Substrate processing method

Abstract

To provide a sheath heater, a substrate processing apparatus and a control method of the substrate processing apparatus, capable of achieving high temperature controllability.SOLUTION: A deposition method in substrate processing includes: a step S1 of preparing for a substrate; a step S2 of depositing a barrier film of any of AlN, TiAlN, TiCN on the substrate; and a step S4 of depositing a metal film of any of Ru, Mo, Ni, Co, Cu on the barrier film. Even by forming a metal film after barrier film deposition to execute anneal processing S5 of 950 degrees, no aggregation of the metal film occurs, and it is thus possible to prevent an increase in the resistance of the metal film.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] This disclosure , basis It relates to a plate processing method. [Background technology]

[0002] For example, in the wiring structure of a semiconductor device, it is known to form a metal film such as ruthenium on a silicon oxide film (e.g., a gate oxide film), and to form a barrier film such as TiN under the metal film in order to improve the adhesion of the metal film.

[0003] Patent Document 1 discloses a method for forming a polysilicon layer on a substrate, a silicide layer on the polysilicon layer, a barrier layer on the silicide layer, and a ruthenium layer on the barrier layer, and further discloses that the barrier layer contains TiN. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2019-530981 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a substrate on which a TiN film and a ruthenium film are formed is subjected to an annealing treatment at 950°C or higher, the ruthenium diffuses into the TiN film, the TiN film and the ruthenium film are mixed, and the resistance value of the ruthenium film increases. In addition, the adhesion of the ruthenium film decreases, causing the ruthenium film to aggregate. For this reason, there is a demand for improving the heat resistance of the ruthenium film.

[0006] In one aspect, the present disclosure provides a method for improving the heat resistance of a metal film. Base A method for treating a plate is provided. [Means for solving the problem]

[0007] In order to solve the above problems, according to one aspect, a method for manufacturing a semiconductor device comprising the steps of: forming a barrier film made of any one of AlN, TiAlN, and TiCN on a substrate; Ruthenium Film and annealing the substrate at 950° C. or higher. Ruthenium Film does not diffuse into the barrier film. Effect of the Invention

[0008] According to one aspect, the present disclosure provides a method for improving the heat resistance of a metal film. Base A method for treating a plate can be provided. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram illustrating an example of a configuration of a substrate processing system. [Diagram 2] FIG. 1 is a cross-sectional view of an example of a substrate processing apparatus that forms a barrier film. [Diagram 3] FIG. 2 is a cross-sectional view of an example of a substrate processing apparatus for performing a pre-clean process. [Figure 4] FIG. 1 is a cross-sectional view of an example of a substrate processing apparatus for forming a ruthenium film. [Diagram 5] 1 is a flowchart showing an example of a substrate processing. [Figure 6] 1 is a schematic cross-sectional view of a substrate; [Figure 7] FIG. 4 is an example of a diagram showing a state of a film after an annealing treatment in the first embodiment. [Figure 8] FIG. 11 is a diagram showing a state of a film after an annealing process in the second embodiment. [Figure 9] FIG. 13 is a diagram showing a state of a film after an annealing treatment in a reference example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment 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 duplicated descriptions may be omitted.

[0011] <Substrate processing equipment> A substrate processing system 200 according to the present embodiment will be described with reference to Fig. 1. Fig. 1 is a diagram showing an example of the configuration of the substrate processing system 200.

[0012] The substrate processing system 200 includes substrate processing apparatuses 211 to 213 , a vacuum transfer chamber 220 , a load lock chamber 230 , and an atmospheric transfer chamber 240 .

[0013] The substrate processing apparatuses 211-213 are depressurized to a predetermined vacuum atmosphere, and perform a predetermined process on a substrate W such as a semiconductor wafer therein. The substrate processing apparatuses 211-213 are disposed adjacent to a vacuum transfer chamber 220. The substrate processing apparatuses 211-213 communicate with the vacuum transfer chamber 220 by opening and closing a gate valve (not shown). In the substrate processing system 200 of this embodiment, the substrate processing apparatus 211 is an apparatus that forms a barrier film on the substrate W. The substrate processing apparatus 212 is an apparatus that removes impurities (pre-cleaning process) from the surface of a barrier film formed on the substrate W before forming a metal film (to be described later). The substrate processing apparatus 213 is an apparatus that forms a metal film such as a ruthenium film on the barrier film formed on the substrate W. The substrate processing apparatuses 211-213 will be described later with reference to FIG. 2 to FIG. 4.

[0014] The vacuum transfer chamber 220 is connected to a plurality of chambers (substrate processing apparatus 211-213, load lock chamber 230) via a gate valve (not shown), and is depressurized to a predetermined vacuum atmosphere. A substrate transfer device (not shown) for transferring a substrate W is provided inside the vacuum transfer chamber 220. The substrate transfer device transfers the substrate W from one chamber (substrate processing apparatus 211-213, load lock chamber 230) to another chamber (substrate processing apparatus 211-213, load lock chamber 230) via the vacuum transfer chamber 220 in response to opening and closing of the gate valve.

[0015] The load lock chamber 230 is provided between the vacuum transfer chamber 220 and the atmospheric transfer chamber 240. The load lock chamber 230 has a placement section (not shown) on which the substrate W is placed. The load lock chamber 230 is capable of switching between an atmospheric atmosphere and a vacuum atmosphere. The load lock chamber 230 and the vacuum transfer chamber 220 in the vacuum atmosphere are communicated by opening and closing a gate valve (not shown). The load lock chamber 230 and the atmospheric transfer chamber 240 in the atmospheric atmosphere are communicated by opening and closing a door valve (not shown).

[0016] The atmospheric transfer chamber 240 has an atmospheric atmosphere, and for example, a downflow of clean air is formed. A load port (not shown) is provided on a wall surface of the atmospheric transfer chamber 240. A carrier (not shown) containing a substrate W or an empty carrier is attached to the load port. For example, a FOUP (Front Opening Unified Pod) or the like can be used as the carrier. A substrate transfer device (not shown) that transfers the substrate W is provided inside the atmospheric transfer chamber 240. The substrate transfer device transfers the substrate W between the load lock chamber 230 and a carrier attached to the load port via the atmospheric transfer chamber 240 in response to the opening and closing of a door valve.

[0017] In this manner, the substrate processing system 200 of this embodiment can form a barrier film on a substrate W in the substrate processing apparatus 211 while maintaining a vacuum atmosphere, remove impurities from the surface of the barrier film (pre-clean processing) in the substrate processing apparatus 212, and form a metal film (e.g., a ruthenium film) on the barrier film in the substrate processing apparatus 213.

[0018] <Substrate processing apparatus 211> Next, the substrate processing apparatus 211 will be described with reference to Fig. 2. Fig. 2 is an example of a cross-sectional view of the substrate processing apparatus 211 that forms a barrier film. The substrate processing apparatus 211 forms a barrier film by an ALD (Atomic Layer Deposition) method in a processing chamber in a vacuum atmosphere.

[0019] As shown in FIG. 2, the substrate processing apparatus 211 includes a processing container 1, a mounting table 2, a shower head 3, an exhaust unit 4, a gas supply mechanism 5, and a controller 9.

[0020] 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. A loading / unloading port 11 is formed in a side wall of the processing vessel 1 for loading or unloading the substrate W, and 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.

[0021] The mounting table 2 horizontally supports 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 circumferential region of the upper surface and the side surfaces.

[0022] A support member 23 that supports 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, and a bellows 26 that 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 is provided between the bottom surface of the processing vessel 1 and the flange 25.

[0023] Three substrate support pins 27 (only two shown) are provided near the bottom surface of the processing vessel 1 so as to protrude upward from a lifting plate 27a. The substrate support pins 27 are raised and lowered via the lifting plate 27a by a lifting mechanism 28 provided below the processing vessel 1. The substrate 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 substrate support pins 27.

[0024] 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 fixed to the ceiling wall 14 of the processing vessel 1, and a shower plate 32 connected below the main body 31. A gas diffusion space 33 is formed between the main body 31 and the shower plate 32, and 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 surface 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.

[0025] 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.

[0026] The gas supply mechanism 5 supplies gas into the processing chamber 1 from the gas inlet 36 via a gas supply line 56. The gas supply mechanism 5 supplies a precursor gas, a reducing gas (e.g., NH 3 gas), purge gas (N 2 The precursor gas is, for example, trimethylaluminum (TMA) gas, TiCl 4 Gas, TaCl 5 A gas containing a metal element such as a gas can be selected and used depending on the type of the barrier film. The gas supply mechanism 5 may also be configured to be capable of supplying a gas for doping the barrier film with other elements (e.g., Al, C, Si).

[0027] 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 211. The control unit 9 may be provided inside or outside the substrate processing apparatus 211. When the control unit 9 is provided outside the substrate processing apparatus 211, the control unit 9 can control the substrate processing apparatus 211 by a communication means such as a wired or wireless communication means.

[0028] The process of the control unit 9 includes, for example, a step of supplying a precursor gas into the processing vessel 1 to adsorb the precursor onto the substrate W, a step of supplying a purge gas into the processing vessel 1 to purge excess precursor gas and the like from within the processing vessel 1, a step of supplying a reducing gas into the processing vessel 1 to reduce (nitride) the precursor adsorbed onto the substrate W, and a step of supplying a purge gas into the processing vessel 1 to purge excess reducing gas and the like from within the processing vessel 1, which constitute one cycle, and a barrier film is formed by the ALD method.

[0029] This allows the use of TMA gas as the precursor gas and NH 3 By using the gas, an AlN film can be formed.

[0030] In addition, TiCl was used as a precursor gas. 4 Gas, NH as reducing gas 3 By using the gas, a TiN film can be formed.

[0031] In addition, TaCl was used as a precursor gas. 5 Gas, NH as reducing gas 3 By using the gas, a TaN film can be formed.

[0032] The process by the control unit 9 may include a step of supplying TMA gas into the process vessel 1 to dope the barrier film with Al. 4 Gas, NH as reducing gas 3 By using a gas such as TMA gas as the doping gas, a TiAlN film can be formed.

[0033] The process by the control unit 9 may include a step of supplying a carbon-containing gas into the process vessel 1 to dope the barrier film with C. This allows the precursor gas to be TiCl 4 Gas, NH as reducing gas 3 By using a gas containing carbon as the doping gas, a TiCN film can be formed.

[0034] In addition, the control unit 9 performs the process by removing SiH 4 The barrier film may be doped with Si by supplying a gas, thereby forming a barrier film having a TiCl 4 Gas, NH as reducing gas 3 The gas used is SiH 4 By using the gas, a TiSiN film can be formed.

[0035] Here, the AlN film refers to a film that contains Al and N elements, and contains inevitable impurities but does not contain other elements. The same applies to TiN and TaN films. The TiAlN film refers to a film that contains Ti, N, and doped Al elements, and contains inevitable impurities but does not contain other elements. The TiCN film refers to a film that contains Ti, N, and doped C elements, and contains inevitable impurities but does not contain other elements. The same applies to TiSiN films.

[0036] <Substrate processing apparatus 212> Next, the substrate processing apparatus 212 will be described with reference to Fig. 3. Fig. 3 is an example of a cross-sectional view of the substrate processing apparatus 212 for performing a pre-clean process. The substrate processing apparatus 212 generates plasma in a processing chamber with a vacuum atmosphere under reduced pressure to remove impurities from the surface of a barrier film (pre-clean process).

[0037] 3, the substrate processing apparatus 212 includes a processing vessel 1, a mounting table 2, a shower head 3, an exhaust unit 4, a gas supply mechanism 5, an RF power supply unit 7, an RF power supply unit 8, and a control unit 9. Note that the same components as those in the substrate processing apparatus 211 are denoted by the same reference numerals, and redundant explanations will be omitted.

[0038] The substrate processing apparatus 212 is a capacitively coupled plasma apparatus, in which the mounting table 2 serves as a lower electrode and the shower head 3 serves as an upper electrode.

[0039] A lower electrode 29 is provided on the mounting table 2. A high frequency bias power is supplied to the lower electrode 29 by an RF power supply unit 7. The RF power supply unit 7 has a power feed line 71, a matching box 72, and a high frequency power supply 73. The power feed line 71 connects the lower electrode 29 (mounting table 2) and the high frequency power supply 73 via the matching box 72. The matching box 72 has a circuit for matching the output reactance of the high frequency power supply 73 and the reactance of the load (lower electrode). The high frequency power supply 73 supplies high frequency power of, for example, 13.56 MHz.

[0040] The shower head 3 serving as the upper electrode is supplied with high frequency power serving as a plasma source for generating plasma by an RF power supply unit 8. The RF power supply unit 8 has a power feed line 81, a matching box 82, and a high frequency power supply 83. The power feed line 81 connects the upper electrode (shower head 3) and the high frequency power supply 83 via the matching box 82. The matching box 82 has a circuit for matching the output reactance of the high frequency power supply 83 and the reactance of the load (lower electrode). The high frequency power supply 83 supplies high frequency power of, for example, 60.0 MHz.

[0041] The gas supply mechanism 5 supplies gas from the gas inlet 36 into the processing chamber 1 through a gas supply line 56. The gas supply mechanism 5 supplies H 2 The gas supply system is configured to be capable of supplying gas and Ar gas.

[0042] The process by the control unit 9 is carried out by, for example, injecting H 2 Gas and Ar gas are supplied, and RF power supply units 7 and 8 are controlled to generate plasma in the processing chamber 1, and impurities are removed from the surface of the barrier film (pre-cleaning process). For example, carbon is removed from the surface of the barrier film, and a natural oxide film is removed from the surface of the barrier film. This can improve adhesion to a metal film (e.g., a ruthenium film) formed on the barrier film.

[0043] <Substrate processing apparatus 213> Next, the substrate processing apparatus 213 will be described with reference to Fig. 4. Fig. 4 is an example of a cross-sectional view of the substrate processing apparatus 213 that forms a metal film (for example, a ruthenium film). The substrate processing apparatus 213 processes triruthenium dodecacarbonyl Ru in a processing vessel with a vacuum atmosphere under reduced pressure. 3 (CO) 12 A ruthenium-containing gas such as ruthenium fluoride is supplied, and a ruthenium film is formed on the barrier film by a CVD (Chemical Vapor Deposition) method.

[0044] The main body vessel 101 is a bottomed vessel having an opening on the upper side. The support member 102 supports a gas introduction mechanism 103. Furthermore, the support member 102 closes the upper opening of the main body vessel 101, thereby sealing the main body vessel 101 and forming a processing chamber 101c. The gas supply unit 104 supplies a process gas, such as a ruthenium-containing gas, to the gas introduction mechanism 103 via the support member 102 having a supply pipe 102a. The ruthenium-containing gas supplied from the gas supply unit 104 is supplied from the gas introduction mechanism 103 into the processing chamber 101c.

[0045] The stage 105 is formed in a flat disk shape using, for example, aluminum nitride or quartz, and is a member on which the substrate W is placed. A heater 106 for heating the substrate W is embedded inside the stage 105. The heater 106 is, for example, made of a sheet-like resistance heating element, and generates heat when power is supplied from a power supply unit (not shown), thereby heating the placement surface of the stage 105 and thereby raising the temperature of the substrate W to a predetermined process temperature suitable for film formation. For example, the heater 106 heats the substrate W placed on the stage 105 to, for example, 100°C to 300°C.

[0046] The stage 105 also has a support portion 105 a which extends downward from the center of the lower surface of the stage 105 and has one end which penetrates the bottom of the main container 101 and is supported by a lifting mechanism 110 via a lifting plate 109 .

[0047] A temperature control jacket 108 is provided as a temperature control member below the stage 105. The temperature control jacket 108 has a plate portion 108a formed on the upper part, which is approximately the same size as the stage 105, and a shaft portion 108b formed on the lower part, which has a diameter larger than that of the support portion 105a. The temperature control jacket 108 also has a hole portion 108c formed in the center in the vertical direction, which passes through the plate portion 108a and the shaft portion 108b.

[0048] The temperature control jacket 108 accommodates the support portion 105a in the hole 108c, and is disposed so that the hole 108c covers the support portion 105a and covers the entire back surface of the stage 105. Since the hole 108c has a larger diameter than the support portion 105a, a gap (not shown) is formed between the support portion 105a and the temperature control jacket 108.

[0049] The temperature control jacket 108 has a refrigerant flow path 108d formed inside the plate portion 108a, and two refrigerant pipes 118a, 118b provided inside the shaft portion 108b. One end of the refrigerant flow path 108d is connected to one refrigerant pipe 118a, and the other end is connected to the other refrigerant pipe 118b. The refrigerant pipes 118a, 118b are connected to the refrigerant unit 118.

[0050] The refrigerant unit 118 is, for example, a chiller unit. The refrigerant unit 118 is capable of controlling the temperature of the refrigerant, and supplies the refrigerant at a predetermined temperature to the refrigerant pipe 118a. The refrigerant is supplied to the refrigerant flow path 108d from the refrigerant unit 118 via the refrigerant pipe 118a. The refrigerant supplied to the refrigerant flow path 108d returns to the refrigerant unit 118 via the refrigerant pipe 118b. The temperature control jacket 108 is capable of adjusting the temperature by circulating a refrigerant, for example, cooling water, in the refrigerant flow path 108d.

[0051] An insulating ring 107 is disposed as an insulating member between the stage 105 and the temperature control jacket 108. The insulating ring 107 is formed in a disk shape from, for example, SUS316, A5052, Ti (titanium), ceramics, or the like.

[0052] A gap is formed between the heat insulating ring 107 and the stage 105 in all circumferential directions, which gap communicates from the hole 108c of the temperature control jacket 108 to the edge of the temperature control jacket 108. For example, the heat insulating ring 107 has a plurality of protrusions on its upper surface facing the stage 105.

[0053] A plurality of protrusions, for example, two rows, are formed concentrically at intervals in the circumferential direction on the heat insulating ring 107. It is sufficient that the protrusions are formed in at least one concentric row.

[0054] Shaft 108b of temperature control jacket 108 penetrates the bottom of main container 101. The lower end of temperature control jacket 108 is supported by lifting mechanism 110 via lifting plate 109 arranged below main container 101. Bellows 111 are provided between the bottom of main container 101 and lifting plate 109, so that the airtightness inside main container 101 is maintained even when lifting plate 109 moves up and down.

[0055] By the lifting mechanism 110 raising and lowering the lifting plate 109, the stage 105 can be raised and lowered between a processing position (see FIG. 1) where the substrate W is processed and a transfer position (not shown) where the substrate W is transferred to and from an external transport mechanism (not shown) via the load / unload port 101a.

[0056] When transferring the substrate W to and from an external transport mechanism (not shown), the lifting pins 112 support the substrate W from its underside and lift the substrate W from the mounting surface of the stage 105. The lifting pins 112 have a shaft and a head having a larger diameter than the shaft. The stage 105 and the plate portion 108a of the temperature control jacket 108 are formed with a through hole through which the shaft of the lifting pin 112 passes. In addition, a groove for accommodating the head of the lifting pin 112 is formed on the mounting surface side of the stage 105. An abutment member 113 is arranged below the lifting pin 112.

[0057] When the stage 105 is moved to a processing position for the substrate W (see FIG. 1), the heads of the lift pins 112 are housed in the grooves, and the substrate W is placed on the mounting surface of the stage 105. The heads of the lift pins 112 are engaged in the grooves, and the shafts of the lift pins 112 penetrate the stage 105 and the plate portion 108a of the temperature-controlled jacket 108, and the lower ends of the shafts of the lift pins 112 protrude from the plate portion 108a of the temperature-controlled jacket 108. On the other hand, when the stage 105 is moved to a transfer position for the substrate W (not shown), the lower ends of the lift pins 112 abut against the abutment member 113, and the heads of the lift pins 112 protrude from the mounting surface of the stage 105. As a result, the heads of the lift pins 112 support the substrate W from the lower surface thereof, and lift the substrate W from the mounting surface of the stage 105.

[0058] The abutment member 113 has an abutment portion 113a that abuts against the lift pin 112, and a shaft portion 113b that extends downward from the abutment portion 113a. The shaft portion 113b of the abutment member 113 penetrates the bottom of the main body container 101. The lower end of the abutment member 113 is supported by a lift mechanism 115 via a lift plate 114 arranged below the main body container 101. A bellows 116 is provided between the bottom of the main body container 101 and the lift plate 114, and the airtightness inside the main body container 101 is maintained even by the up and down movement of the lift plate 114. The lift mechanism 115 can raise and lower the abutment member 113 by raising and lowering the lift plate 114. The lower end of the lift pin 112 abuts against the upper surface of the abutment member 113, so that the upper end of the lift pin 112 can be supported from the lower surface of the substrate W.

[0059] The annular member 117 is disposed above the stage 105. When the stage 105 has been moved to a processing position for the substrate W (see FIG. 1), the annular member 117 comes into contact with the outer periphery of the upper surface of the substrate W, and presses the substrate W against the placement surface of the stage 105 by the weight of the annular member 117. On the other hand, when the stage 105 has been moved to a transfer position for the substrate W (not shown), the annular member 117 is locked by a locking portion (not shown) above the loading / unloading port 101a so as not to impede the transfer of the substrate W by a transport mechanism (not shown).

[0060] The heat transfer gas supply / exhaust unit 119 supplies a heat transfer gas such as He gas to a back surface space between the back surface of the substrate W placed on the stage 105 and the front surface of the stage 105 via a pipe 119a.

[0061] The purge gas supply unit 120 supplies a purge gas, such as CO gas, between the lower surface of the annular member 117 and the upper surface of the stage 105 via the pipe 120a, a gap (not shown) formed between the support portion 105a of the stage 105 and the hole portion 108c of the temperature control jacket 108, a flow path (not shown) formed between the stage 105 and the heat insulating ring 107 and extending radially outward, and a vertical flow path (not shown) formed on the outer periphery of the stage 105. This prevents the process gas from flowing into the space between the lower surface of the annular member 117 and the upper surface of the stage 105, thereby preventing a film from being formed on the lower surface of the annular member 117 or the upper surface of the outer periphery of the stage 105.

[0062] A side wall of the main container 101 is provided with a load / unload port 101a for loading / unloading the substrate W, and a gate valve 121 for opening and closing the load / unload port 101a.

[0063] An exhaust unit 122 including a vacuum pump and the like is connected via an exhaust pipe 101b to the lower sidewall of the main body container 101. The inside of the main body container 101 is exhausted by the exhaust unit 122, and a predetermined vacuum atmosphere (e.g., 1.33 Pa) is set and maintained inside the processing chamber 101c.

[0064] The control unit 130 controls the operation of the substrate processing apparatus 213 by controlling the gas supply unit 104, the heater 106, the lifting mechanism 110, the refrigerant unit 118, the heat transfer gas supply and exhaust unit 119, the purge gas supply unit 120, the gate valve 121, the exhaust unit 122, etc.

[0065] The process of the control unit 9 is carried out by supplying Ru gas from the gas supply unit 104 through the supply pipe 102a and the gas introduction mechanism 103 to the upper space 101d of the process chamber 101c. 3 (CO) 12 Gas and CO gas are supplied.3 (CO) 12 The gas is a gas containing ruthenium. 3 (CO) 12 The gas suppresses the decomposition of Ru on the surface of the substrate W. 3 (CO) 12 The decomposition of xenon forms a ruthenium film on the substrate W. An example of the film formation conditions is a film formation temperature of 135° C. to 250° C., a film formation pressure of 15 to 100 mT, and a CO flow rate of 30 to 300 sccm. The processed gas passes through a flow path on the upper surface side of the annular member 117 from the upper space 101d to the lower space 101e, and is exhausted by the exhaust unit 122 via the exhaust pipe 101b.

[0066] <Substrate processing method> Next, a substrate processing method using the substrate processing system 200 according to this embodiment will be described with reference to Fig. 5 and Fig. 6. Fig. 5 is a flow chart showing an example of substrate processing. Fig. 6 is a schematic cross-sectional view of a substrate W.

[0067] In step S1, a substrate W is prepared. Here, the substrate W is a SiO 2 A membrane 510 is formed.

[0068] In step S2, the substrate W is transported to the substrate processing apparatus 211 (see FIG. 2), and the SiO 2 A barrier film 520 is formed (barrier film forming process) on the film 510. The barrier film 520 is made of any one of AlN, TiAlN, and TiCN.

[0069] In step S3, the substrate W is transferred to the substrate processing apparatus 212 (see FIG. 3), and impurities are removed from the surface of the barrier film 520 of the substrate W (pre-cleaning process).

[0070] In step S4, the substrate W is transported to the substrate processing apparatus 213 (see FIG. 4), and a metal film 530 is formed (metal film forming process) on the barrier film 520 of the substrate W. Note that the metal film 530 is described as being a ruthenium film, but is not limited thereto. The metal film 530 may be any of Ru, Mo, Ni, Co, and Cu.

[0071] Through the processes in steps S1 to S4 described above, the barrier film 520 and the metal film 530 are formed on the substrate W in the substrate processing system 200. The substrate W that has been subjected to the film formation process is unloaded from the substrate processing system 200.

[0072] Thereafter, the substrate W on which the barrier film 520 and the metal film 530 have been formed is further subjected to other processing by another substrate processing system or substrate processing apparatus.

[0073] Then, in step S5, an annealing device (not shown) performs an annealing process on the substrate W on which the barrier film 520 and the metal film 530 have been formed in the substrate processing system 200. The annealing process is a process performed, for example, to activate various films formed on the substrate W. For example, the annealing process coarsens crystal grains in the ruthenium film, thereby reducing the resistance value of the ruthenium film.

[0074] <Film state after annealing treatment> Next, the state of the barrier film 520 and the metal film 530 after the annealing process will be described for the first and second examples, in comparison with the reference example. Fig. 7 is an example of a diagram showing the state of the film after the annealing process in the first example. Fig. 8 is an example of a diagram showing the state of the film after the annealing process in the second example. Fig. 9 is an example of a diagram showing the state of the film after the annealing process in the reference example.

[0075] In the first embodiment shown in FIG. 7, an AlN film was formed as the barrier film 520, and a ruthenium film was formed as the metal film 530 on the barrier film 520.

[0076] In the second embodiment shown in FIG. 8, a TiAlN film, which is an example of a TiXN film (X=Al, Si, or C), is formed as a barrier film 520, and a ruthenium film is formed as a metal film 530 on the barrier film 520.

[0077] In the reference example shown in FIG. 9, a TiN film was formed as the barrier film 520, and a ruthenium film was formed as the metal film 530 on the barrier film 520.

[0078] 7 and 8, the upper part shows cross-sectional images (TEM: Transmission Electron Microscope) and the lower part shows the results of elemental analysis (EDX: Energy dispersive X-ray spectroscopy) for the cases where the substrate W was not annealed (No anneal), where the substrate W was annealed at 900° C. (900° C. anneal), where the substrate W was annealed at 950° C. (950° C. anneal), and where the substrate W was annealed at 1000° C. (1000° C. anneal). In the results of elemental analysis, the horizontal axis indicates the height position of the substrate W, and the SiO 2 The direction in which the film 510, the barrier film 520, and the metal film 530 are stacked is taken as the positive direction. The vertical axis represents the normalized detected intensity.

[0079] In the reference example shown in FIG. 9, when no annealing treatment was performed (No anneal) and when annealing treatment was performed at 900° C. (900° C. anneal), the intensity of Si and O decreased and the intensity of Ru increased at a height position (around 60 to 80 nm), in other words, SiO 2 A peak in the Ti intensity appears at the boundary between the film 510 and the metal film 530 .

[0080] On the other hand, in the reference example shown in FIG. 9, when annealing was performed at 950° C. (950° C. anneal), SiO 2The Ti intensity peak at the boundary (around 60 to 80 nm) between the film 510 and the metal film 530 disappears. In other words, ruthenium diffuses into the TiN film (barrier film 520), and the TiN film and the ruthenium film are mixed. As a result, when the ruthenium film is used as a wiring structure of a semiconductor device, the resistance value increases.

[0081] Similarly, in the reference example shown in FIG. 9, when annealing was performed at 1000° C. (1000° C. anneal), SiO 2 The Ti intensity peak at the boundary (around 60 to 80 nm) between the film 510 and the metal film 530 disappears. In other words, ruthenium diffuses into the TiN film (barrier film 520), and the TiN film and the ruthenium film are mixed. As a result, when the ruthenium film is used as a wiring structure of a semiconductor device, the resistance value increases.

[0082] In addition, in the reference example shown in FIG. 9, when annealing was performed at 1000° C. (1000° C. anneal), as shown in the TEM image, the TiN film was mixed with the ruthenium film, forming a SiO 2 The adhesion to film 510 is reduced, causing the ruthenium film to agglomerate.

[0083] In contrast, in the first embodiment shown in FIG. 7, in all cases where no annealing was performed (No anneal), where annealing was performed at 900° C. (900° C. anneal), where annealing was performed at 950° C. (950° C. anneal), and where annealing was performed at 1000° C. (1000° C. anneal), the intensity of Si and O decreased and the intensity of Ru increased (around 60 to 80 nm), in other words, the intensity of SiO 2 A peak in the intensity of Al appears at the boundary between the AlN film 510 and the metal film 530. In other words, it was confirmed that ruthenium does not diffuse into the AlN film (barrier film 520). This makes it possible to prevent an increase in resistance when the ruthenium film is used as a wiring structure of a semiconductor device. In addition, in the first embodiment shown in FIG. 7, as shown in the TEM image, no aggregation of the ruthenium film occurs, and the SiO 2 Adhesion to the film 510 is maintained.

[0084] In the second embodiment shown in FIG. 8, in all cases where no annealing was performed (No anneal), where annealing was performed at 900° C. (900° C. anneal), where annealing was performed at 950° C. (950° C. anneal), and where annealing was performed at 1000° C. (1000° C. anneal), the intensity of Si and O decreased and the intensity of Ru increased (around 60 to 80 nm), in other words, the intensity of SiO 2 Peaks in the intensities of Ti and Al appear at the boundary between the film 510 and the metal film 530. In other words, it was confirmed that ruthenium does not diffuse into the TiAlN film (barrier film 520). This makes it possible to prevent an increase in resistance when the ruthenium film is used as a wiring structure for a semiconductor device. In addition, in the second embodiment shown in FIG. 8, as shown in the TEM image, no aggregation of the ruthenium film occurs, and the SiO 2 Adhesion to the film 510 is maintained.

[0085] Although not shown in the figure, in the case where a TiCN film is formed as the barrier film 520 and a ruthenium film is formed as the metal film 530 on the barrier film 520, it is possible to prevent an increase in resistance due to the annealing treatment and maintain adhesion, as in the second embodiment.

[0086] As described above, the substrate processing system according to this embodiment can process the metal film 530 and the SiO 2 By forming a barrier film 520 made of any one of AlN, TiAlN, and TiCN between the metal film 530 and the film 510, it is possible to suppress diffusion of the metal film 530 caused by annealing treatment and to suppress mixing of the barrier film 520 and the metal film 530. This makes it possible to suppress an increase in the resistance value of the metal film 530 and a decrease in adhesion caused by annealing treatment. In other words, it is possible to improve the heat resistance of the metal film 530.

[0087] The above describes one embodiment of a substrate processing apparatus, but the present disclosure is not limited to the above 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]

[0088] 200 Substrate Processing System 211~213 Substrate processing equipment 500 Si substrate 510SiO 2 film 520 Barrier Film 530 Metal film (ruthenium film) W substrate

Claims

1. forming a barrier film on the substrate, the barrier film being any one of AlN, TiAlN, and TiCN; forming a ruthenium film on the barrier film; Annealing the substrate at 950° C. or higher; the ruthenium film does not diffuse into the barrier film; A method for processing a substrate.

2. The annealing step reduces the resistance value of the ruthenium film. The method of claim 1 .

3. After the step of forming the barrier film and before the step of forming the ruthenium film, removing impurities from a surface of the barrier film; The substrate processing method according to claim 1 or 2.

4. The substrate is made of SiO ２ A membrane is provided. The step of forming the barrier film includes the step of forming the SiO ２ depositing the barrier film on the film; The substrate processing method according to claim 1 .

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