as possible in order to increase the reaction rate. However, since hydrogen peroxide in the supplied hydrogen peroxide water is easily decomposed at a temperature higher than 100 ° C., for example, 70 ° C. to 100 ° C. is preferable.

  In particular, in the conventional processing method in which sulfuric acid and hydrogen peroxide water are mixed and stored in a processing tank, the chemical reaction shown in Formula (3) occurs at a high temperature, and hydrogen peroxide in hydrogen peroxide water is decomposed. Although there is a problem, according to the present embodiment, since the hydrogen peroxide solution is not kept at a high temperature for a long time, the hydrogen peroxide in the supplied hydrogen peroxide solution is immediately expressed by the equations (4) and ( The chemical reaction of 5) occurs to generate caroic acid. Therefore, in a high temperature region that cannot normally be used, hydrogen peroxide can be stably used to generate caroic acid. As a result, substrate processing for efficiently removing the resist residue on the substrate surface can be performed.

  In this embodiment, since the substrate is continuously pulled up with the mist continuously supplied, the step S15 of the liquid film forming step and the step S16 of the vapor / mist step are performed simultaneously. It is done continuously. However, when the process of step S15 is performed, the supply of mist of hydrogen peroxide solution is stopped, and the pulling up of the substrate from the sulfuric acid cleaning solution is stopped halfway, and in this state, the hydrogen peroxide is directed toward the vicinity of the liquid surface of the sulfuric acid cleaning solution. In the case of repeating the process of restarting the supply of water mist, then stopping the supply of hydrogen peroxide mist and restarting the substrate from the sulfuric acid cleaning solution, the process of step S15 and step S16 are repeated. The steps can be performed in order.

  Further, after performing the steps S15 and S16, the cycle of lowering the substrate again and immersing it in the sulfuric acid cleaning solution, and performing the steps S15 and S16 again can be repeated several times as necessary. By repeating this, the resist residue on the substrate surface can be removed more cleanly. The speed at which the substrate is lowered can be set to 150 mm / sec, for example.

  Next, an end process including steps S17 and S18 is performed.

  First, step S17 is performed. Step S17 is a step of replacing the atmosphere in the processing container. FIG. 4C (g) is a schematic cross-sectional view schematically showing the inside of the processing container when step S17 is performed.

  The on-off valve 29 is closed to stop the supply of hydrogen peroxide mist from the steam / mist supply nozzle 40. At this time, the supply of the sulfuric acid cleaning liquid from the jet nozzle 42 may be stopped, or the sulfuric acid cleaning liquid may be continuously supplied from the jet nozzle 42 as shown in FIG. 4C (g).

  At this time, the inert gas supply nozzle is kept open and the inside of the processing container is replaced with gas for about 30 seconds, for example. This is to inactivate the atmosphere in the processing container in order to open the upper lid of the subsequent processing container, and to stop the reaction between sulfuric acid and water vapor. As the inert gas, for example, various inert gases such as nitrogen gas heated to room temperature or above or other He, Ar, and Xe can be used.

  Finally, step S18 is performed. Step S18 is a step of unloading the substrate from the processing container. FIG. 4C (h) is a schematic cross-sectional view schematically showing the inside of the processing container when step S18 is performed.

  After the supply valve (not shown) is closed and the supply of the inert gas is stopped, the upper lid 5c of the processing vessel 5 is opened, the wafer boat 30 is raised by the substrate lifting mechanism 31, and the wafer W is carried out of the processing vessel 5. It is gripped by a wafer chuck (not shown) and taken out to the outside.

  As described above, according to the present embodiment, since hot sulfuric acid and hydrogen peroxide on the surface of the substrate react with each other to generate caroic acid, the resist residue on the surface of the substrate is removed while using hydrogen peroxide water that is easily decomposed at high temperature. Substrate processing for efficient removal can be performed.

In the present embodiment, the substrate is dipped in the first processing liquid (step S13), and then the substrate is pulled up, thereby forming a liquid film of the first processing liquid held at a temperature higher than normal temperature on the substrate. (Step S15), the mist of the second processing liquid is supplied to the portion of the substrate to be lifted that is in contact with the liquid surface of the first processing liquid or near the liquid surface (Step S16). By immersing in the treatment liquid, a liquid film of the first treatment liquid that is held at a temperature higher than room temperature is formed on the substrate, and the part of the substrate that is pulled down is in contact with the liquid surface of the first treatment liquid or near the liquid surface, A mist of the second processing liquid may be supplied. In this case, step S13 is a step of pulling up the substrate from the high-temperature first processing liquid stored in the processing tank or holding it in the pulled state, and step S15 is a step of holding the substrate in the first processing liquid. It is a step of forming a liquid film of the first processing liquid held at a high temperature on the substrate by dipping (lowering), and step S16 is a liquid of the first processing liquid of the substrate to be dipped (lowered) This is a step of supplying the mist of the second processing liquid to a portion in contact with the surface or in the vicinity of the liquid surface.
(Modification of the first embodiment)
Next, a substrate processing apparatus and a substrate processing method according to a modification of the first embodiment will be described.

  The substrate processing method according to this modification is characterized in that the hydrogen peroxide solution vapor is used instead of the hydrogen peroxide solution mist in the substrate processing apparatus and the substrate processing method according to the first embodiment.

  That is, in this modification, the second treatment liquid supplied from the steam / mist supply nozzle 40 is not decomposed by hydrogen peroxide solution vapor or hydrogen peroxide solution but hydrogen peroxide solution mist. Supplied as water vapor and active oxygen. At this time, the temperature of the vapor is not particularly limited as long as the temperature of the liquid film of the first treatment liquid containing sulfuric acid formed on the surface of the substrate does not fall below a predetermined temperature. When the temperature of the liquid film of the first treatment liquid containing 110 ° C. can be maintained at a temperature around 110 ° C.

  In addition, the steam / mist supply process in this modification corresponds to the mist supply process in the present invention. That is, the mist supply step in the present invention is not limited to the case where the mist of the second processing liquid is supplied, but the vapor of the second processing liquid or the second processing liquid is decomposed together with the mist of the second processing liquid. When the generated steam is supplied, the mist of the second processing liquid supplied from the steam / mist supply nozzle is generated while the second processing liquid vapor or the second processing liquid decomposes in the middle. This includes the case where it is supplied by changing into steam.

  Also in this modified example, when supplying the hydrogen peroxide solution vapor toward the vicinity of the surface of the sulfuric acid cleaning solution, the effect of removing the resist residue on the substrate surface is the same as that of the first embodiment. is there.

  That is, in the conventional processing method in which sulfuric acid and hydrogen peroxide water are mixed and stored in the processing tank, when the concentration of hydrogen peroxide in the hydrogen peroxide water is high, the chemical reaction shown in Formula (3) occurs at a high temperature, Although there is a problem that hydrogen peroxide is decomposed, according to the present embodiment, since hydrogen peroxide is not held at a high temperature for a long time, the supplied hydrogen peroxide is immediately expressed by the formula (4). And a chemical reaction of the formula (5) occurs to generate caroic acid. Moreover, even if it decomposes | disassembles, the water vapor | steam and active oxygen which generate | occur | produce by decomposition | disassembly can be supplied. Therefore, caroic acid can be stably generated in a high temperature region that cannot be normally used. As a result, substrate processing for efficiently removing the resist residue on the substrate surface can be performed.

In this modification, the substrate is dipped in the first processing liquid (step S13), and then the substrate is pulled up to form a liquid film of the first processing liquid held at a temperature higher than normal temperature on the substrate. (Step S15) The vapor of the second processing liquid is supplied to the portion of the substrate that is pulled up in contact with or near the liquid surface of the first processing liquid (Step S16), but the substrate is pulled down to perform the first processing. By immersing in the liquid, a liquid film of the first processing liquid maintained at a temperature higher than room temperature is formed on the substrate, and the part of the substrate that is lowered is in contact with the liquid surface of the first processing liquid or in the vicinity of the liquid surface. The vapor | steam of 2 process liquids may be supplied. In this case, step S13 is a step of pulling up the substrate from the high-temperature first processing liquid stored in the processing tank or holding it in the pulled state, and step S15 is a step of holding the substrate in the first processing liquid. It is a step of forming a liquid film of the first processing liquid held at a high temperature on the substrate by dipping (lowering), and step S16 is a liquid of the first processing liquid of the substrate to be dipped (lowered) This is a step of supplying the vapor of the second processing liquid to a portion in contact with the surface or in the vicinity of the liquid surface.
(Second Embodiment)
Next, a substrate processing apparatus and a substrate processing method according to the second embodiment of the present invention will be described with reference to FIGS.

  First, the substrate processing apparatus according to the present embodiment will be described with reference to FIG. FIG. 6 is a schematic configuration diagram schematically showing the configuration of the substrate processing apparatus according to the present embodiment.

  The substrate processing apparatus in this embodiment includes a spin chuck 61 that is a mounting table on which a semiconductor wafer W (hereinafter referred to as a wafer W) that is a substrate to be processed is rotatably mounted, and a rotational drive that rotationally drives the spin chuck 61. A motor 62 as a means, a processing liquid supply means 63 for supplying a first processing liquid containing sulfuric acid to the surface of the wafer W held by the spin chuck 61, and a surface of the wafer W held by the spin chuck 61. Steam / mist supply means 64 for supplying the second treatment liquid made of hydrogen oxide water by steam or mist, and a control means 65 for controlling at least the timing for supplying the treatment liquid and the timing for removing the treatment liquid are the main parts. It is configured.

  In this case, a cup 66 is disposed around and below the spin chuck 61 and the wafer W held by the spin chuck 61, and the cup 66 allows the first processing liquid and the second processing liquid to flow. Prevents splashing outside. A drain port 67 and an exhaust port 68 are provided at the bottom of the cup 66.

  In this embodiment, an example in which sulfuric acid is used as the first processing liquid and hydrogen peroxide water is used as the second processing liquid will be described. However, the first treatment liquid is not particularly limited as long as it contains sulfuric acid, and the second treatment liquid is not particularly limited as long as it contains hydrogen peroxide water.

  The processing liquid supply means 63 is configured to be horizontally movable above the wafer W by the moving mechanism 69a and to be close to the vicinity of the surface of the wafer W, so that it can also be vertically moved. A processing liquid supply nozzle 63a that supplies (discharges) one processing liquid is provided, and a processing liquid supply source 63b is connected to a processing liquid supply pipe 63c that connects the processing liquid supply nozzle 63a and the processing liquid supply source 63b. In order from the side, a processing liquid supply pump 63d, a filter 63e, a temperature controller 63f for adjusting the temperature of the first processing liquid to a predetermined temperature, and an on-off valve 63g are provided.

  The vapor / mist supply means 64 is configured to be horizontally movable and vertically movable above the wafer W by the moving mechanism 69b, and supplies the second processing liquid made of water to the upper surface of the wafer W by vapor or mist. A steam / mist supply nozzle 64a for discharging (injecting or jetting) is provided, and a steam / mist supply source 64b connecting the steam / mist supply nozzle 64a and the steam / mist supply source 64b is connected to a steam / mist supply source 64b. In order from the 64b side, a flow rate controller 64d, a filter 64e, an on-off valve 64f, and a temperature controller 64g that is a temperature adjusting means for adjusting the temperature of the vapor or mist of the second processing liquid to a predetermined temperature are interposed. A supply source of a rinse liquid (not shown) such as pure water is connected between the temperature controller 64g of the steam / mist supply pipe 64c and the steam / mist supply nozzle 64a via a switching valve (not shown). Yes.

  On the other hand, the control means 65 is formed by, for example, a central processing unit (CPU), and a control signal from the control means 65 (hereinafter referred to as CPU 65) moves the motor 62 and the processing liquid supply nozzle 63a. A drive system such as a mechanism 69a and a moving mechanism 69b of the steam / mist supply nozzle 64a, a processing liquid supply pump 63d of the processing liquid supply means 63, a temperature controller 63f and an on-off valve 63g, and a flow rate controller 64d of the steam / mist supply means 64; It is configured to be transmitted to the on-off valve 64f and the temperature controller 64g.

  Therefore, the motor 62 can be switched between a low speed rotation of a predetermined rotation number, for example, 1 to 150 rpm, a medium speed rotation of 100 to 500 rpm, and a high speed rotation of 500 to 3000 rpm, by a control signal from the CPU 65. In this case, the low-speed rotation refers to rotation that does not spread as a liquid film due to centrifugal force even if the first processing liquid is supplied to the surface of the wafer W, and the medium-speed rotation refers to supply to the surface of the wafer W. Rotation to such an extent that the first processing liquid spreads by centrifugal force and a liquid film is formed, and high-speed rotation is rotation that shakes off the liquid film formed on the surface of the wafer W by centrifugal force. .

  Further, the processing liquid supply nozzle 63 a or the vapor / mist supply nozzle 64 a can be moved horizontally and vertically above the wafer W, that is, relative to the wafer W by a control signal from the CPU 65. Further, a predetermined amount of vapor or mist of the first processing liquid or the second processing liquid is supplied to the wafer W by a control signal from the CPU 65.

  Next, a substrate processing method according to the present embodiment will be described with reference to FIGS.

  FIG. 7 is a flowchart for explaining the procedure of each step of the substrate processing method according to the present embodiment. FIG. 8 is a diagram for explaining the substrate processing method according to the present embodiment, and is a schematic cross-sectional view schematically showing the inside of the cup in each step. The state in the cup when or after each of the steps S21 to S24 of FIG. 7 corresponds to the schematic cross-sectional views of FIGS. 8A to 8D. FIG. 9 is a diagram for explaining the substrate processing method according to the present embodiment, in which the vapor / mist of the second processing liquid is supplied to the surface of the substrate on which the liquid film of the first processing liquid is formed. It is a figure which shows a mode that it is performed typically.

  As shown in FIG. 7, the substrate processing method according to the present embodiment includes a placing process, a liquid film forming process, a vapor / mist supplying process, and a removing process. The placement process includes the process of step S21, the liquid film formation process includes the process of step S22, the steam / mist supply process includes the process of step S23, and the removal process includes the process of step S24.

  First, the mounting process including the process of step S21 is performed. Step S21 is a step of placing the substrate on a spin chuck that is a placement table. Fig.8 (a) is a schematic sectional drawing which shows typically the mode in the cup after the process of step S21 was performed.

  The wafer W is transferred onto the spin chuck 61 by a transfer means (not shown), and the wafer W is placed and held by the spin chuck 61. Then, the processing liquid supply nozzle 63a is moved above the center of the wafer W by driving the moving mechanism 69a. In this state, the motor 62 is driven to rotate the spin chuck 61 and the wafer W at a low speed, for example, 35 rpm. Then, the first processing liquid 1 containing a predetermined amount of sulfuric acid is discharged (supplied) from the processing liquid supply nozzle 63a, and this state is performed for a predetermined time (for example, 3 seconds) to apply the first processing liquid 1 to the surface of the wafer W. Make contact. As a result, the sulfuric acid as the first processing liquid 1 enters the concave and convex portions of the resist residue remaining on the surface of the wafer W. At this time, in order to supply the first processing liquid 1 held at a high temperature, the temperature of the first processing liquid 1 is adjusted to a high temperature of, for example, 150 ° C. by the temperature controller 63f. The temperature of the first treatment liquid is such that sulfuric acid efficiently reacts with the hydrogen peroxide water vapor / mist, which is the second treatment liquid supplied in the vapor / mist supply process described later, so that caroic acid is efficiently generated. There is no particular limitation, and the resist residue on the substrate can be efficiently removed by setting the temperature to, for example, 150 ° C. or higher.

  Next, a liquid film forming process including step S22 is performed. Step S22 is a step of forming a liquid film of the first processing liquid held at a temperature higher than normal temperature on the substrate by supplying a first processing liquid containing sulfuric acid held at a high temperature on the substrate. . FIG. 8B is a schematic cross-sectional view schematically showing the inside of the cup when the step S22 is performed.

  In a state where a predetermined amount of the first processing liquid 1 is discharged from the processing liquid supply nozzle 63a, the spin chuck 61 and the wafer W are rotated at a rotation speed of, for example, 200 rpm, and this state is performed for a predetermined time (for example, 30 seconds). A liquid film of the first processing liquid 1 is formed on the entire surface of the wafer W.

  Next, a steam / mist supply process including step S23 is performed. Step S23 is a step of supplying hydrogen peroxide water as the second processing liquid by vapor or mist onto the surface of the substrate on which the liquid film of sulfuric acid is formed as the first processing liquid. FIG.8 (c) is a schematic sectional drawing which shows typically the mode in a cup at the time of the process of step S23 being performed.

  The spin chuck 61 and the wafer W are rotated at a rotational speed of, for example, 300 rpm in a state where a predetermined amount of vapor or mist of the second processing liquid is discharged from the vapor / mist supply means 64, and this state is maintained for a predetermined time (for example, 60 seconds) And supplying the vapor or mist of the second processing liquid to the entire surface of the wafer W.

  Here, referring to FIG. 9, when supplying the hydrogen peroxide vapor as the second processing liquid toward the liquid film made of sulfuric acid as the first processing liquid, the resist residue on the substrate surface is removed. The function and effect will be described.

  Referring to FIG. 9, a liquid film of the first processing liquid 1 made of sulfuric acid is formed on the upper surface of the wafer W placed on the spin chuck 61. In the wafer W, since the first treatment liquid 1 made of sulfuric acid supplied onto the wafer W is held at a temperature higher than room temperature, the temperature of the liquid film formed on the wafer W is the surface of the wafer W. It becomes equal to the high temperature with which the 1st processing liquid supplied to is held.

  When the hydrogen peroxide solution vapor is supplied to the surface of the substrate on which the liquid film held at such a high temperature is formed, the sulfuric acid of the liquid film formed on the substrate surface at the high temperature and the supplied hydrogen peroxide Reacts with water vapor. The vapor of the high-temperature hydrogen peroxide solution causes the chemical reaction shown in the equations (4) and (5) described in the first embodiment, dissociates to generate active oxygen, and further reacts with sulfuric acid. Generates caroic acid.

  Also in the present embodiment, in order to promote the chemical reaction of the above formulas (4) and (5), the liquid film is kept at a high temperature, and the supplied hydrogen peroxide solution forms a liquid film as a vapor. It is desirable to dissolve in sulfuric acid. However, since hydrogen peroxide in the supplied hydrogen peroxide water is easily decomposed at a temperature higher than 100 ° C., for example, 70 ° C. to 100 ° C. is preferable.

  In the present embodiment also, the process of step S22 and the process of step S23 are sequentially repeated to form a liquid film of the first treatment liquid containing sulfuric acid on the substrate, and a liquid film is formed. The process of supplying the hydrogen peroxide solution vapor or mist to the formed surface can be alternately repeated. Supplying the first processing liquid 1 to the surface of the wafer W, forming a liquid film of the first processing liquid on the surface of the wafer W, and supplying vapor or mist of the second processing liquid to the surface of the wafer W The first treatment liquid 1 that has been chemically reacted in contact with the surface of the wafer W and has become less reactive is frequently replaced with an unreacted new first treatment liquid 1 by sequentially repeating the steps. Therefore, the concentration of components effective for substrate processing such as the concentration of caroic acid can be kept constant.

  Finally, step S24 is performed. Step S24 is a step of removing the substrate from the mounting table. FIG. 8D is a schematic cross-sectional view schematically showing the inside of the cup after the step S24 is performed.

  While the supply of the first processing liquid 1 from the processing liquid supply means 63 is stopped, the spin chuck 61 and the wafer W are rotated at a low speed, for example, 35 rpm, and pure water is discharged from a pure water supply source (not shown). Then, this state is performed for a predetermined time (for example, 3 seconds), and the first processing liquid, the second processing liquid, and the resist residue adhering to the surface of the wafer W are washed away.

After performing the rinsing process as described above, N ₂ gas is supplied (injected) to the surface of the wafer W from an N ₂ gas supply nozzle (not shown) to remove water droplets of pure water adhering to the wafer surface. In this case, the drying process can be efficiently performed by adjusting the temperature of the N ₂ gas to be higher than the room temperature by the temperature controller 64g. Further, by combining the rotation of the wafer W and the reciprocating movement of the N ₂ gas supply nozzle in the horizontal direction, the drying process can be performed more quickly. After the drying process, the wafer W is unloaded from the spin chuck 61 and the process ends.
(Modification of the second embodiment)
Next, a substrate processing apparatus and a substrate processing method according to a modification of the second embodiment will be described with reference to FIGS.

  FIG. 10 is a flowchart for explaining the procedure of each step of the substrate processing method according to the present modification. FIG. 11 is a diagram for explaining the substrate processing method according to this modification, and is a schematic cross-sectional view schematically showing the inside of the cup in each step. The state in the cup when or after each of the steps S31 to S34 of FIG. 10 corresponds to the schematic cross-sectional views of FIGS. 11 (a) to 11 (d).

  The substrate processing method according to this modification is the same as the substrate processing apparatus and the substrate processing method according to the second embodiment, instead of applying the first processing liquid held at a temperature higher than normal temperature on the substrate. The first treatment liquid is applied onto a substrate held at a high temperature.

  That is, in this modification, instead of supplying the hydrogen peroxide solution vapor or mist kept at a temperature higher than normal temperature onto the substrate on which the liquid film of the first treatment liquid made of sulfuric acid is formed, the spin chuck 61a A temperature control mechanism 61b is provided to control the temperature of the substrate placed on the spin chuck 61a by heat transfer from the spin chuck 61a.

  As shown in FIG. 10, the substrate processing method according to this modification includes a placement process, a liquid film forming process, a vapor / mist supply process, and a removal process. The placement process includes the process of step S31, the liquid film formation process includes the process of step S32, the steam / mist supply process includes the process of step S33, and the removal process includes the process of step S34.

  First, the mounting process including the process of step S31 is performed. Step S31 is a step of placing the substrate on the spin chuck 61a, which is a placement table, and is the same step as step S21 in the second embodiment. Fig.11 (a) is a schematic sectional drawing which shows typically the mode in the cup after the process of step S21 was performed.

  Next, a liquid film forming process including step S32 is performed. Step S32 is a step of forming a liquid film of the first processing liquid held at a temperature higher than normal temperature on the substrate by supplying the first processing liquid containing sulfuric acid onto the substrate held at a high temperature. . FIG.11 (b) is a schematic sectional drawing which shows typically the mode in a cup at the time of the process of step S32 being performed.

  Step S32 is different from step S22 in the second embodiment. That is, in order to maintain the temperature of the liquid film formed on the surface of the wafer W at a temperature higher than room temperature, in the second embodiment, the temperature of the first processing liquid 1 for forming the liquid film is increased to a high temperature by the temperature controller 63f. Unlike the holding, in this modification, the wafer W on which the liquid film is formed is held at a high temperature of, for example, 150 ° C. by the temperature control mechanism 61b provided in the spin chuck 61a.

  In a state where a predetermined amount of the first processing liquid 1 is discharged from the processing liquid supply nozzle 63a, the spin chuck 61 and the wafer W are rotated at a rotation speed of, for example, 200 rpm, and this state is performed for a predetermined time (for example, 30 seconds). A liquid film of the first processing liquid 1 is formed on the entire surface of the wafer W.

  Next, a steam / mist supply process including step S33 is performed. Step S33 is a step of supplying hydrogen peroxide water as the second processing liquid by vapor or mist to the surface of the substrate on which the liquid film of sulfuric acid is formed as the first processing liquid. Second Embodiment This is the same step as step S23. FIG.11 (c) is a schematic sectional drawing which shows typically the mode in a cup at the time of the process of step S33.

  Finally, step S34 is performed. Step S34 is a step of removing the substrate from the mounting table, and is the same step as step S24 in the second embodiment. FIG.11 (d) is a schematic sectional drawing which shows typically the mode in the cup after the process of step S34 was performed.

  Also in this modification, hydrogen peroxide solution vapor is supplied to the surface of the substrate on which the liquid film held at a high temperature is formed, and the active oxygen generated by the hydrogen peroxide solution reacts with sulfuric acid on the substrate surface. Since caloic acid is generated, the reaction rate is high and the substrate treatment for efficiently removing the resist residue on the substrate surface can be performed while using hydrogen peroxide solution that is easily decomposed at high temperature.

  The preferred embodiments of the present invention have been described above, but the present invention is not limited to such specific embodiments, and various modifications can be made within the scope of the gist of the present invention described in the claims. Can be modified or changed.

  In particular, in the above-described embodiments, the semiconductor wafer is described as an example of the substrate to be processed. .

It is a schematic sectional drawing which shows typically the structure of the substrate processing apparatus which concerns on the 1st Embodiment of this invention. 1 is a perspective view schematically showing a configuration of a substrate processing apparatus of a substrate processing apparatus according to a first embodiment of the present invention. It is a flowchart for demonstrating the procedure of each process of the substrate processing method which concerns on the 1st Embodiment of this invention. It is a figure for demonstrating the substrate processing method which concerns on the 1st Embodiment of this invention, and is a schematic sectional drawing (the 1) which shows typically the mode in the processing container in each process. It is a figure for demonstrating the substrate processing method which concerns on the 1st Embodiment of this invention, and is a schematic sectional drawing (the 2) which shows typically the mode in the processing container in each process. It is a figure for demonstrating the substrate processing method which concerns on the 1st Embodiment of this invention, and is a schematic sectional drawing (the 3) which shows typically the mode in the processing container in each process. It is a figure for demonstrating the substrate processing method which concerns on the 1st Embodiment of this invention, and the vapor | steam of a 2nd process liquid is near the liquid level of the 1st cleaning liquid stored in the processing tank of the pulled-up substrate. -It is a figure which shows a mode that mist is supplied typically. It is a schematic block diagram which shows typically the structure of the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a flowchart for demonstrating the procedure of each process of the substrate processing method of the 2nd Embodiment of this invention. It is a figure for demonstrating the substrate processing method of the 2nd Embodiment of this invention, and is a schematic sectional drawing which shows typically the mode in the cup in each process. It is a figure for demonstrating the substrate processing method of the 2nd Embodiment of this invention, and the vapor | steam and mist of a 2nd process liquid are supplied to the surface in which the liquid film of the 1st process liquid was formed of the board | substrate. It is a figure which shows a mode that it is performed typically. It is a flowchart for demonstrating the procedure of each process of the substrate processing method which concerns on the modification of the 2nd Embodiment of this invention. It is a figure for demonstrating the substrate processing method which concerns on the modification of the 2nd Embodiment of this invention, and is a schematic sectional drawing which shows typically the mode in the cup in each process. It is a schematic block diagram which shows the structure of a general substrate processing apparatus. It is a graph which makes the ratio (molar ratio) of the sulfuric acid with respect to hydrogen peroxide water a horizontal axis, and the production rate of a caroic acid is a vertical axis.

Explanation of symbols

5 Processing container 10 Processing tank 10a, 11a, 67 Drain port 11 Outer tank 12, 53 Drain valve 13, 52, 54 Drain pipe 17 Mesh 18 First processing liquid take-out pipe 19 Resistivity detector 20 First processing Liquid storage tank 24a Upper limit sensor 24b Lower limit sensor 24c Appropriate amount sensor 26 Supply pipe 26a Hydrogen peroxide supply pipe 28 Supply nozzle 29, 63g, 64f On-off valve 30 Wafer boat 31 Substrate elevating mechanism 32 Mounting member 32a Bolt 33 Support member 34 Center holding Bar 35 Side holding rods 34a, 35a Holding grooves 40, 64a Steam / mist supply nozzle (steam / mist supply means)
40a, 42a, 50a Nozzle body 40b, 42b, 50b Nozzle hole 42 Jet nozzle 43 Circulation line 44 Pump 45 Damper 46, 63e, 64e Filter 47, 49, 51 Switch valve 49a First processing liquid supply source 61, 61a Spin Chuck 62 Motor 63 Treatment liquid supply means 63a Treatment liquid supply nozzle 63b Treatment liquid supply source 63c Treatment liquid supply pipe 63d Treatment liquid supply pump 63f, 64g Temperature controller 64 Steam / mist supply means 64b Steam / mist supply source 64c Steam / mist supply Supply line 64d Flow rate controller 65 CPU (control means)
66 Cup 68 Exhaust port 69a, 69b Movement mechanism

Claims (8)

A substrate processing apparatus for processing a substrate using a first processing liquid containing sulfuric acid and a second processing liquid containing hydrogen peroxide.
A treatment tank for storing the first treatment liquid at a temperature higher than room temperature;
A processing container disposed above the processing tank and processing a substrate using the first processing liquid and the second processing liquid;
A substrate lifting mechanism for lifting and lowering the substrate between the processing tank and the processing container;
When the substrate is lifted from the processing tank by the substrate raising / lowering mechanism or immersed in the processing tank, the second treatment liquid is disposed near the liquid surface of the first processing liquid stored in the processing tank of the substrate. A substrate processing apparatus comprising: mist supply means for supplying a mist of a processing solution. An outer tank for receiving the first processing liquid overflowed from the processing tank;
The substrate processing apparatus according to claim 1, further comprising a processing liquid circulating unit that recovers the first processing liquid from the outer tank and supplies the first processing liquid to the processing tank again.   3. The substrate processing apparatus according to claim 2, wherein the mist supply means is provided in the vicinity of the liquid surface of the first processing liquid stored in the processing tank inside the processing container.   The substrate processing apparatus according to claim 3, further comprising an inert gas supply unit that is provided inside the processing container and supplies an inert gas into the processing container.   The substrate processing apparatus according to claim 4, wherein the inert gas supply unit is provided above the mist supply unit. A substrate processing method for processing a substrate using a first processing liquid containing sulfuric acid and a second processing liquid containing hydrogen peroxide.
The substrate held at a temperature higher than room temperature by immersing the substrate in the first treatment liquid held at a temperature higher than room temperature or pulling up the substrate from the first treatment liquid held at a temperature higher than room temperature. A liquid film forming step of forming a liquid film of the first treatment liquid;
And a mist supply step of supplying a mist of the second processing liquid in the vicinity of the liquid surface of the first processing liquid on the substrate.   The substrate processing method according to claim 6, wherein an inert gas is supplied into a processing container for processing the substrate in an airtight manner.   The substrate processing method according to claim 7, wherein the inert gas is supplied from above a mist supply unit that supplies mist of the second processing liquid.

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