Substrate treatment method and substrate treatment device

Abstract

Provided is a substrate treatment method comprising: a step for preparing a substrate that has a base film; a step for hydrophobizing the surface of the substrate; a step for selectively hydrophilizing a peripheral edge portion of the substrate; a step for setting the treatment pressure to a first pressure and forming, on the substrate, a carbon-containing film that has a film stress of 1 GPa or more; and a step for setting the treatment pressure to a second pressure that is higher than the first pressure and selectively removing the carbon-containing film in the peripheral edge portion of the hydrophilized substrate.

Description

Substrate processing method and substrate processing apparatus

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

[0002] For example, Patent Document 1 discloses a method for removing SiO2 from the bevel of a substrate by rotating a stage on which the substrate is placed, supplying an active gas into a processing chamber, and irradiating a laser beam onto the bevel of the substrate. ２ It is proposed to remove the membrane.

[0003] For example, Patent Document 2 proposes that a cleaning gas is supplied to a processing chamber, RF power is supplied to a bottom edge electrode, and a top edge electrode is grounded, thereby generating a cleaning plasma near the bevel and edge of the substrate, thereby cleaning the bevel and edge of the substrate.

[0004] For example, Patent Document 3 proposes forming a masking film on the peripheral edge of a substrate, then forming a hard mask on the surface of the substrate, and then removing the hard mask on the peripheral edge of the substrate and the masking film on the peripheral edge of the substrate.

[0005] JP 2007-157828 A JP 2010-520646 A JP 2014-45171 A

[0006] The present disclosure provides a technique that can selectively remove a carbon-containing film on the peripheral edge of a substrate by controlling the state of the substrate surface.

[0007] According to one aspect of the present disclosure, there is provided a substrate processing method including the steps of: preparing a substrate having an underlayer film; hydrophobizing a surface of the substrate; selectively hydrophilizing a peripheral portion of the substrate; setting a processing pressure to a first pressure and forming a carbon-containing film having a film stress of 1 GPa or more on the substrate; and setting the processing pressure to a second pressure higher than the first pressure and selectively removing the carbon-containing film from the hydrophilized peripheral portion of the substrate.

[0008] According to one aspect, the carbon-containing film on the peripheral edge of the substrate can be selectively removed by controlling the state of the substrate surface.

[0009] 1. An example of a schematic cross-sectional view of a substrate processed by a substrate processing method. A diagram showing an example of the result of film peeling of a carbon-containing film on a surface of a Si substrate. A diagram showing an example of the result of film peeling of a carbon-containing film on a surface of a TiN substrate. A flowchart showing an example of a substrate processing method according to a first embodiment. A diagram for explaining the substrate processing method of FIG. 4. A flowchart showing an example of a substrate processing method according to a second embodiment. A diagram for explaining the substrate processing method of FIG. 6. A flowchart showing an example of a substrate processing method according to a third embodiment. A diagram for explaining the substrate processing method of FIG. 8. A flowchart showing an example of a substrate processing method according to a fourth embodiment. A diagram for explaining the substrate processing method of FIG. 10. A diagram showing an example of a substrate processing system. A schematic cross-sectional view showing an example of a substrate processing apparatus that performs a hydrofluoric acid treatment, an ammonia hydrogen peroxide treatment, or a pure water rinse treatment. A configuration diagram showing an example of a substrate processing apparatus that performs a hydrofluoric acid treatment or a pure water rinse treatment. A schematic cross-sectional view showing an example of a substrate processing apparatus that performs a hydrophobic treatment using a Si-containing gas. A schematic cross-sectional view showing an example of a substrate processing apparatus that performs a carbon-containing film formation treatment or a series of treatments of a substrate processing method.

[0010] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and redundant explanations may be omitted.

[0011] [Technique for Suppressing Film Peeling] For example, as shown in FIG. 1, a carbon-containing film 103 (e.g., DLC: Diamond Like Carbon) is formed on a substrate W having a first layer 101 and a second layer 102. The first layer 101 is, for example, a magnetic tunnel junction (MTJ) element. The second layer 102 is, for example, a Si-containing film (Si, SiO ２ , SiN, etc.) The second layer 102 may also be, for example, a metal-containing film (TiN, W, Co, etc.).

[0012] When the second layer 102 is made of TiN, the second layer 102 and the carbon-containing film 103 can be used as a hard mask for the first layer 101 (e.g., an MTJ element). In this case, the thickness of the TiN film (second layer 102) is preferably 20 nm to 100 nm. The thickness of the carbon-containing film 103 (carbon-containing film) is preferably 20 nm to 100 nm. This allows the formation of a thin hard mask with high etching resistance.

[0013] The carbon-containing film 103 has high stress (compressive stress), which may result in poor adhesion to the second layer 102, and may cause peeling of the carbon-containing film 103 formed on the second layer 102.

[0014] Figure 2 shows the state of a substrate surface when a DLC film is formed as a carbon-containing film. Here, DLC films with compressive stresses of -1.6 GPa, -2.1 GPa, and -2.9 GPa were formed on (a) a brand new Si substrate and (b) an Si substrate that had been hydrophobized with hydrofluoric acid (DHF). In the figure, "○" indicates no film peeling, and "×" indicates film peeling. Note that when the film stress has a negative value, a film with compressive stress is formed, and when it has a positive value, a film with tensile stress is formed.

[0015] As shown in Figure 2, (a) on a new Si substrate, film peeling was confirmed for DLC films with compressive stresses of -1.6 GPa, -2.1 GPa, and -2.9 GPa. This is because the surface of a new Si substrate is hydrophilic, with many Si-OH groups terminated with OH groups, resulting in poor adhesion and film peeling.

[0016] As shown in Figure 2 (b), on a Si substrate hydrophobized with DHF, no film peeling occurred for a DLC film with a compressive stress of -2.1 GPa. Furthermore, on a Si substrate hydrophobized with DHF, no film peeling occurred for a DLC film with a compressive stress of -2.9 GPa. This is because the surface of a Si substrate hydrophobized with DHF has many Si-H groups terminated with H groups, making it a hydrophobic surface, which provides good adhesion and prevents film peeling.

[0017] Next, the state of film peeling when a carbon-containing film was formed on a metal-containing film was examined. Figure 3 shows the state when the metal-containing film was TiN and a DLC film was formed as a carbon-containing film on the surface of the metal-containing film. Here, (a) is a TiN substrate, and (b) is a TiN substrate treated with dichlorosilane (DCS:SiH ２ Cl ２ (c) TiN substrate hydrophobized by exposing it to dichlorosilane (DCS:SiH ２ Cl ２ A DLC film with a compressive stress of -3.0 GPa was formed on a TiN substrate that had been hydrophobized by exposing it to HCl gas for 20 seconds. After the DLC film was formed, the condition was checked before exposure to the atmosphere, immediately after exposure to the atmosphere, and 10 minutes after exposure to the atmosphere. "○" indicates no film peeling, and "×" indicates film peeling.

[0018] As shown in Figure 3, (a) on the TiN substrate, no film peeling was observed before exposure to the atmosphere. However, film peeling was observed immediately after exposure to the atmosphere and 10 minutes after exposure to the atmosphere. This is because the TiN film is a hydrophilic film, while the DLC film is an organic film primarily composed of C=C bonds, C-C bonds, and C-H bonds, and is a hydrophobic film. Therefore, the bonding surface between the TiN film and the DLC film is a bonding between a hydrophilic film and a hydrophobic film, resulting in poor adhesion and a small adhesive force. For this reason, when a DLC film with a film stress of 1 GPa or more was formed on the TiN film, peeling of the DLC film occurred due to the film stress of the DLC film itself.

[0019] As shown in FIG. 3, (b) the TiN substrate was treated with dichlorosilane (DCS:SiH ２ Cl２ (c) TiN substrate hydrophobized by exposing it to dichlorosilane (DCS:SiH ２ Cl ２ In a TiN substrate that was hydrophobized by exposing it to a DLC gas for 20 seconds, no film peeling occurred before exposure to the atmosphere, immediately after exposure to the atmosphere, or 10 minutes after exposure to the atmosphere. This is because hydrophobic groups (SiHx) containing Si atoms and H atoms physically adsorb and / or chemically bond to the surface of the TiN film. Therefore, the bonding surface between the TiN film and the DLC film is a bonding between a hydrophobic surface and a hydrophobic film, resulting in good adhesion and strong adhesion. Therefore, even if a DLC film with a film stress of 1 GPa or more is formed on the TiN film, film peeling of the DLC film can be suppressed.

[0020] From the above, it was found that when the second layer 102 is a Si-containing film or a TiN film, peeling of the carbon-containing film 103 can be suppressed if the surface is hydrophobic, and peeling of the carbon-containing film 103 occurs if the surface is hydrophilic.

[0021] The carbon-containing film 103 attached to the bevel of the substrate and the front and back surfaces of the edge of the substrate (hereinafter also referred to as the "periphery of the substrate") may rub against other parts of the transfer device or the like during substrate transport and become particles. For this reason, a post-etching process is provided to remove the carbon-containing film 103 attached to the peripheral edge of the substrate. In the post-etching process of this embodiment, after the carbon-containing film 103 is formed, only the carbon-containing film 103 attached to the peripheral edge of the substrate is removed. Specifically, using the above-described substrate surface state control (film peeling control), a process is performed to form a hydrophobic surface in the center of the substrate and a hydrophilic surface in the peripheral edge of the substrate. Thereafter, a carbon-containing film is formed on the substrate at a first pressure, and then the process is performed at a second pressure higher than the first pressure, thereby selectively removing only the carbon-containing film formed on the peripheral edge of the substrate.

[0022] In the substrate processing methods according to the first to fourth embodiments described below, the carbon-containing film 103 on the peripheral edge of the substrate is selectively removed by utilizing surface treatment of the second layer 102. The substrate processing methods according to each embodiment will be described in order below. Hereinafter, the numerical values ​​of the film stress are indicated as absolute values, whether the carbon-containing film 103 has compressive stress or tensile stress. The film stress of the carbon-containing film 103 may be in either the compressive direction or the tensile direction. That is, a carbon-containing film 103 (DLC film) having a film stress with an absolute value of 1 GPa or more is formed.

[0023] First Embodiment First, a substrate processing method according to a first embodiment will be described with reference to Fig. 4 and Fig. 5. Fig. 4 is a flowchart showing an example of the substrate processing method according to the first embodiment. Fig. 5 is a diagram for explaining the substrate processing method of Fig. 4.

[0024] In the substrate processing method according to the first embodiment, first, in step S1, a substrate W having an undercoat film is prepared on a stage in a processing chamber of a substrate processing apparatus (described later). The prepared substrate W has a first layer 101 and a second layer 102 (FIG. 1). In this embodiment, the second layer 102 as an undercoat film is a Si-containing film. That is, the surface of the prepared substrate W is the surface of the second layer 102, and contains Si, SiO ２ , or SiN.

[0025] 5A shows a prepared substrate W. For example, the surface of the second layer 102 of the substrate W is terminated with OH groups to form Si—OH, making it hydrophilic.

[0026] Next, in step S2, the surface of the substrate W is hydrophobized by exposing the substrate to a first processing solution. In this embodiment, the first processing solution is hydrofluoric acid (DHF). As shown in FIG. 5B-1, in the DHF processing, hydrofluoric acid (DHF) is supplied from a nozzle located at the center of the stage while rotating the stage on which the substrate W is placed, thereby processing the entire surface of the second layer 102. Note that the first processing solution is not limited to hydrofluoric acid (DHF), but may also contain at least one of BHF, TMSDMA, HMDS, and a silane coupling agent. For example, if the surface of the second layer 102 of the substrate W is made of Si, the hydrophobizing solution may contain at least one of hydrofluoric acid and BHF. Furthermore, if the surface of the second layer 102 of the substrate W is made of SiO or SiN, the hydrophobizing solution may contain at least one of TMSDMA, HMDS, and a silane coupling agent. 5(b-2), the surface of the second layer 102 of the substrate W is terminated with H groups to form Si—H groups, and is hydrophobicized, thereby modifying the surface of the second layer 102 of the substrate W.

[0027] Next, in step S3, the surface of the substrate W is made hydrophilic by selectively exposing the peripheral edge of the substrate to a second processing solution different from the first processing solution. In this embodiment, as shown in FIG. 5(c-1), ammonia-hydrogen peroxide mixture is supplied to the peripheral edge of the substrate from a nozzle disposed on the peripheral edge of the substrate while the stage is rotating, and the peripheral edge of the substrate (the front and rear surfaces of the bevel and edge of the substrate) is processed with the ammonia-hydrogen peroxide mixture (SC1). The second processing solution may be ammonia-hydrogen peroxide mixture, hydrochloric acid-hydrogen peroxide mixture (a mixture of hydrochloric acid and hydrogen peroxide), or ozone water (O ３ ) water, hydrogen peroxide solution (H ２ O ２ ), sulfuric acid / hydrogen peroxide, and aqueous ammonium peroxodisulfate solution.

[0028] This selectively makes the peripheral edge of the substrate hydrophilic, as shown in (c-2) of Figure 5. As a result, the surface of the peripheral edge of the substrate is terminated with OH groups to form Si-OH, making it hydrophilic. The area other than the peripheral edge of the substrate, i.e., the central surface of the substrate, remains Si-H and is hydrophobic. This makes it possible to selectively form hydrophobic and hydrophilic surfaces on the substrate.

[0029] Next, in step S4, the pressure in the processing chamber (processing pressure) is controlled to a first pressure, and a carbon-containing film 103 having a film stress of 1 GPa or more is formed on the substrate W. Hereinafter, in the first to fourth embodiments, a case where the carbon-containing film 103 is a DLC film (DLC film 103) is described. For example, the first pressure may be 0.13 Pa to 13.3 Pa. The step of forming the DLC film 103 includes exposing the substrate W to plasma generated from a third processing gas containing a carbon-containing gas. The carbon-containing gas includes at least one of a gas containing carbon and hydrogen, a gas containing carbon and fluorine, a gas containing carbon and oxygen, and a gas containing carbon and a metal. The carbon-containing gas may be a hydrocarbon gas. The third processing gas may further include an inert gas. The inert gas may be argon (Ar) gas, helium (He) gas, nitrogen (N ２ The gas contains at least one of xenon (Xe) gas, krypton (Kr) gas, and a DLC film 103 having a high film stress (1 GPa or more) as shown in FIG.

[0030] Next, in step S5, the processing pressure is controlled to a second pressure higher than the first pressure, and the hydrophilized DLC film 103 on the peripheral edge of the substrate is selectively removed. The second pressure is, for example, atmospheric pressure. The second pressure may be, for example, equal to or higher than the maximum value of the first pressure (13.3 Pa). The second pressure may be, for example, equal to or higher than atmospheric pressure or 10,000 Pa to 100,000 Pa inclusive, which is lower than atmospheric pressure or the atmosphere, in an environment where moisture and oxygen are present in the processing vessel. The moisture (humidity) at this time may be 10% to 100%, and the oxygen concentration may be 1% to 20%.

[0031] According to this method, for example, by placing the substrate W in an atmospheric pressure environment, only the DLC film 103 on the hydrophilized peripheral edge of the substrate begins to peel off. The DLC film 103 on the hydrophobic surface of the substrate does not peel off. As a result, as shown in Figure 5(e), the adhesion of only the DLC film on the peripheral edge of the substrate becomes poor and film peeling occurs, making it possible to selectively remove the DLC film on the peripheral edge of the substrate.

[0032] Next, in step S6, the substrate W is cleaned. A chemical solution is supplied from a nozzle to clean the peripheral edge of the substrate by a deionized water (DIW) rinse process. The process of cleaning the substrate W includes exposing the substrate W to a third processing solution. The third processing solution may be deionized water (DIW). As a result, as shown in FIG. 5(f), the peeled DLC film 103 can be washed away and removed with the deionized water. The deionized water rinse may be an ultrasonic deionized water rinse. Instead of the deionized water rinse, the peeled DLC film may be removed using a diluted ammonia hydrogen peroxide solution.

[0033] According to the substrate processing method of the first embodiment, the DLC film 103 on the peripheral edge of the substrate can be selectively removed by utilizing the phenomenon that, at a desired pressure, the DLC film 103 on the hydrophilized peripheral edge of the substrate peels off, while the DLC film 103 on the hydrophobic surface of the substrate does not peel off.

[0034] Second Embodiment Next, a substrate processing method according to a second embodiment will be described with reference to Fig. 6 and Fig. 7. Fig. 6 is a flowchart showing an example of the substrate processing method according to the second embodiment. Fig. 7 is a diagram for explaining the substrate processing method of Fig. 6.

[0035] In the substrate processing method according to the second embodiment, first, in step S11, a substrate having an underlayer is prepared. Here, the prepared substrate W has a first layer 101 and a second layer 102 (FIG. 1). In this embodiment, the second layer 102 as the underlayer is a TiN film or a Si-containing film. That is, the substrate surface of the prepared substrate W is the surface of the second layer 102, and Si, SiO ２, SiN, or TiN. When the second layer 102 is a Si-containing film, the surface of the second layer 102 of the prepared substrate W is terminated with OH groups to form Si—OH and is hydrophilic. When the second layer 102 is TiN, the surface of the second layer 102 of the prepared substrate W is either terminated with OH groups to form Ti—OH and is hydrophilic, or remains TiN and is not terminated with OH groups, as shown in FIG. 7( a). In this case, the surface of the TiN is hydrophilic.

[0036] If the second layer 102 is made of TiN, its surface will remain hydrophilic even after treatment with hydrofluoric acid (DHF). Therefore, in step S12, the surface of the substrate W is hydrophobized by exposing the substrate W to a first process gas. Note that if the second layer 102 is a Si-containing film, the surface of the substrate W can be hydrophobized by exposing the substrate to the first process gas or the first process solution.

[0037] The first process gas is a Si-containing gas containing Si—H bonds. ４ ), disilane (Si ２ H ６ ), trisilane (Si ３ H ８ ), higher silanes, dichlorosilane (DCS: SiH ２ Cl ２ ), trichlorosilane (SiHCl ３ ), organosilicon compounds.

[0038] For example, as shown in (b-1) of FIG. 7, when the second layer 102 is made of TiN, the second layer 102 is exposed to dichlorosilane gas (DCS), an example of a Si-containing gas. As a result, as shown in (b-2) of FIG. 7, hydrophobic groups having Si—H bonds are physically adsorbed and / or chemically bonded to the surface of the TiN film on the surface of the second layer 102 of the substrate W. That is, Si and / or Si—H are physically adsorbed to the surface of the TiN film. This modifies the hydrophilic surface of the TiN film to a hydrophobic surface. Alternatively, Ti and Si—H in the TiN film chemically bond to form Ti—Si—H. In other words, the terminal groups on the surface are (—Si—H).

[0039] Next, in step S13, the peripheral portion of the substrate is treated with ammonia-hydrogen peroxide (SC1). As shown in FIG. 7(c-1), ammonia-hydrogen peroxide is supplied to the peripheral portion of the substrate from a nozzle disposed on the peripheral portion of the substrate while the stage is rotating. As a result, as shown in FIG. 7(c-2), the surface of the peripheral portion of the substrate is terminated with OH groups to form Ti—Si—OH, Si—OH, or Ti—OH, making it hydrophilic. The area other than the peripheral portion of the substrate, i.e., the central surface of the substrate, remains hydrophobic as Ti—Si—H or Si—H. This allows for selective formation of hydrophobic and hydrophilic surfaces on the substrate.

[0040] Next, in step S14, the pressure inside the processing chamber (processing pressure) is controlled to a first pressure, and a DLC film 103 having a film stress of 1 GPa or more is formed on the substrate W. For example, the first pressure may be 0.13 Pa to 13.3 Pa. As a result, a DLC film 103 having a high film stress (1 GPa or more) is formed, as shown in FIG. 7D.

[0041] Next, in step S15, the processing pressure is controlled to a second pressure higher than the first pressure, and the DLC film 103 on the hydrophilized peripheral edge of the substrate is selectively removed. For example, the substrate W is exposed to atmospheric pressure. As a result, as shown in FIG. 7E, adhesion of only the DLC film 103 on the peripheral edge of the substrate, which has a hydrophilic substrate surface, becomes poor, causing film peeling, and the DLC film 103 on the peripheral edge of the substrate can be selectively removed.

[0042] Next, in step S16, a chemical solution is supplied from a nozzle to clean the peripheral edge of the substrate by a deionized water (DIW) rinse process, thereby removing the peeled DLC film as shown in FIG.

[0043] Third Embodiment Next, a substrate processing method according to a third embodiment will be described with reference to Fig. 8 and Fig. 9. Fig. 8 is a flowchart showing an example of the substrate processing method according to the third embodiment. Fig. 9 is a diagram for explaining the substrate processing method of Fig. 8.

[0044] In the substrate processing method according to the third embodiment, first, in step S21, a substrate having an underlayer is prepared. The prepared substrate W has a first layer 101 and a second layer 102 (FIG. 1). In this embodiment, the second layer 102 serving as the underlayer is a Si-containing film or a TiN film.

[0045] Next, in step S22, the surface of the substrate W is hydrophobized by exposing the substrate W to a first process gas. For example, as shown in FIG. 9B-1, the second layer 102 is exposed to dichlorosilane gas (DCS), an example of a Si-containing gas. On the surface of the second layer 102 of the substrate W, hydrophobic groups having Si—H bonds are physically adsorbed and / or chemically bonded to the surface of the TiN film. That is, Si and / or Si—H are physically adsorbed to the surface of the TiN film. This modifies the hydrophilic surface of the TiN film to a hydrophobic surface. Alternatively, Ti and Si—H in the TiN film chemically bond to form Ti—Si—H. In other words, the terminal groups on the surface are (—Si—H).

[0046] Next, in step S23, the peripheral portion of the substrate is selectively exposed to plasma generated from a second process gas different from the first process gas. The second process gas is water (H ２ O), hydrogen peroxide (H ２ O ２ ), ozone water (O ３ In the example of (c-1) in FIG. 9, H generated from water (steam) ２ An O plasma is formed at the periphery of the substrate.

[0047] As a result, the peripheral edge of the substrate is selectively made hydrophilic, and as shown in (c-2) of Figure 9, the surface of the peripheral edge of the substrate is terminated with OH groups to form Ti-Si-OH, Si-OH, or Ti-OH, making it hydrophilic. The area other than the peripheral edge of the substrate, i.e., the central surface of the substrate, remains hydrophobic as Ti-Si-H or Si-H. As a result, hydrophobic surfaces and hydrophilic surfaces can be selectively formed on the substrate.

[0048] Next, in step S24, the processing pressure in the processing container is controlled to a first pressure, and a DLC film 103 having a film stress of 1 GPa or more is formed on the substrate W. As a result, a DLC film 103 having a high film stress (1 GPa or more) is formed, as shown in FIG.

[0049] Next, in step S25, the processing pressure is controlled to a second pressure higher than the first pressure, and the hydrophilized DLC film 103 on the peripheral edge of the substrate is selectively removed. For example, the substrate W is exposed to atmospheric pressure. As a result, as shown in FIG. 9E, the adhesion of only the DLC film 103 on the peripheral edge of the substrate becomes poor, causing film peeling, and the DLC film 103 on the peripheral edge of the substrate can be selectively removed.

[0050] Next, in step S26, the substrate W is cleaned by exposing it to a fourth process gas. For example, N ２ In step S26, N 2 is supplied as a purge gas to remove the peeled DLC film from the processing vessel. ２ The step of purging the peeled DLC film 103 by supplying gas and the step of evacuating the processing chamber by an exhaust device such as a vacuum pump may be repeated a set number of times.

[0051] This allows the peeled DLC film to be removed, as shown in Fig. 9(f). It is preferable that the peeled DLC film be removed using a filter provided in the gas exhaust piping before being sucked into an exhaust device such as a vacuum pump.

[0052] 8, the hydrophobizing step (S22), the hydrophilizing step (S23), the carbon-containing film forming step (S24), the carbon-containing film selectively removing step (S25), and the substrate cleaning step (S26) can be performed in the same processing vessel of the substrate processing apparatus 700 described below. This can improve throughput and productivity.

[0053] Fourth Embodiment Next, a substrate processing method according to a fourth embodiment will be described with reference to Fig. 10 and Fig. 11. Fig. 10 is a flowchart showing an example of the substrate processing method according to the fourth embodiment. Fig. 11 is a diagram for explaining the substrate processing method of Fig. 10.

[0054] In the substrate processing method according to the fourth embodiment, first, in step S31, a substrate having an undercoat film is prepared. Here, the prepared substrate W has a first layer 101 and a second layer 102 ( FIG. 1 ). After being prepared on a stage, the surface of the substrate W is made hydrophilic using a method similar to that of the other embodiments. However, a substrate W whose surface has been made hydrophilic may also be prepared. In this embodiment, the second layer 102 serving as the undercoat film is a Si-containing film or a TiN film, and the surface of the substrate W is hydrophilic.

[0055] Next, in step S32, clamps 150 that cover the peripheral edge of the substrate are attached to the peripheral edge of the substrate as shown in FIG. 11A. The clamps 150 are an example of a fixing device. Thereafter, in step S33, the surface of the substrate W is hydrophobized as shown in FIG. 11B-1. The hydrophobization of the surface of the substrate W can be performed using a method similar to that used in other embodiments. For example, in a method of hydrophobizing the surface of the substrate W by exposing it to dichlorosilane gas (DCS), the clamps 150 prevent the peripheral edge of the substrate from being exposed to DCS. As a result, the surface of the substrate W other than the peripheral edge of the substrate covered by the clamps 150 is hydrophobized as shown in FIG. 11B-2.

[0056] Next, in step S34, the clamps 150 are removed from the peripheral edge of the substrate as shown in Fig. 11(c-1). At this time, as shown in Fig. 11(c-2), the peripheral edge of the substrate that was covered by the clamps 150 is hydrophilic, and the other surface of the substrate W is hydrophobic.

[0057] Next, in step S35, the pressure inside the processing chamber (processing pressure) is controlled to a first pressure, and a DLC film 103 having a film stress of 1 GPa or more is formed on the substrate W. As a result, a DLC film 103 having a high film stress (1 GPa or more) is formed, as shown in FIG. 11(d).

[0058] Next, in step S36, the processing pressure is controlled to a second pressure higher than the first pressure, and the hydrophilized DLC film 103 on the peripheral edge of the substrate is selectively removed. For example, the substrate W is exposed to atmospheric pressure. As a result, as shown in FIG. 11( e), adhesion of only the DLC film 103 on the peripheral edge of the substrate becomes poor, causing film peeling, and the DLC film 103 on the peripheral edge of the substrate can be selectively removed.

[0059] Next, in step S37, the peripheral edge of the substrate is cleaned by a deionized water (DIW) rinse process, thereby removing the peeled DLC film as shown in FIG.

[0060] In the first to fourth embodiments, the second layer 102 may be a metal film, a metal oxide, or a metal nitride. The metal contained in the metal film, the metal oxide, or the metal contained in the metal nitride may be any of Ti, Ru, Mo, Mg, W, Co, Fe, and Cu.

[0061] [Substrate Processing System] A processing system 100 used in the substrate processing methods according to the first to fourth embodiments will be described with reference to Fig. 12. Fig. 12 is a diagram showing an example of the processing system 100 according to one embodiment.

[0062] The processing system 100 includes substrate processing apparatuses 201 to 204 , a vacuum transfer chamber 205 , load lock chambers 210 , 212 , and 213 , an atmospheric transfer chamber 220 , load ports 231 to 234 , and a control device 250 .

[0063] The substrate processing apparatuses 201 to 204 are connected to a vacuum transfer chamber 205 via gate valves G11 to G14, respectively. The interiors of the substrate processing apparatuses 201 to 204 are depressurized to a predetermined vacuum atmosphere, and desired processing is performed on the substrates W therein. The substrate processing apparatuses 201, 202, 203, and 204 are realized by any one of the substrate processing apparatuses 400, 500, 600, and 700, which will be described later.

[0064] The substrate processing apparatus 201 is a substrate processing apparatus (film forming apparatus) that forms a metal-containing film as the second layer 102 of the substrate W. The metal-containing film is, for example, a TiN film. The substrate processing apparatus 201 is realized by a substrate processing apparatus 700 described later. An example of the substrate processing apparatus 201 will be described later with reference to FIG. 16 .

[0065] Specifically, the substrate processing apparatus 201 is configured to supply a Ti-containing gas (e.g., TiCl) into a processing chamber. ４ gas) and a reactive gas (nitriding gas, for example, ammonia gas or N ２ The substrate processing apparatus 201 alternately supplies a TiN film and a TiN gas (a TiN film) to form the TiN film on the substrate W by atomic layer deposition (ALD). Note that the substrate processing apparatus 201 has been described as a film formation apparatus that forms a TiN film (metal-containing film) on the substrate W by ALD, but is not limited to this. For example, the substrate processing apparatus 201 may be a film formation apparatus that forms a metal-containing film on the substrate W by chemical vapor deposition (CVD). Alternatively, the substrate processing apparatus 201 may be a film formation apparatus that forms a metal-containing film on the substrate W by physical vapor deposition (PVD).

[0066] The substrate processing apparatus 202 performs step S12 ( FIG. 6 ), step S22 ( FIG. 8 ), and step S33 ( FIG. 10 ) to modify the surface of the second layer 102 formed on the substrate W with a Si-containing gas. This makes the surface of the substrate W hydrophobic. The substrate processing apparatus 202 is realized by a substrate processing apparatus 600, which will be described later. An example of the substrate processing apparatus 202 will be described later with reference to FIG. 15 .

[0067] The substrate processing apparatus 203 is a substrate processing apparatus (film forming apparatus) that forms a DLC film 103 (carbon-containing film) on the second layer 102 of the substrate W. The substrate processing apparatus 203 is realized by a substrate processing apparatus 700 described later. An example of the substrate processing apparatus 203 will be described later with reference to FIG. 16 .

[0068] The substrate processing apparatus 204 may be a substrate processing apparatus that performs the same processing process as any of the substrate processing apparatuses 201 to 203, or a substrate processing apparatus (e.g., an annealing apparatus or an etching apparatus) that performs a processing process different from any of the substrate processing apparatuses 201 to 203. Furthermore, the processing of forming the second layer 102 on the substrate W and the processing of modifying the surface of the second layer 102 formed on the substrate W with a Si-containing gas may be performed in the same substrate processing apparatus.

[0069] The interior of the vacuum transfer chamber 205 is depressurized to a predetermined vacuum atmosphere. The vacuum transfer chamber 205 is an example of a transfer device that transfers the substrate W. The vacuum transfer chamber 205 is provided with a transfer mechanism 106 that can transfer the substrate W in a depressurized state. The transfer mechanism 106 transfers the substrate W to the substrate processing apparatuses 201 to 204 and the load lock chambers 210, 212, and 213.

[0070] The load lock chambers 210, 212, and 213 are connected to the vacuum transfer chamber 205 via gate valves G21 to G23, respectively, and are connected to the atmospheric transfer chamber 220 via gate valves G31 to G33. The interiors of the load lock chambers 210, 212, and 213 can be switched between an atmospheric atmosphere and a vacuum atmosphere.

[0071] The atmospheric transfer chamber 220 has an atmospheric atmosphere, and for example, a downflow of clean air is formed. An aligner (not shown) that aligns the substrate W is provided inside the atmospheric transfer chamber 220. The atmospheric transfer chamber 220 also has a transfer mechanism 222. The transfer mechanism 222 transfers the substrate W to the load lock chambers 210, 212, 213, and the carriers C and aligners of the load ports 231 to 234 (described later).

[0072] The load ports 231 to 234 are provided on the wall surface of the atmospheric transfer chamber 220. Carriers C containing substrates W or empty carriers C are attached to the load ports 231 to 234 via gate valves G41 to G44. As the carriers C, for example, FOUPs (Front Opening Unified Pods) can be used.

[0073] The control device 250 controls each part of the processing system 100. For example, the control device 250 executes the operations of the substrate processing devices 201 to 204, the operation of the transfer mechanisms 106 and 222, the opening and closing of the gate valves G11 to G14, G21 to G23, G31 to G33, and G41 to G44, and the switching of the atmospheres in the load lock chambers 210, 212, and 213.

[0074] [Substrate Processing Apparatus 400] An example of the configuration of a substrate processing apparatus 400 used for hydrofluoric acid (DHF) processing (S2 (FIG. 4)), ammonia hydrogen peroxide processing (S3 (FIG. 4), S13 (FIG. 6)), or deionized water (DIW) rinse processing (S6 (FIG. 4), S16 (FIG. 6), S37 (FIG. 10)) will be described with reference to FIG. 13. FIG. 13 is a schematic cross-sectional view showing an example of a substrate processing apparatus 400 that performs hydrofluoric acid processing, ammonia hydrogen peroxide processing, and deionized water rinse processing.

[0075] The substrate processing apparatus 400 includes a processing chamber 410, a rotatable stage 420 for supporting a substrate W, and a chemical supply unit 430. The chemical supply unit 430 includes a chemical tank 431, a pump 432, a heater 433, a filter 434, a circulation path 435, and a supply path 436. The circulation path 435 is formed to circulate the chemical tank 431, the pump 432, the heater 433, and the filter 434. The arrows indicate the circulation direction of the chemical 450. By circulating the chemical, the chemical 450 in the chemical tank 431 can be heated to a predetermined temperature. The chemical 450 in the chemical tank 431 is supplied to the surface of the substrate in the processing chamber 410 via the supply path 436. As the stage 420 rotates, the chemical 450 flows toward the outer periphery of the substrate W and is discharged through the discharge path 411. Furthermore, the supply of the chemical solution 450 from the chemical solution supply unit 430 to the processing chamber 410 is stopped, and the stage 420 on which the substrate W is placed is rotated to dry the substrate W.

[0076] In the hydrofluoric acid (DHF) treatment, the chemical solution 450 (hydrofluoric acid) in the chemical solution tank 431 is supplied from the nozzle 437 via the supply path 436, and the stage 420 is rotated to supply the chemical solution 450 to the entire surface of the substrate W. This makes it possible to make the surface of the substrate hydrophobic.

[0077] In the ammonia hydrogen peroxide treatment, the nozzle 437 is moved to the edge of the substrate W, and then the chemical solution 450 (ammonia hydrogen peroxide) in the chemical solution tank 431 is supplied from the nozzle 437 via the supply path 436. The stage 420 is rotated to supply the ammonia hydrogen peroxide to the edge of the substrate W. This makes it possible to make the surface of the substrate hydrophilic.

[0078] In the deionized water (DIW) rinse process, the chemical liquid supply unit 430 is not necessary. Deionized water is supplied from a nozzle 439 via a utility line 438. This makes it possible to clean the substrate W. The nozzle 439 is movable in the horizontal direction.

[0079] During the pure water rinse process, when the pure water (chemical solution 450) is discharged from the discharge path 411, a bypass line 416 is provided in the discharge path 411 to prevent the peeled DLC film 103 from flowing directly into the exhaust device 415.

[0080] During the hydrofluoric acid treatment and the ammonia hydrogen peroxide treatment, the valve 413 of the bypass line 416 is closed, the valve 412 is opened, and the chemical solution 450 is directly discharged from the discharge path 411 by the exhaust device 415. During the pure water rinse treatment, the valve 413 of the bypass line 416 is opened, the valve 412 is closed, and the pure water is allowed to flow from the discharge path 411 to the bypass line 416. This causes the pure water to pass through a filter 414 provided in the bypass line 416, and after the DLC film 103 contained in the pure water is removed by the filter 414, the pure water is discharged by the exhaust device 415. This makes it possible to protect the exhaust device 415.

[0081] [Substrate Processing Apparatus 500] For hydrofluoric acid (DHF) processing or deionized water (DIW) rinsing processing, a batch-type substrate processing apparatus 500 shown in Fig. 14 may be used. Furthermore, when the ammonia-hydrogen peroxide processing is performed on the entire surface of the substrate W, the substrate processing apparatus 500 can be used for the ammonia-hydrogen peroxide processing. Fig. 14 is a structural diagram showing an example of a substrate processing apparatus 500 that performs hydrofluoric acid processing, ammonia-hydrogen peroxide processing (when processing the entire surface of the substrate W), and deionized water rinsing processing.

[0082] The substrate processing apparatus 500 has an inner bath 510 for accommodating substrates W, an outer bath 520, a heater 531, a pump 532, a filter 533, and a flow path 534. The inner bath 510 and the outer bath 520 store a chemical solution 550 (hydrofluoric acid, ammonia hydrogen peroxide) or pure water. The chemical solution 550 or pure water discharged from the inner bath 510 flows into the outer bath 520. The chemical solution 550 in the outer bath 520 passes through the flow path 534, the heater 433, the pump 432, and the filter 434, is heated to a predetermined temperature, and is then supplied to the inner bath 510. The arrows indicate the direction of circulation of the chemical solution.

[0083] [Substrate Processing Apparatus 600] An example of the configuration of a substrate processing apparatus 600 used for hydrophobizing the substrate surface using dichlorosilane gas (DCS) (S12 (FIG. 6), S22 (FIG. 8), S33 (FIG. 10)) will be described with reference to FIG. 15. FIG. 15 is a schematic cross-sectional view showing an example of a substrate processing apparatus 600 that performs hydrophobizing using a Si-containing gas. DCS and HMDS are examples of Si-containing gases. Hydrophobizing using DCS is a thermal process in which gas is sprayed without generating plasma.

[0084] The substrate processing apparatus 600 includes a processing chamber 610, a stage 620 on which a substrate W is placed, a heater 630 provided on the stage 620 for heating the stage 620 and the substrate W, and a gas supply unit 640. The gas supply unit 640 includes a vaporizer and vaporizes a chemical solution. The vaporized chemical solution 650 is a Si-containing gas. The vaporized chemical solution 650 is supplied to the processing chamber 610. After processing, the vaporized chemical solution 650 is discharged from an exhaust path 611.

[0085] For example, in step S22 (FIG. 8), the substrate W is exposed to a Si-containing gas, and the hydrophobicized substrate surface is treated with H ２ The peripheral edge of the substrate is hydrophilized by O plasma treatment. Thereafter, in step S24 (FIG. 8), a carbon-containing film (DLC film 103) having a film stress of 1 GPa or more is formed by the substrate processing apparatus 700.

[0086] [Substrate Processing Apparatus 700] The carbon-containing film (DLC film 103) forming process (S4 (FIG. 4), S14 (FIG. 6), S24 (FIG. 8), S35 (FIG. 10)) and H ２ An example of the configuration of a substrate processing apparatus 700 used in the O plasma treatment (S23 (FIG. 8)) will be described with reference to FIG. 16. FIG. 16 is a schematic cross-sectional view showing an example of a substrate processing apparatus 700 that performs a series of processes in the carbon-containing film formation process or the substrate processing method. The substrate processing apparatus 700 is a plasma processing apparatus.

[0087] The substrate processing apparatus 700 is an apparatus for forming a carbon-containing film (for example, the DLC film 103) on a substrate W by a CVD (Chemical Vapor Deposition) method in a processing chamber 702 under reduced pressure.

[0088] The substrate processing apparatus 700 includes a substantially cylindrical, airtight processing vessel 702. An exhaust chamber 721 is provided in the center of the bottom wall of the processing vessel 702. The exhaust chamber 721 has, for example, a substantially cylindrical shape that protrudes downward. An exhaust passage 722 is connected to the exhaust chamber 721, for example, at a side surface of the exhaust chamber 721. An exhaust unit 724 is connected to the exhaust passage 722 via a pressure adjustment unit 723. The pressure adjustment unit 723 includes a pressure adjustment valve such as a butterfly valve. The exhaust passage 722 is configured to reduce the pressure inside the processing vessel 702 by the exhaust unit 724. The exhaust unit 724 includes a vacuum pump. A transfer port 725 is provided in a side surface of the processing vessel 702. The transfer port 725 is configured to be freely opened and closed by a gate valve 726. The substrate W is loaded and unloaded between the processing vessel 702 and a transfer chamber (not shown) through the transfer port 725.

[0089] A mounting table 703 for holding a substrate W substantially horizontally is provided within the processing vessel 702. The mounting table 703 is substantially circular in plan view and supported by a support member 731. A substantially circular recess 732 for mounting a substrate W having a diameter of, for example, 300 mm is formed in the surface of the mounting table 703. The recess 732 has an inner diameter slightly larger (for example, about 1 mm to 4 mm) than the diameter of the substrate W. The depth of the recess 732 is configured to be substantially the same as the thickness of the substrate W. The mounting table 703 is made of a ceramic material such as aluminum nitride (AlN). Alternatively, the mounting table 703 may be made of a metal material such as nickel (Ni). Note that instead of the recess 732, a guide ring for guiding the substrate W may be provided around the periphery of the surface of the mounting table 703.

[0090] A lower electrode 733 is embedded in the mounting table 703. A temperature adjustment mechanism 734 is embedded below the lower electrode 733. The temperature adjustment mechanism 734 adjusts the temperature of the substrate W placed on the mounting table 703 to a set temperature based on a control signal from the control unit 709.

[0091] An RF power supply 735 is connected to the lower electrode 733 via a matcher 735a. The RF power supply 735 applies power of a frequency (LF; Low Frequency) lower than the frequency of an RF power supply 751 (described later) to the lower electrode 733. The low frequency power generated by the RF power supply 735 is used as low frequency power for biasing to attract ions into the substrate W. The frequency of the RF power supply 735 is 450 kHz to 27 MHz, for example, 13.56 MHz.

[0092] The mounting table 703 is provided with a plurality of (e.g., three) lift pins 741 for holding and lifting the substrate W mounted on the mounting table 703. The lift pins 741 may be made of, for example, ceramics such as alumina (Al2O3) or quartz. The lower ends of the lift pins 741 are attached to a support plate 742. The support plate 742 is connected via a lift shaft 743 to a lift mechanism 744 provided outside the processing vessel 702.

[0093] The lifting mechanism 744 is installed, for example, at the bottom of the exhaust chamber 721. The bellows 745 is provided between the lifting mechanism 744 and an opening 721a for the lifting shaft 743 formed in the bottom surface of the exhaust chamber 721. The support plate 742 may be shaped so that it can be raised and lowered without interfering with the support member 731 of the mounting table 703. The lifting pins 741 are configured to be able to be raised and lowered between an upper side and a lower side of the surface of the mounting table 703 by the lifting mechanism 744. In other words, the lifting pins 741 are configured to be able to protrude from the top surface of the mounting table 703.

[0094] The lower end of the support member 731 passes through an opening 721b of the exhaust chamber 721 and is supported by a lifting mechanism 746 via a lifting plate 747 disposed below the processing vessel 702. A bellows 748 is provided between the bottom of the exhaust chamber 721 and the lifting plate 747, so that the airtightness inside the processing vessel 702 is maintained even when the lifting plate 747 moves up and down.

[0095] The lifting mechanism 746 lifts and lowers the lifting plate 747, thereby lifting and lowering the mounting table 703. This makes it possible to adjust the gap between the mounting table 703 and the lower surface of the upper electrode plate 705.

[0096] An upper electrode plate 705 is provided on a ceiling wall 727 of the processing vessel 702 via an insulating member 728. The upper electrode plate 705 serves as an upper electrode and is disposed parallel to and facing the lower electrode 733. An RF power source 751 is connected to the upper electrode plate 705 via a matching unit 751a. The RF power source 751 supplies high frequency (HF) power to the upper electrode plate 705, the high frequency power being higher than the frequency of the RF power source 735. The high frequency power generated by the RF power source 751 is used as high frequency power for generating plasma required for film formation on the substrate W. The frequency of the RF power source 751 is, for example, 450 KHz to 2.45 GHz. RF power is applied from the RF power source 751 to the upper electrode plate 705. This generates an RF electric field between the mounting table 703 and the upper electrode plate 705. The upper electrode plate 705 includes a hollow gas diffusion chamber 752. A number of holes 753 for dispersively supplying the processing gas into the processing vessel 702 are arranged, for example, uniformly, on the lower surface of the gas diffusion chamber 752. A heating mechanism 754 is embedded in the upper electrode plate 705, for example, above the gas diffusion chamber 752. The heating mechanism 754 is heated to a set temperature by receiving power from a power supply unit (not shown) based on a control signal from the control unit 709.

[0097] The gas diffusion chamber 752 is provided with a gas supply path 706. The gas supply path 706 is in communication with the gas diffusion chamber 752. A gas source 761 is connected to the upstream side of the gas supply path 706 via a gas line 762. The gas source 761 includes, for example, supply sources of various process gases, mass flow controllers, and valves (none of which are shown). The process gas used in the method for forming a carbon-containing film includes a carbon-containing gas. The carbon-containing gas includes a gas containing carbon and hydrogen (CxHy), a gas containing carbon and fluorine (CxFy), a gas containing carbon and oxygen (e.g., CO ２ ), and a gas containing carbon and a metal (for example, an organometallic precursor such as TDMAT) (where x and y are arbitrary numbers). The carbon-containing gas may be, for example, CH ４ , C ２ H ２ , C ２ H４ , C ３ H ６ , C ６ H ６ The process gas may also contain an inert gas or a dilution gas (e.g., H ２ , Ar, He, O ２ , N ２ The process gas may further include hydrogen gas. Various gases are introduced into the gas diffusion chamber 752 from a gas source 761 via a gas line 762.

[0098] The substrate processing apparatus 700 includes a control unit 709. The control unit 709 is, for example, a computer, and includes a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read Only Memory), an auxiliary storage device, etc. The CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the substrate processing apparatus 700. The control unit 709 may be provided inside or outside the substrate processing apparatus 700. When the control unit 709 is provided outside the substrate processing apparatus 700, the control unit 709 can control the substrate processing apparatus 700 via communication means such as wired or wireless.

[0099] With this configuration, the substrate processing apparatus 700 forms a carbon-containing film on the surface of the substrate. Specifically, the control unit 709 forms the carbon-containing film using plasma of a carbon-containing gas. The substrate processing apparatus 700 also forms a carbon-containing film on the surface of the substrate using H ２ The control unit 709 controls the temperature adjustment mechanism 734 to adjust the temperature of the substrate W to a predetermined temperature. The temperature adjustment mechanism 734 also controls the pressure adjustment unit 723 and the exhaust unit 724 to adjust the pressure inside the processing vessel 702 to a predetermined pressure. The control unit 709 also controls the gas source 761 to supply a carbon-containing gas into the processing vessel 702. The control unit 709 also controls the RF power supply 751 to apply high-frequency power (HF) to the upper electrode plate 705. The control unit 709 also controls the RF power supply 735 to apply low-frequency power (LF) to the lower electrode 733. This generates plasma of the carbon-containing gas, and this plasma forms a carbon-containing film on the substrate W.

[0100] An example of the film formation conditions for the DLC film 103 having a film stress of 1 GPa or more will be given below.

[0101] Processing pressure: 5 mT to 200 mT (0.67 Pa to 2.67 Pa) Plasma power: 10 W to 2000 W DLC film thickness: 20 nm to 1 μm

[0102] In the above, an example has been described in which high frequency power (HF) is applied to the upper electrode plate 705 and low frequency power (LF) is applied to the lower electrode 733, but this is not limitative. For example, two frequencies, high frequency power (HF) and low frequency power (LF), may be applied to the upper electrode plate 705, or two frequencies, high frequency power (HF) and low frequency power (LF) may be applied to the lower electrode 733.

[0103] In step S23 (FIG. 8), H is applied under process conditions in which plasma is generated only near the edge of the substrate. ２ In the case where the second layer 102 is made of SiO or TiO, H plasma may be generated under process conditions that generate plasma only near the edge of the substrate, and the H plasma may be used to make the peripheral edge of the substrate hydrophilic in step S23 (FIG. 8).

[0104] As described above, according to the substrate processing method and substrate processing apparatus of this embodiment, the state of the substrate surface can be controlled to selectively remove the carbon-containing film on the peripheral edge of the substrate.

[0105] The substrate processing method and substrate processing apparatus according to the presently disclosed embodiments should be considered to be illustrative in all respects and not restrictive. The embodiments can be modified and improved in various ways without departing from the spirit and scope of the appended claims. The features described in the above embodiments can be configured in other ways as long as they are not inconsistent, and can be combined as long as they are not inconsistent.

[0106] This international application claims priority based on Japanese Patent Application No. 2023-132928, filed on August 17, 2023, the entire contents of which are incorporated herein by reference.

[0107] 101 First layer 102 Second layer 103 Carbon-containing film (DLC film) 500 to 700 Substrate processing apparatus

Claims

1. A substrate processing method comprising the steps of: preparing a substrate having an undercoat film; hydrophobizing a surface of the substrate; selectively hydrophilizing a peripheral portion of the substrate; setting a processing pressure to a first pressure and forming a carbon-containing film having a film stress of 1 GPa or more on the substrate; and setting the processing pressure to a second pressure higher than the first pressure and selectively removing the carbon-containing film from the hydrophilized peripheral portion of the substrate.

2. A substrate processing method comprising the steps of: preparing a substrate having an undercoat film; hydrophilizing a surface of the substrate; attaching a fixture covering a peripheral portion of the substrate and then hydrophobizing a surface of the substrate not covered by the fixture; removing the fixture from the peripheral portion of the substrate; setting a processing pressure to a first pressure and forming a carbon-containing film having a film stress of 1 GPa or more on the substrate; and setting the processing pressure to a second pressure higher than the first pressure and selectively removing the carbon-containing film from the hydrophilized peripheral portion of the substrate.

3. The substrate processing method according to claim 1 or 2, wherein the hydrophobizing step terminates the surface of the substrate with Si--H groups or H groups.

4. The substrate processing method according to claim 3, wherein the surface of the substrate contains Si, and the hydrophobizing step includes exposing the substrate to a first processing solution.

5. The method of claim 4, wherein the first processing solution includes at least one of DHF, BHF, TMSDMA, HMDS, and a silane coupling agent.

6. The surface of the substrate is Si, SiO ２ 5. The substrate processing method according to claim 4, wherein the material is either SiN or SiN.

7. The surface of the substrate is Si, TiN, SiO ２ 4. The substrate processing method according to claim 3, wherein the hydrophobicity-imparting step comprises exposing the substrate to a first processing gas.

8. The substrate processing method according to claim 7, wherein the first processing gas is a Si-containing gas containing Si-H bonds.

9. The Si-containing gas containing the Si-H bond is silane (SiH ４ ), disilane (Si ２ H ６ ), trisilane (Si ３ H ８ ), higher silanes, DCS (SiH ２ C ２ ), trichlorosilane (SiHCl ３ 9. The method of claim 8, further comprising at least one of the following:

10. The substrate processing method according to claim 7, wherein the metal film, the metal contained in the metal oxide, and the metal contained in the metal nitride are any one of Ti, Ru, Mo, Mg, W, Co, Fe, and Cu.

11. The substrate processing method according to claim 1 or 2, wherein the hydrophilizing step terminates the surface of the substrate with OH groups.

12. The substrate processing method according to claim 4, wherein the step of hydrophilizing includes selectively exposing a peripheral portion of the substrate to a second processing solution different from the first processing solution.

13. The second processing solution is ammonia hydrogen peroxide, hydrochloric acid hydrogen peroxide, or ozone water (O ３ ), hydrogen peroxide (H ２ O ２ 13. The method of claim 12, further comprising at least one of a sulfuric acid / hydrogen peroxide solution and an aqueous solution of ammonium peroxodisulfate.

14. The substrate processing method according to claim 7, wherein the hydrophilizing step includes selectively exposing a peripheral portion of the substrate to plasma generated from a second processing gas different from the first processing gas.

15. The second process gas is water (H ２ O), hydrogen peroxide (H ２ O ２ ), ozone water (O ３ 15. The method of claim 14, further comprising at least one of:

16. The substrate processing method according to claim 1 or 2, wherein the step of forming the carbon-containing film includes exposing the substrate to plasma generated from a third process gas that includes a carbon-containing gas.

17. The substrate processing method according to claim 16, wherein the carbon-containing gas includes at least one of a gas containing carbon and hydrogen, a gas containing carbon and fluorine, a gas containing carbon and oxygen, and a gas containing carbon and a metal.

18. The method of claim 17, wherein the carbon-containing gas is a hydrocarbon gas.

19. The method of claim 16, wherein the third process gas further comprises an inert gas.

20. The inert gas is argon (Ar) gas, helium (He) gas, nitrogen (N ２ 20. The method of claim 19, further comprising at least one of a nitrogen gas, a xenon (Xe) gas, and a krypton (Kr) gas.

21. The substrate processing method according to claim 1 or 2, wherein the first pressure is 0.13 Pa to 13.3 Pa.

22. The substrate processing method according to claim 1 or 2, further comprising the step of cleaning the substrate after the step of forming the carbon-containing film.

23. The method of processing a substrate according to claim 22, wherein cleaning the substrate comprises exposing the substrate to a third processing solution.

24. The method of claim 23, wherein the third processing solution comprises deionized water (DIW).

25. The method of claim 22, wherein cleaning the substrate comprises exposing the substrate to a fourth process gas.

26. The fourth process gas is N ２ The method of claim 25 , comprising:

27. The substrate processing method according to claim 22, wherein the hydrophobizing step, the hydrophilizing step, the carbon-containing film forming step, the carbon-containing film selectively removing step, and the substrate cleaning step are carried out in a same processing vessel.

28. A substrate processing apparatus comprising: a processing vessel; a substrate support having a mounting surface on which a substrate is placed; a shower head facing the substrate support and supplying a processing gas toward the substrate; a gas supply source; a plasma power source connected to the showerhead and supplying plasma; and a control unit, wherein the control unit controls the steps of: preparing a substrate having an undercoat film; hydrophobizing a surface of the substrate; selectively hydrophilizing a peripheral portion of the substrate; setting a processing pressure to a first pressure and forming a carbon-containing film having a film stress of 1 GPa or more on the substrate; setting the processing pressure to a second pressure higher than the first pressure and selectively removing the carbon-containing film from the hydrophilized peripheral portion of the substrate; and cleaning the substrate after the carbon-containing film forming step, wherein the hydrophobizing step, the hydrophilizing step, the carbon-containing film forming step, the selectively removing the carbon-containing film, and the cleaning step are performed within the same processing vessel.

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