TWI888083B - Substrate processing method - Google Patents

Abstract

The substrate processing method of the present invention includes: a step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on the main surface; an oxidant supplying step of supplying an oxidant to the main surface of the substrate; and an organic matter removal step of removing an organic substance existing on the main surface of the substrate by a reaction product between the sulfonic acid group in the polymer film and the oxidant. The removal target substance may include at least one of an anti-etching agent and a residue after dry etching. The oxidant supplying step may supply a liquid or vapor of the oxidant to the main surface of the substrate. The oxidant may include at least one of hydrogen peroxide and ozone.

Description

Substrate processing method

The present invention relates to a substrate processing method for processing a substrate. The substrate to be processed includes, for example, semiconductor wafers, liquid crystal display devices and organic EL (electroluminescence) display devices, FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, mask substrates, ceramic substrates, solar cell substrates, etc.

In the manufacturing process of semiconductor devices, an anti-etching agent (photoresist) is used as a mask for forming a pattern on a substrate or injecting ions into an active area. As a wet treatment for removing the anti-etching agent from a substrate after use, a treatment using a sulfuric acid and hydrogen peroxide mixture (SPM) is known. Specifically, as described in Patent Document 1, sulfuric acid and hydrogen peroxide are mixed to generate SPM, and the SPM is supplied to the surface of the substrate to remove the anti-etching agent on the substrate. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2009-16497

[The problem the invention is trying to solve]

Sulfuric acid is an expensive chemical and also has a high environmental impact. Therefore, from the perspective of reducing treatment costs and environmental impact, it is required to reduce the amount of sulfuric acid used.

One embodiment of the present invention provides a substrate processing method, which can reduce the amount of liquid chemicals (especially sulfuric acid) used and efficiently remove organic substances on the substrate. [Technical means for solving the problem]

One embodiment of the present invention provides a substrate processing method having the following exemplary features.

1. A substrate processing method, comprising: a step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on a main surface; an oxidant supplying step of supplying an oxidant to the main surface of the substrate; and an organic matter removal step of removing an organic matter to be removed on the main surface of the substrate by a reaction product between the sulfonic acid group in the polymer film and the oxidant.

2. The substrate processing method as described in item 1, wherein the above-mentioned removal target substance includes at least one of an anti-etching agent and residues after dry etching.

3. The substrate processing method as described in item 1 or 2, wherein the oxidant supplying step is to supply the liquid or vapor of the oxidant to the main surface of the substrate.

4. The substrate processing method as described in any one of items 1 to 3, wherein the oxidizing agent comprises at least one of hydrogen peroxide and ozone.

5. The substrate processing method as described in item 1 or 2, wherein the oxidant supply step includes at least one of the following steps: A continuous supply step, which is to supply hydrogen peroxide water or ozone water in the form of a continuous flow from a nozzle to the main surface of the substrate; A mist supply step, which is to spray hydrogen peroxide water, ozone water or sulfuric acid hydrogen peroxide water mixture (SPM) from a nozzle in the form of a mist to the main surface of the substrate; and A vapor supply step, which is to mix hydrogen peroxide or ozone with water vapor and supply it to the main surface of the substrate.

6. A substrate processing method as described in item 1 or 2, wherein the polymer film is in a solidified state (e.g., semi-solid or solid) before the oxidant supplying step is started, and the oxidant supplying step includes a liquid oxidant supplying step (continuous flow or mist) of supplying the liquid oxidant to the main surface of the substrate.

7. A substrate processing method as described in item 1 or 2, wherein before the oxidant supplying step begins, the polymer film is in an uncured state (e.g., a flowing state, a liquid state, etc.), and the oxidant supplying step includes an oxidant vapor supplying step of supplying the oxidant vapor to the main surface of the substrate.

8. The substrate processing method as described in any one of items 1 to 7, further comprising a parallel heating step of heating the substrate in parallel with the oxidant supplying step.

9. The substrate processing method as described in item 8, wherein the above-mentioned parallel heating step is started before the above-mentioned oxidizing agent starts to be supplied.

10. A substrate processing method as described in any one of items 1 to 9, wherein the step of preparing the substrate comprises: A polymer coating step, which is to coat a polymer containing sulfonic acid groups (typically a polymer solution) on the main surface of the substrate; A baking step, which is to bake the polymer coated on the main surface of the substrate.

11. The substrate processing method as described in item 10, wherein the polymer coating step is performed in the first chamber, the baking step is performed in the second chamber different from the first chamber, the oxidant supply step is performed in the third chamber different from the first chamber and the second chamber.

12. A substrate processing method as described in any one of items 1 to 11, wherein the step of preparing the substrate is performed by a first substrate processing device, and the step of supplying the oxidant is performed by a second substrate processing device different from the first substrate processing device.

13. A substrate processing method as described in any one of items 1 to 12, wherein the above-mentioned polymer containing sulfonic acid groups comprises at least one of vinyl sulfonic acid-vinyl alcohol copolymer (PVS-VA), vinyl sulfonic acid-styrene copolymer (PVS-St), polyvinyl sulfonic acid (PVS), polystyrene sulfonic acid (PSS), polystyrene partial sulfonate (PS-S), ammonium sulfonate salt and sulfonate metal salt.

The above-mentioned object or other objects, features and effects of the present invention will become clear through the following description of the embodiments described with reference to the attached drawings.

FIG. 1 shows an example of a substrate processing method according to a first embodiment of the present invention, and FIG. 2 shows an example of a substrate processing method according to a second embodiment of the present invention.

The substrate processing method of the first embodiment (FIG. 1) and the second embodiment (FIG. 2) includes: a step of preparing a substrate W having a polymer film P containing a polymer containing a sulfonic acid group on its main surface (FIG. 1(b)(c), FIG. 2(b)(c)); an oxidant supplying step of supplying an oxidant to the main surface of the substrate W (FIG. 1(d), FIG. 2(d)); and an organic matter removal step of removing an organic substance existing on the main surface of the substrate W by a reaction product between the sulfonic acid group in the polymer film P and the oxidant (typically by a chemical reaction between the reaction product and the organic substance) (FIG. 1(d), FIG. 2(d)). The organic matter removal step is typically performed simultaneously with the oxidant supplying step.

The polymer film P is typically a coating film of a polymer material. The polymer film P is typically formed on the outermost surface of the substrate W so as to be exposed in a manner that the polymer film P contacts the oxidant by supplying the oxidant.

The polymer film P may be a liquid film or a cured film. A liquid film is typically a liquid film of a polymer solution formed by dissolving a polymer in a solvent (an example of a coated film). A cured film is typically a film fixed to the main surface of the substrate W by curing such a liquid film (another example of a coated film), for example, formed by reducing fluidity by evaporating the solvent after the liquid film is formed. The cured film may be a semi-cured film in which a solvent remains in a manner that has some fluidity, or a solid film solidified by evaporating most of the solvent.

Typically, there is an organic substance to be removed between the polymer film P and the substrate material (such as silicon). Specifically, the substance to be removed includes at least one of an anti-etching agent and residues after dry etching.

According to the substrate processing method, a reaction product is generated by the reaction of the sulfonic acid group contained in the polymer in the polymer film P disposed on the main surface of the substrate W with the oxidant. The reaction product is a compound based on Caro's acid, and therefore chemically reacts with organic matter to decompose the organic matter. Through the decomposition reaction, the organic removal target substance present on the main surface of the substrate W can be removed from the substrate W. Since the polymer in the polymer film P contains a sulfonic acid group, the organic removal target substance can be decomposed even if sulfuric acid is not supplied to the main surface of the substrate W, and the organic removal performance substantially equivalent to the case where a sulfuric acid-hydrogen peroxide mixed solution (SPM) is continuously supplied to the substrate W can be achieved. The following chemical formula 1 shows an example of a chemical reaction in which a polymer (R-SO ₃ H) having a sulfonic acid group (-SO ₃ H) reacts with an oxidant to generate a reaction product. The following chemical formula 2 shows an example of a chemical reaction in which the reaction product reacts with an organic substance (containing carbon atoms, hydrogen atoms, and oxygen atoms) to decompose the organic substance into a liquid or gas. In these chemical formulas, R means a substituent such as an alkyl group or an aryl group. [Chemistry 1] [Chemistry 2]

The oxidant supplying step may be a liquid oxidant supplying step of supplying a liquid oxidant (liquid oxidant) or an oxidant vapor supplying step (vapor supplying step) of supplying a vapor of the oxidant (oxidant vapor) to the main surface of the substrate W. The liquid oxidant supplying step may be a continuous supplying step of supplying the liquid oxidant in the form of a continuous flow, or may be a mist supplying step of supplying the liquid oxidant in the form of a mist (spray supply). The oxidant preferably includes at least one of hydrogen peroxide and ozone.

In the first embodiment shown in FIG. 1 , the oxidant supplying step is a step of supplying a liquid oxidant (liquid oxidant) to the main surface of the substrate W (see FIG. 1( d )). An example of the liquid oxidant supplying step is a step of supplying hydrogen peroxide water or ozone water to the main surface of the substrate W by spraying it from a nozzle (N2) in the form of a continuous flow. In this case, a carboxylic acid-based compound can be generated on the substrate W without using sulfuric acid to remove the organic removal target substance on the substrate W. In addition, another example of the liquid oxidant supply step is a mist supply step of spraying hydrogen peroxide, ozone water or sulfuric acid hydrogen peroxide mixed solution (SPM) from a spray nozzle (N2) to the main surface of the substrate W. In the mist spraying from the spray nozzle (N2), since the amount of liquid supplied is small, even when the sulfuric acid hydrogen peroxide mixed solution is used, its usage amount is also small, so the usage amount of sulfuric acid can be suppressed. Therefore, the usage amount of sulfuric acid can be suppressed, and a carboxylic acid-based compound is generated on the substrate W to remove the organic removal target substance on the substrate W. When hydrogen peroxide or ozone water is used, there is no need to use sulfuric acid. Therefore, a carboxylic acid-based compound can be generated on the substrate W without using sulfuric acid to remove the organic removal target substance on the substrate W.

In the second embodiment shown in FIG. 2 , the oxidant supply step is an oxidant vapor supply step (steam supply step) in which the oxidant vapor (oxidant vapor) is supplied from the vapor nozzle (N2) to the main surface of the substrate W (see FIG. 2 (d)). The oxidant vapor supply step may be a step in which hydrogen peroxide or ozone is mixed with water vapor and supplied to the main surface of the substrate W. For example, a mixed gas of hydrogen peroxide and water vapor may be generated by passing an inert gas such as nitrogen into hydrogen peroxide. In addition, a mixed gas of ozone and water vapor (wet ozone gas) may be generated by passing ozone gas into water (typically deionized water). By supplying the mixed gases to the vapor nozzle (N2), the mixed gas of hydrogen peroxide or ozone and water vapor can be supplied to the main surface of the substrate W from the vapor nozzle (N2).

When the polymer film P is in a solidified state (semi-solid or solid) before the oxidant supply step starts, the oxidant supply step may be a liquid oxidant supply step of supplying (in the form of a continuous flow or mist) a liquid oxidant to the main surface of the substrate W (see FIG. 1( d )). This can promote the dissolution of the polymer and the reaction between the sulfonic acid group in the polymer and the oxidant, thereby promoting the formation of carboxylic acid-based compounds. This can suppress the amount of sulfuric acid used or eliminate the need to supply sulfuric acid, and efficiently remove the organic removal target on the substrate W.

When the polymer film P is in an uncured state (flowing state, liquid state) before the oxidant supply step is started, the oxidant supply step is preferably an oxidant vapor supply step of supplying oxidant vapor to the main surface of the substrate W (refer to FIG. 2( d)). In this way, the polymer film P can be inhibited from flowing out (dissolving) from the substrate W, while the sulfonic acid group in the polymer reacts with the oxidant efficiently to generate a carboxylic acid-based compound. In this way, the organic removal target substance on the substrate W can be efficiently removed without supplying sulfuric acid. However, the oxidant vapor supply step can also be applied to the case where the polymer film P is in a cured state.

In any of the substrate processing methods of the first and second embodiments, it is preferred to further perform a parallel heating step of heating the substrate W in parallel with the oxidant supply step (see FIG. 1( d ) and FIG. 2( d )). This can promote the reaction between the sulfonic acid group in the polymer and the oxidant, and further promote the reaction between the carboxylic acid-based compound generated by the reaction and the organic substance to be removed. This can efficiently remove the removal target substance.

The parallel heating step may be a step of heating the substrate W by a heater unit 14 (typically a heating plate), which is arranged close to the substrate W in a contact or non-contact manner (see FIG. 1( d) and FIG. 2( d)). In addition, the substrate W may be heated by an infrared lamp or a high-temperature inert gas (e.g., high-temperature nitrogen or high-temperature clean air). Furthermore, the substrate W may be heated by a combination of any two or more of the above.

The parallel heating step is preferably started before the supply of the oxidant is started. This can further promote the reaction between the oxidant and the sulfonic acid group, and the reaction between the carboxylic acid-based compound generated by the reaction and the organic substance to be removed.

The step of preparing the substrate W may include: a polymer coating step (refer to FIG. 1( b) and FIG. 2( b)), which is to coat a polymer containing a sulfonic acid group on the main surface of the substrate W; and a baking step (refer to FIG. 1( c) and FIG. 2( c)), which is to bake the polymer coated on the main surface of the substrate W. In this case, the polymer film P becomes a solidified film (semi-solid or solid). For example, if the baking step (refer to FIG. 2( c)) is omitted, the polymer film P is a liquid film in an unsolidified state before the oxidant supply step starts. In this case, in the oxidant supply step, the oxidant vapor supply step (refer to FIG. 2( d)) is more suitable than the liquid oxidant supply step (refer to FIG. 1( d)).

The polymer coating step (see FIG. 1(b) and FIG. 2(b)), the baking step (see FIG. 1(c) and FIG. 2(c)), the oxidant supply step (see FIG. 1(d) and FIG. 2(d)), and the organic matter removal step (see FIG. 1(d) and FIG. 2(d)) of removing the organic matter can be performed in one chamber. More specifically, in a state where a substrate W is held by a substrate holding unit (substrate holder) (e.g., a rotary chuck 8) holding the substrate W, the polymer coating step, the baking step, the oxidant supply step, and the organic matter removal step can be performed on the substrate W.

After the substrate W is loaded into the rotary chuck 8 in the substrate loading step (refer to Figures 1(a) and 2(a)), the substrate W can be rotated by the rotary chuck 8 while performing the polymer coating step (refer to Figures 1(b) and 2(b)), the baking step (refer to Figures 1(c) and 2(c)), the oxidant supply step (refer to Figures 1(d) and 2(d)) and the organic matter removal step (refer to Figures 1(d) and 2(d)).

For example, the polymer coating step (see FIG. 1(b) and FIG. 2(b)) can be a rotation coating step in which the substrate W is rotated by a rotary chuck 8 (for example, at a rotation speed of 10 to 3000 rpm) while the polymer solution is supplied to the main surface of the substrate W, and the polymer solution is coated on the main surface of the substrate W by centrifugal force.

The baking step (FIG. 1(c) and FIG. 2(c)) may be a step of heating the substrate W by the heater unit 14. When the heater unit 14 is in contact with the substrate W, it is preferable to stop the rotation of the substrate W. When the heater unit 14 and the substrate W are heated in a non-contact state, the substrate W may be in a rotating state.

In the oxidant supply step and the organic matter removal step performed simultaneously therewith (see FIG. 1( d ) and FIG. 2( d )), it is preferred that the substrate W is rotated by the rotary chuck 8 (for example, at a rotation speed of 10 to 3000 rpm) while the substrate W is heated by the heater unit 14 in parallel. In this case, the substrate W and the heater unit are preferably in non-contact.

After the oxidant supply step and the organic matter removal step (see FIG. 1(d) and FIG. 2(d)) performed simultaneously therewith, it is preferred to perform the following rinsing step (see FIG. 1(e) and FIG. 2(e)), that is, supply a rinsing liquid to the main surface of the substrate W to rinse the processing liquid (oxidant, reaction product, etc.) and the residue of the removal target substance on the substrate W out of the main surface of the substrate W. In the rinsing step, it is preferred to rotate the substrate W by the rotary chuck 8 (for example, at a rotation speed of 10 to 3000 rpm) to utilize the effect of centrifugal force.

Furthermore, preferably, after the rinsing step, a drying step is performed to remove the liquid components on the substrate W (see FIG. 1( f) and FIG. 2( f)). The drying step may be a rotary drying step in which the rotary chuck 8 is rotated at a drying speed (eg, 10 to 3000 rpm).

The polymer containing a sulfonic acid group is preferably at least one selected from the group consisting of vinyl sulfonic acid-vinyl alcohol copolymer (PVS-VA), vinyl sulfonic acid-styrene copolymer (PVS-St), polyvinyl sulfonic acid (PVS), polystyrene sulfonic acid (PSS), polystyrene partial sulfonate (PS-S), ammonium sulfonate (R-SO ₃ NH ₄ ) and metal sulfonate (R-SO ₃ M). M represents a metal, typically comprising one of Li, Na and K. By using these polymers, a carboxylic acid-based compound can be generated by reacting with an oxidant.

The following chemical formula 3 shows a part of the above polymer (R-SO ₃ H). [Chemical 3]

As shown in the following chemical formula 4, ammonium sulfonate (R-SO ₃ NH ₄ ) ionizes into R-SO ₃ ^- and NH ₄ ⁺ in aqueous solution, and generates NH ₃ (ammonia) and R-SO ₃ H under heating conditions. As shown in the following chemical formula 5, metal sulfonate (R-SO ₃ M) ionizes into R-SO ₃ ^- and M ⁺ in aqueous solution. [Chemistry 4] [Chemistry 5]

Therefore, by supplying an oxidizing agent, a reaction product based on carboxylic acid can be generated through the reaction of the following chemical formula 6. [Chemical formula 6]

Furthermore, in processes where metal contamination is an issue, it is best to avoid the use of metal sulfonates.

The polymer coating step (see FIG. 1(b) and FIG. 2(b)), the baking step (see FIG. 1(c) and FIG. 2(c)), and the oxidant supply step (see FIG. 1(d) and FIG. 2(d)) can be performed in one chamber. In addition, the polymer coating step (see FIG. 1(b) and FIG. 2(b)) can be performed in the first chamber, the baking step (see FIG. 1(c) and FIG. 2(c)) can be performed in the second chamber different from the first chamber, and the oxidant supply step (see FIG. 1(d) and FIG. 2(d)) can be performed in the third chamber different from the first chamber and the second chamber.

In addition, the step of preparing the substrate W (see Figures 1(b)(c) and 2(b)(c)) can be performed by a first substrate processing device, and the step of supplying the oxidant (see Figures 1(d) and 2(d)) can be performed by a second substrate processing device that is different from the first substrate processing device.

FIG3 is a schematic top view for explaining a configuration example of a substrate processing apparatus 1 for executing a substrate processing method according to an embodiment of the present invention. The substrate processing apparatus 1 is a single-chip apparatus for processing substrates W one by one. In the embodiment, the substrate W has a disk shape. The substrate W is a substrate W such as a silicon wafer, and has a pair of main surfaces.

The substrate processing device 1 includes: a plurality of processing units 2, which process substrates W; a loading port LP (container holding unit) for placing a carrier C (container), which holds a plurality of substrates W processed by the processing unit 2; a transfer robot (in this example, the first transfer robot IR and the second transfer robot CR), which transfers the substrates W between the loading port LP and the processing unit 2; and a controller 3, which controls the various components of the substrate processing device 1.

The first transfer robot IR transfers the substrate W between the carrier C and the second transfer robot CR. The second transfer robot CR transfers the substrate W between the first transfer robot IR and the processing unit 2. Each transfer robot is, for example, a multi-joint arm robot.

The plurality of processing units 2 are arranged on both sides of the transport path TR along which the second transport robot CR transports the substrate W, and are arranged in layers in the vertical direction. The plurality of processing units 2 have, for example, the same configuration.

The plurality of processing units 2 form four processing towers TW respectively arranged at four positions separated horizontally. Each processing tower TW includes a plurality of processing units 2 stacked in the vertical direction. The four processing towers TW are arranged in units of two on both sides of the transport path TR extending from the loading port LP toward the second transport robot CR.

The substrate processing apparatus 1 includes: a plurality of fluid boxes 4, which contain valves or pipes, etc.; and a storage box 5, which contains chemical solution, rinse solution, organic solvent, or a tank for storing these raw materials. The processing unit 2 and the fluid box 4 are arranged inside a frame 6 which is roughly quadrilateral in plan view.

The processing unit 2 has a chamber 7 for accommodating a substrate W during substrate processing. The chamber 7 includes an inlet and outlet (not shown) for carrying the substrate W into or out of the chamber 7 by the second transfer robot CR, and a shutter unit (not shown) for opening and closing the inlet and outlet. The processing liquid supplied to the substrate W in the chamber 7 is described in detail below, but examples thereof include a chemical solution, a rinse solution, an organic solvent, and the like.

Fig. 4 is a schematic diagram for explaining a configuration example of the processing unit 2, and shows a configuration example for executing the substrate processing method of the first embodiment shown in Fig. 1. The processing unit 2 includes: a rotary chuck 8, which holds the substrate W in a predetermined processing posture while rotating the substrate W around a rotation axis A1; and a plurality of nozzles (a first moving nozzle N1, a second moving nozzle N2, a third moving nozzle N3, and a fourth moving nozzle N4) which spray a processing liquid toward the substrate W.

The processing unit 2 further includes: a heater unit 14 that heats the substrate W held by the rotary chuck 8; and a processing cup 15 that receives the processing liquid scattered from the substrate W held by the rotary chuck 8.

The rotary chuck 8, a plurality of movable nozzles, a heater unit 14, and a processing cup 15 are disposed in the chamber 7.

The rotation axis A1 passes through the center of the substrate W and is orthogonal to each main surface of the substrate W held in a processing posture. The processing posture is, for example, the posture of the substrate W shown in FIG. 4 , which is a horizontal posture in which the main surface of the substrate W becomes a horizontal plane, but is not limited to the horizontal posture. That is, the processing posture may be different from FIG. 4 , and may be a posture in which the main surface of the substrate W is inclined relative to the horizontal plane. When the processing posture is a horizontal posture, the rotation axis A1 extends straight.

The rotary chuck 8 is an example of a substrate holding member (substrate holding unit, substrate holder) that holds the substrate W in a processing posture, and is also an example of a rotation holding member that rotates the substrate W around the rotation axis A1 while holding the substrate W in a processing posture.

The rotary chuck 8 includes: a rotary base 21 having a disk shape along the horizontal direction; a plurality of holding pins 20 holding the substrate W above the rotary base 21 and holding the peripheral portion of the substrate W above the rotary base 21; a rotary shaft 22 connected to the rotary base 21 and extending in the vertical direction; and a rotary drive mechanism 23 that rotates the rotary shaft 22 around its central axis (rotation axis A1). The rotary base 21 is an example of a disk-shaped base.

The plurality of holding pins 20 are arranged on the upper surface of the rotating base 21 at intervals in the circumferential direction of the rotating base 21. The rotating drive mechanism 23 includes an actuator such as an electric motor. The rotating drive mechanism 23 rotates the rotating base 21 and the plurality of holding pins 20 around the rotating axis A1 by rotating the rotating shaft 22. Thereby, the substrate W rotates around the rotating axis A1 together with the rotating base 21 and the plurality of holding pins 20.

The plurality of holding pins 20 can move between a closed position where the pins 20 contact the periphery of the substrate W to hold the substrate W and an open position where the pins 20 release the substrate W. The plurality of holding pins 20 are moved by an opening and closing mechanism (not shown).

When the plurality of holding pins 20 are in the closed position, they hold the periphery of the substrate W and keep the substrate W horizontal. When the plurality of holding pins 20 are in the open position, they release the holding of the substrate W and support the periphery of the substrate W from below. The opening and closing mechanism includes, for example, a link mechanism and an actuator that applies a driving force to the link mechanism.

The plurality of movable nozzles include: a first movable nozzle N1, which sprays a polymer solution toward the upper surface (upper main surface) of the substrate W held by the rotary chuck 8; a second movable nozzle N2, which sprays a liquid oxidizer toward the upper surface of the substrate W held by the rotary chuck 8; a third movable nozzle N3, which selectively sprays a continuous flow of a chemical solution and a continuous flow of a rinse solution toward the upper surface of the substrate W held by the rotary chuck 8; and a fourth movable nozzle N4, which sprays an organic solvent toward the upper surface of the substrate W held by the rotary chuck 8.

The first movable nozzle N1 is an example of a polymer solution nozzle that supplies a polymer solution toward the main surface (upper surface) of the substrate W held by the rotary chuck 8. The second movable nozzle N2 is an example of a liquid oxidant nozzle that sprays a liquid oxidant toward the main surface (upper surface) of the substrate W held by the rotary chuck 8. The second movable nozzle N2 may be a straight nozzle that sprays the liquid oxidant in the form of a continuous flow, or may be a spray nozzle that sprays the liquid oxidant in the form of a mist (i.e., droplet state). The spray nozzle may be a two-fluid nozzle that mixes and sprays a liquid oxidant and an inert gas (nitrogen or clean air). The third movable nozzle N3 is an example of a liquid nozzle that sprays a liquid toward the main surface (upper surface) of the substrate W held by the rotary chuck 8, and is an example of a rinse liquid nozzle that sprays a rinse liquid toward the main surface (upper surface) of the substrate W held by the rotary chuck 8. The fourth movable nozzle N4 is an example of an organic solvent nozzle that sprays an organic solvent toward the main surface (upper surface) of the substrate W held by the rotary chuck 8.

The plurality of movable nozzles are moved in the horizontal direction respectively by a plurality of nozzle driving mechanisms (a first nozzle driving mechanism 24, a second nozzle driving mechanism 25, a third nozzle driving mechanism 26, and a fourth nozzle driving mechanism 27).

Each nozzle driving mechanism can move the corresponding movable nozzle between a processing position and a retreat position. The processing position is typically a central position where the movable nozzle is opposite to the central area of the upper surface of the substrate W. The central area of the upper surface of the substrate W refers to an area on the upper surface of the substrate W including the rotation center (central part) and the peripheral part of the rotation center. The retreat position is a position where the movable nozzle is not opposite to the upper surface of the substrate W and is a position outside the processing cup 15.

Each nozzle driving mechanism includes: an arm (the first arm 24a, the second arm 25a, the third arm 26a and the fourth arm 27a) that supports the corresponding movable nozzle; and an arm driving mechanism (the first arm driving mechanism 24b, the second arm driving mechanism 25b, the third arm driving mechanism 26b and the fourth arm driving mechanism 27b) that moves the corresponding arm in the horizontal direction. Each arm driving mechanism includes an actuator such as an electric motor and a cylinder.

The movable nozzle may be a rotary nozzle that rotates around a predetermined rotation axis, or a linear nozzle that moves linearly in the direction in which the corresponding arm extends. The movable nozzle may be configured to be movable in a linear direction.

The processing unit 2 includes a polymer solution supply unit 9 for supplying a polymer solution to a substrate W held by a rotary chuck 8. The polymer solution supply unit 9 includes a first movable nozzle N1, a polymer solution pipe 40, a polymer solution valve 50A, and a polymer solution flow rate regulating valve 50B.

The polymer solution pipe 40 is connected to the polymer solution supply source and the first moving nozzle N1 , and guides the polymer solution from the polymer solution supply source to the first moving nozzle N1 . The polymer solution valve 50A and the polymer solution flow rate regulating valve 50B are provided in the polymer solution pipe 40 .

The polymer solution valve 50A is disposed in the polymer solution pipe 40, which may also mean that the polymer solution valve 50A is installed in the polymer solution pipe 40. The same is true for other valves described below.

The polymer solution valve 50A opens and closes the flow path in the polymer solution piping 40. The polymer solution flow rate regulating valve 50B regulates the flow rate of the polymer solution flowing through the flow path in the polymer solution piping 40. When the polymer solution valve 50A is opened, the polymer solution is supplied to the first movable nozzle N1 at the flow rate regulated by the polymer solution flow rate regulating valve 50B.

Although not shown, the polymer solution valve 50A includes: a valve body having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator that moves the valve body between an open position and a closed position. Other valves also have the same configuration.

The processing unit 2 further includes a liquid oxidant supply unit 10 (an example of an oxidant supply unit) that supplies liquid oxidant to the substrate W held by the rotary chuck 8. The liquid oxidant supply unit 10 includes a second movable nozzle N2, a liquid oxidant pipe 45, a liquid oxidant valve 55A, and a liquid oxidant flow rate regulating valve 55B.

The liquid oxidant pipe 45 is connected to the liquid oxidant supply source and the second movable nozzle N2, and guides the liquid oxidant from the liquid oxidant supply source to the second movable nozzle N2. The liquid oxidant valve 55A and the liquid oxidant flow regulating valve 55B are provided in the liquid oxidant pipe 45. The liquid oxidant valve 55A opens and closes the flow path in the liquid oxidant pipe 45. The liquid oxidant flow regulating valve 55B regulates the flow rate of the liquid oxidant flowing through the flow path in the liquid oxidant pipe 45. When the liquid oxidant valve 55A is opened, the liquid oxidant is supplied to the second movable nozzle N2 at the flow rate adjusted by the liquid oxidant flow rate adjusting valve 55B.

The chemical liquid sprayed from the third movable nozzle N3 may be, for example, APM liquid (ammonia-hydrogen peroxide mixture, more specifically, SC1). In addition, chemical liquids containing hydrofluoric acid (HF), dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid (HCl), HPM liquid (hydrochloric acid-hydrogen peroxide mixture), ammonia water, TMAH liquid (Tetramethylammonium hydroxide solution), or hydrogen peroxide (H ₂ O ₂ ) may be sprayed from the third movable nozzle N3.

The rinse liquid sprayed from the third movable nozzle N3 is, for example, deionized water (DIW) or other water. However, the rinse liquid is not limited to deionized water, and may be deionized water, carbonated water, electrolytic water, hydrochloric acid water of dilute concentration (e.g., 1 ppm or more and 100 ppm or less), ammonia water of dilute concentration (e.g., 1 ppm or more and 100 ppm or less), or reducing water (hydrogen water), or a mixed solution containing at least two of these.

The third moving nozzle N3 is connected to a common pipe 41 that guides fluid to the third moving nozzle N3. A liquid pipe 42 that supplies liquid medicine to the common pipe 41 and a flushing liquid pipe 43 that supplies flushing liquid to the common pipe 41 are connected to the common pipe 41. The common pipe 41 may also be connected to the liquid pipe 42 and the flushing liquid pipe 43 via a mixing valve (not shown).

The common pipe 41 is provided with a common valve 51 for opening and closing the common pipe 41. The chemical pipe 42 is provided with a chemical valve 52A for opening and closing the chemical pipe 42, and a chemical flow regulating valve 52B for regulating the flow of the chemical in the chemical pipe 42. The flushing liquid pipe 43 is provided with a flushing liquid valve 53A for opening and closing the flushing liquid pipe 43, and a flushing liquid flow regulating valve 53B for regulating the flow of the flushing liquid in the flushing liquid pipe 43.

When the liquid medicine valve 52A and the common valve 51 are opened, a continuous flow of liquid medicine is ejected from the third movable nozzle N3. The third movable nozzle N3 as the liquid medicine nozzle, the liquid medicine pipe 42, the liquid medicine valve 52A, the liquid medicine flow rate adjustment valve 52B, the common valve 51, etc. constitute a liquid medicine supply unit for supplying liquid medicine from a liquid medicine supply source to the substrate W held by the rotary chuck 8.

When the rinse liquid valve 53A and the common valve 51 are opened, a continuous flow of rinse liquid is ejected from the third movable nozzle N3. The third movable nozzle N3 as a rinse liquid nozzle, the rinse liquid pipe 43, the rinse liquid valve 53A, the rinse liquid flow rate adjustment valve 53B, the common valve 51, etc. constitute a rinse liquid supply unit that supplies the rinse liquid from the rinse liquid supply source to the substrate W held by the rotary chuck 8.

The organic solvent sprayed from the fourth movable nozzle N4 contains at least one of the following: alcohols such as ethanol (EtOH) and isopropyl alcohol (IPA); ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE); lactic acid esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone.

The fourth movable nozzle N4 is connected to an organic solvent pipe 44 for guiding the organic solvent to the fourth movable nozzle N4. The organic solvent pipe 44 is provided with an organic solvent valve 54A for opening and closing the organic solvent pipe 44 and an organic solvent flow regulating valve 54B for regulating the flow rate of the organic solvent in the organic solvent pipe 44. The fourth movable nozzle N4 as an organic solvent nozzle, the organic solvent pipe 44, the organic solvent valve 54A, the organic solvent flow rate adjustment valve 54B, etc. constitute an organic solvent supply unit that supplies the organic solvent from the organic solvent supply source to the substrate W held by the rotary chuck 8.

The processing cup 15 includes: a plurality of (3 in FIG. 4 ) baffles 28 for receiving the processing liquid flying outward from the substrate W held by the rotary chuck 8; a plurality of (3 in FIG. 4 ) cups 29 for receiving the processing liquid guided downward by the plurality of baffles 28; and a cylindrical outer wall member 30 that surrounds the plurality of baffles 28 and the plurality of cups 29.

Each baffle 28 has a cylindrical shape surrounding the rotating chuck 8 in a top view. The upper end of each baffle 28 is inclined inwardly toward the center side of the baffle 28. Each cup 29 has a shape of an annular groove open upward. The plurality of baffles 28 and the plurality of cups 29 are arranged on the same axis.

The plurality of baffles 28 are individually raised and lowered by a baffle lifting drive mechanism (not shown). The baffle lifting drive mechanism, for example, includes a plurality of actuators that drive the plurality of baffles 28 to be raised and lowered individually. The plurality of actuators include at least one of an electric motor and a pneumatic cylinder.

The processing unit 2 includes: an air supply unit 31 such as FFU (Fan Filter Units) that delivers inert gas from outside the chamber 7 to inside the chamber 7; and an exhaust pipe 32 that exhausts the chamber 7. The air supply unit 31 is disposed on the upper wall 7a of the chamber 7. The exhaust pipe 32 is connected to the outer wall member 30. The inert gas delivered to the chamber 7 by the air supply unit 31 can be, for example, nitrogen, a rare gas, or a mixed gas thereof. The rare gas is, for example, argon.

The exhaust pipe 32 is connected to an exhaust pipe (not shown). The gas in the exhaust pipe is sucked by a suction device (not shown). The gas in the chamber 7 is discharged to the exhaust pipe through the exhaust pipe 32. The suction device includes a suction pump for sucking the exhaust pipe. The suction device is installed in the exhaust pipe or connected to the exhaust pipe. The exhaust pipe and the suction device are arranged at the following location: a clean room where the substrate processing device 1 is installed or in equipment attached to the clean room. The exhaust pipe and the suction device can also be part of the substrate processing device 1.

The air supply unit 31 and the exhaust pipe 32 form an air flow from the upper side to the lower side in the inner space 7 c of the chamber 7 . The air flow passes through the inside of the processing cup 15 and flows into the exhaust pipe 32 .

The processing liquid supplied to the substrate W is scattered from the periphery of the substrate W and received by any baffle 28. The processing liquid received by the baffle 28 is guided to the corresponding cup 29, and is recovered or discarded through the drain pipe 35 corresponding to each cup 29.

In this embodiment, the heater unit 14 is in the form of a circular plate-shaped heating plate for heating the substrate W from below. The heater unit 14 is disposed between the upper surface of the rotating base 21 and the lower surface of the substrate W. The heater unit 14 has a heating surface 14a facing the lower surface of the substrate W from below.

The heater unit 14 includes a plate body 60 and a heater 61. The plate body 60 is slightly smaller than the substrate W in a plan view. The upper surface of the plate body 60 constitutes a heating surface 14a. The heater 61 may be a resistor built into the plate body 60. By energizing the heater 61, the heating surface 14a is heated.

The heater 61 is configured to heat the substrate W within a temperature range of a room temperature (eg, a temperature of 5° C. or higher and 25° C. or lower) and, for example, 400° C. or lower.

The processing unit 2 further includes a temperature sensor 62, which detects the temperature of the heater unit 14. In the example shown in FIG4, the temperature sensor 62 is built into the board body 60, but the arrangement of the temperature sensor 62 is not particularly limited. The temperature sensor 62 may also be mounted on the board body 60 from the outside, for example.

The heater 61 is connected to a power supply unit 63 via a feed line 64. The temperature of the heater 61 is adjusted by adjusting the current supplied from the power supply unit 63 to the heater 61. For example, the current supplied from the power supply unit 63 to the heater 61 is adjusted based on the temperature detected by the temperature sensor 62.

A heater lifting shaft 65 is connected to the lower surface of the heater unit 14. The heater lifting shaft 65 is inserted into a through hole 21a formed in the center of the rotating base 21 and the inner space of the rotating shaft 22.

The processing unit 2 further includes a heater drive mechanism 66 that drives the heater unit 14 to move in the up-down direction. The heater drive mechanism 66, for example, includes a heater actuator (not shown) that drives the heater lift shaft 65 to move in the up-down direction. The heater actuator, for example, includes at least one of an electric motor and a cylinder. The heater drive mechanism 66 moves the heater unit 14 in the up-down direction via the heater lift shaft 65. The heater unit 14 can move in the up-down direction between the lower surface of the substrate W and the upper surface of the rotating base 21.

When the heater unit 14 is raised, it can receive the substrate W from the plurality of holding pins 20 located in the open position. The heater unit 14 can heat the substrate W by arranging the heating surface 14a at a contact position in contact with the lower surface of the substrate W or at a proximity position close to the lower surface of the substrate W in a non-contact manner. The position where the heater unit 14 is sufficiently retreated from the lower surface of the substrate W to a degree where the heating of the substrate W by the heater unit 14 is relieved is referred to as a retreat position. The heating of the substrate W being sufficiently relieved can be referred to as stopping the heating of the substrate W.

When the heater unit 14 is arranged at the retreat position, the amount of heat transferred from the heater unit 14 to the substrate W is less than the amount of heat transferred from the heater unit 14 to the substrate W when the heater unit 14 is arranged at the approach position. The contact position and the approach position are also referred to as heating positions. The retreat position is also referred to as a heating mitigation position, and is also referred to as a heating stop position.

Fig. 5 is a schematic diagram for explaining another configuration example of the processing unit 2, and shows a configuration example for executing the substrate processing method of the second embodiment shown in Fig. 2. In Fig. 5, the corresponding parts of the parts shown in Fig. 4 are marked with the same reference symbols and the description is omitted.

This configuration example includes an oxidant vapor supply unit 110 for supplying oxidant vapor (oxidant vapor) instead of the liquid oxidant supply unit 10 (see FIG. 4 ). In this configuration example, the second movable nozzle N2 is an example of an oxidant vapor nozzle for supplying oxidant vapor to the main surface of the substrate W held by the rotary chuck 8. The oxidant vapor supply unit 110 (an example of an oxidant supply unit) supplies oxidant vapor to the main surface of the substrate W from an oxidant vapor supply source. The oxidant vapor supply unit 110 includes: an oxidant vapor piping 145 connected to the oxidant vapor supply source and the second movable nozzle N2; and an oxidant vapor valve 155A and an oxidant vapor flow rate regulating valve 155B, which are provided in the oxidant vapor piping 145. The oxidant vapor valve 155A opens and closes the flow path in the oxidant vapor piping 145. The oxidant vapor flow rate regulating valve 155B regulates the flow rate of the oxidant vapor flowing through the oxidant vapor piping. By opening the oxidant vapor valve 155A, the oxidant vapor is sprayed from the second movable nozzle N2 at a flow rate adjusted by the oxidant vapor flow rate regulating valve 155B. The opening and closing of the oxidant vapor valve 155A and the opening degree of the oxidant vapor flow rate regulating valve 155B are controlled by the controller 3 (see FIG. 6 ).

The oxidant vapor supply source may be configured to supply a mixed gas of an oxidant and water vapor as the oxidant vapor. The oxidant may include hydrogen peroxide or ozone, or may include two or more oxidants.

For example, the oxidant supply source may also be configured as a tank for storing hydrogen peroxide, and a nitrogen pipe for supplying an inert gas (e.g., nitrogen, clean air, etc.) to the hydrogen peroxide stored in the tank, and the inert gas flowing out of the nitrogen pipe is introduced into the hydrogen peroxide. According to this configuration, an oxidant vapor containing a mixed gas of hydrogen peroxide and water vapor is generated in the space above the liquid level of hydrogen peroxide. Therefore, by configuring the tank as a closed container and connecting the space above the liquid level of hydrogen peroxide to the oxidant vapor pipe 145 in the tank, an oxidant vapor containing a mixed gas of hydrogen peroxide and water vapor can be supplied. Furthermore, according to the structure of heating the hydrogen peroxide solution stored in the tank, a mixed gas of hydrogen peroxide and water vapor can be generated above the liquid surface of the hydrogen peroxide solution.

In addition, the oxidant supply source may also be configured as a tank having water (typically deionized water) stored therein, and an ozone gas pipe for supplying ozone gas to the water stored in the tank, and passing ozone gas flowing out of the ozone gas pipe into the water. With this configuration, oxidant vapor containing a mixed gas of ozone and water vapor, i.e., moist ozone gas, is generated in the space above the water surface. Therefore, by configuring the tank as a closed container and connecting the space above the water surface to the oxidant vapor pipe 145 in the tank, oxidant vapor containing moist ozone gas can be supplied.

An ozone removal device 33 (ozone remover) is provided between the exhaust pipe 32 and the exhaust pipe, or in the exhaust pipe 32. Ozone gas contained in the gas exhausted from the chamber 7 is decomposed when passing through the ozone removal device 33.

Fig. 6 is a block diagram for explaining the electrical structure of the substrate processing device 1. The controller 3 is a computer including a computer body 3a and a peripheral device 3d connected to the computer body 3a. The computer body 3a includes a processor (CPU, Central Processing Unit) 3b for executing various commands and a memory 3c for storing information.

The peripheral device 3d includes: an auxiliary storage device 3e that stores information such as programs; a reading device 3f that reads information from a removable medium (not shown); and a communication device 3g that communicates with other devices such as a host computer (not shown).

The controller 3 is connected to the input device 3A, the display device 3B, and the alarm device 3C. The input device 3A is operated by an operator such as a user or a maintenance person when inputting information to the substrate processing device 1. The information is displayed on the screen of the display device 3B. The input device 3A can be any one of a keyboard, a pointing device, and a touch panel, or a device other than these. A touch panel display that serves as both the input device 3A and the display device 3B can also be provided in the substrate processing device 1. The alarm device 3C uses one or more of light, sound, text, and graphics to issue an alarm. When the input device 3A is a touch panel display, the input device 3A can also serve as the alarm device 3C.

The auxiliary memory device 3e is a non-volatile memory that retains memory even when no power is supplied. The auxiliary memory device 3e is, for example, a magnetic memory device such as a hard disk.

The auxiliary memory device 3e stores a plurality of recipes. The recipe is information that specifies the processing content, processing conditions, and processing steps of the substrate W. The plurality of recipes are different from each other in at least one of the processing content, processing conditions, and processing steps of the substrate W.

The controller 3 controls each component of the substrate processing apparatus 1 so that the substrate W is processed according to a recipe specified by an external device such as a host computer.

The objects to be controlled by the controller 3 include: the first transport robot IR, the second transport robot CR, the rotation drive mechanism 23, the first nozzle drive mechanism 24, the second nozzle drive mechanism 25, the third nozzle drive mechanism 26, the fourth nozzle drive mechanism 27, the heater drive mechanism 66, the power supply unit 63, the air supply unit Element 31, temperature sensor 62, heater 61, polymer solution valve 50A, polymer solution flow regulating valve 50B, common valve 51, chemical solution valve 52A, chemical solution flow regulating valve 52B, flushing liquid valve 53A, flushing liquid flow regulating valve 53B, organic solvent valve 54A, organic solvent flow regulating valve 54B, etc. When the configuration example of FIG. 4 is applied, the control object of controller 3 further includes liquid oxidant valve 55A and liquid oxidant flow regulating valve 55B. Moreover, when the configuration example of FIG. 5 is applied, the control object of controller 3 further includes oxidant vapor valve 155A and oxidant vapor flow regulating valve 155B.

6 , although representative components are shown, it does not mean that components not shown are not controlled by the controller 3 . The controller 3 can appropriately control each component of the substrate processing apparatus 1 .

Each step described with reference to the following FIG7 and FIG8 is executed by controlling the substrate processing apparatus 1 through the controller 3. In other words, the controller 3 is programmed in such a manner as to execute each of the following steps.

FIG. 7 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1. The substrate processing is an example of the case where the processing unit 2 of the configuration example shown in FIG. 4 is used, and is an example of substrate processing of the second embodiment shown in FIG. 2 mentioned above. The example of substrate processing is explained while referring to FIG. 1 mentioned above.

An anti-etchant (typically a film-like anti-etchant) is formed on at least one of the main surfaces of a substrate W used in substrate processing. The anti-etchant is typically an organic material and can be an anti-etchant used as a mask in a pattern forming process (dry etching or wet etching) or an ion implantation process. The anti-etchant is an example of an organic substance to be removed from the main surface of the substrate W. Instead of the anti-etchant, polymer residues as residues after dry etching may exist on the main surface of the substrate W, or in addition to the anti-etchant, polymer residues as residues after dry etching may exist. Polymer residues are another example of an organic substance to be removed from the main surface of the substrate W.

In the substrate processing performed by the substrate processing device 1, for example, a substrate carrying-in step (step S1), a polymer coating step (step S2), a baking step (step S3), a liquid oxidant supplying step (step S4A), a parallel heating step (step S5), a rinsing step (step S6), an organic solvent supplying step (step S7), a drying step (step S8) and a substrate carrying-out step (step S9) are performed.

The unprocessed substrate W is transported from the carrier C to the processing unit 2 by the transport robots IR and CR (see FIG. 3 ), and is handed over to the rotary chuck 8 as shown in FIG. 1( a) (substrate carrying step: step S1). Thus, the substrate W is held horizontally by the rotary chuck 8 (substrate holding step). At this time, the substrate W is held by the rotary chuck 8 in such a manner that the main surface formed with the anti-etching agent (the main surface formed with the organic removal target substance) becomes the upper surface. The substrate W is continuously held by the rotary chuck 8 until the drying step (step S8) is completed.

With the substrate W held by the rotary chuck 8, the rotary drive mechanism 23 starts rotating the substrate W (substrate rotating step). During the substrate processing, an airflow from top to bottom is continuously formed in the inner space 7c of the chamber 7, and the airflow passes through the inside of the processing cup 15 and flows into the exhaust pipe 32.

On the other hand, the first nozzle driving mechanism 24 moves the first movable nozzle N1 to a processing position (e.g., a central position) where the first movable nozzle N1 faces the main surface of the substrate W (the main surface on which the anti-etching agent is formed) and can supply the polymer solution to the main surface of the substrate W.

When the first movable nozzle N1 is located at the processing position, the polymer solution valve 50A is opened, thereby starting to supply the polymer solution to the first movable nozzle N1. Thus, the polymer solution is ejected from the first movable nozzle N1 and supplied to the upper surface of the rotating substrate W. Thus, as shown in FIG. 1(b), the polymer solution is applied to the upper surface of the substrate W (the main surface on which the anti-etching agent is formed), and a liquid film of the polymer solution (polymer film P) is formed on the upper surface of the substrate W (step S2). The liquid film of the polymer solution is in direct contact with the anti-etching agent formed on the main surface of the substrate W.

During the polymer coating step (step S2), the first nozzle driving mechanism 24 typically stops the first movable nozzle N1 at a position (central position) where the polymer solution lands on the rotation center of the substrate W. However, if necessary, the first nozzle driving mechanism 24 may also move the first movable nozzle N1 along the rotation radius direction so that the landing point of the polymer solution on the upper surface of the substrate W moves along the radius direction of the substrate W.

When a predetermined time has passed after the start of supplying the polymer solution, the polymer solution valve 50A is closed to stop supplying the polymer solution from the first moving nozzle N1 to the upper surface of the substrate W.

After stopping the ejection of the polymer solution, the first nozzle driving mechanism 24 causes the first movable nozzle N1 to retreat to a retreat position set outside the substrate W. On the other hand, by heating the substrate W, a baking step is performed to bake the polymer, i.e., the liquid film of the polymer solution, coated on the main surface of the substrate W (step S3).

Specifically, the heater 61 starts to increase in temperature by supplying current to the power supply unit 63. In addition, the heater drive mechanism 66 moves the heater unit 14 from the retreat position to the baking treatment position. For example, the baking treatment position may be a contact position where the heating surface 14a of the heater unit 14 contacts the lower surface of the substrate W (the main surface opposite to the main surface on which the anti-etching agent is formed). In this case, the rotation of the substrate W is stopped, and contact heating is performed by bringing the heater unit 14 into contact with the substrate W in the rotation-stopped state to perform heat transfer. In addition, the baking treatment position may be a close position where the heating surface 14a of the heater unit 14 is located below the lower surface of the substrate W at a slight distance. In this case, the substrate W can continue to rotate while the heater unit 14 performs non-contact heating (heating by convection and radiation heat of the surrounding gas) on the rotating substrate W.

By baking for a predetermined time, the solvent in the polymer liquid film evaporates, and a polymer film P (cured film, see FIG. 1(c) ) formed by solidifying the polymer solution is formed on the main surface of the substrate W. The polymer film P contacts the anti-etching agent formed on the main surface of the substrate W. As described above, the polymer film P can be in a semi-solid state or a solid state.

After the baking step (step S3), a liquid oxidant supplying step (step S4A, oxidant supplying step) is performed to supply a liquid oxidant to the main surface of the substrate W. Specifically, the substrate W is rotated, and the second movable nozzle N2 is arranged at a processing position (e.g., a central position) opposite to the upper surface of the substrate W. When the baking processing position of the heater unit 14 is a contact position in contact with the substrate W, the heater unit 14 is lowered to a proximity position spaced downward from the lower surface of the substrate W, and then the rotation of the substrate W is started. In parallel with the liquid oxidant supplying step (step S4A), the heating of the substrate W by the heater unit 14 arranged at the proximity position is performed (step S5: parallel heating step). Since the heater unit 14 is powered on continuously from the baking step, the parallel heating step starts earlier than the liquid oxidant supplying step.

Thus, while the substrate W is rotated and heated, the liquid oxidant is ejected from the second movable nozzle N2 toward the upper surface (the main surface on which the anti-etching agent is formed) of the substrate W. Specifically, by opening the liquid oxidant valve 55A, the liquid oxidant is ejected from the second movable nozzle N2 at a predetermined flow rate.

The liquid oxidant contacts the cured polymer film P on the substrate W. Then, a compound based on carboxylic acid is generated by the reaction shown in the above chemical formula 1. The compound decomposes the anti-etching agent by the reaction shown in the above chemical formula 2. Therefore, in the liquid oxidant supply step (step S4A), the organic matter removal step of decomposing and removing the anti-etching agent on the substrate W is simultaneously performed.

During the liquid oxidant supply step (step S4A), the second nozzle driving mechanism 25 typically stops the second movable nozzle N2 at a position (central position) where the liquid oxidant lands on the rotation center of the substrate W. However, if necessary, the second nozzle driving mechanism 25 may also move the second movable nozzle N2 along the rotation radius direction so that the landing point of the liquid oxidant on the upper surface of the substrate W moves along the radius direction of the substrate W.

After the liquid oxidant supply step (step S4A) of the predetermined time, the liquid oxidant valve 55A is closed to stop the supply of the liquid oxidant (the liquid oxidant supply step is completed). In addition, the second movable nozzle N2 is retreated to the retreat position. In addition, the heater drive mechanism 66 moves the heater unit 14 from the approach position to the retreat position. By arranging the heater unit 14 at the retreat position (the position shown in FIG. 1(e)), the heating of the substrate W is stopped (the parallel heating step is completed).

Next, a rinsing step of cleaning the upper surface of the substrate W is performed (step S6). Specifically, the third nozzle driving mechanism 26 moves the third movable nozzle N3 to the processing position. The processing position is, for example, the central position. When the third movable nozzle N3 is located at the processing position, the common valve 51 and the rinsing liquid valve 53A are opened. Thereby, as shown in FIG. 1(e), the rinsing liquid is sprayed from the third movable nozzle N3, and the supply of the rinsing liquid toward the upper surface of the substrate W is started (rinsing liquid supplying step). The rinsing liquid deposited on the upper surface of the substrate W moves toward the peripheral portion of the upper surface of the substrate W, and the rinsing liquid diffuses on the entire upper surface of the substrate W. Thereby, the liquid oxidant on the substrate W is replaced by the rinse liquid, and the residue on the substrate W is rinsed by the flow of the rinse liquid.

After a predetermined time has passed since the supply of the rinse liquid was started, the common valve 51 and the rinse liquid valve 53A are closed. Thus, the supply of the rinse liquid to the upper surface of the substrate W is stopped. Thus, the rinse step is completed. Through the rinse step, the liquid oxidant on the upper surface of the substrate W is replaced with the rinse liquid, and the anti-etching agent or its residue peeled off from the upper surface of the substrate W is rinsed and discharged from the upper surface of the substrate W to the outside of the substrate W.

The flushing step (step S6) may include a chemical liquid treatment using a chemical liquid. For example, the flushing step may include a first flushing liquid supplying step (step S61), a chemical liquid supplying step (step S62), and a second flushing liquid supplying step (step S63), and these steps are performed in sequence. Specifically, the common valve 51 and the flushing liquid valve 53A are opened to allow the flushing liquid to be ejected from the third movable nozzle N3, and the first flushing liquid supplying step (step S61) is performed. After a predetermined time, the flushing liquid valve 53A is closed, the liquid medicine valve 52A is opened, and the liquid medicine (e.g., SC1) is ejected from the third movable nozzle N3, and the liquid medicine supply step is performed (step S62). After a predetermined time, the liquid medicine valve 52A is closed, the flushing liquid valve 53A is opened, and the flushing liquid is ejected from the third movable nozzle N3, and the second flushing liquid supply step is performed (step S63). After a predetermined time, the flushing step is terminated by closing the flushing liquid valve 53A and the common valve 51. Thereafter, the third movable nozzle N3 is moved to the retreat position. The rinsing step including the chemical solution treatment has the advantage of being able to efficiently remove the residue on the substrate W.

During the rinsing step (step S6), the third nozzle driving mechanism 26 typically stops the third movable nozzle N3 at a position (central position) where the rinsing liquid/chemical solution lands on the rotation center of the substrate W. However, if necessary, the third nozzle driving mechanism 26 may also move the third movable nozzle N3 along the rotation radius direction so that the landing point of the rinsing liquid/chemical solution on the upper surface of the substrate W moves along the radius direction of the substrate W.

After the rinsing step (step S6), an organic solvent supply step (step S7) is performed to supply an organic solvent to the upper surface of the substrate W. Specifically, the fourth nozzle driving mechanism 27 is arranged at a processing position (e.g., a central position) where the fourth movable nozzle N4 faces the upper surface of the substrate W, and in this state, the organic solvent valve 54A is opened. Thereby, a continuous flow of the organic solvent is sprayed (supplied) from the fourth movable nozzle N4 toward the upper surface of the substrate W (step S7, organic solvent supply step). Thereby, the rinsing liquid on the upper surface of the substrate W is replaced by the organic solvent.

During the organic solvent supply step, the fourth nozzle driving mechanism 27 typically stops the fourth movable nozzle N4 at a position (central position) where the organic solvent lands on the rotation center of the substrate W. However, if necessary, the fourth nozzle driving mechanism 27 may also move the fourth movable nozzle N4 along the rotation radius direction so that the landing point of the organic solvent on the upper surface of the substrate W moves along the radius direction of the substrate W.

It is preferred that the volatility of the organic solvent used in the substrate processing is higher than that of the rinsing liquid. In this way, by replacing the rinsing liquid with the organic solvent, the substrate W can be dried well in the subsequent drying step (step S8). It is preferred that the surface tension of the organic solvent used in the substrate processing is lower than that of the rinsing liquid. In this way, when a concave-convex pattern is formed on the upper surface of the substrate W, the surface tension acting on the concave-convex pattern when the upper surface of the substrate W is dried can be reduced, and the collapse of the concave-convex pattern can be suppressed.

Next, a drying step is performed to dry the upper surface of the substrate W by rotating the substrate W at high speed (step S8, rotation drying step) (refer to FIG. 1( f)). Specifically, the organic solvent valve 54A is closed to stop supplying the organic solvent to the upper surface of the substrate W. In addition, the rotation drive mechanism 23 accelerates the rotation of the substrate W, so that the substrate W rotates at a high speed (e.g., 1500 rpm). As a result, a larger centrifugal force acts on the rinse liquid attached to the substrate W, and the organic solvent is thrown off to the periphery of the substrate W.

After the drying step (step S8), the rotation drive mechanism 23 stops the rotation of the substrate W. Thereafter, the second transport robot CR enters the processing unit 2, receives the processed substrate W from the spin chuck 8, and carries it out of the processing unit 2 (substrate carrying out step: step S9). The substrate W is handed over from the second transport robot CR to the first transport robot IR, and is stored in the carrier C by the first transport robot IR.

FIG8 is a flowchart for explaining another example of substrate processing performed by the substrate processing apparatus 1. This substrate processing is another example of the case where the processing unit 2 of the configuration example shown in FIG5 is used, and is an example of the substrate processing of the second embodiment shown in the aforementioned FIG2. In FIG8, steps of performing substantially the same processing as in FIG7 are represented by the same symbols.

The substrate W to be processed is the same as the substrate processing of FIG7. In addition, the substrate carrying step (step S1, see FIG2(a)), polymer coating step (step S2, see FIG2(b)), baking step (step S3, see FIG2(c)), parallel heating step (step S5, see FIG2(d)), rinsing step (step S6, see FIG2(e)), organic solvent supply step (step S7), drying step (step S8, see FIG2(f)) and substrate carrying out step (step S9) are substantially the same as the substrate processing of FIG7.

On the other hand, the oxidant supply step in the substrate processing of Figure 7 is a step of supplying a liquid oxidant (step S4A), whereas in the substrate processing of Figure 8 it is an oxidant vapor supply step of supplying oxidant vapor to the main surface of the substrate W (step S4B, refer to Figure 2(d)).

Specifically, after the baking step, an oxidant vapor supplying step (step S4B) of supplying oxidant vapor to the main surface of the substrate W is performed. More specifically, the substrate W is rotated, and the second movable nozzle N2 (oxidant vapor nozzle) is arranged at a processing position (e.g., a central position) opposite to the upper surface of the substrate W. When the baking processing position of the heater unit 14 is a contact position in contact with the substrate W, the heater unit 14 is lowered to a proximity position spaced downward from the lower surface of the substrate W, and then the rotation of the substrate W is started. In parallel with the oxidant vapor supplying step (step S4B), the heating of the substrate W by the heater unit 14 arranged at the proximity position is performed (step S5: parallel heating step). Thus, while the substrate W is rotated and heated, the oxidant vapor is sprayed from the second movable nozzle N2 toward the upper surface (the main surface on which the anti-etching agent is formed) of the substrate W. Specifically, by opening the oxidant vapor valve 155A, the oxidant vapor is sprayed from the second movable nozzle N2 at a predetermined flow rate. The heater unit 14 is powered on continuously from the baking step, so the parallel heating step is started earlier than the oxidant vapor supply step.

The oxidant vapor contacts the cured polymer film P on the substrate W. Thus, a carboxylic acid-based compound is generated by the reaction shown in the above chemical formula 1. The compound decomposes the anti-etching agent by the reaction shown in the above chemical formula 2. Therefore, in the oxidant vapor supply step (step S4B), an organic matter removal step of decomposing and removing the anti-etching agent on the substrate W is simultaneously performed.

During the oxidant vapor supply step (step S4B), the second nozzle driving mechanism 25 typically stops the second movable nozzle N2 at a position (central position) where the oxidant vapor is sprayed toward the rotation center of the substrate W. However, if necessary, the second nozzle driving mechanism 25 may also move the second movable nozzle N2 along the rotation radius direction so that the spraying target position of the oxidant vapor on the upper surface of the substrate W moves along the radius direction of the substrate W.

After the oxidant vapor supply step (step S4B) of the predetermined time, the oxidant vapor valve 155A is closed to stop the supply of the oxidant vapor (the oxidant vapor supply step is completed). In addition, the second movable nozzle N2 is retreated to the retreat position. In addition, the heater drive mechanism 66 moves the heater unit 14 from the approach position to the retreat position. By arranging the heater unit 14 at the retreat position (the position shown in FIG. 2(e)), the heating of the substrate W is stopped (the parallel heating step is completed).

Furthermore, in the substrate processing example of FIG8 , the baking step (step S3, see FIG2 (c)) can be omitted. In this case, although the polymer film P is a liquid film in an uncured state, the oxidant is supplied in the form of vapor, thereby suppressing the polymer film P from flowing out of the substrate W while allowing the carboxylic acid-based compound to be efficiently generated on the substrate W, thereby efficiently removing the organic matter on the substrate W.

In any of the substrate processing examples in FIG. 7 and FIG. 8 , the organic solvent supply step ( S7 ) may be omitted. Furthermore, in any of the substrate processing examples in FIG. 7 and FIG. 8 , the processing of steps S2 to S8 may be repeated two or more times as needed. In this way, the anti-etching agent on the substrate W can be fully removed.

Fig. 9 is a schematic top view showing a schematic structure of a substrate processing apparatus 1 for executing a substrate processing method according to another embodiment of the present invention. In Fig. 9, the same reference numerals are used to designate the corresponding parts of the parts shown in Fig. 3.

In this embodiment, the plurality of processing units 2 include a coating unit 2C, a baking unit 2B, and a liquid processing unit 2L. In this example, a plurality of coating units 2C are stacked in a vertical direction in one processing tower TW, and a plurality of liquid processing units 2L are stacked in a vertical direction in another processing tower TW. In addition, a plurality of baking units 2B are stacked in a vertical direction in the other two processing towers TW.

The coating unit 2C performs a polymer coating step of coating a polymer solution on the main surface of the substrate W. Specifically, the coating unit 2C is equipped with a rotary chuck 70 and a polymer solution nozzle 71 in the chamber 7. The coating unit 2C is a rotary coating unit that holds and rotates a substrate W by the rotary chuck 70, and supplies a polymer solution to the main surface (upper surface) of the substrate W from the polymer solution nozzle 71, and spreads a coating film (liquid film) of the polymer solution on the entire main surface of the substrate W by centrifugal force.

The baking unit 2B has a heating plate 80 for placing the substrate W, a cooling plate 81 which also serves as a transfer station for the substrate W, and a zone transfer robot 82 in the chamber 7. The zone transfer robot 82 transfers the substrate W between the heating plate 80 and the cooling plate 81 in the chamber 7 of the baking unit 2B. The transfer of the substrate W to the second transfer robot CR is performed at the cooling plate 81. The substrate W transferred to the cooling plate 81 is transferred to the heating plate 80 by the zone transfer robot 82. The heating plate 80 performs the following baking treatment by heating the substrate W from the lower surface side, that is, heating the coating film of the polymer solution formed on its main surface (the upper surface in this example), evaporating the solvent in the coating film, solidifying the polymer solution, and making a polymer film P in a solidified state (semi-solid or solid state). The substrate W after the baking treatment is transported to the cooling plate 81 by the area transport robot 82 and cooled (for example, cooled to room temperature). After the cooling, the second transport robot CR transports the treated substrate W from the cooling plate 81. In this way, the baking unit 2B performs the baking step.

The liquid processing unit 2L performs an oxidant supply step, a parallel heating step, and a drying step (rotation drying step). The liquid processing unit 2L can further perform an organic solvent supply step as needed. The liquid processing unit 2L has a rotary chuck 90, an oxidant nozzle 91, a parallel heating unit 92, and a flushing liquid nozzle 93 in the chamber 7, and further has an organic solvent nozzle 94 as needed. The oxidant nozzle 91 can be a liquid oxidant nozzle that sprays a liquid oxidant (a nozzle that sprays a liquid oxidant in the form of a continuous flow or a mist), and can also be a vapor nozzle that sprays oxidant vapor. The parallel heating unit 92 can be a lamp heater that heats the substrate W from the upper surface side, or a heating plate that heats the substrate W from the lower surface side, and can be a high-temperature inert gas nozzle that supplies heated inert gas (typically nitrogen or clean air) toward the upper surface or lower surface of the substrate W.

The liquid processing unit 2L holds a substrate W with a rotary chuck 90 and rotates it, while supplying an oxidant (liquid oxidant or oxidant vapor) from an oxidant nozzle 91 to the main surface (upper surface) of the substrate W. In parallel, the substrate W is heated by a parallel heating unit 92. Thus, a compound based on carboxylic acid is generated by the reaction of the oxidant with the sulfonic acid group in the polymer film P, and the anti-etching agent is decomposed by the reaction of the compound with the anti-etching agent. Thereafter, a rinse liquid (or a chemical solution as needed) is sprayed from a rinse liquid nozzle 93 toward the main surface of the substrate W to perform a rinse step. After the rinsing step, a drying step (rotation drying step) is performed by rotating the rotary chuck 90 at high speed to remove the liquid components on the substrate W. Between the rinsing step and the drying step, an organic solvent supplying step can be performed as needed to supply the organic solvent from the organic solvent nozzle 94 toward the main surface of the rotating substrate W.

The first transfer robot IR takes out the substrate W to be processed from the carrier C. The substrate W is carried into the coating unit 2C by the second transfer robot CR. Thereby, the polymer coating step is performed in the chamber 7 (first chamber) of the coating unit 2C. When the polymer coating step is completed, the second transfer robot CR takes out the substrate W from the coating unit 2C and carries it into the baking unit 2B. Thereby, the baking step is performed in the chamber 7 (second chamber) of the baking unit 2B. When the baking step is completed, the second transfer robot CR takes out the substrate W from the baking unit 2B and carries it into the liquid processing unit 2L. Thus, in the chamber 7 (third chamber) of the liquid processing unit 2L, an oxidant supply step (organic matter removal step), a parallel heating step, a rinsing step, an organic solvent supply step as required, and a drying step are performed. The processed substrate W is taken out of the liquid processing unit 2L by the second transfer robot CR, and then transferred to the first transfer robot IR and stored in the carrier C. In this way, substrate processing for removing the resist on the substrate W is performed by moving the substrate W to four locations among a plurality of processing units.

In the configuration shown in FIG. 3 , the polymer coating step, the baking step, the oxidant supply step, the parallel heating step, the rinsing step, the organic solvent supply step, and the drying step are performed in one processing unit 2 (i.e., in one chamber 7). In contrast, in the configuration shown in FIG. 9 , a series of steps are performed by moving the substrate W between a plurality of processing units 2. The configuration of FIG. 3 is advantageous in that the substrate W need not be transported between steps. On the other hand, the configuration of FIG. 9 is advantageous in that the time taken by one processing unit to process one substrate W is shorter.

The above describes the implementation of the present invention, but the present invention can also be implemented in other forms.

For example, another substrate processing apparatus 101 (see FIG. 3 , an example of the first substrate processing apparatus) can be used to perform the polymer coating step and the baking step, and the carrier C containing the substrate W having the polymer film P on the main surface is introduced into the substrate processing apparatus 1 (an example of the second substrate processing apparatus). In this case, the processing unit 2 of the substrate processing apparatus 1 only needs to perform the steps after the oxidant supply step, and it is sufficient as long as it has a structure for performing these steps.

In the above embodiments, the processing liquid (liquid or vapor) is ejected from a plurality of movable nozzles. However, unlike the above embodiments, the processing liquid may be ejected from a fixed nozzle fixed in a horizontal direction, or all the processing liquids may be ejected from a single nozzle.

The heating of the substrate W is not limited to the heating performed by the heater unit 14 of the aforementioned structure. Specifically, the heater unit may include an infrared lamp opposite to the upper surface of the substrate W, and may also include a heater opposite to the upper surface of the substrate W. Alternatively, the heater unit may include a heating fluid nozzle that supplies a heating fluid such as nitrogen or warm water to the lower surface of the substrate W. The heater unit may be configured to heat the plate body 60 by allowing the heating fluid to flow through the plate body 60. When a heating fluid is used, the temperature of the substrate W is adjusted by adjusting the opening of a valve that controls the flow of the heating fluid.

In the above embodiments, the rotary chuck 8 is a fixed rotary chuck that uses a plurality of fixing pins 20 to fix the periphery of the substrate W, but the rotary chuck 8 is not limited to a fixed rotary chuck. For example, the rotary chuck 8 can be a vacuum suction rotary chuck that allows the substrate W to be adsorbed on the rotating base 21.

In the above embodiments, the controller 3 controls the entire substrate processing apparatus 1. However, the controllers for controlling the components of the substrate processing apparatus 1 may be distributed in a plurality of locations. In addition, the controller 3 does not need to directly control the components, but the signals output from the controller 3 may be received by the slave controllers for controlling the components of the substrate processing apparatus 1.

Furthermore, in the above-mentioned embodiment, the substrate processing apparatus 1 has a transport robot (a first transport robot IR and a second transport robot CR), a plurality of processing units 2, and a controller 3. However, the substrate processing apparatus 1 may also be composed of a single processing unit 2 and a controller 3, without a transport robot. Alternatively, the substrate processing apparatus 1 may be composed of only a single processing unit 2. In other words, the processing unit 2 may be an example of a substrate processing apparatus.

Although the implementation methods of the present invention are described in detail, they are only used to clarify the specific examples of the technical content of the present invention. The present invention should not be limited to such specific examples for interpretation. The scope of the present invention is only limited by the scope of the attached patent application. [Related Applications]

This application claims priority to Japanese Patent Application No. 2023-62810 filed on April 7, 2023, the entire contents of which are incorporated herein by reference.

1: Substrate processing device 2: Processing unit 2B: Baking unit 2C: Coating unit 2L: Liquid processing unit 3: Controller 3a: Computer body 3A: Input device 3b: Processor 3B: Display device 3c: Memory 3C: Alarm device 3d: Peripheral device 3e: Auxiliary memory device 3f: Reading device 3g: Communication device 4: Fluid box 5: Storage box 6: Frame 7: Chamber 7a: Upper wall 7c: Internal space 8: Rotary chuck 9: Polymer solution supply unit 10: Liquid oxidant supply unit 14: Heater unit 14a: Heating surface 15: Processing cup 20: Retaining pin 21: Rotating base 21a: Through hole 22: Rotating shaft 23: Rotating drive mechanism 24: No. 1 nozzle drive mechanism 24a: No. 1 arm 24b: No. 1 arm drive mechanism 25: No. 2 nozzle drive mechanism 25a: No. 2 arm 25b: No. 2 arm drive mechanism 26: No. 3 nozzle drive mechanism 26a: No. 3 arm 26b: No. 3 arm drive mechanism 27: No. 4 nozzle drive mechanism 27a: No. 4 arm 27b: No. 4 arm drive mechanism 28: Baffle 29: Cup 30: Outer wall component 31: Air supply unit 32: Exhaust piping 33: Ozone removal device 35: Drain piping 40: Polymer solution piping 41: Common piping 42: Chemical piping 43: Rinsing liquid piping 44: Organic solvent piping 45: Liquid oxidant piping 50A: Polymer solution valve 50B: Polymer solution flow regulating valve 51: Common valve 52A: Chemical valve 52B: Chemical flow regulating valve 53A: Rinsing liquid valve 53B: Rinsing liquid flow regulating valve 54A: Organic solvent valve 54B: Organic solvent flow regulating valve 55A: Liquid oxidant valve 55B: Liquid oxidant flow regulating valve 60: Plate body 61: Heater 62: Temperature sensor 63: Power supply unit 64: Feeder wire 65: Heater lifting shaft 66: Heater drive mechanism 70: Rotary chuck 71: Polymer solution nozzle 80: Heating plate 81: Cooling plate 82: Area transfer robot 90: Rotary chuck 91: Oxidant nozzle 92: Parallel heating unit 93: Rinse liquid nozzle 94: Organic solvent nozzle 101: Substrate processing device 110: Oxidant vapor supply unit 145: Oxidant vapor piping 155A: Oxidant vapor valve 155B: Oxidant vapor flow rate adjustment valve A1: Rotation axis C: Carrier CR: Second transport robot IR: First transport robot LP: Loading port N1: First mobile nozzle N2: Second mobile nozzle N3: Third mobile nozzle N4: Fourth mobile nozzle P: Polymer film S1~S9, S4A, S4B, S61~S63: Steps TR: Transport path TW: Processing tower W: Substrate

FIG. 1 (a) to (f) show an example of a substrate processing method according to the first embodiment of the present invention. FIG. 2 (a) to (f) show an example of a substrate processing method according to the second embodiment of the present invention. FIG. 3 is a schematic top view for illustrating a configuration example of a substrate processing device for executing a substrate processing method according to an embodiment of the present invention. FIG. 4 is a schematic diagram for illustrating a configuration example of a processing unit provided in the substrate processing device, and shows a configuration example for executing the substrate processing method according to the first embodiment shown in FIG. 1. FIG. 5 is a schematic diagram for illustrating another configuration example of a processing unit provided in the substrate processing device, and shows a configuration example for executing the substrate processing method according to the second embodiment shown in FIG. 2. FIG. 6 is a block diagram for explaining the electrical structure of the substrate processing device. FIG. 7 is a flow chart for explaining an example of substrate processing performed by the substrate processing device. FIG. 8 is a flow chart for explaining another example of substrate processing performed by the substrate processing device. FIG. 9 is a schematic top view showing the schematic structure of a substrate processing device for performing a substrate processing method of another embodiment of the present invention.

8: Rotating chuck

14: Heater unit

N2: 2nd mobile nozzle

N3: 3rd mobile nozzle

P: polymer film

W: substrate

Claims (14)

A substrate processing method, comprising: a step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on a main surface; an oxidant supplying step of supplying an oxidant to the main surface of the substrate; and an organic matter removal step of removing an organic matter to be removed on the main surface of the substrate by a reaction product between the sulfonic acid group in the polymer film and the oxidant. A substrate processing method as claimed in claim 1, wherein the above-mentioned removal target material includes at least one of an anti-etching agent and residues after dry etching. The substrate processing method of claim 1, wherein the oxidant supplying step is to supply the liquid or vapor of the oxidant to the main surface of the substrate. A substrate processing method as claimed in claim 1, wherein the oxidant comprises at least one of hydrogen peroxide and ozone. The substrate processing method of claim 1, wherein the oxidant supply step includes at least one of the following steps: A continuous supply step, which is to supply hydrogen peroxide water or ozone water in the form of a continuous flow from a nozzle to the main surface of the substrate; A mist supply step, which is to spray hydrogen peroxide water, ozone water or a mixture of sulfuric acid and hydrogen peroxide water in the form of a mist from a nozzle to the main surface of the substrate; and A vapor supply step, which is to mix hydrogen peroxide or ozone with water vapor and supply it to the main surface of the substrate. The substrate processing method of claim 1, wherein the polymer film is in a solidified state before the oxidant supplying step is started, and the oxidant supplying step includes a liquid oxidant supplying step of supplying the liquid oxidant to the main surface of the substrate. The substrate processing method of claim 1, wherein the polymer film is in an uncured state before the oxidant supply step begins, and the oxidant supply step includes an oxidant vapor supply step of supplying oxidant vapor to the main surface of the substrate. The substrate processing method of claim 1 further comprises a parallel heating step of heating the substrate in parallel with the oxidant supplying step. A substrate processing method as claimed in claim 8, wherein the parallel heating step starts before the supply of the oxidant starts. A substrate processing method as claimed in any one of claims 1 to 9, wherein the step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on the main surface comprises: A polymer coating step, which is to coat the polymer containing a sulfonic acid group on the main surface of the substrate. The substrate processing method of claim 10, wherein the step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on the main surface further includes: A baking step, which is to bake the polymer coated on the main surface of the substrate. The substrate processing method of claim 11, wherein the polymer coating step is performed in the first chamber, the baking step is performed in the second chamber different from the first chamber, and the oxidant supply step is performed in the third chamber different from the first chamber and the second chamber. A substrate processing method as claimed in any one of claims 1 to 9, wherein the step of preparing a substrate having a polymer film containing a polymer containing a sulfonic acid group on the main surface is performed by a first substrate processing device, and the step of supplying the oxidant is performed by a second substrate processing device different from the first substrate processing device. A substrate processing method as in any one of claims 1 to 9, wherein the polymer containing sulfonic acid groups comprises at least one of vinyl sulfonic acid-vinyl alcohol copolymer, vinyl sulfonic acid-styrene copolymer, polyvinyl sulfonic acid, polystyrene sulfonic acid, partial polystyrene sulfonate, ammonium sulfonate salt and metal sulfonate salt.