Modification method and modification system

Abstract

To suppress a generation of a void in a metal used in a wiring.SOLUTION: A modification method includes a step a), a step b), and a step c). In the step a), a carbon-containing film is formed on a surface of metal wiring with a film deposition apparatus in a substrate in which the metal wiring is arranged. In the step b), the substrate in which the carbon-containing film is formed is transported into a chamber of an annealing apparatus. In the step c), an oxygen-containing gas is supplied into the chamber and the substrate on which the carbon-containing film is formed is annealed in a state where a pressure in the chamber is lower than an atmospheric pressure and a temperature of the substrate is higher than that of the substrate in the step a).SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] Various aspects and embodiments of the present disclosure relate to reforming methods and reforming systems. [Background technology]

[0002] For example, Patent Document 1 listed below discloses that "the process controller 23 controls the second heat treatment module 13d to perform a third heat treatment on the wafer W (S105). Specifically, the process controller 23 controls the butterfly valve 42 and the vacuum pump 43 of the second heat treatment module 13d to reduce the pressure inside the chamber 26 to a predetermined vacuum level. The process controller 23 then supplies argon gas from the second gas supply source 28b and oxygen gas from the third gas supply source 28c into the chamber 26 via the shower plate 38, each at a predetermined flow rate. The process controller 23 then controls the heater power supply 37 to set the temperature of the wafer W to a predetermined temperature. This removes excess carbon adhering to the surface of the metal catalyst 51, for example, as shown in FIG. 4(d)." [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-35047 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a modification method and a modification system that can suppress the occurrence of voids in metal wiring. [Means for solving the problem]

[0005] One aspect of the present disclosure is a modification method including steps a), b), and c). In step a), a carbon-containing film is formed on a surface of a metal wiring provided on a substrate by a film formation device. In step b), the substrate on which the carbon-containing film has been formed is loaded into a chamber of an annealing device. In step c), an oxygen-containing gas is supplied into the chamber, and the substrate on which the carbon-containing film has been formed is annealed in a state where the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a). [Effects of the Invention]

[0006] According to various aspects and embodiments of the present disclosure, it is possible to suppress the occurrence of voids in metal wiring. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a system configuration diagram showing an example of a reforming system according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a diagram showing an example of a plasma processing apparatus. [Figure 3] FIG. 3 is a diagram showing an example of an annealing apparatus. [Figure 4] FIG. 4 is a flowchart showing an example of the modification method according to the first embodiment. [Figure 5] FIG. 5 is a cross-sectional view showing an example of the structure of the substrate. [Figure 6A] FIG. 6A is a schematic diagram showing an example of a modification process in the first embodiment. [Figure 6B] FIG. 6B is a schematic diagram showing an example of the modification process in the first embodiment. [Figure 6C] FIG. 6C is a schematic diagram showing an example of the modification process in the first embodiment. [Figure 7] FIG. 7 is a diagram showing an example of the relationship between Gibbs free energy and temperature. [Figure 8] FIG. 8 is a diagram showing an example of a change in the sheet resistance of a wiring layer. [Figure 9]FIG. 9 is a flowchart showing an example of the modification method according to the second embodiment. [Figure 10A] FIG. 10A is a schematic diagram showing an example of a modification process in the second embodiment. [Figure 10B] FIG. 10B is a schematic diagram showing an example of a modification process in the second embodiment. [Figure 10C] FIG. 10C is a schematic diagram showing an example of a modification process in the second embodiment. [Figure 10D] FIG. 10D is a schematic diagram showing an example of a modification process in the second embodiment. [Figure 11] FIG. 11 is a diagram showing an example of a change in the sheet resistance of a wiring layer. [Figure 12] FIG. 12 is a flowchart showing an example of the modification method according to the third embodiment. [Figure 13A] FIG. 13A is a schematic diagram showing an example of a modification process in the third embodiment. [Figure 13B] FIG. 13B is a schematic diagram showing an example of a modification process in the third embodiment. [Figure 13C] FIG. 13C is a schematic diagram showing an example of a modification process in the third embodiment. [Figure 13D] FIG. 13D is a schematic diagram showing an example of a modification process in the third embodiment. [Figure 14] FIG. 14 is a flowchart showing an example of the modification method according to the fourth embodiment. [Figure 15A] FIG. 15A is a schematic diagram showing an example of a modification process in the fourth embodiment. [Figure 15B] FIG. 15B is a schematic diagram showing an example of a modification process in the fourth embodiment. [Figure 15C] FIG. 15C is a schematic diagram showing an example of a modification process in the fourth embodiment. [Figure 15D] FIG. 15D is a schematic diagram showing an example of the modification process in the fourth embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the disclosed reforming method and reforming system will be described in detail with reference to the drawings. Note that the disclosed reforming method and reforming system are not limited to the following embodiments.

[0009] When metal wiring is provided on a semiconductor layer, a barrier layer and an adhesive layer may be provided between the semiconductor layer and the metal wiring. In this case, the metal of the adhesive layer may pass through the grain boundaries of the metal wiring and precipitate on the surface of the metal wiring. When the metal of the adhesive layer precipitates on the surface of the metal wiring, cracks may occur at the grain boundaries of the metal wiring through which the metal of the adhesive layer passes, and the cracks may spread due to stress in the metal wiring. When the cracks in the metal wiring spread, they become voids in the metal wiring.

[0010] When voids occur in the metal wiring, the resistance of the metal wiring increases. Also, when the metal of the adhesive layer precipitates on the surface of the metal wiring, the amount of metal in the adhesive layer between the semiconductor layer and the metal wiring decreases, and the adhesion between the semiconductor layer and the metal wiring decreases. When the adhesion between the semiconductor layer and the metal wiring decreases, the resistance between the semiconductor layer and the metal wiring increases.

[0011] Therefore, the present disclosure provides a technique that can suppress the occurrence of voids in metal wiring.

[0012] (First embodiment) [Configuration example of reforming system 10] FIG. 1 is a system configuration diagram illustrating an example of a modification system 10 according to an embodiment of the present disclosure. The modification system 10 includes a plasma processing apparatus 200-1, a plasma processing apparatus 200-2, an annealing apparatus 300-1, and an annealing apparatus 300-2. The modification system 10 according to this embodiment is a multi-chamber vacuum processing system. Hereinafter, the plasma processing apparatuses 200-1 and 200-2 will be referred to collectively as the plasma processing apparatus 200 without distinction, and the annealing apparatuses 300-1 and 300-2 will be referred to collectively as the annealing apparatus 300 without distinction. The plasma processing apparatus 200 is an example of a film formation apparatus.

[0013] 1 includes two plasma processing devices 200, but as another example, the modification system 10 may include one or three or more plasma processing devices 200. Also, while the modification system 10 includes two annealing devices 300, as another example, the modification system 10 may include one or three or more annealing devices 300.

[0014] The plasma processing apparatus 200 deposits graphene on a substrate having a base layer, an adhesive layer, and a wiring layer stacked in this order. The wiring layer is a layer of metal used for wiring. As a result, graphene is deposited on the metal of the wiring layer. Graphene is an example of a carbon-containing film. Note that, in addition to graphene, amorphous carbon, diamond-like carbon, or the like can also be used as the carbon-containing film.

[0015] The annealing apparatus 300 anneals the substrate on which graphene has been formed by the plasma processing apparatus 200 in an atmosphere of an oxygen-containing gas. In this embodiment, the oxygen-containing gas is, for example, O gas. Annealing the substrate can modify the metal of the wiring layer.

[0016] Plasma processing apparatus 200-1, plasma processing apparatus 200-2, annealing apparatus 300-1, and annealing apparatus 300-2 are connected to the four side walls of vacuum transfer chamber 101, which has a heptagonal planar shape, via gate valves G. Three load lock chambers 102 are connected to the other three side walls of vacuum transfer chamber 101 via gate valves G1. Each of the three load lock chambers 102 is connected to atmospheric transfer chamber 103 via gate valves G2.

[0017] The vacuum transfer chamber 101 is evacuated by a vacuum pump and maintained at a predetermined vacuum level. A transfer device 106 such as a robot arm is provided inside the vacuum transfer chamber 101. The transfer device 106 transfers substrates W between the plasma processing device 200-1, the plasma processing device 200-2, the annealing device 300-1, the annealing device 300-2, and each of the load lock chambers 102. The transfer device 106 has two arms 107a and 107b that can move independently.

[0018] A plurality of ports 105 are provided on the side of the atmospheric transfer chamber 103 for attaching carriers C (e.g., FOUPs (Front-Opening Unified Pods)) that accommodate substrates W. An alignment chamber 104 is also provided on the side wall of the atmospheric transfer chamber 103 for aligning the substrates W. A downflow of clean air is formed within the atmospheric transfer chamber 103.

[0019] A transfer device 108 such as a robot arm is provided in the atmospheric transfer chamber 103. The transfer device 108 transfers substrates W between each carrier C, each load lock chamber 102, and the alignment chamber 104.

[0020] The control device 100 has a memory, a processor, and an input / output interface. The memory stores programs to be executed by the processor, recipes including conditions for each process, etc. The processor reads the programs from the memory, executes them, and controls each part of the reforming system 10 via the input / output interface based on the recipes stored in the memory.

[0021] [Configuration example of plasma processing apparatus 200] Fig. 2 is a diagram showing an example of a plasma processing apparatus 200. The plasma processing apparatus 200 shown in Fig. 2 is configured as, for example, an RLSA (registered trademark) microwave plasma type plasma processing apparatus.

[0022] The plasma processing apparatus 200 includes a chamber 201 , a stage 202 , a microwave introduction mechanism 203 , a gas supply mechanism 204 , and an exhaust mechanism 205 .

[0023] The chamber 201 is formed in a substantially cylindrical shape, and an opening 210 is formed in the approximate center of a bottom wall 201a of the chamber 201. An exhaust chamber 211 that communicates with the opening 210 and protrudes downward is provided in the bottom wall 201a. An opening 217 through which a substrate (hereinafter also referred to as a wafer) W passes is formed in a side wall 201s of the chamber 201, and the opening 217 is opened and closed by a gate valve G.

[0024] A substrate W to be processed is placed on the stage 202. The stage 202 is generally disk-shaped and made of ceramics such as AlN (aluminum nitride). The stage 202 is supported by a cylindrical support member 212 made of ceramics such as AlN that extends upward from approximately the center of the bottom of the exhaust chamber 211. An edge ring 213 is provided on the outer edge of the stage 202 so as to surround the substrate W placed on the stage 202. Furthermore, inside the stage 202, lifting pins (not shown) for lifting and lowering the substrate W are provided so as to be able to protrude and retract from the upper surface of the stage 202.

[0025] Furthermore, a resistance heating heater 214 is embedded inside the stage 202, and the heater 214 heats the substrate W placed on the stage 202 in accordance with power supplied from a heater power supply 215. A thermocouple (not shown) is also inserted into the stage 202, and the temperature of the substrate W can be controlled to, for example, 350 to 850°C based on a signal from the thermocouple. Furthermore, an electrode 216 having a size approximately the same as that of the substrate W is embedded above the heater 214 inside the stage 202, and a bias power supply 219 is electrically connected to the electrode 216. The bias power supply 219 supplies bias power of a predetermined frequency and magnitude to the electrode 216. The bias power supplied to the electrode 216 attracts ions to the substrate W placed on the stage 202. Note that the bias power supply 219 may not be provided depending on the characteristics of the plasma processing.

[0026] The microwave introduction mechanism 203 is provided at the top of the chamber 201 and includes an antenna 221, a microwave output unit 222, and a microwave transmission mechanism 223. The antenna 221 has a large number of slots 221a that are through-holes. The microwave output unit 222 outputs microwaves. The microwave transmission mechanism 223 guides the microwaves output from the microwave output unit 222 to the antenna 221.

[0027] A dielectric window 224 made of a dielectric material is provided below the antenna 221. The dielectric window 224 is supported by a support member 232 that is ring-shaped and provided at the top of the chamber 201. A slow-wave plate 226 is provided above the antenna 221. A shield member 225 is provided above the antenna 221. A flow path (not shown) is provided inside the shield member 225, and the shield member 225 cools the antenna 221, the dielectric window 224, and the slow-wave plate 226 by a fluid such as water that flows through the flow path.

[0028] The antenna 221 is formed of, for example, a copper plate or an aluminum plate whose surface is plated with silver or gold, and has a plurality of slots 221a for radiating microwaves arranged in a predetermined pattern. The arrangement pattern of the slots 221a is appropriately set so that the microwaves are radiated uniformly. An example of a suitable pattern is a radial line slot, in which two slots 221a arranged in a T-shape form a pair, and multiple pairs of slots 221a are arranged concentrically. The length and arrangement interval of the slots 221a are appropriately determined depending on the effective wavelength (λg) of the microwaves. The slots 221a may also have other shapes, such as a circular shape or an arc shape. Furthermore, the arrangement form of the slots 221a is not particularly limited, and they may be arranged in a spiral or radial shape in addition to a concentric shape. The pattern of the slots 221a is appropriately set so that microwave radiation characteristics that obtain a desired plasma density distribution are achieved.

[0029] Slow-wave plate 226 is made of a dielectric material having a dielectric constant greater than that of a vacuum, such as quartz, ceramics (Al2O3), polytetrafluoroethylene, or polyimide. Slow-wave plate 226 has the function of shortening the wavelength of the microwave compared to that in a vacuum, thereby reducing the size of antenna 221. Dielectric window 224 is also made of a similar dielectric material.

[0030] The thicknesses of the dielectric window 224 and the slow-wave plate 226 are adjusted so that the equivalent circuit formed by the slow-wave plate 226, the antenna 221, the dielectric window 224, and the plasma satisfies the resonance condition. The phase of the microwave can be adjusted by adjusting the thickness of the slow-wave plate 226. By adjusting the thickness of the slow-wave plate 226 so that the junction of the antenna 221 becomes the "antinode" of the standing wave, microwave reflection can be minimized and the radiated energy of the microwave can be maximized. Furthermore, by using the same material for the slow-wave plate 226 and the dielectric window 224, interface reflection of the microwave can be prevented.

[0031] The microwave output unit 222 has a microwave oscillator. The microwave oscillator may be a magnetron type or a solid-state type. The frequency of the microwave generated by the microwave oscillator is, for example, 300 MHz to 10 GHz. As an example, the microwave output unit 122 outputs a microwave of 2.45 GHz using a magnetron type microwave oscillator.

[0032] The microwave transmission mechanism 223 includes a waveguide 227 and a coaxial waveguide 228. It may further include a mode conversion mechanism. The waveguide 227 guides the microwaves output from the microwave output unit 222. The coaxial waveguide 228 includes an inner conductor connected to the center of the antenna 221 and an outer conductor on the outside thereof. The mode conversion mechanism is provided between the waveguide 227 and the coaxial waveguide 228. The microwaves output from the microwave output unit 222 propagate through the waveguide 227 in TE mode and are converted from TE mode to TEM mode by the mode conversion mechanism. The microwaves converted to TEM mode propagate through the coaxial waveguide 228 to the slow-wave plate 226 and are radiated from the slow-wave plate 226 into the chamber 201 through the slot 221a of the antenna 221 and the dielectric window 224. In addition, a tuner (not shown) for matching the impedance of the load (plasma) in the chamber 201 to the output impedance of the microwave output part 222 is provided midway along the waveguide 227.

[0033] The gas supply mechanism 204 has a shower ring 242 that is ring-shaped and arranged along the inner wall of the chamber 201. The shower ring 242 has a ring-shaped flow path 266 arranged therein and a number of outlets 267 that are connected to the flow path 266 and open to the inside of the flow path 266. A gas supply unit 263 is connected to the flow path 266 via a pipe 261. The gas supply unit 263 is provided with a number of gas sources and a number of flow rate controllers. In one embodiment, the gas supply unit 263 is configured to supply at least one process gas to the shower ring 242 from a corresponding gas source via a corresponding flow rate controller. The gas supplied to the shower ring 242 is then supplied into the chamber 201 through the multiple outlets 267.

[0034] When a graphene film is formed on the substrate W, the gas supply unit 263 supplies a carbon-containing gas, a hydrogen-containing gas, and a rare gas (noble gas) controlled at predetermined flow rates into the chamber 201 via the shower ring 242. In this embodiment, the carbon-containing gas is, for example, C2H2 gas. In addition to acetylene (C2H2) gas, any of ethylene (C2H4) gas, methane (CH4) gas, ethane (C2H6) gas, propane (C3H8) gas, propylene (C3H6) gas, methanol (CH3OH) gas, and ethanol (C2H5OH) gas may be used. In this embodiment, the hydrogen-containing gas is, for example, hydrogen gas. Note that, instead of or in addition to hydrogen gas, a halogen-based gas such as F2 (fluorine) gas, Cl2 (chlorine) gas, or Br2 (bromine) gas may be used. In this embodiment, the rare gas is, for example, Ar gas. Instead of Ar gas, other rare gases such as He gas may be used.

[0035] The exhaust mechanism 205 includes an exhaust chamber 211, an exhaust pipe 281 provided on the side wall of the exhaust chamber 211, and an exhaust device 282 connected to the exhaust pipe 281. The exhaust device 282 includes a vacuum pump, a pressure control valve, and the like.

[0036] [Configuration example of annealing apparatus 300] 3 is a diagram showing an example of an annealing apparatus 300. The annealing apparatus 300 includes a chamber 301, an exhaust pipe 302, a supply pipe 303, a stage 304, a lamp house 305, and a lamp 306.

[0037] A stage 304 on which a substrate W is placed is provided within the chamber 301. A lamp house 305 is provided at a position opposite to the surface of the stage 304 on which the substrate W is placed. A lamp 306 such as an infrared lamp is disposed within the lamp house 305.

[0038] A gas supply unit 307 is connected to a sidewall of the chamber 301 via a supply pipe 303. The gas supply unit 307 supplies an oxygen-containing gas into the chamber 301 via the supply pipe 303. In this embodiment, the oxygen-containing gas is, for example, O gas. An opening 301a is formed in the sidewall of the chamber 301 to allow the substrate W to be loaded and unloaded. The opening 301a is opened and closed by a gate valve G.

[0039] An exhaust device 308 is connected to the bottom of the chamber 301 via an exhaust pipe 302. The exhaust device 308 has a pressure adjustment valve. The exhaust device 308 exhausts gas from the chamber 301 and controls the pressure adjustment valve so that the pressure inside the chamber 301 becomes a predetermined pressure.

[0040] With the substrate W placed on the stage 304 and oxygen-containing gas being supplied into the chamber 301 via the supply pipe 303, the lamp 306 is turned on, whereby the substrate W can be heated to a predetermined temperature in an atmosphere of oxygen-containing gas.

[0041] [Modification method] Fig. 4 is a flowchart showing an example of a modification method according to the first embodiment. The modification method shown in Fig. 4 is realized by the control device 100 controlling each part of the modification system 10. Note that, before step S10 is started, pre-processing such as cleaning the inside of the chamber 201 of the plasma processing device 200 may be performed.

[0042] First, the substrate W is loaded into the chamber 201 of the plasma processing apparatus 200 (step S10). In step S10, the substrate W having a structure such as that shown in FIG. 5 is loaded into the plasma processing apparatus 200. The substrate W has an underlayer 40, an adhesive layer 41, and a wiring layer 42. The underlayer 40 includes a semiconductor layer and a barrier layer. The adhesive layer 41 is made of a metal such as titanium. The wiring layer 42 is made of a metal such as ruthenium. Grain boundaries 420 exist in the wiring layer 42.

[0043] Next, graphene is deposited on the surface of the wiring layer 42 of the substrate W by the plasma processing apparatus 200 (step S11). Step S11 is an example of the process a). As a result, graphene 43 is deposited on the wiring layer 42, as shown in FIG. 6A, for example. In step S11, graphene is deposited under the following processing conditions, for example. In the following values, 1 sccm is approximately 1.69×10 -3 pa·m 3 / s, and 1 Torr is approximately 133 Pa. Microwave: 100~5000W Pressure in chamber 201: 0.001 to 1 Torr (for example, 50 mTorr) Gas species contained in the processing gas: Ar / C2H2 Temperature of substrate W: 100 to 1000°C (e.g., 300°C) Processing time: 140 seconds

[0044] In addition, the description "A to B (for example, C)" in the above processing conditions indicates that the value of the corresponding parameter is in the range of A or more and B or less, and indicates that the value C may be taken as an example.

[0045] Next, the substrate W is transferred from the plasma processing apparatus 200 to the annealing apparatus 300 (step S12). In step S12, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 201 of the plasma processing apparatus 200 and into the chamber 301 of the annealing apparatus 300. Step S12 is an example of process b).

[0046] Next, the substrate W is annealed by the annealing apparatus 300 (step S13). Step S13 is an example of process c). In step S13, an oxygen-containing gas is supplied into the chamber 301 of the annealing apparatus 300, and the pressure inside the chamber 301 is controlled to be lower than atmospheric pressure. Then, the substrate W is annealed in a state where the temperature of the substrate W is higher than in step S11.

[0047] In step S13, annealing is performed under the following processing conditions, for example. Pressure in chamber 301: 0.0001 to 100 Torr (for example, 1 Torr) Flow rate of oxygen-containing gas: Ar / O2 = 0 to 1000 sccm / 0.1 to 1000 sccm Temperature of substrate W: 300 to 1100°C (e.g., 1000°C) Processing time: 600 seconds

[0048] In the above example, oxygen gas (O gas) is used as the oxygen-containing gas, but the disclosed technology is not limited to this. The oxygen-containing gas used in step S13 may be, for example, ozone gas, CO gas, or NO gas (x is an integer).

[0049] In step S13, the substrate W is annealed in an oxygen-containing gas atmosphere, whereby, for example, as shown in FIG. 6B , the carbon 421 of the graphene 43 is dissolved in the wiring layer 42. The carbon 421 dissolved in the wiring layer 42 is also dissolved in the grain boundaries 420. The carbon 421 dissolved in the grain boundaries 420 prevents the metal of the adhesive layer 41 from passing through the grain boundaries 420 and precipitating onto the surface of the wiring layer 42. This makes it possible to prevent the metal of the adhesive layer 41 from passing through the grain boundaries 420 and precipitating onto the surface of the wiring layer 42. This makes it possible to prevent voids from being generated in the wiring layer 42.

[0050] In addition, in step S13, the substrate W is annealed in an oxygen-containing gas atmosphere, whereby, for example, as shown in FIG. 6B, the thickness of the graphene 43 is reduced and part of the wiring layer 42 is oxidized, forming a metal oxide 422 in the wiring layer 42.

[0051] 7, for example, the reaction of gasifying graphene 43 with oxygen requires less energy than the reaction of oxidizing the wiring layer 42 (e.g., ruthenium). Therefore, in step S13, the reaction of gasifying graphene 43 with oxygen proceeds more rapidly than the reaction of oxidizing the wiring layer 42. Note that the oxidation reaction of the wiring layer 42 also occurs in step S13, although to a lesser extent than the reaction of gasifying graphene 43 with oxygen.

[0052] Furthermore, in this embodiment, the metal oxide 422 of the metal in the wiring layer 42 has a lower melting point than the metal in the wiring layer 42. Specifically, the metal in the wiring layer 42 is, for example, ruthenium, and the oxide of ruthenium (RuO2) has a lower melting point than ruthenium. Therefore, annealing can cause fluidity in the metal oxide 422. Because the metal oxide 422 is formed in greater amounts at the grain boundaries 420, when fluidity is generated in the metal oxide 422 at the grain boundaries 420, material transport through the grain boundaries 420 is promoted, and metal crystal grains grow, as shown in FIG. 6C, for example. This increases the size of the metal crystal grains in the wiring layer 42, thereby reducing the resistance of the wiring layer 42. In addition to ruthenium, examples of metals whose oxides have a lower melting point include manganese and iron. These metals can also be used for the wiring layer 42.

[0053] Next, the substrate W is unloaded from the annealing apparatus 300 (step S14), and the modifying method shown in this flowchart is then completed.

[0054] FIG. 8 is a diagram showing an example of the change in sheet resistance of the wiring layer 42. For example, as shown in FIG. 8, when graphene 43 was formed, the resistance of the wiring layer 42 decreased. Specifically, the sheet resistance of the wiring layer 42 after the graphene 43 was formed was reduced by 24.4% compared to the sheet resistance before the graphene 43 was formed. Furthermore, when annealing was performed, the sheet resistance of the wiring layer 42 was further reduced. Specifically, the sheet resistance of the wiring layer 42 after annealing was reduced by 51.3% compared to the sheet resistance of the wiring layer 42 before the graphene 43 was formed. Furthermore, no voids were observed in the wiring layer 42.

[0055] The first embodiment has been described above. As described above, the modification method in the embodiment includes steps a), b), and c). In step a), a carbon-containing film (graphene 43) is formed on the surface of a substrate (substrate W) on which metal wiring (wiring layer 42) is provided, using a film-forming apparatus (plasma processing apparatus 200). In step b), the substrate on which the carbon-containing film has been formed is loaded into a chamber (chamber 301) of an annealing apparatus (annealing apparatus 300). In step c), an oxygen-containing gas is supplied into the chamber, and the substrate on which the carbon-containing film has been formed is annealed in a state in which the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a). This makes it possible to suppress the generation of voids in the metal wiring.

[0056] In the first embodiment described above, the pressure inside the chamber 301 in step S13 is set to a pressure in the range of 0.0001 Torr or more and 100 Torr or less. This allows carbon to be efficiently dissolved in the wiring layer 42.

[0057] In the first embodiment described above, the temperature of the substrate in step S13 is within a range of 300° C. to 1100° C. This allows carbon to be efficiently dissolved in the wiring layer 42, and also allows oxides in the wiring layer 42 to be fluidized, thereby increasing the size of the crystal grains in the wiring layer 42.

[0058] In the first embodiment, the melting point of the oxide of the metal wiring is lower than the melting point of the metal wiring. The metal wiring is, for example, ruthenium, manganese, or iron. This allows the oxide of the wiring layer 42 to be easily fluidized, thereby increasing the crystal grain size of the wiring layer 42.

[0059] In the first embodiment described above, the oxygen-containing gas supplied into the chamber 301 in step S13 is oxygen gas, ozone gas, COx gas, or NOx gas (x is an integer), thereby making it possible to easily oxidize the wiring layer 42.

[0060] In the first embodiment described above, the carbon-containing film formed on the surface of the wiring layer 42 is graphene. This allows carbon to be efficiently dissolved in the wiring layer 42.

[0061] The first embodiment described above is a modification system including a film forming apparatus (plasma processing apparatus 200), an annealing apparatus (annealing apparatus 300), a transfer apparatus (transfer apparatus 106), and a control apparatus (control apparatus 100). The control apparatus executes steps a), b), and c). In step a), a film forming apparatus is controlled to form a carbon-containing film (graphene 43) on the surface of a substrate (substrate W) provided with metal wiring (wiring layer 42). In step b), the transfer apparatus is controlled to transfer the substrate on which the carbon-containing film has been formed from the chamber (chamber 201) of the film forming apparatus and into the chamber (chamber 301) of the annealing apparatus. In step c), an oxygen-containing gas is supplied into the chamber, and the substrate on which the carbon-containing film has been formed is annealed in a state where the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a). This can prevent voids from being generated in the metal wiring.

[0062] (Second embodiment) In the first embodiment, annealing is performed once after the carbon-containing film is formed. In contrast, in the second embodiment, annealing is performed twice after the carbon-containing film is formed, which is different from the first embodiment. The following description will focus on the differences from the first embodiment.

[0063] [Modification method] Fig. 9 is a flowchart showing an example of a reforming method in the second embodiment. In the reforming method illustrated in Fig. 9, the processes with the same reference numerals as those in Fig. 4 are the same as those described in Fig. 4, and therefore will not be described again except for the points described below.

[0064] After step S11, the substrate W is transferred from the plasma processing apparatus 200 to the annealing apparatus 300-1 (step S12). In step S12, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 201 of the plasma processing apparatus 200 and into the chamber 301 of the annealing apparatus 300-1.

[0065] Next, the annealing apparatus 300-1 performs a first annealing (step S20). Step S20 is an example of the process c). The first annealing is performed under the same processing conditions as step S13 in the first embodiment.

[0066] Next, the substrate W is transferred from the annealing apparatus 300-1 to the annealing apparatus 300-2 (step S21). In step S21, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 301 of the annealing apparatus 300-1 and into the chamber 301 of the annealing apparatus 300-2.

[0067] Next, a second annealing is performed by the annealing apparatus 300-2 (step S22). Step S22 is an example of process d). In step S22, an oxygen-free gas is supplied into the chamber 301 of the annealing apparatus 300-2. The pressure inside the chamber 301 is controlled to be lower than atmospheric pressure. The substrate W is then annealed at a temperature higher than that in step S11.

[0068] In step S21, annealing is performed under the following processing conditions, for example. Pressure in chamber 301: 0.0001 to 100 Torr (for example, 1 Torr) Flow rate of oxygen-free gas: Ar = 1 to 2000 sccm Temperature of substrate W: 300 to 1100°C (e.g., 1000°C) Processing time: 5 to 3600 seconds

[0069] In this embodiment, in step S11, graphene 43 is formed on the wiring layer 42, as shown in FIG. 10A, for example. Then, in step S20, a first annealing process is performed in an oxygen-containing gas atmosphere. As a result, as shown in FIG. 10B, for example, carbon 421 dissolves in the grain boundaries 420 of the wiring layer 42, and metal oxide 422 is formed in the grain boundaries 420 near the surface of the wiring layer 42. The graphene 43 reacts with oxygen to be gasified, reducing its thickness. As shown in FIG. 10C, for example, the graphene 43 is partially or completely lost, such that the surface of the wiring layer 42 is oxidized in the next step. Then, in step S22, a second annealing process is performed, which causes fluidity in the metal oxide 422 and causes the crystal grains of the wiring layer 42 to grow, as shown in FIG. 10D, for example. This increases the crystal grain size of the wiring layer 42, thereby reducing the resistance of the wiring layer 42.

[0070] 11 is a diagram showing an example of the change in sheet resistance of the wiring layer 42. For example, as shown in FIG. 11, the sheet resistance of the wiring layer 42 after the first annealing is reduced by approximately 51.3% compared to the sheet resistance of the wiring layer 42 before the graphene 43 is formed. Furthermore, the sheet resistance of the wiring layer 42 after the second annealing is reduced by approximately 52.6% compared to the sheet resistance of the wiring layer 42 before the graphene 43 is formed. Therefore, by performing the second annealing after the first annealing, the resistance of the wiring layer 42 can be further reduced.

[0071] In the second embodiment described above, the first annealing is performed in the annealing apparatus 300-1 and the second annealing is performed in the annealing apparatus 300-2, but the disclosed technology is not limited to this. In another embodiment, the first annealing and the second annealing may be performed in the same annealing apparatus 300.

[0072] Furthermore, in the second embodiment described above, the second annealing is performed in an atmosphere of a gas containing no oxygen, but the disclosed technology is not limited to this. Alternatively, the second annealing may be performed in an atmosphere of a gas containing oxygen. In this case, however, the flow rate of the oxygen-containing gas supplied into the chamber 301 during the second annealing is lower than the flow rate of the oxygen-containing gas supplied into the chamber 301 during the first annealing. This prevents the wiring layer 42 from being excessively oxidized during the second annealing.

[0073] In another embodiment, the second annealing is performed under the following processing conditions, for example: Pressure in chamber 301: 0.0001 to 100 Torr (for example, 1 Torr) Flow rate of oxygen-containing gas: Ar / O2 = 1 to 1000 sccm / 0.1 to 1000 sccm Temperature of substrate W: 300 to 1100°C (e.g., 1000°C) Processing time: 5 to 3600 seconds

[0074] The second embodiment has been described above. The modification method in this embodiment further includes step d). Step d) is performed after step c), in which an oxygen-free gas is supplied into a chamber (chamber 301) of an annealing apparatus (annealing apparatus 300), and the substrate on which the carbon-containing film has been formed is annealed in a state in which the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a). This makes it possible to suppress the generation of voids in the metal wiring.

[0075] Furthermore, step d) in the second embodiment described above may be performed after step c), and the substrate on which the carbon-containing film has been formed may be annealed in a state in which an oxygen-containing gas is supplied into the chamber of the annealing apparatus, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in step a). In this case, the flow rate of the oxygen-containing gas supplied into the chamber in step d) is smaller than the flow rate of the oxygen-containing gas supplied into the chamber in step c). This makes it possible to suppress excessive oxidation of the wiring layer 42.

[0076] In the second embodiment described above, the pressure in the chamber in step d) is within the range of 0.0001 Torr or more and 100 Torr or less.

[0077] In the second embodiment described above, the temperature of the substrate in step d) is within the range of 300°C or higher and 1100°C or lower.

[0078] (Third embodiment) In the second embodiment, the second annealing is performed following the first annealing. In contrast, the present embodiment differs from the second embodiment in that a plasma treatment is performed between the first annealing and the second annealing. The following description will focus on the differences from the second embodiment.

[0079] [Modification method] Fig. 12 is a flowchart showing an example of a modification method according to the third embodiment. In the modification method shown in Fig. 12, the processes denoted by the same reference numerals as those in Fig. 4 or 9 are the same as those described in Fig. 4 or 9, and therefore will not be described again except for the points described below.

[0080] First, the substrate W is loaded into the chamber 201 of the plasma processing apparatus 200-1 (step S10), and the plasma processing apparatus 200-1 deposits graphene on the surface of the wiring layer 42 of the substrate W (step S11). Then, the substrate W is transferred from the plasma processing apparatus 200-1 to the annealing apparatus 300-1 (step S12), and the first annealing is performed by the annealing apparatus 300-1 (step S20).

[0081] Next, the substrate W is transferred from the annealing apparatus 300-1 to the plasma processing apparatus 200-2 (step S30). In step S30, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 301 of the annealing apparatus 300-1 and into the chamber 201 of the plasma processing apparatus 200-2.

[0082] Next, plasma processing is performed by the plasma processing apparatus 200-2 (step S31). Step S31 is an example of process e). In step S31, the surface of the wiring layer 42 on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-free gas into plasma. The plasma processing in step S31 is performed at a pressure lower than atmospheric pressure.

[0083] In step S31, plasma processing is performed under the following processing conditions, for example. Microwave: 100~5000W Pressure in chamber 201: 0.001 to 10 Torr Flow rate of oxygen-free gas: Ar / H2 = 0 to 1000 sccm / 0.1 to 1000 sccm Temperature of substrate W: 20 to 1000°C (e.g., 300°C) Processing time: 5 to 900 seconds

[0084] Next, the substrate W is transferred from the plasma processing apparatus 200-2 to the annealing apparatus 300-2 (step S32). In step S32, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 201 of the plasma processing apparatus 200-2 and into the chamber 301 of the annealing apparatus 300-2. Then, the processes from step S22 onwards are executed.

[0085] In this embodiment, in step S11, graphene 43 is formed on the wiring layer 42, as shown in FIG. 13A, for example. Then, in step S20, a first annealing process is performed in an oxygen-containing gas atmosphere. As a result, as shown in FIG. 13B, for example, carbon 421 dissolves in the grain boundaries 420 of the wiring layer 42, and metal oxide 422 is formed in the grain boundaries 420 near the surface of the wiring layer 42. The graphene 43 reacts with oxygen to be gasified, reducing its thickness. Then, in step S31, a plasma process is performed, and the graphene 43 is removed by the plasma generated in the chamber 201, as shown in FIG. 13C, for example. Then, in step S22, a second annealing process is performed, which causes fluidity in the metal oxide 422 and causes the crystal grains of the wiring layer 42 to grow, as shown in FIG. 13D, for example. This increases the crystal grain size of the wiring layer 42, thereby reducing the resistance of the wiring layer 42.

[0086] In this embodiment, the excess graphene 43 can be quickly removed by performing a plasma treatment between the first annealing and the second annealing.

[0087] In the third embodiment described above, the graphene 43 is deposited in the plasma processing apparatus 200-1 and the plasma processing is performed in the plasma processing apparatus 200-2, but the disclosed technology is not limited to this. As another embodiment, the graphene 43 may be deposited and the plasma processing may be performed in the same plasma processing apparatus 200.

[0088] In the plasma treatment (step S31) in the third embodiment described above, the substrate W is exposed to plasma generated by converting a gas that does not contain oxygen into plasma, but the disclosed technology is not limited to this. As another embodiment, the plasma treatment may be performed by exposing the substrate W to plasma generated by converting a gas that contains oxygen into plasma. This makes it possible to remove excess graphene 43 more quickly, and also to oxidize the wiring layer 42 and remove the graphene 43.

[0089] The plasma treatment in another form is carried out, for example, under the following treatment conditions. Microwave: 100~5000W Pressure in chamber 201: 0.001 to 10 Torr Flow rate of oxygen-containing gas: Ar / O2 = 0 to 1000 sccm / 0.1 to 1000 sccm Temperature of substrate W: 20 to 1000°C (e.g., 300°C) Processing time: 5 to 900 seconds

[0090] The third embodiment has been described above. The modification method in this embodiment further includes step e). Step e) is performed after step c) and before step d), and exposes the surface of the metal wiring (wiring layer 42) on which the carbon-containing film (graphene 43) is formed to plasma generated by converting an oxygen-free gas into plasma. This allows excess graphene 43 to be quickly removed.

[0091] Furthermore, step e) in the third embodiment may be performed after step c) and before step d), and the surface of the metal wiring on which the carbon-containing film is formed may be exposed to plasma generated by converting an oxygen-containing gas into plasma. This allows the excess graphene 43 to be removed more quickly, and also allows the wiring layer 42 to be oxidized and the graphene 43 to be removed.

[0092] In the third embodiment described above, the pressure in the chamber (chamber 201) in step e) is lower than atmospheric pressure. Specifically, the pressure in the chamber in step e) is, for example, in the range of 0.001 Torr or more and 10 Torr or less.

[0093] (Fourth embodiment) In the first embodiment, annealing after the graphene 43 is formed reduces the graphene 43, dissolves the carbon 421 in the wiring layer 42, oxidizes the wiring layer 42, and grows crystals of the wiring layer 42. In contrast, in the present embodiment, after the substrate W on which the graphene 43 is formed is annealed, the substrate W is exposed to plasma generated by converting an oxygen-containing gas into plasma. As a result, the graphene 43 is reduced in thickness and dissolves the carbon 421 in the wiring layer 42 by the annealing, and the plasma treatment oxidizes the wiring layer 42 and grows crystals of the wiring layer 42. As a result, the oxidation of the wiring layer 42 and the growth of crystals of the wiring layer 42 can be more efficiently performed. The following mainly describes the differences from the first embodiment. [Modification method] Fig. 14 is a flowchart showing an example of a modification method according to the fourth embodiment. In the modification method shown in Fig. 14, the processes denoted by the same reference numerals as those in Fig. 4 are the same as those described in Fig. 4, and therefore will not be described again except for the points described below.

[0094] First, the substrate W is loaded into the chamber 201 of the plasma processing apparatus 200-1 (step S10), and the plasma processing apparatus 200-1 deposits graphene on the surface of the wiring layer 42 of the substrate W (step S11). Then, the substrate W is transferred from the plasma processing apparatus 200-1 to the annealing apparatus 300 (step S12), and annealing is performed by the annealing apparatus 300 (step S13).

[0095] Next, the substrate W is transferred from the annealing apparatus 300 to the plasma processing apparatus 200-2 (step S40). In step S40, the transfer device 106 in the vacuum transfer chamber 101 transfers the substrate W out of the chamber 301 of the annealing apparatus 300 and into the chamber 201 of the plasma processing apparatus 200-2.

[0096] Next, plasma processing is performed by the plasma processing apparatus 200-2 (step S41). Step S41 is an example of process f). In step S41, the surface of the wiring layer 42 on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-containing gas into plasma.

[0097] In step S41, plasma processing is performed under the following processing conditions, for example. Microwave: 100~5000W Pressure in chamber 201: 0.001 to 10 Torr Flow rate of oxygen-containing gas: Ar / O2 = 0 to 1000 sccm / 0.1 to 1000 sccm Temperature of substrate W: 20 to 1000°C (e.g., 300°C) Processing time: 5 to 900 seconds

[0098] Next, the substrate W is unloaded from the plasma processing apparatus 200-2 (step S14), and the modifying method shown in this flowchart is completed.

[0099] In this embodiment, in step S11, graphene 43 is formed on the wiring layer 42, for example, as shown in FIG. 15A. Then, in step S13, annealing is performed in an oxygen-containing gas atmosphere. As a result, carbon 421 is dissolved in the grain boundaries 420 of the wiring layer 42, for example, as shown in FIG. 15B. The graphene 43 reacts with oxygen to be gasified, reducing the thickness of the graphene 43. Then, in step S41, the graphene 43 is removed by treatment with plasma of the oxygen-containing gas, for example, as shown in FIG. 15C. Furthermore, metal oxide 422 is formed in the grain boundaries 420 near the surface of the wiring layer 42. Fluidity is then generated in the metal oxide 422, and the crystal grains of the wiring layer 42 grow, for example, as shown in FIG. 15D. This increases the crystal grain size of the wiring layer 42, thereby reducing the resistance of the wiring layer 42.

[0100] The fourth embodiment has been described above. The modification method in this embodiment further includes step f). Step f) is performed after step c), and exposes the surface of the metal wiring (wiring layer 42) on which the carbon-containing film (graphene 43) is formed to plasma generated by converting an oxygen-containing gas into plasma. This allows oxidation of the wiring layer 42 and growth of crystals in the wiring layer 42 to be performed more efficiently.

[0101] [others] The technology disclosed in this application is not limited to the above-described embodiment, and various modifications are possible within the scope of the gist thereof.

[0102] For example, in each of the above-described embodiments, the graphene 43 is deposited and the plasma treatment is performed using the annealing apparatus 300 having a plurality of microwave radiation mechanisms 243, but the disclosed technology is not limited to this. As another embodiment, the graphene 43 may be deposited and the plasma treatment performed using a plasma treatment apparatus having, for example, one microwave radiation mechanism.

[0103] Furthermore, in each of the above-described embodiments, the annealing apparatus 300 that forms the graphene 43 and performs the plasma processing using microwave plasma as a plasma source has been described as an example, but the disclosed technology is not limited to this. As long as the apparatus forms the graphene 43 on the substrate W and performs the plasma processing using plasma, the plasma source is not limited to microwave plasma, and any plasma source such as capacitively coupled plasma, inductively coupled plasma, or magnetron plasma can be used.

[0104] It should be noted that the disclosed embodiments are illustrative in all respects and should not be considered limiting. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims.

[0105] Furthermore, the following supplementary notes are disclosed regarding the above-described embodiment.

[0106] (Appendix 1) a) forming a carbon-containing film on a surface of a metal wiring on a substrate by using a film forming device; b) carrying the substrate on which the carbon-containing film is formed into a chamber of an annealing apparatus; c) annealing the substrate on which the carbon-containing film has been formed in a state in which an oxygen-containing gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in step a); A modification method comprising: (Appendix 2) d) a step performed after the step c), in which an oxygen-free gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in the step a), and the step is performed to anneal the substrate on which the carbon-containing film is formed. The modification method according to claim 1, further comprising: (Appendix 3) e) a step that is carried out after the step c) and before the step d), in which the surface of the metal wiring on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-free gas into plasma. The modification method according to claim 2, further comprising: (Appendix 4) e) a step that is carried out after the step c) and before the step d), in which the surface of the metal wiring on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-containing gas into plasma. The modification method according to claim 2, further comprising: (Appendix 5) 5. The method for modifying a surface of a substrate according to claim 3, wherein the pressure in the chamber in step e) is lower than atmospheric pressure. (Appendix 6) 6. The modification method according to claim 5, wherein the pressure in the chamber in step e) is within a range of 0.001 Torr or more and 10 Torr or less. (Appendix 7) d) a step performed after the step c), in which an oxygen-containing gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in the step a), and the step is performed to anneal the substrate on which the carbon-containing film is formed. further comprising 2. The reforming method according to claim 1, wherein the flow rate of the oxygen-containing gas supplied into the chamber in the step d) is smaller than the flow rate of the oxygen-containing gas supplied into the chamber in the step c). (Appendix 8) 8. The modifying method according to any one of appendixes 2 to 7, wherein the pressure in the chamber in step d) is in the range of 0.0001 Torr or more and 100 Torr or less. (Appendix 9) 9. The modification method according to any one of appendices 2 to 8, wherein the temperature of the substrate in step d) is within a range of 300°C or higher and 1100°C or lower. (Appendix 10) f) a step performed after the step c), of exposing the surface of the metal wiring on which the carbon-containing film is formed to plasma generated by converting an oxygen-containing gas into plasma. The modification method according to claim 1, further comprising: (Appendix 11) 11. The modifying method according to any one of claims 1 to 10, wherein the pressure in the chamber in step c) is in the range of 0.0001 Torr or more and 100 Torr or less. (Appendix 12) 12. The modification method according to any one of claims 1 to 11, wherein the temperature of the substrate in step c) is in the range of 300°C or higher and 1100°C or lower. (Appendix 13) 13. The method for modifying the metal wiring according to any one of claims 1 to 12, wherein the melting point of the oxide of the metal wiring is lower than the melting point of the metal wiring. (Appendix 14) 14. The method for modifying a surface according to claim 13, wherein the metal wiring is made of ruthenium, manganese, or iron. (Appendix 15) 15. The reforming method according to any one of claims 1 to 14, wherein the oxygen-containing gas is oxygen gas, ozone gas, COx gas, or NOx gas (x is an integer). (Appendix 16) 16. The modification method according to any one of claims 1 to 15, wherein the carbon-containing film is graphene. (Appendix 17) a film forming device; an annealing device; A conveying device; Control device and Equipped with The control device a) forming a carbon-containing film on a surface of a metal wiring provided on a substrate by controlling the film forming apparatus; b) controlling the transfer device to transfer the substrate on which the carbon-containing film has been formed from the chamber of the film-forming device and into the chamber of the annealing device; c) controlling the annealing apparatus to supply an oxygen-containing gas into the chamber, annealing the substrate on which the carbon-containing film has been formed in a state in which the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a); A reforming system that performs the above. [Explanation of symbols]

[0107] C Carrier W substrate 10. Reforming System 100 control device 101 Vacuum transfer chamber 102 Load Lock Chamber 103 Atmospheric Transfer Chamber 104 Alignment Room 106 Transport equipment 200 Plasma processing equipment 201 Chamber 202 Stages 203 Microwave introduction mechanism 204 Gas supply mechanism 205 Exhaust mechanism 211 Exhaust chamber 300 Annealing Equipment 40 Base layer 41 Adhesive layer 42 Wiring layer 420 Grain boundary 421 Carbon 422 Metal Oxides 43 Graphene

Claims

1. a) forming a carbon-containing film on a surface of a metal wiring on a substrate using a film forming device; b) loading the substrate on which the carbon-containing film is formed into a chamber of an annealing apparatus; c) annealing the substrate on which the carbon-containing film has been formed in a state in which an oxygen-containing gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in step a); A modification method comprising:

2. d) a step performed after the step c), in which an oxygen-free gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in the step a), and the step is performed to anneal the substrate on which the carbon-containing film is formed. The method of claim 1 further comprising:

3. e) a step that is carried out after the step c) and before the step d), in which the surface of the metal wiring on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-free gas into plasma. The method of claim 2 further comprising:

4. e) a step that is carried out after the step c) and before the step d), in which the surface of the metal wiring on which the carbon-containing film is formed is exposed to plasma generated by converting an oxygen-containing gas into plasma. The method of claim 2 further comprising:

5. 5. The method according to claim 3, wherein the pressure in the chamber in step e) is lower than atmospheric pressure.

6. 6. The method according to claim 5, wherein the pressure in the chamber in step e) is in the range of 0.001 Torr or more and 10 Torr or less.

7. d) a step performed after the step c), in which an oxygen-containing gas is supplied into the chamber, the pressure in the chamber is lower than atmospheric pressure, and the temperature of the substrate is higher than the temperature of the substrate in the step a), and the step is performed to anneal the substrate on which the carbon-containing film is formed. further comprising 2. The method according to claim 1, wherein the flow rate of the oxygen-containing gas supplied into the chamber in step d) is smaller than the flow rate of the oxygen-containing gas supplied into the chamber in step c).

8. 8. The method according to claim 7, wherein the pressure in the chamber in step d) is in the range of 0.0001 Torr or more and 100 Torr or less.

9. 8. The method according to claim 7, wherein the temperature of the substrate in step d) is within a range of 300°C or more and 1100°C or less.

10. f) a step performed after the step c) of exposing the surface of the metal wiring on which the carbon-containing film is formed to plasma generated by converting an oxygen-containing gas into plasma. The method of claim 1 further comprising:

11. 2. The method according to claim 1, wherein the pressure in the chamber in step c) is in the range of 0.0001 Torr or more and 100 Torr or less.

12. The modifying method according to claim 10, wherein the temperature of the substrate in step c) is within a range of 300°C or more and 1100°C or less.

13. The modifying method according to claim 10, wherein the melting point of the oxide of the metal wiring is lower than the melting point of the metal wiring itself.

14. The modifying method according to claim 13, wherein the metal wiring is made of ruthenium, manganese, or iron.

15. 11. The reforming method according to claim 10, wherein the oxygen-containing gas is oxygen gas, ozone gas, COx gas, or NOx gas (x is an integer).

16. The modifying method according to claim 10 , wherein the carbon-containing film is graphene.

17. a film forming device; an annealing device; A conveying device; Control device and Equipped with The control device a) forming a carbon-containing film on a surface of a metal wiring on a substrate by controlling the film forming apparatus; b) controlling the transfer device to transfer the substrate on which the carbon-containing film has been formed from the chamber of the film-forming device and into the chamber of the annealing device; c) controlling the annealing apparatus to supply an oxygen-containing gas into the chamber, annealing the substrate on which the carbon-containing film has been formed in a state in which the pressure in the chamber is lower than atmospheric pressure and the temperature of the substrate is higher than the temperature of the substrate in step a); A reforming system that performs the above.

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