Substrate processing method, plasma processing apparatus and substrate processing system

Abstract

The present invention provides a substrate processing method, a plasma processing apparatus, and a substrate processing system capable of suppressing defects when bonding a substrate having an insulating layer and a conductive layer containing Cu. The substrate processing method includes: a step of exposing a substrate having an insulating layer and a conductive layer including Cu to plasma of a first processing gas to activate a surface of the substrate; a step of exposing the substrate after the step of activating the surface of the substrate to plasma of a second processing gas, and forming an oxidation suppression layer for suppressing oxidation of the Cu on the surface of the conductive layer; a step for forming a hydroxyl group on the surface of the substrate by supplying water to the surface of the substrate after the step for forming the oxidation-inhibiting layer; a step of bonding the one substrate after the step of forming the hydroxyl group to the other substrate after the step of forming the hydroxyl group; and a step of performing heat treatment on the bonded substrate.

Description

Technical Field

[0001] The present invention relates to a substrate processing method, a plasma processing apparatus, and a substrate processing system. Background Art

[0002] Patent Document 1 discloses a method for manufacturing a semiconductor device, which includes: a step of preparing a semiconductor substrate in a state where a copper or copper-containing metal film is exposed on the surface; a step of forming a metal film composed of either a cobalt-tungsten-based metal or tungsten on the copper or copper-containing metal film; a step of introducing Si into the metal film; and a step of nitriding the metal film into which Si has been introduced.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2009-16520 Summary of the Invention

[0006] Technical Problem to be Solved by the Invention

[0007] In one aspect of the present invention, there are provided a substrate processing method, a plasma processing apparatus, and a substrate processing system that can suppress defects when bonding a substrate having a conductive layer containing Cu and an insulating layer.

[0008] Means for Solving the Technical Problem

[0009] To solve the above technical problem, according to one aspect of the present invention, there is provided a substrate processing method, which includes: a step of exposing a substrate having a conductive layer containing Cu and an insulating layer to a plasma of a first processing gas to activate the surface of the substrate; a step of exposing the substrate after the step of activating the surface of the substrate to a plasma of a second processing gas to form an oxidation-inhibiting layer on the surface of the conductive layer for inhibiting the oxidation of Cu; a step of supplying water to the surface of the substrate after the step of forming the oxidation-inhibiting layer to form hydroxyl groups on the surface of the substrate; a step of bonding one substrate after the step of forming hydroxyl groups to another substrate after the step of forming hydroxyl groups; and a step of heat-treating the bonded substrate.

[0010] Advantages of the Invention

[0011] According to one aspect of the present invention, there are provided a substrate processing method, a plasma processing apparatus, and a substrate processing system that can suppress defects when bonding a substrate having a conductive layer containing Cu and an insulating layer. Brief Description of the Drawings

[0012] Figure 1It is a flowchart showing an example of a method for bonding a substrate.

[0013] Figure 2A It is an example of a cross-sectional view of the substrate at each step.

[0014] Figure 2B It is an example of a cross-sectional view of the substrate at each step.

[0015] Figure 2C It is an example of a cross-sectional view of the substrate at each step.

[0016] Figure 2D It is an example of a cross-sectional view of the substrate at each step.

[0017] Figure 3A It is an example of a cross-sectional view of the substrate at each step.

[0018] Figure 3B It is an example of a cross-sectional view of the substrate at each step.

[0019] Figure 3C It is an example of a cross-sectional view of the substrate at each step.

[0020] Figure 3D It is an example of a cross-sectional view of the substrate at each step.

[0021] Figure 4A It is an example of a cross-sectional view of the substrate at each step.

[0022] Figure 4B It is an example of a cross-sectional view of the substrate at each step.

[0023] Figure 5 It is an example of a cross-sectional view of the substrate for explaining photoetching.

[0024] Figure 6A It is an example of a model diagram showing the oxidation of the conductive layer in the reference example.

[0025] Figure 6B It is an example of a model diagram showing the oxidation of the conductive layer in the reference example.

[0026] Figure 7A It is an example of a model diagram showing the oxidation of the conductive layer in the present invention.

[0027] Figure 7B It is an example of a model diagram showing the oxidation of the conductive layer in the present invention.

[0028] Figure 8 It is a diagram showing an example of the XPS analysis results.

[0029] Figure 9 It is a diagram showing an example of the XPS analysis result.

[0030] Figure 10 It is a diagram showing an example of the XPS analysis result.

[0031] Figure 11 It is a diagram showing an example of the XPS analysis result. Detailed implementation mode

[0032] Hereinafter, the mode for implementing the present invention will be described with reference to the accompanying drawings. In each of the drawings, the same reference numerals are assigned to the same components, and repeated descriptions are omitted.

[0033] <Substrate bonding>

[0034] Use Figures 1 to 4B The bonding method of the substrate W in one embodiment will be described. Figure 1 It is an example of a flowchart showing the bonding method of the substrate W. Here, substrates W (W1, W2) having an insulating layer 110 and a conductive layer 120 are bonded. In addition, Figures 2A to 4B In, a part of the surface of the substrate W is illustrated, and the illustration of other parts is omitted.

[0035] In step S101, the substrate W is prepared.

[0036] Figure 2A It is an example of a cross-sectional schematic view of the substrate W prepared in step S101. The substrate W has an insulating layer 110 and a conductive layer 120. The insulating layer 110 is formed of an insulating material. The insulating layer 110 is, for example, SiO2. Recesses 111 such as vias, holes, and trenches are formed in the insulating layer 110. The conductive layer 120 is formed of Cu or a metal material containing Cu. The conductive layer 120 is formed so as to cover the recesses 111 of the insulating layer 110 and the upper surface of the insulating layer 110. The conductive layer 120 is, for example, a wiring layer connected to a semiconductor device (not shown) formed on the substrate W. That is, the substrate W is a substrate W having a semiconductor device formed through a semiconductor device forming step and having a back end (BEOL: back end of line) including an insulating layer 110 and a conductive layer 120 formed through a wiring step.

[0037] In step S102, a chemical mechanical polishing (CMP) process module is used to perform CMP processing on the substrate W. By the CMP processing, the surface of the substrate W is polished to remove the conductive layer 120 formed on the upper surface of the insulating layer 110. In addition, by the CMP processing, the upper surface of the insulating layer 110 and the upper surface of the conductive layer 120 are formed to be coplanar.

[0038] In addition, considering that the conductive layer 120 will thermally expand during the annealing process (refer to step S109) described later, the surface of the conductive layer 120 can be formed to be lower than the surface of the insulating layer 110. For example, after the CMP processing, the conductive layer 120 can be etched with water containing CO2 so that the surface of the conductive layer 120 is lower than the surface of the insulating layer 110. In addition, when etching the conductive layer 120 with water containing CO2, in order to suppress the photo-corrosion described later, it is preferably performed in a dark room.

[0039] Figure 2B FIG. is an example of a cross-sectional view of the substrate W after the processing of step S102. Here, the surface (upper surface) of the substrate W has a first region formed by the insulating layer 110 and a second region formed by the conductive layer 120. In addition, the surface of the conductive layer 120 is formed to be lower than the surface of the insulating layer 110.

[0040] In addition, as Figure 2B shown, a modified layer 121 is formed on the surface of the conductive layer 120. The modified layer 121 is a layer generated during the CMP processing and also includes a layer formed to suppress the outermost surface corrosion and oxidation of the conductive layer 120. The modified layer 121 is formed, for example, by an adsorption layer of benzotriazole (BTA) and CuO, CuO2, Cu(OH)2, etc. generated during CMP.

[0041] In step S103, a plasma processing apparatus is used to perform plasma activation processing on the substrate W. Here, the substrate W is exposed to the plasma of the first processing gas 200 to clean the surface of the conductive layer 120 and perform activation processing on the surface of the insulating layer 110. Here, it is preferable to use a plasma of a gas containing H (hydrogen) and / or N (nitrogen), a noble gas such as Ar, etc. The gas containing H (hydrogen) and / or N (nitrogen) is H2 gas, N2 gas, NH3 gas, a mixed gas of H2 and N2, or a mixed gas of H2 and NH3. In addition, in order to suppress the oxidation of the surface of the conductive layer 120, it is preferable to use a plasma generated from a gas containing no O (oxygen).

[0042] Figure 2CThis is an example of a cross-sectional schematic diagram of the substrate W during the process of step S103. By exposing the surface of the substrate W to plasma, substances such as benzotriazole (BTA) on the surface of the substrate W are removed. Additionally, by exposing the surface of the substrate W to plasma, a reduction treatment is performed on the surface of the conductive layer 120. Thereby, the modified layer 121 (refer to Figure 2B ) is removed from the surface of the conductive layer 120, cleaning the surface of the conductive layer 120.

[0043] Furthermore, by exposing the surface of the substrate W to plasma, the terminal groups on the surface of the insulating layer 110 are cut off, forming an active surface (not shown) on the surface of the insulating layer 110. Thereby, the surface of the insulating layer 110 becomes a state in which the hydroxyl group 410 (refer to Figure 3B ) described later is easily adsorbed.

[0044] In step S104, using a plasma processing apparatus, a second processing gas 300 is supplied to the substrate W to perform a selective surface treatment on the conductive layer 120. Here, the second processing gas 300 uses a gas containing atoms that easily form bonds with Cu in the conductive layer 120 and have a stronger bond with O (oxygen) than the Cu - O bond. In other words, the second processing gas 300 uses a gas containing atoms with a high diffusion rate into Cu in the conductive layer 120 and a higher oxide stability than Cu (preferably oxidized before Cu). Further in other words, a gas containing atoms with a smaller Gibbs energy than Cu in the bonding reaction with O (oxygen) is used.

[0045] Specifically, as the second processing gas 300, a gas containing Si or a gas containing Al can be used. As the gas containing Si, for example, any one of SiH4, Si2H6, SiCl4, Si2Cl2H2, Si2Cl6 (HCD), SiH2(C2H5)2, Si2H3Cl3, Si(SiH3)4, N[Si(CH3)3][SiHCH3N(CH3)2]2, N(SiH3)3, N(Si2H5)3, SiH[N(CH3)2]3, SiCl2(CH3)2, SiH2[NH(t-C4H9)]2, SiH3[N(i-C4H7)2], SiH(CH3)3, etc. can be used. As the gas containing Al, for example, any one of AlCl3, Al(CH3)3 (TMA), AlH(CH3)2 (DMAH), Al(CH3)2Cl, Al(C2H5)3, Al(C4H9)3, Al[N(C2H5)2]3, Al[N(C2H5)2]2[C3H6N(CH3)2], Al[O(CH3)2CH2OCH3]3, Al[N(i-C3H7)2]3, Al(CH3)2[C3H6(CH3)2], AlH2[N(t-C4H9)CH2CH2N(CH3)2], etc. can be used. In the following description, the case where SiH4 gas is used as the second processing gas 300 will be described.

[0046] Figure 2D FIG. is an example of a cross-sectional view of the substrate W in the process of step S104. Here, SiH4 is selectively adsorbed on the conductive layer 120 with respect to the insulating layer 110. By selectively adsorbing SiH4 on the conductive layer 120, an oxidation-inhibiting layer 130 for suppressing the oxidation of Cu is formed on the surface of the conductive layer 120. The oxidation-inhibiting layer 130 is formed by bonding Cu with atoms (such as Si and / or Al) whose bonding with O (oxygen) is stronger than the bonding of Cu - O.

[0047] In addition, the step of selectively forming the oxidation-inhibiting layer 130 on the surface of the conductive layer 120 can be performed in a single step.

[0048] Furthermore, the process of step S104 is performed, for example, in a low-temperature region such as 100°C. In addition, the process of step S104 can also use a temperature range of 0°C to 400°C.

[0049] In addition, the processes shown in steps S103 to S104 are preferably carried out in a vacuum atmosphere, and may also be processes with atmosphere control. In addition, in the case of atmosphere control, the atmosphere gas can be a gas that does not react with or hardly reacts with the active surface. Additionally, the process shown in step S103 and the process shown in step S104 can be carried out in the same plasma processing apparatus. Alternatively, it can also be a structure in which the plasma processing apparatus for carrying out the process shown in step S103 and the plasma processing apparatus for carrying out the process shown in step S104 are connected by a vacuum transfer chamber or a transfer chamber with atmosphere control. Thereby, it is possible to suppress the formation of a natural oxide film on the surface of the conductive layer 120 after the process shown in step S103 and before the process shown in step S104.

[0050] In step S105, the substrate W is spin-cleaned using a water washing processing module. In step S106, the substrate W is dried using the water washing processing module.

[0051] Figure 3A is an example of a cross-sectional view of the substrate W in the process of step S105. Figure 3B is an example of a cross-sectional view of the substrate W after step S106. The water washing processing module supplies water from a liquid supply unit (not shown) to the surface of the substrate W placed on a rotating table (not shown) in an atmospheric atmosphere, and rotates the rotating table to rotate the substrate W, thereby spin-cleaning the surface of the substrate W. Here, as Figure 3A shown, water molecules 400 exist on the surface of the substrate W. By the reaction of the water molecules 400 with the active surface (not shown) formed on the surface of the insulating layer 110, as Figure 3B shown, hydroxyl groups 410 are bonded to the surface of the insulating layer 110.

[0052] Here, the oxidation inhibition layer 130 formed on the surface of the conductive layer 120, as will be described later using Figure 7A 、 7B can inhibit the bonding of O (oxygen) to Cu. Additionally, the oxidation inhibition layer 130, as will be described later using Figure 5 can inhibit photo-corrosion.

[0053] In step S107, using a substrate bonding processing module, substrate position alignment is carried out as a preparation for bonding two substrates W.

[0054] Figure 3CThis is an example of a cross-sectional view of the substrate W after step S107. The lower substrate W1 and the upper substrate W2 have respectively undergone the processes of steps S101 to S106. That is, hydroxyl groups 410 are bonded to the surface of the insulating layer 110, and an oxidation inhibition layer 130 is formed on the surface of the conductive layer 120. Here, the alignment of the positions of the substrates W1 and W2 is performed.

[0055] In step S108, two substrates W are bonded using a substrate bonding processing module.

[0056] Figure 3D This is an example of a cross-sectional view of the substrate W in step S108. The hydroxyl groups 410 formed on the surface of the lower substrate W1 are bonded to the hydroxyl groups 410 formed on the surface of the upper substrate W2 to remove H2O, thereby bonding the substrates W1 and W2.

[0057] In step S109, the bonded substrate W3 is annealed using a heat treatment module. In addition, the annealing temperature is, for example, in the range of 300°C to 400°C. In addition, the annealing temperature is not limited to this.

[0058] Figure 4A This is an example of a cross-sectional view of the substrate W3 before the annealing treatment. By bonding the substrates W1 and W2 (refer to Figure 3D ), the bonded substrate W3 is formed. Here, an oxidation inhibition layer 130 is formed at the interface of the upper and lower conductive layers 120. In addition, it is possible to make the oxidation inhibition layer 130 (especially the oxidation inhibition layer using Si) also have the same bonding as the substrates W1 and W2. Therefore, bonding can also be formed between the oxidation inhibition layers 130 to improve the bonding strength.

[0059] Figure 4B This is an example of a cross-sectional view of the substrate W3 after the annealing treatment. Through the annealing treatment, the Cu in the conductive layer 120 of the lower substrate W1 (refer to Figure 3D ) diffuses mutually with the Cu in the conductive layer 120 of the upper substrate W2 (refer to Figure 3D ), thereby bonding the upper and lower conductive layers 120.

[0060] As described above, two substrates W (W1, W2) having an insulating layer 110 and a conductive layer 120 are bonded. That is, the bonding of the insulating layer 110 is performed through the bonding of the hydroxyl groups 410 of the insulating layer 110 to each other. In addition, the bonding of the conductive layer 120 is performed through the mutual diffusion of Cu generated by heat treatment (annealing treatment).

[0061] In addition, implement Figures 2A to 4BThe substrate processing system for substrate bonding processing shown includes a CMP processing module, one or more plasma processing devices, a water washing processing module, a substrate bonding processing module, and a heat treatment module.

[0062] Here, Figure 5 is used to illustrate photoetching during spin cleaning of the conductive layer 120 (refer to step S105). Figure 5 is an example of a cross-sectional schematic diagram of the substrate W for explaining photoetching. In addition, in Figure 5 a part of the surface of the substrate W is illustrated, and illustration of other parts is omitted.

[0063] Here, a case where a semiconductor device (not illustrated) having a PN junction is formed on the substrate W, the conductive layer 120A is connected to the P-type semiconductor, and the conductive layer 120B is connected to the N-type semiconductor is taken as an example for explanation.

[0064] In the water washing processing module, when spin cleaning the substrate W and bonding the hydroxyl group 410 to the active surface of the insulating layer 110, water (water molecules 400) is supplied to the surface of the substrate W.

[0065] Here, when spin cleaning is performed while maintaining the active surface state on the surface of the substrate W, the active surface of Cu (conductive layer 120) reacts with water and corrodes. As a result, the planarity of the bonding surface of the substrate W may be reduced. In addition, since light is irradiated onto the surface of the substrate W for position alignment (refer to step S106) while the surface of the substrate W is wetted with water due to spin cleaning, an electromotive force is generated due to the photovoltaic effect in the semiconductor device having a PN junction. As a result, Cu 126 dissolves out from the conductive layer 120A, and the dissolved Cu 126 precipitates 127 on the conductive layer 120B side. Therefore, the planarity of the bonding surface of the substrate W may be reduced.

[0066] According to Figures 2A to 4B the bonding method of the substrate W shown, an oxidation inhibition layer 130 is formed on the surface of the conductive layer 120 through the selective surface treatment in step S104. Thereby, the reaction of the active surface of Cu (conductive layer 120) with water can be inhibited. In addition, even if a potential difference caused by the photovoltaic effect is generated between the conductive layers 120A and 120B shown in steps S105 and S106, the dissolution of Cu from the conductive layer 120A can be inhibited. Thereby, the precipitation of Cu in the conductive layer 120B can also be inhibited. In addition, poor bonding can be prevented when bonding the substrates W1 and W2.

[0067] Next, use Figure 6A , 6B and Figure 7A , 7BTo describe the oxidation of the conductive layer 120 during the rotational cleaning of the substrate W (refer to step S105).

[0068] Figure 6A , 6B is an example of a model diagram showing the oxidation of the conductive layer 120 in the reference example. Here, in the bonding method of the reference example, after the plasma activation treatment (refer to S103), the substrate W is rotationally cleaned (refer to S105). As Figure 2C shown, the outermost surface of the conductive layer 120 before rotational cleaning is formed of Cu. Figure 6A Schematically shows the state of the outermost surface of the conductive layer 120 before rotational cleaning. The outermost surface of the conductive layer 120 is formed of Cu.

[0069] Here, the rotational cleaning is performed in an atmospheric atmosphere. Therefore, as Figure 6B shown, Cu bonds with O in the atmosphere and / or O in the cleaning water to form copper oxide. At this time, fine defects (voids) are formed on the surface of the conductive layer 120. As a result, the reliability of the bonded conductive layer 120 may be reduced. In addition, the resistance of the bonded conductive layer 120 may increase.

[0070] Figure 7A , 7B is an example of a model diagram showing the oxidation of the conductive layer 120 in the present invention. Here, in the bonding method of the present invention, after the plasma activation treatment (refer to S103), an oxidation-inhibiting layer 130 is formed on the surface of the conductive layer 120 (refer to S104), and the substrate W is rotationally cleaned (refer to S105). As Figure 2D shown, an oxidation-inhibiting layer 130 is formed on the outermost surface of the conductive layer 120 before rotational cleaning. Figure 7A Schematically shows the state of the outermost surface of the conductive layer 120 before rotational cleaning. In the oxidation-inhibiting layer 130, Cu bonds with Si.

[0071] Here, the bond of Si - O is stronger than the bond of Cu - O. Therefore, as Figure 7B shown, O bonds with Si. Thereby, the bond of Cu - O can be inhibited. Thereby, an increase in the resistance of the conductive layer 120 after the annealing treatment can be inhibited.

[0072] Use Figures 8 to 10 to further illustrate the effect of the substrate bonding method in the present invention. Here, a Cu film is formed on a substrate to simulate the conductive layer 120, and XPS analysis of the Cu film is performed.

[0073] Figures 8 to 11It is a diagram showing an example of the XPS analysis results of the Cu film formed on the substrate. Here, the simulated conductive layer 120, and experimentally, XPS analysis is performed on the substrate with a Cu film formed by PVD (Physical Vapor Deposition). "Initial" indicated by a single dotted line represents the XPS analysis results of the substrate with a Cu film formed by PVD. "After reduction, exposed to air" indicated by a dashed line represents the XPS analysis results of the substrate that has been exposed to air after the Cu film on the substrate formed by PVD is reduced using H2 plasma. "After reduction + SiH4 flow, exposed to air" indicated by a solid line represents the XPS analysis results of the substrate that has been exposed to SiH4 gas and then to air after the Cu film on the substrate formed by PVD is reduced using H2 plasma. The horizontal axis represents the binding energy, and the vertical axis represents the number of detections per unit time.

[0074] In addition, Figure 8 It represents the XPS analysis results of Cu 2 / 3p. Figure 9 It represents the XPS analysis results of Cu LMM. Figure 10 It represents the XPS analysis results of O1s. Figure 11 It represents the XPS analysis results of Si 2p.

[0075] According to Figure 8 the XPS results of Cu 2 / 3p shown and Figure 9 the XPS results of Cu LMM shown, in "After reduction, exposed to air" indicated by a dashed line, Cu is oxidized due to exposure to air, and thus a trend of gradually returning to the state of "Initial" indicated by a single dotted line can be seen. While in "After reduction + SiH4 flow, exposed to air" indicated by a solid line, it does not return to the state of "Initial" indicated by a single dotted line after exposure to air, indicating that the oxidation of Cu is inhibited.

[0076] In addition, according to Figure 10 the peak of the XPS results of O1s shown, in terms of the bonding state of oxygen, "Initial" indicated by a single dotted line and "After reduction, exposed to air" indicated by a dashed line show a shift to the low energy side, tending to bond with Cu. While "After reduction + SiH4 flow, exposed to air" indicated by a solid line shows a shift to the high energy side, with the bonding with Si as the center.

[0077] In addition, according to Figure 11 the XPS results of Si 2p shown, the Si 2p signal appears only in "After reduction + SiH4 flow, exposed to air" indicated by a solid line. From this bonding state, it also shows that oxygen exists in the state of SiO x .

[0078] As described above, in "after reduction + after SiH4 flow, exposed to the atmosphere" represented by a solid line, oxygen (O) bonds to Si, thereby suppressing the oxidation of Cu caused by exposure to the atmosphere.

[0079] The substrate processing method has been described above. However, the present invention is not limited to the above-described embodiments and the like, and various modifications and improvements can be made within the scope of the gist of the present invention described in the claims.

[0080] In addition, this application claims priority based on Japanese Patent Application No. 2022-184422 filed on November 17, 2022, and incorporates the entire contents of these Japanese patent applications by reference in this application.

[0081] Explanation of reference numerals

[0082] W substrate, 110 insulating layer, 111 recess, 120, 120A, 120B conductive layer, 121 modified layer, 130 oxidation-inhibiting layer, 200 first processing gas, 300 second processing gas, 400 water molecule, 410 hydroxyl group.

Claims

1. A substrate processing method, characterized in that, Comprising: Exposing a substrate having a conductive layer containing Cu and an insulating layer to a plasma of a first processing gas to activate the surface of the substrate; Exposing the substrate after the step of activating the surface of the substrate to a plasma of a second processing gas to form an oxidation-inhibiting layer on the surface of the conductive layer for inhibiting oxidation of the Cu; Supplying water to the surface of the substrate after the step of forming the oxidation-inhibiting layer to form hydroxyl groups on the surface of the substrate; Bonding one substrate after the step of forming hydroxyl groups to another substrate after the step of forming hydroxyl groups; and Performing a heat treatment on the bonded substrate.

2. The substrate processing method according to claim 1, wherein: The first processing gas is a gas containing H and / or N.

3. The substrate processing method according to claim 2, wherein: The first processing gas is any one of H2 gas, N2 gas, NH3 gas, a mixed gas of H2 and N2, and a mixed gas of H2 and NH3.

4. The substrate processing method according to any one of claims 1 to 3, wherein: In the step of forming the oxidation-inhibiting layer, the oxidation-inhibiting layer is formed on the conductive layer selectively with respect to the insulating layer.

5. The substrate processing method according to claim 4, wherein: The second processing gas is a gas containing Si and / or Al.

6. The substrate processing method according to claim 5, wherein: The second processing gas is any one of SiH4, Si2H6, SiCl4, Si2Cl2H2, Si2Cl6, AlCl3, Al(CH3)3, and AlH(CH3)2.

7. The substrate processing method according to claim 1, wherein: Before the step of activating the surface of the substrate, a step of polishing the surface of the substrate is included.

8. The substrate processing method according to claim 7, wherein: After the step of performing the polishing treatment and before the step of activating the surface of the substrate, a step of making the surface of the conductive layer lower than the surface of the insulating layer is included.

9. A plasma processing apparatus, wherein: It can perform in a vacuum atmosphere: Exposing a substrate having a conductive layer containing Cu and an insulating layer to a plasma of a first processing gas to activate the surface of the substrate; And Exposing the substrate after the step of activating the surface of the substrate to a plasma of a second processing gas to form an oxidation-inhibiting layer on the surface of the conductive layer for inhibiting oxidation of the Cu.

10. A substrate processing system, characterized in that, Comprising: The plasma processing apparatus according to claim 9; A module for polishing the substrate in an atmospheric atmosphere; A module for supplying water to the surface of the substrate in an atmospheric atmosphere; A module for bonding the substrates in an atmospheric atmosphere; And A module for performing a heat treatment on the substrate.

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