JP5390873B2 - Substrate processing method and substrate processing apparatus - Google Patents

Description

  The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and photomasks. Substrate etc. are included.

  In a manufacturing process of a semiconductor device or a liquid crystal display device, a substrate processing apparatus for processing a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is used. A single-wafer type substrate processing apparatus that processes substrates one by one is held by, for example, a spin chuck that holds a substrate horizontally and rotates the substrate around a vertical rotation axis that passes through the center of the substrate, and a spin chuck. In addition, a nozzle for supplying a processing solution such as a chemical solution or a rinsing solution is provided on the upper surface of the substrate (see, for example, Patent Document 1).

  In the processing of the substrate according to Patent Document 1, for example, the chemical solution and the pure water are sequentially supplied to the upper surface of the rotating substrate, and the chemical solution processing and the rinsing processing are sequentially performed. Thereafter, IPA (isopropyl alcohol) is supplied to the upper surface of the substrate. Thereby, the pure water on the substrate is replaced with IPA, and an IPA liquid film covering the entire upper surface of the substrate is formed. And the drying process which rotates a board | substrate and dries a board | substrate is performed. Patent Document 1 discloses a drying method in which a substrate is rotated while nitrogen gas is blown onto the center of the upper surface of the substrate.

Japanese Patent Laid-Open No. 9-38595

  When the substrate is rotated while nitrogen gas is blown onto the central portion of the upper surface of the substrate while the IPA liquid film covering the entire upper surface of the substrate is held on the substrate, the IPA is supplied from the central portion of the upper surface of the substrate by the supply pressure of nitrogen gas. Is removed. Therefore, a hole is formed in the center of the IPA liquid film held on the substrate, and the IPA liquid film becomes annular. Further, since centrifugal force acts on the IPA on the substrate, the IPA moves outward (in a direction away from the rotation axis of the substrate), and the inner diameter of the annular liquid film increases. Furthermore, since the nitrogen gas sprayed on the substrate spreads radially from the center of the upper surface of the substrate toward the peripheral edge of the upper surface, the inner diameter of the liquid film that is formed into an annular shape by being pushed by the nitrogen gas increases. Furthermore, since nitrogen gas is blown onto the IPA liquid film, the IPA evaporates. Therefore, the circular IPA liquid film is pushed outward by centrifugal force or nitrogen gas supply pressure, and the inner diameter is increased by evaporation of IPA.

  On the other hand, the centrifugal force acting on the IPA held on the substrate increases as the distance from the rotation axis of the substrate increases. Therefore, the IPA held on the peripheral edge of the upper surface of the substrate moves outward at a higher speed than the IPA inside. Therefore, there is a case where IPA disappears from the peripheral edge of the upper surface of the substrate in a state where IPA remains in a region inside the peripheral edge of the upper surface of the substrate. In addition, since the centrifugal force acting on the IPA remaining on the substrate (IPA held in the region inside the peripheral portion on the upper surface of the substrate) is relatively small, the IPA on the substrate moves outward by the centrifugal force. The speed is relatively small. That is, the IPA liquid film covering the entire upper surface of the substrate becomes annular, and then the inner diameter becomes larger due to the supply pressure of nitrogen gas and the evaporation of IPA, whereas the outer diameter has an acting centrifugal force. The speed of increasing because it is small is relatively small. Therefore, the speed at which the inner diameter spreads may be larger than the speed at which the outer diameter of the IPA liquid film spreads.

  In this way, when the substrate is rotated while blowing the nitrogen gas to the central portion of the upper surface of the substrate while the liquid film of IPA covering the entire upper surface of the substrate is held on the substrate, the liquid film of IPA held on the substrate After becoming annular, the inner diameter increases. Therefore, the upper surface of the substrate is dried outward from the central portion. Further, as described above, IPA may disappear from the peripheral edge of the upper surface of the substrate when IPA remains on the inner side, so that the region inside the peripheral edge on the upper surface of the substrate is not completely dry. The upper surface periphery of the substrate may be dried. Furthermore, since the speed at which the inner diameter expands may be larger than the speed at which the outer diameter of the IPA liquid film that has become annular expands, an annular region (hereinafter referred to as the center area) between the upper surface central portion and the upper surface peripheral portion of the substrate. Then, the IPA is finally left in the “intermediate area”), and the final drying position on the upper surface of the substrate may become the intermediate area. That is, drying of the entire upper surface of the substrate may end when the intermediate region is dried.

  However, when the final drying position becomes the intermediate area, drying defects such as watermarks and pattern collapse may occur in the intermediate area. That is, IPA is an organic solvent that has higher volatility than pure water and can easily dissolve pure water. Therefore, if pure water remains on the substrate without being replaced by IPA in the processing of the substrate according to Patent Document 1 described above, the remaining pure water dissolves in the IPA liquid film formed on the substrate. Therefore, when the substrate is rotated while nitrogen gas is blown to the center of the upper surface of the substrate in a state where pure water is dissolved in the IPA liquid film, the circular IPA liquid film becomes pure water by evaporation of IPA. The inner diameter increases as the concentration increases. As a result, IPA having a high concentration of pure water may remain in the intermediate region, and poor drying due to pure water in the IPA may occur in the intermediate region. In addition, such a problem is not limited to removing the IPA liquid film from the substrate while blowing nitrogen gas to the central portion of the upper surface of the substrate, but from pure water while blowing an inert gas to the central portion of the upper surface of the substrate. This can also occur when removing a liquid film of a highly volatile treatment liquid from the substrate.

  Accordingly, an object of the present invention is to suppress or prevent the occurrence of poor drying when removing a liquid film of a volatile treatment liquid having higher volatility than pure water from the substrate and drying the substrate. An object of the present invention is to provide a substrate processing method and a substrate processing apparatus.

In order to achieve the above object, according to the first aspect of the present invention , the rinsing liquid is supplied to the upper surface of the horizontally held substrate, and the rinsing liquid film covering the entire upper surface of the substrate with the rinsing liquid supplied to the substrate is provided. After the rinsing liquid film forming step to be formed and the rinsing liquid film forming step, a volatile treatment liquid having a higher volatility than pure water is supplied to the upper surface of the horizontally held substrate (W), so that replacing the rinsing liquid, volatile treatment liquid obtained by replacing the rinsing liquid, a volatile treatment liquid film forming step of forming a volatile treatment liquid film covering the entire upper surface of the substrate, the volatile treatment liquid film on the substrate A substrate rotation step of rotating the substrate around a vertical rotation axis (L1) passing through the central portion of the substrate while being held, and a gas supply step of blowing a gas to the central portion of the upper surface of the substrate in parallel with the substrate rotation step If, after the volatile treatment liquid film forming step, the group In parallel with the rotating step and the gas supplying step includes a volatile treatment liquid supply step of Chakueki volatile treatment liquid at a predetermined position (P1) in the upper surface of the substrate wherein a position outside from a rotational axis The substrate processing method. In this section, alphanumeric characters in parentheses indicate corresponding components in the embodiments described later.

According to the present invention, the rinsing liquid is supplied to the upper surface of the substrate held horizontally to form the rinsing liquid film covering the entire upper surface of the substrate. Thereafter, a volatile processing liquid having a higher volatility than pure water is supplied to the upper surface of the substrate held horizontally to form a liquid film of the volatile processing liquid covering the entire upper surface of the substrate. Then, the substrate is rotated around a vertical rotation axis passing through the central portion of the substrate while the liquid film of the volatile processing liquid is held on the substrate. At this time, the volatile processing liquid is deposited at a predetermined position apart from the rotation axis other than the central portion on the upper surface of the substrate while blowing gas on the central portion of the upper surface of the substrate.

  By blowing gas onto the center of the upper surface of the substrate, the volatile processing liquid is removed from the center of the upper surface of the substrate by the gas supply pressure. Therefore, a hole is formed in the central portion of the liquid film of the volatile processing liquid held on the substrate, and the liquid film of the volatile processing liquid becomes annular. In addition, since the centrifugal force acts on the volatile processing liquid on the substrate due to the rotation of the substrate, the volatile processing liquid moves outward (in the direction away from the rotation axis of the substrate) and the inner diameter of the annular liquid film Is getting bigger. Further, since the gas blown onto the substrate spreads radially from the center of the upper surface of the substrate toward the peripheral edge of the upper surface, the inner diameter of the annular liquid film that is pushed by the gas increases. Furthermore, since the gas is blown onto the liquid film of the volatile processing liquid, the volatile processing liquid evaporates. Therefore, the liquid film of the volatile processing liquid that is in an annular shape is pushed outward by centrifugal force or gas supply pressure, and the inner diameter is increased by evaporation of the volatile processing liquid.

  Further, the centrifugal force acting on the volatile processing liquid held on the substrate increases as the distance from the rotation axis of the substrate increases. Therefore, the volatile processing liquid held at the upper peripheral edge of the substrate moves outward at a higher speed than the inner volatile processing liquid. On the other hand, the volatile treatment liquid deposited on a predetermined position of the substrate moves outward by receiving a centrifugal force due to the rotation of the substrate. Therefore, although the volatile treatment liquid held at the peripheral edge of the upper surface of the substrate moves outward at a higher speed than the inner volatile treatment liquid, the volatile treatment liquid that has landed at the predetermined position remains on the upper surface of the substrate. Since it is supplied to the peripheral portion, the volatile processing liquid does not completely disappear from the upper surface peripheral portion of the substrate, and the state where the volatile processing liquid is held at the upper peripheral portion of the substrate is maintained. Therefore, drying of the upper peripheral edge of the substrate in a state where the region inside the peripheral edge on the upper surface of the substrate is not completely dried is suppressed or prevented.

  As described above, according to the present invention, it is possible to increase the inner diameter of the liquid film of the volatile processing liquid that is in an annular shape while maintaining the state in which the volatile processing liquid is held on the peripheral edge of the upper surface of the substrate. it can. Therefore, the volatile processing liquid on the substrate spreads outward from the center of the upper surface of the substrate while being discharged from the peripheral portion of the upper surface of the substrate to the periphery. Therefore, the upper surface of the substrate is dried outward from the central portion, and the peripheral portion becomes the final drying position. As a result, even when pure water is dissolved in the volatile treatment liquid on the substrate, drying defects such as watermarks and pattern collapse are present in the intermediate region (annular region between the upper surface center portion of the substrate and the peripheral edge portion of the upper surface). Can be suppressed or prevented. In addition, since all volatile processing liquid is removed from the substrate while discharging the volatile processing liquid from the peripheral edge of the upper surface of the substrate, the volatile processing liquid mixed with pure water is removed without leaving on the substrate. be able to. Thereby, it can suppress or prevent that the dry defect resulting from a pure water generate | occur | produces on the upper surface of a board | substrate.

  In addition, according to the present invention, the volatile processing liquid is removed from the substrate while blowing gas to the central portion of the upper surface of the substrate. Therefore, when the substrate is being dried, the exposed portion (volatile) The entire area of the portion from which the chemical treatment liquid has been removed can be continuously covered with the gas. Therefore, it is possible to suppress or prevent foreign matters such as particles and mist of the processing liquid from adhering to the exposed portion of the upper surface of the substrate when the substrate is being dried. Thereby, the upper surface of a board | substrate can be dried rapidly and also the contamination of the board | substrate by adhesion of a foreign material or mist can be suppressed or prevented.

  In order to maintain the state in which the volatile processing liquid is held at the peripheral edge of the upper surface of the substrate, for example, the position where the volatile processing liquid is deposited on the upper surface of the substrate is moved from the central portion to the peripheral portion while rotating the substrate. It is conceivable that the volatile processing liquid is supplied to the peripheral edge of the upper surface of the substrate (by scanning the upper surface of the substrate with the volatile processing liquid). However, when the upper surface of the substrate is scanned with the volatile processing liquid, the volatile processing liquid landing position is near the center of the upper surface of the substrate unless the flow rate of the volatile processing liquid landing on the substrate is relatively large. In some cases, the volatile processing liquid is not sufficiently supplied to the peripheral edge of the upper surface of the substrate, and the state where the volatile processing liquid is held at the peripheral edge of the upper surface of the substrate may not be maintained. On the other hand, according to the present invention, it is possible to maintain the state in which the volatile processing liquid is held at the peripheral edge of the upper surface of the substrate with a smaller flow rate than when the upper surface of the substrate is scanned with the volatile processing liquid. In addition, if the liquid deposition position (predetermined position) of the volatile processing liquid on the upper surface of the substrate is appropriately set, the volatile processing liquid is reliably supplied to an area where the substrate upper surface is prone to drying defects such as an intermediate area. Can continue.

According to a second aspect of the present invention, the volatile treatment liquid in which the rinsing liquid is replaced in the volatile treatment liquid film forming step moves from the center of the upper surface of the substrate in a direction away from the rotation axis , and the volatile treatment liquid supply The substrate processing method according to claim 1, wherein the process is continued until reaching the vicinity of a landing position of a volatile processing liquid supplied to the substrate in the process.
According to the present invention, the inner diameter of the liquid film of the volatile processing liquid that has become an annular shape is expanded, and the inner periphery of the liquid film reaches the vicinity of the predetermined position, which is the liquid deposition position of the volatile processing liquid. The supply of the volatile treatment liquid to the upper surface of is continued. Therefore, it is possible to suppress or prevent the volatile treatment liquid that has landed in the region where the volatile treatment liquid on the upper surface of the substrate has been removed from entering the substrate and preventing drying of the substrate. Thereby, a board | substrate can be dried rapidly.

The invention according to claim 3 is a process in which the substrate rotation process is continued at least from the substrate until the volatile processing liquid film disappears, and the gas supply process is performed from at least the substrate on the volatile processing liquid film. The substrate processing method according to claim 1, wherein the substrate processing method is a process that is continued until there is no more.
According to the present invention, the rotation of the substrate and the supply of gas to the upper surface of the substrate are continued until at least the volatile treatment liquid is removed from the substrate. Thus, the entire upper surface of the substrate can be dried while covering the entire upper surface of the substrate with the gas. Therefore, the entire upper surface of the substrate can be quickly dried, and contamination of the substrate due to adhesion of foreign matter or mist can be reliably suppressed or prevented.

Invention of Claim 4 is a substrate processing method as described in any one of Claims 1-3 which is a process continued until the said substrate rotation process complete | finishes the said gas supply process.
According to the present invention, the gas supply to the upper surface of the substrate is continued until the rotation of the substrate is stopped. That is, the upper surface of the substrate continues to be covered with gas until the airflow such as turbulence generated by the rotation of the substrate disappears or weakens. Therefore, it is possible to protect the substrate from foreign matters and mist of the processing liquid carried to the substrate side by the air flow accompanying the rotation of the substrate. As a result, it is possible to reliably suppress or prevent the contamination of the substrate due to the adhesion of foreign matter or mist.

The invention according to claim 5 includes a substrate holding means (3) for horizontally holding the substrate (W), and a vertical rotation axis (L1) passing through the central portion of the substrate held by the substrate holding means. Substrate rotating means (11) for rotating the substrate, rinsing liquid supply means (5) for supplying a rinsing liquid to the upper surface of the substrate held by the substrate holding means, and a central portion of the upper surface of the substrate held by the substrate holding means Gas supply means (4, 16, 17, 13, 14, 15; 104) for spraying gas on the substrate and a plurality of locations on the upper surface of the substrate including the central portion of the upper surface of the substrate held by the substrate holding means. Volatile processing liquid supply means (6, 7, 18, 19, 20, 25, 26, 27, 28; 29, 30, 31, 32, 33, which can deposit a volatile processing liquid having high volatility. 34), the substrate holding means, and the substrate rotating hand Rinsing liquid supplying means, and a control means for controlling the gas supply means and volatile treatment liquid supply means (12), a substrate processing apparatus (1, 101).
The control means supplies a rinsing liquid to the upper surface of the substrate held horizontally, and a rinsing liquid film forming step of forming a rinsing liquid film covering the entire upper surface of the substrate with the rinsing liquid supplied to the substrate; and After the rinsing liquid film formation step, volatile treatment liquid with higher volatility than pure water is supplied to the upper surface of the horizontally held substrate to replace the rinsing liquid on the substrate, and the volatile liquid is replaced with the rinsing liquid A volatile treatment liquid film forming step for forming a volatile treatment liquid film covering the entire upper surface of the substrate with the treatment liquid; and a vertical passage through the center of the substrate while holding the volatile treatment liquid film on the substrate. Substrate rotation after rotating the substrate around the rotation axis, in parallel with the substrate rotation step, a gas supply step for blowing gas to the center of the upper surface of the substrate, and the volatile treatment liquid film forming step In parallel with the process and the gas supply process, Serial to perform a volatile treatment liquid supply step of Chakueki volatile treatment liquid at a predetermined position in the upper surface of the substrate is a position outside from the rotational axis.

According to the present invention, it is possible to achieve the same effects as those described in relation to the invention of claim 1.
According to a sixth aspect of the present invention, the volatile processing liquid supply means includes a first fixed nozzle (6) and a second fixed nozzle (7) provided to discharge the volatile processing liquid in a fixed state. The first fixed nozzle is provided so that a volatile treatment liquid is deposited on the center of the upper surface of the substrate held by the substrate holding means, and the second fixed nozzle is The substrate processing apparatus according to claim 5, wherein the volatile processing liquid is provided at the predetermined position .

According to this invention, a volatile processing liquid can be discharged from a 1st fixed nozzle, and a volatile processing liquid can be made to adhere to the upper surface center part of a board | substrate. The volatile processing liquid deposited on the center of the upper surface of the substrate is pushed by the subsequent volatile processing liquid and spreads outward on the substrate. Thereby, a volatile processing liquid can be supplied to the whole upper surface of a board | substrate, and the liquid film of the volatile processing liquid which covers the whole upper surface of a board | substrate can be formed ( volatile processing liquid film formation process).

  According to the invention, the rotation axis other than the central portion on the upper surface of the substrate is formed by discharging the volatile treatment liquid from the second fixed nozzle while rotating the substrate held by the substrate holding means by the substrate rotating means. The volatile treatment liquid can be deposited at a predetermined position that is a certain distance away. The volatile treatment liquid deposited on a predetermined position of the substrate moves outward due to the centrifugal force generated by the rotation of the substrate. Thereby, a volatile processing liquid can be supplied to the upper surface of a board | substrate (volatile processing liquid supply process).

Invention according to claim 7, wherein the volatile treatment liquid supplying means includes a moving nozzle (29) for discharging the volatile treatment liquid, volatile treatment liquid from the mobile nozzle to the substrate held by the substrate holding means Nozzle moving means (32) for moving the moving nozzle so that the liquid deposition position moves between the center of the upper surface of the substrate and the predetermined position, and supply and stop of supply of volatile processing liquid to the moving nozzle And switching means (33) for switching between, and the control means controls the nozzle moving means and the switching means to stop the movement of the volatile processing liquid from the moving nozzle in a stopped state. The substrate processing apparatus according to claim 5, wherein a nozzle moving step for moving the nozzle is executed.

According to this invention, by controlling the nozzle moving means and the switching means by the control means, the volatile processing liquid discharged from the moving nozzle can be deposited on the center of the upper surface of the substrate. The volatile processing liquid deposited on the center of the upper surface of the substrate is pushed by the subsequent volatile processing liquid and spreads outward on the substrate. Thereby, a volatile processing liquid can be supplied to the whole upper surface of a board | substrate, and the liquid film of the volatile processing liquid which covers the whole upper surface of a board | substrate can be formed ( volatile processing liquid film formation process).

In addition, according to the present invention, the nozzle moving means and the switching means are controlled by the control means, and the moving nozzle can be moved in a state where the discharge of the volatile processing liquid from the moving nozzle is stopped (nozzle movement). Process). Therefore, the amount of the volatile processing liquid used can be reduced, and the cost required for processing the substrate can be suppressed. In addition, after the volatile processing liquid film forming step is executed, the nozzle moving step is executed, and the switching means is controlled again by the control means, so that the volatile processing liquid is attached to the predetermined position of the rotating substrate. It can be liquidated. Thereby, a volatile processing liquid can be supplied to the upper surface of a board | substrate (volatile processing liquid supply process).

It is an illustration figure which shows schematic structure of the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is an illustration figure which shows schematic structure of the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating an example of the process of the board | substrate by the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is an illustration figure which shows the modification of a gas nozzle.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is an illustrative view showing a schematic configuration of a substrate processing apparatus 1 according to a first embodiment of the present invention.
The substrate processing apparatus 1 is a single wafer processing apparatus that processes substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 includes a spin chuck 3 (substrate holding means) that horizontally holds and rotates a single substrate W in a processing chamber 2 partitioned by partition walls, and a substrate W held by the spin chuck 3. A gas nozzle 4 for supplying a gas to the upper surface, and a plurality of processing liquid nozzles for supplying a processing liquid to the upper surface of the substrate W held by the spin chuck 3 (in this embodiment, first to third processing liquids) Nozzles 5, 6 and 7).

  The spin chuck 3 includes a rotary shaft 8 extending in a vertical direction, a disk-shaped spin base 9 attached horizontally to the upper end of the rotary shaft 8, a plurality of clamping members 10 disposed on the spin base 9, And a spin motor 11 (substrate rotating means) coupled to the rotation shaft 8. The plurality of clamping members 10 are arranged at appropriate intervals on the circumference corresponding to the outer peripheral shape of the substrate W at the peripheral edge of the upper surface of the spin base 9. The spin chuck 3 can hold the substrate W in a horizontal posture above the spin base 9 by bringing each holding member 10 into contact with the peripheral end surface of the substrate W. The substrate W is rotated around the vertical rotation axis L1 passing through the center of the substrate W by inputting the driving force of the spin motor 11 to the rotation shaft 8 in a state where the substrate W is sandwiched by the plurality of clamping members 10. Can do. The spin motor 11 is controlled by a control unit 12 (control means).

The spin chuck 3 is not limited to such a configuration. For example, the substrate W is held in a horizontal posture by vacuum-sucking the lower surface (back surface) of the substrate W, and the vertical state is further maintained in that state. A vacuum chucking type (vacuum chuck) that can rotate the held substrate W by rotating around the axis may be employed.
The gas nozzle 4 is disposed above the spin chuck 3 with the discharge port directed downward. The gas nozzle 4 can discharge gas, for example, vertically downward. In this embodiment, for example, a tubular member having an inner diameter of about 10 mm is used as the gas nozzle 4. The gas nozzle 4 is attached to the tip of a nozzle arm 13 that extends horizontally. The nozzle arm 13 is supported by a support shaft 14 extending vertically. The support shaft 14 is disposed around the spin chuck 3 and is swingable about its central axis. By swinging the support shaft 14 around the central axis, the gas nozzle 4 can be moved horizontally along an arcuate path passing above the center of the substrate W held by the spin chuck 3.

  Further, the support shaft 14 is coupled to a nozzle swinging mechanism 15 configured by, for example, a motor or the like. By inputting the driving force of the nozzle swing mechanism 15 to the support shaft 14, the gas nozzle 4 and the nozzle arm 13 can be horizontally moved integrally around the central axis of the support shaft 14. Thereby, the gas nozzle 4 can be disposed above the substrate W held on the spin chuck 3, or the gas nozzle 4 can be retracted from above the spin chuck 3.

  Gas from a gas supply source (not shown) is supplied to the gas nozzle 4 via a gas supply pipe 17 in which a gas valve 16 is interposed. Examples of the gas supplied to the gas nozzle 4 include inert gas such as nitrogen gas and helium gas, or dry air (air adjusted to low humidity). The opening and closing of the gas valve 16 is controlled by the control unit 12. The nozzle swinging mechanism 15 is controlled by the control unit 12. The control unit 12 can discharge gas from the gas nozzle 4 toward the center of the upper surface of the substrate W with the gas nozzle 4 positioned above the center of the substrate W held by the spin chuck 3. Thereby, gas can be sprayed on the center part of the upper surface of the substrate W held by the spin chuck 3.

  In this embodiment, the gas nozzle 4, the gas valve 16, the gas supply pipe 17, the nozzle arm 13, the support shaft 14, and the nozzle swing mechanism 15 constitute gas supply means. As described above, the gas nozzle 4 may be configured to be horizontally moved by the nozzle swing mechanism 15, or the center of the upper surface of the substrate W on which the discharged gas is held by the spin chuck 3. It may be fixed at a fixed position so as to be sprayed on the surface.

  Each of the processing liquid nozzles 5, 6, and 7 is, for example, a straight nozzle that discharges the processing liquid in a continuous flow state. Each of the treatment liquid nozzles 5, 6, and 7 is disposed above the spin chuck 3 with the discharge port facing downward. Each of the processing liquid nozzles 5, 6, and 7 can discharge the processing liquid, for example, vertically downward. Each of the processing liquid nozzles 5, 6, 7 is attached to the tip of a horizontally extending nozzle arm 18 provided for each of the processing liquid nozzles 5, 6, 7. Each nozzle arm 18 is supported by a vertically extending support shaft 19 provided for each nozzle arm 18 (in FIG. 1, the support shafts corresponding to the first and second treatment liquid nozzles 5 and 6 are shown. Is omitted.) Each support shaft 19 is disposed around the spin chuck 3 and can swing around its central axis. By swinging each support shaft 19 around the central axis, the corresponding processing liquid nozzles 5, 6, and 7 are moved horizontally along an arc-shaped trajectory passing above the central portion of the substrate W held by the spin chuck 3. Can be made.

  Each support shaft 19 is coupled to a nozzle swing mechanism 20 provided for each support shaft 19 (in FIG. 1, nozzle swing mechanisms corresponding to the first and second processing liquid nozzles 5 and 6 are connected. (The illustration is omitted.) By inputting the driving force of the nozzle swing mechanism 20 to the support shaft 19, the corresponding processing liquid nozzles 5, 6, 7 and the nozzle arm 18 can be horizontally moved integrally around the central axis of the support shaft 19. . Accordingly, the processing liquid nozzles 5, 6, and 7 are disposed above the substrate W held on the spin chuck 3, and the processing liquid nozzles 5, 6, and 7 are retracted from above the spin chuck 3. Can do.

  Connected to the first treatment liquid nozzle 5 are a chemical liquid supply pipe 22 provided with a chemical liquid valve 21 and a rinse liquid supply pipe 24 provided with a rinse liquid valve 23. A chemical liquid from a chemical liquid supply source (not shown) is supplied to the first processing liquid nozzle 5 via a chemical liquid supply pipe 22. In addition, the first treatment liquid nozzle 5 is supplied with a rinse liquid from a rinse liquid supply source (not shown) via a rinse liquid supply pipe 24. The first treatment liquid nozzle 5 is selectively supplied with a chemical solution and a rinse solution.

  Examples of the chemical solution supplied to the first treatment liquid nozzle 5 include sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, aqueous ammonia, hydrogen peroxide, organic acids (for example, citric acid and oxalic acid), and organic alkalis (for example, TMAH). : Tetramethylammonium hydroxide, etc.), a surfactant, and a liquid containing at least one of a corrosion inhibitor. The rinse liquid supplied to the first treatment liquid nozzle 5 includes pure water (deionized water), carbonated water, electrolytic ionic water, hydrogen water, ozone water, and a diluted concentration (for example, about 10 to 100 ppm). Examples thereof include hydrochloric acid water.

  In addition, a volatile processing liquid having higher volatility than pure water is supplied to the second processing liquid nozzle 6 via a second processing liquid supply pipe 26 in which a second processing liquid valve 25 is interposed. Supplied from a source. Similarly, a volatile processing liquid having a higher volatility than pure water is supplied to the third processing liquid nozzle 7 via a third processing liquid supply pipe 28 in which a third processing liquid valve 27 is interposed. Supplied from a liquid supply source.

  The volatile treatment liquid supplied to the second and third treatment liquid nozzles 6 and 7 is a liquid containing at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, and acetone. Can be illustrated. That is, the volatile processing liquid may be composed of only a single component or may be mixed with other components. For example, a mixed solution of IPA and pure water or a mixed solution of IPA and HFE may be used. IPA, HFE, methanol, ethanol, and acetone are organic solvents that have higher volatility than pure water and can easily dissolve pure water. In addition, the volatile processing liquid supplied to the second and third processing liquid nozzles 6 and 7 may be the same type of volatile processing liquid or different types of volatile processing liquid.

  Opening and closing of the chemical liquid valve 21 and the rinse liquid valve 23 is controlled by the control unit 12. The nozzle swing mechanism corresponding to the first processing liquid nozzle 5 is controlled by the control unit 12. The control unit 12 moves the processing liquid from the first processing liquid nozzle 5 toward the center of the upper surface of the substrate W with the first processing liquid nozzle 5 positioned above the central part of the substrate W held by the spin chuck 3. Can be discharged. As a result, the processing liquid can be deposited on the center of the upper surface of the substrate W held by the spin chuck 3 and supplied to the upper surface of the substrate W.

  In this embodiment, the substrate W is processed by the first processing liquid nozzle 5, the chemical liquid valve 21, the chemical liquid supply pipe 22, the rinse liquid valve 23, the rinse liquid supply pipe 24, the nozzle arm 18, the support shaft 19, and the nozzle swing mechanism 20. A treatment liquid supply means for supplying the liquid is configured. As described above, the first processing liquid nozzle 5 may be configured to be moved horizontally by the nozzle swing mechanism 20, or the substrate W on which the discharged processing liquid is held by the spin chuck 3. It may be fixed at a fixed position so as to be deposited on the central portion of the upper surface.

  The opening and closing of the second and third processing liquid valves 25 and 27 is controlled by the control unit 12. Further, the nozzle swinging mechanism corresponding to the second processing liquid nozzle 6 and the nozzle swinging mechanism 20 corresponding to the third processing liquid nozzle 7 are controlled by the control unit 12. The controller 12 is volatile from the second processing liquid nozzle 6 toward the center of the upper surface of the substrate W with the second processing liquid nozzle 6 positioned above the center of the substrate W held by the spin chuck 3. The treatment liquid can be discharged. Thereby, the volatile processing liquid can be deposited on the center of the upper surface of the substrate W held by the spin chuck 3, and the volatile processing liquid can be supplied to the upper surface of the substrate W. Further, the control unit 12 has positioned the third processing liquid nozzle 7 above a predetermined position P1 that is a fixed distance away from the rotation axis L1 of the substrate W excluding the central portion on the upper surface of the substrate W held by the spin chuck 3. In this state, the volatile processing liquid can be discharged from the third processing liquid nozzle 7 toward the predetermined position P1 of the substrate W. Accordingly, the volatile processing liquid can be applied to the predetermined position P1 of the substrate W held by the spin chuck 3 and the volatile processing liquid can be supplied to the upper surface of the substrate W.

  In this embodiment, the second and third processing liquid nozzles 6 and 7, the second and third processing liquid valves 25 and 27, the second and third processing liquid supply pipes 26 and 28, the nozzle arm 18, the support shaft 19, The nozzle swing mechanism 20 constitutes a volatile processing liquid supply means. In this embodiment, the second processing liquid nozzle 6 functions as a first fixed nozzle, and the third processing liquid nozzle 7 functions as a second fixed nozzle. As described above, the second and third processing liquid nozzles 6 and 7 may be configured so as to be horizontally moved by the nozzle swinging mechanism 20, and the discharged processing liquid may be disposed on the substrate W, respectively. It may be fixed at a fixed position so as to land on the center of the upper surface and the predetermined position P1.

2A to 2G are process diagrams for explaining an example of processing of the substrate W by the substrate processing apparatus 1 according to the first embodiment of the present invention. Hereinafter, an example of processing of the substrate W by the substrate processing apparatus 1 will be described with reference to FIG. In each step of this processing example, FIGS. 2A to 2G are referred to as appropriate.
The unprocessed substrate W is carried into the processing chamber 2 by a transfer robot (not shown), and is transferred to the spin chuck 3 with the surface, which is a device formation surface, facing upward, for example. When the substrate W is carried into the processing chamber 2, the configuration inside the processing chamber 2 such as the gas nozzle 4 is retracted from above the spin chuck 3 so as not to collide with the transfer robot or the substrate W. .

  Next, a chemical solution treatment for treating the substrate W with hydrofluoric acid, which is an example of a chemical solution, is performed. Specifically, the control unit 12 controls the nozzle swing mechanism corresponding to the first processing liquid nozzle 5, and the first processing liquid nozzle 5 is disposed above the central portion of the substrate W held by the spin chuck 3. The Further, after the substrate W is held on the spin chuck 3, the control unit 12 controls the spin motor 11 to rotate the substrate W at a predetermined rotation speed (for example, 800 rpm). Thereafter, the chemical liquid valve 21 is opened by the control unit 12, and hydrofluoric acid is discharged from the first processing liquid nozzle 5 toward the center of the upper surface of the substrate W.

  As shown in FIG. 2A, the hydrofluoric acid discharged from the first treatment liquid nozzle 5 is deposited on the central portion of the upper surface of the substrate W, and receives the centrifugal force generated by the rotation of the substrate W to remove the hydrofluoric acid from the substrate W. (In a direction away from the rotation axis L1). As a result, hydrofluoric acid is supplied to the entire upper surface of the substrate W, and a chemical solution treatment using hydrofluoric acid is performed on the entire upper surface of the substrate W. When the chemical processing is performed for a predetermined time, the control portion 12 closes the chemical valve 21 and stops the discharge of hydrofluoric acid from the first processing liquid nozzle 5.

  Next, a rinsing process in which the substrate W is washed away with pure water which is an example of a rinsing liquid is performed. Specifically, the spin motor 11 is controlled by the controller 12, and the rotation speed of the substrate W is changed (for example, changed to 1200 rpm). Thereafter, the rinsing liquid valve 23 is opened by the control unit 12, and pure water is discharged from the first processing liquid nozzle 5 toward the center of the upper surface of the rotating substrate W.

  As shown in FIG. 2B, the pure water discharged from the first treatment liquid nozzle 5 is deposited on the central portion of the upper surface of the substrate W, and receives the centrifugal force generated by the rotation of the substrate W to remove the surface of the substrate W. It spreads toward you. Thereby, pure water is supplied to the entire upper surface of the substrate W, and the hydrofluoric acid on the substrate W is washed away by the pure water. In this way, hydrofluoric acid is removed from the substrate W, and the top surface of the substrate W is rinsed with pure water.

  Next, a paddle process using pure water is performed in which the process proceeds while the liquid film of pure water is held on the substrate W. Specifically, the spin motor 11 is controlled by the control unit 12 in a state where the pure water is continuously discharged from the first treatment liquid nozzle 5, and the substrate W is in a low-speed rotation state (for example, at a rotation speed of about 10 rpm). Rotating state). As a result, the centrifugal force acting on the pure water on the substrate W is weakened, and the amount of pure water discharged around the substrate W is reduced. Accordingly, the pure water supplied from the first processing liquid nozzle 5 is accumulated on the upper surface of the substrate W, and liquid piling with the pure water is performed. As a result, a pure water liquid film covering the entire upper surface of the substrate W is formed.

  After the liquid film of pure water is formed on the substrate W, the rinsing liquid valve 23 is closed by the control unit 12, and the pure water from the first treatment liquid nozzle 5 is closed as shown in FIG. Discharge is stopped. The state in which the liquid film of pure water is held on the substrate W is maintained for a predetermined time. In this manner, the paddle process using pure water is performed on the upper surface of the substrate W, in which the process is performed in a state where the liquid film of pure water is held on the substrate W. When the paddle processing with pure water is performed for a predetermined time, the control unit 12 controls the nozzle swinging mechanism corresponding to the first processing liquid nozzle 5 so that the first processing liquid nozzle 5 is retracted from above the substrate W. Be made.

  Next, an IPA replacement process is performed in which the liquid film of pure water on the substrate W is replaced by IPA, which is an example of a volatile processing liquid having higher volatility than pure water. Specifically, the control unit 12 controls the nozzle swing mechanism corresponding to the second processing liquid nozzle 6, and the second processing liquid nozzle 6 is disposed above the central portion of the substrate W held by the spin chuck 3. The Thereafter, the second processing liquid valve 25 is opened by the control unit 12, and IPA is discharged from the second processing liquid nozzle 6 toward the center of the upper surface of the substrate W at a predetermined discharge flow rate (for example, 100 mL / min). Further, while IPA is being discharged from the second processing liquid nozzle 6, the spin motor 11 is controlled by the controller 12, and the substrate W in the low-speed rotation state is accelerated to a predetermined rotation speed. In the IPA replacement process in the processing example of the substrate W, for example, the rotation of the substrate W is accelerated stepwise in the order of 10 rpm, 50 rpm, 75 rpm, 100 rpm, and 500 rpm, and the rotation speed of the substrate W is maintained at 500 rpm.

  The IPA discharged from the second processing liquid nozzle 6 is deposited on the center of the upper surface of the substrate W, and spreads outward on the substrate W under the centrifugal force due to the rotation of the substrate W. Further, the IPA that has landed on the central portion of the upper surface of the substrate W is pushed outward by the IPA that is successively supplied. Accordingly, the pure water liquid film held on the substrate W is gradually replaced with IPA from the center of the upper surface of the substrate W outward as shown in FIG. Further, since IPA is an organic solvent that can easily dissolve pure water used as a rinsing liquid in an example of the processing of the substrate W, the pure water on the substrate W is dissolved in the IPA while the substrate W is dissolved. The pure water above is replaced by IPA. Further, in the IPA replacement process in the processing example of the substrate W, since the rotation of the substrate W is accelerated stepwise, the centrifugal force acting on the pure water and the IPA on the substrate W increases stepwise, The liquid film of pure water held on the substrate W is surely replaced with IPA outward from the center of the upper surface of the substrate W. In this way, the IPA replacement process for replacing the pure water liquid film on the substrate W with the IPA liquid film is performed for a predetermined time (for example, 60 seconds), and the entire upper surface of the substrate W is covered with the IPA liquid film ( Liquid film forming step).

  Next, a drying process (spin drying) for drying the substrate W is performed. Specifically, the nozzle swing mechanism 15 corresponding to the gas nozzle 4 is controlled by the control unit 12, and the gas nozzle 4 is disposed in the vicinity of the second processing liquid nozzle 6 located above the center of the substrate W. . Further, the control unit 12 controls the nozzle swing mechanism 20 corresponding to the third processing liquid nozzle 7, and the third processing liquid nozzle 7 is disposed above the predetermined position P 1 of the substrate W held by the spin chuck 3. The More specifically, when processing a circular substrate having a diameter of 300 mm, for example, a position 40 mm inside from the outer peripheral edge of the upper surface of the substrate W is set as the predetermined position P1 and discharged from the third processing liquid nozzle 7. The third treatment liquid nozzle 7 is arranged so that the volatile treatment liquid is deposited at the predetermined position P1.

  After the gas nozzle 4 is disposed in the vicinity of the second processing liquid nozzle 6, the second processing liquid valve 25 is closed by the control unit 12, and the discharge of IPA from the second processing liquid nozzle 6 is stopped. Further, almost simultaneously with the stop of the discharge of IPA from the second processing liquid nozzle 6, the control unit 12 controls the nozzle swinging mechanism corresponding to the second processing liquid nozzle 6, and the second processing liquid nozzle 6. Is retracted from above the substrate W held by the spin chuck 3. Further, almost simultaneously with the withdrawal of the second processing liquid nozzle 6 from above the substrate W, the control unit 12 controls the nozzle swinging mechanism 15 corresponding to the gas nozzle 4 so that the gas nozzle is positioned above the center of the substrate W. 4 is arranged. The control unit 12 opens the gas valve 16 immediately after the gas nozzle 4 is disposed above the central portion of the substrate W, and as shown in FIG. It is discharged from the gas nozzle 4 toward the center of the upper surface of the rotating substrate W (for example, 20 L / min) (gas supply step). Therefore, the nitrogen gas discharged from the gas nozzle 4 is sprayed on the central portion of the upper surface of the substrate W almost simultaneously with the supply of IPA from the second processing liquid nozzle 6 being stopped. At this time, the control unit 12 controls the spin motor 11 to change the rotation speed of the substrate W to a predetermined rotation speed (for example, 700 rpm) and hold the IPA liquid film on the substrate W. The substrate W is rotated at (substrate rotating step).

  On the other hand, after the third processing liquid nozzle 7 is disposed above the predetermined position P1 of the substrate W held by the spin chuck 3, the control section 12 opens the third processing liquid valve 27, and FIG. ), IPA, which is an example of a volatile processing liquid having a higher volatility than pure water, is discharged from the third processing liquid nozzle 7 toward the predetermined position P1 of the substrate W in the rotating state. The IPA discharged from the third treatment liquid nozzle 7 is deposited on a predetermined position P1 of the substrate W, and receives the centrifugal force due to the rotation of the substrate W and spreads outward on the substrate W (supply of volatile treatment liquid). Process). Thereby, the IPA discharged from the third processing liquid nozzle 7 is supplied to the upper surface of the substrate W.

  The timing at which IPA is discharged from the third treatment liquid nozzle 7 may be simultaneously with the discharge of nitrogen gas from the gas nozzle 4 or may be before the nitrogen gas is discharged from the gas nozzle 4. For example, IPA may be discharged from the third processing liquid nozzle 7 while IPA is discharged from the second processing liquid nozzle 6. In addition, the timing of discharging the IPA from the third treatment liquid nozzle 7 may be after the nitrogen gas is discharged from the gas nozzle 4, but in this case, as described later, the annular IPA is discharged. It is preferable that the discharge of IPA from the third treatment liquid nozzle 7 is started before the inner periphery of the liquid film reaches the predetermined position P1. Furthermore, in the case where IPA is discharged from the third treatment liquid nozzle 7 after the nitrogen gas is discharged from the gas nozzle 4, the IPA is removed from at least the upper surface periphery of the substrate W, and the upper surface periphery of the substrate W is dried. It is preferable to discharge the IPA from the third treatment liquid nozzle 7 before starting the operation.

  As described above, the nitrogen gas discharged from the gas nozzle 4 is blown to the center of the upper surface of the substrate W. By blowing nitrogen gas onto the central portion of the upper surface of the substrate W, IPA is removed from the central portion of the upper surface of the substrate W by the supply pressure of the nitrogen gas. Accordingly, as shown in FIG. 2E, a hole is formed in the central portion of the IPA liquid film held on the substrate W, and the IPA liquid film becomes annular. Further, since the centrifugal force acts on the IPA on the substrate W by the rotation of the substrate W, the IPA moves outward and the inner diameter of the annular liquid film becomes larger. Furthermore, since the nitrogen gas sprayed onto the substrate W spreads radially from the center of the upper surface of the substrate W toward the peripheral edge of the upper surface, the inner diameter of the liquid film that is pressed by the nitrogen gas and becomes annular increases. Furthermore, nitrogen gas is blown onto the IPA liquid film, and IPA evaporates. Therefore, the circular IPA liquid film is pushed outward by centrifugal force or nitrogen gas supply pressure, and the inner diameter is increased by evaporation of IPA.

  Further, the centrifugal force acting on the IPA held on the substrate W increases as the distance from the rotation axis L1 of the substrate W increases. Therefore, the IPA held on the peripheral edge of the upper surface of the substrate W moves outward at a higher speed than the IPA inside. On the other hand, the IPA that has landed on the predetermined position P <b> 1 of the substrate W moves outward under the centrifugal force due to the rotation of the substrate W. Therefore, although the IPA held at the peripheral edge of the upper surface of the substrate W moves outward at a higher speed than the IPA inside the IPA, the IPA that has landed at the predetermined position P1 is supplied to the peripheral edge of the upper surface of the substrate W. The IPA does not completely disappear from the peripheral edge of the upper surface of the substrate W, and the state where the IPA is held at the peripheral edge of the upper surface of the substrate W is maintained. Therefore, it is possible to suppress or prevent the upper surface peripheral portion of the substrate W from being dried first in a state where the region inside the peripheral portion on the upper surface of the substrate W is not completely dried.

  As described above, in the drying process in the processing example of the substrate W, the inner diameter of the liquid film of the IPA that is annular increases while the state where the IPA is held on the peripheral edge of the upper surface of the substrate W is increased. When the inner periphery of the annular IPA liquid film reaches a position before the predetermined position P1, which is the IPA liquid deposition position, the control unit 12 closes the third processing liquid valve 27, and FIG. ), The discharge of IPA from the third treatment liquid nozzle 7 is stopped. Accordingly, it is possible to suppress or prevent the IPA discharged from the third processing liquid nozzle 7 from entering the region where the IPA on the upper surface of the substrate W has been removed, thereby preventing the drying of the substrate W. Thereby, the board | substrate W can be dried rapidly.

  After the discharge of IPA from the third processing liquid nozzle 7 is stopped, the IPA on the substrate W spreads outward in a state where nitrogen gas is continuously blown to the center of the upper surface of the rotating substrate W. While being discharged from the peripheral edge of the upper surface of the substrate W. As a result, as shown in FIG. 2G, the IPA is removed from the substrate W, and all the IPAs are removed. When all the IPAs are removed from the substrate W, the spin motor 11 is controlled by the control unit 12 and the rotation of the substrate W by the spin chuck 3 is stopped. Thereafter, the gas valve 16 is closed by the controller 12 and the discharge of the nitrogen gas from the gas nozzle 4 is stopped. Further, the nozzle swinging mechanism 15 corresponding to the gas nozzle 4 and the nozzle swinging mechanism 20 corresponding to the third processing liquid nozzle 7 are controlled by the control unit 12 so that the gas nozzle 4 and the third processing liquid nozzle 7 become the substrate. Retreated from above W. Then, the processed substrate W is unloaded from the processing chamber 2 by the transfer robot.

  As described above, in the drying process in the processing example of the substrate W, the IPA on the substrate W spreads outward from the center of the upper surface of the substrate W and is discharged from the peripheral edge of the upper surface of the substrate W to the periphery. . Therefore, the upper surface of the substrate W is dried outward from the central portion, and the peripheral portion becomes the final drying position. As a result, even when pure water is dissolved in the IPA on the substrate W, poor drying such as a watermark or pattern collapse occurs in the intermediate region (the annular region between the upper surface central portion and the upper surface peripheral portion of the substrate W). Occurrence can be suppressed or prevented. Further, since IPA is removed from the substrate W while discharging the IPA from the peripheral edge of the upper surface of the substrate W, the IPA mixed with pure water can be removed without remaining on the substrate W. As a result, it is possible to suppress or prevent the occurrence of poor drying due to pure water on the upper surface of the substrate W.

  In addition, in the drying process in the processing example of the substrate W, the IPA on the substrate W is removed while blowing nitrogen gas to the central portion of the upper surface of the substrate W. Therefore, when the drying of the substrate W is in progress, the substrate W The entire exposed portion of the upper surface (portion from which IPA has been removed) can be continuously covered with nitrogen gas. Further, in the drying process in this processing example of the substrate W, the supply of nitrogen gas to the upper surface of the substrate W is continued until all the IPAs are removed from the substrate W, so that the entire upper surface of the substrate W is covered with nitrogen gas. it can. Thereby, it is possible to suppress or prevent foreign matters such as particles and mist of the processing liquid from adhering to the exposed portion of the upper surface of the substrate W while the substrate W is being dried. Therefore, the entire upper surface of the substrate W can be quickly dried, and contamination of the substrate W due to adhesion of foreign matter or mist can be suppressed or prevented. Furthermore, in the drying process in this processing example of the substrate W, the supply of nitrogen gas to the upper surface of the substrate W is continued until the rotation of the substrate W is stopped, so that the foreign matter carried by the turbulence accompanying the rotation of the substrate W It is possible to suppress or prevent the mist from adhering to the substrate W. Thereby, the contamination of the substrate W can be further suppressed or prevented.

FIG. 3 is an illustrative view showing a schematic configuration of a substrate processing apparatus 101 according to the second embodiment of the present invention. 3, the same components as those shown in FIG. 1 and the like described above are denoted by the same reference numerals as those in FIG. 1 and the description thereof is omitted.
The main difference between the second embodiment and the first embodiment described above is that instead of the second and third processing liquid nozzles 6 and 7 provided in the substrate processing apparatus 1 according to the first embodiment, a spin is provided. The fourth processing liquid nozzle 29 (moving nozzle) for supplying a volatile processing liquid having higher volatility than pure water is provided on the upper surface of the substrate W held by the chuck 3. The fourth processing liquid nozzle 29 is, for example, a straight nozzle that discharges the volatile processing liquid in a continuous flow state, and is disposed above the spin chuck 3 with the discharge port facing downward. For example, the fourth treatment liquid nozzle 29 can discharge a volatile treatment liquid vertically downward.

  The 4th process liquid nozzle 29 is attached to the front-end | tip part of the nozzle arm 30 extended horizontally. The nozzle arm 30 is supported by a support shaft 31 that extends vertically. The support shaft 31 is disposed around the spin chuck 3 and can swing around its central axis. By swinging the support shaft 31 around the central axis, the fourth processing liquid nozzle 29 can be moved horizontally along an arcuate path passing above the center of the substrate W held by the spin chuck 3. The support shaft 31 can be swung by a nozzle rocking mechanism 32 (nozzle moving means). A volatile processing liquid is supplied to the fourth processing liquid nozzle 29 from a processing liquid supply source (not shown) via a fourth processing liquid supply pipe 34 in which a fourth processing liquid valve 33 (switching means) is interposed. Is done.

  Opening and closing of the fourth processing liquid valve 33 is controlled by the control unit 12. Further, the nozzle swinging mechanism 32 corresponding to the fourth processing liquid nozzle 29 is controlled by the control unit 12. The controller 12 discharges the volatile processing liquid from the fourth processing liquid nozzle 29 toward the upper surface of the substrate W in a state where the fourth processing liquid nozzle 29 is positioned above the substrate W held by the spin chuck 3. Can be made. Further, the control unit 12 can horizontally move the fourth processing liquid nozzle 29 in a state where the discharge of the volatile processing liquid from the fourth processing liquid nozzle 29 is stopped. Further, the control unit 12 horizontally moves the fourth processing liquid nozzle 29 so that the liquid deposition position of the volatile processing liquid from the fourth processing liquid nozzle 29 with respect to the upper surface of the substrate W is changed to the upper surface central portion and upper surface peripheral edge of the substrate W. It can be moved between parts. In this embodiment, the fourth processing liquid nozzle 29, the fourth processing liquid valve 33, the fourth processing liquid supply pipe 34, the nozzle arm 30, the support shaft 31, and the nozzle swing mechanism 32 constitute a volatile processing liquid supply means. ing.

FIGS. 4A to 4H are process diagrams for explaining an example of processing of the substrate W by the substrate processing apparatus 101 according to the second embodiment of the present invention. Hereinafter, an example of processing of the substrate W by the substrate processing apparatus 101 will be described with reference to FIG. In each step of this processing example, FIGS. 4A to 4H are referred to as appropriate.
The difference between the processing example of the substrate W described below and an example of the processing of the substrate W by the substrate processing apparatus 1 described above is that, in the processing example of the substrate W by the substrate processing apparatus 1, two processing liquid nozzles (second In the processing example of the substrate W, one processing liquid nozzle (fourth processing liquid nozzle 29) is used, while the volatile processing liquid is supplied to the upper surface of the substrate W using the third processing liquid nozzles 6 and 7). Is to supply a volatile treatment liquid to the upper surface of the substrate W.

The unprocessed substrate W is carried into the processing chamber 2 by a transfer robot (not shown), and is transferred to the spin chuck 3 with the surface, which is a device formation surface, facing upward, for example. When the substrate W is carried into the processing chamber 2, the configuration inside the processing chamber 2 such as the gas nozzle 4 is retracted from above the spin chuck 3 so as not to collide with the transfer robot or the substrate W. .
Next, a chemical solution treatment for treating the substrate W with hydrofluoric acid, which is an example of a chemical solution, is performed. Specifically, the control unit 12 controls the nozzle swing mechanism corresponding to the first processing liquid nozzle 5, and the first processing liquid nozzle 5 is disposed above the central portion of the substrate W held by the spin chuck 3. The Further, after the substrate W is held on the spin chuck 3, the control unit 12 controls the spin motor 11 to rotate the substrate W at a predetermined rotation speed (for example, 800 rpm). Thereafter, the chemical liquid valve 21 is opened by the control unit 12, and hydrofluoric acid is discharged from the first processing liquid nozzle 5 toward the center of the upper surface of the substrate W.

  As shown in FIG. 4A, the hydrofluoric acid discharged from the first treatment liquid nozzle 5 is deposited on the central portion of the upper surface of the substrate W, and receives the centrifugal force generated by the rotation of the substrate W to remove the hydrofluoric acid. (In a direction away from the rotation axis L1). As a result, hydrofluoric acid is supplied to the entire upper surface of the substrate W, and a chemical solution treatment using hydrofluoric acid is performed on the entire upper surface of the substrate W. When the chemical processing is performed for a predetermined time, the control portion 12 closes the chemical valve 21 and stops the discharge of hydrofluoric acid from the first processing liquid nozzle 5.

  Next, a rinsing process in which the substrate W is washed away with pure water which is an example of a rinsing liquid is performed. Specifically, the spin motor 11 is controlled by the controller 12, and the rotation speed of the substrate W is changed (for example, changed to 1200 rpm). Thereafter, the rinsing liquid valve 23 is opened by the control unit 12, and pure water is discharged from the first processing liquid nozzle 5 toward the center of the upper surface of the rotating substrate W.

  As shown in FIG. 4B, the pure water discharged from the first treatment liquid nozzle 5 is deposited on the central portion of the upper surface of the substrate W, and receives the centrifugal force generated by the rotation of the substrate W to remove the surface of the substrate W. It spreads toward you. Thereby, pure water is supplied to the entire upper surface of the substrate W, and the hydrofluoric acid on the substrate W is washed away by the pure water. In this way, hydrofluoric acid is removed from the substrate W, and the top surface of the substrate W is rinsed with pure water.

  Next, a paddle process using pure water is performed in which the process proceeds while the liquid film of pure water is held on the substrate W. Specifically, the spin motor 11 is controlled by the control unit 12 in a state where the pure water is continuously discharged from the first treatment liquid nozzle 5, and the substrate W is in a low-speed rotation state (for example, at a rotation speed of about 10 rpm). Rotating state). As a result, the centrifugal force acting on the pure water on the substrate W is weakened, and the amount of pure water discharged around the substrate W is reduced. Accordingly, the pure water supplied from the first processing liquid nozzle 5 is accumulated on the upper surface of the substrate W, and liquid piling with the pure water is performed. As a result, a pure water liquid film covering the entire upper surface of the substrate W is formed.

  After the liquid film of pure water is formed on the substrate W, the rinsing liquid valve 23 is closed by the controller 12, and the pure water from the first treatment liquid nozzle 5 is closed as shown in FIG. Discharge is stopped. The state in which the liquid film of pure water is held on the substrate W is maintained for a predetermined time. In this manner, the paddle process using pure water is performed on the upper surface of the substrate W, in which the process is performed in a state where the liquid film of pure water is held on the substrate W. When the paddle processing with pure water is performed for a predetermined time, the control unit 12 controls the nozzle swinging mechanism corresponding to the first processing liquid nozzle 5 so that the first processing liquid nozzle 5 is retracted from above the substrate W. Be made.

  Next, an IPA replacement process is performed in which the liquid film of pure water on the substrate W is replaced by IPA, which is an example of a volatile processing liquid having higher volatility than pure water. Specifically, the control unit 12 controls the nozzle swinging mechanism 32 corresponding to the fourth processing liquid nozzle 29, and the fourth processing liquid nozzle 29 is disposed above the central portion of the substrate W held by the spin chuck 3. Is done. Thereafter, the fourth processing liquid valve 33 is opened by the control unit 12, and IPA is discharged from the fourth processing liquid nozzle 29 toward the center of the upper surface of the substrate W at a predetermined discharge flow rate (for example, 100 mL / min). Further, while IPA is being discharged from the fourth processing liquid nozzle 29, the spin motor 11 is controlled by the control unit 12, and the substrate W in the low-speed rotation state is accelerated to a predetermined rotation speed. In the IPA replacement process in the processing example of the substrate W, for example, the rotation of the substrate W is accelerated stepwise in the order of 10 rpm, 50 rpm, 75 rpm, 100 rpm, and 500 rpm, and the rotation speed of the substrate W is maintained at 500 rpm.

  The IPA discharged from the fourth processing liquid nozzle 29 is deposited on the center of the upper surface of the substrate W, and spreads outward on the substrate W under the centrifugal force due to the rotation of the substrate W. Further, the IPA that has landed on the central portion of the upper surface of the substrate W is pushed outward by the IPA that is successively supplied. Therefore, the pure water liquid film held on the substrate W is gradually replaced with IPA from the center of the upper surface of the substrate W outward as shown in FIG. Further, since IPA is an organic solvent that can easily dissolve pure water used as a rinsing liquid in an example of the processing of the substrate W, the pure water on the substrate W is dissolved in the IPA while the substrate W is dissolved. The pure water above is replaced by IPA. Further, in the IPA replacement process in the processing example of the substrate W, since the rotation of the substrate W is accelerated stepwise, the centrifugal force acting on the pure water and the IPA on the substrate W increases stepwise, The liquid film of pure water held on the substrate W is surely replaced with IPA outward from the center of the upper surface of the substrate W. In this way, the IPA replacement process for replacing the pure water liquid film on the substrate W with the IPA liquid film is performed for a predetermined time (for example, 60 seconds), and the entire upper surface of the substrate W is covered with the IPA liquid film ( Liquid film forming step).

  Next, a drying process (spin drying) for drying the substrate W is performed. Specifically, the control unit 12 controls the nozzle swinging mechanism 15 corresponding to the gas nozzle 4, so that the fourth process is located above the central part of the substrate W above the substrate W held by the spin chuck 3. The gas nozzle 4 is disposed at a position close to the liquid nozzle 29. Thereafter, the fourth processing liquid valve 33 is closed by the control unit 12, and the discharge of IPA from the fourth processing liquid nozzle 29 is stopped. Further, almost simultaneously with the stop of the discharge of IPA from the fourth processing liquid nozzle 29, the nozzle swing mechanism 32 corresponding to the fourth processing liquid nozzle 29 is controlled by the control unit 12, and FIG. 4, the fourth processing liquid nozzle 29 is horizontally moved from above the central portion of the substrate W held by the spin chuck 3 to above the predetermined position P1 (nozzle moving step). At this time, it is preferable that the rotation of the substrate W held by the spin chuck 3 is stopped or the rotation speed is low. By stopping the rotation of the substrate W or reducing the rotation speed of the substrate W, it is possible to suppress or prevent the IPA from spilling from the peripheral edge of the upper surface of the substrate W and exposing the peripheral edge of the upper surface of the substrate W. .

  When the fourth processing liquid nozzle 29 moves from above the center of the substrate W, the control unit 12 controls the nozzle swinging mechanism 15 corresponding to the gas nozzle 4 to move the substrate W held on the spin chuck 3. The gas nozzle 4 is disposed above the center of the nozzle. Then, the control unit 12 opens the gas valve 16 immediately after the gas nozzle 4 is disposed above the center of the substrate W, and rotates nitrogen gas, which is an example of gas, at a predetermined discharge flow rate (for example, 20 L / min). The gas is discharged from the gas nozzle 4 toward the center of the upper surface of the substrate W in a state (gas supply process). Accordingly, the nitrogen gas discharged from the gas nozzle 4 is blown onto the central portion of the upper surface of the substrate W almost simultaneously with the supply of IPA from the fourth processing liquid nozzle 29 being stopped. At this time, the control unit 12 controls the spin motor 11 to change the rotation speed of the substrate W to a predetermined rotation speed (for example, 700 rpm) and hold the IPA liquid film on the substrate W. The substrate W is rotated at (substrate rotating step).

  On the other hand, after the fourth processing liquid nozzle 29 is disposed above the predetermined position P1 of the substrate W held by the spin chuck 3, the control section 12 opens the fourth processing liquid valve 33, and FIG. ), The IPA is discharged from the fourth processing liquid nozzle 29 toward the predetermined position P1 of the rotating substrate W. The IPA discharged from the fourth processing liquid nozzle 29 is applied to a predetermined position P1 of the substrate W, and spreads outward on the substrate W by receiving a centrifugal force due to the rotation of the substrate W (supply of volatile processing liquid). Process). Thereby, the IPA discharged from the fourth processing liquid nozzle 29 is supplied to the upper surface of the substrate W.

  The timing at which IPA is discharged from the fourth treatment liquid nozzle 29 may be simultaneously with the discharge of nitrogen gas from the gas nozzle 4 or may be before the nitrogen gas is discharged from the gas nozzle 4. Further, the timing of discharging the IPA from the fourth treatment liquid nozzle 29 may be after the nitrogen gas is discharged from the gas nozzle 4, but in this case, as described later, the annular IPA is discharged. It is preferable that the discharge of IPA from the fourth treatment liquid nozzle 29 is started before the inner periphery of the liquid film reaches the predetermined position P1. Furthermore, in the case where IPA is discharged from the fourth treatment liquid nozzle 29 after the nitrogen gas is discharged from the gas nozzle 4, the IPA is removed from at least the upper surface periphery of the substrate W, and the upper surface periphery of the substrate W is dried. It is preferable to discharge the IPA from the fourth treatment liquid nozzle 29 before starting the operation.

  As described above, the nitrogen gas discharged from the gas nozzle 4 is blown to the center of the upper surface of the substrate W. By blowing nitrogen gas onto the central portion of the upper surface of the substrate W, IPA is removed from the central portion of the upper surface of the substrate W by the supply pressure of the nitrogen gas. Therefore, as shown in FIG. 4F, a hole is formed in the center of the IPA liquid film held on the substrate W, and the IPA liquid film becomes annular. Further, since the centrifugal force acts on the IPA on the substrate W by the rotation of the substrate W, the IPA moves outward and the inner diameter of the annular liquid film becomes larger. Furthermore, since the nitrogen gas sprayed onto the substrate W spreads radially from the center of the upper surface of the substrate W toward the peripheral edge of the upper surface, the inner diameter of the liquid film that is pressed by the nitrogen gas and becomes annular increases. Furthermore, nitrogen gas is blown onto the IPA liquid film, and IPA evaporates. Therefore, the circular IPA liquid film is pushed outward by centrifugal force or nitrogen gas supply pressure, and the inner diameter is increased by evaporation of IPA.

  Further, the centrifugal force acting on the IPA held on the substrate W increases as the distance from the rotation axis L1 of the substrate W increases. Therefore, the IPA held on the peripheral edge of the upper surface of the substrate W moves outward at a higher speed than the IPA inside. On the other hand, the IPA that has landed on the predetermined position P <b> 1 of the substrate W moves outward under the centrifugal force due to the rotation of the substrate W. Therefore, although the IPA held at the peripheral edge of the upper surface of the substrate W moves outward at a higher speed than the IPA inside the IPA, the IPA that has landed at the predetermined position P1 is supplied to the peripheral edge of the upper surface of the substrate W. The IPA does not completely disappear from the peripheral edge of the upper surface of the substrate W, and the state where the IPA is held at the peripheral edge of the upper surface of the substrate W is maintained. Therefore, drying of the upper surface peripheral portion of the substrate W in a state where the region inside the peripheral portion on the upper surface of the substrate W is not completely dried is suppressed or prevented.

  As described above, in the drying process in the processing example of the substrate W, the inner diameter of the liquid film of the IPA that is annular increases while the state where the IPA is held on the peripheral edge of the upper surface of the substrate W is increased. When the inner periphery of the annular IPA liquid film reaches a position before the predetermined position P1, which is the IPA liquid deposition position, the control unit 12 closes the fourth processing liquid valve 33, and FIG. ), The discharge of IPA from the fourth treatment liquid nozzle 29 is stopped. Accordingly, it is possible to suppress or prevent the IPA discharged from the fourth processing liquid nozzle 29 from entering the area where the IPA on the upper surface of the substrate W has been removed, and hindering the drying of the substrate W. Thereby, the board | substrate W can be dried rapidly.

  After the discharge of IPA from the fourth processing liquid nozzle 29 is stopped, the IPA on the substrate W spreads outward in a state where nitrogen gas is continuously blown to the center of the upper surface of the rotating substrate W. While being discharged from the peripheral edge of the upper surface of the substrate W. As a result, as shown in FIG. 4H, the IPA is removed from the substrate W, and all the IPAs are removed. When all the IPAs are removed from the substrate W, the spin motor 11 is controlled by the control unit 12 and the rotation of the substrate W by the spin chuck 3 is stopped. Thereafter, the gas valve 16 is closed by the controller 12 and the discharge of the nitrogen gas from the gas nozzle 4 is stopped. Further, the nozzle swinging mechanism 15 corresponding to the gas nozzle 4 and the nozzle swinging mechanism 20 corresponding to the fourth processing liquid nozzle 29 are controlled by the control unit 12 so that the gas nozzle 4 and the fourth processing liquid nozzle 29 become the substrate. Retreated from above W. Then, the processed substrate W is unloaded from the processing chamber 2 by the transfer robot.

  As described above, in the drying process in the processing example of the substrate W, the IPA on the substrate W is directed outward from the center of the upper surface of the substrate W, as in the processing example of the substrate W according to the first embodiment. And then discharged from the peripheral edge of the upper surface of the substrate W to the periphery. Therefore, the upper surface of the substrate W is dried outward from the central portion, and the peripheral portion becomes the final drying position. As a result, even when pure water is dissolved in the IPA on the substrate W, poor drying such as a watermark or pattern collapse occurs in the intermediate region (the annular region between the upper surface central portion and the upper surface peripheral portion of the substrate W). Occurrence can be suppressed or prevented. Further, since IPA is removed from the substrate W while discharging the IPA from the peripheral edge of the upper surface of the substrate W, the IPA mixed with pure water can be removed without remaining on the substrate W. As a result, it is possible to suppress or prevent the occurrence of poor drying due to pure water on the upper surface of the substrate W.

  In addition, in the drying process in the processing example of the substrate W, the IPA on the substrate W is removed while blowing nitrogen gas to the central portion of the upper surface of the substrate W. Therefore, when the drying of the substrate W is in progress, the substrate W The entire exposed portion of the upper surface (portion from which IPA has been removed) can be continuously covered with nitrogen gas. Further, in the drying process in this processing example of the substrate W, the supply of nitrogen gas to the upper surface of the substrate W is continued until all the IPAs are removed from the substrate W, so that the entire upper surface of the substrate W is covered with nitrogen gas. it can. Thereby, it is possible to suppress or prevent foreign matters such as particles and mist of the processing liquid from adhering to the exposed portion of the upper surface of the substrate W while the substrate W is being dried. Therefore, the entire upper surface of the substrate W can be quickly dried, and contamination of the substrate W due to adhesion of foreign matter or mist can be suppressed or prevented. Furthermore, in the drying process in this processing example of the substrate W, the supply of nitrogen gas to the upper surface of the substrate W is continued until the rotation of the substrate W is stopped, so that the foreign matter carried by the turbulence accompanying the rotation of the substrate W It is possible to suppress or prevent the mist from adhering to the substrate W. Thereby, the contamination of the substrate W can be further suppressed or prevented.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the contents of the first and second embodiments described above, and various modifications can be made within the scope of the claims. is there. For example, in the first and second embodiments described above, the case where a tubular member having an inner diameter of about 10 mm is used as the gas nozzle 4 is described. However, the gas nozzle 4 is limited to such a configuration. I can't. For example, as shown in FIG. 5, a gas nozzle 104 including a cylindrical housing 35 and a diffusion plate 36 (two diffusion plates 36 in FIG. 5) may be used.

  The housing 35 is a cylindrical member having an inner diameter of about 34 mm, for example, and gas is supplied from one end (the upper end in FIG. 5) to the inside through the gas supply pipe 17. A gas discharge port 37 for discharging gas is formed at the other end (lower end in FIG. 5) of the housing 35. The interior of the housing 35 is partitioned in the axial direction by a diffusion plate 36. The diffusion plate 36 is formed with a plurality of flow holes 38 through which gas flows in the thickness direction (vertical direction in FIG. 5).

  The gas supplied into the housing 35 strikes the diffusion plate 36 and diffuses into the housing 35. Further, the gas supplied into the housing 35 flows from one end side to the other end side of the housing 35 while flowing through the flow holes 38 formed in the diffusion plate 36. The gas supplied to the inside of the housing 35 is discharged from the gas discharge port 37 with a pressure weaker than when supplied. Therefore, if the gas nozzle 104 is used in the above-described processing example of the substrate W, the pressure of the gas sprayed on the upper surface of the substrate W can be reduced.

  In the first and second embodiments described above, the case where the chemical liquid and the rinsing liquid are selectively discharged from the first processing liquid nozzle 5 has been described. However, two processing liquid nozzles corresponding to the chemical liquid and the rinsing liquid, respectively. May be provided. In the processing example of the substrate W according to the first and second embodiments described above, the case where the rotation of the substrate W is accelerated stepwise in the IPA replacement processing has been described. The rotation of the substrate W may be continuously accelerated up to the speed. In addition, various design changes can be made within the scope of matters described in the claims.

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 3 Spin chuck 4 Gas nozzle 6 2nd process liquid nozzle 7 3rd process liquid nozzle 11 Spin motor 12 Control part 13 Nozzle arm 14 Support shaft 15 Nozzle rocking mechanism 16 Gas valve 17 Gas supply pipe 18 Nozzle arm 19 Support shaft 20 Nozzle swing mechanism 25 Second process liquid valve 26 Second process liquid supply pipe 27 Third process liquid valve 28 Third process liquid supply pipe 29 Fourth process liquid nozzle 30 Nozzle arm 31 Support shaft 32 Nozzle swing mechanism 33 Fourth processing liquid valve 34 Fourth processing liquid supply pipe 101 Substrate processing apparatus 104 Gas nozzle L1 Rotation axis P1 Predetermined position W Substrate

Claims (7)

A rinsing liquid film forming step of supplying a rinsing liquid to the upper surface of the substrate held horizontally and forming a rinsing liquid film covering the entire upper surface of the substrate with the rinsing liquid supplied to the substrate;
After the rinsing liquid film forming step, a volatile treatment liquid having higher volatility than pure water is supplied to the upper surface of the horizontally held substrate to replace the rinsing liquid on the substrate, and the volatile liquid obtained by replacing the rinsing liquid A volatile treatment liquid film forming step of forming a volatile treatment liquid film covering the entire upper surface of the substrate with a neutral treatment liquid ;
A substrate rotation step of rotating the substrate around a vertical rotation axis passing through the central portion of the substrate while holding the volatile treatment liquid film on the substrate;
In parallel with the substrate rotation step, a gas supply step of blowing gas to the center of the upper surface of the substrate,
After the volatile treatment liquid film forming step, in parallel with the substrate rotation step and the gas supply step, the volatile treatment liquid is deposited at a predetermined position in the upper surface of the substrate that is a position outside the rotation axis . And a volatile processing liquid supply step. Said volatile treatment liquid supplying step, said volatile treatment liquid to replace the rinsing liquid in the volatile treatment liquid film forming step is moved from the central portion of the upper surface of the substrate in a direction away from said axis of rotation, said volatile treatment liquid The substrate processing method according to claim 1, wherein the substrate processing method is a step that is continued until the vicinity of a landing position of a volatile processing liquid supplied to the substrate in the supplying step. The substrate rotation step is a step that continues until at least the volatile treatment liquid film disappears from the substrate,
The substrate processing method according to claim 1, wherein the gas supply process is a process that is continued until at least the volatile processing liquid film is removed from the substrate.   The substrate processing method according to claim 1, wherein the gas supply process is a process that is continued until the substrate rotation process is completed. Substrate holding means for holding the substrate horizontally;
Substrate rotating means for rotating the substrate held by the substrate holding means around a vertical rotation axis passing through the central portion of the substrate;
Rinsing liquid supply means for supplying a rinsing liquid to the upper surface of the substrate held by the substrate holding means;
A gas supply means for blowing gas onto the center of the upper surface of the substrate held by the substrate holding means;
Volatile processing liquid supply means capable of depositing a volatile processing liquid having a higher volatility than pure water at a plurality of locations on the upper surface of the substrate including the center of the upper surface of the substrate held by the substrate holding means;
Control means for controlling the substrate holding means, substrate rotating means, rinsing liquid supply means, gas supply means and volatile treatment liquid supply means ,
The control means includes
A rinsing liquid film forming step of supplying a rinsing liquid to the upper surface of the substrate held horizontally and forming a rinsing liquid film covering the entire upper surface of the substrate with the rinsing liquid supplied to the substrate;
After the rinsing liquid film forming step , the volatile processing liquid is supplied to the upper surface of the substrate held horizontally to replace the rinsing liquid on the substrate, and the entire surface of the upper surface of the substrate is replaced with the volatile processing liquid replaced with the rinsing liquid. A volatile treatment liquid film forming step of forming a volatile treatment liquid film covering
A substrate rotation step of rotating the substrate around the rotation axis while holding the volatile treatment liquid film on the substrate;
In parallel with the substrate rotation step, a gas supply step of blowing gas to the center of the upper surface of the substrate,
After the volatile treatment liquid film forming step, in parallel with the substrate rotation step and the gas supply step, the volatile treatment liquid is deposited at a predetermined position in the upper surface of the substrate that is a position outside the rotation axis . performing a volatile treatment liquid supply step of the substrate processing apparatus. The volatile treatment liquid supply means has a first fixed nozzle and a second fixed nozzle provided to discharge the volatile treatment liquid in a fixed state,
The first fixed nozzle is provided so that a volatile treatment liquid is deposited on the center of the upper surface of the substrate held by the substrate holding means,
The substrate processing apparatus according to claim 5, wherein the second fixed nozzle is provided so that a volatile processing liquid is deposited at the predetermined position . Said volatile treatment liquid supplying means includes a moving nozzle for discharging the volatile treatment liquid deposition liquid position of volatile treatment liquid from the mobile nozzle to the substrate held by the substrate holding means, the center part of the upper surface of the substrate And a nozzle moving means for moving the moving nozzle to move between the predetermined position and a switching means for switching between supply and stop of supply of volatile processing liquid to the moving nozzle,
The control means controls the nozzle moving means and the switching means to execute a nozzle moving step of moving the moving nozzle in a state where the discharge of the volatile processing liquid from the moving nozzle is stopped. The substrate processing apparatus according to claim 5.

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