Substrate processing method and substrate processing apparatus

Abstract

To provide a technology that can suppress contamination of substrates in liquid processing.SOLUTION: A substrate processing method according to an aspect of the present disclosure includes a processing fluid dispensing step and a mixed fluid dispensing step. In the processing fluid dispensing step, a processing fluid generated by mixing sulfuric acid and hydrogen peroxide water is dispensed onto the substrate. In the mixed fluid dispensing step, a mixed fluid generated by mixing the processing fluid and vapor or mist of pure water is dispensed onto the substrate onto which the processing fluid is dispensed.SELECTED DRAWING: Figure 16

Description

Technical Field

[0001] The disclosed embodiments relate to a substrate processing method and a substrate processing apparatus.

Background Art

[0002] Conventionally, a technique for removing a resist film formed on a substrate such as a semiconductor wafer (hereinafter also referred to as a wafer) by SPM (Sulfuric Acid Hydrogen Peroxide Mixture) treatment is known. Such SPM treatment is performed by supplying an SPM solution generated by mixing sulfuric acid and hydrogen peroxide solution to the resist film on the substrate (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technique capable of suppressing contamination of a substrate in liquid processing.

Means for Solving the Problems

[0005] A substrate processing method according to an aspect of the present disclosure includes a treatment liquid discharging step and a mixed fluid discharging step. The treatment liquid discharging step discharges a treatment liquid onto a substrate. The mixed fluid discharging step discharges a mixed fluid, which is generated by mixing the treatment liquid and vaporous or misty pure water, onto the substrate onto which the treatment liquid is being discharged.

Effects of the Invention

[0006] According to the present disclosure, it is possible to suppress contamination of a substrate in liquid processing.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

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Figure 4

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Figure 7

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Figure 9

Figure 10

Figure 11

Figure 12

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Figure 14

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Figure 16

Figure 17

Figure 18

Mode for Carrying Out the Invention

[0008] Hereinafter, embodiments of the substrate processing method and the substrate processing apparatus disclosed in the present application will be described in detail with reference to the accompanying drawings. Note that the present disclosure is not limited by the following embodiments. Also, the drawings are schematic, and it should be noted that the dimensional relationships between elements, the ratios of the elements, etc. may be different from reality. Furthermore, there may be parts where the dimensional relationships and ratios are different from each other among the drawings.

[0009] Conventionally, a technique for removing a resist film formed on a substrate such as a semiconductor wafer (hereinafter also referred to as a wafer) by SPM (Sulfuric Acid Hydrogen Peroxide Mixture) treatment is known. Such SPM treatment is performed by supplying an SPM solution generated by mixing sulfuric acid and hydrogen peroxide water to the resist film on the substrate.

[0010] Also, in the prior art, a technique for efficiently performing SPM treatment by discharging high-temperature steam onto a substrate prior to discharging the SPM solution and performing the SPM treatment in a high-temperature environment has been disclosed.

[0011] On the other hand, in the above-described prior art, when impurities are mixed in the steam, there is a risk that the substrate may be contaminated due to the adhesion of such impurities to the substrate.

[0012] Therefore, a technique that can overcome the above problems and suppress contamination of the substrate in liquid treatment such as SPM treatment is expected.

[0013] <Outline of Substrate Processing System> First, with reference to FIG. 1, the schematic configuration of the substrate processing system 1 according to the embodiment will be described. FIG. 1 is a diagram showing the schematic configuration of the substrate processing system 1 according to the embodiment. Note that the substrate processing system 1 is an example of a substrate processing apparatus. Hereinafter, in order to clarify the positional relationship, X-axis, Y-axis, and Z-axis orthogonal to each other are defined, and the positive direction of the Z-axis is the vertically upward direction.

[0014] As shown in FIG. 1, the substrate processing system 1 includes a loading / unloading station 2 and a processing station 3. The loading / unloading station 2 and the processing station 3 are provided adjacent to each other.

[0015] The loading / unloading station 2 includes a carrier placement unit 11 and a transfer unit 12. A plurality of carriers C for horizontally accommodating a plurality of substrates, in this embodiment, semiconductor wafers W (hereinafter referred to as wafers W), are placed on the carrier placement unit 11.

[0016] The transfer unit 12 is provided adjacent to the carrier placement unit 11 and includes a substrate transfer device 13 and a delivery unit 14 inside. The substrate transfer device 13 includes a wafer holding mechanism for holding the wafer W. Further, the substrate transfer device 13 can move in the horizontal and vertical directions and turn around the vertical axis, and transfers the wafer W between the carrier C and the delivery unit 14 using the wafer holding mechanism.

[0017] The processing station 3 is provided adjacent to the transfer unit 12. The processing station 3 includes a transfer unit 15 and a plurality of processing units 16. The processing unit 16 is an example of a substrate processing unit. The plurality of processing units 16 are arranged side by side on both sides of the transfer unit 15.

[0018] The transfer unit 15 includes a substrate transfer device 17 inside. The substrate transfer device 17 includes a wafer holding mechanism for holding the wafer W. Further, the substrate transfer device 17 can move in the horizontal and vertical directions and turn around the vertical axis, and transfers the wafer W between the delivery unit 14 and the processing unit 16 using the wafer holding mechanism.

[0019] The processing unit 16 performs predetermined substrate processing on the wafer W conveyed by the substrate transfer device 17. Details of such a processing unit 16 will be described later.

[0020] In addition, the substrate processing system 1 includes a control device 4. The control device 4 is, for example, a computer and includes a control unit 18 and a storage unit 19. Programs for controlling various processes executed in the substrate processing system 1 are stored in the storage unit 19. The control unit 18 controls the operation of the substrate processing system 1 by reading and executing the programs stored in the storage unit 19.

[0021] Note that such a program may be recorded on a computer-readable storage medium and installed from the storage medium into the storage unit 19 of the control device 4. Examples of computer-readable storage media include a hard disk (HD), a flexible disk (FD), a compact disk (CD), a magneto-optical disk (MO), and a memory card.

[0022] In the substrate processing system 1 configured as described above, first, the substrate transfer device 13 of the loading / unloading station 2 takes out the wafer W from the carrier C placed on the carrier placement unit 11 and places the taken-out wafer W on the transfer unit 14. The wafer W placed on the transfer unit 14 is taken out from the transfer unit 14 by the substrate transfer device 17 of the processing station 3 and carried into the processing unit 16.

[0023] The wafer W carried into the processing unit 16 is processed by the processing unit 16 and then carried out from the processing unit 16 by the substrate transfer device 17 and placed on the transfer unit 14. Then, the processed wafer W placed on the transfer unit 14 is returned to the carrier C on the carrier placement unit 11 by the substrate transfer device 13.

[0024] <Configuration of the processing unit> Next, the configuration of the processing unit 16 will be described with reference to FIGS. 2 and 3. FIG. 2 is a schematic diagram showing a configuration example of the processing unit 16 according to the embodiment. As shown in FIG. 2, the processing unit 16 includes a chamber 20, a liquid processing unit 30, a liquid supply unit 40, and a recovery cup 50.

[0025] The chamber 20 houses the liquid processing unit 30, the liquid supply unit 40, and the recovery cup 50. An FFU (Fan Filter Unit) 21 is provided on the ceiling of the chamber 20. The FFU 21 forms a downflow in the chamber 20.

[0026] The liquid processing unit 30 includes a holding unit 31, a support column unit 32, and a driving unit 33, and performs liquid processing on the placed wafer W. The holding unit 31 holds the wafer W horizontally. The support column unit 32 is a member extending in the vertical direction, the base end portion of which is rotatably supported by the driving unit 33, and the holding unit 31 is horizontally supported at the tip end portion. The driving unit 33 rotates the support column unit 32 around the vertical axis.

[0027] Such a liquid processing unit 30 rotates the holding unit 31 supported by the support column unit 32 by rotating the support column unit 32 using the driving unit 33, thereby rotating the wafer W held by the holding unit 31.

[0028] On the upper surface of the holding unit 31 included in the liquid processing unit 30, a holding member 31a for holding the wafer W from the side is provided. The wafer W is horizontally held in a state slightly separated from the upper surface of the holding unit 31 by such a holding member 31a. Note that the wafer W is held by the holding unit 31 with the surface on which the substrate processing is performed facing upward.

[0029] The liquid supply unit 40 supplies a processing liquid to the wafer W. The liquid supply unit 40 includes nozzles 41a, 41b, arms 42a, 42b for horizontally supporting such nozzles 41a, 41b, and turning and elevating mechanisms 43a, 43b for turning and elevating the arms 42a, 42b, respectively. The nozzle 41a is an example of a liquid discharge portion.

[0030] The nozzle 41a is, for example, a bar nozzle, and is connected to the SPM liquid supply unit 44 through the SPM liquid supply path 47 and to the steam supply unit 45 through the steam supply path 48. The SPM liquid supply unit 44 is an example of the first supply unit, and the steam supply unit 45 is an example of the second supply unit.

[0031] The SPM liquid supplied from the SPM liquid supply unit 44 is an example of a processing liquid, and is a chemical solution generated by mixing sulfuric acid (H2SO4) and hydrogen peroxide solution (H2O2) at a given ratio (for example, H2SO4:H2O2 = 10:1). The SPM liquid is used, for example, for removing a resist film formed on the surface of the wafer W.

[0032] The SPM liquid supply unit 44 includes a sulfuric acid supply source 44a, a valve 44b, a flow regulator 44c, a perhydrol supply source 44d, a valve 44e, a flow regulator 44f, and a confluence part 44g.

[0033] The sulfuric acid supply source 44a supplies sulfuric acid maintained at a given temperature (for example, 120°C) to the confluence part 44g through the valve 44b and the flow regulator 44c. The flow regulator 44c adjusts the flow rate of the sulfuric acid supplied to the confluence part 44g.

[0034] The perhydrol supply source 44d supplies hydrogen peroxide solution to the confluence part 44g through the valve 44e and the flow regulator 44f. The flow regulator 44f adjusts the flow rate of the hydrogen peroxide solution supplied to the confluence part 44g. Further, the confluence part 44g is connected to the SPM liquid supply path 47.

[0035] Then, the SPM liquid generated by mixing sulfuric acid and hydrogen peroxide solution at the confluence part 44g is supplied to the nozzle 41a through the SPM liquid supply path 47. Since the SPM liquid generates heat when sulfuric acid and hydrogen peroxide solution are mixed, it is heated to a temperature higher than the temperature of sulfuric acid (for example, 140°C) when it reaches the nozzle 41a.

[0036] The steam supply unit 45 includes a DIW supply source 45a, a steam generation mechanism 45b, a valve 45c, and a flow regulator 45d.

[0037] The DIW supply source 45a supplies DIW (DeIonized Water) to the steam generation mechanism 45b. The steam generation mechanism 45b generates steam V (see FIG. 5) using the DIW supplied from the DIW supply source 45a as a raw material. The steam V is an example of vaporous pure water.

[0038] The flow rate regulator 45d adjusts the flow rate of the steam V supplied to the steam supply path 48 through the valve 45c. Then, the steam V generated by the steam supply unit 45 is supplied to the nozzle 41a through the steam supply path 48.

[0039] FIG. 3 is a cross-sectional view showing a configuration example of the nozzle 41a according to the embodiment. As shown in FIG. 3, inside the nozzle 41a, one SPM liquid supply path 47 and two steam supply paths 48 are inserted side by side along the longitudinal direction of the nozzle 41a.

[0040] Also, a discharge path 62 is connected between the discharge port 61 formed on the lower surface of the nozzle 41a and the SPM liquid supply path 47, and a discharge path 63 is connected between the discharge port 61 and the steam supply path 48.

[0041] That is, the SPM liquid (described as SPM in the following drawings) is supplied to the discharge port 61 of the nozzle 41a through the discharge path 62, and the steam V is supplied through the discharge path 63.

[0042] And in the nozzle 41a according to the embodiment, the SPM liquid and the steam V are mixed at the discharge port 61 to generate a mixed fluid M. That is, in the present disclosure, the mixed fluid M is generated by mixing the SPM liquid and the steam V after they are discharged from the nozzle 41a until they reach the wafer W. Note that a plurality of discharge ports 61 are arranged side by side along the longitudinal direction of the nozzle 41a.

[0043] As a result, the nozzle 41a according to the embodiment can discharge the mixed fluid M generated by mixing the SPM liquid and the water vapor V from the plurality of discharge ports 61 onto the wafer W. Further, in this mixed fluid M, the temperature of the SPM liquid is further increased by the water vapor V (for example, 160°C to 200°C).

[0044] Therefore, according to the embodiment, by treating the surface of the wafer W with the mixed fluid M in which the temperature of the SPM liquid is increased, the resist film formed on the surface of the wafer W can be efficiently removed.

[0045] Returning to the description of FIG. 2. The nozzle 41b is connected to the rinse liquid supply unit 46. The rinse liquid R (see FIG. 4) supplied from the rinse liquid supply unit 46 is used, for example, for the rinse process. The rinse liquid R according to the embodiment is, for example, hydrogen peroxide water, DIW, ozone water, diluted ammonia water, and the like.

[0046] The rinse liquid supply unit 46 includes a rinse liquid supply source 46a, a valve 46b, and a flow regulator 46c. The rinse liquid supply source 46a supplies the rinse liquid R to the nozzle 41b. The flow regulator 46c adjusts the flow rate of the rinse liquid R supplied to the nozzle 41b through the valve 46b.

[0047] The recovery cup 50 is arranged so as to surround the holding unit 31 and collects the processing liquid scattered from the wafer W due to the rotation of the holding unit 31. A drain port 51 is formed at the bottom of the recovery cup 50, and the processing liquid collected by the recovery cup 50 is discharged to the outside of the processing unit 16 through the drain port 51.

[0048] Further, an exhaust port 52 for discharging the gas supplied from the FFU 21 to the outside of the processing unit 16 is formed at the bottom of the recovery cup 50.

[0049] <Details of substrate processing> Next, the details of the substrate processing according to the embodiment will be described with reference to FIGS. 4 to 9. FIGS. 4 to 9 are schematic diagrams showing one step of the substrate processing according to the embodiment.

[0050] First, as shown in FIG. 4, the control unit 18 (see FIG. 1) holds the wafer W by the holding unit 31 (see FIG. 2). Next, the control unit 18 arranges the nozzle 41b above the central portion Wc of the wafer W and arranges the nozzle 41a above the wafer W and in the vicinity of the nozzle 41b.

[0051] Then, the control unit 18 rotates the wafer W at a given rotational speed and discharges the rinse liquid R from the nozzle 41b to the central portion Wc of the wafer W. That is, the control unit 18 supplies the rinse liquid R so that the rinse liquid R that has spread when the rinse liquid R contacts the wafer W hits the center of the wafer W. Thereby, the control unit 18 forms a liquid film of the rinse liquid R on the entire surface of the wafer W.

[0052] Here, in the embodiment, the water vapor V used in the immediately preceding wafer process may condense inside the water vapor supply path 48 (see FIG. 2), and such condensed water droplets may directly fall from the nozzle 41a onto the surface of the wafer W.

[0053] And, in the embodiment, since impurities may be mixed into the water vapor V by the vapor generation mechanism 45b (see FIG. 2) or the like, there is a risk that a large amount of impurities are contained in the water droplets remaining in the water vapor supply path 48. Therefore, if the water droplets directly fall onto the surface of the wafer W, the wafer W may be contaminated by the impurities contained in such water droplets.

[0054] However, in the embodiment, since a liquid film of the rinse liquid R is formed in advance on the entire surface of the wafer W, the impurities contained in the water droplets can be scattered from the wafer W without directly adhering to the surface of the wafer W.

[0055] That is, in the embodiment, it is possible to suppress the impurities remaining in the water vapor supply path 48 from directly adhering to the surface of the wafer W. Therefore, according to the embodiment, by forming a liquid film of the rinse liquid R in advance on the entire surface of the wafer W, it is possible to suppress the wafer W from being contaminated by the impurities contained in the water vapor V.

[0056] Further, as shown in FIG. 5, the control unit 18 may discharge water vapor V from the nozzle 41a toward the surface of the wafer W on which the liquid film of the rinse liquid R is formed. That is, in the process shown in FIG. 5, no SPM liquid is supplied to the nozzle 41a, and only the water vapor V is supplied.

[0057] Thereby, the water droplets generated by condensation inside the water vapor supply path 48 can be surely pushed out from the water vapor supply path 48 together with the water vapor V. Therefore, according to the embodiment, it is possible to further suppress the wafer W from being contaminated by impurities contained in the water vapor V.

[0058] Further, in the embodiment, by discharging the water vapor V from the nozzle 41a toward the surface of the wafer W on which the liquid film of the rinse liquid R is formed, the nozzle 41a and the water vapor supply path 48 can be heated up. Thereby, when discharging the water vapor V from the nozzle 41a in a later process, it is possible to suppress the water vapor V from condensing.

[0059] Therefore, according to the embodiment, it is possible to further suppress the wafer W from being contaminated by impurities contained in the water vapor V.

[0060] Further, in the embodiment, by heating up the nozzle 41a and the water vapor supply path 48 in advance with the water vapor V, when discharging the water vapor V from the nozzle 41a in a later process, it is possible to promote the rise in temperature.

[0061] Next, as shown in FIG. 6, the control unit 18 stops discharging the water vapor V from the nozzle 41a at the timing when the water droplets remaining in the water vapor supply path 48 (see FIG. 2) are discharged to the outside (for example, about 10 seconds after the start of discharging the water vapor V). Thereby, the control unit 18 can remove the water droplets remaining in the water vapor supply path 48.

[0062] Further, the control unit 18 stops the discharge of the rinse liquid R from the nozzle 41b simultaneously with the stop of the discharge of the steam V from the nozzle 41a, and moves the nozzle 41b to the standby position. In the process shown in FIG. 6, a liquid film of the rinse liquid R continues to be formed on the surface of the wafer W.

[0063] Next, as shown in FIG. 7, the control unit 18 rotates the wafer W at a given first rotation speed and discharges the SPM liquid from the nozzle 41a toward the surface of the wafer W on which the liquid film of the rinse liquid R is formed. For example, the control unit 18 discharges the SPM liquid from the nozzle 41a, which is a bar nozzle, from the center to the peripheral portion of the wafer W on which the liquid film of the rinse liquid R is formed.

[0064] That is, in the process shown in FIG. 7, no steam V is supplied to the nozzle 41a, and only the SPM liquid is supplied. Thereby, the control unit 18 forms a liquid film of the SPM liquid on the surface of the wafer W.

[0065] Here, in the embodiment, by discharging the SPM liquid toward the surface of the wafer W on which the liquid film of the rinse liquid R is formed, the SPM liquid having a relatively high viscosity can be quickly spread over the entire surface of the wafer W.

[0066] That is, in the embodiment, the SPM liquid having a high viscosity spreads unevenly on the surface of the wafer W, so that splashing of such SPM liquid by the holding member 31a (see FIG. 2) or the like can be suppressed. Therefore, according to the embodiment, it is possible to suppress contamination of the wafer W due to such splashing.

[0067] Next, as shown in FIG. 8, the control unit 18 starts discharging the mixed fluid M from the nozzle 41a at the timing when the SPM liquid has spread over the entire surface of the wafer W (for example, about 3 seconds after the start of the discharge of the SPM liquid). For example, the control unit 18 discharges the mixed fluid M from the nozzle 41a, which is a bar nozzle, from the center to the peripheral portion of the wafer W.

[0068] That is, in the process shown in FIG. 8, both the SPM liquid and the water vapor V are supplied to the nozzle 41a. Thereby, the control unit 18 forms a liquid film of the mixed fluid M on the surface of the wafer W.

[0069] And in the embodiment, since the wafer W is subjected to SPM treatment with the SPM liquid heated by the water vapor V, the resist film formed on the surface of the wafer W can be efficiently removed.

[0070] Further, as shown in FIGS. 7 and 8, the control unit 18 first discharges only the SPM liquid from the nozzle 41a during the SPM treatment, and then discharges the water vapor V by adding it from the nozzle 41a. That is, the control unit 18 discharges the water vapor V by adding it to the surface of the wafer W on which the liquid film of the SPM liquid is formed.

[0071] Thereby, the control unit 18 can scatter the impurities contained in the water vapor V from the wafer W without directly adhering them to the surface of the wafer W.

[0072] That is, in the embodiment, it is possible to suppress the impurities contained in the water vapor V from directly adhering to the surface of the wafer W. Therefore, according to the embodiment, in liquid treatment such as SPM treatment, it is possible to suppress the wafer W from being contaminated.

[0073] Also, in the embodiment, the control unit 18 may perform a process of discharging only the water vapor V from the nozzle 41a (see FIG. 5) prior to the SPM treatment. Thereby, when generating the mixed fluid M at the nozzle 41a, it is possible to suppress the water droplets remaining in the water vapor supply path 48 from reacting with the SPM liquid and boiling over, and the occurrence of liquid splashing.

[0074] Therefore, according to the embodiment, it is possible to suppress the wafer W from being contaminated due to such liquid splashing.

[0075] Also, in the embodiment, in the discharge process of the mixed fluid M shown in FIG. 8, the rotation speed of the wafer W may be set to a second rotation speed smaller than the first rotation speed in the discharge process of the SPM solution shown in FIG. 7. That is, in the embodiment, the discharge process of the SPM solution may be performed at a larger first rotation speed, and the discharge process of the mixed fluid M may be performed at a smaller second rotation speed.

[0076] In this way, by performing the discharge process of the SPM solution at a larger first rotation speed, a liquid film of the SPM solution can be quickly formed on the entire surface of the wafer W, so that the process can quickly shift to the discharge process of the mixed fluid M.

[0077] Also, by performing the discharge process of the mixed fluid M at a smaller second rotation speed, the contact time between the surface of the wafer W and the mixed fluid M can be lengthened, so that the resist film formed on the surface of the wafer W can be removed more efficiently.

[0078] That is, in the embodiment, by performing the discharge process of the mixed fluid M at a second rotation speed smaller than the first rotation speed, the resist film can be efficiently removed in a short processing time.

[0079] In addition, in the embodiment, the discharge process of the SPM solution shown in FIG. 7 may be performed at a larger first discharge flow rate, and the discharge process of the mixed fluid M shown in FIG. 8 may be performed at a smaller second discharge flow rate. By this also, the resist film can be efficiently removed in a short processing time.

[0080] Also, in the embodiment, when ending the discharge process of the mixed fluid M shown in FIG. 8, the supply of the water vapor V may be stopped before the SPM solution. If the supply of the SPM solution is stopped before the water vapor V, there is a possibility that the water vapor V containing impurities directly adheres to the surface of the wafer W, so the wafer W may be contaminated.

[0081] On the other hand, in the embodiment, by stopping the supply of the water vapor V before the supply of the SPM liquid, it is possible to suppress the direct adhesion of the water vapor V containing impurities to the surface of the wafer W. Therefore, according to the embodiment, it is possible to suppress the contamination of the wafer W by the impurities contained in the water vapor V.

[0082] Note that in the embodiment, when ending the discharge process of the mixed fluid M, it is not limited to the case where the supply of the water vapor V is stopped before the supply of the SPM liquid, and the supply of the SPM liquid and the supply of the water vapor V may be stopped simultaneously.

[0083] Also by this, since it is possible to suppress the direct adhesion of the water vapor V containing impurities to the surface of the wafer W, it is possible to suppress the contamination of the wafer W by the impurities contained in the water vapor V.

[0084] After the discharge process of the mixed fluid M described so far is completed, as shown in FIG. 9, the control unit 18 moves the nozzle 41b above the central portion Wc of the wafer W and discharges the rinse liquid R from such nozzle 41b onto the wafer W. That is, the control unit 18 supplies the rinse liquid R so that the rinse liquid R that has spread when the rinse liquid R comes into contact with the wafer W hits the center of the wafer W. Thereby, the control unit 18 performs the rinse process of the wafer W.

[0085] Note that in the embodiment, the rinse process of the wafer W shown in FIG. 9 may be performed with hydrogen peroxide water. That is, in the embodiment, hydrogen peroxide water may be used as the rinse liquid R. Thereby, the rinse process of the wafer W can be efficiently performed.

[0086] Then, following this rinse process, the control unit 18 performs a drying process (for example, spin drying) of the wafer W and a series of substrate processes is completed.

[0087] In the above-described embodiment, an example in which an SPM solution is used as the processing liquid that is a raw material of the mixed fluid M together with the water vapor V has been shown. However, the present disclosure is not limited to such an example. For example, as the processing liquid that is a raw material of the mixed fluid M together with the water vapor V, dilute sulfuric acid, a mixed solution of sulfuric acid and ozone water, phosphoric acid, SC1 (a mixed solution of ammonia and hydrogen peroxide water), DHF (dilute hydrofluoric acid), and a mixed solution of fluonitric acid and hydrogen peroxide water may be used.

[0088] On the other hand, since the SPM solution is used as the processing liquid that is a raw material of the mixed fluid M together with the water vapor V, the SPM treatment can be performed at a high temperature, so that the resist film formed on the surface of the wafer W can be efficiently removed.

[0089] <Modification Example 1> Next, various modification examples of the embodiment will be described with reference to FIGS. 10 to 15. FIG. 10 is a schematic diagram showing a configuration example of a processing unit 16 according to Modification Example 1 of the embodiment.

[0090] As shown in FIG. 10, the processing unit 16 according to Modification Example 1 is different from the embodiment in that a water mist supply unit 45A is provided instead of the water vapor supply unit 45. Therefore, in the following examples, the same reference numerals are given to the same parts as in the embodiment, and detailed descriptions thereof are omitted.

[0091] The nozzle 41a is, for example, a bar nozzle, and is connected to the SPM solution supply unit 44 through the SPM solution supply path 47 and is connected to the water mist supply unit 45A through the water mist supply path 48A. The water mist supply unit 45A is another example of the second supply unit.

[0092] The water mist supplied from the water mist supply unit 45A is an example of mist-like pure water, and is generated by mixing DIW and nitrogen (N2). Such a water mist is used for heating the SPM solution in the same manner as the water vapor V in the embodiment.

[0093] The water mist supply unit 45A includes a DIW supply source 45a, a valve 45c, a flow regulator 45d, a nitrogen supply source 45f, a valve 45g, a flow regulator 45h, a mixer 45i, and a heater 45j.

[0094] The DIW supply source 45a supplies DIW to the mixer 45i through the valve 45c and the flow regulator 45d. The flow regulator 45d adjusts the flow rate of the DIW supplied to the mixer 45i.

[0095] The nitrogen supply source 45f supplies nitrogen gas to the mixer 45i through the valve 45g and the flow regulator 45h. The flow regulator 45h adjusts the flow rate of the nitrogen gas supplied to the mixer 45i.

[0096] The mixer 45i has a function as an atomizer. In the first modification, when the normal-temperature liquid-state DIW in the mixer 45i is mixed with the normal-temperature nitrogen gas, it is atomized into water mist and flows out to the downstream heater 45j.

[0097] The heater 45j is connected to the water mist supply path 48A. Then, the heater 45j raises the temperature of the water mist supplied from the mixer 45i to a given temperature (for example, about 100°C) and supplies the heated water mist to the water mist supply path 48A.

[0098] The water mist supplied to the nozzle 41a through the water mist supply path 48A is discharged from the discharge port 61 (see FIG. 3) of the nozzle 41a through the discharge path 63 (see FIG. 3), similar to the water vapor V in the embodiment. Thereby, the processing unit 16 according to the first modification can discharge the mixed fluid M generated by mixing the SPM liquid and the water mist from the nozzle 41a onto the wafer W.

[0099] In Modification 1, since the mist-like DIW is mixed with the SPM solution after being ejected, the mixing of the SPM solution and the water mist is completed promptly, and a rapid temperature rise due to the heat of hydration is achieved. Therefore, according to Modification 1, the resist film formed on the surface of the wafer W can be efficiently removed by the mixed fluid M in which the SPM solution has been heated up.

[0100] And in Modification 1, similar to the above-described embodiment, the control unit 18 may form a liquid film of the rinse liquid R on the surface of the wafer W prior to the ejection of the water mist (see FIG. 5). Thereby, it is possible to suppress water droplets generated by condensation of the water mist remaining in the water mist supply path 48A from being directly ejected onto the surface of the wafer W.

[0101] Therefore, according to Modification 1, since it is possible to suppress scale and the like due to such water droplets from remaining on the surface of the wafer W, it is possible to suppress the wafer W from being contaminated by such scale and the like.

[0102] Also, in Modification 1, during the SPM treatment, the control unit 18 may first eject only the SPM solution from the nozzle 41a, and then add and eject the water mist from the nozzle 41a (see FIGS. 7 and 8). That is, the control unit 18 may eject the water mist onto the surface of the wafer W on which the liquid film of the SPM solution has been formed.

[0103] Thereby, the control unit 18 can suppress the scale contained in the water mist from directly adhering to the surface of the wafer W. Therefore, according to Modification 1, it is possible to suppress the wafer W from being contaminated by such scale and the like.

[0104] Also, in Modification 1, the control unit 18 may perform a process of ejecting only the water mist from the nozzle 41a (see FIG. 5) prior to the SPM treatment. Thereby, when generating the mixed fluid M with the nozzle 41a, it is possible to suppress the water droplets remaining in the water mist supply path 48A from reacting with the SPM solution and causing bumping and splashing of the liquid.

[0105] Therefore, according to Modification 1, it is possible to suppress the contamination of the wafer W due to such liquid splashing.

[0106] <Modification 2> FIG. 11 is a schematic diagram showing a configuration example of the processing unit 16 according to Modification 2 of the embodiment. As shown in FIG. 11, in the processing unit 16 according to Modification 2, the nozzle 41c is further provided on the arm 42b, and a difference from the embodiment is that a perhydro supply unit 49 connected to such nozzle 41c is provided.

[0107] The perhydro supply unit 49 includes a perhydro supply source 49a, a valve 49b, and a flow rate regulator 49c. The perhydro supply source 49a supplies hydrogen peroxide water to the nozzle 41c through the valve 49b and the flow rate regulator 49c. The flow rate regulator 49c adjusts the flow rate of the hydrogen peroxide water supplied to the nozzle 41c.

[0108] Also, in Modification 2, DIW is supplied as the rinse liquid R (see FIG. 13) from the rinse liquid supply source 46a of the rinse liquid supply unit 46 to the nozzle 41b.

[0109] FIGS. 12 and 13 are schematic diagrams showing one step of the substrate processing according to Modification 2 of the embodiment. Note that, in the substrate processing according to Modification 2, since the various processes up to the discharge process of the mixed fluid M shown in FIG. 8 are the same as those in the embodiment, the description thereof is omitted.

[0110] Following the discharge process of the mixed fluid M shown in FIG. 8, as shown in FIG. 12, the control unit 18 moves the nozzle 41c above the central portion Wc of the wafer W and discharges hydrogen peroxide water from such nozzle 41c onto the wafer W. Thereby, the control unit 18 processes the surface of the wafer W with hydrogen peroxide water.

[0111] Thereby, in Modification 2, when the sulfur (S) component contained in the SPM liquid used for the SPM process remains on the surface of the wafer W, by reacting such sulfur component with hydrogen peroxide water, the sulfur component can be removed from the surface of the wafer W.

[0112] Next, as shown in FIG. 13, the control unit 18 moves the nozzle 41b above the central portion of the wafer W and discharges the rinse liquid R, which is DIW, from the nozzle 41b onto the wafer W. Thereby, the control unit 18 performs a rinse process on the wafer W.

[0113] Also, in Modification 2, by such a rinse process, the sulfur component that has reacted with the hydrogen peroxide solution can be removed from the surface of the wafer W.

[0114] As described so far, in Modification 2, after the discharge process of the mixed fluid M, by continuously performing the perhydrol discharge process and the rinse process, the surface of the wafer W that has been subjected to a liquid process such as SPM processing can be further cleaned.

[0115] <Modification 3> FIGS. 14 and 15 are schematic diagrams showing one step of the substrate process according to Modification 3 of the embodiment. Note that, in the substrate process according to Modification 3, since various processes up to the discharge process of the mixed fluid M shown in FIG. 8 are the same as those in the embodiment, the description thereof is omitted.

[0116] Following the discharge process of the mixed fluid M shown in FIG. 8, as shown in FIG. 14, the control unit 18 moves the nozzle 41b above the intermediate portion Wm between the central portion Wc and the peripheral portion We of the wafer W and discharges the rinse liquid R from the nozzle 41b onto the wafer W.

[0117] That is, the control unit 18 supplies the rinse liquid R so that the rinse liquid R that has spread when contacting the wafer W reaches the intermediate portion Wm and the peripheral portion We of the wafer W. Thereby, the control unit 18 performs a rinse process on the wafer W.

[0118] This intermediate portion Wm of the wafer W is, for example, a portion that is separated from the peripheral portion We of the wafer W by a given distance (for example, about 50 (mm) from the peripheral portion We) toward the central portion Wc.

[0119] Next, as shown in FIG. 15, the control unit 18 gradually moves the nozzle 41b from above the intermediate portion Wm of the wafer W to above the central portion Wc while continuing to discharge the rinse liquid R from the nozzle 41b (so-called scan-in operation). Thereby, the control unit 18 can perform the rinse process also on the central portion Wc of the wafer W.

[0120] For example, in the rinse process of the wafer W, when the rinse liquid R at room temperature is discharged onto the central portion Wc of the wafer W which is very hot (for example, about 200 (°C)) immediately after the SPM process, the temperature difference between the central portion Wc and the peripheral portion We of the wafer W becomes very large.

[0121] Therefore, in this case, while the peripheral portion We of the wafer W extends greatly, the central portion Wc contracts rapidly, so there is a risk of variation in the wafer W at the initial stage of the rinse process. In particular, in the SPM process using a bar nozzle, since the temperatures of the central portion Wc and the peripheral portion We of the wafer W become substantially equal, such variation may occur significantly at the initial stage of the rinse process.

[0122] Therefore, in this Modification 3, in the rinse process of the wafer W, the rinse liquid R is first discharged onto the intermediate portion Wm of the wafer W closer to the peripheral portion We than the central portion Wc. Thereby, the temperature difference between the central portion Wc and the peripheral portion We of the wafer W can be reduced at the initial stage of the rinse process.

[0123] Therefore, according to Modification 3, it is possible to suppress the occurrence of variation in the wafer W at the initial stage of the rinse process performed immediately after the SPM process using a bar nozzle.

[0124] In the examples of FIGS. 14 and 15, an example in which the rinse process performed immediately after the SPM process in which the wafer W is in a high-temperature state is performed by a scan-in operation has been shown, but the present disclosure is not limited to such an example. For example, in the removal process of the sulfur component by hydrogen peroxide water performed immediately after the SPM process in which the wafer W is in a high-temperature state, the discharge of the hydrogen peroxide water may be performed by a scan-in operation.

[0125] The substrate processing apparatus (substrate processing system 1) according to the embodiment includes a holding unit 31, a liquid discharge unit (nozzle 41a), a first supply unit (SPM liquid supply unit 44), a second supply unit (steam supply unit 45, water mist supply unit 45A), and a control unit 18. The holding unit 31 holds a substrate (wafer W). The liquid discharge unit (nozzle 41a) discharges a fluid onto the substrate (wafer W) held by the holding unit 31. The first supply unit (SPM liquid supply unit 44) supplies a processing liquid (SPM liquid) generated by mixing sulfuric acid and hydrogen peroxide water to the liquid discharge unit (nozzle 41a). The second supply unit (steam supply unit 45, water mist supply unit 45A) supplies steam-like or mist-like pure water to the liquid discharge unit (nozzle 41a). The control unit 18 controls each unit. Further, the control unit 18 discharges the processing liquid (SPM liquid) from the liquid discharge unit (nozzle 41a) onto the substrate (wafer W) held by the holding unit 31. Furthermore, the control unit 18 discharges a mixed fluid M generated by mixing the processing liquid (SPM liquid) and steam-like or mist-like pure water from the liquid discharge unit (nozzle 41a) onto the substrate (wafer W) onto which the processing liquid (SPM liquid) has been discharged. Thereby, it is possible to suppress the wafer W from being contaminated in the SPM process.

[0126] <Procedure of substrate processing> Next, the procedure of substrate processing according to the embodiment and various modifications will be described with reference to FIGS. 16 to 18. FIG. 16 is a flowchart showing the procedure of substrate processing executed by the substrate processing system 1 according to the embodiment.

[0127] First, the control unit 18 controls the processing unit 16 and the like to hold the wafer W by the holding unit 31 (step S101). Then, the control unit 18 controls the rinse liquid supply unit 46 and the like to discharge the rinse liquid R onto the rotating wafer W. Thereby, the control unit 18 forms a liquid film of the rinse liquid R on the surface of the wafer W (step S102).

[0128] Next, the control unit 18 controls the steam supply unit 45 and the like to discharge steam V onto the wafer W (step S103). Thereby, the control unit 18 discharges the water droplets remaining in the steam supply path 48 to the outside.

[0129] Next, the control unit 18 controls the steam supply unit 45, the rinse liquid supply unit 46, and the like to stop discharging the rinse liquid R and the steam V onto the wafer W (step S104). Then, the control unit 18 controls the SPM liquid supply unit 44 and the like to discharge the SPM liquid onto the wafer W (step S105).

[0130] Next, the control unit 18 controls the SPM liquid supply unit 44, the steam supply unit 45, and the like to supply both the SPM liquid and the steam V to the nozzle 41a, thereby discharging the mixed fluid M onto the wafer W (step S106).

[0131] Next, the control unit 18 controls the steam supply unit 45 and the like to stop discharging the steam V from the nozzle 41a (step S107), and then controls the SPM liquid supply unit 44 and the like to stop discharging the SPM liquid from the nozzle 41a (step S108).

[0132] Next, the control unit 18 controls the rinse liquid supply unit 46 and the like to perform a rinse process of the wafer W with the rinse liquid R (step S109). Note that the process of step S109 may be performed by scanning the nozzle 41b in. Then, the control unit 18 controls the processing unit 16 to perform a drying process (for example, spin drying) of the wafer W (step S110), and a series of substrate processes is completed.

[0133] FIG. 17 is a flowchart showing the procedure of the substrate process executed by the substrate process system 1 according to Modification 1 of the embodiment.

[0134] First, the control unit 18 controls the processing unit 16 and the like to hold the wafer W in the holding unit 31 (step S201). Then, the control unit 18 controls the rinse liquid supply unit 46 and the like to discharge the rinse liquid R onto the rotating wafer W. Thereby, the control unit 18 forms a liquid film of the rinse liquid R on the surface of the wafer W (step S202).

[0135] Next, the control unit 18 controls the water mist supply unit 45A and the like to discharge the water mist onto the wafer W (step S203). Thereby, the control unit 18 discharges the water droplets remaining in the water mist supply path 48A to the outside.

[0136] Next, the control unit 18 controls the water mist supply unit 45A, the rinse liquid supply unit 46, and the like to stop discharging the rinse liquid R and the water mist onto the wafer W (step S204). Then, the control unit 18 controls the SPM liquid supply unit 44 and the like to discharge the SPM liquid onto the wafer W (step S205).

[0137] Next, the control unit 18 controls the SPM liquid supply unit 44, the water mist supply unit 45A, and the like to supply both the SPM liquid and the water mist to the nozzle 41a, thereby discharging the mixed fluid M onto the wafer W (step S206).

[0138] Next, the control unit 18 controls the water mist supply unit 45A and the like to stop discharging the water mist from the nozzle 41a (step S207), and then controls the SPM liquid supply unit 44 and the like to stop discharging the SPM liquid from the nozzle 41a (step S208).

[0139] Next, the control unit 18 controls the rinse liquid supply unit 46 and the like to perform a rinsing process of the wafer W with the rinse liquid R (step S209). Note that the process of step S209 may be performed by scanning the nozzle 41b in the in-motion. Then, the control unit 18 controls the processing unit 16 to perform a drying process (for example, spin drying) of the wafer W (step S210), and a series of substrate processes is completed.

[0140] FIG. 18 is a flowchart showing the procedure of substrate processing executed by the substrate processing system 1 according to the embodiment.

[0141] First, the control unit 18 controls the processing unit 16 and the like to hold the wafer W in the holding unit 31 (step S301). Then, the control unit 18 controls the rinse liquid supply unit 46 and the like to discharge the rinse liquid R onto the rotating wafer W. Thereby, the control unit 18 forms a liquid film of the rinse liquid R on the surface of the wafer W (step S302).

[0142] Next, the control unit 18 controls the water vapor supply unit 45 and the like to discharge the water vapor V onto the wafer W (step S303). Thereby, the control unit 18 discharges the water droplets remaining in the water vapor supply path 48 to the outside.

[0143] Next, the control unit 18 controls the water vapor supply unit 45, the rinse liquid supply unit 46, and the like to stop discharging the rinse liquid R and the water vapor V onto the wafer W (step S304). Then, the control unit 18 controls the SPM liquid supply unit 44 and the like to discharge the SPM liquid onto the wafer W (step S305).

[0144] Next, the control unit 18 controls the SPM liquid supply unit 44, the water vapor supply unit 45, and the like to supply both the SPM liquid and the water vapor V to the nozzle 41a, and discharges the mixed fluid M onto the wafer W (step S306).

[0145] Next, the control unit 18 controls the water vapor supply unit 45 and the like to stop discharging the water vapor V from the nozzle 41a (step S307), and then controls the SPM liquid supply unit 44 and the like to stop discharging the SPM liquid from the nozzle 41a (step S308).

[0146] Next, the control unit 18 controls the peroxide supply unit 49 or the like to discharge hydrogen peroxide water onto the wafer W (step S309). Note that the process of step S309 may be performed by performing a scan-in operation on the nozzle 41c. Then, the control unit 18 controls the rinse liquid supply unit 46 or the like to perform a rinse process on the wafer W with the rinse liquid R which is DIW (step S310).

[0147] Next, the control unit 18 controls the processing unit 16 to perform a drying process (for example, spin drying) on the wafer W (step S311), and a series of substrate processes are completed.

[0148] The substrate processing method according to the embodiment includes a processing liquid discharge step (steps S105, S205, S305) and a mixed fluid discharge step (steps S106, S206, S306). In the processing liquid discharge step (steps S105, S205, S305), a processing liquid (SPM liquid) generated by mixing sulfuric acid and hydrogen peroxide water is discharged onto a substrate (wafer W). In the mixed fluid discharge step (steps S106, S206, S306), a mixed fluid M generated by mixing the processing liquid (SPM liquid) and vaporous or misty pure water is discharged onto the substrate (wafer W) onto which the processing liquid (SPM liquid) has been discharged. Thereby, in liquid processing such as SPM processing, it is possible to suppress the wafer W from being contaminated.

[0149] Further, the substrate processing method according to the embodiment further includes a liquid film forming step (steps S102, S202, S302) and a pure water discharge step (steps S103, S203, S303). In the liquid film forming step (steps S102, S202, S302), the rinse liquid R is discharged onto the substrate (wafer W) to form a liquid film of the rinse liquid R on the surface of the substrate (wafer W). In the pure water discharge step (steps S103, S203, S303), vaporous or misty pure water is discharged onto the liquid film of the rinse liquid R formed on the surface of the substrate (wafer W). Then, the processing liquid discharge step (steps S105, S205, S305) is performed after the pure water discharge step (steps S103, S203, S303). Thereby, it is possible to suppress the wafer W from being contaminated by impurities, scale, or the like.

[0150] Also, in the substrate processing method according to the embodiment, the treatment liquid discharge step (steps S105, S205, S305) is performed on the surface of the substrate (wafer W) on which the liquid film of the rinse liquid R is formed. Thereby, it is possible to suppress the wafer W from being contaminated due to liquid splashing.

[0151] Also, in the substrate processing method according to the embodiment, the rinse liquid R is hydrogen peroxide water. Thereby, the rinse process of the wafer W can be efficiently performed.

[0152] Also, the substrate processing method according to the embodiment further includes a perhydrol discharge step (step S309) and a rinse step (step S310). In the perhydrol discharge step (step S309), hydrogen peroxide water is discharged onto the substrate (wafer W) after the mixed fluid discharge step (step S306). In the rinse step (step S310), the rinse liquid R which is pure water is discharged onto the substrate (wafer W) after the perhydrol discharge step (step S309). Thereby, the surface of the wafer W subjected to liquid processing such as SPM processing can be further cleaned.

[0153] Also, in the substrate processing method according to the embodiment, in the treatment liquid discharge step (steps S105, S205, S305), the substrate (wafer W) rotates at the first rotation speed. Also, in the mixed fluid discharge step (steps S106, S206, S306), the substrate (wafer W) rotates at a second rotation speed smaller than the first rotation speed. Thereby, the resist film can be efficiently removed in a short treatment time.

[0154] Also, in the substrate processing method according to the embodiment, when ending the mixed fluid discharge step (steps S106, S206, S306), the supply of pure water in a vapor state or a mist state is stopped before the treatment liquid (SPM liquid). Thereby, it is possible to suppress the wafer W from being contaminated by impurities, scale, etc.

[0155] Further, in the substrate processing method according to the embodiment, the mixed fluid M is generated by mixing the processing liquid (SPM liquid) and vaporous or misty pure water after they are discharged from the nozzle 41a and before they reach the substrate (wafer W). Thereby, the high-temperature mixed fluid M can be supplied to the wafer W.

[0156] Further, in the substrate processing method according to the embodiment, the mixed fluid M is supplied from the center to the peripheral portion of the substrate (wafer W), and the rinse liquid R is supplied so that the rinse liquid R that has spread when it contacts the substrate (wafer W) reaches the center of the substrate (wafer W). Thereby, liquid processing such as SPM processing can be efficiently performed.

[0157] Further, the substrate processing method according to the embodiment further includes a rinse step (S109, S209) of discharging a rinse liquid onto the substrate (wafer W) after the mixed fluid discharge step (steps S106, S206, S306). Also, in the rinse step (S109, S209), first, the rinse liquid is discharged toward the intermediate portion Wm between the central portion Wc and the peripheral portion We of the substrate (wafer W), and then the discharge position of the rinse liquid is gradually moved toward the central portion Wc of the substrate (wafer W). Thereby, it is possible to suppress the occurrence of variations in the wafer W at the initial stage of the rinse process.

[0158] Further, in the substrate processing method according to the embodiment, the processing liquid is an SPM liquid generated by mixing sulfuric acid and hydrogen peroxide solution. Thereby, the resist film formed on the surface of the wafer W can be efficiently removed.

[0159] As described above, the embodiments of the present disclosure have been described. However, the present disclosure is not limited to the above-described embodiments, and various modifications are possible without departing from the spirit thereof. For example, in the above-described embodiment, an example in which a rinse process and a drying process are performed after the SPM process using the mixed fluid M has been shown. However, a cleaning process or the like may be performed between the SPM process and the rinse process. Such a cleaning process can be performed, for example, by discharging SC-1 (a mixed solution of ammonia and hydrogen peroxide solution) onto the surface of the wafer W.

[0160] Also, in the above-described embodiment, an example in which spin drying is performed as the drying process has been shown. However, spin drying may be performed after discharging a drying liquid (for example, IPA (isopropyl alcohol)) onto the surface of the wafer W.

[0161] The embodiments disclosed this time should be considered as illustrative in all respects and not restrictive. Indeed, the above-described embodiments can be embodied in various forms. Also, the above embodiments may be omitted, substituted, or changed in various forms without departing from the scope and spirit of the appended claims.

Explanation of Reference Numerals

[0162] W Wafer (an example of a substrate) Wc Central portion We Peripheral portion Wm Intermediate portion 1 Substrate processing system (an example of a substrate processing apparatus) 16 Processing unit 18 Control unit 31 Holding unit 41a Nozzle (an example of a liquid discharge unit) 41b, 41c Nozzles 44 SPM liquid supply unit (an example of a first supply unit) 45 Steam supply unit (an example of a second supply unit) 45A Water mist supply unit (another example of a second supply unit) 46 Rinse liquid supply unit 47 SPM liquid supply path 48 Steam supply path 48A Water mist supply path 49 Overwater supply unit

Claims

1. A processing liquid discharging step of discharging a processing liquid onto a substrate, A mixed fluid discharging step of discharging, onto the substrate onto which the processing liquid has been discharged, a mixed fluid generated by mixing the processing liquid with vaporous or mist-like pure water, A substrate processing method comprising the above steps.

2. A liquid film forming step of discharging a rinse liquid onto the substrate to form a liquid film of the rinse liquid on the surface of the substrate, A pure water discharging step of discharging vaporous or mist-like pure water onto the liquid film of the rinse liquid formed on the surface of the substrate, Further comprising: The processing liquid discharging step is performed after the pure water discharging step. The substrate processing method according to Claim 1.

3. The processing liquid discharging step is performed on the surface of the substrate on which the liquid film of the rinse liquid is formed. The substrate processing method according to Claim 2.

4. Further comprising a rinsing step of discharging a rinse liquid onto the substrate after the mixed fluid discharging step, In the rinsing step, first, the rinse liquid is discharged toward an intermediate portion between the central portion and the peripheral portion of the substrate, and then the discharge position of the rinse liquid is gradually moved toward the central portion of the substrate. The substrate processing method according to any one of Claims 1 to 3.

5. The rinse liquid is hydrogen peroxide water. The substrate processing method according to any one of Claims 2 to 4.

6. A perhydrol discharging step of discharging perhydrol onto the substrate after the mixed fluid discharging step, A rinsing step of discharging, as a rinse liquid, pure water onto the substrate after the perhydrol discharging step, Further comprising: The substrate processing method according to any one of Claims 1 to 3.

7. The mixed fluid is supplied from the center to the peripheral portion of the substrate, The rinse liquid is supplied so that the spread rinse liquid when contacting the substrate reaches the center of the substrate. The substrate processing method according to any one of Claims 2 to 6.

8. In the processing liquid discharging step, the substrate rotates at a first rotational speed, In the mixed fluid discharging step, the substrate rotates at a second rotational speed smaller than the first rotational speed. The substrate processing method according to any one of Claims 1 to 7.

9. When ending the mixed fluid discharging step, the supply of vaporous or mist-like pure water is stopped prior to the processing liquid. The substrate processing method according to any one of Claims 1 to 8.

10. The mixed fluid is generated by mixing the processing liquid with vaporous or mist-like pure water after being discharged from a nozzle and before reaching the substrate. The substrate processing method according to any one of Claims 1 to 9.

11. The processing liquid is an SPM liquid produced by mixing sulfuric acid and hydrogen peroxide solution. The substrate processing method according to any one of claims 1 to 10.

12. A holding unit for holding a substrate, A liquid discharge unit for discharging a fluid onto the substrate held by the holding unit, A first supply unit for supplying a processing liquid to the liquid discharge unit, A second supply unit for supplying vaporous or misty pure water to the liquid discharge unit, A control unit for controlling each unit, Comprising: The control unit: Discharges the processing liquid from the liquid discharge unit onto the substrate held by the holding unit, Discharges, from the liquid discharge unit, a mixed fluid produced by mixing the processing liquid with vaporous or misty pure water onto the substrate onto which the processing liquid has been discharged. A substrate processing apparatus.

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