Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method and a substrate processing apparatus for selectively forming a blocking layer.SOLUTION: A substrate processing method includes the steps of: (a) preparing a substrate having a first surface including a dielectric film, a second surface including a metal nitride film, and a third surface including a conductive film in different regions of the substrate surface; (b) supplying to the substrate a first organic compound having any one of a thiol group, a phosphonic acid group, and a carboxylic acid group, as a first reactive group; and (c) supplying to the substrate a second organic compound having a carbon-carbon double bond or a carbon-carbon triple bond, as a second reactive group, in which a blocking layer is selectively formed on the second surface and the third surface relative to the first surface.SELECTED DRAWING: Figure 2

Description

[Technical field]

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

[0002] Patent document 1 discloses a method for forming a blocking layer, the method comprising the step of exposing a substrate including a metallic material having a first surface and a non-metallic material having a second surface to an unsaturated hydrocarbon to selectively form a blocking layer on the first surface relative to the second surface. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Application Publication No. 2020 / 347493 Summary of the Invention [Problem to be solved by the invention]

[0004] In one aspect, the present disclosure provides a substrate processing method and substrate processing apparatus for selectively forming a blocking layer. [Means for solving the problem]

[0005] In order to solve the above problem, according to one aspect, there is provided a substrate processing method comprising the steps of: (a) preparing a substrate having a first surface including a dielectric film, a second surface including a metal nitride film, and a third surface including a conductive film in different regions of the substrate surface; (b) supplying a first organic compound having any one of a thiol group, a phosphonic acid group, or a carboxylic acid group as a first reactive group to the substrate; and (c) supplying a second organic compound having a carbon-carbon double bond or a carbon-carbon triple bond as a second reactive group to the substrate, wherein a blocking layer is selectively formed on the second surface and the third surface relative to the first surface. Effect of the Invention

[0006] According to one aspect, it is possible to provide a substrate processing method and a substrate processing apparatus for selectively forming a blocking layer. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view showing an example of a substrate processing apparatus according to an embodiment; [Diagram 2] 4 is a flowchart showing an example of a substrate processing method according to the first embodiment. [Diagram 3] 3A to 3C are schematic cross-sectional views illustrating examples of states of a substrate in each process of the substrate processing method according to the first embodiment. [Figure 4] 3A to 3C are schematic cross-sectional views illustrating examples of states of a substrate in each process of the substrate processing method according to the first embodiment. [Diagram 5] 10 is a flowchart showing an example of a substrate processing method according to a second embodiment. [Figure 6] 10A to 10C are schematic cross-sectional views illustrating examples of states of a substrate in each process of a substrate processing method according to a second embodiment. [Figure 7] 10A to 10C are schematic cross-sectional views illustrating examples of states of a substrate in each process of a substrate processing method according to a second embodiment. [Figure 8] 1A to 1C are schematic cross-sectional views each showing a state of a substrate in a substrate processing method according to a reference example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all of the accompanying drawings, the same or corresponding members or parts are designated by the same or corresponding reference numerals, and duplicated descriptions will be omitted.

[0009] An example of a substrate processing apparatus according to an embodiment will be described with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing the example of the substrate processing apparatus according to an embodiment. The substrate processing apparatus includes a processing vessel 1, a mounting table 2, a shower head 3, an exhaust unit 4, a gas supply unit 5, an RF power supply unit 8, a control unit 9, and the like.

[0010] The processing vessel 1 is made of a metal such as aluminum and has a substantially cylindrical shape. The processing vessel 1 accommodates a substrate W such as a wafer. A loading / unloading port 11 is formed in a side wall of the processing vessel 1 for loading or unloading the substrate W. The loading / unloading port 11 is opened and closed by a gate valve 12. An annular exhaust duct 13 having a rectangular cross section is provided on the main body of the processing vessel 1. A slit 13a is formed along the inner peripheral surface of the exhaust duct 13. An exhaust port 13b is formed in the outer wall of the exhaust duct 13. A top wall 14 is provided on the upper surface of the exhaust duct 13 so as to close the upper opening of the processing vessel 1 via an insulating member 16. A seal ring 15 is used to hermetically seal the space between the exhaust duct 13 and the insulating member 16. The partition member 17 partitions the inside of the processing vessel 1 into upper and lower sections when the mounting table 2 (and the cover member 22) is raised to a processing position described later.

[0011] The mounting table (substrate support) 2 horizontally supports (holds) the substrate W in the processing chamber 1. The mounting table 2 is formed in a disk shape having a size corresponding to the substrate W, and is supported by a support member 23. The mounting table 2 is made of a ceramic material such as AlN or a metal material such as an aluminum or nickel alloy, and has a heater 21 embedded therein for heating the substrate W. The heater 21 generates heat when power is supplied from a heater power source (not shown). The output of the heater 21 is controlled by a temperature signal from a thermocouple (not shown) provided near the upper surface of the mounting table 2, thereby controlling the substrate W to a predetermined temperature. The mounting table 2 is provided with a cover member 22 made of ceramic such as alumina so as to cover the outer peripheral region of the upper surface and the side surfaces.

[0012] A support member 23 for supporting the mounting table 2 is provided on the bottom surface of the mounting table 2. The support member 23 extends from the center of the bottom surface of the mounting table 2 through a hole formed in the bottom wall of the processing vessel 1 to below the processing vessel 1, and its lower end is connected to a lifting mechanism 24. The lifting mechanism 24 raises and lowers the mounting table 2 via the support member 23 between a processing position shown in FIG. 1 and a transfer position shown by a two-dot chain line below the processing position where the substrate W can be transferred. A flange 25 is attached to the support member 23 below the processing vessel 1. A bellows 26 is provided between the bottom surface of the processing vessel 1 and the flange 25. The bellows 26 separates the atmosphere inside the processing vessel 1 from the outside air, and expands and contracts with the lifting and lowering operation of the mounting table 2.

[0013] Three wafer support pins 27 (only two shown) are provided near the bottom surface of the processing vessel 1 so as to protrude upward from a lift plate 27a. The wafer support pins 27 are raised and lowered via the lift plate 27a by a lift mechanism 28 provided below the processing vessel 1. The wafer support pins 27 are inserted into through holes 2a provided in the mounting table 2 at the transfer position, and can be protruded and retracted from the upper surface of the mounting table 2. The substrate W is transferred between the transfer mechanism (not shown) and the mounting table 2 by raising and lowering the wafer support pins 27.

[0014] The shower head 3 supplies a processing gas into the processing vessel 1 in a shower-like manner. The shower head 3 is made of metal, is provided to face the mounting table 2, and has approximately the same diameter as the mounting table 2. The shower head 3 has a main body 31 and a shower plate 32. The main body 31 is fixed to the ceiling wall 14 of the processing vessel 1. The shower plate 32 is connected below the main body 31. A gas diffusion space 33 is formed between the main body 31 and the shower plate 32. A gas introduction hole 36 is provided in the gas diffusion space 33 so as to penetrate the center of the ceiling wall 14 and the main body 31 of the processing vessel 1. An annular protrusion 34 protruding downward is formed on the periphery of the shower plate 32. A gas discharge hole 35 is formed on the inner flat portion of the annular protrusion 34. When the mounting table 2 is in the processing position, a processing space 38 is formed between the mounting table 2 and the shower plate 32, and the upper surface of the cover member 22 and the annular protrusion 34 are close to each other to form an annular gap 39.

[0015] The exhaust unit 4 exhausts the inside of the processing vessel 1. The exhaust unit 4 has an exhaust pipe 41 connected to the exhaust port 13b, and an exhaust mechanism 42 having a vacuum pump, a pressure control valve, etc. connected to the exhaust pipe 41. During processing, gas inside the processing vessel 1 reaches the exhaust duct 13 through the slit 13a, and is exhausted by the exhaust mechanism 42 from the exhaust duct 13 through the exhaust pipe 41.

[0016] The gas supply unit 5 supplies various process gases to the shower head 3. The gas supply unit 5 includes a gas source 51 and a gas line 52. The gas source 51 includes, for example, a supply source of various process gases, a mass flow controller, and a valve (none of which are shown). The various process gases are introduced from the gas source 51 through the gas line 52 and the gas introduction hole 36 into the gas diffusion space 33.

[0017] The substrate processing apparatus is a capacitively coupled plasma apparatus, in which the mounting table 2 functions as a lower electrode and the shower head 3 functions as an upper electrode. The mounting table 2 is grounded via a capacitor (not shown). However, the mounting table 2 may be grounded, for example, without a capacitor, or may be grounded via a circuit combining a capacitor and a coil. The shower head 3 is connected to an RF power supply unit 8.

[0018] The RF power supply unit 8 supplies high frequency power (hereinafter also referred to as "RF power") to the shower head 3. The RF power supply unit 8 includes an RF power source 81, a matching box 82, and a feed line 83. The RF power source 81 is a power source that generates RF power. The RF power has a frequency suitable for generating plasma. The frequency of the RF power is, for example, within a range from 450 KHz in the low frequency band to 2.45 GHz in the microwave band. The RF power source 81 is connected to the main body 31 of the shower head 3 via the matching box 82 and the feed line 83. The matching box 82 includes a circuit for matching the load impedance to the internal impedance of the RF power source 81. Note that the RF power supply unit 8 has been described as supplying RF power to the shower head 3 serving as the upper electrode, but is not limited thereto. It may be configured to supply RF power to the mounting table 2 serving as the lower electrode.

[0019] The control unit 9 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a 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. The control unit 9 may be provided inside or outside the substrate processing apparatus. When the control unit 9 is provided outside the substrate processing apparatus, the control unit 9 can control the substrate processing apparatus via a communication means such as a wired or wireless communication means.

[0020] Next, an example of the substrate processing method according to the present embodiment will be described with reference to Fig. 2 to Fig. 4. Fig. 2 is a flow chart showing an example of the substrate processing method according to the first embodiment. Fig. 3 and Fig. 4 are examples of schematic cross-sectional views showing the state of the substrate W in each step of the substrate processing method according to the first embodiment.

[0021] In step S101, the control unit 9 prepares the substrate W. The control unit 9 controls the lifting mechanism 24 to lower the mounting table 2 to the transfer position, and then opens the gate valve 12. Next, the transfer arm (not shown) loads the substrate W into the processing chamber 1 through the load / unload port 11, and places the substrate W on the mounting table 2 heated to a predetermined temperature by the heater 21. Next, the control unit 9 controls the lifting mechanism 24 to raise the mounting table 2 to the processing position, and reduces the pressure inside the processing chamber 1 to a predetermined vacuum level by the exhaust mechanism 42.

[0022] Here, an example of a schematic cross-sectional view of the prepared substrate W will be described with reference to Fig. 3(a). Fig. 3(a) is an example of a schematic cross-sectional view of the substrate W prepared in step S101. The substrate W has a dielectric film 110, a barrier metal film 120, and a conductive film 130.

[0023] The dielectric film 110 is made of a dielectric material (insulating material) containing silicon (Si). Specifically, the dielectric film 110 may be any of SiO, SiN, SiC, SiOC, SiCN, SiOCN, etc. Also, it may be a film in which the above films are doped with impurities. It may be a dielectric material (insulating material) containing aluminum (Al) and the like in addition to silicon (Si).

[0024] The barrier metal film 120 is formed of a metal nitride film and is provided between the dielectric film 110 and the conductive film 130. Specifically, the barrier metal film 120 may be, for example, any one of TaN, TiN, and the like.

[0025] The conductive film 130 is made of a conductive material such as a metal. The conductive film 130 shown in FIG. 3(a) has a conductive layer 131 and a liner layer 132 covering the conductive layer 131. The conductive layer 131 is made of, for example, Cu. The liner layer 132 is provided so as to cover the conductive layer 131 and is made of, for example, Co. The conductive film 130 has been described as having the conductive layer 131 and the liner layer 132, but is not limited thereto, and may be made of only the conductive layer 131 without the liner layer 132. The conductive film 130 may be, for example, any of Cu, Cu, Co, Ru, W, etc., whose surface is covered with Co. In addition, an oxide layer 135 oxidized by natural oxidation or the like is formed on the exposed portion of the conductive film 130 (liner layer 132).

[0026] In step S102, the control unit 9 performs a pretreatment on the substrate W. Here, the pretreatment is a pretreatment for forming a blocking layer 150 (see FIG. 4(a) described later) and a dielectric film 160 (see FIG. 4(b) described later). The pretreatment includes, for example, removal (reduction treatment) of the oxide layer 135 formed on the surface of the conductive film 130 and removal of contaminants attached to the substrate surface of the substrate W.

[0027] For example, the control unit 9 controls the gas supply unit 5 to supply H2 gas to the processing space 38, and controls the RF power supply unit 8 to generate plasma in the processing space 38, and performs a reduction process on the substrate W with the hydrogen plasma. This removes the oxide layer 135 from the surface of the conductive film 130. Note that if the surface of the substrate W is clean (having little metal oxide layer and little attached contaminants), pretreatment may not be performed.

[0028] Fig. 3(b) is an example of a schematic cross-sectional view of the substrate W after the processing of step S102. As shown in Fig. 3(b), the substrate surface of the substrate W is, for example, the upper surface of the substrate W. The substrate W has a first surface S1 including a dielectric film 110, a second surface S2 including a barrier metal film 120, and a third surface S3 including a conductive film 130, which are located in different regions of the substrate surface.

[0029] In step S103, the control unit 9 forms on the substrate W a first self-assembled monolayer (SAM) 151 (hereinafter also referred to as a first SAM 151).

[0030] For example, the control unit 9 controls the gas supply unit 5 to supply the first organic compound gas to the processing space 38, thereby exposing the substrate W to the first organic compound gas.

[0031] The first organic compound gas has a first main chain composed of a hydrocarbon and a first reactive group formed at one end of the first main chain. The first reactive group is a reactive group that selectively adsorbs (bonds) onto the third surface S3. That is, the first reactive group is a reactive group that selectively adsorbs (bonds) onto the third surface S3 relative to the first surface S1, and selectively adsorbs (bonds) onto the third surface S3 relative to the second surface S2. The first organic compound gas may be any of a thiol compound, a phosphonic acid compound, a carboxylic acid compound, and the like.

[0032] A thiol compound is represented by the general formula "R-SH". R is, for example, a hydrocarbon group or a hydrocarbon group in which at least a portion of the hydrogen has been replaced with fluorine, and corresponds to the first main chain. The SH group is formed at one end of the first main chain and corresponds to the first reactive group. Specific examples of thiol compounds include CH3(CH2) x CH2SH (X is an integer of 0 to 18).

[0033] Phosphonic acid compounds are represented by the general formula "RP(=O)(OH)2". R is, for example, a hydrocarbon group or a hydrocarbon group in which at least a portion of the hydrogen has been replaced with fluorine, and corresponds to the first main chain. The P(=O)(OH)2 group is formed at one end of the first main chain and corresponds to the first reactive group. Specific examples of phosphonic acid compounds include CH3(CH2) x CH2P(=O)(OH)2 (X is an integer of 0 to 18).

[0034] Carboxylic acid compounds are represented by the general formula "R-COOH". R is, for example, a hydrocarbon group or a hydrocarbon group in which at least a portion of the hydrogen has been replaced with fluorine, and corresponds to the first main chain. The COOH group is formed at one end of the first main chain and corresponds to the first reactive group. Specific examples of carboxylic acid compounds include CH3(CH2) x Examples include CH2COOH (X is an integer from 0 to 18), propionic acid (CH3CH2COOH), and octanoic acid (CH3(CH2)6COOH).

[0035] 3(c) is an example of a schematic cross-sectional view of the substrate W after the process of step S103. As shown in FIG. 3(c), the first reactive group of the first organic compound gas is adsorbed onto the third surface S3, and the first main chains are oriented due to an interaction between the first main chains, thereby forming a first SAM 151. That is, the first SAM 151 is formed on the third surface S3 of the conductive film 130.

[0036] In step S104, the control unit 9 forms a second self-assembled monolayer 152 (hereinafter, also referred to as a second SAM 152) on the substrate W.

[0037] For example, the control unit 9 controls the gas supply unit 5 to supply a second organic compound gas different from the first organic compound gas to the processing space 38, thereby exposing the substrate W to the second organic compound gas.

[0038] The second organic compound gas has a second main chain composed of a hydrocarbon and a second reactive group formed at one end of the second main chain. The second reactive group is a reactive group that selectively adsorbs (bonds) at least to the second surface S2. That is, the second reactive group is a reactive group that selectively adsorbs (bonds) to the second surface S2 relative to the first surface S1. The second reactive group is also a reactive group that selectively adsorbs (bonds) to the second surface S2 and the third surface S3. That is, the second reactive group is a reactive group that selectively adsorbs (bonds) to the second surface S2 relative to the first surface S1, and selectively adsorbs (bonds) to the third surface S3 relative to the first surface S1. An olefin-based compound can be used as the second organic compound gas.

[0039] Olefin compounds are represented by the general formula "RC=CH2" or "RC≡CH". R is, for example, a hydrocarbon group or a hydrocarbon group in which at least a portion of the hydrogen has been replaced with fluorine, and corresponds to the second main chain. The second reactive group is formed at one end of the second main chain and has a CC double bond or triple bond. Specific examples of olefin compounds include CH3(CH2) x CH=CH2 (X is an integer between 0 and 18), CH3(CH2) x C≡CH (X is an integer of 0 to 18).

[0040] 4(a) is an example of a schematic cross-sectional view of the substrate W after the processing of step S104. As shown in FIG. 4(a), the second reactive groups of the second organic compound gas are adsorbed to the second surface S2 and the third surface S3, and the second main chains are oriented due to an interaction between the second main chains, thereby forming a second SAM 152. That is, the second SAM 152 is formed on the second surface S2 of the barrier metal film 120 and the third surface S3 of the conductive film 130.

[0041] Moreover, the first SAM 151 formed in step S103 and the second SAM 152 formed in step S104 constitute the blocking layer 150. That is, the processes shown in steps S103 and S104 selectively form the blocking layer 150 on the second surface S2 and the third surface S3 with respect to the first surface S1.

[0042] In this manner, according to the substrate processing method in accordance with the first embodiment, as shown in the processes of steps S101 to S104, the blocking layer 150 can be selectively formed on the second surface S2 and the third surface S3.

[0043] Next, in step S105, the control unit 9 forms a dielectric film 160 on the substrate W. Here, the dielectric film 160 may be any of SiO, SiO containing Al, and the like.

[0044] For example, the control unit 9 controls the gas supply unit 5 to alternately supply a metal-containing catalyst gas and a silicon precursor gas to the processing space 38 to form a dielectric film 160 on the first surface S1 on which the dielectric film 110 is formed.

[0045] The metal-containing catalytic gas may be TMA (Trimethylaluminum) gas, which is selectively adsorbed on the first surface S1 on which the dielectric film 110 is formed, relative to the second surface S2 and the third surface S3 on which the blocking layer 150 is formed.

[0046] The silicon precursor gas may be TPSOL (Tris(tert-pentoxy)silanol) gas. The silicon precursor gas reacts with the metal-containing catalyst adsorbed on the first surface S1 to form a silicon oxide film. As a result, the dielectric film 160 is selectively formed on the first surface S1 on which the dielectric film 110 is formed, relative to the second surface S2 and the third surface S3 on which the blocking layer 150 is formed.

[0047] 4(b) is an example of a schematic cross-sectional view of the substrate W after the processing of step S105. The dielectric film 160 is formed isotropically. That is, as shown in FIG. 4(b), the dielectric film 160 grows from the first surface S1 in the film thickness direction and also in the lateral direction. Therefore, the dielectric film 160 is formed so as to protrude onto the conductive film 130.

[0048] In step S106, the control unit 9 performs an etching process on the substrate W. The etching process is preferably dry etching, and for example, a chemical oxide removal process (COR) may be used.

[0049] For example, the control unit 9 controls the gas supply unit 5 to supply an etching gas (e.g., a mixed gas of HF gas and NH3 gas, plasmatized NF3 gas, alternating supply of TMA gas and HF gas, etc.) to the processing space 38 to etch a portion of the dielectric film 160.

[0050] 4(c) is an example of a schematic cross-sectional view of the substrate W after the process of step S106. Here, the dielectric film 160 formed on the second surface S2 and the third surface S3 is a film including the blocking layer 150 (first SAM 151, second SAM 152), and therefore has low etching resistance. That is, the amount of etching of the dielectric film 160 formed on the second surface S2 and the third surface S3 in the lateral direction is greater than the amount of etching of the dielectric film 160 formed on the first surface S1 in the thickness direction. For this reason, the dielectric film 160 on the second surface S2 and the third surface S3 is suitably removed.

[0051] In this manner, according to the substrate processing method in accordance with the first embodiment, the dielectric film 160 can be selectively formed on the dielectric film 110, as shown by the processes in steps S101 to S106.

[0052] Note that the processes from step S102 to step S106 or the processes from step S103 to step S106 may be regarded as one cycle, and this cycle may be repeated, thereby making it possible to increase the thickness of the dielectric film 160 formed on the first surface S1.

[0053] Next, another example of the substrate processing method according to the present embodiment will be described with reference to Fig. 5 to Fig. 7. Fig. 5 is a flow chart showing an example of the substrate processing method according to the second embodiment. Figs. 6 and 7 are schematic cross-sectional views showing the state of the substrate W in each step of the substrate processing method according to the second embodiment.

[0054] In step S201, similarly to step S101, the control unit 9 prepares a substrate W. Fig. 6(a) is an example of a schematic cross-sectional view of the substrate W prepared in step S201. The substrate W has a dielectric film 110, a barrier metal film 120, and a conductive film 130.

[0055] In step S202, similarly to step S102, the control unit 9 performs pre-processing on the substrate W. Fig. 6(b) is an example of a schematic cross-sectional view of the substrate W after the processing in step S202. The substrate W has a first surface S1 including a dielectric film 110, a second surface S2 including a barrier metal film 120, and a third surface S3 including a conductive film 130, which are located in different regions on the substrate surface.

[0056] In step S203, the control unit 9 forms a second self-assembled monolayer (second SAM) 152 on the substrate W.

[0057] For example, similarly to step S104, the control unit 9 controls the gas supply unit 5 to supply the second organic compound gas to the processing space 38, thereby exposing the substrate W to the second organic compound gas.

[0058] Fig. 6(c) is an example of a schematic cross-sectional view of the substrate W after the process of step S203. As shown in Fig. 6(c), the second reactive groups of the second organic compound gas are adsorbed onto the second surface S2 and the third surface S3, and the second main chains are oriented due to an interaction between the second main chains, thereby forming a second SAM 152. That is, the second SAM 152 is formed on the second surface S2 of the barrier metal film 120 and the third surface S3 of the conductive film 130.

[0059] In step S204, the control unit 9 forms a first self-assembled monolayer (first SAM) 151 on the substrate W.

[0060] For example, similarly to step S103, the control unit 9 controls the gas supply unit 5 to supply the first organic compound gas to the processing space 38, thereby exposing the substrate W to the first organic compound gas.

[0061] 7(a) is an example of a schematic cross-sectional view of the substrate W after the process of step S204. As shown in FIG. 7(a), the first reactive group of the first organic compound gas is adsorbed onto the third surface S3, and the first main chains are oriented due to an interaction between the first main chains, thereby forming a first SAM 151. That is, the first SAM 151 is formed on the third surface S3 of the conductive film 130.

[0062] Moreover, the second SAM 152 formed in step S203 and the first SAM 151 formed in step S204 constitute the blocking layer 150. That is, the processes shown in steps S203 and S204 selectively form the blocking layer 150 on the second surface S2 and the third surface S3 with respect to the first surface S1.

[0063] In this manner, according to the substrate processing method in accordance with the second embodiment, as shown in the processes of steps S201 to S204, the blocking layer 150 can be selectively formed on the second surface S2 and the third surface S3.

[0064] Next, in step S205, similarly to step S105, the control unit 9 forms a dielectric film 160 on the substrate W. Figure 7(b) is an example of a schematic cross-sectional view of the substrate W after the processing in step S205.

[0065] In step S206, similarly to step S106, the control unit 9 performs an etching process on the substrate W. Fig. 7(c) is an example of a schematic cross-sectional view of the substrate W after the process in step S206.

[0066] In this manner, according to the substrate processing method in accordance with the second embodiment, the dielectric film 160 can be selectively formed on the dielectric film 110, as shown by the processes in steps S201 to S206.

[0067] Note that the processes from step S202 to step S206 or the processes from step S203 to step S206 may be regarded as one cycle, and this cycle may be repeated, thereby making it possible to increase the thickness of the dielectric film 160 formed on the first surface S1.

[0068] When the blocking layer 150 is selectively formed on the second surface S2 and the third surface S3, in the substrate processing method according to the first embodiment (see FIGS. 2 to 4), the first organic compound gas is supplied (see S103) and then the second organic compound gas is supplied (see S104). In the substrate processing method according to the second embodiment (see FIGS. 5 to 7), the second organic compound gas is supplied (see S203) and then the first organic compound gas is supplied (see S204). The supply of the first organic compound gas and the second organic compound gas is not limited to this. The first organic compound gas and the second organic compound gas may be supplied simultaneously. Even in this case, the blocking layer 150 can be selectively formed on the second surface S2 and the third surface S3.

[0069] Alternatively, the first organic compound gas may be supplied to the substrate W first (see S103), and then the second organic compound gas may be supplied to the substrate W (see S104). In this way, the first organic compound is pre-adsorbed onto the third surface S3 (see S103), thereby reducing the number of adsorption sites on the third surface S3 in advance. Therefore, when the second organic compound gas is supplied to the substrate W (see S104), the second organic compound can be preferably adsorbed onto the second surface S2. That is, the blocking layer 150 can be preferably formed on the second surface S2.

[0070] Here, the blocking layer 150 formed by the substrate processing method according to this embodiment and the blocking layer 150C formed by the substrate processing method according to a reference example will be described in comparison.

[0071] 8 is an example of a cross-sectional schematic diagram showing the state of a substrate W in a substrate processing method according to a reference example. In the substrate processing method according to the reference example, a blocking layer 150C has a first self-assembled monolayer (first SAM) 151. That is, the blocking layer 150C is selectively formed only on the third surface S3.

[0072] Therefore, in the substrate processing method according to the reference example, when forming the dielectric film 160 on the substrate W, the first surface S1 and the second surface S2 serve as the film formation start surfaces of the dielectric film 160. The dielectric film 160 grows in the film thickness direction and the lateral direction from this film formation start surface. For this reason, as shown in FIG. 8, the dielectric film 160 is formed with X2 in the film thickness direction and is formed with Y2 in the lateral direction from the boundary between the first surface S1 and the second surface S2 toward the third surface S3.

[0073] On the other hand, in the substrate processing method according to the present embodiment, the blocking layer 150 has a first self-assembled monolayer (first SAM) 151 and a second self-assembled monolayer (second SAM) 152. That is, the blocking layer 150 is selectively formed on the second surface S2 and the third surface S3.

[0074] Therefore, in the substrate processing method according to the present embodiment, when forming the dielectric film 160 on the substrate W, the first surface S1 serves as the film formation start surface of the dielectric film 160. The dielectric film 160 grows in the film thickness direction and the lateral direction from this film formation start surface. For this reason, as shown in FIG. 4(b), the dielectric film 160 is formed with X1 in the film thickness direction and is formed with Y1 in the lateral direction from the boundary between the first surface S1 and the second surface S2 toward the third surface S3.

[0075] Here, when the film thicknesses of the dielectric films 160 are equal (X1 = X2), the film formation amount Y1 in the lateral direction in the present embodiment is less than the film formation amount Y2 in the lateral direction in the reference example (Y1 < Y2). For example, the film formation amount Y1 in the lateral direction in the present embodiment is less than the film formation amount Y2 in the lateral direction in the reference example by the width of the barrier metal film 120. Thereby, when forming the dielectric film 160, it is possible to suppress the dielectric film 160 from protruding onto the conductive film 130. Further, the controllability of the shape of the dielectric film 160 is improved.

[0076] Furthermore, according to the substrate processing method of this embodiment, the number of etching processes (S106, S206) can be reduced and / or the etching time can be reduced, thereby reducing the effect of the etching processes on the conductive film 130.

[0077] Furthermore, according to the substrate processing method of the reference example, when the dielectric film 160 formed on the second surface S2 is etched in the lateral direction, the dielectric film 160 formed on the first surface S1 is also etched in the thickness direction. For this reason, the number of cycles required to form the dielectric film 160 of the desired thickness on the first surface S1, which includes the steps of forming the blocking layer 150C, forming the dielectric film 160, and etching, may increase. Furthermore, if the amount of etching in the thickness direction and the amount of etching in the lateral direction are equal, the dielectric film 160 of the desired thickness may not be formed on the first surface S1 even if the cycle is repeated.

[0078] In contrast, according to the substrate processing method of this embodiment, the dielectric film 160 formed on the second surface S2 is formed by involving the second self-assembled monolayer (second SAM) 152. Therefore, the dielectric film 160 formed on the second surface S2 has a lower etching resistance than the dielectric film 160 formed on the first surface S1. Therefore, in the etching process (S106, S206), the dielectric film 160 formed on the second surface S2 can be etched in the lateral direction faster than the dielectric film 160 formed on the first surface S1 is etched in the thickness direction. This allows the dielectric film 160 of a desired thickness to be formed on the first surface S1.

[0079] The above describes the substrate processing method according to this embodiment using the substrate processing apparatus. However, the present disclosure is not limited to the above-described embodiment, and various modifications and improvements are possible within the scope of the gist of the present disclosure described in the claims. [Explanation of symbols]

[0080] W substrate 1 Processing vessel 2. Placement table (substrate support part) 2a Through hole 3. Shower head 4 Exhaust section 5 Gas supply section 8 RF power supply section 9. Control Unit 38 Processing Space 110 Dielectric film 120 Barrier metal film (metal nitride film) 130 Conductive Film 131 Conductive layer 132 Liner layer 135 Oxide layer 150 Blocking Layer 151 1st self-assembled monolayer (1st SAM) 152 2nd self-assembled monolayer (2nd SAM) 160 Dielectric Film S1 1st surface S2 2nd surface S3 3rd surface

Claims

1. (a) providing a substrate having a first surface including a dielectric film, a second surface including a metal nitride film, and a third surface including a conductive film in different regions of the substrate surface; (b) supplying to the substrate a first organic compound having a first reactive group selected from the group consisting of a thiol group, a phosphonic acid group, and a carboxylic acid group; (c) supplying to the substrate a second organic compound having a carbon-carbon double bond or a carbon-carbon triple bond as a second reactive group; selectively forming a blocking layer on the second surface and the third surface relative to the first surface; A method for processing a substrate.

2. After the step (b), the step (c) is carried out. The method of claim 1 .

3. After the step (c), the step (b) is carried out. The method of claim 1 .

4. The step (b) and the step (c) are carried out simultaneously. The method of claim 1 .

5. the first organic compound selectively adsorbs to the third surface relative to the first surface and selectively adsorbs to the third surface relative to the second surface; the second organic compound selectively adsorbs to the second surface relative to the first surface and selectively adsorbs to the third surface relative to the first surface; The substrate processing method according to claim 1 .

6. The step (b) includes forming a first self-assembled monolayer on the third surface; The step (c) includes forming a second self-assembled monolayer on the second surface and the third surface; the blocking layer includes the first self-assembled monolayer and the second self-assembled monolayer; The substrate processing method according to claim 5 .

7. the metal nitride film is a barrier metal film provided between the dielectric film and the conductive film; The substrate processing method according to claim 1 .

8. The metal nitride film is either TaN or TiN. The substrate processing method according to claim 1 .

9. The first organic compound is CH ３ (CH ２ ) ｘ CH ２ SH (X is an integer from 0 to 18), CH ３ (CH ２ ) ｘ CH ２ COOH (X is an integer from 0 to 18), The second organic compound is CH ３ (CH ２ ) ｘ CH=CH ２ (X is an integer from 0 to 18), CH ３ (CH ２ ) ｘ C≡CH (X is an integer of 0 to 18); The substrate processing method according to claim 1 .

10. A processing vessel; a substrate support for supporting a substrate within the processing chamber; a gas supply unit that supplies a gas into the processing vessel; A control unit, The control unit is (a) providing a substrate having a first surface including a dielectric film, a second surface including a metal nitride film, and a third surface including a conductive film in different regions of the substrate surface; (b) supplying to the substrate a first organic compound having a first reactive group selected from the group consisting of a thiol group, a phosphonic acid group, and a carboxylic acid group; (c) supplying to the substrate a second organic compound having a carbon-carbon double bond or a carbon-carbon triple bond as a second reactive group; selectively forming a blocking layer on the second surface and the third surface relative to the first surface; Substrate processing equipment.

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