Substrate processing method and substrate processing device

Abstract

To provide a substrate processing method and a substrate processing device capable of effectively removing etching residues when etching a metal polycrystalline film formed on the surface of a substrate.SOLUTION: A substrate processing method includes a first step of supplying an etching solution to the peripheral edge of a substrate while rotating the substrate on which a metal polycrystalline film is formed on the surface, a second step of supplying a rinsing liquid to the center side of the substrate from the etching liquid supply position in the first step while rotating the substrate, a third step of supplying an etching solution to the peripheral edge of the substrate while rotating the substrate, a fourth step of supplying the rinsing liquid to the center side of the substrate rather than the etching liquid supply position in the third step while rotating the substrate, and a fifth step of drying the substrate after the fourth step.SELECTED DRAWING: Figure 11

Description

[Technical Field]

[0001] The present disclosure relates to a substrate processing method and a substrate processing apparatus. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method in which a chemical solution such as hydrofluoric acid is supplied to a portion of a native oxide film formed on the surface of a substrate that is located on the periphery of the substrate, and the film is removed by etching. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-040958 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure describes a substrate processing method and a substrate processing apparatus that can effectively remove etching residues when etching a metal polycrystalline film formed on the surface of a substrate. [Means for solving the problem]

[0005] An example of a substrate processing method includes a first step of rotating a substrate having a metal polycrystalline film formed on its surface and supplying an etching liquid to the peripheral edge of the substrate to partially etch the metal polycrystalline film at the peripheral edge in the thickness direction; a second step of rotating the substrate and supplying a rinse liquid to a position closer to the center of the substrate than the position where the etching liquid was supplied in the first step, to wash away etching residues generated in the first step with the rinse liquid; a third step of rotating the substrate and supplying an etching liquid to the peripheral edge of the substrate to etch away remaining portions of the metal polycrystalline film at the peripheral edge; a fourth step of rotating the substrate and supplying a rinse liquid to a position closer to the center of the substrate than the position where the etching liquid was supplied in the third step, to wash away etching residues generated in the third step with the rinse liquid; and a fifth step of drying the substrate after the fourth step. [Effects of the Invention]

[0006] According to the substrate processing method and substrate processing apparatus of the present disclosure, etching residues can be effectively removed when etching a metal polycrystalline film formed on the surface of a substrate. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a plan view schematically illustrating an example of a substrate processing system. [Figure 2] FIG. 2 is a cross-sectional view schematically showing an example of a substrate and a metal polycrystalline film. [Figure 3] FIG. 3 is a side view schematically illustrating an example of a processing unit. [Figure 4] FIG. 4 is a perspective view showing a part of the processing unit of FIG. [Figure 5] FIG. 5 is a block diagram showing an example of a main part of a substrate processing system. [Figure 6] FIG. 6 is a schematic diagram illustrating an example of a hardware configuration of the controller. [Figure 7] FIG. 7 is a flowchart illustrating an example of a substrate processing procedure. [Figure 8]FIG. 8 is a cross-sectional view for explaining an example of a substrate processing procedure. [Figure 9] FIG. 9 is a cross-sectional view for explaining an example of a substrate processing procedure. [Figure 10] FIG. 10 is a cross-sectional view for explaining an example of a procedure subsequent to that shown in FIG. [Figure 11] FIG. 11 is a diagram showing changes over time in the flow rate of each liquid, the flow rate of gas, and the rotation speed of the substrate in an example of substrate processing. [Figure 12] FIG. 12 is a cross-sectional view for explaining a comparative example of a substrate processing procedure. [Figure 13] FIG. 13 is a diagram showing changes over time in the flow rate of each liquid, the flow rate of gas, and the rotation speed of the substrate in another example of substrate processing. [Figure 14] FIG. 14 is a cross-sectional view for explaining another example of the substrate processing procedure. [Figure 15] FIG. 15 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 16] FIG. 16 is a perspective view showing a part of another example of a processing unit. [Figure 17] FIG. 17 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 18] FIG. 18 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 19] FIG. 19 is a top view for explaining a change in the discharge angle of the rinse liquid from the nozzle in another example of substrate processing. [Figure 20] FIG. 20 is a cross-sectional view for explaining another example of the substrate processing procedure. [Figure 21] FIG. 21 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 22] FIG. 22 is a diagram showing an example of the relationship between the distance from the center of the substrate and the etching rate of a polycrystalline metal film. [Figure 23]FIG. 23 is a cross-sectional view for explaining another example of the substrate processing procedure. [Figure 24] FIG. 24 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 25] FIG. 25 is a cross-sectional view for explaining another example of the substrate processing procedure. [Figure 26] FIG. 26(a) is an enlarged view showing a part of FIG. 25(b), and FIG. 26(b) is an enlarged view showing a part of FIG. 25(c). [Figure 27] FIG. 27 is a diagram showing the change over time in the flow rate of each liquid and the rotation speed of the substrate in another example of substrate processing. [Figure 28] FIG. 28 is a side view schematically showing another example of the processing unit. [Figure 29] FIG. 29 is a cross-sectional view for explaining another example of the substrate processing procedure. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the following description, the same elements or elements having the same functions will be designated by the same reference numerals, and redundant explanations will be omitted. Note that in this specification, when referring to the top, bottom, right, and left of a figure, the directions of the reference numerals in the figure will be used as the reference.

[0009] [Substrate processing system] 1, a substrate processing system 1 (substrate processing apparatus) configured to process a substrate W will be described. The substrate processing system 1 includes a loading / unloading station 2, a processing station 3, and a controller Ctr (controller). The loading / unloading station 2 and the processing station 3 may be aligned in a horizontal line, for example.

[0010] The substrate W may be disk-shaped or may be a non-circular plate-shaped such as a polygon. The substrate W may have a cutout portion cut out of a portion. The cutout portion may be, for example, a notch (a U-shaped, V-shaped groove, or the like) or a linear portion extending linearly (so-called orientation flat). The substrate W may be, for example, a semiconductor substrate (silicon wafer), a glass substrate, a mask substrate, an FPD (Flat Panel Display) substrate, or any other type of substrate. The diameter of the substrate W may be, for example, approximately 200 mm to 450 mm.

[0011] As illustrated in Fig. 2, a metal polycrystalline film F is formed on the surface Wa of the substrate W. The metal polycrystalline film F is composed of polycrystals formed by an aggregation of numerous metal crystal grains G. The metal may be, for example, titanium nitride, titanium oxide, titanium, tungsten, tantalum, tantalum nitride, aluminum, aluminum oxide, copper, ruthenium, zirconium oxide, hafnium oxide, or the like. The interfaces between these crystal grains G are called grain boundaries B, and are discontinuous surfaces where the crystal grains G are oriented in different directions.

[0012] Returning to FIG. 1, the loading / unloading station 2 includes a mounting section 4, a loading / unloading section 5, and a shelf unit 6. The mounting section 4 includes a plurality of mounting tables (not shown) arranged in the width direction (the vertical direction in FIG. 1). Each mounting table is configured to be able to mount a carrier 7 (storage container). The carrier 7 is configured to store at least one substrate W in a sealed state. The carrier 7 includes an opening / closing door (not shown) for loading and unloading the substrate W.

[0013] The loading / unloading section 5 is disposed adjacent to the mounting section 4 in the direction in which the loading / unloading stations 2 and the processing stations 3 are lined up (the left-right direction in FIG. 1). The loading / unloading section 5 includes an opening / closing door (not shown) provided in correspondence with the mounting section 4. When the carrier 7 is placed on the mounting section 4, the opening / closing door of the carrier 7 and the opening / closing door of the loading / unloading section 5 are both opened, thereby connecting the interior of the carrier 7 to the interior of the loading / unloading section 5.

[0014] The loading / unloading section 5 incorporates a transport arm A1 and a shelf unit 6. The transport arm A1 is configured to be able to move horizontally in the width direction of the loading / unloading section 5 (the vertical direction in FIG. 1), move up and down in the vertical direction, and pivot about a vertical axis. The transport arm A1 is configured to take out a substrate W from a carrier 7 and pass it to the shelf unit 6, and also to receive a substrate W from the shelf unit 6 and return it to the carrier 7. The shelf unit 6 is located near the processing station 3, and is configured to act as an intermediary for the transfer of substrates W between the loading / unloading section 5 and the processing station 3.

[0015] The processing station 3 includes a transport section 8 and a plurality of processing units 10. The transport section 8 extends horizontally, for example, in the direction in which the loading / unloading station 2 and the processing station 3 are lined up (the left-right direction in FIG. 1). The transport section 8 incorporates a transport arm A2. The transport arm A2 is configured to be able to move horizontally in the longitudinal direction of the transport section 8 (the left-right direction in FIG. 1), move up and down in the vertical direction, and pivot about a vertical axis. The transport arm A2 is configured to take out substrates W from the shelf unit 6 and deliver them to each processing unit 10, and to receive substrates W from each processing unit 10 and return them to the shelf unit 6.

[0016] The processing units 10 are arranged on both sides of the transport section 8 so as to be aligned in a row along the longitudinal direction (left-right direction in FIG. 1) of the transport section 8. The processing units 10 are configured to perform predetermined processing on the substrates W (e.g., etching of the metal polycrystalline film F, cleaning of the substrates W, etc.). Details of the processing units 10 will be described later.

[0017] The controller Ctr is configured to partially or entirely control the substrate processing system 1. The controller Ctr will be described in detail later.

[0018] [Processing unit] 3 and 4, the processing unit 10 will be described in detail. The processing unit 10 includes a spin holder 20, a chemical liquid supply unit 30, a rinse liquid supply unit 40, a heating unit 50, and an imaging unit 60.

[0019] The rotation holding unit 20 includes a rotating unit 21, a shaft 22, and a holding unit 23. The rotating unit 21 is configured to operate based on an operation signal from the controller Ctr and rotate the shaft 22. The rotating unit 21 may be a power source such as an electric motor.

[0020] The holder 23 is provided at the tip of the shaft 22. The holder 23 is configured to suck and hold the back surface Wb of the substrate W, for example, by suction. That is, the spin holder 20 may be configured to rotate the substrate W around a central axis (rotation axis) perpendicular to the front surface Wa of the substrate W while the substrate W is in a substantially horizontal position. As exemplified in FIG. 3 and other figures, the spin holder 20 may rotate the substrate W clockwise when viewed from above. The holder 23 may be configured to suck and hold the entire back surface Wb of the substrate W. In this case, even if the substrate W is warped, the substrate W is corrected so that it is substantially horizontal.

[0021] The chemical liquid supply unit 30 is configured to supply an etching liquid L1 to the substrate W. The etching liquid L1 includes, for example, an alkaline or acidic chemical liquid for removing the metal polycrystalline film F on the surface Wa of the substrate W. The alkaline chemical liquid includes, for example, an SC-1 liquid (a mixture of ammonia, hydrogen peroxide, and pure water). The acidic chemical liquid includes, for example, an SC-2 liquid (a mixture of hydrochloric acid, hydrogen peroxide, and pure water), an SPM (a mixture of sulfuric acid and hydrogen peroxide), an HF / HNO3 liquid (a mixture of hydrofluoric acid and nitric acid), etc.

[0022] The chemical liquid supply unit 30 includes a liquid source 31, a pump 32, a valve 33, a nozzle 34, a pipe 35, and a drive source 36. The liquid source 31 is a supply source of the etching liquid L1. The pump 32 operates based on an operation signal from the controller Ctr, and is configured to pump the etching liquid L1 sucked from the liquid source 31 to the nozzle 34 via the pipe 35 and the valve 33.

[0023] The valve 33 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 35 and a closed state that prevents the fluid from flowing through the pipe 35. The nozzle 34 is disposed above the substrate W so that the discharge port 34a faces the front surface Wa of the substrate W. As illustrated in Fig. 4, the nozzle 34 is configured to discharge the etching liquid L1 delivered from the pump 32 from the discharge port 34a toward the peripheral edge portion We of the substrate W.

[0024] Because the substrate W is rotated by the rotary holder 20, the etching liquid L1 discharged onto the peripheral edge Wc spreads over the entire circumference of the substrate W along the peripheral edge Wc, and is then thrown outward from the peripheral edge of the substrate W. Therefore, the width of the etching liquid L1 in the radial direction of the substrate W is relatively large near the landing point of the etching liquid L1 on the substrate W. On the other hand, the width of the etching liquid L1 in the radial direction of the substrate W is relatively small downstream of the etching liquid L1.

[0025] 3, the pipe 35 connects, in order from the upstream side, the liquid source 31, the pump 32, the valve 33, and the nozzle 34. The drive source 36 is directly or indirectly connected to the nozzle 34. The drive source 36 operates based on an operation signal from the controller Ctr, and is configured to move the nozzle 34 above the substrate W in the horizontal or vertical direction.

[0026] The rinse liquid supply unit 40 is configured to supply a rinse liquid L2 to the substrate W. The rinse liquid L2 is a liquid for removing (washing away) from the substrate W, for example, the etching liquid L1 supplied to the surface Wa of the substrate W, components of the metal polycrystalline film F dissolved by the etching liquid L1, etching residues RE described below, etc. The rinse liquid L2 includes, for example, pure water (DIW: deionized water), ozone water, carbonated water (CO2 water), ammonia water, etc.

[0027] The rinse liquid supply unit 40 includes a liquid source 41, a pump 42, a valve 43, a nozzle 44, a pipe 45, and a drive source 46. The liquid source 41 is a supply source of the rinse liquid L2. The pump 42 operates based on an operation signal from the controller Ctr, and is configured to suck in the rinse liquid L2 from the liquid source 41 and send it to the nozzle 44 via the pipe 45 and the valve 43.

[0028] The valve 43 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the flow of fluid through the pipe 45 and a closed state that prevents the flow of fluid through the pipe 45. The nozzle 44 is disposed above the substrate W so that the outlet 44a is directed toward the surface Wa of the substrate W. Like the nozzle 34, the nozzle 44 is configured to eject the rinsing liquid L2 delivered from the pump 42 from the outlet 44a toward the peripheral edge Wc of the substrate W. In order to wash away the etching liquid L1 and the like on the substrate W with the rinsing liquid L2, the landing point of the rinsing liquid L2 on the substrate W is set closer to the center of the substrate W than the landing point of the etching liquid L1.

[0029] Because the substrate W is rotated by the rotation holder 20, the rinsing liquid L2 discharged onto the peripheral edge Wc spreads over the entire circumference of the substrate W along the peripheral edge Wc, and is then thrown off outward from the peripheral edge of the substrate W, similar to the etching liquid L1. Therefore, the width of the rinsing liquid L2 in the radial direction of the substrate W is relatively large near the landing point of the rinsing liquid L2 on the substrate W. On the other hand, the width of the rinsing liquid L2 in the radial direction of the substrate W is relatively small downstream of the rinsing liquid L2.

[0030] The pipe 45 connects, in order from the upstream side, the liquid source 41, the pump 42, the valve 43, and the nozzle 44. The drive source 46 is directly or indirectly connected to the nozzle 44. The drive source 46 operates based on an operation signal from the controller Ctr, and is configured to move the nozzle 44 above the substrate W in the horizontal or vertical direction.

[0031] The heating unit 50 is configured to operate based on an operation signal from the controller Ctr and heat the substrate W. The heating unit 50 includes a gas source 51, a nozzle 52, a pipe 53, and a heat source 54. The gas source 51 is a supply source of an inert gas such as nitrogen.

[0032] The nozzle 52 is disposed below the substrate W so that the discharge port 52a faces the back surface Wb of the substrate W. The nozzle 52 is configured to discharge the inert gas from the gas source 51 toward the back surface Wb of the substrate W. The pipe 53 connects the gas source 51 and the nozzle 52.

[0033] The heat source 54 is, for example, a resistance heater, and is configured to heat the inert gas flowing through the pipe 53. Therefore, the heated inert gas is supplied to the back surface Wb of the substrate W. Therefore, the substrate W is heated to a predetermined temperature (for example, about 50°C to 80°C). This promotes the etching process of the metal polycrystalline film F by the etching liquid L1 supplied to the substrate W.

[0034] 3 and 4, the imaging unit 60 is disposed above the peripheral edge Wc of the substrate W. The imaging unit 60 is configured to operate based on an operation signal from the controller Ctr and to capture an image of a portion of the peripheral edge Wc of the substrate W. The imaging unit 60 is configured to transmit the captured image to the controller Ctr. The imaging unit 60 may be, for example, a CCD camera or a CMOS camera. There are no particular limitations on where the imaging unit 60 is installed as long as it is within the processing unit 10.

[0035] 4, the imaging unit 60 may be configured to image a portion of the peripheral edge Wc of the substrate W that is downstream of the etching liquid L1. This is because the etching residue RE is more likely to remain on the substrate W toward the downstream side of the etching liquid L1, and the contrast of the etching residue RE is easier to recognize by image processing.

[0036] [Controller Details] As shown in Fig. 5, the controller Ctr has a reading unit M1, a memory unit M2, a processing unit M3, and an instruction unit M4 as functional modules. These functional modules are merely a division of the functions of the controller Ctr into a plurality of modules for convenience, and do not necessarily mean that the hardware constituting the controller Ctr is divided into such modules. Each functional module is not limited to being realized by the execution of a program, but may also be realized by a dedicated electric circuit (for example, a logic circuit) or an integrated circuit (ASIC: Application Specific Integrated Circuit) that integrates such circuits.

[0037] The reading unit M1 is configured to read a program from a computer-readable recording medium RM. The recording medium RM stores a program for operating each part of the substrate processing system 1, including the processing unit 10. The recording medium RM may be, for example, a semiconductor memory, an optical recording disk, a magnetic recording disk, or a magneto-optical recording disk. In the following description, each part of the substrate processing system 1 may include a spinning holder 20, a chemical liquid supplying unit 30, a rinsing liquid supplying unit 40, a heating unit 50, and an imaging unit 60.

[0038] The memory unit M2 is configured to store various data. For example, the memory unit M2 may store a program read from the recording medium RM by the reading unit M1, setting data input by an operator via an external input device (not shown), etc. The memory unit M2 may store data of images captured by the imaging unit 60. The memory unit M2 may also store processing conditions for processing the substrate W, etc.

[0039] The processing unit M3 is configured to process various data, and may generate signals for operating each unit of the substrate processing system 1 based on the various data stored in the storage unit M2, for example.

[0040] The instruction unit M4 is configured to transmit the operation signal generated in the processing unit M3 to each unit of the substrate processing system 1.

[0041] The hardware of the controller Ctr may be configured, for example, by one or more control computers. As shown in Fig. 6, the controller Ctr may include a circuit C1 as a hardware configuration. The circuit C1 may be configured by electric circuit elements. The circuit C1 may include, for example, a processor C2, a memory C3, a storage C4, a driver C5, and an input / output port C6.

[0042] The processor C2 may be configured to execute a program in cooperation with at least one of the memory C3 and the storage C4 and to implement each of the above-mentioned functional modules by inputting and outputting signals via the input / output port C6. The memory C3 and the storage C4 may function as the storage unit M2. The driver C5 may be a circuit configured to drive each component of the substrate processing system 1. The input / output port C6 may be configured to mediate the input and output of signals between the driver C5 and each component of the substrate processing system 1.

[0043] The substrate processing system 1 may include one controller Ctr, or may include a controller group (controller) composed of multiple controllers Ctr. When the substrate processing system 1 includes a controller group, each of the above-mentioned functional modules may be realized by one controller Ctr, or may be realized by a combination of two or more controllers Ctr. When the controller Ctr is composed of multiple computers (circuits C1), each of the above-mentioned functional modules may be realized by one computer (circuit C1), or may be realized by a combination of two or more computers (circuits C1). The controller Ctr may include multiple processors C2. In this case, each of the above-mentioned functional modules may be realized by one processor C2, or may be realized by a combination of two or more processors C2.

[0044] [Substrate processing method] 7 to 11, a method for etching a metal polycrystalline film F formed on a substrate W will be described. Before starting the method, a carrier 7 is placed in advance on the mounting table of the mounting unit 4. The carrier 7 contains at least one substrate W having a metal polycrystalline film F formed on its surface Wa.

[0045] First, the controller Ctr controls the transport arms A1 and A2 to take out one substrate W from the carrier 7 and transport it into one of the processing units 10. The substrate W transported into the processing unit 10 is placed on the holder .

[0046] Next, the controller Ctr controls the spin holder 20 to suck and hold the back surface of the substrate W with the holder 23 and rotate the substrate W. In this state, the controller Ctr controls the chemical liquid supply unit 30 to supply the etching liquid L1 from the nozzle 34 to the peripheral edge Wc of the substrate W for a predetermined time (see step S11 of FIG. 7 and FIG. 8(a)). For example, as shown in FIG. 8(a), while the etching liquid L1 is still being discharged from the nozzle 34, the drive source 36 may move the nozzle 34 from the outside of the substrate W, past the peripheral edge of the substrate W, toward the center of the substrate W. After the predetermined time has elapsed, while the etching liquid L1 is still being discharged from the nozzle 34, the drive source 36 may move the nozzle 34 from the center of the substrate W, past the peripheral edge of the substrate W, toward the outside of the substrate W.

[0047] The etching liquid L1 supplied to the peripheral edge Wc spreads over the entire circumference of the substrate W along the peripheral edge Wc due to the rotation of the substrate W, and is thrown outward from the peripheral edge of the substrate W. Therefore, while the etching liquid L1 continues to be supplied from the nozzle 34, a liquid film of the etching liquid L1 is formed on the peripheral edge Wc. This etches the portion of the metal polycrystalline film F located on the peripheral edge Wc. In step S11, the metal polycrystalline film F is partially etched in its thickness direction by the etching liquid L1.

[0048] 9(a), the etching solution L1 penetrates into the grain boundaries B before the metal polycrystalline film F dissolves, and the metal polycrystalline film F is partially peeled off at the grain boundaries B. As a result, a part of the peeled metal polycrystalline film F remains dissolved in the etching solution L1, generating an etching residue RE.

[0049] In step S11, for example, the etching liquid L1 may be supplied to the substrate W under the following processing conditions (see FIG. 11). Substrate W rotation speed: Approximately 2400 rpm The landing point of the etching solution L1: about 1.0 mm from the edge of the substrate W Etching solution L1 supply time: about 70 seconds Etching solution L1 discharge flow rate: Approximately 15 ml / min

[0050] Prior to step S11, the controller Ctr may control the heating unit 50 to supply heated inert gas to the substrate W. In this case, the substrate W is heated to a predetermined temperature, and etching of the metal polycrystalline film F by the etching solution L1 is promoted. As illustrated in FIG. 11, the supply flow rate of the inert gas may be about 250 l / min.

[0051] Next, the controller Ctr controls the rotation holder 20 and the rinse liquid supply unit 40 to supply the rinse liquid L2 from the nozzle 44 to the peripheral edge Wc of the substrate W for a predetermined time while maintaining the rotation of the substrate W (see step S12 in FIG. 7 and FIG. 8(b)). For example, as shown in FIG. 8(b), the drive source 46 may move the nozzle 44 from the outside of the substrate W, past the peripheral edge of the substrate W, toward the center of the substrate W, while the rinse liquid L2 is still being discharged from the nozzle 44. After the predetermined time has elapsed, the drive source 46 may move the nozzle 44 from the center of the substrate W, past the peripheral edge of the substrate W, toward the outside of the substrate W, while the rinse liquid L2 is still being discharged from the nozzle 44.

[0052] The rinsing liquid L2 supplied to the peripheral edge Wc spreads over the entire circumference of the substrate W along the peripheral edge Wc due to the rotation of the substrate W, and is thrown outward from the peripheral edge of the substrate W. Therefore, while the supply of the rinsing liquid L2 from the nozzle 44 continues, a liquid film of the rinsing liquid L2 is formed on the peripheral edge Wc. As a result, as shown in FIG. 9(b), the etching residue RE generated in step S11 is washed away by the rinsing liquid L2.

[0053] In step S12, for example, the rinse liquid L2 may be supplied to the substrate W under the following processing conditions (see FIG. 11). Substrate W rotation speed: Approximately 2400 rpm Rinse liquid L2 landing point: Approximately 1.5 mm from the edge of the substrate W Rinse liquid L2 supply time: Approximately 20 seconds Rinse liquid L2 discharge flow rate: Approximately 15 ml / min

[0054] If the substrate W has been heated by the heating unit 50 prior to step S11, the substrate W may continue to be heated in step S12. In this case, too, the supply flow rate of the inert gas may be about 250 l / min, as illustrated in FIG.

[0055] Next, similarly to step S11, the controller Ctr controls the spin holder 20 and the chemical liquid supply unit 30 to supply the etching liquid L1 from the nozzle 34 to the peripheral edge Wc of the substrate W for a predetermined time while maintaining the rotation of the substrate W (see step S13 in FIG. 7 and FIG. 8(c)). Also in step S13, similarly to step S11, as shown in FIG. 8(c), the drive source 36 may move the nozzle 34 from the outside of the substrate W beyond the peripheral edge of the substrate W toward the center of the substrate W while the etching liquid L1 is still being discharged from the nozzle 34. After the predetermined time has elapsed, the drive source 36 may move the nozzle 34 from the center of the substrate W beyond the peripheral edge of the substrate W toward the outside of the substrate W while the etching liquid L1 is still being discharged from the nozzle 34.

[0056] In step S13, the etching liquid L1 etches all of the portion of the metal polycrystalline film F located in the peripheral edge portion Wc. At this time, as shown in FIG. 10(a), etching residue RE is generated in the same manner as in step S11. In step S13, for example, the etching liquid L1 may be supplied to the substrate W under the same processing conditions as in step S11 (see FIG. 11).

[0057] If the substrate W is being heated by the heating unit 50 prior to step S11, the heating of the substrate W may continue in step S13. In this case, the supply flow rate of the inert gas may be approximately 250 l / min. Alternatively, as illustrated in FIG. 11, the controller Ctr may control the heating unit 50 to reduce the supply flow rate of the inert gas to, for example, approximately 100 l / min before the supply of the etching liquid L1 is stopped. In this case, the temperature of the substrate W decreases before the rinsing liquid L2 is supplied to the substrate W in the subsequent step S14.

[0058] Next, similarly to step S12, the controller Ctr controls the rotation holder 20 and the rinse liquid supply unit 40 to supply the rinse liquid L2 from the nozzle 44 to the peripheral portion Wc of the substrate W for a predetermined time while maintaining the rotation of the substrate W (see step S14 of FIG. 7 and FIG. 8(d)). Also in step S14, similarly to step S12, as shown in FIG. 8(d), the drive source 46 may move the nozzle 44 from the outside of the substrate W, past the peripheral portion of the substrate W, toward the center of the substrate W, while the rinse liquid L2 is still being discharged from the nozzle 44. After the predetermined time has elapsed, the drive source 46 may move the nozzle 44 from the center of the substrate W, past the peripheral portion of the substrate W, toward the outside of the substrate W, while the rinse liquid L2 is still being discharged from the nozzle 44.

[0059] As in step S12, the rinse liquid L2 supplied to the peripheral edge Wc spreads over the entire circumference of the substrate W at the peripheral edge Wc due to the rotation of the substrate W, and is thrown outward from the peripheral edge of the substrate W. Therefore, in step S14, as shown in FIG. 10(b), the etching residue RE generated in step S13 is washed away by the rinse liquid L2.

[0060] In step S14, for example, the rinse liquid L2 may be supplied to the substrate W under the following processing conditions (see FIG. 11). Substrate W rotation speed: Approximately 2400 rpm Rinse liquid L2 landing point: Approximately 1.5 mm from the edge of the substrate W Rinse liquid L2 supply time: Approximately 30 seconds Rinse liquid L2 discharge flow rate: Approximately 15 ml / min

[0061] If the heating unit 50 has been heating the substrate W prior to step S11, the heating of the substrate W may continue in step S13. In this case, the supply flow rate of the inert gas may be approximately 250 l / min. Alternatively, as illustrated in FIG. 11 , if the supply flow rate of the inert gas has decreased in the previous step S13, the controller Ctr may control the heating unit 50 to increase the supply flow rate of the inert gas to, for example, approximately 250 l / min after the supply of the rinse liquid L2. In this case, the temperature of the substrate W increases before drying of the substrate W begins in the subsequent step S15.

[0062] Next, the controller Ctr controls the rotation holder 20 to maintain the rotation of the substrate W. As a result, the rinse liquid L2 is shaken off from the substrate W, and the substrate W is dried (see step S15 in FIG. 7 and FIG. 8(e)). This completes the processing of the substrate W.

[0063] In step S15, the substrate W may be dried under the following processing conditions, for example (see FIG. 11). Substrate W rotation speed: Approximately 2500 rpm Drying time for substrate W: about 20 seconds

[0064] If the substrate W has been heated by the heating unit 50 prior to step S11, the heating of the substrate W may continue in step S15. In this case, too, the supply flow rate of the inert gas may be about 250 l / min, as illustrated in FIG.

[0065] [Effect] Incidentally, when etching liquid L1 is supplied to a metal polycrystalline film F and etching residues RE are generated (see FIG. 12(a)), most of them are discharged from the substrate W together with the etching liquid L1, but some of them may collect at the interface between the etching liquid L1 and the atmosphere (gas-liquid interface). Once the etching residues RE dry and solidify, even if a rinse liquid L2 is subsequently supplied to the substrate W (see FIG. 12(b)), the etching residues RE cannot be removed from the substrate W (see FIG. 12(c)).

[0066] However, in the above example, the rinse liquid L2 is supplied during the etching of the metal polycrystalline film F (step S12). Therefore, the etching residue RE generated during the etching of the metal polycrystalline film F is washed away by the rinse liquid L2 before it dries and solidifies. Therefore, when etching the metal polycrystalline film F formed on the surface Wa of the substrate W, the etching residue RE can be effectively removed.

[0067] In the above example, in steps S11 to S15, the heating unit 50 may heat the substrate W so that the temperature of the substrate W is relatively low before and after the start of supply of the rinse liquid L2 in step S14. In this case, the relatively low temperature of the substrate W before and after the start of supply of the rinse liquid L2 in step S14 suppresses drying and solidification of the etching residue RE. On the other hand, the relatively high temperature of the substrate W at times other than before and after the start of supply of the rinse liquid L2 in step S14 promotes etching of the metal polycrystalline film F. This makes it possible to achieve both an increase in the speed of the etching process and effective removal of the etching residue RE. Note that the heating unit 50 may heat the substrate W so that the temperature of the substrate is relatively low not only before and after the start of supply of the rinse liquid L2 in step S14 (immediately before drying the substrate W), but also before and after the start of supply of the rinse liquid L2 in step S12 (during the etching process of the metal polycrystalline film F).

[0068] [Variations] The disclosure in this specification should be considered to be illustrative in all respects and not restrictive. Various omissions, substitutions, modifications, etc. may be made to the above examples without departing from the scope and spirit of the claims.

[0069] (1) In the above examples, the etching liquid L1 and the rinse liquid L2 are supplied from above the substrate W toward the front surface Wa in order to etch the metal polycrystalline film F formed on the front surface Wa of the substrate W. However, if the metal polycrystalline film F is formed on the back surface Wb of the substrate W, the etching liquid L1 and the rinse liquid L2 may be supplied from below the substrate W toward the back surface Wb.

[0070] Alternatively, when a metal polycrystalline film F is formed on both surfaces of the substrate W, the etching liquid L1 and the rinsing liquid L2 may be supplied from above and below the substrate W toward the front surface Wa and the back surface Wb, respectively. In this case, as illustrated in FIG. 13 , after the supply of the etching liquid L1 to the front surface Wa is started, the supply of the etching liquid L1 to the back surface Wb may be started, and after the supply of the etching liquid L1 to the back surface Wb is stopped, the supply of the etching liquid L1 to the front surface Wa may be stopped. Similarly, after the supply of the rinsing liquid L2 to the front surface Wa is started, the supply of the rinsing liquid L2 to the back surface Wb may be started, and after the supply of the rinsing liquid L2 to the back surface Wb is stopped, the supply of the rinsing liquid L2 to the front surface Wa may be stopped. In these cases, it is possible to prevent the etching liquid L1 or the rinsing liquid L2 from flowing around from the back surface Wb to the front surface Wa.

[0071] (2) As illustrated in Figures 14(a) to 14(c) and 15, during the etching process of the metal polycrystalline film F, the rinse liquid L2 may be supplied to the substrate W while the supply of the etching liquid L1 continues (while the etching liquid L1 is being discharged from the nozzle 34). Thereafter, as illustrated in Figures 14(d) and 14(e) and 15, the final supply of the rinse liquid L2 and drying of the substrate W may be performed, similar to steps S14 and S15. In this case, since the supply of the liquid (etching liquid L1 or rinse liquid L2) to the substrate W is continued (uninterrupted), the peripheral edge Wc is maintained in a wet state, and the etching residue RE is unlikely to dry and solidify. This makes it possible to more effectively remove the etching residue RE.

[0072] When the etching liquid L1 and the rinsing liquid L2 are simultaneously supplied to the substrate W, the nozzles 34 and 44 may be provided on the same arm (not shown) or on different arms (not shown). In other words, the nozzles 34 and 44 may be physically close to each other or physically separated from each other. In the latter case, splashing is less likely to occur when the etching liquid L1 and the rinsing liquid L2 are simultaneously supplied to the substrate W. As illustrated in FIG. 16, the nozzle 34 and the nozzle 44 may be arranged to face each other with the center of the substrate W between them.

[0073] (3) Although not shown, the supply of the final rinse liquid L2 (e.g., step S14) may be started before the supply of the etching liquid L1 supplied to the substrate W in the previous step (e.g., step S13) is stopped. Alternatively, as illustrated in FIG. 17, the supply of the final rinse liquid L2 may be started while the etching liquid L1 is being supplied. In these cases, the supply of the liquid (etching liquid L1 or rinse liquid L2) to the substrate W is continued (uninterrupted), so the peripheral edge Wc is kept wet, and the etching residue RE is less likely to dry and solidify. This makes it possible to more effectively remove the etching residue RE.

[0074] (4) When etching residues RE are generated, the contrast difference between the etching residues RE and their vicinity tends to increase. Therefore, the controller Ctr may determine whether etching residues RE are generated in the peripheral edge portion Wc based on the captured image captured by the imaging unit 60. Specifically, the controller Ctr may determine that etching residues RE are generated when detecting a change in contrast (e.g., a change in brightness value) equal to or greater than a predetermined threshold value in the captured image. In this case, image processing can automatically detect whether etching residues RE are generated.

[0075] When it is determined that etching residues RE have been generated, the controller Ctr may control the rinse liquid supply unit 40 to supply the rinse liquid L2 to the substrate W. In this case, when etching residues RE are generated, the etching residues RE are automatically washed away with the rinse liquid L2. Therefore, it is possible to improve the efficiency of substrate processing compared to when the supply of the etching liquid L1 and the rinse liquid L2 is started and stopped based on preset processing conditions.

[0076] The controller Ctr may determine whether the generation interval of the etching residues RE is shorter or longer than a predetermined reference value. If it is determined that the generation interval of the etching residues RE is shorter or longer than the predetermined reference value, the etching of the metal polycrystalline film F is progressing too quickly or too slowly, and the controller Ctr may change at least one of various processing conditions. The processing conditions may include, for example, the position of the nozzle 34, the position of the nozzle 44, the movement speed of the nozzle 34, the movement speed of the nozzle 44, the flow rate of the etching liquid L1, the flow rate of the rinsing liquid L2, the supply time of the etching liquid L1, the supply time of the rinsing liquid L2, the temperature of the substrate W (such as the flow rate of the inert gas and the temperature of the inert gas), and the rotation speed of the substrate W.

[0077] (5) In steps S12 and S14, when the nozzle 44 is moved from the outside of the substrate W past the periphery of the substrate W toward the center of the substrate W while the rinse liquid L2 is being discharged from the nozzle 44, the flow rate of the rinse liquid L2 may be changed before and after the nozzle 44 passes the periphery of the substrate W. For example, as illustrated in Fig. 18, the rinse liquid L2 may be discharged from the nozzle 44 at a first flow rate (e.g., about 7.5 ml) until the nozzle 44 passes the periphery of the substrate W. After the nozzle 44 passes the periphery of the substrate W, the rinse liquid L2 may be discharged from the nozzle 44 at a second flow rate (e.g., about 15.0 ml) that is greater than the first flow rate.

[0078] In this case, the flow rate from the nozzle 44 when the nozzle 44 crosses the periphery of the substrate W is relatively small. Therefore, even if the rinsing liquid L2 discharged from the nozzle 44 collides with the liquid film of the etching liquid L1 previously supplied to the substrate W, splashing of the etching liquid L1 is unlikely to occur. This makes it possible to suppress contamination of the substrate W due to diffusion of the etching liquid L1 into the atmosphere. On the other hand, once the rinsing liquid L2 has been supplied to the substrate W, the flow rate from the nozzle 44 becomes relatively large. This makes it possible to effectively wash away the etching residue RE from the substrate W.

[0079] (6) In steps S12 and S14, while the rinsing liquid L2 is being discharged from the nozzle 44, the discharge angle of the rinsing liquid L2 from the nozzle 44 may be changed when the nozzle 44 is moved from the outside of the substrate W past the periphery of the substrate W toward the center of the substrate W. Here, as illustrated in FIG. 19, the discharge angle may be defined as the angle of a streamline F2 of the rinsing liquid connecting the landing point of the rinsing liquid L2 discharged from the nozzle 44 on the substrate W and the discharge outlet 44a of the nozzle 44, relative to a reference line F1 connecting the landing point of the rinsing liquid L2 on the substrate W and the center of the substrate W. For example, the rinsing liquid L2 may be discharged from the nozzle 44 at a first discharge angle θ1 (e.g., approximately 30° to 70°) until the nozzle 44 moves beyond the periphery of the substrate W (see FIG. 19(a)). After the nozzle 44 passes the periphery of the substrate W, the rinsing liquid L2 may be discharged from the nozzle 44 at a second discharge angle θ2 (for example, about 70° to 90°) larger than the first discharge angle θ1 (see FIG. 19(b)).

[0080] In this case, the discharge angle of the rinsing liquid L2 when the nozzle 44 crosses the peripheral edge of the substrate W is relatively small (first discharge angle θ1). That is, the rinsing liquid L2 discharged from the nozzle 44 is likely to be directed toward the outer side of the substrate W in the radial direction of the substrate W. Therefore, even if splashing of the etching liquid L1 occurs when the rinsing liquid L2 discharged from the nozzle 44 collides with the liquid film of the etching liquid L1 previously supplied to the substrate W, the etching liquid L1 is likely to diffuse toward the outer side of the substrate W. Therefore, the diffused etching liquid L1 is less likely to adhere to the substrate W, making it possible to suppress contamination of the substrate W. On the other hand, once the rinsing liquid L2 is supplied to the substrate W, the discharge angle becomes relatively large (second discharge angle θ2). That is, when viewed from the landing point, the direction of the streamline F2 of the rinsing liquid L2 approaches the direction of the tangent to the substrate W. Therefore, the rinsing liquid L2 supplied to the substrate W flows over a wider range around the peripheral edge Wc of the substrate W. Therefore, the etching residue RE can be washed away from the substrate W effectively.

[0081] (7) The movement speed of the nozzle 34 may be changed when the nozzle 34 is moved from the outside of the substrate W past the periphery of the substrate W toward the center of the substrate W while discharging the etching liquid L1 from the nozzle 34. For example, as illustrated in FIGS. 20 and 21, the nozzle 34 may be moved at a first speed while discharging the etching liquid L1 from the nozzle 34 until the nozzle 34 passes the periphery of the substrate W and reaches a first position (see FIGS. 20(a) and 21). The first position may be, for example, a position where the landing point of the etching liquid L1 is about 0.5 mm from the periphery of the substrate W. The first speed may be, for example, about 10 mm / sec. The nozzle 34 may be moved at a second speed slower than the first speed while discharging the etching liquid L1 from the nozzle 34 until the nozzle 34 passes the first position and reaches a second position (target position) (see FIGS. 20(b), (c), and 21). The second position may be, for example, a position where the landing point is about 1.0 mm from the periphery of the substrate W. The second speed may be, for example, about 0.1 mm / sec. Thereafter, as in steps S14 and S15, the supply of the rinsing liquid L2 and the drying of the substrate W may be performed, as illustrated in Figures 20(d) and 20(e) and 21.

[0082] In this case, the nozzle 34 that discharges the etching liquid L1 moves at a relatively slow speed from the first position to the second position. Therefore, when the nozzle 34 reaches the second position and stops, the inertial force acting on the etching liquid L1 discharged from the nozzle 34 is reduced, making it difficult for the etching liquid L1 to flow toward the center of the substrate W. This prevents the etching liquid L1 from spreading toward the center of the substrate W, making it difficult for the etching liquid L1 to stagnate at the gas-liquid interface. As a result, the etching residue RE is less likely to dry and solidify, and the subsequent supply of a rinse liquid L2 allows the etching residue RE to be effectively removed. Meanwhile, in this case, the nozzle 34 that discharges the etching liquid L1 moves at a relatively high speed to the first position. This reduces the overall etching processing time. This improves the efficiency of substrate processing.

[0083] (8) Incidentally, as illustrated in Figure 22, the etching rate of the metal polycrystalline film F by the etching liquid L1 is highest at the point where the etching liquid L1 lands. Therefore, if the etching process is performed without changing the position of the nozzle 34 that ejects the etching liquid L1, etching of the metal polycrystalline film F is completed relatively quickly at the point where the etching liquid L1 lands, but it takes a relatively long time for the portion of the metal polycrystalline film F closer to the peripheral edge of the substrate W than the point where the etching liquid L1 lands to be completely etched. In this case, etching residues are likely to dry and solidify at the gas-liquid interface.

[0084] Therefore, as illustrated in FIGS. 23 and 24, first, the etching liquid L1 may be supplied to a first position on the peripheral edge Wc of the substrate W, and the metal polycrystalline film F may be etched at the first position (see FIGS. 23(a) and 24). The first position may be, for example, a position where the liquid landing point is approximately 0.5 mm from the peripheral edge of the substrate W. Thereafter, the etching liquid L1 may be supplied to a second position closer to the center of the substrate W than the first position, and the metal polycrystalline film F may be etched at the second position (see FIGS. 23(b) and 24). The second position may be, for example, a position where the liquid landing point is approximately 1.0 mm from the peripheral edge of the substrate W. Thereafter, as illustrated in FIGS. 23(c) and 23(d) and 24, a rinse liquid L2 may be supplied and the substrate W may be dried, similar to steps S14 and S15.

[0085] In this case, the etching liquid is first supplied to a first position on the peripheral edge Wc of the substrate W, and then supplied to a second position on the peripheral edge closer to the center of the substrate W than the first position (see FIGS. 23(a) and 24). Therefore, when etching the metal polycrystalline film F at the second position, the metal polycrystalline film F has already been etched on the peripheral side of the first position (see FIGS. 23(b) and 24). Therefore, the etching process at the second position is completed in a relatively short time. As a result, the etching residue RE is less likely to dry and solidify, and therefore, by subsequently supplying a rinse liquid L2, the etching residue RE can be effectively removed. Furthermore, in this case, the etching process time as a whole is shortened (see FIG. 24). Therefore, it is possible to improve the efficiency of substrate processing.

[0086] 25 to 27, after the metal polycrystalline film F on the peripheral edge Wc of the substrate W is etched with the etching liquid L1, the rotation speed of the substrate W may be reduced. First, the controller Ctr controls the rotation holder 20 and the chemical liquid supply unit 30 to supply the etching liquid L1 from the nozzle 34 to the peripheral edge Wc of the substrate W rotating at the rotation speed ω1 while maintaining the rotation of the substrate W (see FIG. 25(a) and FIG. 27).

[0087] In the supplying process of the etching liquid L1, the etching liquid L1 may be supplied to the substrate W under the following processing conditions (see FIG. 27). The landing point of the etching solution L1: about 1.0 mm from the edge of the substrate W Etching solution L1 supply time: about 70 seconds Etching solution L1 discharge flow rate: Approximately 15 ml / min

[0088] This removes the metal polycrystalline film F from the peripheral edge Wc of the substrate W outside the landing point of the etching liquid L1 (see FIGS. 25(b) and 26(a)). That is, during the etching process of the metal polycrystalline film F, most of the etching liquid L1 flows from the landing point toward the peripheral edge of the substrate W due to centrifugal force, and is then thrown off outward from the peripheral edge of the substrate W. The rotation speed ω1 of the substrate W may be, for example, about 2400 rpm, or about 1200 rpm to 3000 rpm.

[0089] Next, the controller Ctr controls the spin holder 20 and the chemical liquid supply unit 30 to change the rotation speed of the substrate W to rotation speed ω2 while the etching liquid L1 is being supplied to the peripheral edge Wc of the substrate W (see FIGS. 25(c), 26(b), and 27). The rotation speed ω2 of the substrate W is set to a value smaller than the rotation speed ω1.

[0090] The rotation speed ω2 of the substrate W may be, for example, about 600 rpm, or may be about 600 rpm to 2400 rpm. The timing at which the rotation speed of the substrate W is changed may be any time before the supply of the etching liquid L1 is stopped. The timing at which the rotation speed of the substrate W is changed may be, for example, about 1 second before the supply of the etching liquid L1 is stopped, or about 1 to 5 seconds before. When the rotation speed of the substrate W is changed, the nozzle 34 may or may not move. When the rotation speed of the substrate W is changed, the landing point of the etching liquid L1 may be the same position or a different position.

[0091] Next, the controller Ctr controls the spin holder 20 and the rinse liquid supply unit 40 to maintain the rotation of the substrate W at the rotation speed ω2, and moves the nozzle 44 from the outside of the substrate W beyond the periphery of the substrate W toward the center of the substrate W while continuing to discharge the rinse liquid L2 from the nozzle 44 (see FIGS. 25(d) and 27). Note that the rotation speed of the substrate W when the supply of the rinse liquid L2 to the substrate W starts may be a value smaller than the rotation speed ω1, or may be approximately 600 rpm to 2400 rpm.

[0092] In the supplying process of the rinsing liquid L2, the rinsing liquid L2 may be supplied to the substrate W under the following processing conditions (see FIG. 27). Rinse liquid L2 landing point: Approximately 1.5 mm from the edge of the substrate W Rinse liquid L2 supply time: about 10 seconds Rinse liquid L2 discharge flow rate: Approximately 15 ml / min

[0093] Next, the controller Ctr controls the spin holder 20 and the rinse liquid supply unit 40 to change the rotation speed of the substrate W to rotation speed ω1 while the etching liquid L1 is being supplied to the peripheral edge Wc of the substrate W (see FIG. 25(e) and FIG. 27). The timing at which the rotation speed of the substrate W is changed may be after the rinse liquid L2 discharged from the nozzle 44 has reached the liquid landing point. The timing at which the rotation speed of the substrate W is changed may be, for example, about 1 second after the start of supply of the rinse liquid L2, or about 1 to 5 seconds after. The changed rotation speed of the substrate W may be a value greater than the rotation speed ω2, or may be about 600 rpm to 2400 rpm.

[0094] Next, the controller Ctr controls the rotation holder 20 to maintain the rotation of the substrate W. This causes the rinse liquid L2 to be shaken off from the substrate W, and the substrate W is dried (see FIG. 25(f) and FIG. 27). This completes the processing of the substrate W.

[0095] In the drying process, the substrate W may be dried under the following processing conditions (see FIG. 27). Substrate W rotation speed: Approximately 2500 rpm Drying time for substrate W: about 5 seconds

[0096] 25 to 27, the rotation speed of the substrate W is changed from rotation speed ω1 to a smaller rotation speed ω2 while continuing to supply the etching liquid L1 to the peripheral edge Wc of the substrate W. Therefore, as the rotation speed of the substrate W is changed, the centrifugal force acting on the etching liquid L1 decreases, and the interface between the etching liquid L1 and the atmosphere (gas-liquid interface) moves toward the center of the substrate W (see FIG. 26(b)). Therefore, the etching liquid L1 that has moved toward the center removes the etching residues RE that have collected at the gas-liquid interface during the etching process and inhibits the etching residues RE that have collected at the gas-liquid interface during the etching process from drying and solidifying. Therefore, by subsequently supplying a rinse liquid L2 to the peripheral edge Wc of the substrate W, the etching residues RE can be effectively removed. Furthermore, according to the examples of FIGS. 25 to 27, it is only necessary to change the rotation speed of the substrate W, and therefore there is no need to change the supply process of the etching liquid L1 or the rinse liquid L2. This allows the substrate W to be processed efficiently. 25 to 27, the supply of the rinse liquid L2 to the substrate W is started when the rotation speed of the substrate W is lower than the rotation speed ω1. That is, the supply of the rinse liquid L2 to the substrate W is started when the interface (gas-liquid interface) between the etching liquid L1 and the atmosphere is maintained near the center of the substrate W. This also prevents the etching residue RE from drying and solidifying between the end of the supply of the etching liquid L1 and the start of the supply of the rinse liquid L2. This makes it possible to remove the etching residue RE even more effectively.

[0097] (10) An etching liquid L1 and a rinsing liquid L2 may be supplied to the rear surface Wb of the substrate W. The processing unit 10 illustrated in FIG. 28 differs from the processing unit 10 illustrated in FIG. 3 in that it includes a spin holder 20, a chemical liquid supply unit 30, and a rinsing liquid supply unit 40 in order to supply the etching liquid L1 and the rinsing liquid L2 to the rear surface Wb of the substrate W. The following mainly describes the differences. Note that the heating unit 50 and the imaging unit 60 are not shown in FIG. 28.

[0098] The rotation holding unit 20 includes a rotation unit 210 and an elevation unit 220. The rotation unit 210 includes a rotation shaft 211, a drive mechanism 212, a support plate 213, and a plurality of support pins 214. The rotation shaft 211 is a hollow tubular member extending in the vertical direction. The rotation shaft 211 is configured to be rotatable around a central axis Ax.

[0099] The drive mechanism 212 is connected to the rotary shaft 211. The drive mechanism 212 is configured to operate based on an operation signal from the controller Ctr and rotate the rotary shaft 211. The drive mechanism 212 may be a power source such as an electric motor.

[0100] The support plate 213 is, for example, a flat plate having an annular shape and extends horizontally. That is, a through-hole is formed in the center of the support plate 213. The inner periphery of the support plate 213 is connected to the tip end of the rotation shaft 211. Therefore, the support plate 213 is configured to rotate around the central axis Ax of the rotation shaft 211 in conjunction with the rotation of the rotation shaft 211.

[0101] The plurality of support pins 214 are provided on the support plate 213 so as to protrude upward from the upper surface of the support plate 213. The plurality of support pins 214 are configured to support the substrate W approximately horizontally by abutting their tips against the back surface Wb of the substrate W.

[0102] The lifting unit 220 includes a shaft member 221, a drive mechanism 222, and a plurality of support pins 223. The shaft member 221 is a hollow tubular member extending in the vertical direction. The shaft member 221 is configured to be able to move up and down in the up and down direction. The shaft member 221 is inserted into the interior of the rotation shaft 211.

[0103] The drive mechanism 222 is connected to the shaft member 221. The drive mechanism 222 is configured to operate based on an operation signal from the controller Ctr and to raise and lower the shaft member 221. By the drive mechanism 222 raising and lowering the shaft member 221, the shaft member 221 may move up and down between an elevated position where the plurality of support pins 223 are positioned above the plurality of support pins 214, and a lowered position where the plurality of support pins 223 are positioned below the plurality of support pins 214. The drive mechanism 222 may be a power source such as a linear actuator, for example.

[0104] The plurality of support pins 223 are provided on the shaft member 221 so as to protrude upward from the upper end of the shaft member 221. The plurality of support pins 223 are configured to support the substrate W by abutting their tips against the back surface Wb of the substrate W.

[0105] 28 does not include a nozzle 34. Instead, the downstream end of the pipe 35 is fluidly connected to the shaft member 221. Therefore, the chemical liquid supply unit 30 is configured to supply the etching liquid L1 from the liquid source 31 to the back surface Wb of the substrate W through the inside of the shaft member 221.

[0106] 28 does not include a nozzle 44. Instead, the downstream end of the pipe 45 is fluidly connected to the shaft member 221. Therefore, the rinse liquid supply unit 40 is configured to supply the rinse liquid L2 from the liquid source 41 to the back surface Wb of the substrate W through the inside of the shaft member 221.

[0107] Next, with reference to FIGS. 28 and 29, a method for etching a metal polycrystalline film F formed on a substrate W using the processing unit 10 illustrated in FIG. 28 will be described.

[0108] First, the controller Ctr controls the transport arms A1 and A2 to take out one substrate W from the carrier 7 and transport it into one of the processing units 10. At this time, the controller Ctr controls the drive mechanism 222 to position the shaft member 221 in the raised position. The substrate W transported into the processing unit 10 is transferred from the transport arm A2 to the support pins 223. As a result, the substrate W is placed on the support pins 223 (elevating section 220) so that the back surface Wb abuts against the support pins 223.

[0109] Next, the controller Ctr controls the drive mechanism 222 to lower the shaft member 221 to the lowered position. During the process of lowering the shaft member 221, the substrate W is transferred from the support pins 223 to the support pins 214. As a result, the substrate W is placed on the support pins 214 (rotating part 210) so that the back surface Wb abuts against the support pins 214.

[0110] Next, the controller Ctr controls the drive mechanism 212 to rotate the substrate W together with the rotation unit 210. The rotation speed of the substrate W may be, for example, approximately 100 rpm to 3000 rpm. In this state, the controller Ctr controls the chemical liquid supply unit 30 to supply the etching liquid L1 from the shaft member 221 to the back surface Wb of the substrate W for a predetermined time (step X1: see FIG. 29(a)). The supply time of the etching liquid L1 to the back surface Wb of the substrate W may be approximately 10 seconds to 180 seconds. As illustrated in FIG. 29(a), the etching liquid L1 supplied to the back surface Wb of the substrate W flows along the back surface Wb toward the outer periphery of the substrate W due to centrifugal force, then flows around the outer periphery of the substrate W, is supplied to the peripheral portion Wc of the front surface Wa of the substrate W, and is then thrown off to the outside. As a result, a liquid film of the etching liquid L1 is formed on the peripheral portion Wc while the etching liquid L1 is continuously supplied from the shaft member 221. Therefore, the portion of the metal polycrystalline film F located in the peripheral edge portion Wc is etched.

[0111] Next, the controller Ctr controls the rinse liquid supply unit 40 to supply the rinse liquid L2 from the shaft member 221 to the back surface Wb of the substrate W for a predetermined time (step X2: see FIG. 29(b)). The supply time of the rinse liquid L2 to the back surface Wb of the substrate W may be approximately 10 to 180 seconds. As illustrated in FIG. 29(b), the rinse liquid L2 supplied to the back surface Wb of the substrate W flows along the back surface Wb toward the outer periphery of the substrate W due to centrifugal force, then flows around the outer periphery of the substrate W to be supplied to the peripheral portion Wc of the front surface Wa of the substrate W, and is then thrown off to the outside. As a result, while the supply of the rinse liquid L2 from the shaft member 221 continues, a liquid film of the rinse liquid L2 is formed on the peripheral portion Wc. Therefore, the etching residue RE generated when the etching liquid L1 is supplied is washed away by the rinse liquid L2.

[0112] Next, steps X1 and X2 (supply of etching liquid L1 and rinse liquid L2) are repeated one or more times. The number of repetitions may be approximately 1 to 20 times. Thereafter, the controller Ctr controls the chemical liquid supply unit 30 and the rinse liquid supply unit 40 to stop the supply of the etching liquid L1 and the rinse liquid L2. Then, the controller Ctr controls the rotation unit 210 to maintain the rotation of the substrate W. As a result, the rinse liquid L2 is shaken off from the substrate W, and the substrate W is dried. With the above, the processing of the substrate W is completed.

[0113] 28 and 29, the etching process on the peripheral edge Wc of the substrate W is divided into multiple steps and performed. Therefore, the etching residues RE generated in the etching process are removed by the rinse liquid L2 before they dry and solidify. As a result, the etching residues RE can be effectively removed.

[0114] [Other examples] Example 1. An example of a substrate processing method includes a first step of supplying an etching liquid to the peripheral edge of a substrate having a metal polycrystalline film formed on its surface while rotating the substrate, thereby partially etching the metal polycrystalline film at the peripheral edge in the thickness direction; a second step of supplying a rinse liquid to a region closer to the center of the substrate than the position where the etching liquid was supplied in the first step while rotating the substrate, thereby rinsing away etching residues generated in the first step with the rinse liquid; a third step of supplying an etching liquid to the peripheral edge of the substrate while rotating the substrate, thereby etching away remaining portions of the metal polycrystalline film at the peripheral edge; a fourth step of supplying a rinse liquid to a region closer to the center of the substrate than the position where the etching liquid was supplied in the third step while rotating the substrate, thereby rinsing away etching residues generated in the third step with the rinse liquid; and a fifth step of drying the substrate after the fourth step.

[0115] Metal polycrystalline films (e.g., titanium nitride, tungsten, etc.) are composed of polycrystals, which are aggregates of numerous crystal grains. The interfaces between these crystal grains are called grain boundaries (or simply grain boundaries), and are discontinuous surfaces where the crystal grains are oriented in different directions. Therefore, when an etching solution is supplied to a metal polycrystalline film, the etching solution penetrates the grain boundaries before dissolving the metal polycrystalline film, causing partial peeling of the metal polycrystalline film at the grain boundaries. As a result, a portion of the peeled metal polycrystalline film remains dissolved in the etching solution, resulting in etching residue. Although most of the etching residue is discharged from the substrate along with the etching solution supplied to the substrate, some of it may collect at the interface between the etching solution and the atmosphere (gas-liquid interface). This is because liquid stagnation occurs at the landing point of the etching solution supplied to the substrate, and the etching solution supplied to the substrate flows to some extent not only around the periphery but also around the center of the substrate. During substrate processing, the substrate rotates and may be heated to promote etching. Therefore, if the etching residue dries and solidifies, it will no longer be possible to remove the etching residue from the substrate even if a rinse liquid is subsequently supplied to the substrate.

[0116] However, in Example 1, a rinse liquid is supplied during the etching of the metal polycrystalline film. Therefore, etching residues generated during the etching of the metal polycrystalline film are washed away by the rinse liquid before drying and solidifying. Therefore, when etching a metal polycrystalline film formed on the surface of a substrate, etching residues can be effectively removed.

[0117] Example 2: In the method of Example 1, the second step may include starting to supply a rinse liquid while the etching liquid is being supplied in the first step. In this case, the supply of liquid to the substrate is continued, so that the etching residue is less likely to dry and solidify. Therefore, the etching residue can be removed more effectively.

[0118] Example 3 In the method of Example 1 or Example 2, the fourth step may include starting to supply a rinse liquid while the etching liquid is being supplied in the third step. In this case, the same effects as in Example 2 can be obtained.

[0119] Example 4: In the method of Example 2 or Example 3, the second or fourth step may include discharging a rinse liquid from the nozzle while the nozzle is moving from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing the flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate. In this case, the flow rate from the nozzle when the nozzle crosses the periphery of the substrate is relatively small. Therefore, even if the rinse liquid discharged from the nozzle collides with the liquid film of the etching liquid previously supplied to the substrate, splashing of the etching liquid is unlikely to occur. Therefore, contamination of the substrate due to diffusion of the etching liquid into the atmosphere can be suppressed. On the other hand, once the rinse liquid is supplied to the substrate, the flow rate from the nozzle is relatively large. Therefore, etching residue can be effectively washed away from the substrate.

[0120] Example 5: In any of the methods of Examples 2 to 4, when viewed from above, the angle of the streamline of the rinse liquid connecting the nozzle outlet and the landing point of the rinse liquid on the substrate relative to a reference line connecting the center of the substrate and the landing point of the rinse liquid discharged from the nozzle may be defined as the discharge angle of the rinse liquid from the nozzle. The second or fourth step may include discharging the rinse liquid from the nozzle while moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing the discharge angle after the nozzle has passed the periphery of the substrate. In this case, the discharge angle of the rinse liquid when the nozzle crosses the periphery of the substrate is relatively small. That is, the rinse liquid discharged from the nozzle is likely to be directed toward the outside of the substrate in the radial direction of the substrate. Therefore, even if splashing of the etching liquid occurs when the rinse liquid discharged from the nozzle collides with a liquid film of the etching liquid previously supplied to the substrate, the etching liquid is likely to diffuse toward the outside of the substrate. Therefore, the diffused etching liquid is less likely to adhere to the substrate, thereby suppressing substrate contamination. On the other hand, once the rinse liquid is supplied to the substrate, the discharge angle becomes relatively large. That is, when viewed from the landing point, the direction of the rinse liquid flow line approaches the direction of the tangent to the substrate. Therefore, the rinse liquid supplied to the substrate flows over a wider area around the peripheral edge of the substrate. This makes it possible to effectively wash away etching residue from the substrate.

[0121] Example 6: Any of the methods of Examples 1 to 5 may further include a sixth step of heating the substrate during the first to fourth steps, and the sixth step may include heating the substrate so that the temperature of the substrate before and after the start of supplying the rinse liquid in the fourth step is lower than the temperature of the substrate during the supply of the etching liquid in the first and third steps. In this case, the relatively low temperature of the substrate before and after the start of supplying the rinse liquid suppresses drying and solidification of the etching residue, while the relatively high temperature of the substrate at times other than before and after the start of supplying the rinse liquid promotes etching of the metal polycrystalline film. This makes it possible to achieve both high-speed etching and effective removal of the etching residue.

[0122] Example 7: The methods of Examples 1 to 6 may further include a seventh step of capturing an image of the peripheral edge of the substrate with an imaging unit while the etching liquid is being supplied to the substrate, and an eighth step of determining whether or not etching residue has occurred on the peripheral edge based on a change in contrast of the image captured by the imaging unit. In this case, the presence or absence of etching residue can be automatically detected by image processing.

[0123] Example 8: In the method of Example 7, if it is determined in step 8 that etching residues have occurred, a second or fourth step may be performed in which a rinse liquid is supplied to the substrate to wash away the etching residues with the rinse liquid. The timing at which etching residues occur can vary depending on the etching conditions (e.g., the material of the metal polycrystalline film, the type of etching liquid, etc.). Therefore, by determining this timing through prior testing or the like and appropriately setting the timing for supplying the rinse liquid according to the etching conditions, etching residues can be removed more efficiently. However, in Example 8, when etching residues occur, the etching residues are automatically washed away with the rinse liquid. Therefore, prior testing or the like can be omitted, thereby improving the efficiency of substrate processing.

[0124] Example 9. Another example of a substrate processing method includes a first step of etching the metal polycrystalline film on the peripheral edge of the substrate while rotating the substrate and discharging an etching solution from the nozzle, by moving the nozzle from the outside of the substrate beyond the periphery of the substrate toward the center of the substrate at a first speed; a second step of etching the metal polycrystalline film on the peripheral edge of the substrate while rotating the substrate and discharging the etching solution from the nozzle, by moving the nozzle beyond the periphery of the substrate to a predetermined position toward the center of the substrate at a second speed slower than the first speed; a third step of supplying a rinse liquid to a position toward the center of the substrate relative to the supply position of the etching solution in the second step while rotating the substrate, to wash away etching residues generated in the second step with the rinse liquid; and a fourth step of drying the substrate after the third step. In Example 9, the nozzle discharging the etching solution moves at a relatively slow speed from halfway until it reaches the predetermined position. Therefore, when the nozzle reaches a predetermined position and stops, the inertial force acting on the etching solution discharged from the nozzle is reduced, making it difficult for the etching solution to flow toward the center of the substrate. Therefore, the etching solution is prevented from spreading toward the center of the substrate, making it difficult for the etching solution to stagnate at the gas-liquid interface. As a result, the etching residue is less likely to dry and solidify, and the subsequent supply of a rinse liquid makes it possible to effectively remove the etching residue. Meanwhile, in Example 9, the nozzle discharging the etching solution moves at a relatively high speed until partway through the process. Therefore, the overall etching processing time is shortened. This makes it possible to improve the efficiency of substrate processing.

[0125] Example 10: Another example of a substrate processing method includes a first step of supplying an etching liquid to a first position on the periphery of a substrate while rotating the substrate having a metal polycrystalline film formed on its surface, thereby etching the metal polycrystalline film at the first position; a second step of supplying the etching liquid to a second position on the periphery that is closer to the center of the substrate than the first position, while rotating the substrate, thereby etching the metal polycrystalline film at the second position; a third step of supplying a rinse liquid to a position closer to the center of the substrate than the second position while rotating the substrate, thereby rinsing away etching residues produced in the second step with the rinse liquid; and a fourth step of drying the substrate after the third step.

[0126] The etching rate of a metal polycrystalline film by an etching solution is highest at the point where the etching solution lands. Therefore, if the etching process is performed without changing the position of the nozzle that ejects the etching solution, etching of the metal polycrystalline film at the point where the etching solution lands is completed relatively quickly, but it takes a relatively long time for the portion of the metal polycrystalline film closer to the peripheral edge of the substrate than the point where the etching solution lands to be completely etched. In this case, etching residue is likely to dry and solidify at the gas-liquid interface.

[0127] However, in Example 10, the etching liquid is first supplied to a first position on the peripheral edge of the substrate, and then supplied to a second position on the peripheral edge closer to the center of the substrate than the first position. Therefore, when etching the metal polycrystalline film at the second position, the metal polycrystalline film has already been etched on the peripheral side of the first position. Therefore, the etching process at the second position is completed in a relatively short time. As a result, the etching residue is less likely to dry and solidify, and the etching residue can be effectively removed by subsequently supplying a rinse liquid. Furthermore, in Example 10, the overall etching process time is shortened. Therefore, it is possible to improve the efficiency of substrate processing.

[0128] Example 11. Another example of a substrate processing method includes a first step of supplying an etching solution to a peripheral edge of a substrate having a metal polycrystalline film formed on its surface while rotating the substrate at a first rotation speed to etch the metal polycrystalline film at the peripheral edge, a second step of changing the rotation speed of the substrate to a second rotation speed lower than the first rotation speed while the etching solution is still being supplied to the peripheral edge of the substrate, a third step of supplying a rinse solution to a portion of the substrate closer to the center than the supply position of the etching solution in the first and second steps while rotating the substrate, to wash away etching residues generated in the first and second steps with the rinse solution, and a fourth step of drying the substrate after the third step. In Example 11, after the metal polycrystalline film at the peripheral edge of the substrate rotating at the first rotation speed is etched, the rotation speed of the substrate is changed to a second rotation speed lower than the first rotation speed while the supply of the etching solution to the peripheral edge continues. As a result, the centrifugal force acting on the etching solution decreases, and the interface between the etching solution and the atmosphere (gas-liquid interface) moves toward the center of the substrate. Therefore, the etching solution that has moved toward the center removes the etching residue that has collected at the gas-liquid interface in the first step, and also inhibits the etching residue that has collected at the gas-liquid interface in the first step from drying and solidifying. Therefore, by subsequently supplying a rinse liquid to the peripheral portion of the substrate, the etching residue can be effectively removed. Furthermore, in Example 11, the rotation speed of the substrate can be changed, so there is no need to change the supply process of the etching solution or rinse liquid. This allows for efficient substrate processing.

[0129] Example 12: Another example of a substrate processing method includes a first step of supplying an etching solution to the backside of a substrate while rotating the substrate having a metal polycrystalline film formed on its surface, and etching the metal polycrystalline film at the peripheral edge of the substrate with the etching solution that has spread from the backside to the peripheral edge of the substrate; a second step of supplying a rinse solution to the backside of the substrate while rotating the substrate after the first step, and using the rinse solution that has spread from the backside to the peripheral edge to wash away etching residues generated in the first step; a third step of repeating the first and second steps one or more times after the second step; and a fourth step of drying the substrate after the third step. In this case, the etching process at the peripheral edge of the substrate is performed in multiple steps. Therefore, the etching residues generated during the etching process are removed by the rinse solution before they dry and solidify. As a result, the etching residues can be effectively removed.

[0130] Example 13. An example of a substrate processing apparatus includes a spin holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface, a chemical liquid supply unit configured to supply an etching liquid to the surface of the substrate, a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate, and a control unit, wherein the control unit controls the spin holder to hold and rotate the substrate, while controlling the chemical liquid supply unit to supply an etching liquid to the peripheral edge of the substrate, thereby performing a first process of partially etching the metal polycrystalline film on the peripheral edge in the thickness direction, and a rinse liquid supply unit to hold and rotate the substrate, while controlling the spin holder to hold and rotate the substrate, while controlling the chemical liquid supply unit to supply an etching liquid to a position closer to the center of the substrate than the supply position of the etching liquid in the first process. a second process in which the chemical liquid supply unit is controlled to supply an etching liquid to the peripheral edge of the substrate while controlling the rotation holder to hold and rotate the substrate, thereby etching the remaining portion of the metal polycrystalline film at the peripheral edge; a fourth process in which the chemical liquid supply unit is controlled to supply a rinse liquid to the center of the substrate relative to the supply position of the etching liquid in the third process while controlling the rotation holder to hold and rotate the substrate, thereby washing away the etching residue generated in the third process with the rinse liquid; and a fifth process in which the rotation holder is controlled to hold and rotate the substrate, thereby drying the substrate. In this case, the same effects as those of the method of Example 1 can be obtained.

[0131] Example 14 In the apparatus of Example 13, the second process may include starting to supply a rinse liquid while the etching liquid is being supplied in the first process. In this case, the same effects as those of the method of Example 2 can be obtained.

[0132] Example 15 In the apparatus of Example 13 or Example 14, the fourth process may include starting to supply a rinse liquid while the etching liquid is being supplied in the third process. In this case, the same effects as those of the method of Example 3 can be obtained.

[0133] Example 16 In the apparatus of Example 14 or Example 15, the second process or the fourth process may include discharging the rinse liquid from the nozzle of the rinse liquid supply unit, moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing the flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate. In this case, the same effects as those of the method of Example 4 can be obtained.

[0134] Example 17: In the apparatus of any of Examples 14 to 16, when viewed from above, if the angle of the streamline of the rinse liquid connecting the nozzle outlet and the landing point of the rinse liquid discharged from the nozzle of the rinse liquid supply unit relative to a reference line connecting the landing point of the rinse liquid on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle, the second process or the fourth process may include discharging the rinse liquid from the nozzle of the rinse liquid supply unit while moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing the discharge angle after the nozzle has passed the periphery of the substrate. In this case, the same effects as those of the method of Example 5 can be obtained.

[0135] Example 18: The apparatus of any one of Examples 13 to 17 further includes a heating unit configured to heat the substrate, and the control unit is configured to control the heating unit to further perform a sixth process of heating the substrate in the first process to the fourth process, and the sixth process may include the heating unit heating the substrate so that the temperature of the substrate before and after the start of supply of the rinse liquid in the fourth process is lower than the temperature of the substrate during supply of the etching liquid in the first process and the third process. In this case, the same effects as those of the method of Example 6 can be obtained.

[0136] EXAMPLE 19 The devices of Examples 13 to 18 may further include an imaging unit configured to image the peripheral edge portion, and the control unit may be configured to control the imaging unit to further execute a seventh process of imaging the peripheral edge portion while the etching liquid is being supplied to the substrate, and an eighth process of determining whether or not etching residue has occurred in the peripheral edge portion based on a change in contrast of the image captured by the imaging unit. In this case, the same effects as those of the method of Example 7 can be obtained.

[0137] Example 20: In the apparatus of Example 19, if the control unit determines that etching residues have occurred in the eighth process, the control unit may supply a rinse liquid to the substrate and execute the second process or the fourth process to wash away the etching residues with the rinse liquid. In this case, the same effects as those of the method of Example 8 can be obtained.

[0138] Example 21: Another example of a substrate processing apparatus includes a spin holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface, a chemical liquid supply unit configured to supply an etching liquid to the surface of the substrate, a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate, and a control unit, wherein the control unit controls the spin holder to hold and rotate the substrate, and controls the chemical liquid supply unit to move the nozzle at a first speed from the outside of the substrate beyond the periphery of the substrate toward the center of the substrate while discharging the etching liquid from the nozzle of the chemical liquid supply unit, thereby etching the metal polycrystalline film on the periphery of the substrate, a first process; and controls the spin holder to hold and rotate the substrate. The method is configured to perform a second process of etching the metal polycrystalline film on the peripheral edge of the substrate by controlling the chemical liquid supply unit to move the nozzle beyond the peripheral edge of the substrate to a predetermined position toward the center of the substrate at a second speed slower than the first speed while discharging the etching liquid from the nozzle, a third process of washing away etching residues generated in the second process with the rinse liquid by controlling the rotation holder to hold and rotate the substrate and to supply a rinse liquid to a position closer to the center of the substrate than the supply position of the etching liquid in the second process, and a fourth process of drying the substrate by controlling the rotation holder to hold and rotate the substrate. In this case, the same effects as those of the method of Example 9 can be obtained.

[0139] Example 22: Another example of a substrate processing apparatus includes a spin holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface, a chemical liquid supply unit configured to supply an etching liquid to the surface of the substrate, a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate, and a control unit, wherein the control unit controls the spin holder to hold and rotate the substrate, while controlling the chemical liquid supply unit to supply the etching liquid to a first position on the peripheral edge of the substrate, thereby etching the metal polycrystalline film at the first position; a second process in which the chemical liquid supply unit is controlled to supply an etching liquid to a second position on the peripheral edge closer to the center of the substrate than the first position while controlling the rotation holder to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a position closer to the center of the substrate than the second position, thereby washing away etching residues produced in the second process with the rinse liquid; and a fourth process in which the rotation holder is controlled to hold and rotate the substrate, thereby drying the substrate. In this case, the same effects as those of the method of Example 10 can be obtained.

[0140] Example 23. Another example of a substrate processing apparatus includes a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface, a chemical liquid supply unit configured to supply an etching liquid to the surface of the substrate, a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate, and a control unit. The control unit is configured to perform the following operations: a first process in which the spin holder holds the substrate and rotates it at a first rotation speed, while controlling the chemical liquid supply unit to supply an etching solution to the peripheral edge of the substrate, thereby etching the metal polycrystalline film on the peripheral edge; a second process in which the spin holder controls the chemical liquid supply unit to continuously supply the etching solution to the peripheral edge of the substrate and controls the spin holder to change the rotation speed of the substrate to a second rotation speed lower than the first rotation speed; a third process in which the spin holder holds the substrate and rotates it, while controlling the rinse liquid supply unit to supply a rinse liquid to a position closer to the center of the substrate than the supply position of the etching solution in the first and second processes, thereby rinsing away etching residues generated in the first and second processes with the rinse liquid; and a fourth process in which the spin holder holds the substrate and rotates it, thereby drying the substrate. In this case, the same effects as those of the method of Example 11 can be obtained.

[0141] Example 24: Another example of a substrate processing apparatus includes a spin holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface, a chemical liquid supply unit configured to supply an etching liquid to the backside of the substrate, a rinse liquid supply unit configured to supply a rinse liquid to the backside of the substrate, and a control unit. The control unit is configured to perform the following steps: a first process in which the spin holder controls the spin holder to hold and rotate the substrate and the chemical liquid supply unit to supply the etching liquid to the backside, thereby etching the metal polycrystalline film on the peripheral edge of the substrate with the etching liquid that has spread from the backside to the peripheral edge; a second process in which, after the first process, the spin holder controls the spin holder to hold and rotate the substrate and the rinse liquid supply unit to supply the rinse liquid to the backside, thereby washing away etching residues generated in the first process with the rinse liquid that has spread from the backside to the peripheral edge; a third process in which, after the second process, the first and second processes are repeated one or more times; and a fourth process in which the spin holder controls the spin holder to hold and rotate the substrate and dry the substrate after the third process. In this case, the same effects as those of the method of Example 12 can be obtained.

[0142] Example 25. An example of a computer-readable recording medium may have a program recorded thereon for causing a substrate processing apparatus to execute any one of the methods of Examples 1 to 11. In this case, the same effects as those of the method of Example 1 can be obtained. In this specification, the computer-readable recording medium may include a non-transitory computer recording medium (e.g., various main storage devices or auxiliary storage devices) or a propagated signal (e.g., a data signal that can be provided via a network). [Explanation of symbols]

[0143] 1...substrate processing system (substrate processing apparatus), 10...processing unit, 20...rotating holding section, 30...chemical liquid supply section, 34...nozzle, 34a...discharge outlet, 44...nozzle, 44a...discharge outlet, 40...rinse liquid supply section, 50...heating section, 60...imaging section, Ctr...controller (control section), F...metal polycrystalline film, L1...etching liquid, L2...rinse liquid, RE...etching residue, RM...recording medium, W...substrate, Wa...surface, Wc...periphery.

Claims

1. a first step of supplying an etching liquid to a peripheral edge of a substrate having a metal polycrystalline film formed on its surface while rotating the substrate, thereby partially etching the metal polycrystalline film at the peripheral edge in a thickness direction; and a second step of supplying a rinse liquid to a central portion of the substrate closer to the center than the supply position of the etching liquid in the first step while rotating the substrate, thereby washing away etching residues generated in the first step with the rinse liquid. a third step of supplying an etching solution to the peripheral edge of the substrate while rotating the substrate, thereby etching the remaining portion of the metal polycrystalline film at the peripheral edge; a fourth step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the third step while rotating the substrate, thereby washing away etching residues generated in the third step with the rinse liquid; a fifth step of drying the substrate after the fourth step; the second step includes starting to supply a rinse liquid during the supply of the etching liquid in the first step; the second step or the fourth step includes moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate while discharging a rinse liquid from the nozzle, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has moved past the periphery of the substrate.

2. When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from a nozzle on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid discharged from the nozzle on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle, 2. The method according to claim 1, wherein the second step or the fourth step comprises moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate while ejecting the rinse liquid from the nozzle, and increasing the ejection angle after the nozzle has passed the periphery of the substrate.

3. a first step of supplying an etching solution to a peripheral edge portion of a substrate, the peripheral edge portion of which has a metal polycrystalline film formed on its surface, while rotating the substrate, thereby partially etching the metal polycrystalline film in the thickness direction; a second step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the first step while rotating the substrate, thereby washing away etching residues generated in the first step with the rinse liquid; a third step of supplying an etching solution to the peripheral edge of the substrate while rotating the substrate, thereby etching the remaining portion of the metal polycrystalline film at the peripheral edge; a fourth step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the third step while rotating the substrate, thereby washing away etching residues generated in the third step with the rinse liquid; a fifth step of drying the substrate after the fourth step; the second step includes starting to supply a rinse liquid during the supply of the etching liquid in the first step; When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from a nozzle on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid discharged from the nozzle on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle, the second step or the fourth step includes moving the nozzle from the outside of the substrate toward the center of the substrate, past the periphery of the substrate, while ejecting a rinse liquid from the nozzle, and increasing the ejection angle after the nozzle has moved past the periphery of the substrate.

4. 4. The method according to claim 1, wherein the fourth step includes starting to supply a rinse liquid while the etching liquid is being supplied in the third step.

5. a first step of supplying an etching solution to a peripheral edge portion of a substrate, the peripheral edge portion of which has a metal polycrystalline film formed on its surface, while rotating the substrate, thereby partially etching the metal polycrystalline film in the thickness direction; a second step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the first step while rotating the substrate, thereby washing away etching residues generated in the first step with the rinse liquid; a third step of supplying an etching solution to the peripheral edge of the substrate while rotating the substrate, thereby etching the remaining portion of the metal polycrystalline film at the peripheral edge; a fourth step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the third step while rotating the substrate, thereby washing away etching residues generated in the third step with the rinse liquid; a fifth step of drying the substrate after the fourth step; the fourth step includes starting to supply a rinse liquid during the supply of the etching liquid in the third step; the second step or the fourth step includes moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate while discharging a rinse liquid from the nozzle, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has moved past the periphery of the substrate.

6. a first step of supplying an etching solution to a peripheral edge portion of a substrate, the peripheral edge portion of which has a metal polycrystalline film formed on its surface, while rotating the substrate, thereby partially etching the metal polycrystalline film in the thickness direction; a second step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the first step while rotating the substrate, thereby washing away etching residues generated in the first step with the rinse liquid; a third step of supplying an etching solution to the peripheral edge of the substrate while rotating the substrate, thereby etching the remaining portion of the metal polycrystalline film at the peripheral edge; a fourth step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the third step while rotating the substrate, thereby washing away etching residues generated in the third step with the rinse liquid; a fifth step of drying the substrate after the fourth step; When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from a nozzle on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid discharged from the nozzle on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle, the second step or the fourth step includes moving the nozzle from the outside of the substrate toward the center of the substrate, past the periphery of the substrate, while ejecting a rinse liquid from the nozzle, and increasing the ejection angle after the nozzle has moved past the periphery of the substrate.

7. 7. The method according to claim 6, wherein the second step or the fourth step comprises moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate while discharging the rinse liquid from the nozzle, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate.

8. a sixth step of heating the substrate in the first step to the fourth step; 8. The method according to claim 1, wherein the sixth step comprises heating the substrate so that the temperature of the substrate before and after start of supply of the rinse liquid in the fourth step is lower than the temperature of the substrate during supply of the etching liquid in the first step and the third step.

9. a seventh step of capturing an image of the peripheral edge portion by an imaging unit while the etching liquid is being supplied to the substrate; The method according to any one of claims 1 to 8, further comprising: an eighth step of determining whether or not etching residue has occurred in the peripheral edge portion based on a change in contrast of the captured image captured by the imaging unit.

10. 10. The method according to claim 9, wherein, when it is determined that etching residues have been generated in the eighth step, the second step or the fourth step is performed by supplying a rinse liquid to the substrate to wash away the etching residues with the rinse liquid.

11. a first step of etching the metal polycrystalline film on the peripheral portion of the substrate by rotating the substrate having the metal polycrystalline film formed on its surface and discharging an etching solution from a nozzle while the nozzle moves from the outside of the substrate beyond the peripheral edge of the substrate toward the center of the substrate at a first speed; a second step of etching the metal polycrystalline film on the peripheral portion of the substrate by moving the nozzle beyond the peripheral portion of the substrate at a second speed slower than the first speed to a predetermined position on the central portion of the substrate while rotating the substrate and discharging an etching solution from the nozzle; a third step of supplying a rinse liquid to a central portion of the substrate relative to a supply position of the etching liquid in the second step while rotating the substrate, thereby washing away etching residues generated in the second step with the rinse liquid; a fourth step of drying the substrate after the third step.

12. a first step of supplying an etching solution to a first position on a peripheral edge of a substrate while rotating the substrate having a metal polycrystalline film formed on its surface, thereby etching the metal polycrystalline film at the first position; a second step of supplying an etching solution to a second position on the peripheral edge portion that is closer to the center of the substrate than the first position while rotating the substrate, thereby etching the metal polycrystalline film at the second position; a third step of supplying a rinse liquid to a center side of the substrate relative to the second position while rotating the substrate, thereby washing away etching residues generated in the second step with the rinse liquid; a fourth step of drying the substrate after the third step.

13. a first step of supplying an etching solution to a peripheral portion of a substrate having a metal polycrystalline film formed on a surface thereof while rotating the substrate at a first rotation speed, thereby etching the metal polycrystalline film at the peripheral portion; a second step of changing the rotation speed of the substrate to a second rotation speed that is lower than the first rotation speed while the etching liquid is still being supplied to the peripheral edge portion of the substrate; a third step of supplying a rinse liquid to a central portion of the substrate relative to the supply positions of the etching liquid in the first step and the second step while rotating the substrate, thereby washing away etching residues generated in the first step and the second step with the rinse liquid; a fourth step of drying the substrate after the third step.

14. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process for partially etching the metal polycrystalline film in the thickness direction at the peripheral edge portion of the substrate by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a second process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the first process, thereby washing away etching residues generated in the first process with the rinse liquid; a third process of etching the remaining portion of the metal polycrystalline film at the peripheral edge portion by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a fourth process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the third process, thereby washing away etching residues generated in the third process with the rinse liquid; and a fifth process of controlling the rotation holding unit to hold and rotate the substrate, and drying the substrate. the second process includes starting to supply a rinse liquid during the supply of the etching liquid in the first process; the second process or the fourth process includes discharging a rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate.

15. When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from the nozzle of the rinse liquid supply unit on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle:

15. The apparatus according to claim 14, wherein the second process or the fourth process includes discharging the rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from outside the substrate toward a center of the substrate beyond the periphery of the substrate, and increasing the discharge angle after the nozzle has passed the periphery of the substrate.

16. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process for partially etching the metal polycrystalline film in the thickness direction at the peripheral edge portion of the substrate by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a second process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the first process, thereby washing away etching residues generated in the first process with the rinse liquid; a third process of etching the remaining portion of the metal polycrystalline film at the peripheral edge portion by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a fourth process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the third process, thereby washing away etching residues generated in the third process with the rinse liquid; and a fifth process of controlling the rotation holding unit to hold and rotate the substrate, and drying the substrate. the second process includes starting to supply a rinse liquid during the supply of the etching liquid in the first process; When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from the nozzle of the rinse liquid supply unit on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle: the second process or the fourth process includes discharging a rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from outside the substrate to beyond the periphery of the substrate toward the center of the substrate, and increasing the discharge angle after the nozzle has passed the periphery of the substrate.

17. 17. The apparatus according to claim 14, wherein the fourth process includes starting to supply a rinse liquid while the etching liquid is being supplied in the third process.

18. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process for partially etching the metal polycrystalline film in the thickness direction at the peripheral edge portion of the substrate by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a second process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the first process, thereby washing away etching residues generated in the first process with the rinse liquid; a third process of etching the remaining portion of the metal polycrystalline film at the peripheral edge portion by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a fourth process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the third process, thereby washing away etching residues generated in the third process with the rinse liquid; and a fifth process of controlling the rotation holding unit to hold and rotate the substrate, and drying the substrate. the fourth process includes starting to supply a rinse liquid during the supply of the etching liquid in the third process; the second process or the fourth process includes discharging a rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate.

19. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process for partially etching the metal polycrystalline film in the thickness direction at the peripheral edge portion of the substrate by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a second process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the first process, thereby washing away etching residues generated in the first process with the rinse liquid; a third process of etching the remaining portion of the metal polycrystalline film at the peripheral edge portion by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold and rotate the substrate; a fourth process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the third process, thereby washing away etching residues generated in the third process with the rinse liquid; and a fifth process of controlling the rotation holding unit to hold and rotate the substrate, and drying the substrate. the fourth process includes starting to supply a rinse liquid during the supply of the etching liquid in the third process; When viewed from above, the angle of a streamline of the rinse liquid connecting a landing point of the rinse liquid discharged from the nozzle of the rinse liquid supply unit on the substrate and a discharge outlet of the nozzle with respect to a reference line connecting the landing point of the rinse liquid on the substrate and the center of the substrate is defined as the discharge angle of the rinse liquid from the nozzle: the second process or the fourth process includes discharging a rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from outside the substrate to beyond the periphery of the substrate toward the center of the substrate, and increasing the discharge angle after the nozzle has passed the periphery of the substrate.

20. 20. The apparatus according to claim 19, wherein the second process or the fourth process includes: discharging a rinse liquid from a nozzle of the rinse liquid supply unit, moving the nozzle from the outside of the substrate past the periphery of the substrate toward the center of the substrate, and increasing a flow rate of the rinse liquid discharged from the nozzle after the nozzle has passed the periphery of the substrate.

21. further comprising an imaging unit configured to image the peripheral edge portion; The control unit a seventh process of controlling the imaging unit to image the peripheral edge portion while the etching liquid is being supplied to the substrate; and an eighth process of determining whether or not etching residue has occurred in the peripheral portion based on a change in contrast of the captured image captured by the imaging unit.

22. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process of controlling the rotation holding unit to hold and rotate the substrate, and controlling the chemical solution supply unit to move the nozzle at a first speed from the outside of the substrate beyond the periphery of the substrate toward the center of the substrate while discharging an etching solution from the nozzle of the chemical solution supply unit, thereby etching the metal polycrystalline film on the periphery of the substrate; a second process in which the rotation holding unit is controlled to hold and rotate the substrate, and the chemical solution supply unit is controlled to move the nozzle beyond the periphery of the substrate to a predetermined position on the central side of the substrate at a second speed slower than the first speed while discharging an etching solution from the nozzle, thereby etching the metal polycrystalline film on the periphery of the substrate; a third process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid was supplied in the second process, thereby washing away etching residues generated in the second process with the rinse liquid; and a fourth process of drying the substrate by controlling the rotation holding unit to hold and rotate the substrate.

23. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process of controlling the chemical solution supply unit to supply an etching solution to a first position on a peripheral edge of the substrate while controlling the rotation holding unit to hold and rotate the substrate, thereby etching the metal polycrystalline film at the first position; a second process in which the chemical solution supply unit is controlled to supply an etching solution to a second position on the peripheral edge portion that is closer to the center of the substrate than the first position, while controlling the rotation holding unit to hold and rotate the substrate, thereby etching the metal polycrystalline film at the second position; a third process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a center side of the substrate relative to the second position, thereby washing away etching residues generated in the second process with the rinse liquid; and a fourth process of drying the substrate by controlling the rotation holding unit to hold and rotate the substrate.

24. a rotary holder configured to hold and rotate a substrate having a metal polycrystalline film formed on its surface; a chemical solution supply unit configured to supply an etching solution to the surface of the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the surface of the substrate; a control unit; The control unit a first process of etching the metal polycrystalline film on the peripheral edge portion by controlling the chemical solution supply unit to supply an etching solution to the peripheral edge portion of the substrate while controlling the rotation holding unit to hold the substrate and rotate it at a first rotation speed; a second process of controlling the rotation holding unit to change the rotation speed of the substrate to a second rotation speed lower than the first rotation speed, while controlling the chemical solution supply unit to continuously supply the etching solution to the peripheral edge portion of the substrate; a third process in which the rotation holding unit is controlled to hold and rotate the substrate, and the rinse liquid supply unit is controlled to supply a rinse liquid to a central portion of the substrate closer to a position where the etching liquid is supplied in the first process and the second process, thereby washing away etching residues generated in the first process and the second process with the rinse liquid; and a fourth process of drying the substrate by controlling the rotation holding unit to hold and rotate the substrate.

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