Substrate processing method and substrate processing apparatus

Abstract

The present invention provides a substrate processing method and a substrate processing apparatus for efficiently atomically etching a metal film containing ruthenium. [Solution] The substrate processing method includes the steps of: processing the surface of a metal film containing ruthenium with a first processing solution to form metal chlorides on the surface of the metal film; and removing the metal chlorides with a second processing solution. The first processing solution contains 0.01 to 1.0 wt% trichloroisocyanuric acid. The second processing solution is TMAH (tetramethylammonium hydroxide) or an aqueous choline solution.

Description

Technical Field

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

Background Art

[0002] In recent years, in the manufacturing process of semiconductor devices, the requirements for miniaturization have been increasing more and more. To meet this requirement, the development of Atomic Layer Etching (ALE) technology for etching a target substance on the atomic layer order has been underway. For example, a technology for atomic layer etching of a metal film containing cobalt or copper by a wet process has been disclosed (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technology capable of efficiently atomic layer etching a metal film containing ruthenium.

Means for Solving the Problems

[0005] A substrate processing method according to an aspect of the present disclosure includes a step of treating a surface of a metal film containing ruthenium with a first treatment liquid to form metal chloride on the surface of the metal film, and a step of removing the metal chloride with a second treatment liquid.

Effects of the Invention

[0006] According to the present disclosure, a metal film containing ruthenium can be efficiently atomic layer etched. Note that the effects described here are not necessarily limited, and any of the effects described in the present disclosure may be applicable. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a schematic diagram showing the general configuration of the substrate processing system according to the embodiment. [Figure 2] Figure 2 is a schematic diagram showing an example of a specific configuration of the processing unit according to the embodiment. [Figure 3] Figure 3 is a flowchart showing an example of the substrate processing procedure according to the embodiment. [Figure 4] Figure 4 is an enlarged cross-sectional view showing an example of the wafer surface state after the preparation process according to the embodiment. [Figure 5] Figure 5 is an enlarged cross-sectional view showing an example of the wafer surface condition after the chloride formation treatment according to the embodiment. [Figure 6] Figure 6 is an enlarged cross-sectional view showing an example of the wafer surface condition after chloride removal treatment according to the embodiment. [Figure 7] Figure 7 shows the relationship between the number of processing cycles for substrate processing according to the embodiment and the etching thickness of various materials. [Modes for carrying out the invention]

[0008] The embodiments of the substrate processing method and substrate processing apparatus disclosed herein will be described in detail below with reference to the attached drawings. However, the embodiments described below do not limit this disclosure. Furthermore, it should be noted that the drawings are schematic, and the dimensional relationships and ratios of each element may differ from reality. Moreover, there may be differences in dimensional relationships and ratios between drawings.

[0009] In recent years, the demand for miniaturization in semiconductor device manufacturing processes has been increasing. To meet this demand, the development of atomic layer etching technology, which etches target materials at the atomic layer level, is progressing. For example, a technology for atomic layer etching of metal films containing cobalt or copper using a wet process has been disclosed.

[0010] On the other hand, in the above prior art, there is still room for further improvement in efficiently performing atomic layer etching on a metal film containing ruthenium, which is being considered for application to semiconductor devices.

[0011] Therefore, it is expected to realize a technology that can overcome the above problems and efficiently perform atomic layer etching on a metal film containing ruthenium.

[0012] <Overview of the substrate processing system> First, referring to FIG. 1, the schematic configuration of a substrate processing system 1 according to an embodiment will be described. FIG. 1 is a schematic diagram showing the schematic configuration of the substrate processing system 1 according to the embodiment. Hereinafter, in order to clarify the positional relationship, X-axis, Y-axis, and Z-axis orthogonal to each other are defined, and the positive direction of the Z-axis is the vertically upward direction.

[0013] The substrate processing system 1 is an example of a substrate processing apparatus. As shown in FIG. 1, the substrate processing system 1 includes a loading / unloading station 2 and a processing station 3. The loading / unloading station 2 and the processing station 3 are provided adjacent to each other.

[0014] The loading / unloading station 2 includes a carrier placement unit 11 and a transfer unit 12. On the carrier placement unit 11, a plurality of carriers C for horizontally accommodating a plurality of substrates, in this embodiment, semiconductor wafers W (hereinafter referred to as wafers W), are placed.

[0015] The transfer unit 12 is provided adjacent to the carrier placement unit 11 and includes a substrate transfer device 13 and a delivery unit 14 inside. The substrate transfer device 13 includes a wafer holding mechanism for holding the wafer W. Further, the substrate transfer device 13 can move in the horizontal and vertical directions and turn around the vertical axis, and transfers the wafer W between the carrier C and the delivery unit 14 using the wafer holding mechanism.

[0016] The processing station 3 is provided adjacent to the transfer unit 12. The processing station 3 includes a transfer unit 15 and a plurality of processing units 16. The plurality of processing units 16 are arranged side by side on both sides of the transfer unit 15.

[0017] The transfer unit 15 includes a substrate transfer device 17 inside. The substrate transfer device 17 includes a wafer holding mechanism for holding the wafer W. Further, the substrate transfer device 17 can move in the horizontal and vertical directions and can turn around a vertical axis, and transfers the wafer W between the delivery unit 14 and the processing unit 16 using the wafer holding mechanism.

[0018] The processing unit 16 performs a predetermined substrate process on the wafer W transferred by the substrate transfer device 17.

[0019] Also, the substrate processing system 1 includes a control device 4. The control device 4 is, for example, a computer, and includes a control unit 18 and a storage unit 19. Programs for controlling various processes executed in the substrate processing system 1 are stored in the storage unit 19. The control unit 18 controls the operation of the substrate processing system 1 by reading and executing the programs stored in the storage unit 19.

[0020] Note that such a program may be recorded on a computer-readable storage medium and installed from the storage medium into the storage unit 19 of the control device 4. Examples of computer-readable storage media include a hard disk (HD), a flexible disk (FD), a compact disk (CD), a magneto-optical disk (MO), a memory card, and the like.

[0021] In the substrate processing system 1 configured as described above, first, the substrate transport device 13 of the loading / unloading station 2 takes out a wafer W from the carrier C placed on the carrier mounting section 11 and places the removed wafer W on the transfer section 14. The wafer W placed on the transfer section 14 is then taken out of the transfer section 14 by the substrate transport device 17 of the processing station 3 and transported to the processing unit 16.

[0022] The wafer W, which has been brought into the processing unit 16, is processed by the processing unit 16 and then removed from the processing unit 16 by the substrate transport device 17 and placed on the transfer unit 14. The processed wafer W, which has been placed on the transfer unit 14, is then returned to the carrier C of the carrier placement unit 11 by the substrate transport device 13.

[0023] <Processing Unit Configuration> Next, the configuration of the processing unit 16 will be described with reference to Figure 2. Figure 2 is a schematic diagram showing an example of a specific configuration of the processing unit 16 according to the embodiment. As shown in Figure 2, the processing unit 16 comprises a chamber 20, a substrate processing unit 30, a liquid supply unit 40, and a recovery cup 50.

[0024] Chamber 20 houses a substrate processing unit 30, a liquid supply unit 40, and a recovery cup 50. An FFU (Fan Filter Unit) 21 is provided on the ceiling of chamber 20. The FFU 21 creates a downflow within chamber 20.

[0025] The substrate processing unit 30 comprises a holding unit 31, a support column 32, and a drive unit 33, and performs liquid treatment on the placed wafer W. The holding unit 31 holds the wafer W horizontally. The support column 32 is a member that extends in the vertical direction, with its base end rotatably supported by the drive unit 33, and its tip horizontally supporting the holding unit 31. The drive unit 33 rotates the support column 32 around a vertical axis.

[0026] The substrate processing unit 30 rotates the support column 32 using the drive unit 33, thereby rotating the holding unit 31 supported by the support column 32, and thereby rotating the wafer W held in the holding unit 31.

[0027] A holding member 31a is provided on the upper surface of the holding portion 31 of the substrate processing unit 30 to hold the wafer W from the side. The wafer W is held horizontally by this holding member 31a, slightly separated from the upper surface of the holding portion 31. The wafer W is held in the holding portion 31 with the surface to be processed facing upwards.

[0028] The liquid supply unit 40 supplies processing fluid to the wafer W. The liquid supply unit 40 includes nozzles 41a and 41b, an arm 42a that horizontally supports the nozzles 41a and 41b, and a swivel and lifting mechanism 43a that rotates and raises the arm 42a. The liquid supply unit 40 also includes nozzles 41c and 41d, an arm 42b that horizontally supports the nozzles 41c and 41d, and a swivel and lifting mechanism 43b that rotates and raises the arm 42b.

[0029] The nozzle 41a is connected to the first supply unit 46a via a valve 44a and a flow regulator 45a. The first processing liquid supplied from the first supply unit 46a is composed of, for example, ethyl acetate, acetone, or acetonitrile as a solvent and trichloroisocyanuric acid (TCCA) as a solute. The concentration of trichloroisocyanuric acid in the first processing liquid is, for example, 0.01 wt% to 1.0 wt%.

[0030] The nozzle 41b is connected to the second supply unit 46b via a valve 44b and a flow regulator 45b. The second processing liquid supplied from the second supply unit 46b is, for example, TMAH (tetramethylammonium hydroxide) or an aqueous choline solution.

[0031] The nozzle 41c is connected to the third supply unit 46c via a valve 44c and a flow regulator 45c. The third processing liquid supplied from the third supply unit 46c is, for example, ethyl acetate, acetone, or acetonitrile.

[0032] The nozzle 41d is connected to the fourth supply unit 46d via a valve 44d and a flow regulator 45d. The rinsing liquid supplied from the fourth supply unit 46d is, for example, DIW (Deionized Water).

[0033] The first processing liquid supplied from the first supply unit 46a is discharged from nozzle 41a. The second processing liquid supplied from the second supply unit 46b is discharged from nozzle 41b. The third processing liquid supplied from the third supply unit 46c is discharged from nozzle 41c. The rinsing liquid supplied from the fourth supply unit 46d is discharged from nozzle 41d.

[0034] The collection cup 50 is positioned to surround the holding unit 31 and collects the processing liquid scattered from the wafer W as the holding unit 31 rotates. A drain port 51 is formed at the bottom of the collection cup 50, and the processing liquid collected by the collection cup 50 is discharged to the outside of the processing unit 16 through this drain port 51. An exhaust port 52 is also formed at the bottom of the collection cup 50 to discharge the gas supplied from the FFU 21 to the outside of the processing unit 16.

[0035] <Substrate processing> Next, the details of the substrate processing according to the embodiment will be explained with reference to Figures 3 to 7. Figure 3 is a flowchart showing an example of the substrate processing procedure according to the embodiment.

[0036] As shown in Figure 3, in the substrate processing according to this embodiment, a preparation process is first performed (step S101). In this preparation process, for example, a wafer W is prepared in which the surface is in the state shown in Figure 4. Figure 4 is an enlarged cross-sectional view showing an example of the state of the wafer W surface after the preparation process according to this embodiment.

[0037] The state shown in Figure 4 is achieved by first using a known film deposition method to deposit SiO on the surface of the wafer W. x Silicon oxide film, SiCN (silicon carbonitride) film, TiN (titanium nitride) film, Ru (ruthenium) film, SiCN film, SiOx Thin films are deposited in the following order.

[0038] A Ru film is an example of a metal film. In this disclosure, the Ru film is not limited to being composed solely of ruthenium, but may contain at least ruthenium.

[0039] Next, one or more (multiple in the figure) recesses T are formed on the surface of the wafer W using a known etching method. These recesses T are formed on the uppermost layer of SiO x It is formed so as to penetrate from the film to the TiN film. This completes the preparation process according to the embodiment.

[0040] As shown in Figure 4, in the wafer W after the preparation process is complete, multiple residues A are attached to the side surface of the Ru film exposed in the recess T. These residues A are generated, for example, during the etching process that forms the recess T, and consist of Ru oxide and Ru chloride. The substrate processing described below is primarily performed to remove these multiple residues A.

[0041] Returning to the explanation of Figure 3, following the preparation process described so far, the control unit 18 (see Figure 1) sets the counter n for counting the number of substrate processing cycles to 1 (step S102).

[0042] In the substrate processing according to this embodiment, a chloride formation process is then performed (step S103). In this chloride formation process, the control unit 18 holds the wafer W in the holding unit 31 (see Figure 2), and then controls the liquid supply unit 40 (see Figure 2) and the like to supply the first processing liquid from the nozzle 41a (see Figure 2) to the rotating wafer W.

[0043] As a result, as shown in Figure 5, a film of Ru chloride RuCl3 is formed on the surface of the Ru film exposed in the recess T. Figure 5 is an enlarged cross-sectional view showing an example of the state of the wafer surface W after the chloride formation treatment according to the embodiment.

[0044] Ru chloride (RuCl3) is an example of a metal chloride. A film of this Ru chloride (RuCl3) has a thickness on the order of atomic layers, for example, less than 1 nm thick.

[0045] Thus, in this embodiment, trichloroisocyanuric acid contained in the first treatment solution reacts with ruthenium in the Ru film, forming an atomic layer-sized film of Ru chloride RuCl3 on the surface of the Ru film.

[0046] Furthermore, in this embodiment, the first treatment solution may contain 0.01 to 1.0 wt% trichloroisocyanuric acid. This allows for the efficient formation of an atomic-layer-scale Ru chloride RuCl3 film on the surface of the Ru film.

[0047] Furthermore, in the embodiment, ethyl acetate, acetone, or acetonitrile, which are organic solvents, may be used as the solvent for the first treatment solution. By using an organic solvent instead of water as the solvent for the first treatment solution in this way, it is possible to suppress the unexpected etching of the surface of the Ru film on which the Ru chloride RuCl3 film is formed by water.

[0048] Returning to the explanation of Figure 3, in the substrate processing according to this embodiment, a rinsing process is then performed (step S104).

[0049] In this rinsing process, the control unit 18 controls the liquid supply unit 40 and the like to supply a third processing liquid, which is ethyl acetate, acetone, or acetonitrile, from the nozzle 41c (see Figure 2) to the rotating wafer W that has been wetted with the first processing liquid. As a result, the first processing liquid is removed from the surface of the wafer W, and the reaction between the Ru film and the first processing liquid is stopped.

[0050] In this embodiment, ethyl acetate, acetone, or acetonitrile, which are organic solvents, may be used as the third treatment solution for rinsing. By using an organic solvent instead of water for rinsing, it is possible to suppress the unexpected etching of the surface of the Ru film, on which the Ru chloride RuCl3 film is formed, by water.

[0051] Furthermore, in this embodiment, it is preferable to use ethyl acetate as the third treatment solution. This allows the drying treatment described later to be carried out at a suitable drying rate.

[0052] In the substrate processing according to this embodiment, a drying process is subsequently performed (step S105). In this drying process, the control unit 18 controls the substrate processing unit 30 and the liquid supply unit 40, etc., to stop the supply of the third processing liquid from the nozzle 41c, and rotates the wafer W at high speed to shake off the third processing liquid. As a result, the wafer W is subjected to a drying process.

[0053] In the substrate processing according to this embodiment, a chloride removal process is subsequently performed (step S106). In this chloride removal process, the control unit 18 controls the substrate processing unit 30 and the liquid supply unit 40, etc., to supply a second processing liquid, TMAH or a choline aqueous solution, to the rotating wafer W from the nozzle 41b (see Figure 2).

[0054] As a result, the Ru chloride RuCl3 (see Figure 5) film formed on the surface of the Ru film is removed, as shown in Figure 6. Figure 6 is an enlarged cross-sectional view showing an example of the state of the wafer W surface after the chloride removal treatment according to the embodiment. Note that, as shown in Figure 6, the Ru film itself is not etched by the third treatment solution.

[0055] As explained above, in the substrate processing according to the embodiment, the Ru film can be efficiently atomically etched by using the first processing solution and the third processing solution.

[0056] Furthermore, in this embodiment, multiple residues A (see Figure 5) adhering to the Ru chloride RuCl3 film are removed from the Ru film together with the Ru chloride RuCl3 film. This allows for efficient removal of multiple residues A.

[0057] Furthermore, in this embodiment, since the film thickness of Ru chloride RuCl3 is on the order of atomic layers, damage to the Ru film can be minimized, and the increase in surface roughness of the Ru film due to the etching process can be suppressed.

[0058] Furthermore, in this embodiment, TMAH or a choline aqueous solution may be used as the third processing solution. By using TMAH or a choline aqueous solution that does not contain metal elements as the third processing solution for removing the Ru chloride RuCl3 film, contamination of the wafer W with metal elements can be suppressed.

[0059] Returning to the explanation of Figure 3, in the substrate processing according to this embodiment, a rinsing treatment is performed following the chloride removal treatment described so far (step S107).

[0060] In this rinsing process, the control unit 18 controls the liquid supply unit 40 and the like to supply the rinsing liquid DIW from the nozzle 41d (see Figure 2) to the rotating wafer W that has been wetted with the second processing liquid. This removes the second processing liquid from the surface of the wafer W.

[0061] In the substrate processing according to this embodiment, a drying process is then performed (step S108). In this drying process, the control unit 18 controls the substrate processing unit 30 and the liquid supply unit 40, etc., to stop the supply of rinsing liquid from the nozzle 41d, and rotates the wafer W at high speed to shake off the rinsing liquid. This dries the wafer W.

[0062] In the substrate processing according to the embodiment, the control unit 18 then determines whether the counter n, which indicates the number of substrate processing steps, is equal to or greater than a given number N (step S109).

[0063] Then, if the counter n is equal to or greater than the given number N (step S109, Yes), the series of substrate processing is terminated. On the other hand, if the counter n is not equal to or greater than the given number N (step S109, No), the control unit 18 increments the counter n, which indicates the number of substrate processing steps (step S110), and returns to the process in step S103.

[0064] Thus, in this embodiment, it is preferable that the processes in steps S103 to S108 be repeated sequentially. This allows the surface of the Ru film to be etched accurately to the desired thickness.

[0065] Furthermore, in the embodiment, the Ru film is made of SiO x It is preferable that it be located on a film of at least one of SiCN, SiN (silicon nitride), SiOC (silicon carbide), and TiN. This allows the substrate treatment according to the embodiment to be performed on SiO x This can suppress the etching of at least one film from among SiCN, SiN, SiOC, and TiN together with the Ru film.

[0066] Figure 7 shows the relationship between the number of substrate processing cycles and the etching thickness of various materials according to the embodiment. In the example in Figure 7, the first processing solution used is ethyl acetate with 1.0 wt% trichloroisocyanuric acid added, the second processing solution is ethyl acetate, and the third processing solution is 1 mol / L TMAH. In the example in Figure 7, the temperature of each processing solution is room temperature.

[0067] As shown in Figure 7, in the substrate processing according to the embodiment, the amount of Ru etching increases linearly as the number of processing cycles increases. On the other hand, SiO x Furthermore, it can be seen that the amount of etching hardly increases even when the number of processing cycles is increased for SiCN, SiN, SiOC, and TiN.

[0068] In other words, in the substrate processing according to the embodiment, Ru, SiO xOf SiCN, SiN, SiOC, and TiN, only Ru can be selectively etched. Therefore, according to the embodiment, in a device structure as shown in Figure 4, only the Ru film can be selectively etched, thus maintaining the device structure well.

[0069] The substrate processing method according to the embodiment includes a forming step (step S103) and a removal step (step S106). In the forming step (step S103), the surface of a ruthenium-containing metal film (Ru film) is treated with a first processing solution to form metal chlorides (Ru chloride RuCl3) on the surface of the metal film (Ru film). In the removal step (step S106), the metal chlorides (Ru chloride RuCl3) are removed with a second processing solution. This allows for efficient atomic layer etching of the Ru film.

[0070] Furthermore, in the substrate processing method according to the embodiment, the first processing solution contains 0.01 to 1.0 wt% trichloroisocyanuric acid. This makes it possible to efficiently form an atomic layer-order Ru chloride RuCl3 film on the surface of the Ru film.

[0071] Furthermore, in the substrate processing method according to this embodiment, the solvent of the first processing solution is ethyl acetate, acetone, or acetonitrile. This makes it possible to suppress the unexpected etching of the surface of the Ru film on which the Ru chloride RuCl3 film is formed by water.

[0072] Furthermore, in the substrate processing method according to the embodiment, the metal film (Ru film) is SiO x It is located on top of at least one film from SiCN, SiN, SiOC, and TiN. This allows for good maintenance of the device structure on the wafer W.

[0073] Furthermore, in the substrate processing method according to the embodiment, the second processing solution is TMAH or a choline aqueous solution. This makes it possible to suppress contamination of the wafer W and other materials with metal elements.

[0074] Furthermore, the substrate processing method according to the embodiment further includes a rinsing step (step S104) and a drying step (step S105). The rinsing step (step S104) is performed after the forming step (step S103) and involves rinsing the surface of the metal chloride (Ru chloride RuCl3) with a third processing solution. The drying step (step S105) is performed after the rinsing step (step S104) and involves drying the surface of the metal chloride (Ru chloride RuCl3). This makes it possible to suppress the formation of excessively thick Ru chloride RuCl3 on the surface of the Ru film.

[0075] Furthermore, in the substrate processing method according to the embodiment, the third processing solution is ethyl acetate, acetone, or acetonitrile. This makes it possible to suppress the unexpected etching of the surface of the Ru film on which the Ru chloride RuCl3 film is formed by water.

[0076] Furthermore, in the substrate processing method according to the embodiment, the forming step (step S103) and the removal step (step S106) are performed sequentially and repeatedly. This makes it possible to accurately etch the surface of the Ru film to a desired thickness.

[0077] Furthermore, in the substrate processing method according to this embodiment, the film thickness of the metal chloride (Ru chloride RuCl3) is 1 nm or less. This minimizes damage to the Ru film and suppresses an increase in the surface roughness of the Ru film.

[0078] Furthermore, the substrate processing apparatus according to the embodiment comprises a holding unit 31, a liquid supply unit 40, and a control unit 18. The holding unit 31 holds and rotates a substrate (wafer W) on which a metal film containing ruthenium (Ru film) is formed. The liquid supply unit 40 supplies processing liquid to the substrate (wafer W) held by the holding unit 31. The control unit 18 controls each unit. The control unit 18 also processes the surface of the metal film (Ru film) with a first processing liquid to form metal chloride (Ru chloride RuCl3) on the surface of the metal film (Ru film), and removes the metal chloride (Ru chloride RuCl3) with a second processing liquid. This allows for efficient atomic layer etching of the Ru film.

[0079] While embodiments of the present disclosure have been described above, the present disclosure is not limited to the embodiments described above, and various modifications are possible without departing from its spirit. For example, the above embodiments show an example in which the technology of the present disclosure is applied to a wafer W having the surface structure shown in Figure 4, but the present disclosure is not limited to such an example.

[0080] For example, the technology of this disclosure may be applied to a Ru film embedded in a recess formed on a wafer W, with its upper surface exposed. This also allows for efficient atomic layer etching of the Ru film.

[0081] The embodiments disclosed herein should be considered in all respects as illustrative and not restrictive. Indeed, the embodiments described above can be embodied in a variety of forms. Furthermore, the embodiments described above may be omitted, replaced, or modified in various ways without departing from the scope and spirit of the appended claims. [Explanation of Symbols]

[0082] W wafer (an example of a substrate) 1. Substrate Processing System (An Example of a Substrate Processing Device) 18 Control Unit 31 Holding part 40 Liquid supply section

Claims

1. A step of treating the surface of a metal film containing ruthenium with a first treatment solution to form a metal chloride on the surface of the metal film, The process involves removing the metal chloride with a second processing solution, A substrate processing method including the following.

2. The first treatment solution contains 0.01 to 1.0 wt% trichloroisocyanuric acid. The substrate processing method according to claim 1.

3. The solvent of the first treatment solution is ethyl acetate, acetone, or acetonitrile. The substrate processing method according to claim 2.

4. The aforementioned metal film is SiO ｘ Located on a film of at least one of SiCN, SiN, SiOC, and TiN A substrate processing method according to any one of claims 1 to 3.

5. The second treatment solution is TMAH or an aqueous choline solution. A substrate processing method according to any one of claims 1 to 3.

6. A step performed after the forming step, in which the surface of the metal chloride is rinsed with a third treatment solution, A step performed after the rinsing step, to dry the surface of the metal chloride, Includes A substrate processing method according to any one of claims 1 to 3.

7. The processing solution described in the third above is ethyl acetate, acetone, or acetonitrile. The substrate processing method according to claim 6.

8. The forming step and the removal step are carried out sequentially and repeatedly. A substrate processing method according to any one of claims 1 to 3.

9. The thickness of the metal chloride film is 1 nm or less. A substrate processing method according to any one of claims 1 to 3.

10. A holding part that holds and rotates a substrate on which a metal film containing ruthenium has been formed, A liquid supply unit that supplies processing liquid to the substrate held by the holding unit, A control unit that controls each part, Equipped with, The control unit, The surface of the metal film is treated with a first treatment solution to form metal chlorides on the surface of the metal film. The aforementioned metal chloride is removed with a second treatment solution. Circuit board processing equipment.

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