JP4891187B2 - Substrate processing apparatus and substrate processing method - Google Patents

Description

  The present invention relates to an organic material formed on the surface of a substrate by immersing a substrate such as a semiconductor substrate, a glass substrate for a liquid crystal display device, or a glass substrate for a photomask in a treatment solution containing sulfuric acid and hydrogen peroxide solution. The present invention relates to a substrate processing apparatus and a substrate processing method for peeling a film.

In the photolithographic process of the substrate, a photoresist formed on the main surface of the substrate by immersing the substrate in a processing solution containing sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide (H ₂ O ₂ ). A substrate processing apparatus for peeling a film is used. In the treatment liquid containing sulfuric acid and hydrogen peroxide solution, sulfuric acid and hydrogen peroxide solution react to generate Caro acid (H ₂ SO ₅ ), which is a strong oxidizing agent. The conventional substrate processing apparatus immerses the substrate in such a processing solution, decomposes the photoresist film that is an organic substance by the action of the Caro acid generated in the processing solution, and starts the photoresist film from the main surface of the substrate. Was peeling off.

  The configuration of such a conventional substrate processing apparatus is disclosed in Patent Document 1, for example.

JP-A-5-166780

In the substrate processing apparatus as described above, in order to satisfactorily remove the photoresist film from the main surface of the substrate, it is desirable to uniformly generate Caro acid in the processing tank. Further, since the hydrogen peroxide solution naturally deteriorates with time and changes to water (H ₂ O), hydrogen peroxide solution was supplied into the treatment liquid in order to efficiently generate Caro acid. It is desirable to mix sulfuric acid and hydrogen peroxide water as soon as possible. However, in the conventional substrate processing apparatus, in order to efficiently mix sulfuric acid and hydrogen peroxide solution in the processing tank, it cannot be said that the discharge position and discharge direction of these chemical solutions are necessarily optimized.

  The present invention has been made in view of such circumstances, and by efficiently mixing sulfuric acid and hydrogen peroxide inside the treatment tank and uniformly generating Caro acid inside the treatment tank, It is an object of the present invention to provide a substrate processing apparatus and a substrate processing method that can satisfactorily remove an organic film from the surface.

  In order to solve the above-mentioned problem, the invention according to claim 1 is a substrate processing apparatus for peeling an organic film formed on a surface of a substrate by immersing the substrate in a processing solution containing sulfuric acid and hydrogen peroxide solution. A treatment tank for storing a treatment liquid containing sulfuric acid and hydrogen peroxide solution, a holding means for holding a substrate in the treatment tank, and a liquid containing a sulfuric acid component are discharged into the treatment tank. It is characterized by comprising first discharge means and second discharge means for discharging hydrogen peroxide solution toward the liquid discharged from the first discharge means.

  A second aspect of the present invention is the substrate processing apparatus according to the first aspect, wherein the first discharge means includes a liquid containing a sulfuric acid component from a pair of opposing side portions of the processing tank toward a central portion. A pair of first discharge portions for discharging, and the second discharge means includes a pair of second discharge portions for discharging hydrogen peroxide solution toward the liquid discharged from each of the pair of first discharge portions. It is characterized by having.

  The invention according to claim 3 is the substrate processing apparatus according to claim 2, further comprising control means for alternately discharging hydrogen peroxide solution from the pair of second discharge portions.

  A fourth aspect of the present invention is the substrate processing apparatus according to any one of the first to third aspects, wherein the processing tank includes the holding unit, the first discharge unit, and the second discharge unit. Has an inner tank disposed inside, and an outer tank that receives the processing liquid overflowed from the upper part of the inner tank, and a circulation line that feeds the processing liquid from the outer tank to the first discharge means, And sulfuric acid supply means for supplying sulfuric acid to the outer tank.

  The invention according to claim 5 is the substrate processing apparatus according to any one of claims 1 to 4, wherein the first discharge means and the second discharge means each have a plurality of discharge ports. The plurality of discharge ports of the first discharge unit and the plurality of discharge ports of the second discharge unit have a one-to-one correspondence.

  The invention according to claim 6 is the substrate processing apparatus according to claim 5, wherein the holding unit arranges and holds a plurality of substrates in parallel inside the processing tank, and the first discharge unit and The plurality of discharge ports of the second discharge unit are formed at positions corresponding to the gaps between the plurality of substrates held by the holding unit.

  The invention according to claim 7 is a substrate processing method for peeling an organic film formed on a surface of a substrate by immersing the substrate in a processing solution containing sulfuric acid and hydrogen peroxide solution, A discharge step of discharging hydrogen peroxide solution toward the liquid while discharging a liquid containing a sulfuric acid component therein, and an immersion step of immersing the substrate in the processing liquid stored in the processing tank. It is characterized by including.

  The invention according to claim 8 is the substrate processing method according to claim 7, wherein, in the discharging step, the processing tank is formed of a pair of discharge portions disposed on a pair of opposite side portions of the processing tank. While discharging the liquid containing the sulfuric acid component toward the center, the hydrogen peroxide solution is alternately discharged toward the liquid discharged from one of the pair of discharge portions and the liquid discharged from the other. Features.

  According to the first to sixth aspects of the present invention, the substrate processing apparatus includes a first discharge unit that discharges a liquid containing a sulfuric acid component into the inside of the processing tank, and an excess liquid toward the liquid discharged from the first discharge unit. Second discharge means for discharging hydrogen oxide water. For this reason, sulfuric acid and hydrogen peroxide can be mixed efficiently, whereby Caro acid can be uniformly generated inside the treatment tank. Therefore, the organic film can be favorably peeled from the surface of the substrate.

  In particular, according to the second aspect of the present invention, the first discharge means has a pair of first discharge portions that discharge a liquid containing a sulfuric acid component from a pair of opposite side portions of the treatment tank toward the central portion. The second discharge means has a pair of second discharge portions that discharge the hydrogen peroxide solution toward the liquid discharged from each of the pair of first discharge portions. For this reason, it is possible to mix sulfuric acid and hydrogen peroxide solution while uniformly stirring the treatment liquid in the entire interior of the treatment tank.

  In particular, according to the invention described in claim 3, the substrate processing apparatus further includes control means for alternately discharging the hydrogen peroxide solution from the pair of second discharge portions. For this reason, sulfuric acid and hydrogen peroxide solution can be mixed more uniformly without causing a difference in the discharge amount of hydrogen peroxide solution between the pair of second discharge units.

  In particular, according to the invention described in claim 4, the processing tank includes an inner tank and an outer tank, and the substrate processing apparatus includes a circulation line that feeds the processing liquid from the outer tank to the first discharge means, Sulfuric acid supply means for supplying sulfuric acid to the tank. For this reason, sulfuric acid can be introduced into the inner tank using a circulation line.

  In particular, according to the fifth aspect of the present invention, each of the first discharge unit and the second discharge unit includes a plurality of discharge ports, and the plurality of discharge ports of the first discharge unit and the plurality of second discharge units. The discharge ports correspond one-to-one. For this reason, the sulfuric acid discharged from the plurality of discharge ports of the first discharge unit and the hydrogen peroxide solution discharged from the plurality of discharge ports of the second discharge unit can be appropriately mixed.

  In particular, according to the sixth aspect of the invention, the plurality of discharge ports of the first discharge unit and the second discharge unit are formed at positions corresponding to the gaps between the plurality of substrates held by the holding unit. . For this reason, sulfuric acid and hydrogen peroxide solution can be mixed well at the position where the plurality of substrates are held in the processing tank and in the vicinity thereof.

  Further, according to the seventh and eighth aspects of the invention, the hydrogen peroxide solution is discharged toward the liquid while discharging the liquid containing the sulfuric acid component into the processing tank. For this reason, sulfuric acid and hydrogen peroxide can be mixed efficiently, whereby Caro acid can be uniformly generated inside the treatment tank. Therefore, the organic film can be favorably peeled from the surface of the substrate.

  In particular, according to the invention described in claim 8, while discharging a liquid containing a sulfuric acid component from a pair of discharge portions disposed on a pair of side portions opposed to each other to the center portion of the processing tank, The hydrogen peroxide solution is alternately discharged toward the liquid discharged from one of the discharge portions and the liquid discharged from the other. For this reason, sulfuric acid and hydrogen peroxide solution can be mixed more uniformly inside the treatment tank.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

<1. Configuration of substrate processing apparatus>
FIG. 1 is a longitudinal sectional view of a substrate processing apparatus 1 according to an embodiment of the present invention, cut along a plane parallel to the main surface of a substrate W. FIG. 1 also shows the configuration of a piping system and a control system that the substrate processing apparatus 1 has. FIG. 2 is a longitudinal sectional view of the substrate processing apparatus 1 cut along a plane perpendicular to the main surface of the substrate W. 1 shows a state where the substrate W is immersed in the processing liquid, and FIG. 2 shows a state where the substrate W is pulled up above the processing tank 10. Further, FIGS. 1 and 2 show a common XYZ orthogonal coordinate system in order to clarify the positional relationship of each part in the apparatus.

The substrate processing apparatus 1 includes a photoresist film (organic film) formed on a main surface of a substrate W by immersing a plurality of substrates (hereinafter simply referred to as “substrates”) W, which are semiconductor wafers, in a processing solution. ). This substrate processing apparatus 1 uses a processing liquid containing sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide water (H ₂ O ₂ ), and sulfuric acid reacts with hydrogen peroxide water in the processing liquid. The photoresist film formed on the main surface of the substrate W is decomposed and removed by the action of the generated Caro acid (H ₂ SO ₅ ).

  As shown in FIGS. 1 and 2, the substrate processing apparatus 1 mainly includes a processing tank 10 for storing a processing liquid, a lifter 20 for holding the substrate W up and down, and a processing tank 10. A circulation line 30 that circulates the treatment liquid collected from the waste water and supplies it again to the inside of the treatment tank, a sulfuric acid supply unit 40 for supplying sulfuric acid, and a hydrogen peroxide solution supply unit for supplying hydrogen peroxide solution 50 and a control unit 60 for controlling the operation of each unit in the apparatus.

  The processing tank 10 is a storage container made of quartz or chemical resistant resin. The processing tank 10 includes an inner tank 11 in which the substrate W is immersed in the processing liquid stored therein, and an outer tank 12 formed on the outer peripheral portion of the inner tank 11. The inner tank 11 has a bottom wall 111 located below the substrate W and side walls 112a to 112d located on the sides of the substrate W when the substrate W is immersed in the processing liquid. The upper part of 11 is open. For this reason, the processing liquid stored up to the upper part of the inner tank 11 overflows from the upper part of the inner tank 11 to the outer tank 12. Out of the side walls 112a to 112d of the inner tank 11, discharge pipes 36a and 36b constituting a part of the circulation line 30 are provided at the lower ends of the pair of side walls 112a and 112b parallel to the arrangement direction of the substrates W. ing. In addition, discharge pipes 55 a and 55 b that constitute a part of the hydrogen peroxide solution supply unit 50 are disposed inside the inner tank 11.

  The lifter 20 is a transport mechanism for moving the substrate W up and down between the inside of the inner tank 11 and the upper position of the processing tank 10 while holding the substrate W. The lifter 20 has three holding bars 21 extending in the arrangement direction of the substrates W, and each holding bar 21 is provided with a plurality of holding grooves 21a. The board | substrate W is hold | maintained in the standing attitude | position in parallel with each other on the three holding | maintenance rods 21 in the state which fitted the peripheral part to the holding groove 21a. The lifter 20 is connected to a drive unit 22 configured by a known mechanism in which a motor, a ball screw, or the like is combined. When the drive unit 22 is operated, the lifter 20 moves up and down, and the substrate W held on the lifter 20 is pulled up in the immersion position (the state in FIG. 1) inside the processing tank 10 and above the processing tank 10. It is conveyed between the positions (state of FIG. 2).

  The circulation line 30 is a piping system for recovering the processing liquid from the outer tank 12, circulating the recovered processing liquid, and supplying the recovered processing liquid to the inner tank 11 again. As shown in FIG. 1, the circulation line 30 includes a main pipe 31, branch pipes 32a and 32b, a circulation pump 33, a heater 34, a filter 35, and a pair of discharge pipes 36a and 36b. Yes. The upstream end of the main pipe 31 is connected to the outer tub 12 and a circulation pump 33, a heater 34, and a filter 35 are inserted in the middle of the main pipe 31 from the upstream side. Yes. Further, the downstream end of the main pipe 31 is branched into two and connected to the branch pipes 32a and 32b, respectively, and the downstream ends of the branch pipes 32a and 32b are respectively connected to a pair of discharge pipes. The flow paths are connected to 36a and 36b.

  The pair of discharge pipes 36a and 36b are pipe-like members formed horizontally at the lower ends of the pair of side walls 112a and 112b. In each of the discharge pipes 36 a and 36 b, a plurality of discharge ports 361 that discharge the processing liquid inwardly along the bottom wall 111 of the inner tank 11 and a plurality of discharges that discharge the processing liquid slightly upward inside the inner tank 11. The discharge port 362 is formed. As shown in FIG. 2, the positions of the plurality of ejection ports 361 in the X-axis direction are positions corresponding to the gap of the substrate W held on the lifter 20 and the outside of both end portions. Although not shown in FIG. 2, the positions of the plurality of ejection ports 362 in the X-axis direction are also the positions corresponding to the gaps of the substrate W held on the lifter 20 and the outer sides of both ends. It has become.

  When the processing liquid is stored in the inner tank 11 and the outer tank 12, when the circulation pump 33 of the circulation line 30 is operated, the discharge pipes 36a and 36b pass from the outer tank 12 through the main pipe 31 and the branch pipes 32a and 32b. The processing liquid is fed to the inner tank 11 and discharged from the plurality of discharge ports 361 and 362 of the discharge pipes 36a and 36b. That is, when the circulation pump 33 is operated, the treatment liquid is circulated between the inside of the treatment tank 10 and the circulation line 30. The processing liquid to be circulated is heated by the heater 34 in the course of the main pipe 31 and maintained at a predetermined temperature. Further, the particles floating in the processing liquid are removed by the filter 35.

  The sulfuric acid supply unit 40 is a liquid supply mechanism for supplying sulfuric acid, which is a component of the processing liquid, to the outer tank 12 of the processing tank 10. As shown in FIG. 1, the sulfuric acid supply unit 40 includes a sulfuric acid supply source 41, a supply pipe 42, and an on-off valve 43. The upstream end of the supply pipe 42 is connected to the sulfuric acid supply source 41, and the downstream end of the supply pipe 42 is connected to the outer tub 12. In addition, an on-off valve 43 is interposed in the middle of the supply pipe 42. For this reason, when the on-off valve 43 is opened, sulfuric acid is supplied from the sulfuric acid supply source 41 through the supply pipe 42 to the outer tank 12. The sulfuric acid supplied to the outer tank 12 flows into the circulation line 30 together with the processing liquid overflowing from the inner tank 11 to the outer tank 12, and is discharged into the inner tank 11 through the discharge pipes 36a and 36b.

  The hydrogen peroxide solution supply unit 50 is a liquid supply mechanism for supplying hydrogen peroxide solution, which is one component of the treatment liquid, to the inner tank 11 of the treatment tank 10. As shown in FIG. 1, the hydrogen peroxide solution supply unit 50 includes a hydrogen peroxide solution supply source 51, a main pipe 52, branch pipes 53a and 53b, on-off valves 54a and 54b, and a pair of discharge pipes 55a. , 55b. The upstream end of the main pipe 52 is connected to the hydrogen peroxide solution supply source 51, and the downstream end of the main pipe 52 is branched into two, and the flow paths are connected to the branch pipes 53a and 53b, respectively. It is connected. On the way of the branch pipes 53a and 53b, on-off valves 54a and 54b are respectively inserted, and downstream ends of the branch pipes 53a and 53b are connected to the pair of discharge pipes 55a and 55b, respectively. Has been.

  The pair of discharge pipes 55 a and 55 b are pipe-shaped members having a bent shape immersed in the inner tank 11. As shown in FIG. 2, the discharge pipes 55 a and 55 b are respectively arranged along the arrangement direction of the substrates W on the downstream side of the introduction pipe part 551 and the introduction pipe part 551 extending downward along the side wall 112 d of the inner tank 11. A horizontal pipe portion 552 that extends horizontally and a distal end pipe portion 553 that extends upward along the side wall 112c of the inner tank 11 on the downstream side of the horizontal pipe portion 552, and has a substantially U-shape as a whole. . A plurality of discharge ports 554 are formed on the lower surface of the horizontal tube portion 552 of the discharge tubes 55a and 55b. The plurality of discharge ports 554 are formed at substantially the same positions as the discharge ports 361 and 362 of the discharge pipes 36a and 36b in the X-axis direction. That is, the positions of the plurality of ejection ports 554 in the X-axis direction are positions corresponding to the gaps between the substrates W held on the lifter 20 and the outer sides of both ends.

  When the on-off valve 54b is closed and the on-off valve 54a is opened in the hydrogen peroxide solution supply unit 50, the hydrogen peroxide solution is supplied from the hydrogen peroxide solution supply unit 50 to the discharge pipe 55a through the main pipe 52 and the branch pipe 53a. The hydrogen peroxide solution is supplied and discharged into the inner tank 11 from the plurality of discharge ports 554 of the discharge pipe 55a. In the hydrogen peroxide solution supply unit 50, when the on / off valve 54a is closed and the on / off valve 54b is opened, the hydrogen peroxide solution supply unit 50 passes through the main pipe 52 and the branch pipe 53b to the discharge pipe 55b. Water is supplied, and hydrogen peroxide solution is discharged into the inner tank 11 from the plurality of discharge ports 554 of the discharge pipe 55b.

  FIG. 3 is an enlarged longitudinal sectional view showing the flow of the processing liquid discharged from the discharge pipe 36a and the flow of hydrogen peroxide solution discharged from the discharge pipe 55a. As shown in FIG. 3, a part of the processing liquid supplied to the discharge pipe 36a is arranged from the plurality of discharge ports 361 of the discharge pipe 36a toward the inside of the inner tank 11 slightly downward (that is, at the immersion position). The liquid is discharged (toward the lower position of the substrate W at the time) to form a liquid flow F1 of the processing liquid. Further, the other part of the processing liquid supplied to the discharge pipe 36a is directed from the plurality of discharge ports 362 of the discharge pipe 36a toward the inside of the inner tank 11 slightly upward (that is, the substrate when placed in the immersion position). The liquid is discharged (toward the gap of W) to form a liquid flow F2 of the processing liquid.

  As shown in FIG. 3, the horizontal pipe portion 552 of the discharge pipe 55a is higher than the liquid flow F1 of the processing liquid discharged from the discharge port 361 of the discharge pipe 36a and is discharged from the discharge port 362 of the discharge pipe 36a. The liquid is disposed at a position lower than the liquid flow F2 of the processing liquid. The discharge pipe 55a discharges hydrogen peroxide water downward from the plurality of discharge ports 554, that is, toward the liquid flow F1 of the processing liquid discharged from the discharge ports 362 of the discharge pipe 36a. For this reason, the hydrogen peroxide solution discharged from the discharge pipe 55a immediately joins the treatment liquid flow F1 and efficiently mixes with the sulfuric acid in the treatment liquid. The liquid discharge operation in the discharge pipe 36b and the discharge pipe 55b is the same as the discharge operation of the discharge pipe 36a and the discharge pipe 55a except that the left and right are reversed. Therefore, the hydrogen peroxide solution discharged from the discharge pipe 55b immediately joins the liquid flow of the processing liquid and efficiently mixes with the sulfuric acid in the processing liquid. Thereafter, the treatment liquid containing sulfuric acid and hydrogen peroxide water forms an upward liquid flow at the center of the inner tank 11 and is stirred throughout the inner tank 11.

  Returning to FIG. 1 and FIG. 2, the control unit 60 is a computer device for controlling the operation of each unit of the substrate processing apparatus 1. The control unit 60 is electrically connected to the driving unit 22, the circulation pump 33, the heater 34, and the on-off valves 43, 54a, and 54b. The control unit 60 controls the operation of the drive unit 22, the circulation pump 33, the heater 34, and the on-off valves 43, 54 a and 54 b in accordance with programs installed in the control unit 60 and various instruction inputs in advance. Proceed with the process.

<2. Operation of substrate processing apparatus>
Subsequently, an operation when the substrate W is processed in the substrate processing apparatus 1 will be described with reference to a flowchart of FIG. When processing the substrate W in the substrate processing apparatus 1, first, the substrate processing apparatus 1 opens the on-off valve 43 of the sulfuric acid supply unit 40. Thereby, sulfuric acid is supplied to the outer tank 12 from the sulfuric acid supply source 41 via the supply piping 42 (step S1). When the supply of sulfuric acid is started, the substrate processing apparatus 1 starts the operation of the circulation pump 33 and the heater 34. As a result, sulfuric acid is introduced from the outer tank 12 to the discharge pipes 36a and 36b via the main pipe 31 and the branch pipes 32a and 32b, and into the inner tank 11 from the plurality of discharge ports 361 and 362 of the discharge pipes 36a and 36b. Sulfuric acid is discharged toward

  The sulfuric acid is heated by the heater 34 and supplied to the discharge pipes 36 a and 36 b while being filtered by the filter 35. The sulfuric acid discharged from the discharge pipes 36 a and 36 b is gradually stored in the inner tank 11. Eventually, when sulfuric acid overflows from the upper part of the inner tank 11 to the outer tank 12, and the sulfuric acid circulates between the inner tank 11, the outer tank 12, and the circulation line 30, the substrate processing apparatus 1 opens the on-off valve 43. Close and stop the supply of sulfuric acid.

  Next, the substrate processing apparatus 1 starts supplying the hydrogen peroxide solution from the hydrogen peroxide solution supply unit 50 while continuing the operation of the circulation pump 33 (step S2). FIG. 5 is a flowchart showing a detailed flow of the hydrogen peroxide supply operation in step S2. When supplying the hydrogen peroxide solution, first, the on-off valve 54a is opened with the on-off valve 54b closed. Thereby, the hydrogen peroxide solution is supplied from the hydrogen peroxide solution supply source 51 to the discharge pipe 55a through the main pipe 52 and the branch pipe 53a, and the hydrogen peroxide solution is discharged from the plurality of discharge ports 554 of the discharge pipe 55a. (Step S21).

  FIG. 6 is a diagram showing the flow of the processing liquid formed in the processing tank 10 in step S21. As shown in FIG. 6, in step S21, the treatment liquid containing sulfuric acid is discharged into the inner tank 11 from the discharge pipes 36a and 36b. The processing liquid discharged from the discharge pipes 36 a and 36 b forms an upward liquid flow inside the inner tank 11 and is stirred throughout the inner tank 11. In step S21, the hydrogen peroxide solution is discharged downward from the plurality of discharge ports 554 of the discharge pipe 55a. Since the hydrogen peroxide solution is discharged toward the processing liquid discharged from the plurality of discharge ports 361 of the discharge pipe 36a, it is efficiently mixed with sulfuric acid in the processing liquid. And since the process liquid containing a sulfuric acid and hydrogen peroxide solution is stirred by the whole inside of the inner tank 11, Caro acid is produced | generated in large quantities and uniformly in the inside of the inner tank 11. FIG.

  After discharging the hydrogen peroxide solution from the discharge pipe 55a for a predetermined time, the substrate processing apparatus 1 closes the on-off valve 54a and opens the on-off valve 54b. As a result, the supply of the hydrogen peroxide solution from the discharge pipe 55a is stopped and the supply of the hydrogen peroxide solution from the discharge pipe 55b is started. That is, the substrate processing apparatus 1 supplies the hydrogen peroxide solution from the hydrogen peroxide solution supply source 51 to the discharge pipe 55a through the main pipe 52 and the branch pipe 53b, and performs peroxide from a plurality of discharge ports 554 of the discharge pipe 55b. Hydrogen water is discharged (step S22).

  FIG. 7 is a diagram illustrating the flow of the processing liquid formed in the processing tank 10 in step S22. As shown in FIG. 7, in step S22, the treatment liquid containing sulfuric acid is discharged into the inner tank 11 from the discharge pipes 36a and 36b. The processing liquid discharged from the discharge pipes 36 a and 36 b forms an upward liquid flow inside the inner tank 11 and is stirred throughout the inner tank 11. In step S22, the hydrogen peroxide solution is discharged downward from the plurality of discharge ports 554 of the discharge pipe 55b. Since the hydrogen peroxide solution is discharged toward the processing liquid discharged from the plurality of discharge ports 361 of the discharge pipe 36b, it is efficiently mixed with sulfuric acid in the processing liquid. And since the process liquid containing a sulfuric acid and hydrogen peroxide solution is stirred by the whole inside of the inner tank 11, Caro acid is produced | generated in large quantities and uniformly in the inside of the inner tank 11. FIG.

  Thereafter, the substrate processing apparatus 1 determines whether or not the above-described ejection operations of Step S21 and Step S22 have been repeated a predetermined number of times (Step S23). Then, when the discharge operations of Step S21 and Step S22 are not repeated a predetermined number of times, the process returns to Step S21, and the discharge operations of Step S21 and Step S22 are repeated. Moreover, when the discharge operation of step S21 and step S22 is repeated a predetermined number of times, the discharge operation of hydrogen peroxide solution in step S2 is completed, and the process proceeds to the subsequent step S3.

  Thus, in step S2, the substrate processing apparatus 1 alternately discharges the hydrogen peroxide solution from the discharge pipe 55a and discharges the hydrogen peroxide solution from the discharge pipe 55b, and performs these discharge operations. Repeat a predetermined number of times. For this reason, the treatment liquid containing sulfuric acid and hydrogen peroxide solution can be uniformly stirred in the inner tank 11. In addition, by alternately discharging the hydrogen peroxide solution from the pair of discharge tubes 55a and 55b, the hydrogen peroxide solution can be evenly discharged from the pair of discharge tubes 55a and 55b. That is, if hydrogen peroxide water is simultaneously discharged from the pair of discharge pipes 55a and 55b, a slight difference in discharge amount occurs between the discharge pipes 55a and 55b due to the difference in flow path resistance between the discharge pipes 55a and 55b. End up. On the other hand, such a problem does not occur if the hydrogen peroxide solution is alternately discharged from the pair of discharge pipes 55a and 55b as in the present embodiment.

  Returning to the flowchart of FIG. When the discharge of the hydrogen peroxide solution in step S <b> 2 is completed, the substrate W transported from another apparatus by a predetermined transport mechanism is subsequently placed on the lifter 20 that stands by at a position above the processing bath 10. When the substrate W is placed on the lifter 20, the substrate processing apparatus 1 operates the driving unit 22 to lower the lifter 20 and immerse the substrate W in the processing liquid stored in the processing tank 10. (Step S3). When the substrate W is immersed in the processing liquid, the photoresist film formed on the main surface of the substrate W is decomposed by the action of the Caro acid in the processing liquid, and the photoresist film is peeled off from the main surface of the substrate W. . Since a large amount and uniform amount of Caro acid is generated in the processing liquid as described above, the photoresist film is favorably peeled from the main surface of the substrate W.

  When the immersion treatment for a predetermined time is completed, the substrate processing apparatus 1 operates the drive unit 22 to raise the lifter 20 and pulls up the substrate W from the processing liquid stored in the inner tank 11 (step S4). Thereafter, the substrate W is transferred from the lifter 20 to a predetermined transfer device, and is transferred by the transfer device to an apparatus that performs subsequent processing. With the above, a series of processes for one set of substrates W is completed.

  As described above, the substrate processing apparatus 1 according to the present embodiment passes the discharge pipes 36a and 36b that discharge the liquid containing the sulfuric acid component into the inner tank 11 and the liquid discharged from the discharge pipes 36a and 36b. Discharge pipes 55a and 55b for discharging hydrogen oxide water are provided. For this reason, sulfuric acid and hydrogen peroxide water can be mixed efficiently, whereby a large amount and uniform amount of Caro acid can be generated inside the treatment tank 10. Therefore, the photoresist film can be favorably peeled from the main surface of the substrate W.

<3. Modification>
Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. For example, in the above embodiment, the hydrogen peroxide solution is alternately discharged from the pair of discharge pipes 55a and 55b. However, the hydrogen peroxide solution may be discharged simultaneously from these discharge pipes 55a and 55b. . However, as described above, in order to avoid the possibility of a difference in the discharge amount between the discharge pipes 55a and 55b, it is desirable to alternately discharge the hydrogen peroxide solution from the pair of discharge pipes 55a and 55b.

  In the above embodiment, the hydrogen peroxide solution is discharged to the processing liquid discharged from the discharge port 361 among the plurality of discharge ports 361 and 362 of the pair of discharge pipes 36a and 36b. You may make it discharge hydrogen peroxide water with respect to the process liquid discharged from the exit 362. FIG. Further, in the above embodiment, the substrate W is immersed in the processing liquid after completing the supply of the hydrogen peroxide solution. However, even if the hydrogen peroxide solution is supplied in the state where the substrate W is immersed, the substrate W is immersed. Good. For example, the hydrogen peroxide solution may be discharged to the liquid while discharging a liquid containing sulfuric acid toward the substrate W while the substrate W is immersed in the processing liquid.

  In the above-described embodiment, a plurality of substrates W are immersed in the processing solution at a time. However, the substrates W may be immersed in the processing solution one by one. In the above embodiment, the substrate W, which is a semiconductor wafer, is a processing target. However, the present invention targets other substrates such as a glass substrate for a liquid crystal display device and a glass substrate for a photomask. May be.

It is the longitudinal cross-sectional view which cut | disconnected the substrate processing apparatus by the plane parallel to the main surface of a board | substrate. It is the longitudinal cross-sectional view which cut | disconnected the substrate processing apparatus by the plane perpendicular | vertical to the main surface of a board | substrate. It is an enlarged vertical sectional view of a discharge pipe and its vicinity. It is the flowchart which showed the operation | movement procedure of the substrate processing in a substrate processing apparatus. It is the flowchart which showed the detailed flow of the supply operation | movement of hydrogen peroxide water. It is the figure which showed the flow of the process liquid in a process tank when supplying hydrogen peroxide water. It is the figure which showed the flow of the process liquid in a process tank when supplying hydrogen peroxide water.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 10 Processing tank 11 Inner tank 12 Outer tank 20 Lifter 30 Circulation line 36a, 36b Discharge pipe 361,362 Discharge port 40 Sulfuric acid supply part 50 Hydrogen peroxide solution supply part 54a, 54b On-off valve 55a, 55b Discharge pipe 554 Discharge port 60 Control unit W substrate

Claims (8)

A substrate processing apparatus for peeling an organic film formed on a surface of a substrate by immersing the substrate in a processing solution containing sulfuric acid and hydrogen peroxide solution,
A treatment tank for storing a treatment liquid containing sulfuric acid and hydrogen peroxide solution;
Holding means for holding the substrate inside the processing tank;
First discharge means for discharging a liquid containing a sulfuric acid component into the treatment tank;
Second discharge means for discharging hydrogen peroxide solution toward the liquid discharged from the first discharge means;
A substrate processing apparatus comprising: The substrate processing apparatus according to claim 1,
The first discharge means has a pair of first discharge portions for discharging a liquid containing a sulfuric acid component from a pair of opposing side portions of the processing tank toward a central portion,
The substrate processing apparatus, wherein the second discharge means includes a pair of second discharge portions that discharge hydrogen peroxide solution toward the liquid discharged from each of the pair of first discharge portions. The substrate processing apparatus according to claim 2,
The substrate processing apparatus further comprising control means for alternately discharging the hydrogen peroxide solution from the pair of second discharge portions. A substrate processing apparatus according to any one of claims 1 to 3, wherein
The treatment tank includes an inner tank in which the holding means, the first discharge means, and the second discharge means are disposed, and an outer tank that receives a treatment liquid overflowing from an upper portion of the inner tank,
A circulation line for feeding the processing liquid from the outer tank to the first discharge means;
Sulfuric acid supply means for supplying sulfuric acid to the outer tank;
A substrate processing apparatus further comprising: A substrate processing apparatus according to any one of claims 1 to 4, wherein
Each of the first discharge means and the second discharge means has a plurality of discharge ports,
The substrate processing apparatus according to claim 1, wherein the plurality of discharge ports of the first discharge unit and the plurality of discharge ports of the second discharge unit have a one-to-one correspondence. The substrate processing apparatus according to claim 5,
The holding means holds a plurality of substrates arranged in parallel with each other in the processing tank,
The substrate processing apparatus, wherein the plurality of discharge ports of the first discharge unit and the second discharge unit are formed at positions corresponding to gaps between the plurality of substrates held by the holding unit. A substrate processing method for peeling an organic film formed on a surface of a substrate by immersing the substrate in a processing solution containing sulfuric acid and hydrogen peroxide water,
A discharge step of discharging a hydrogen peroxide solution toward the liquid while discharging a liquid containing a sulfuric acid component into the treatment tank;
An immersion step of immersing the substrate in the processing liquid stored in the processing tank;
A substrate processing method comprising: The substrate processing method according to claim 7, comprising:
In the discharge step, a liquid containing a sulfuric acid component is discharged from a pair of discharge portions disposed on a pair of opposing side portions of the treatment tank toward a central portion of the treatment tank, and the pair of discharge portions A substrate processing method characterized by alternately discharging hydrogen peroxide solution toward a liquid discharged from one side and a liquid discharged from the other side.

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