JP2016219486A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently use a water repellent treatment liquid.SOLUTION: A substrate processing apparatus 1 comprises a water repellent treatment liquid nozzle 51 for discharging a water repellent treatment liquid containing a water repellent agent toward the main surface of a substrate 9 facing upward, and an active agent nozzle 52 for discharging toward the main surface an active agent that imparts a higher water repellency to the main surface than the case where only the water repellent agent is used by mixing the active agent with the water repellent agent. The water repellent treatment solution contains a water repellent and the active agent. Even when the activity of the water repellent treatment liquid remaining in the water repellent treatment liquid nozzle 51 is lowered due to some time elapsing from the mixing of the water repellent and the active agent, by mixing the active agent from the active agent nozzle 52 on the substrate 9 with the residual water repellent treatment solution, the activity can be increased. As a result, it is possible to efficiently use the water repellent treatment liquid.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a substrate processing apparatus and a substrate processing method.

  Conventionally, in a manufacturing process of a semiconductor substrate (hereinafter simply referred to as “substrate”), various processes are performed on the substrate using a substrate processing apparatus. For example, by supplying a chemical solution to a substrate having a resist pattern formed on the surface, a process such as etching is performed on the surface of the substrate. After the chemical solution is supplied, a rinsing process for supplying pure water to the substrate to remove the chemical solution on the surface and a drying process for removing the pure water on the surface by rotating the substrate at a high speed are further performed.

  When a large number of fine pattern elements are formed on the surface of the substrate, if the rinse treatment with pure water and the drying treatment are sequentially performed, the surface tension of pure water acts on the pattern elements during the drying, and the pattern elements May collapse. In view of this, a method has been proposed in which the pattern element is prevented from collapsing due to the surface tension of pure water by making the surface of the substrate water repellent (hydrophobic). Further, in the water repellency treatment of the substrate surface, a silylating agent is often used as a water repellent, and in order to improve the water repellency effect of the silylating agent, an activator may be mixed with the silylating agent. It has been broken.

  By the way, in the case of providing a tank for storing a water repellent treatment liquid in which a water repellent and an activator are mixed, the activity of the water repellent treatment liquid decreases with the elapse of a predetermined time from the mixing of the two. Even if a water treatment liquid is used, it becomes impossible to produce high water repellency on the substrate surface. Therefore, in Patent Document 1, a merging portion in which an activator supply channel is connected is formed in the middle of a supply channel for supplying a silylating agent to the substrate, and the activator is supplied in the middle of supplying the silylating agent to the substrate. A method of adding is disclosed. In this method, the silylating agent is supplied to the substrate while maintaining the activated state by the action of the activator, and the surface of the substrate can be made water-repellent satisfactorily. In Patent Document 2, in parallel with the supply of the hydrophobizing liquid to the substrate, the hydrophobizing liquid flowing on the substrate is warmed by heating at least one of the substrate and the supplied hydrophobizing liquid. A technique for increasing the activation of selenium is disclosed.

  Note that Patent Document 3 discloses a technique in which a substrate on which an oxide film and a nitride film are formed is etched by supplying an etchant after the substrate is silylated by supplying a silylating agent. In this method, since the oxide film is suppressed from being etched by silylation, the selectivity (nitride film removal amount / oxide film removal amount) can be improved.

JP2013-206929A JP 2014-197571 A JP2013-207220A

  As described above, in a water repellent treatment liquid in which a water repellent and an activator are mixed, the activity becomes maximum with the passage of time corresponding to the type of the mixture, and thereafter the activity gradually decreases. Therefore, after discharging the water repellent treatment liquid from the nozzle toward one substrate, when the water repellent treatment liquid is discharged toward the next substrate after a certain period of time, the water repellent remaining in the nozzle The activity of the treatment liquid is reduced. When a large amount of water-repellent treatment liquid is used, a highly active water-repellent treatment liquid is discharged after discharge of a water-repellent treatment liquid with reduced activity, so that high water repellency can be generated on the entire substrate surface. It is. However, in recent years, water-repellent treatment liquids such as water-repellent treatment liquids remaining in the nozzles have been efficiently used to reduce water-repellent treatment costs and environmental considerations. A technique that is often used is required.

  This invention is made | formed in view of the said subject, and aims at using a water-repellent processing liquid efficiently.

  The invention according to claim 1 is a substrate processing apparatus, wherein a water repellent treatment liquid nozzle that discharges a water repellent treatment liquid containing a water repellent agent toward the main surface of the substrate facing upward, and the water repellent agent And an activator nozzle that discharges toward the main surface an activator that imparts higher water repellency to the main surface than when only the water repellent is used.

  The invention according to claim 2 is the substrate processing apparatus according to claim 1, wherein the water repellent treatment liquid includes the water repellent and the activator.

  Invention of Claim 3 is a substrate processing apparatus of Claim 2, Comprising: The process liquid supply line which connects a water repellent supply source and the said water repellent process liquid nozzle, an activator supply source, and the said An activator line connecting the mixing position in the processing liquid supply line, and an auxiliary supply line branched from the activator line and connected to the activator nozzle are further provided.

  A fourth aspect of the present invention is the substrate processing apparatus according to any one of the first to third aspects, wherein the substrate is rotated about a rotation axis that passes through the center of the main surface and is perpendicular to the main surface. A substrate rotation mechanism that discharges the water-repellent treatment liquid toward the vicinity of the center, and the activator nozzle is located at a position on the main surface different from the vicinity of the center. Then, the activator is discharged.

  A fifth aspect of the present invention is the substrate processing apparatus according to the fourth aspect, wherein the discharge direction of the activator nozzle is inclined with respect to the rotation axis.

  The invention according to claim 6 is the substrate processing apparatus according to claim 5, wherein when viewed along the rotation axis, the discharge direction of the activator nozzle is approximately the rotation direction of the substrate. Along.

  A seventh aspect of the present invention is the substrate processing apparatus according to any one of the first to third aspects, wherein the substrate is rotated about a rotation axis that passes through the center of the main surface and is perpendicular to the main surface. A substrate rotation mechanism that performs the discharge of the water-repellent treatment liquid to the vicinity of the center by the water-repellent treatment liquid nozzle and the start of the discharge of the active agent to the vicinity of the center by the activator nozzle. And a controller that spreads the liquid mixture of the water repellent treatment liquid and the activator toward the outer edge of the main surface by increasing the rotation speed of the substrate by the substrate rotation mechanism.

  The invention according to claim 8 is a substrate processing method, comprising: a) discharging a water repellent treatment liquid containing a water repellent agent by a water repellent treatment liquid nozzle toward the main surface of the substrate facing upward; b) When used in combination with the water repellent, the activator that imparts higher water repellency to the main surface than when only the water repellent is used is ejected from the activator nozzle toward the main surface. A process.

  The invention according to claim 9 is the substrate processing method according to claim 8, wherein the water-repellent treatment liquid includes the water-repellent agent and the activator.

  The invention described in claim 10 is the substrate processing method according to claim 8 or 9, wherein c) the substrate is rotated about a rotation axis that passes through the center of the main surface and is perpendicular to the main surface. In parallel with the step c), in the step a), the water-repellent treatment liquid is discharged toward the center by the water-repellent treatment solution nozzle, and in the step b) The activator is ejected by the activator nozzle toward a position on the main surface different from the vicinity of the center.

  The invention described in claim 11 is the substrate processing method according to claim 8 or 9, wherein c) the substrate is rotated about a rotation axis that passes through the center of the main surface and is perpendicular to the main surface. And a step of discharging the water-repellent treatment liquid to the vicinity of the center by the water-repellent treatment liquid nozzle in the step a), and the activator to the vicinity of the center by the activator nozzle in the step b). After the elapse of a predetermined time from the start of the discharge, the rotation speed of the substrate is increased, so that the mixed liquid of the water repellent treatment liquid and the activator is spread toward the outer edge of the main surface.

  According to the present invention, the water repellent treatment liquid can be used efficiently.

It is a figure which shows the structure of a substrate processing apparatus. It is a figure which shows the structure of a water repellent treatment liquid supply part. It is a figure which shows the flow of a process of the board | substrate in a substrate processing apparatus. It is a figure which shows the flow of the water-repellent process of a board | substrate. It is a figure which shows the board | substrate in process of water repellent treatment. It is a figure which shows the board | substrate in process of water repellent treatment. It is a figure which shows the board | substrate in process of water repellent treatment. It is a figure which shows the board | substrate in process of water repellent treatment. It is a figure which shows the substrate processing apparatus of a comparative example. It is a figure which shows the other example of an activator nozzle. It is a figure which shows the other example of an activator nozzle. It is a figure which shows the other example of an activator nozzle. It is a figure for demonstrating the other example of the water-repellent process of a board | substrate. It is a figure for demonstrating the other example of the water-repellent process of a board | substrate.

  FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 1 according to an embodiment of the present invention. Each component in the substrate processing apparatus 1 is controlled by the control unit 10. The substrate processing apparatus 1 includes a spin chuck 22 that is a substrate holding unit, a spin motor 21 that is a substrate rotation mechanism, and a cup 23 that surrounds the spin chuck 22. The substrate 9 is placed on the spin chuck 22. The spin chuck 22 holds the substrate 9 by bringing a plurality of holding members into contact with the peripheral edge of the substrate 9. As a result, the substrate 9 is held by the spin chuck 22 in a horizontal posture. In the following description, the main surface 91 of the substrate 9 facing upward is referred to as an “upper surface 91”. A large number of upright pattern elements are formed on the upper surface 91.

  A shaft 221 extending in the vertical direction (vertical direction) is connected to the lower surface of the spin chuck 22. A rotation axis J <b> 1 that is the central axis of the shaft 221 is perpendicular to the upper surface 91 of the substrate 9 and passes through the center of the substrate 9. The spin motor 21 rotates the shaft 221. As a result, the spin chuck 22 and the substrate 9 rotate about the rotation axis J1 that faces in the vertical direction. The spin chuck 22 may have a structure that adsorbs the back surface of the substrate 9.

  The substrate processing apparatus 1 includes a chemical solution supply unit 311, a chemical solution nozzle 312, a rinse solution supply unit 321, a rinse solution nozzle 322, an IPA supply unit 331, and an IPA nozzle 332. In the chemical liquid supply unit 311, a chemical liquid supply source is connected to the chemical liquid nozzle 312 via a valve. In the rinsing liquid supply unit 321, a rinsing liquid supply source is connected to the rinsing liquid nozzle 322 via a valve. In the IPA supply unit 331, an IPA supply source is connected to the IPA nozzle 332 through a valve.

  The substrate processing apparatus 1 further includes a water repellent treatment liquid supply unit 4, a water repellent treatment liquid nozzle 51, an activator nozzle 52, and a nozzle moving mechanism 53. The water repellent treatment liquid nozzle 51 and the activator nozzle 52 are, for example, straight nozzles extending in the vertical direction, and are attached to the arm 531 of the nozzle moving mechanism 53. The nozzle moving mechanism 53 rotates the arm 531 around an axis parallel to the rotation axis J1 so that the water-repellent treatment liquid nozzle 51 and the activator nozzle 52 are opposed to the upper surface 91 of the substrate 9; It is selectively disposed at a standby position away from the substrate 9 in the horizontal direction. The water-repellent treatment liquid nozzle 51 disposed at the facing position faces the central portion of the upper surface 91, and the activator nozzle 52 disposed at the facing position faces a position away from the central portion of the upper surface 91. By other nozzle moving mechanisms not shown, each of the chemical solution nozzle 312 and the IPA nozzle 332 is also selectively set to an opposing position facing the upper surface 91 of the substrate 9 and another standby position away from the substrate 9 in the horizontal direction. Be placed. The rinsing liquid nozzle 322 may be movable in the same manner as the other nozzles.

  FIG. 2 is a diagram illustrating the configuration of the water repellent treatment liquid supply unit 4. The water repellent treatment liquid supply unit 4 includes a water repellent supply source 410, a treatment liquid supply line 41, an activator supply source 420, an activator line 42, and an auxiliary supply line 43. The treatment liquid supply line 41 connects the water repellent supply source 410 and the water repellent treatment liquid nozzle 51. In the treatment liquid supply line 41, a flow meter 411, a flow control valve 412, an on-off valve 413, a connection part 414, an on-off valve 415, and an in-line mixer 416 are sequentially arranged from the water repellent supply source 410 toward the water repellent treatment liquid nozzle 51. Is provided.

  The activator line 42 connects the activator supply source 420 and the connection portion 414 of the processing liquid supply line 41. The activator line 42 is provided with a flow meter 421, a three-way valve 422, a flow control valve 423, and an on-off valve 424 in order from the activator supply source 420 toward the connection portion 414. The auxiliary supply line 43 connects the three-way valve 422 and the activator nozzle 52. In other words, the auxiliary supply line 43 branches from the activator line 42 and connects to the activator nozzle 52. The auxiliary supply line 43 is provided with a flow rate control valve 431. In the present embodiment, the connection portion 414 and the on-off valves 413, 415, and 424 provided in the vicinity of the connection portion 414 are formed as one multiple valve device (mixing valve).

  When processing the substrate 9 to be described later, the water repellent is supplied to the internal space of the connection portion 414 by opening the on-off valve 413 in the processing liquid supply line 41. In the activator line 42, the activator is supplied to the internal space of the connection portion 414 by opening the port on the flow meter 421 side, the port on the flow rate control valve 423 side, and the opening / closing valve 424 of the three-way valve 422. The Thus, the connection part 414 is a mixing position of the water repellent and the activator in the treatment liquid supply line 41. By opening the on-off valve 415 of the treatment liquid supply line 41, a water repellent treatment liquid that is a liquid in which a water repellent and an activator are mixed is supplied to the water repellent treatment liquid nozzle 51.

  At this time, the control unit 10 controls the opening degree of the flow control valve 412 so that the water repellent flows into the connection unit 414 at a predetermined flow rate. Similarly, the control unit 10 controls the opening degree of the flow rate control valve 423 so that the activator flows into the connection unit 414 at a predetermined flow rate. In the connection portion 414, the water repellent and the activator are mixed at a predetermined mixing ratio. Further, the water repellent and the activator are firmly agitated by the in-line mixer 416 provided between the connection portion 414 and the water repellent treatment liquid nozzle 51. Then, the water-repellent treatment liquid in which the water-repellent agent and the activator are agitated is discharged from the water-repellent treatment liquid nozzle 51 at a flow rate corresponding to the opening degree of the flow rate control valve 412 and the flow rate control valve 423. In addition, the control unit 10 controls the opening degree of the flow control valve 431 in a state where the port on the flow meter 421 side and the port on the flow control valve 431 side of the three-way valve 422 are opened, so that the activator is predetermined. Is discharged from the activator nozzle 52 at a flow rate of

  Here, the water repellent imparts water repellency to the main surface of the substrate 9, that is, imparts a property that the adhering water has a high contact angle. For example, a silylating agent is used as the water repellent. By supplying the silylating agent to the main surface, the main surface is in a state where many hydrophobic functional groups (silyl groups) containing silicon (Si) atoms are present, and water repellency is imparted to the main surface. In addition, the activator is used by mixing with a water repellent and imparts higher water repellency to the main surface than when only the water repellent is used. Therefore, the water repellent treatment liquid in which the water repellent and the activator are mixed is in a state of high activity regarding the function of imparting higher water repellency to the substrate 9 than when only the water repellent is used. In other words, the water repellent is chemically activated by the activator. Actually, in the water repellent treatment liquid, the activity becomes maximum with the lapse of time corresponding to the kind of the mixture from the mixture of the water repellent and the activator, and thereafter the activity gradually decreases.

  It should be noted that not only the water repellent but also the activator itself may impart water repellency to the substrate 9. In this case, only the water repellent is obtained by mixing the activator and the water repellent. A higher water repellency is imparted to the main surface of the substrate 9 than in the case of using only the active agent. The water repellency of the main surface provided when using only the active agent may be higher than the water repellency of the main surface provided when using only the water repellent. Various substances can be used as long as the water repellent and the activator are used by mixing them so as to impart high water repellency to the main surface of the substrate 9 as compared with the case where each is used alone. is there.

  FIG. 3 is a diagram illustrating a processing flow of the substrate 9 in the substrate processing apparatus 1. First, an unprocessed substrate 9 is carried into the substrate processing apparatus 1 of FIG. 1 by an external transport mechanism and is held by the spin chuck 22 (step S11). Subsequently, the chemical nozzle 312 is arranged at a facing position facing the central portion of the upper surface 91 of the substrate 9 by a nozzle movement mechanism (not shown). Further, the spin motor 21 starts to rotate the substrate 9 at a predetermined rotation speed (rotation speed). And a chemical | medical solution is continuously supplied to the upper surface 91 via the chemical | medical solution nozzle 312 by the chemical | medical solution supply part 311 (step S12). The chemical solution on the upper surface 91 spreads to the outer edge portion by the rotation of the substrate 9, and the chemical solution is supplied to the entire upper surface 91. Further, the chemical solution scattered from the outer edge is received and collected by the cup 23. The chemical liquid is a cleaning liquid containing, for example, dilute hydrofluoric acid (DHF) or aqueous ammonia. The supply of the chemical solution is continued for a predetermined time and then stopped. In the treatment with the chemical solution, the chemical solution nozzle 312 may swing in the horizontal direction by the nozzle moving mechanism.

  When the treatment with the chemical liquid is completed, the chemical nozzle 312 moves to a standby position away from the substrate 9 in the horizontal direction. Subsequently, the rinsing liquid supply unit 321 continuously supplies the rinsing liquid to the upper surface 91 via the rinsing liquid nozzle 322 located above the substrate 9 (step S13). Thereby, the chemical solution on the upper surface 91 is washed away by the rinse liquid, and a film of the rinse liquid is formed on the upper surface 91. During the supply of the rinse liquid, the rotation of the substrate 9 by the spin motor 21 is continued (the same applies to the processing by IPA described later). The supply of the rinse liquid is continued for a predetermined time, and then stopped.

  Subsequently, the IPA nozzle 332 is arranged at a facing position facing the central portion of the upper surface 91 of the substrate 9 by a nozzle movement mechanism (not shown). Then, IPA is continuously supplied to the upper surface 91 by the IPA supply unit 331 via the IPA nozzle 332 (step S14). The IPA on the upper surface 91 spreads to the outer edge by the rotation of the substrate 9, and the IPA is supplied to the entire upper surface 91. As a result, the rinse liquid on the upper surface 91 is washed away by the IPA, and an IPA film is formed on the upper surface 91. IPA is a replacement agent that replaces the rinse liquid on the substrate 9. In the substrate processing apparatus 1, other substitution agents may be used, and the process itself of replacing the rinse liquid with IPA may be omitted. The supply of IPA is continued for a predetermined time and then stopped.

  When the supply of IPA is completed, the IPA nozzle 332 moves to a standby position away from the substrate 9 in the horizontal direction. Further, the water-repellent treatment liquid nozzle 51 and the activator nozzle 52 are arranged at opposed positions facing the upper surface 91 of the substrate 9 by the nozzle moving mechanism 53. And the water-repellent process of the board | substrate 9 is performed (step S15).

  FIG. 4 is a diagram showing the flow of the water repellent treatment of the substrate 9. Note that step S154 indicated by a broken-line rectangle in FIG. 4 is a process performed in a process example described later, and is not performed in this process example. In the water repellent process, first, the rotation of the substrate 9 at a predetermined set rotational speed by the spin motor 21 is started (step S151). When the substrate 9 has been continuously rotated since the IPA was supplied, the number of rotations of the substrate 9 is adjusted to the set number of rotations. In parallel with the rotation of the substrate 9, as shown in FIG. 5A, the water repellent treatment liquid is continuously discharged from the water repellent treatment solution nozzle 51 toward the upper surface 91 of the substrate 9 (step S152). The discharge port of the water repellent treatment liquid nozzle 51 faces the center of the substrate 9, and the water repellent treatment liquid is discharged toward the vicinity of the center of the upper surface 91.

  Here, when the discharge of the water-repellent treatment liquid from the water-repellent treatment liquid nozzle 51 is started, the water-repellency present in the portion between the connection portion 414 and the water-repellent treatment liquid nozzle 51 in the treatment liquid supply line 41 of FIG. The processing liquid is discharged first. In the substrate processing apparatus 1, after steps S <b> 11 to S <b> 18 of FIG. 3 are completed for one substrate 9, steps S <b> 11 to S <b> 18 of FIG. 3 are performed for the next substrate 9. In the water treatment liquid (hereinafter referred to as “residual water repellent treatment liquid”), a certain amount of time has passed after the water repellent and the activator are mixed. As described above, in the water repellent treatment liquid, the activity becomes the maximum with the passage of time corresponding to the kind of the mixture from the mixture of the water repellent and the activator, and thereafter the activity gradually decreases. Movement from the connecting portion 414 to the water-repellent treatment liquid nozzle 51 so that the activity of the water-repellent treatment liquid discharged from the water-repellent treatment liquid nozzle 51 is approximately maximized during continuous discharge of the water-repellent treatment liquid. In the substrate processing apparatus 1 in which the time required for this is set, the activity in the residual water repellent treatment liquid is reduced (deteriorated). In FIG. 5A, the parallel water slanting is given to the residual water-repellent treatment liquid whose activity has decreased (the same applies to other drawings showing the residual water-repellent treatment liquid on the substrate 9).

  The water repellent treatment liquid on the upper surface 91 spreads to the outer edge by the rotation of the substrate 9. In the water-repellent treatment liquid supply unit 4, when all the remaining water-repellent treatment liquid is ejected from the water-repellent treatment liquid nozzle 51, a highly active water-repellent treatment liquid is subsequently ejected. The water repellent treatment liquid having high activity is produced by mixing the water repellent and the activator after the water repellent treatment liquid nozzle 51 starts discharging the water repellent treatment liquid. In FIG. 5B, the highly active water-repellent treatment liquid is blacked out (the same applies to other drawings showing the highly active water-repellent treatment liquid on the substrate 9).

  On the other hand, the activator is continuously ejected from the activator nozzle 52 toward the upper surface 91 of the substrate 9 slightly after the start of ejection of the water repellent treatment liquid (step S153). The discharge port of the activator nozzle 52 faces, for example, a region outside the half of the radius of the substrate 9 (that is, the outer edge portion) in the radial direction. Therefore, the activator nozzle 52 discharges the activator toward a position on the upper surface 91 different from the vicinity of the center of the substrate 9 as shown in FIG. 5B. In FIG. 5B, the activator is painted white (the same applies to other drawings showing the remaining water repellent treatment liquid on the substrate 9).

  At the outer edge portion of the upper surface 91, the residual water repellent treatment liquid is activated (reactivated) by mixing the activator with the residual water repellent treatment liquid. That is, the activity of the remaining water repellent treatment liquid on the outer edge is increased. In FIG. 5C, the activated residual water-repellent treatment liquid is also blacked out (the same applies to other drawings showing the residual water-repellent treatment liquid activated on the substrate 9). The discharge of the water repellent treatment liquid from the water repellent treatment liquid nozzle 51 and the discharge of the activator from the activator nozzle 52 are continued for a predetermined time. As a result, as shown in FIG. 5D, the entire upper surface 91 of the substrate 9 is covered with a highly active water repellent treatment liquid.

  When the supply of the water repellent treatment liquid and the activator is stopped and the water repellent treatment is completed, the water repellent treatment liquid nozzle 51 and the activator nozzle 52 are separated from the substrate 9 in the horizontal direction by the nozzle moving mechanism 53 of FIG. Move to the standby position. Further, the IPA nozzle 332 is disposed at a facing position facing the top surface 91 of the substrate 9. Then, the IPA supply unit 331 continuously supplies IPA to the upper surface 91 via the IPA nozzle 332 (FIG. 3: step S16). The IPA on the upper surface 91 spreads to the outer edge by the rotation of the substrate 9, and the IPA is supplied to the entire upper surface 91. Accordingly, the water repellent treatment liquid on the upper surface 91 is washed away by IPA, and an IPA film is formed on the upper surface 91. The supply of IPA is continued for a predetermined time and then stopped. The water repellent treatment liquid on the upper surface 91 may be washed away by the rinse liquid discharged from the rinse liquid nozzle 322.

  When the supply of IPA is completed, the substrate 9 is rotated by the spin motor 21 at a higher rotational speed than the rotational speed in the above processing. Thereby, IPA adhering to the upper surface 91 of the board | substrate 9 is shaken off around by a centrifugal force. As a result, the IPA on the upper surface 91 is removed, and the substrate 9 is dried (step S17). At this time, since the upper surface 91 has high water repellency, collapse of the pattern element during drying is suppressed or prevented. The dried substrate 9 is unloaded from the substrate processing apparatus 1 by an external transport mechanism, and the processing in the substrate processing apparatus 1 is completed (step S18).

  FIG. 6 is a view showing a substrate processing apparatus 8 of a comparative example. In the substrate processing apparatus 8 of the comparative example, the activator nozzle 52 and the auxiliary supply line 43 are omitted as compared with the substrate processing apparatus 1 of FIG. At the start of discharge of the water repellent treatment liquid from the water repellent treatment liquid nozzle 81 in the substrate processing apparatus 8 of the comparative example, the residue present in the portion between the connection portion 83 and the water repellent treatment liquid nozzle 81 in the treatment liquid supply line 82. The water repellent treatment liquid is discharged first. The residual water repellent treatment liquid on the upper surface 91 of the substrate 9 spreads to the outer edge due to the rotation of the substrate 9. Therefore, a large amount of residual water-repellent treatment liquid with reduced activity adheres to the outer edge portion of the upper surface 91. Further, at the outer edge portion of the upper surface 91, the surface area is large, and the arrival amount of the water repellent treatment liquid having high activity generated by mixing the water repellent and the activator after the start of discharge is reduced. Therefore, the water repellency at the outer edge portion is lower than the vicinity of the center (center portion) of the upper surface 91. In this case, when the substrate 9 is dried, the pattern element collapses at the outer edge portion. When a large amount of water repellent liquid is used, a highly active water repellent liquid discharged after consumption of the residual water repellent liquid is distributed over the entire upper surface 91, resulting in high water repellency on the entire upper surface 91. It is possible to make it. However, the amount of water repellent treatment liquid used is increased, the cost of the water repellent treatment is increased, and the environmental load is also increased.

  On the other hand, in the substrate processing apparatus 1 of FIG. 1, in addition to the water repellent treatment liquid nozzle 51 that ejects the water repellent treatment liquid toward the upper surface 91 of the substrate 9, the activator that ejects the activator toward the upper surface 91. A nozzle 52 is provided. As a result, the remaining water repellent treatment liquid can be activated on the substrate 9 by the activator from the activator nozzle 52, and a state where the activity of the water repellent treatment liquid is high can be maintained on the entire upper surface 91 of the substrate 9. As a result, it is possible to improve the water repellency of the entire top surface 91 of the substrate 9 while using the residual water repellent treatment liquid. That is, the entire upper surface 91 of the substrate 9 can be appropriately made water-repellent while using the water-repellent treatment liquid efficiently (without waste). In addition, it is possible to reduce the amount of the water repellent treatment liquid used to reduce the cost of the water repellent treatment and to reduce the environmental load.

  Further, an activator line 42 for supplying an activator to the mixing position of the treatment liquid supply line 41 through which the water repellent flows is provided, and the auxiliary branching from the predetermined position of the activator line 42 is connected to the activator nozzle 52. A supply line 43 is further provided. As a result, a part of the line for supplying the active agent from the active agent supply source 420 to the mixing position and a part of the line for supplying the active agent from the active agent supply source 420 to the active agent nozzle 52 are shared with each other. Thus, the structure of the substrate processing apparatus 1 can be simplified.

  Further, in the substrate processing apparatus 1, the water repellent treatment liquid nozzle 51 discharges the water repellent treatment liquid toward the vicinity of the center of the upper surface 91, and the activator nozzle 52 is on the upper surface 91 different from the vicinity of the center of the upper surface 91. The activator is discharged toward the position. As a result, the activator from the activator nozzle 52 is efficiently mixed with the remaining water-repellent treatment liquid that moves to the outer edge on the upper surface 91 of the substrate 9 that is rotated by the spin motor 21 that is the substrate rotation mechanism. As a result, the water repellency at the outer edge portion of the upper surface 91 where high water repellency hardly occurs can be improved more reliably. Further, the water repellent treatment liquid contains the water repellent and the activator, so that the water repellent treatment and the activator are mixed after the water repellent treatment liquid nozzle 51 starts discharging the water repellent treatment liquid. The liquid is supplied to the vicinity of the center of the upper surface 91 after all the remaining water-repellent treatment liquid is discharged. Thereby, the water repellent treatment liquid having a high activity can be supplied to the entire upper surface 91, and the water repellency of the entire upper surface 91 of the substrate 9 can be improved more reliably.

  In the substrate processing apparatus 1 of FIG. 1, a straight nozzle is used as the activator nozzle 52. For example, as shown in FIG. 7, the lower portion including the discharge port of the activator nozzle 52 is inclined with respect to the vertical direction. There may be. In this case, the discharge direction of the activator nozzle 52 (indicated by an arrow with the symbol A1) is inclined with respect to the rotation axis J1. Thereby, it is possible to suppress the occurrence of liquid splashing when the activator is mixed with the water repellent treatment liquid adhering to the upper surface 91 as compared with the example of FIG.

  More preferably, the component parallel to the upper surface 91 of the substrate 9 in the ejection direction A1 is along the direction of rotation of the substrate 9 by the spin motor 21 (indicated by the arrow with reference R1) as shown in FIG. It is preferable to follow the tangential direction of the circle with the rotation axis J1 as the center and go to the downstream side in the rotation direction R1. As described above, when viewed along the rotation axis J1, the discharge direction A1 of the activator nozzle 52 is approximately along the rotation direction R1 of the substrate 9, whereby the active agent discharged onto the substrate 9 is denoted by reference numeral A2. As indicated by a broken-line arrow with a mark, it is possible to stay on the upper surface 91 for a relatively long time. Thereby, activation of a residual water-repellent treatment liquid can be accelerated | stimulated, suppressing a liquid splash. In order to further promote the activation of the residual water repellent treatment liquid, as shown in FIG. 9, a plurality of activator nozzles 52 having a similar structure may be provided to facilitate spreading of the activator at the outer edge portion of the upper surface 91. preferable. In each activator nozzle 52, a component parallel to the upper surface 91 in the ejection direction A1 is along the rotation direction R1 of the substrate 9.

  In the substrate processing apparatus 1, a water repellent that is not mixed with the activator may be discharged onto the substrate 9. In the example shown in FIG. 10, the water repellent is discharged from the water repellent liquid nozzle 51 toward the vicinity of the center of the upper surface 91 as the water repellent liquid, and the active agent is discharged from the activator nozzle 52 on the upper surface 91 different from the vicinity of the center. It is discharged toward the position. In this case, the water repellent and the activator are mixed in the outer edge portion of the upper surface 91, and the water repellent treatment liquid (water repellent) activated by the activator increases the water repellency of the outer edge portion. In the vicinity of the center of the upper surface 91, a certain degree of water repellency is secured by providing water repellency by the water repellent agent itself. In the example of FIG. 10, the water repellent treatment liquid discharged from the water repellent treatment liquid nozzle 51 may contain a slight amount of activator. In this case, higher water repellency can be generated near the center of the upper surface 91.

  Next, another example of the water repellent treatment in the substrate processing apparatus 1 will be described. In the present processing example, the process of step S154 in FIG. 4 is performed. First, the rotation of the substrate 9 at a predetermined set rotational speed by the spin motor 21 is started (step S151). The set rotational speed in this processing example is sufficiently smaller than the set rotational speed in the above processing example, and the set rotational speed may be zero.

  Subsequently, as shown in FIG. 11, the water repellent agent is continuously discharged from the water repellent treatment liquid nozzle 51 toward the vicinity of the center of the upper surface 91 as a water repellent treatment liquid (step S152). Further, in parallel with the discharge of the water repellent agent from the water repellent treatment liquid nozzle 51, the activator is continuously discharged from the activator nozzle 52 toward the vicinity of the center of the upper surface 91 (step S153). Thereby, in the vicinity of the center of the upper surface 91, the water repellent (water repellent treatment liquid) and the activator are mixed. At this time, the rotation of the substrate 9 is slow or stopped, and the liquid mixture of the water repellent and the activator stays in the vicinity of the center of the upper surface 91. The discharge of the water repellent from the water repellent treatment liquid nozzle 51 and the discharge of the activator from the activator nozzle 52 are continued for a predetermined time, and then stopped. Note that the water repellent agent discharged from the water repellent treatment liquid nozzle 51 and the activator discharged from the activator nozzle 52 may collide with each other and be mixed above the upper surface 91.

  Further, when a predetermined time (for example, several seconds to 10 seconds) elapses from the discharge of the water repellent from the water repellent treatment liquid nozzle 51 and the start of the discharge of the activator from the activator nozzle 52, Then, the rotation speed of the substrate 9 by the spin motor 21 is increased (step S154). At this time, while the liquid mixture of the water repellent and the activator stays in the vicinity of the center of the upper surface 91, the activation of the liquid mixture proceeds, and the liquid mixture becomes a highly active water repellent treatment liquid. ing. Then, as the rotation speed of the substrate 9 increases, the water repellent treatment liquid is spread toward the outer edge portion of the upper surface 91, and the entire upper surface 91 is covered with the highly active water repellent treatment solution. Thereafter, similar to the above processing example, the water repellent treatment liquid on the upper surface 91 is removed (FIG. 3: step S16), and the substrate 9 is dried (step S17). Note that after the rotation speed of the substrate 9 is increased in step S154, the discharge of the water repellent treatment liquid from the water repellent treatment liquid nozzle 51 and the discharge of the activator from the activator nozzle 52 may be stopped.

  As described above, a predetermined time has elapsed from the start of discharge of the water-repellent treatment liquid to the vicinity of the center of the substrate 9 by the water-repellent treatment liquid nozzle 51 and the discharge of the active agent to the vicinity of the center by the activator nozzle 52. Later, the control unit 10 increases the rotation speed of the substrate 9 by the spin motor 21. Thereby, the liquid mixture of the water repellent treatment liquid and the activator, that is, the water repellent treatment liquid having high activity is spread toward the outer edge portion of the upper surface 91. As a result, the water repellency of the entire upper surface 91 can be easily improved. In addition, by mixing the water repellent treatment liquid, which is a water repellent, and the activator on the upper surface 91 of the substrate 9, it is possible to prevent a residual water repellent treatment liquid having low activity from being generated, and to efficiently use the water repellent treatment liquid. Use is realized.

  In the present processing example, the water repellent treatment liquid discharged from the water repellent treatment liquid nozzle 51 may contain a slight amount of activator. However, from the viewpoint of improving the water repellency of the entire upper surface 91 without generating a residual water repellent treatment liquid, in this treatment example, the water repellent treatment liquid discharged from the water repellent treatment liquid nozzle 51 is only a water repellent. It is preferable to contain. In this case, in the water repellent treatment liquid supply unit 4 of FIG. 2, an activator supply line that connects the activator supply source 420 and the activator nozzle 52 is provided instead of the activator line 42 and the auxiliary supply line 43. Further, when the activity of the water repellent is increased in a short time by mixing with the activator, the mixed liquid is discharged to the outer edge portion of the upper surface 91 when the water repellent and the activator are discharged from the nozzles 51 and 52. The substrate 9 may be rotated at a rotational speed that spreads immediately.

  The substrate processing apparatus 1 can be variously modified.

  The water repellent treatment liquid nozzle 51 that ejects the water repellent treatment liquid containing the water repellent and the activator nozzle 52 that ejects the activator may be provided in various modes. For example, each of these nozzles 51 and 52 may be a long member (slit nozzle or the like) having a discharge port extending parallel to the upper surface 91 of the substrate 9. In this case, by providing a mechanism for moving the long member in a direction parallel to the upper surface 91 and intersecting the longitudinal direction, the substrate rotating mechanism for rotating the substrate 9 is omitted, and the entire upper surface 91 of the substrate 9 is provided. It is possible to apply a water repellent treatment liquid and an activator.

  In the above-described embodiment, the water repellent treatment of the substrate 9 is performed substantially as part of the drying treatment, but the water repellent treatment of the substrate 9 may be used in addition to the drying treatment. For example, as in JP2013-207220A (the above Patent Document 3), a substrate on which an oxide film and a nitride film are formed is silylated by supplying a silylating agent, thereby selectively etching the oxide film. In the case of suppressing to the above, the water repellency treatment of the substrate 9 described with reference to FIG. 4 may be performed. In this case, a water repellent treatment liquid containing a silylating agent that is a water repellent is ejected from the water repellent treatment liquid nozzle 51, and the activator is ejected from the activator nozzle 52. As a result, the water repellent treatment liquid can be activated on the upper surface 91 of the substrate 9, and the water repellent treatment that is a silylation treatment can be performed while using the water repellent treatment liquid efficiently.

  The substrate processed by the substrate processing apparatus 1 is not limited to a semiconductor substrate, and may be a glass substrate or another substrate.

  The configurations in the above-described embodiments and modifications may be combined as appropriate as long as they do not contradict each other.

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 9 Substrate 10 Control part 21 Spin motor 41 Process liquid supply line 42 Activator line 43 Auxiliary supply line 51 Water repellent treatment liquid nozzle 52 Activator nozzle 91 Upper surface 410 Water repellent supply source 414 Connection part 420 Activator supply Source A1 Discharge direction J1 Rotating shaft R1 Rotating direction S11 to S18, S151 to S154 Steps

Claims (11)

A substrate processing apparatus,
A water-repellent treatment liquid nozzle for discharging a water-repellent treatment liquid containing a water-repellent agent toward the main surface of the substrate facing upward;
An activator nozzle that discharges toward the main surface an active agent that imparts higher water repellency to the main surface than when only the water repellent agent is used by mixing with the water repellent agent;
A substrate processing apparatus comprising: The substrate processing apparatus according to claim 1,
The substrate processing apparatus, wherein the water repellent treatment liquid contains the water repellent and the activator. The substrate processing apparatus according to claim 2,
A treatment liquid supply line connecting the water repellent supply source and the water repellent treatment liquid nozzle;
An activator line connecting the activator supply source and the mixing position in the treatment liquid supply line;
An auxiliary supply line branched from the activator line and connected to the activator nozzle;
A substrate processing apparatus further comprising: A substrate processing apparatus according to any one of claims 1 to 3,
A substrate rotation mechanism that rotates the substrate about a rotation axis that passes through the center of the main surface and is perpendicular to the main surface;
The water-repellent liquid nozzle discharges the water-repellent liquid toward the vicinity of the center;
The substrate processing apparatus, wherein the activator nozzle discharges the activator toward a position on the main surface different from the vicinity of the center. The substrate processing apparatus according to claim 4,
The substrate processing apparatus, wherein a discharge direction of the activator nozzle is inclined with respect to the rotation axis. The substrate processing apparatus according to claim 5,
The substrate processing apparatus, wherein the discharge direction of the activator nozzle is substantially along the rotation direction of the substrate when viewed along the rotation axis. A substrate processing apparatus according to any one of claims 1 to 3,
A substrate rotation mechanism for rotating the substrate about a rotation axis passing through the center of the main surface and perpendicular to the main surface;
By the substrate rotation mechanism after a predetermined time has elapsed since the discharge of the water repellent treatment liquid to the vicinity of the center by the water repellent treatment liquid nozzle and the start of the discharge of the active agent to the vicinity of the center by the activator nozzle. A controller that spreads the liquid mixture of the water repellent treatment liquid and the activator toward the outer edge of the main surface by increasing the rotation speed of the substrate;
A substrate processing apparatus further comprising: A substrate processing method comprising:
a) a step of discharging a water repellent treatment liquid containing a water repellent by a water repellent treatment liquid nozzle toward the main surface of the substrate facing upward;
b) When used in combination with the water repellent, the activator that imparts higher water repellency to the main surface than when only the water repellent is used is ejected from the activator nozzle toward the main surface. Process,
A substrate processing method comprising: The substrate processing method according to claim 8, comprising:
The substrate treatment method, wherein the water repellent treatment liquid contains the water repellent and the activator. The substrate processing method according to claim 8 or 9, wherein
c) further comprising the step of rotating the substrate about a rotation axis passing through the center of the main surface and perpendicular to the main surface;
In parallel with the step c), in the step a), the water-repellent treatment liquid is discharged toward the vicinity of the center by the water-repellent treatment solution nozzle, and in the step b), by the activator nozzle, The substrate processing method, wherein the activator is discharged toward a position on the main surface different from the vicinity of the center. The substrate processing method according to claim 8 or 9, wherein
c) further comprising the step of rotating the substrate about a rotation axis passing through the center of the main surface and perpendicular to the main surface;
From the discharge of the water-repellent treatment liquid to the vicinity of the center by the water-repellent treatment liquid nozzle in the step a) and the start of the discharge of the active agent to the vicinity of the center by the activator nozzle in the step b) The substrate processing method according to claim 1, wherein the mixed liquid of the water repellent treatment liquid and the activator is spread toward an outer edge portion of the main surface by increasing the rotation speed of the substrate after a predetermined time has elapsed.

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