JP2013074090A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

A temperature drop of a processing solution on a substrate is suppressed during an SPM process.
In a substrate processing apparatus, a liquid is discharged from a processing liquid supply unit toward an upper surface of a substrate that is rotated by a substrate rotating mechanism. The treatment liquid supply unit 3 includes a sulfuric acid supply unit 31, a hydrogen peroxide solution supply unit 32, a mixed solution generation unit 33, and a nozzle 34. In the substrate processing apparatus 1, sulfuric acid heated by the sulfuric acid supply unit 31 is supplied from the nozzle 34 to the substrate 9, and a preliminary heating process is performed on the substrate 9. Thereafter, the heated sulfuric acid from the sulfuric acid supply unit 31 and the hydrogen peroxide solution from the hydrogen peroxide solution supply unit 32 are mixed in the mixed solution generation unit 33 to generate the SPM solution, and the SPM solution is applied to the substrate 9. The supplied SPM process is performed. By performing the preheating process, it is possible to suppress the temperature drop of the high-temperature SPM liquid supplied onto the substrate 9 during the SPM process. As a result, the efficiency of SPM processing can be improved.
[Selection] Figure 1

Description

  The present invention relates to a technique for processing a substrate.

  Conventionally, in a manufacturing process of a semiconductor substrate (hereinafter simply referred to as “substrate”), various processes are performed on a substrate having an insulating film such as an oxide film using a substrate processing apparatus. For example, a process such as etching is performed on the surface of the substrate by supplying a processing liquid to the substrate having a resist pattern formed on the surface. In addition, after the etching or the like is finished, a process for removing the resist on the substrate is also performed.

  For example, in the resist removal apparatus disclosed in Patent Document 1, an SPM (sulfuric acid / hydrogen peroxide mixture) solution, which is a mixed solution of sulfuric acid and hydrogen peroxide solution, is supplied from a nozzle onto a horizontally rotating substrate and is included in the SPM solution. The resist on the substrate is removed by the strong oxidizing power of caloic acid. In the resist removal apparatus, the SPM liquid is generated by mixing heated sulfuric acid and hydrogen peroxide solution at room temperature (that is, a temperature approximately equal to room temperature). Since large reaction heat is generated when sulfuric acid and hydrogen peroxide are mixed, the temperature of the SPM liquid supplied onto the substrate is higher than the temperature of the heated sulfuric acid. In the resist removal process using the SPM solution, it is preferable to keep the temperature of the SPM solution high in order to efficiently remove the resist.

JP 2007-59816 A

  By the way, in the resist removal apparatus of Patent Document 1, immediately after the apparatus is driven, the temperature of the pipe or the like for introducing sulfuric acid to the nozzle is also normal temperature, so the temperature of the SPM liquid supplied from the nozzle is lower than the desired temperature. There is a risk of it. Further, since the high-temperature SPM liquid is supplied onto the normal temperature substrate, the temperature of the SPM liquid is lowered on the substrate, and the resist removal efficiency may be reduced. Furthermore, since the temperature of the SPM liquid decreases while the SPM liquid moves from the central portion of the substrate toward the edge due to the rotation of the substrate, the state of resist removal differs between the central portion of the substrate and the portion near the edge. There is a possibility that a part of the resist may remain without being removed at a portion in the vicinity of the edge.

  The present invention has been made in view of the above problems, and has as its main object to suppress a temperature drop of a processing solution on a substrate during SPM processing.

  The invention according to claim 1 is a substrate processing apparatus for processing a substrate, wherein the substrate holding unit holds the substrate, the sulfuric acid supply unit supplies heated sulfuric acid, and the hydrogen peroxide supplies hydrogen peroxide. By controlling the treatment liquid supply unit having a water supply unit and the treatment liquid supply unit, heated sulfuric acid is supplied to the substrate in a state where supply of hydrogen peroxide solution is stopped, and the substrate is predetermined. Control for performing SPM processing on the substrate by supplying the heated sulfuric acid and the hydrogen peroxide solution to the main surface of the substrate while being mixed by the treatment liquid supply unit. A part.

  Invention of Claim 2 is a substrate processing apparatus of Claim 1, Comprising: The collection | recovery part which collect | recovers the sulfuric acid supplied to the said board | substrate in the case of the said preheating process, and returns to the said sulfuric acid supply part Further prepare.

  A third aspect of the present invention is the substrate processing apparatus according to the first or second aspect, wherein the flow rate of sulfuric acid during the preheating treatment is greater than the flow rate of sulfuric acid during the SPM treatment.

  Invention of Claim 4 is a substrate processing apparatus in any one of Claim 1 thru | or 3, Comprising: The said process liquid supply part is connected to the said sulfuric acid supply part and the said hydrogen peroxide solution supply part, The SPM treatment further includes a mixed solution generation unit that generates a mixed solution by mixing the heated sulfuric acid from the sulfuric acid supply unit and the hydrogen peroxide solution from the hydrogen peroxide solution supply unit.

  Invention of Claim 5 is a substrate processing apparatus in any one of Claim 1 thru | or 4, Comprising: The temperature of the sulfuric acid in the said sulfuric-acid supply part at the time of the said preheating process is the said sulfuric acid at the time of the said SPM process Equal to the temperature of sulfuric acid in the supply section.

  The invention according to claim 6 is a substrate processing method for processing a substrate, and a) supplying heated sulfuric acid to the substrate in a state in which the supply of hydrogen peroxide solution to the substrate is stopped. A step of performing a preheating treatment for heating to a predetermined temperature; and b) supplying the main surface of the substrate that has been subjected to the preheating treatment while mixing heated sulfuric acid and hydrogen peroxide solution to the substrate. And a step of performing SPM processing.

  In the present invention, the temperature drop of the processing liquid on the substrate can be suppressed during the SPM processing.

It is a figure which shows the structure of the substrate processing apparatus which concerns on one embodiment. It is a figure which shows the flow of a 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. As shown in FIG. 1, the substrate processing apparatus 1 is a single-wafer type apparatus that processes semiconductor substrates 9 (hereinafter simply referred to as “substrates 9”) one by one. In the substrate processing apparatus 1, an SPM (sulfuric acid / hydrogen peroxide mixture) solution is supplied to the substrate 9 to perform an SPM process, that is, a resist film removal process on the substrate 9.

  The substrate processing apparatus 1 includes a substrate holding unit 2 that holds the substrate 9 with one main surface 91 (hereinafter referred to as “upper surface 91”) of the substrate 9 facing upward, and an SPM toward the upper surface 91 of the substrate 9. The processing liquid supply unit 3 that discharges liquid such as liquid, the cup unit 4 that surrounds the periphery of the substrate 9 and the substrate holding unit 2, the substrate rotating mechanism 5 that rotates the substrate 9 together with the substrate holding unit 2, and the liquid from the cup unit 4 A recovery part 6 for recovering the liquid, a rinse liquid supply part 7 for supplying a rinse liquid to the upper surface 91 of the substrate 9, and a control part 8 for controlling these mechanisms. The substrate 9 is rotated by the substrate rotating mechanism 5 together with the substrate holding unit 2 about a rotation axis that passes through the center of the substrate 9 and is perpendicular to the upper surface 91 of the substrate 9. In the substrate processing apparatus 1, the substrate holding unit 2, the cup unit 4, the substrate rotating mechanism 5 and the like are accommodated in a chamber (not shown).

  The treatment liquid supply unit 3 generates a mixed liquid connected to the sulfuric acid supply unit 31 that supplies sulfuric acid, the hydrogen peroxide solution supply unit 32 that supplies hydrogen peroxide solution, the sulfuric acid supply unit 31, and the hydrogen peroxide solution supply unit 32. A nozzle 33 that is disposed above the substrate 33 and that discharges liquid toward the substrate 9; and a nozzle rotation mechanism 35 that rotates the nozzle 34 horizontally about a rotation shaft 351. The nozzle rotation mechanism 35 includes an arm 352 that extends in the horizontal direction from the rotation shaft 351 and to which the nozzle 34 is attached.

  The sulfuric acid supply unit 31 is connected to the sulfuric acid storage unit 311 for storing sulfuric acid, the sulfuric acid storage unit 311 and the mixed liquid generation unit 33, and the sulfuric acid storage unit 311 to the mixed liquid generation unit 33 via the sulfuric acid piping 312. And a sulfuric acid pump 313 for supplying sulfuric acid, a sulfuric acid valve 314 provided on the sulfuric acid pipe 312, and a sulfuric acid heating unit 315 provided on the sulfuric acid pipe 312 between the sulfuric acid pump 313 and the sulfuric acid valve 314 for heating sulfuric acid. Prepare. The sulfuric acid pipe 312 branches between the sulfuric acid heating unit 315 and the sulfuric acid valve 314 and is connected to the sulfuric acid storage unit 311. When the sulfuric acid valve 314 is closed, the sulfuric acid heated by the sulfuric acid heating unit 315 is connected. Circulates between the sulfuric acid storage part 311 and the sulfuric acid heating part 315.

  The hydrogen peroxide solution supply unit 32 includes a hydrogen peroxide solution storage unit 321 for storing hydrogen peroxide solution, a hydrogen peroxide solution storage unit 321, and a hydrogen peroxide solution pipe 322 connected to the mixed solution generation unit 33. A hydrogen peroxide solution pump 323 for supplying hydrogen peroxide solution from the hydrogen water storage unit 321 to the mixed solution generating unit 33 through the hydrogen peroxide solution pipe 322, and a peroxide provided on the hydrogen peroxide solution tube 322 A hydrogen water valve 324 is provided. The sulfuric acid storage unit 311 and the hydrogen peroxide solution storage unit 321 may be provided outside the substrate processing apparatus 1, and the sulfuric acid supply unit 31 and the hydrogen peroxide solution supply unit 32 may be connected to each other.

  The mixed liquid generation unit 33 is provided on the mixing valve 331 to which the sulfuric acid pipe 312 and the hydrogen peroxide pipe 322 are connected, the discharge pipe 332 connected to the mixing valve 331 and the nozzle 34, and the discharge pipe 332. A stirring flow pipe 333 is provided. In the mixed solution generation unit 33, the heated sulfuric acid from the sulfuric acid supply unit 31 and the hydrogen peroxide solution at room temperature (that is, a temperature similar to room temperature) from the hydrogen peroxide solution supply unit 32 are mixed with each other. Is mixed to produce an SPM liquid (sulfuric acid / hydrogen peroxide) as a mixed liquid. The SPM liquid passes through the stirring flow pipe 333 and the discharge pipe 332 and is sent to the nozzle 34. In the stirring flow pipe 333, the chemical reaction between sulfuric acid and hydrogen peroxide solution is promoted by stirring the SPM liquid. The SPM liquid is discharged from the discharge port at the tip of the nozzle 34 toward the upper surface 91 of the substrate 9. In the present embodiment, sulfuric acid heated to about 130 ° C. to 150 ° C. by the sulfuric acid heating unit 315 is supplied from the sulfuric acid supply unit 31 to the mixed liquid generation unit 33. Note that the temperature of the sulfuric acid supplied from the sulfuric acid supply unit 31 may be changed as appropriate.

  The recovery part 6 includes a used liquid pipe 61 connected to the bottom of the cup part 4, a three-way valve 62 connected to the used liquid pipe 61, a waste liquid pipe 64 connecting the three-way valve 62 and the waste liquid recovery part 63, three-way A sulfuric acid recovery pipe 65 that connects the valve 62 and the sulfuric acid storage part 311, and a sulfuric acid recovery pump 66 that is provided on the sulfuric acid recovery pipe 65 and sends the sulfuric acid recovered from the cup part 4 to the sulfuric acid storage part 311. .

  FIG. 2 is a diagram illustrating a processing flow of the substrate 9 in the substrate processing apparatus 1. In the substrate processing apparatus 1, first, the substrate 9 is loaded and held by the substrate holding unit 2. Subsequently, when the substrate rotating mechanism 5 is controlled by the control unit 8, the rotation of the substrate 9 is started. In addition, the rotation of the nozzle 34 by the nozzle rotation mechanism 35 is started, and the nozzle 34 repeats reciprocating motion between the center portion and the edge of the substrate 9 (step S11). In the substrate processing apparatus 1, a liquid to be described later may be supplied from the nozzle 34 stopped above the central portion of the substrate 9.

  Next, when the processing liquid supply unit 3 is controlled by the control unit 8, the sulfuric acid valve 314 of the sulfuric acid supply unit 31 is opened, and the sulfuric acid heated to about 130 ° C. to 150 ° C. by the sulfuric acid heating unit 315 is converted into sulfuric acid. It is supplied at a predetermined flow rate to the mixed liquid generation unit 33 via the pipe 312. At this time, the hydrogen peroxide solution valve 324 is closed.

  The heated sulfuric acid passes through the mixing valve 331, the discharge pipe 332 and the stirring flow pipe 333 of the mixed liquid generation unit 33 in a state where the supply of the hydrogen peroxide solution is stopped, and passes from the nozzle 34 to the upper surface 91 of the substrate 9. Supplied to. The sulfuric acid on the substrate 9 moves on the upper surface 91 toward the edge of the substrate 9 by the rotation of the substrate 9, whereby the upper surface 91 of the substrate 9 is heated by the sulfuric acid over the entire surface. The sulfuric acid moving on the substrate 9 scatters from the edge of the substrate 9 to the outside. The sulfuric acid scattered from the substrate 9 travels along the inner surface of the side wall of the cup part 4 or directly moves to the bottom part of the cup part 4 and is collected by the collecting part 6 connected to the bottom part of the cup part 4. In the recovery unit 6, the used liquid pipe 61 and the sulfuric acid recovery pipe 65 are connected by a three-way valve 62, and the sulfuric acid recovered from the cup unit 4 is supplied with sulfuric acid by driving the sulfuric acid recovery pump 66. It returns to the sulfuric acid storage part 311 of the part 31. The sulfuric acid returned to the sulfuric acid storage unit 311 is supplied again from the sulfuric acid supply unit 31 to the mixed solution generation unit 33.

  In the substrate processing apparatus 1, the heated sulfuric acid is continuously supplied to the substrate 9 for a predetermined time, and the temperature of the upper surface 91 of the substrate 9 is heated to a predetermined temperature (for example, about 130 ° C. to 150 ° C.). A preheating process is performed (step S12). During the preheating process, the recovery of the sulfuric acid by the recovery unit 6 and the delivery to the sulfuric acid supply unit 31 are continuously performed. In the sulfuric acid supply unit 31, the heated sulfuric acid flows, so that the sulfuric acid pipe 312, the mixing valve 331, the discharge pipe 332, the stirring flow pipe 333 and the nozzle 34 also reach a predetermined temperature (for example, about 130 ° C. to 150 ° C.). Heated.

  When the preliminary heating process is completed, the sulfuric acid valve 314 is adjusted by the control unit 8, and the flow rate of sulfuric acid supplied from the sulfuric acid supply unit 31 to the mixed solution generation unit 33 is changed to a predetermined flow rate during the SPM process. In the present embodiment, the flow rate of sulfuric acid supplied from the sulfuric acid supply unit 31 to the mixed solution generating unit 33 during the preheating process is greater than the flow rate of sulfuric acid supplied from the sulfuric acid supply unit 31 to the mixed solution generating unit 33 during the SPM process. There are also many. On the other hand, the temperature of sulfuric acid in the sulfuric acid supply unit 31 during the SPM treatment is approximately equal to the temperature of sulfuric acid in the sulfuric acid supply unit 31 during the preheating treatment, and is approximately 130 ° C. to 150 ° C.

  In the treatment liquid supply unit 3, the hydrogen peroxide solution valve 324 is opened by the control unit 8, and normal temperature hydrogen peroxide solution is supplied from the hydrogen peroxide solution storage unit 321 to the mixing valve 331 via the hydrogen peroxide solution pipe 322. And at a predetermined flow rate. In the mixing valve 331, the heated sulfuric acid and the hydrogen peroxide solution at room temperature are mixed to generate the SPM liquid. The temperature of the SPM liquid is higher than the temperature of sulfuric acid supplied from the sulfuric acid supply unit 31 by the reaction between sulfuric acid and hydrogen peroxide solution, and is about 150 ° C. to 195 ° C. The SPM liquid passes through the discharge pipe 332 and the stirring flow pipe 333, and is supplied from the nozzle 34 to the upper surface 91 of the substrate 9 on which the preheating treatment has been performed. In other words, heated sulfuric acid and hydrogen peroxide solution are mixed and supplied to the upper surface 91 of the substrate 9 by the processing liquid supply unit 3.

  The SPM liquid spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9, scatters from the edge of the substrate 9 to the outside, and is received by the cup portion 4. In the recovery unit 6, the three-way valve 62 is switched to connect the used liquid pipe 61 and the waste liquid pipe 64, and the SPM liquid recovered from the cup unit 4 is discarded by driving the waste liquid recovery unit 63. Is done. In the substrate processing apparatus 1, the supply of the SPM liquid to the substrate 9 is continuously performed for a predetermined time, and the SPM process for the substrate 9, that is, the resist film on the substrate 9 due to the strong oxidizing power of caloic acid contained in the SPM liquid. A removal process is performed (step S13).

  When the SPM processing is completed, the sulfuric acid valve 314 is closed with the hydrogen peroxide solution valve 324 opened, and the hydrogen peroxide solution passes through the mixing valve 331, the discharge pipe 332, and the stirring flow pipe 333, and the nozzle 34 To the substrate 9 from which the resist film has been removed (step S14). By the hydrogen peroxide supply process, the SPM liquid remaining in the mixing valve 331, the discharge pipe 332, the stirring flow pipe 333, and the nozzle 34 is removed. Further, the hydrogen peroxide solution supplied onto the substrate 9 spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9, and the SPM liquid remaining on the substrate 9 is moved outward from the edge of the substrate 9. Extrude and remove. The SPM liquid and the hydrogen peroxide solution scattered from the edge of the substrate 9 to the outside are discarded by the recovery unit 6 as described above.

  When the hydrogen peroxide solution supply process is completed, the hydrogen peroxide solution valve 324 is closed and the supply of the hydrogen peroxide solution is stopped, and the nozzle 34 is moved to the standby position outside the substrate 9 by the nozzle rotation mechanism 35. (Step S15). Next, a rinsing process is performed in which pure water (DIW: deionized water) that is a rinsing liquid is supplied from the rinsing liquid supply unit 7 to the upper surface 91 of the substrate 9 (step S16). The rinse liquid spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9. Thereby, the hydrogen peroxide remaining on the substrate 9 is washed away. When the rinsing process is continuously performed for a predetermined time, the supply of the rinsing liquid is stopped. Then, the rotational speed of the substrate 9 is increased, and a drying process is performed to remove the rinse liquid remaining on the substrate 9 by the rotation of the substrate 9 (step S17). Thereafter, the rotation of the substrate 9 is stopped (step S18), and the substrate 9 is unloaded from the substrate processing apparatus 1.

  As described above, in the substrate processing apparatus 1, the heated sulfuric acid is supplied to the substrate 9 by the processing liquid supply unit 3 and the substrate 9 is heated before the SPM process is performed on the substrate 9. Thus, by performing the preheating process with respect to the board | substrate 9, the temperature fall of the high temperature SPM liquid supplied on the board | substrate 9 can be suppressed in the case of SPM processing. As a result, the efficiency of SPM processing can be improved. Moreover, since the temperature drop of the SPM liquid when moving on the upper surface 91 of the substrate 9 can be suppressed, the uniformity of the SPM process on the entire upper surface 91 of the substrate 9 and the uniformity of film reduction and film growth can be reduced. It can also be improved.

  Further, since the sulfuric acid pipe 312, the mixing valve 331, the discharge pipe 332, the agitation flow pipe 333 and the nozzle 34 are also heated before the start of the SPM process, the supply of hydrogen peroxide water to the mixing valve 331 is started. The time until the temperature of the SPM liquid discharged from 34 reaches a desired temperature can be shortened. As a result, the time required for the SPM process can be shortened.

  In the substrate processing apparatus 1, an increase in the amount of sulfuric acid used can be prevented by providing the recovery unit 6 that recovers the sulfuric acid supplied to the substrate 9 during the preheating process and returns it to the sulfuric acid supply unit 31. it can. In addition, the treatment liquid supply unit 3 includes a mixed liquid generation unit 33 that mixes the sulfuric acid from the sulfuric acid supply unit 31 and the hydrogen peroxide solution from the hydrogen peroxide solution supply unit 32 to generate the SPM liquid, thereby And the efficiency of SPM processing can be further improved and the uniformity of SPM processing on the entire upper surface 91 of the substrate 9 can be further improved as compared with the case where the hydrogen peroxide solution and hydrogen peroxide solution are supplied to the substrate 9 from individual discharge ports. be able to.

  As described above, in the substrate processing apparatus 1, the preheating treatment is required by increasing the flow rate of sulfuric acid in the sulfuric acid supply unit 31 during the preheating treatment to be higher than the flow rate of sulfuric acid in the sulfuric acid supply unit 31 during the SPM treatment. Time can be shortened. Furthermore, since the temperature of sulfuric acid in the sulfuric acid supply unit 31 during the preheating treatment is equal to the temperature of sulfuric acid in the sulfuric acid supply unit 31 during the SPM treatment, the sulfuric acid supply unit 31 is used when shifting from the preheating treatment to the SPM treatment. It is not necessary to change the temperature of sulfuric acid in As a result, the time required for the above-described series of processes in the substrate processing apparatus 1 can be shortened.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the said embodiment, A various change is possible.

  The temperature of sulfuric acid in the sulfuric acid supply unit 31 during the preheating treatment may be different from the temperature of sulfuric acid in the sulfuric acid supply unit 31 during the SPM treatment. For example, a heating unit that operates only during the preheating process may be added on the sulfuric acid pipe 312 so that the temperature of the sulfuric acid during the preheating process is approximately equal to the temperature of the SPM liquid during the SPM process. If the time required for the preheating treatment is sufficiently short, the flow rate of sulfuric acid during the preheating treatment may be approximately equal to the flow rate of sulfuric acid during the SPM treatment, for example.

  If the efficiency and uniformity of the SPM process are within an allowable range, the mixed liquid generating unit 33 is omitted from the processing liquid supply unit 3, and heated sulfuric acid is discharged from the sulfuric acid supply unit 31 toward the substrate 9. Hydrogen peroxide water is discharged from the hydrogen oxide water supply unit 32 toward the substrate 9. Also in this case, similar to the above-described embodiment, after the sulfuric acid heated from the sulfuric acid supply unit 31 is supplied to the substrate 9 and the preheating treatment is performed, the heated sulfuric acid and the hydrogen peroxide solution are treated with the treatment liquid. SPM processing is performed on the substrate 9 by being supplied to the upper surface 91 of the substrate 9 while being mixed by the supply unit 3. Thereby, the temperature fall of the process liquid (namely, mixed liquid of a sulfuric acid and hydrogen peroxide solution) supplied on the board | substrate 9 can be suppressed. In addition, the uniformity of the SPM process on the entire upper surface 91 of the substrate 9 can be improved. Furthermore, since the sulfuric acid pipe 312 of the sulfuric acid supply unit 31 can be heated before the SPM process, the time until the temperature of the processing liquid on the substrate 9 reaches a desired temperature can be shortened.

  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 2 Substrate holding part 3 Processing liquid supply part 6 Recovery part 8 Control part 9 Substrate 31 Sulfuric acid supply part 32 Hydrogen peroxide solution supply part 33 Mixed liquid production | generation part 91 Upper surface S11-S18 Step

Claims (6)

A substrate processing apparatus for processing a substrate,
A substrate holder for holding the substrate;
A treatment liquid supply unit having a sulfuric acid supply unit for supplying heated sulfuric acid and a hydrogen peroxide solution supply unit for supplying hydrogen peroxide solution;
After performing a preheating process for supplying heated sulfuric acid to the substrate and heating the substrate to a predetermined temperature in a state where supply of hydrogen peroxide solution is stopped by controlling the treatment liquid supply unit A controller for performing SPM processing on the substrate by supplying heated sulfuric acid and hydrogen peroxide water to the main surface of the substrate while being mixed by the treatment liquid supply unit;
A substrate processing apparatus comprising: The substrate processing apparatus according to claim 1,
A substrate processing apparatus, further comprising a recovery unit that recovers the sulfuric acid supplied to the substrate during the preliminary heating process and returns the sulfuric acid to the sulfuric acid supply unit. The substrate processing apparatus according to claim 1, wherein:
The substrate processing apparatus, wherein the flow rate of sulfuric acid during the preheating treatment is larger than the flow rate of sulfuric acid during the SPM treatment. A substrate processing apparatus according to any one of claims 1 to 3,
The treatment liquid supply unit is
The sulfuric acid supply unit and the hydrogen peroxide solution supply unit are connected, and during the SPM treatment, heated sulfuric acid from the sulfuric acid supply unit and hydrogen peroxide solution from the hydrogen peroxide solution supply unit are mixed. The substrate processing apparatus further comprising a mixed liquid generating unit that generates the mixed liquid. The substrate processing apparatus according to claim 1, wherein:
The substrate processing apparatus, wherein the sulfuric acid temperature in the sulfuric acid supply unit during the preheating treatment is equal to the sulfuric acid temperature in the sulfuric acid supply unit during the SPM treatment. A substrate processing method for processing a substrate, comprising:
a) performing a preheating process of supplying heated sulfuric acid to the substrate and heating the substrate to a predetermined temperature in a state where supply of hydrogen peroxide solution to the substrate is stopped;
b) supplying the main surface of the substrate that has been subjected to the preheating treatment while mixing heated sulfuric acid and hydrogen peroxide solution, and performing SPM treatment on the substrate;
A substrate processing method comprising:

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