JP2017098367A - Substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique capable of preventing occurrence of metal contamination due to a coating film when forming the coating film containing a metal on a surface of a substrate.SOLUTION: A step for forming a coating film containing a metal on a surface of a substrate, a step for supplying a removal liquid of the coating film along a periphery of the substrate to remove the coating film on a peripheral edge section of the substrate and a step for supplying a removal liquid of the metal along the periphery of the substrate are successively performed, so that the metal remaining on the peripheral edge section of the substrate is removed and occurrence of metal contamination is prevented.SELECTED DRAWING: Figure 18

Description

  The present invention relates to a substrate processing method for forming a coating film on a surface of a substrate.

  In the manufacturing process of a semiconductor device, various chemicals such as a resist are applied to the surface of a semiconductor wafer (hereinafter referred to as a wafer), which is a substrate, to form a coating film. In recent years, with the miniaturization of wiring of semiconductor devices, for example, a technique such as multi-patterning in which formation of a resist pattern on the lower layer film, which is the coating film, and etching of the lower layer film are repeated a plurality of times is used. Therefore, the manufacturing process of the semiconductor device is complicated. As the manufacturing process becomes complicated, for example, for the purpose of improving the etching selectivity, it has been studied to apply a chemical solution containing a metal to the wafer to form the lower layer film.

  Further, for example, the resist pattern has a high resolution when exposed using extreme ultraviolet rays (EUV) and has high etching resistance. Therefore, a resist film is formed using a resist containing an inorganic metal. It is being considered. In addition, in order to increase the sensitivity of exposure by generating more secondary electrons during exposure, it has been studied to include a metal in an organic resist. Thus, it has been studied to form a coating film by applying various chemical solutions (coating solutions) containing metal. After the coating film is formed, the coating film solvent is supplied to the peripheral edge of the wafer, whereby the peripheral edge of the unnecessary coating film is removed in a ring shape.

  By the way, the adhesion of metal to an unplanned part of the wafer in the manufacturing process of the semiconductor device greatly affects the electrical characteristics of the semiconductor device. Therefore, it is strictly controlled so that such metal adhesion does not occur. However, the metal constituting the coating film may remain on the ground of the coating film after the peripheral portion of the coating film is removed as described above. Then, when the peripheral portion of the wafer in which the metal remains in such a manner comes into contact with a wafer processing apparatus such as an exposure apparatus or an etching apparatus or a wafer transport mechanism, the wafer is placed behind the wafer via the processing apparatus or the transport mechanism. There is also a possibility that the wafer to be transferred and processed is also contaminated with metal, that is, cross contamination occurs.

  For example, Patent Document 1 describes a resist containing the above metal. However, there is no description about a method for solving the above-described problem concerning the metal remaining on the wafer. Patent Document 2 describes a technique for removing a peripheral portion of a metal film such as a copper film formed on the surface of a substrate, but does not describe a technique for solving the problem with the coating film. .

JP2015-75500A JP 2007-318016 A

  The present invention has been made based on such circumstances, and its purpose is to provide a technique capable of preventing the occurrence of metal contamination due to the coating film in forming a coating film containing metal on the surface of the substrate. Is to provide.

The substrate processing method of the present invention includes a step of forming a coating film containing a metal on the surface of a substrate,
Next, in order to remove the coating film on the peripheral edge of the substrate, supplying a coating liquid removal liquid along the circumference of the substrate;
Thereafter, in order to remove the metal remaining on the peripheral edge of the substrate, supplying a metal removing solution along the circumference of the substrate;
including.

Another substrate processing method of the present invention supplies a coating solution containing a metal to the central portion of the surface of the substrate, and spreads the coating solution toward the peripheral portion of the substrate by centrifugal force. Rotating the
Before the coating liquid reaches the peripheral edge of the substrate, the coating liquid is dried on the inner side of the peripheral edge of the substrate until the coating film containing the metal is formed. Supplying an adhesion preventing liquid for preventing the adhesion of the metal to the peripheral edge;
It is characterized by including.

According to the present invention, since the metal removal liquid is supplied to the peripheral portion of the substrate after the metal-containing coating film is removed, the peripheral portion of the substrate comes into contact with the transport mechanism and the processing apparatus of the substrate. The occurrence of metal contamination due to this can be suppressed.
According to another aspect of the present invention, the peripheral portion of the substrate that rotates until the coating liquid containing metal reaches the peripheral portion of the substrate and the coating solution is dried to form a coating film. Since the metal adhesion preventing liquid is supplied to the metal, the occurrence of the metal contamination can be suppressed.

2 is a plan view of the coating and developing apparatus. FIG. It is a perspective view of the coating and developing apparatus. It is a schematic longitudinal side view of the coating and developing apparatus. It is a vertical side view of a resist film forming module provided in the coating and developing apparatus. It is a vertical side view of the said resist film formation module. It is a top view of the said resist film formation module. It is a vertical side view of the wafer for showing the discharge position of the processing liquid. It is a schematic perspective view of the wafer for showing the process process in the said application | coating and developing apparatus which concerns on 1st Embodiment. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of a wafer for showing a field to which processing liquid concerning a 2nd embodiment is supplied. It is a vertical side view of the wafer for showing the processing process in a 2nd embodiment. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a schematic perspective view of the wafer for showing the processing process concerning a 3rd embodiment. It is a schematic perspective view of the wafer for showing the processing process. It is a schematic perspective view of the wafer for showing the processing process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process. It is a vertical side view of the wafer for showing the said process process.

(First embodiment)
A coating and developing apparatus 1 for carrying out the first embodiment of the substrate processing method of the present invention will be described with reference to FIGS. 1, 2, and 3 are a plan view, a perspective view, and a schematic longitudinal side view of the coating and developing apparatus 1, respectively. The coating and developing device 1 is configured by connecting a carrier block D1, a processing block D2, and an interface block D3 in a straight line in this order in the horizontal direction. Further, the exposure apparatus D4 is connected to the interface block D3 on the side opposite to the processing block D2. In the following description, the arrangement direction of the blocks D1 to D3 is the front-rear direction, the block D1 side is the front side, and the block D3 side is the rear side.

  The coating and developing apparatus 1 applies a chemical solution (coating solution) containing metal to the surface of a wafer W that is a substrate to form an antireflection film that serves as a hard mask during etching. Further, a resist which is a chemical solution (coating liquid) containing a metal is applied to the surface of the wafer W so as to be laminated on the antireflection film, a resist film is formed, and the resist film exposed in the exposure apparatus D4 Is developed to form a pattern. In addition, the chemical | medical solution containing a metal does not mean that the metal is mixed in the chemical | medical solution as an impurity, but means that the chemical | medical solution contains a metal as a main component or a subcomponent. The wafer W is, for example, a circle having a diameter of 300 mm. On the front side and the back side, inclined surfaces that rise and fall toward the peripheral edge of the wafer W, so-called bevels, are perpendicular peripheral end surfaces (side peripheral surfaces). It is formed to be continuous.

  Hereinafter, each block D of the coating and developing apparatus 1 will be described. The carrier block D <b> 1 applies a carrier C in which a plurality of wafers W are stored, and carries it in / out of the developing device 1. The carrier block D <b> 1 includes a mounting table 11 for the carrier C, an opening / closing unit 12, and a transfer mechanism 13 for transferring the wafer W from the carrier C via the opening / closing unit 12.

  The processing block D2 is configured by laminating first to sixth unit blocks E1 to E6 for performing liquid processing on the wafer W in order from the bottom. E1 and E2 are the same unit blocks, E3 and E4 are the same unit blocks, and E5 and E6 are the same unit blocks. In the same unit block, the wafer W is transferred and processed in parallel with each other.

  Here, the unit block E3 as a representative of the unit blocks will be described with reference to FIG. In the unit block E3, a transfer area 14 for the wafer W is formed in the front-rear direction. When viewed from the front to the rear, a plurality of shelf units U are arranged in the front-rear direction on the left side of the transfer region 14, and two resist film forming modules 3 are arranged side by side in the front-rear direction on the right side. The resist film forming module 3 applies the resist to the wafer W to form a resist film on the entire surface of the wafer W, and then supplies a solvent for the resist to the peripheral portion of the wafer W to remove unnecessary resist. Remove the membrane. Further, the resist film forming module 3 supplies a metal removing solution for removing the metal constituting the resist remaining on the peripheral portion of the wafer W from which the resist film has been removed. A cleaning liquid to be removed from the peripheral edge of W is supplied. The detailed configuration of the resist film forming module 3 will be described later.

  The shelf unit U includes a heating module 15 that heats the wafer W. The transfer area 14 is provided with a transfer arm F3 which is a transfer mechanism of the wafer W, and the wafer W is transferred between the modules of the unit block E3.

  The difference between the unit blocks E1, E2, E5, and E6 from the unit blocks E3 and E4 will be described. The unit blocks E1 and E2 are replaced with the antireflection film forming module instead of the resist film forming module 3 and the back surface cleaning module 20. The antireflection film forming module 16 supplies the chemical solution for forming the antireflection film to the wafer W to form the above antireflection film. The antireflection film forming module 16 is configured in the same manner as the resist film forming module 3 except that the chemicals supplied to the wafer W are different. The unit blocks E5 and E6 include a developing module 17 instead of the resist film forming module 3 and the back surface cleaning module 20. The developing module 17 supplies a developing solution to the resist film exposed by the exposure apparatus D4 and develops it to form a resist pattern. Except for such a difference, the unit blocks E1 to E6 are configured in the same manner. In FIG. 3, the transfer arms of the unit blocks E1, E2, and E4 to E6 corresponding to the transfer arm F3 are shown as F1, F2, and F4 to F6, respectively.

  On the carrier block D1 side in the processing block D2, there are provided a tower T1 extending up and down across the unit blocks E1 to E6, and a transport mechanism 18 capable of moving up and down for delivering the wafer W to the tower T1. ing. The tower T1 is composed of a plurality of modules stacked on each other, and the module provided at each height of the unit blocks E1 to E6 is a wafer W between the transfer arms F1 to F6 of the unit blocks E1 to E6. Can be handed over. As these modules, a delivery module TRS provided at the height position of each unit block, a temperature control module CPL for adjusting the temperature of the wafer W, a buffer module for temporarily storing a plurality of wafers W, and a wafer W A hydrophobizing module for hydrophobizing the surface of the surface is included. In order to simplify the description, the hydrophobic treatment module, the temperature control module, and the buffer module are not shown.

  The interface block D3 includes towers T2, T3, and T4 extending up and down across the unit blocks E1 to E6. The interface block D3 is a transport mechanism that can move up and down to transfer the wafer W to and from the tower T2 and the tower T3. Transfer of the wafer W between the interface arm 22, which is a transfer mechanism that can be moved up and down, and the tower T2 and the exposure apparatus D4 to transfer the wafer W to and from the interface arm 21, the tower T2 and the tower T4. An interface arm 23 is provided as a transport mechanism for performing the operation.

  The tower T2 includes a delivery module TRS, a buffer module for storing and retaining a plurality of wafers W before exposure processing, a buffer module for storing a plurality of wafers W after exposure processing, and a temperature for adjusting the temperature of the wafers W. Although the adjustment module and the like are stacked on each other, illustration of the buffer module and the temperature adjustment module is omitted here. In the tower T3, a back surface cleaning module 20 is provided, and pure water is supplied as a cleaning liquid to the back surface of the wafer W by the cleaning liquid supply unit, and the back surface is rubbed with a brush so as to remove the attached foreign matter. . In addition, although the module is provided also in tower T4, description is abbreviate | omitted about this module.

  Next, the resist film forming module 3 will be described with reference to the longitudinal sectional side views of FIGS. 4 and 5 and the transverse plan view of FIG. 4 and 5 show states in which a movable cup 40 that can be moved up and down, which will be described later, is located at the raised position and the lowered position, respectively. In the figure, reference numeral 31 denotes a spin chuck that is a rotation holding unit that sucks the central portion of the back surface of the wafer W to hold the wafer W horizontally, and includes a rotation driving unit 32 including a rotation motor via a vertical shaft portion 31A. It is connected to the. The rotation drive unit 32 rotates the spin chuck 31 around the vertical axis. In the figure, reference numeral 33 denotes three support pins that can be moved up and down (however, only two are shown in FIGS. 4 and 5), which supports the back surface of the wafer W, and includes the transfer arms F3 and F4, the spin chuck 31, and the like. The wafer W is delivered between the two.

  In the drawing, 34 is a circular cup, which is provided so as to surround the side of the wafer W held by the spin chuck 31, and its upper end protrudes inward to form a protrusion 34A. On the bottom wall of the cup 34, standing partition walls 35A and 35B are provided concentrically in a plan view toward the outside of the cup 34 in this order. Then, three annular recesses 36A, 36B, 36C are formed concentrically in this order toward the outside of the cup 34 by the partition walls 35A, 35B and the side wall of the cup 34, and the recesses 36A, 36B. , 36C have an exhaust port 37A, a drain port 37B, and a drain port 37C, respectively.

  On the partition wall 35A, a circular ring plate 38 is provided horizontally through the shaft portion 31A. The ring plate 38 is configured in a vertical cross-sectional view mountain shape in which the top is located below the wafer W so that the liquid spilled from the wafer W can be guided toward the peripheral end of the ring plate 38. The peripheral end portion of the plate 38 is drawn downward and formed so as to enter the recess 36B. On the ring plate 38, backside nozzles 39 </ b> A to 39 </ b> D that discharge each processing liquid to the peripheral edge of the backside of the wafer W are provided. These rear surface side nozzles 39A to 39D are arranged along the circumferential direction of the cup 34 as shown in FIG. 6, for example, but in FIGS. .

  The back side nozzles 39A, 39B, 39C, and 39D are connected to the resist solvent supply source 30A, the SC2 supply source 30B, the SPM supply source 30C, and the pure water supply source 30D, respectively. The processing liquid supplied from the supply source is discharged obliquely upward and outward of the wafer W. Supply source 30A-30D is provided with the pump which pumps the stored processing liquid to nozzle 39A-30D while storing each processing liquid. Further, the supply sources 30B and 30C are configured such that the stored SC2 and SPM can be adjusted to a temperature of 20 ° C. to 90 ° C., and the temperature-adjusted SC2 and SPM are discharged from the nozzles 39B and 39C, respectively. .

  The back surface side nozzle 39A removes the resist adhering to the back surface of the wafer W by discharging a solvent of the resist. The back side nozzles 39B and 39C remove the metal constituting the resist from the wafer W by discharging SC2 and SPM, respectively, as metal removal solutions. The back-side nozzle 39D discharges pure water, which is a cleaning liquid, to wash away and remove SC2 and SPM that have been supplied to the wafer W and adhered thereto. Here, SC2, SPM, and resist solvent will be described. SC2 is a mixed solution of hydrochloric acid, hydrogen peroxide solution, and water, and SPM is a mixed solution of sulfuric acid, hydrogen peroxide solution, and water. . Therefore, SC2 and SPM are inorganic solvents. The resist solvent is, for example, an organic solvent such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, gamma butyl lactone, ethyl lactate.

  In order to discharge the waste liquid of the inorganic solvent and the waste liquid of the organic solvent out of the cup 34 according to the request of the factory where the coating and developing apparatus 1 is installed, two separate drainage paths are provided in the cup 34. A movable cup 40 is provided for forming the. The movable cup 40 is composed of an upper inclined ring plate 41 and a lower inclined ring plate 42 that are circular in plan view and are provided so as to surround the wafer W placed on the spin chuck 31 with an interval in the vertical direction. The upper inclined ring plate 41 and the lower inclined ring plate 42 are inclined so that the opening diameter becomes smaller toward the upper side. The lower inclined ring plate 42 is bent halfway downward, and the lower end portion thereof constitutes a cylindrical portion 43 formed so as to extend in the vertical direction, and the inner peripheral surface of the cylindrical portion 43 has a circumferential direction. A ring-shaped protrusion 43A is provided along the line. In the figure, reference numeral 40A denotes an elevating mechanism that elevates and lowers the inclined ring plates 41 and 42 between the raised position and the lowered position.

  As shown in FIG. 4, when the movable cup 40 is located at the raised position, the upper end of the upper inclined ring plate 41 and the protruding portion 34A of the cup 34 are close to each other, and the lower surface of the inner peripheral edge of the lower inclined ring plate 42 is The wafer W is positioned above the surface of the wafer W so as to receive the processing liquid scattered from the wafer W. Further, the protrusion 43A of the cylindrical portion 43 is located above the partition wall 35B. As shown in FIG. 5, when the movable cup 40 is in the lowered position, the cylindrical portion 43 is located in the recess 36C, and the protrusion 43A is close to the outer peripheral surface of the partition wall 35B. Further, the upper end of the upper inclined ring plate 41 is located at the same or substantially the same height as the surface of the wafer W.

  44A, 44B, 44C and 44D are front side nozzles connected to a resist solvent supply source 45A, an SC2 supply source 45B, an SPM supply source 45C and a pure water supply source 45D, respectively. The processing liquid supplied from each of the supply sources 45A to 45D is discharged obliquely downward and outward of W. The supply sources 45A to 45D are configured in the same manner as the supply sources 30A to 30D. Therefore, the temperature-adjusted SC2 and SPM can be discharged from the nozzles 44B and 44C. In the figure, 46 is a resist supply nozzle, which discharges a resist containing metal vertically downward. The resist supply nozzle 46 is connected to a resist supply source 46A. The resist supply source 46A is configured in the same manner as the supply sources 45A to 45D except that the resist is stored.

  The front side nozzle 44 </ b> A removes an unnecessary resist film by discharging a solvent to the peripheral portion of the surface of the wafer W. The front surface side nozzles 44B and 44C remove the metal contained in the resist film from the wafer W by discharging SC2 and SPM, similarly to the back surface side nozzles 39B and 39C. The front side nozzle 44D removes SC2 and SPM from the wafer W by discharging pure water in the same manner as the back side nozzle 39D.

  The resist supply nozzle 46 is connected to a drive mechanism 47B via a nozzle arm 47A shown in FIG. The drive mechanism 47B allows the resist supply nozzle 46 to move up and down and move in the horizontal direction, and can move between the standby area outside the cup 34 and the center of the wafer W. The front side nozzles 44A to 44D are connected to the drive mechanism 48B via the nozzle arm 48A. By the drive mechanism 48B, the surface side nozzles 44A to 44D are configured to be movable up and down and movable in the horizontal direction, and move between a standby area outside the cup 34 and the peripheral portion of the wafer W, as will be described later. Each of the processing liquids can be discharged to the discharge position set in (1). In the figure, 47C and 48C are guides for horizontal movement of the drive mechanisms 47B and 47C.

  An air supply unit (not shown) is provided above the cup 34 to supply air downward. The supply of air and the exhaust from the exhaust port 37A of the cup 34 are always performed, for example, during the operation of the module 3, and the air supplied from the air supply unit forms a downward air flow toward the cup 34, and The air is exhausted from the exhaust port 37A. The solid arrows in FIGS. 4 and 5 indicate the main flow of air in the cup 34.

  When the movable cup 40 is located at the raised position, the air supplied from above the cup 34 to the surface of the wafer W flows into a space formed relatively large between the ring plate 38 and the lower surface of the lower inclined ring plate 42. The projection 43C is guided between the outer peripheral surface of the ring plate 38 and the inner peripheral surface of the partition wall 35A and is introduced into the concave portion 36B, while flowing into the concave portion 36C outside the concave portion 36B. It is suppressed. The air that has flowed into the recess 36B passes over the partition wall 35A and flows into the exhaust port 37A of the recess 36A to be exhausted. When the movable cup 40 is located at the lowered position, the air supplied from the top of the cup 34 to the surface of the wafer W is a relatively large space between the protrusion 34A of the cup 34 and the upper surface of the upper inclined ring plate 41. And flows between the outer peripheral surface of the cylindrical portion 43 of the lower inclined ring plate 42 and the inner peripheral surface of the side wall of the cup 34 and flows into the recess 36C. And it goes over partition wall 35B, 35A in order, flows into exhaust port 37A, and is exhausted.

  When the solvent and the resist are respectively discharged from the resist supply nozzle 46, the front surface side nozzle 44A, and the back surface side nozzle 39A, the movable cup 40 is disposed at the raised position, and these liquids scattered from the wafer W are discharged from the recess 36B. Guided by the liquid port 37B. The flow of the liquid in the cup 34 is indicated by a dotted arrow in FIG. More specifically, when the movable cup 40 is disposed at the raised position, the liquid scatters between the ring plate 38 and the lower surface of the lower inclined ring plate 42 and is pushed away by the air flow. It is introduced into the recess 36B and is discharged out of the cup 34 through the drainage port 37B.

  Further, when SC2, SPM, and pure water are respectively supplied from the front surface side nozzles 44A, 44C, 44D and the back surface side nozzles 39B, 39C, 39D, the movable cup 40 is disposed at the lowered position, and those scattered from the wafer W are scattered. The liquid is guided to the drainage port 37C of the recess 36C. The flow of the liquid in the cup 34 is indicated by a dotted arrow in FIG. More specifically, when the movable cup 40 is disposed at the lowered position, the liquid flows between the protrusion 34A of the cup 34 and the upper surface of the upper inclined ring plate 41, and the lower inclined ring plate 42 and the upper inclined surface. It is scattered between the ring plate 41 and introduced between the inner peripheral surface of the side wall of the cup 34 and the outer peripheral surface of the cylindrical portion 43. Then, the air is forced into the air flow, introduced into the recess 36C, and discharged out of the cup 34 through the drainage port 37C.

  Next, the discharge position of each processing liquid discharged from the front surface side nozzles 44A to 44D and the back surface side nozzles 39A to 39D will be described with reference to FIG. Here, the discharge position is assumed to be an end portion near the center of the wafer W in a region where the processing liquid is discharged from each nozzle to the wafer W. In other words, the wafer W is directed to the discharge direction of the discharge port of each nozzle. This is an end portion near the center of the wafer W in the projection area. In FIG. 7, the resist film is shown as 4A.

  In the figure, A1 is a solvent discharge position from the surface side nozzle 44A, and a distance A2 between the discharge position A1 and the side end face of the wafer W is, for example, 1.0 mm to 5.0 mm. In the figure, A3 is the SC2 and SPM discharge positions from the surface side nozzles 44B and 44C. If the distance between the discharge position A3 and the side end surface of the wafer W is A4, then distance A2> distance A4. That is, SC2 and SPM are supplied to a position (first position) closer to the outside of the wafer W than the peripheral edge of the resist film 4A from which the peripheral edge has been removed by the solvent on the surface of the wafer W. The pure water discharge position from the front side nozzle 44D is closer to the center of the wafer W than the discharge position A3 and coincides with the discharge position A1 or is closer to the peripheral edge of the wafer W than the discharge position A1. (Second position).

  In the figure, B1 is a solvent discharge position from the back side nozzle 39A, and the distance between this discharge position B1 and the side end face of the wafer W is B2. In the drawing, B3 is the SC2 and SPM discharge positions from the back side nozzles 39B and 39C. If the distance between the discharge position B3 and the side end surface of the wafer W is B4, the distance B2> the distance B4. Further, the discharge position from the back side nozzle 39D is closer to the center of the wafer W than the discharge position B3. As described above, the settable ranges of the distances A4 and B4 are determined by the distances A2 and B2. Specifically, for example, the distances A4 and B4 are 1.0 mm or more. The reason why the discharge position of each processing liquid is set in this way will be described later together with the processing procedure for the wafer W in the resist film forming module 3. The front side nozzles 44A to 44D and the back side nozzles 39A to 39D are described above in order to reliably suppress the processing liquid supplied to the discharge position set in this way from moving toward the center of the wafer W. As described above, the processing liquid is discharged in the oblique direction outside the wafer W, but the processing liquid may be discharged in the vertical direction.

  Next, the control unit 100 provided in the coating and developing apparatus 1 shown in FIG. 1 will be described. The control unit 100 is formed of a computer, for example, and has a program storage unit (not shown). In the program storage unit, instructions (step groups) are provided so that processing of the wafer W in each module, transfer of the wafer W between the modules by each transfer mechanism, and determination based on the above-described image data can be performed. ) Is stored. Then, the control unit 100 outputs a control signal to each part of the coating / developing apparatus 1 by the program, thereby controlling the operation of each part of the coating / developing apparatus 1. This program is stored in the program storage unit while being stored in a storage medium such as a hard disk, a compact disk, a magnetic optical disk, or a memory card.

  The conveyance path and processing of the wafer W in the system composed of the coating, developing apparatus 1 and exposure apparatus D4 will be described. In the following description, refer to FIGS. 8 to 14 which are schematic perspective views showing the surface state of the wafer W and the operation of each nozzle in the resist film forming module 3 and FIGS. 15 to 21 which are longitudinal side views of the wafer W. To explain. For convenience of illustration, in FIGS. 10 to 14, the surface of the resist film 4A is hatched. Therefore, the hatching does not indicate a cross section. Further, the surface side nozzles 44A to 44D are configured to discharge the processing liquid obliquely toward the lower outside of the wafer W as described above, but in order to make the drawings easier to see in FIGS. The processing liquid is shown to be discharged vertically downward.

  First, the wafer W is transferred from the carrier C by the transfer mechanism 13 to the transfer module TRS0 of the tower T1 in the processing block D2. The wafer W is transferred from the delivery module TRS0 to the unit blocks E1 and E2 and transferred. For example, when the wafer W is transferred to the unit block E1, among the transfer modules TRS of the tower T1, the transfer module TRS1 corresponding to the unit block E1 (the transfer module capable of transferring the wafer W by the transfer arm F1). The wafer W is transferred from the TRS0. When the wafer W is transferred to the unit block E2, the wafer W is transferred from the TRS0 to the transfer module TRS2 corresponding to the unit block E2 among the transfer modules TRS of the tower T1. The transfer of these wafers W is performed by the transfer mechanism 18.

  The wafer W thus distributed is transferred from TRS1 (TRS2) to the antireflection film forming module 16 to form an antireflection film. Since this antireflection film forming process is the same as the resist film forming process described later, detailed description thereof is omitted. The wafer W after the formation of the antireflection film is transferred to the heating module 15 and then transferred to TRS1 (TRS2). Subsequently, the transfer mechanism 18 corresponds to the transfer module TRS3 corresponding to the unit block E3 and the unit block E4. It is distributed to the delivery module TRS4.

  The wafer W thus distributed to TRS3 and TRS4 is transferred from TRS3 (TRS4) to the resist film forming module 3 and placed on the spin chuck 31 (FIGS. 8 and 15). Then, the wafer W is rotated at a predetermined rotational speed, the resist is discharged from the resist supply nozzle 46 to the center of the wafer W (FIG. 9), and the resist is expanded toward the peripheral edge of the wafer W by centrifugal force. Spin coating is performed, and the entire surface of the wafer W is coated with the resist. Then, the resist is dried to form a resist film 4A (FIG. 16).

  Thereafter, while the rotation of the wafer W is continued, the solvent is transferred from the front surface side nozzle 44A and the back surface side nozzle 39A to the front surface discharge position A1 and the back surface discharge position B1 at the peripheral edge of the wafer W described in FIG. Each is discharged. The discharged solvent spreads from the discharge positions A1 and B1 toward the peripheral edge of the wafer W due to centrifugal force, wraps around the peripheral edge surface of the wafer W to form the liquid film 51, and is then shaken off and removed from the wafer W. Is done. By this resist solvent liquid film 51, the unnecessary resist film 4 </ b> A at the peripheral edge of the surface of the wafer W is removed over the entire circumference of the wafer W. Further, when the resist goes from the front surface of the wafer W to the peripheral end surface and the back surface, the resist film 4A formed on the peripheral end surface and the back surface is also removed (FIGS. 10 and 17). In the wafer W, the metal 50 constituting the resist film 4A remains in the region where the resist film 4A is thus removed.

  After the discharge of the solvent from the front-side nozzle 44A and the back-side nozzle 39A is stopped, the front-side nozzle 44B and the back-side nozzle 39B to the front-side discharge position A3 of the wafer W described in FIG. SC2 is discharged to B3, respectively. The SC2 thus discharged spreads toward the peripheral edge of the wafer W due to centrifugal force, wraps around the peripheral edge surface from the front and back surfaces of the wafer W to form the liquid film 52, and is then shaken off to be exposed to the wafer W. Removed from. The metal film 50 remaining on the wafer W is removed by the liquid film 52 of SC2 (FIGS. 11 and 18). Since the SC2 ejection position A3 on the surface of the wafer W is closer to the peripheral edge of the wafer W than the peripheral edge of the resist film 4A, the liquid film 52 does not contact the resist film 4A. Therefore, it is possible to prevent the metal contained in the resist film 4A from being dissolved by the SC2 and deteriorating the resist film.

  After the metal 50 is removed by the liquid film 52 over the entire circumference of the wafer W, the SC2 discharge from the front side nozzle 44B and the back side nozzle 39B is stopped, and the front side nozzle 44C and the back side nozzle 39C are stopped. SPM is discharged to a discharge position A3 on the front surface of the wafer W and a discharge position B3 on the back surface of the wafer W, respectively. The discharged SPM forms a liquid film 53 at the same position as the position where the liquid film 52 of SC2 is formed, and the metal 50 remaining on the wafer W is further removed (FIGS. 12 and 19). Since the SPM liquid film 53 does not contact the resist film 4A, the resist film 4A can be prevented from being altered by the SPM.

  After the removal of the metal 50 by the liquid film 53 over the entire circumference of the wafer W, the discharge of SPM from the front surface side nozzle 44C and the back surface side nozzle 39C is stopped, and from the front surface side nozzle 44D and the back surface side nozzle 39D. Pure water is discharged onto the front and back surfaces of the wafer W, respectively. The discharged pure water spreads toward the peripheral edge of the wafer W by centrifugal force, and circulates from the front surface and the back surface of the wafer W to the peripheral end surface to form a liquid film 54, which is shaken off from the peripheral end surface and removed. Is done. The wafer W is cleaned by the liquid film 54, and SC2 and SPM remaining on the wafer W are removed.

  As described with reference to FIG. 7, the pure water discharge position on the surface of the wafer W is closer to the center of the wafer W than the SC2 and SPM discharge positions A3 and outside the resist film 4A. On the back surface of the wafer W, the pure water discharge position is closer to the center of the wafer W than the SC2 and SPM discharge positions B3. Accordingly, the pure water is supplied to the front and back surfaces of the wafer W including the area where SC2 and SPM are supplied and wider than the area, so that SC2 and SPM are surely removed from the wafer W.

  Thereafter, the discharge of pure water from the front surface side nozzle 44D and the back surface side nozzle 39D is stopped, and after the pure water is shaken off from the wafer W by the rotation of the wafer W, the rotation is stopped, and the resist film forming module 3 is completed (FIGS. 14 and 21). During the processing by the resist film forming module 3 described above, the position of the movable cup 40 is switched according to the liquid used as described above.

  Thereafter, the wafer W is transferred in the order of the heating module 15 → the transfer module TRS31 (TRS41) of the tower T2. Thereafter, this wafer W is transferred to the back surface cleaning module 20 of the tower T3 by the interface arm 21 and cleaned on the back surface, and then transferred into the exposure apparatus D4 via the interface arms 21 and 23, and the resist film 4A is formed. The exposure is performed along a predetermined pattern. The exposed wafer W is transferred between the towers T2 and T4 by the interface arms 22 and 23, and transferred to the transfer modules TRS51 and TRS61 of the tower T2 corresponding to the unit blocks E5 and E6, respectively. Thereafter, the wafer W is transferred to the heating module 15 and subjected to heat treatment (post-exposure baking), and then transferred to the developing module 17 and supplied with the developer, and is exposed to the pattern exposed by the exposure device D4. Then, the resist film 4A is dissolved, and a resist pattern is formed on the wafer W. Thereafter, the wafer W is transferred to the transfer module TRS5 (TRS6) of the tower T1, and then returned to the carrier C via the transfer mechanism 13.

  According to the coating and developing apparatus 1 described above, in the resist film forming module 3 and the antireflection film forming module 16, the wafer that rotates after coating the entire surface of the wafer W with the chemical solution containing metal and coating the coating film. An unnecessary coating film is removed by supplying a solvent along the periphery of the wafer W to the peripheral edge of W, and then SC2 and SPM are applied along the periphery of the wafer W to the peripheral edge of the rotating wafer W. The metal remaining on the periphery of the wafer W is removed. Therefore, it is possible to prevent the transfer mechanism and module of the wafer W provided in the coating and developing apparatus 1 and the exposure apparatus D4 from coming into contact with the metal remaining on the peripheral edge of the wafer W and being contaminated. As a result, it is possible to prevent the subsequent wafer W from coming into contact with these modules and the transport mechanism and being contaminated with metal. Accordingly, it is possible to suppress a decrease in the yield of the semiconductor device manufactured from the wafer W.

  By the way, in the resist film forming module 3 described above, even when the resist wraps around the back surface of the wafer W and the resist film 4A is formed, the resist film is removed, the metal 50 is removed, and cleaning with pure water is performed. Backside nozzles 39A to 39D are provided so as to be able to do this. Even if the number of rotations of the wafer W is set appropriately and a resist having an appropriate viscosity is used, the resist is prevented from wrapping around the back surface, and the back surface side nozzles 39A to 39D are not provided for the resist film forming module 3. Good.

(Second Embodiment)
Next, the second embodiment will be described with a focus on differences from the first embodiment. In the second embodiment, the processing in the resist film forming module 3 is different from the processing in the resist film forming module 3 in the first embodiment, and the front side nozzles 44A to 44D are not used and the back side nozzle 39A is used. The processing liquid discharged from .about.39D is passed through the peripheral end surface of the wafer W to the bevel on the surface side of the wafer W, and a liquid film is formed by the processing liquid to perform the processing.

  Processing in the resist film forming module 3 will be described with reference to a longitudinal side view of the peripheral edge of the wafer W in FIG. The discharge positions on the back surface of the wafer W of the back surface side nozzles 39A to 39D are the same as those in the first embodiment, for example. In the figure, C1 indicates the height of the upper end of the bevel contacting the liquid film when the resist solvent wraps around the bevel on the surface side of the wafer W as described above to form the liquid film. This corresponds to the height of the upper end of the bevel on the front side of the wafer W.

  C2 in the figure indicates the height of the upper end of the bevel contacting the liquid film when the liquid film is formed by wrapping SC2 and SPM around the bevel on the surface side of the wafer W as described above. It is located below the height C1. Accordingly, when viewed in the horizontal direction, the position corresponding to the height C2 (third position) is farther outside the wafer W than the position corresponding to the height C1 on the front-side bevel. Further, when a liquid film is formed by flowing pure water around the bevel on the surface side of the wafer W, the upper end of the area in contact with the liquid film on the bevel on the surface side of the wafer W is the same height as C1, or The height is lower than C1 and higher than C2. Such control of the area of the wafer W in contact with the processing liquid is performed by appropriately setting the flow rate of the processing liquid discharged from each nozzle and the rotation speed of the wafer W.

  Subsequently, with reference to FIGS. 23 to 27 which are longitudinal side views of the wafer W, the processing performed in the resist film forming module 3 is followed in order focusing on the differences from the processing of the first embodiment. explain. After the resist film 4A is formed as described with reference to FIGS. 9 and 16, the solvent is discharged from the back surface side nozzle 39A to the peripheral surface of the back surface of the rotating wafer W. The solvent moves the back surface of the wafer W to the peripheral edge of the wafer W by centrifugal force, and rides on the bevel on the front surface side of the wafer W through the bevel and the side end surface on the back surface to form the liquid film 61. It is shaken off from. The bevel on the surface side contacts the liquid film 61 from the lower end to the upper end (height C1 described in FIG. 22). The resist film 4A is removed by the liquid film 61, and the metal 50 remains in the region where the resist film 4A has been removed (FIG. 23).

  Thereafter, SC2 is discharged from the back surface side nozzle 39B to the peripheral surface of the back surface of the rotating wafer W. The SC 2 moves the back surface of the wafer W to the peripheral edge of the wafer W by centrifugal force, rides on the bevel on the front surface side of the wafer W through the side end surface, forms the liquid film 62, and is shaken off from the wafer W. The bevel on the surface side contacts the liquid film 62 from the lower end to the height C2 described in FIG. 22 (FIG. 24). That is, the end portion of the liquid film 62 formed by SC2 wrapping around the surface of the wafer W is positioned closer to the peripheral edge of the wafer W than the peripheral end of the resist film 4A, and the resist film 4A from the position. It is formed so as not to move to the side. That is, the metal 50 is removed by the SC2 in a state where the contact of the resist film 4A of the SC2 is prevented.

  Subsequently, SPM is discharged from the rear surface side nozzle 39C to the peripheral edge of the back surface of the rotating wafer W, and the SPM liquid film is located at the same position as the SC2 liquid film 62 is formed on the peripheral edge of the wafer W. 63 is formed (FIG. 25). Therefore, the liquid film 63 does not contact the resist film 4A. This liquid film 63 prevents the resist film 4A from being altered by SC2, and the metal 50 is further removed from the region where the resist film 4A has been removed by the solvent liquid film 61.

  Thereafter, pure water is discharged from the rear surface side nozzle 39D onto the peripheral surface of the rear surface of the rotating wafer W. As in the first embodiment, the pure water discharge position is closer to the center of the wafer W than the SC2 and SPM discharge positions. Then, the discharged pure water moves the back surface of the wafer W to the peripheral end of the wafer W by centrifugal force, rides on the bevel on the front side of the wafer W through the side end surface, and forms a liquid film 64. It is shaken off from W. As described above, the bevel on the surface side contacts the liquid film 64 from the lower end to the height C1 or a position lower than C1 and higher than C2. That is, since the pure water is supplied to the wafer W including the region where SC2 and SPM are supplied and wider than the region, the SC2 and SPM are surely removed from the wafer W. After the supply of pure water is stopped, the pure water is shaken off by the rotation of the wafer W, and the processing in the resist film forming module 3 is completed (FIG. 27).

  Also in the second embodiment, the metal contamination in the module, the transport mechanism, the exposure apparatus D4, and the subsequent wafer W by the metal 50 can be prevented as in the first embodiment. In the second embodiment, the width of the peripheral portion of the resist film 4 </ b> A to be removed is reduced as compared with the first embodiment by causing the processing liquid to flow from the back surface to the front surface side of the wafer W. Therefore, many semiconductor products can be manufactured from one wafer W. In addition, although the process of the resist film formation module 3 was demonstrated, you may perform a process also in the antireflection film formation module 16 as demonstrated in FIGS.

  By the way, the back surface cleaning module 20 includes a spin chuck 31 and a cup 34 in addition to a brush and a cleaning liquid supply unit that supplies a cleaning liquid (pure water) to the back surface. The cup 34 is provided with a movable cup 40, and the treatment liquid drainage path in the cup 34 is one system. For example, the back surface cleaning module 20 is further provided with back surface side nozzles 39B to 39D and front surface side nozzles 44B to 44D to remove the metal remaining on the wafer W with the metal removal liquid and the metal removal liquid with the cleaning liquid, The prevention film forming module 16 and the resist film forming module 3 may perform only application of a chemical solution and removal of an unnecessary coating film with a solvent. In that case, in the back surface cleaning module 20, for example, in order to prevent metal contamination of the brush, after performing each of the above processes using the nozzles 39 </ b> B to 39 </ b> D and 44 </ b> B to 44 </ b> D, supply of the cleaning liquid by the cleaning liquid supply unit and the brush The back surface is cleaned by rubbing, and then the wafer W is dried by shaking off the cleaning liquid by the rotation of the wafer W by the spin chuck 31.

  In this way, when removing the metal remaining on the wafer W and removing the metal removing liquid in the back surface cleaning module 20, it is not necessary to use SC2 and SPM in the antireflection film forming module 16 and the resist film forming module 3. In addition to the chemical and solvent drain paths, SC2 and SPM drain paths need not be provided in the cups 34 of the modules 3 and 16. That is, the movable cup 40 is not provided, and the drainage path can be made one system. And since the process liquid used in the back surface cleaning module 20 is a pure water, SC2, and SPM, also in the cup 34 of this back surface cleaning module 20, one drainage path may be sufficient. Therefore, there is an advantage that the apparatus configuration can be simplified. Further, when the treatment is performed in this way, the antireflection film forming module 16 and the resist film forming module 3 do not remove the metal remaining on the wafer W and remove the metal removing liquid with the cleaning liquid. Since the removal of these metals and removal of the metal removal liquid are performed only at 20, the processing cost by the coating and developing apparatus 1 can be reduced. However, since the transfer arm F, the transfer module TRS, and the like through which the wafer W passes before the wafer W is transferred to the back surface cleaning module 20, there is a possibility that the metal is contaminated. As described above, it is preferable to remove the metal by the antireflection film forming module 16 and the resist film forming module 3.

  In this way, the resist film forming module 3 and the antireflection film forming module are all subjected to the steps of resist application, removal of the unnecessary peripheral portion of the resist film with a solvent, metal removal with a metal removal solution, and removal of the metal removal solution. It is not limited to each in 16. In addition to the above example, for example, only the step of removing the metal removal solution may be performed by the back surface cleaning module 20.

  By the way, in 1st and 2nd embodiment, in order to remove a metal more reliably, two types of metal removal liquids, SC2 and SPM, are supplied, but there is only one type of metal removal liquid to be supplied. Also good. As the metal removal solution, a solution containing an acid such as hydrofluoric acid in addition to SC2 and SPM may be used. Further, in the above example, the processing liquid is supplied to the peripheral portion of the wafer W by rotating the wafer W with respect to each nozzle, but the processing liquid is supplied to the peripheral portion by moving the nozzle with respect to the wafer W. May be supplied.

(Third embodiment)
Subsequently, a third embodiment will be described. Also in the third embodiment, the processing in the resist film forming module 3 and the antireflection film forming module 16 is different from the processing in the first embodiment. With reference to FIGS. 28 to 30 which are schematic perspective views of the wafer W and FIGS. 31 to 33 which are longitudinal side views of the wafer W, the processing performed in the resist film forming module 3 is the processing of the first embodiment. The difference will be mainly described. First, the resist is discharged from the resist supply nozzle 46 to the central portion of the wafer W, and the wafer W is rotated, and the resist is spread toward the peripheral portion of the wafer W by centrifugal force. Then, before the resist reaches the peripheral edge of the wafer W, the solvent is discharged from the front side nozzle 44A and the back side nozzle 39A to the peripheral edge of the wafer W (FIGS. 28 and 31).

  The resist that has reached the peripheral edge of the wafer W is diluted with a solvent and is shaken off from the wafer W together with the solvent by centrifugal force (FIG. 32). After the discharge of the resist from the resist supply nozzle 46 is stopped, the solvent contained in the resist is volatilized in a region inside the peripheral portion of the wafer W, while the solvent is continuously supplied to the peripheral portion of the wafer W and the resist is shaken off. . This suppresses the metal 50 constituting the resist from adhering to the resist and staying at the peripheral edge of the wafer W (FIGS. 29 and 32).

  The solvent is discharged from the front side nozzle 44A and the back side nozzle 39A until the resist is dried and a resist film is formed in a region inside the peripheral edge of the wafer W. Here, when the resist is dried, it means that the resist does not move from the inner region to the peripheral portion due to the decrease in the fluidity of the resist. After stopping the discharge of the solvent, the solvent is shaken off from the peripheral portion of the wafer W, the peripheral portion is dried, and the processing is completed (FIGS. 30 and 33). Although the description is omitted, the same processing is performed in the antireflection film forming module 16.

  According to the method of the third embodiment, the effect of preventing metal contamination of the module, the transfer mechanism, and the subsequent wafer W can be obtained as in the first embodiment. Further, according to the third embodiment, since it is not necessary to supply SC2 and SPM, it is not necessary to provide the nozzles 39B to 39D and 45B to 45D, and the SC2 and SPM drainage paths are provided in the cup 34. There is no need to provide. Therefore, the manufacturing cost of the apparatus can be reduced.

By the way, also in the third embodiment, it is not necessary to supply the solvent to the back surface of the wafer W by setting the resist so as to suppress the wraparound of the resist to the back surface of the wafer W. In the first to third embodiments, the timing of supplying the resist to the wafer W may be during the rotation of the wafer W or before the rotation is started.

(Evaluation test)
Subsequently, an evaluation test performed in connection with the present invention will be described.
Evaluation test 1
As the resist film containing a metal, the first resist film containing Ti (titanium), the second resist film containing Zr (zirconium), and the third resist film containing Zr are different from each other on the surface of the wafer W. A film was formed. The second resist film and the third resist film are different in main components other than Zr. Then, as evaluation test 1-1, a solvent was supplied to the first resist film to remove the first resist film, and the concentration of Ti remaining on the surface of the wafer W after the supply of the solvent was measured. As evaluation test 1-2, a solvent is supplied to the first resist film to remove the first resist film, SC2 is supplied to the surface of the wafer W from which the resist film has been removed, and then the wafer is removed. The concentration of Ti remaining on the surface of W was measured.

  Further, as evaluation test 1-3, a solvent was supplied to the second resist film to remove the second resist film, and the concentration of Zr remaining on the wafer W after the supply of the solvent was measured. Further, as an evaluation test 1-4, a solvent is supplied to the second resist film to remove the second resist film, and then SC2 is supplied to the surface of the wafer W to measure the residual Zr concentration. did. Further, as the evaluation test 1-5, the same test as the evaluation test 1-3 is performed using the wafer W on which the third resist film is formed, and the third resist film is formed as the evaluation test 1-6. A test similar to the evaluation test 1-4 was performed using the wafer W.

  When the residual concentration of Ti in evaluation test 1-1 was compared with the residual concentration of Ti in evaluation test 1-2, evaluation test 1-2 was lower. When the residual concentration of Zr in evaluation test 1-3 was compared with the residual concentration of Zr in evaluation test 1-4, evaluation test 1-4 was lower. In addition, in the evaluation test 1-5, the concentration of Zr was too high to be measured, but in the evaluation test 1-6, measurement was possible, and between the evaluation test 1-5 and the evaluation test 1-6, In the evaluation test 1-6, it was confirmed that the residual concentration of Zr was lower. Thus, it was confirmed that when SC2 is supplied, the concentration of each metal remaining on the wafer W can be suppressed as compared with the case where SC2 is not supplied. Therefore, it was confirmed that the metal at the peripheral edge of the wafer W can be removed by performing the processing as in the first and second embodiments.

Evaluation test 2
As the evaluation test 2-1, a resist film was formed on the wafer W as described in the third embodiment, and the metal concentration remaining on the peripheral edge of the wafer W was measured. As the evaluation test 2-2, spin coating of the resist is performed in the same manner as in the first embodiment. After the resist covers the entire surface of the wafer W, the solvent is supplied to the peripheral portion of the rotating wafer W for 5 seconds. The metal concentration remaining on the peripheral edge of W was measured. In this evaluation test 2-2, the supply of the metal removal liquid after the solvent supply as in the first embodiment is not performed. Further, as the evaluation test 2-3, the test was performed in the same manner as the evaluation test 2-2 except that the time for supplying the solvent was 120 seconds.

  When the metal concentrations measured in evaluation tests 2-1, 2-2, and 2-3 were compared, no significant difference was found in evaluation tests 2-2 and 2-3, but the metal concentration in evaluation test 2-1 Was significantly lower than the metal concentration in Evaluation Tests 2-2 and 2-3. Therefore, from the result of this evaluation test 2, the effect of the third embodiment was confirmed.

W Wafer 1 Coating and developing device 3 Resist film forming module 31 Spin chucks 39A to 39D Back side nozzles 44A to 44D Front side nozzle 46 Resist supply nozzle

Claims (9)

Forming a coating film containing a metal on the surface of the substrate;
Next, in order to remove the coating film on the peripheral edge of the substrate, supplying a coating liquid removal liquid along the circumference of the substrate;
Thereafter, in order to remove the metal remaining on the peripheral edge of the substrate, supplying a metal removing solution along the circumference of the substrate;
A substrate processing method comprising: The step of supplying the metal removal solution comprises:
The substrate is rotated, and the removal liquid is supplied to the first position on the surface of the substrate closer to the outside of the substrate than the peripheral edge of the coating film, and the liquid extends from the first position to the peripheral edge of the substrate. 2. The substrate processing method according to claim 1, further comprising a step of forming a film.   In order to remove the metal removal solution remaining after the step of supplying the metal removal solution and remaining on the peripheral portion of the substrate, the surface of the substrate is closer to the center of the substrate than the first position. And supplying a cleaning solution for cleaning the substrate to the second position and rotating the substrate to form a liquid film from the second position to the peripheral edge of the substrate. Item 3. A substrate processing method according to Item 2. The step of supplying the metal removal solution comprises:
Supplying the metal removal solution to the back surface of the substrate;
The metal removal liquid is made to circulate through a side end surface of the substrate to a third position on the surface of the substrate away from the peripheral edge of the coating film to the outside of the substrate, and closer to the coating film than the third position. Rotating the substrate so as not to move to form a liquid film from the back surface of the substrate to the third position;
The substrate processing method according to claim 1, comprising: After the step of supplying the metal removal liquid, the center of the substrate is located on the back surface of the substrate to remove the metal removal liquid remaining on the substrate rather than the position where the metal removal liquid is supplied. Supplying a cleaning solution for cleaning the substrate to a position closer to the substrate;
Forming a liquid film by rotating the substrate so that the cleaning liquid flows to a position closer to the coating film than the third position on the surface of the substrate via a side end surface of the substrate;
The substrate processing method according to claim 4, further comprising:   Removing the metal removal liquid and the coating film removal liquid from the first drainage path and the second drainage path individually formed in the cup surrounding the substrate to the outside of the cup. The substrate processing method according to claim 1, comprising: Supplying a coating liquid containing a metal to the center of the surface of the substrate, and rotating the substrate to spread the coating liquid toward the peripheral edge of the substrate by centrifugal force;
Before the coating liquid reaches the peripheral edge of the substrate, the coating liquid is dried on the inner side of the peripheral edge of the substrate until the coating film containing the metal is formed. Supplying an adhesion preventing liquid for preventing the adhesion of the metal to the peripheral edge;
A substrate processing method comprising:   8. The substrate processing method according to claim 7, further comprising a step of stopping the supply of the adhesion preventing liquid to the substrate after the supply of the coating liquid to the substrate is stopped.   9. The substrate processing method according to claim 7, wherein the adhesion preventing liquid is a solvent for the coating film.

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