Production method and production system for semiconductor device

Abstract

A production method for a semiconductor device according to the present invention includes steps a), b), c), d), e), and f). Step a) involves preparing a substrate in a chamber, the substrate having a pattern that includes: a plurality of metal-containing layers that are formed on a base layer; and dielectric layers that are respectively formed on the metal-containing layers. Step b) involves supplying a modification gas into the chamber and modifying a side wall of each of the metal-containing layers. Step c) involves using plasma generated inside the chamber from a first processing gas that includes a carbon-containing gas to form a graphene film on the side walls of the metal-containing layers. Step d) involves embedding a thermally decomposable organic film in grooves formed by adjacent metal-containing layers. Step e) involves forming a sealing film on the organic film embedded in the grooves. Step f) involves heating the substrate to thermally decompose the organic film, removing the organic film through the sealing film, and forming an air gap between the grooves and the sealing film.

Description

Semiconductor device manufacturing method and manufacturing system

[0001] Various aspects and embodiments of the present disclosure relate to methods and systems for manufacturing semiconductor devices.

[0002] For example, Patent Document 1 listed below discloses that "one aspect of the present disclosure is a method for manufacturing a semiconductor device, which includes a first lamination step, a second lamination step, and a desorption step. In the first lamination step, a thermally decomposable organic material is laminated on a substrate having a recess formed therein. In the second lamination step, a silicon nitride film is laminated on the organic material. In the desorption step, the organic material is thermally decomposed by heating the substrate to a predetermined temperature, and the organic material below the silicon nitride film is desorbed through the silicon nitride film, thereby forming an air gap."

[0003] Japanese Patent Application Laid-Open No. 2021-108353

[0004] The present disclosure provides a semiconductor device manufacturing method and manufacturing system capable of manufacturing a semiconductor device with little signal delay.

[0005] One aspect of the present disclosure is a method for manufacturing a semiconductor device, including steps a), b), c), d), e), and f). In step a), a substrate having a pattern including multiple metal-containing layers formed on an underlayer and dielectric layers formed on each of the metal-containing layers is prepared in a chamber. In step b), a modifying gas is supplied into the chamber to modify the sidewalls of each metal-containing layer. In step c), plasma is generated in the chamber from a first process gas including a carbon-containing gas, and a graphene film is formed on the sidewalls of the metal-containing layers using the generated plasma. In step d), a pyrolyzable organic film is embedded in a groove formed by adjacent metal-containing layers. In step e), a sealing film is formed on the organic film embedded in the groove. In step f), the substrate is heated to pyrolyze the organic film, and the organic film is desorbed through the sealing film, thereby forming an air gap between the groove and the sealing film.

[0006] According to various aspects and embodiments of the present disclosure, a semiconductor device with little signal delay can be manufactured.

[0007] FIG. 1 is a system configuration diagram illustrating an example of a manufacturing system according to an embodiment of the present disclosure. FIG. 2 is a diagram illustrating an example of a film forming apparatus. FIG. 3 is a diagram schematically illustrating an example of a ceiling wall portion. FIG. 4 is a diagram illustrating an example of a film forming apparatus. FIG. 5 is a diagram illustrating an example of a plasma processing apparatus. FIG. 6 is a diagram illustrating an example of a heating apparatus. FIG. 7 is a flowchart illustrating an example of a method for manufacturing a semiconductor device according to a first embodiment. FIG. 8A is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8B is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8C is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8D is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8E is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8F is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 8G is a diagram illustrating an example of a manufacturing process for a semiconductor device according to the first embodiment. FIG. 9 is a diagram illustrating an example of a state of an air gap for each thickness of a sealing film. FIG. 10A is a diagram illustrating an example of a resistance value of a metal-containing layer in a comparative example. FIG. 10B is a diagram illustrating an example of a reduction rate of resistance value in a comparative example. FIG. 11A is a diagram showing an example of the resistance value of a metal-containing layer in the first embodiment. FIG. 11B is a diagram showing an example of a reduction rate of the resistance value in the first embodiment. FIG. 12A is a diagram showing an example of the capacitance between metal-containing layers in a comparative example. FIG. 12B is a diagram showing an example of the capacitance between metal-containing layers in the first embodiment. FIG. 13 is a diagram showing an example of a leakage current in the first embodiment. FIG. 14 is a flowchart showing an example of a method for manufacturing a semiconductor device in the second embodiment. FIG. 15 is a diagram showing an example of a manufacturing process of a semiconductor device in the second embodiment. FIG. 16 is a diagram showing an example of a leakage current in the second embodiment.

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

[0009] As semiconductor devices have become more functional and denser in recent years, the internal wiring has become thinner, and the wiring resistance has tended to increase. Furthermore, as the density of semiconductor devices has increased, the spacing between the internal wiring has become narrower, and the wiring capacitance has tended to increase. When the wiring resistance and wiring capacitance increase, the delay of signals flowing through the wiring increases, and the signal quality deteriorates. Therefore, there is a demand for reducing the wiring resistance and wiring capacitance of the wiring inside semiconductor devices.

[0010] Therefore, the present disclosure provides a technique that makes it possible to manufacture a semiconductor device with little signal delay.

[0011] First Embodiment [Configuration Example of Manufacturing System 10] FIG. 1 is a system configuration diagram illustrating an example of a manufacturing system 10 according to an embodiment of the present disclosure. The manufacturing system 10 includes a VTM (Vacuum Transfer Module) 11, multiple LLMs (Load Lock Modules) 12, and an EFEM (Equipment Front End Module) 13. A film formation apparatus 20, a film formation apparatus 30, a plasma processing apparatus 40, a film formation apparatus 50, and a heating apparatus 60 are connected to a sidewall of the VTM 11 via a gate valve G. In the example of FIG. 1, one each of the film formation apparatus 20, the film formation apparatus 30, the plasma processing apparatus 40, the film formation apparatus 50, and the heating apparatus 60 are connected to the VTM 51, but the disclosed technology is not limited thereto. As another example, at least one of the film formation apparatus 20, the film formation apparatus 30, the plasma processing apparatus 40, the film formation apparatus 50, and the heating apparatus 60 may be connected to the VTM 11 in multiple units.

[0012] The film forming apparatus 20 forms a graphene film on a sidewall of a metal-containing layer on a substrate W having a pattern including a plurality of metal-containing layers formed on an underlayer and a dielectric layer formed on each of the metal-containing layers. The film forming apparatus 20 is an example of a first processing apparatus.

[0013] The film forming apparatus 30 fills a thermally decomposable organic film in a groove formed by adjacent metal-containing layers on the substrate W. The film forming apparatus 30 is an example of a second processing apparatus.

[0014] The plasma processing device 40 removes unnecessary organic films formed on the dielectric layer.

[0015] The film forming apparatus 50 forms a sealing film on the organic film embedded in the groove of the substrate W. The film forming apparatus 50 is an example of a third processing apparatus.

[0016] The heating device 60 heats the substrate W to thermally decompose the organic film and detach the organic film through the sealing film, thereby forming an air gap between the groove and the sealing film. The heating device 60 is an example of a fourth processing device.

[0017] A plurality of LLMs 12 are connected to the other side wall of the VTM 11 via gate valves G. In the example of Fig. 1, two LLMs 12 are connected to the VTM 11, but the number of LLMs 12 connected to the VTM 11 may be more than two, or may be one.

[0018] A transfer robot 110 is disposed within the VTM 11. The transfer robot 110 transfers substrates W among the film formation apparatus 20, the film formation apparatus 30, the plasma treatment apparatus 40, the film formation apparatus 50, the heating apparatus 60, and the LLM 12. The interior of the VTM 11 is maintained at a predetermined pressure atmosphere that is lower than atmospheric pressure.

[0019] One side wall of each LLM 12 is connected to the VTM 11 via a gate valve G, and the other side wall is connected to the EFEM 13 via a gate valve G. When a substrate W is loaded from the EFEM 13 into the LLM 12 via the gate valve G, the gate valve G is closed and the pressure inside the LLM 12 is reduced to a pressure approximately equal to the pressure inside the VTM 11. Then, the gate valve G is opened and the substrate W in the LLM 12 is unloaded into the VTM 11 by the transport robot 110.

[0020] Furthermore, with the pressure in the LLM 12 at approximately the same pressure as the pressure in the VTM 11, the transfer robot 110 loads the substrate W from the VTM 11 into the LLM 12 via the gate valve G, and the gate valve G is closed. Then, the pressure in the LLM 12 is increased to approximately the same pressure as the pressure in the EFEM 13. Then, the gate valve G is opened, and the substrate W in the LLM 12 is loaded into the EFEM 13.

[0021] A plurality of load ports 14 are provided on a side wall of the EFEM 13 opposite to the side wall on which the gate valve G is provided. Each load port 14 is connected to a container such as a FOUP (Front Opening Unified Pod) that can accommodate a plurality of substrates W. An aligner module or the like that changes the orientation of the substrates W may be provided inside the EFEM 13.

[0022] The inside of the EFEM 13 is, for example, atmospheric pressure. A transfer robot 130 is provided inside the EFEM 13. The transfer robot 130 transfers substrates W between the LLM 12 and a container connected to the load port 14. An FFU (Fan Filter Unit) or the like is provided above the EFEM 13, and dry air from which particles and the like have been removed is supplied into the EFEM 13 from above, forming a downflow inside the EFEM 13. Note that in this embodiment, the inside of the EFEM 13 is atmospheric pressure, but in another embodiment, the pressure inside the EFEM 13 may be controlled to be positive pressure. This makes it possible to suppress the intrusion of particles and the like into the EFEM 13 from the outside.

[0023] The control device 15 includes a memory, a processor, and an input / output interface. The memory stores a control program, processing recipes, and other data. The processor reads and executes the control program from the memory, and controls each part of the manufacturing system 10 via the input / output interface based on the recipes and other data stored in the memory.

[0024] [Configuration Examples of Film Forming Apparatus 20 and Film Forming Apparatus 50] Fig. 2 is a diagram showing an example of the film forming apparatus 20. The film forming apparatus 50 has the same configuration as the film forming apparatus 20 illustrated in Fig. 2. The film forming apparatus 20 illustrated in Fig. 2 includes a chamber 201, a mounting table 202, a gas supply mechanism 203, an exhaust device 204, and a microwave introducing device 205. The chamber 201 accommodates a substrate W. The mounting table 202 mounts the substrate W. The gas supply mechanism 203 supplies gas into the chamber 201. The exhaust device 204 exhausts gas from the chamber 201. The microwave introducing device 205 generates microwaves for generating plasma in the chamber 201 and introduces the microwaves into the chamber 201.

[0025] Chamber 201 is made of a metal material such as aluminum or an alloy thereof, has a substantially cylindrical shape, and has plate-shaped ceiling wall 211 and bottom wall 213, and a side wall 212 connecting these. Microwave introducing device 205 is provided at the top of chamber 201 and functions as plasma generating means that introduces electromagnetic waves (microwaves) into chamber 201 to generate plasma. Microwave introducing device 205 will be described in detail later.

[0026] The ceiling wall 211 has a plurality of openings into which microwave radiation mechanisms and gas introduction sections (described later) of the microwave introduction device 205 are fitted. The side wall 212 has a loading / unloading port 214 for loading / unloading a substrate W between the chamber 201 and a transfer chamber (not shown) adjacent to the chamber 201. The loading / unloading port 214 is opened and closed by a gate valve G. An exhaust device 204 is provided on the bottom wall 213. The exhaust device 204 is attached to an exhaust pipe 216 connected to the bottom wall 213 and includes a vacuum pump and a pressure control valve. The chamber 201 is evacuated via the exhaust pipe 216 by the vacuum pump of the exhaust device 204. The pressure inside the chamber 201 is controlled by a pressure control valve.

[0027] The mounting table 202 is generally disk-shaped and made of ceramics such as aluminum nitride. The mounting table 202 is supported by a cylindrical support member 220 and a base member 221, both of which are made of ceramics such as aluminum nitride and extend upward from the center of the bottom of the chamber 201. A guide ring 281 for guiding the substrate W is provided on the outer edge of the mounting table 202. Furthermore, inside the mounting table 202, lifting pins (not shown) for lifting and lowering the substrate W are provided so as to be protruding and retracting from the upper surface of the mounting table 202.

[0028] Furthermore, a resistance heating type heater 282 is embedded inside the mounting table 202, and this heater 282 receives power from a heater power supply 283 to heat the substrate W placed thereon via the mounting table 202. A thermocouple (not shown) is also inserted into the mounting table 202, and the heating temperature of the substrate W can be controlled to a predetermined temperature, for example, in the range of 200 to 1000°C, based on a signal from the thermocouple. Furthermore, an electrode 284 having a size approximately the same as that of the substrate W is embedded above the heater 282 inside the mounting table 202, and a radio frequency bias power supply 222 is electrically connected to this electrode 284. A radio frequency bias for attracting ions is applied from this radio frequency bias power supply 222 to the mounting table 202. Note that the radio frequency bias power supply 222 may not be provided depending on the characteristics of the plasma processing.

[0029] A plurality of gas introduction nozzles 223 are fitted into openings formed in the ceiling wall 211 of the chamber 201. A gas supply mechanism 203 is connected to each gas introduction nozzle 223 via a gas supply pipe 291. The gas supply mechanism 203 is a processing gas supply source. For example, when forming a graphene film, a mixed gas containing a rare gas and a carbon-containing gas is used as the processing gas. For example, argon is used as the rare gas. For example, a hydrocarbon gas expressed as CxHy (x and y are natural numbers), such as ethylene (C2H4), is used as the carbon-containing gas. Furthermore, when forming a silicon-containing film, for example, as a sealing film, a mixed gas containing a silicon-containing gas, a reactive gas, and a rare gas is used as the processing gas. For example, silane (SiH4), dichlorosilane (DCS), or the like is used as the silicon-containing gas. Furthermore, nitrogen, ammonia, oxygen, or the like is used as the reactive gas. Furthermore, argon, helium, or the like is used as the rare gas. The gas supply mechanism 203 is provided with a valve and a flow rate controller for each gas type, and the flow rate of each gas type is adjusted accordingly. A hydrogen-containing gas, such as hydrogen gas, may be added to the process gas.

[0030] As described above, the microwave introducing device 205 is provided above the chamber 201 and functions as a plasma generating means for introducing electromagnetic waves (microwaves) into the chamber 201 to generate plasma.

[0031] The microwave introduction device 205 has a ceiling wall 211 of the chamber 201, a microwave output unit 230, and an antenna unit 240. The ceiling wall 211 functions as a top plate. The microwave output unit 230 generates microwaves and distributes the microwaves to multiple paths before outputting them. The antenna unit 240 radiates the microwaves output from the microwave output unit 230 into the chamber 201.

[0032] The microwave output unit 230 includes a microwave power supply, a microwave oscillator, an amplifier, and a distributor. The microwave oscillator is solid-state and generates microwaves at, for example, 860 MHz (e.g., PLL oscillation). The microwave frequency is not limited to 860 MHz, and frequencies in the range of 700 MHz to 10 GHz, such as 2.45 GHz, 8.35 GHz, 5.8 GHz, and 1.98 GHz, can also be used. The amplifier amplifies the microwaves generated by the microwave oscillator. The distributor distributes the microwaves amplified by the amplifier to multiple paths. The distributor distributes the microwaves while matching the impedances on the input and output sides.

[0033] The antenna unit 240 includes a plurality of antenna modules. Each of the plurality of antenna modules introduces microwaves distributed by the distributor of the microwave output unit 230 into the chamber 201. The plurality of antenna modules all have the same configuration. Each antenna module has an amplifier unit 242 that mainly amplifies and outputs the distributed microwaves, and a microwave radiation mechanism 243 that radiates the microwaves output from the amplifier unit 242 into the chamber 201.

[0034] The amplifier unit 242 has a phase shifter, a variable gain amplifier, a main amplifier, and an isolator. The phase shifter changes the phase of the microwave. The variable gain amplifier adjusts the power level of the microwave input to the main amplifier. The main amplifier is configured as a solid-state amplifier. The isolator separates the reflected microwave that is reflected by the antenna unit of the microwave radiation mechanism 243 (described later) and heads toward the main amplifier.

[0035] The plurality of microwave radiation mechanisms 243 are provided on the ceiling wall 211, as shown in FIG. 2 , for example. Each microwave radiation mechanism 243 has a cylindrical outer conductor and an inner conductor disposed coaxially within the outer conductor. The microwave radiation mechanism 243 includes a coaxial tube having a microwave transmission path between the outer conductor and the inner conductor, and an antenna unit that radiates microwaves into the chamber 201. A microwave transmitting plate 263 fitted into the ceiling wall 211 is provided on the lower surface of the antenna unit, and its lower surface is exposed to the internal space of the chamber 201. The microwaves that pass through the microwave transmitting plate 263 generate plasma in the space within the chamber 201. In other words, the microwave radiation mechanism 243 is an example of a plasma source.

[0036] FIG. 3 is a schematic diagram illustrating an example of the top wall portion 211. In this embodiment, as shown in FIG. 3, seven microwave radiation mechanisms 243 are provided on the top wall portion 211, and the corresponding microwave transmission plates 263 are evenly arranged on the top wall portion 211 in a hexagonal close-packed arrangement. That is, one of the seven microwave transmission plates 263 is arranged approximately in the center of the top wall portion 211, and the other six microwave transmission plates 263 are arranged around it. These seven microwave transmission plates 263 are arranged so that the adjacent microwave transmission plates 263 are spaced equally apart. The center of the top wall portion 211 is an example of a central region, and the area around the microwave radiation mechanism 243 arranged in the center of the top wall portion 211 is an example of a peripheral region. That is, one microwave radiation mechanism 243 is arranged in the central region, and six microwave radiation mechanisms 243 are arranged in the peripheral region. Furthermore, the multiple gas introduction nozzles 223 are arranged to surround the central microwave transmission plate 263. In the following, the microwave radiation mechanism 243 arranged in the central region will be referred to as the central microwave radiation mechanism 243, and the microwave radiation mechanisms 243 arranged in the peripheral regions will be referred to as the peripheral microwave radiation mechanisms 243. Furthermore, the number of microwave radiation mechanisms 243 is not limited to seven, and may be less than seven or more than seven.

[0037] 4 is a diagram showing an example of the film formation apparatus 30. The film formation apparatus 30 includes a chamber 31, an exhaust mechanism 32, a gas supply unit 33, a shower head 35, and a stage 36. In this embodiment, the film formation apparatus 30 is, for example, a chemical vapor deposition (CVD) apparatus.

[0038] The exhaust mechanism 32 has a vacuum pump that exhausts gas from the chamber 31 and a pressure adjustment valve that adjusts the pressure inside the chamber 31. The inside of the chamber 31 is controlled by the exhaust mechanism 32 to a vacuum atmosphere at a predetermined pressure.

[0039] A gas supply unit 33 that supplies multiple types of raw material monomers is connected to the chamber 31 via a shower head 35. In this embodiment, the multiple types of raw material monomers are, for example, isocyanate and amine. Isocyanate is an example of a first monomer, and amine is an example of a second monomer. The gas supply unit 33 has a raw material supply source 330a, a raw material supply source 330b, a vaporizer 331a, and a vaporizer 331b. The raw material supply source 330a contains, for example, an isocyanate liquid. The raw material supply source 330b contains, for example, an amine liquid.

[0040] The vaporizer 331a vaporizes the isocyanate liquid supplied from the raw material supply source 330a. The isocyanate vapor vaporized by the vaporizer 331a is introduced into the shower head 35 via the pipe 34a. The vaporizer 331b vaporizes the amine liquid supplied from the raw material supply source 330b. The amine vapor vaporized by the raw material supply source 330b is introduced into the shower head 35 via the pipe 34b.

[0041] The shower head 35 is provided, for example, in the upper part of the chamber 31, and has a number of outlets formed on the bottom surface thereof. The shower head 35 discharges the isocyanate vapor introduced via the pipe 34a and the amine vapor introduced via the pipe 34b into the chamber 31 in a shower-like manner from separate outlets.

[0042] A stage 36 is provided within the chamber 31. The stage 36 has a temperature control mechanism (not shown). A substrate W is placed on the stage 36 and is loaded into the chamber 31 through an opening 31a formed in the sidewall of the chamber 31. The opening 31a is opened and closed by a gate valve G. The stage 36 has a temperature control mechanism, which controls the temperature of the substrate W so that the temperature is suitable for vapor deposition polymerization of the raw material monomers supplied from the gas supply unit 33. The temperature suitable for vapor deposition polymerization can be determined depending on the type of raw material monomer. The temperature suitable for vapor deposition polymerization is, for example, within a range of 60°C to 100°C.

[0043] Using such a film formation apparatus 30, a vapor deposition polymerization reaction of two types of raw material monomers occurs on the surface of the substrate W, thereby forming a polymer organic film on the surface of the substrate W. When the two types of raw material monomers are isocyanate and amine, a polymer organic film having a polyurea bond is formed on the surface of the substrate W.

[0044] 5 is a diagram showing an example of a plasma processing apparatus 40. The plasma processing apparatus 40 has a chamber 41 formed of a conductive material. The chamber 41 is grounded. An exhaust mechanism 42 is connected to the chamber 41, and the exhaust mechanism 42 exhausts gas from the chamber 41, controlling the pressure inside the chamber 41 to a predetermined value.

[0045] A stage 43 on which a substrate W is placed is provided within the chamber 41. The substrate W is loaded into the chamber 41 through an opening 41a formed in the sidewall of the chamber 41 and placed on the stage 43. The opening 41a is opened and closed by a gate valve G. A heater 43a for heating the substrate W is provided within the stage 43. The stage 43 is electrically connected to the bottom of the chamber 41 and functions as an anode electrode. A shower head 44 is provided above the stage 43 so as to face the upper surface of the stage 43. The shower head 44 is supported on the upper part of the chamber 41 via an insulating member 44A. A power source 45 that supplies high-frequency power for generating plasma is connected to the shower head 44. The shower head 44 functions as a cathode electrode relative to the stage 43.

[0046] The gas supply source 46 supplies a process gas. The flow rate controller 47 adjusts the flow rate of the process gas supplied from the gas supply source 46 and supplies it into the diffusion space 44B of the shower head 44. The process gas supplied into the diffusion space 44B diffuses within the diffusion space 44B and is supplied in a shower-like manner into the chamber 41 from a plurality of outlet ports 44C formed on the lower surface of the diffusion space 44B. While one gas supply source 46 and one flow rate controller 47 are shown in FIG. 5 , in reality, a set of a gas supply source 46 and a flow rate controller 47 is provided for each type of gas used.

[0047] The processing gas supplied into the chamber 41 through the shower head 44 is converted into plasma by high-frequency power supplied into the chamber 41 from the power source 45. Then, the substrate W is subjected to processing such as etching by the ions and activated species contained in the plasma.

[0048] 6 is a diagram showing an example of the heating device 60. The heating device 60 has a chamber 61, an exhaust pipe 62, a supply pipe 63, a stage 64, and a lamp house 65.

[0049] A stage 64 on which a substrate W is placed is provided within the chamber 61. A lamp house 65 is provided at a position opposite to the surface of the stage 64 on which the substrate W is placed. A lamp 65a such as an infrared lamp is disposed within the lamp house 65.

[0050] A gas supply unit 63a is connected to the sidewall of the chamber 61 via a supply pipe 63. The gas supply unit 63a supplies an inert gas such as N2 gas into the chamber 61 via the supply pipe 63. An opening 61a for loading and unloading a substrate W is also formed in the sidewall of the chamber 61. The opening 61a is opened and closed by a gate valve G.

[0051] An exhaust device 66 is connected to the bottom of the chamber 61 via an exhaust pipe 62. The exhaust device 66 has a pressure adjustment valve. The exhaust device 66 exhausts gas from the chamber 61 and controls the pressure adjustment valve so that the pressure inside the chamber 61 becomes a predetermined pressure.

[0052] With the substrate W placed on the stage 64 and inert gas being supplied into the chamber 61 via the supply pipe 63, the lamp 65a can be turned on to heat the substrate W to a predetermined temperature in an inert gas atmosphere.

[0053] [Method of Manufacturing Semiconductor Device] Fig. 7 is a flowchart showing an example of a method of manufacturing a semiconductor device according to the first embodiment. The manufacturing method illustrated in Fig. 7 is realized by the control device 15 controlling each part of the manufacturing system 10. The following description will be given with reference to Figs. 8A to 8G.

[0054] First, a substrate W is loaded into the chamber 201 of the film forming apparatus 20 (step S100). Step S100 is an example of process a). In step S100, a substrate W having a structure such as that shown in FIG. 8A is loaded into the plasma processing apparatus 200 by the transfer robot 110 in the VTM 11. The substrate W has a pattern including a plurality of metal-containing layers 71 formed on an underlayer 70 and a dielectric layer 72 formed on each of the metal-containing layers 71. A semiconductor device is fabricated from the substrate W. In this embodiment, at least the surface of the underlayer 70 is formed of, for example, TiN or TaN. The metal-containing layer 71 contains at least one of, for example, Ru, Co, Cu, Mo, Ni, or W. The metal-containing layer 71 is used, for example, as wiring within the semiconductor device. The dielectric layer 72 is, for example, a silicon-containing film such as a silicon nitride film.

[0055] Next, pretreatment is performed on the substrate W (step S101). Step S101 is an example of process b). In step S101, a modifying gas is supplied into the chamber 201 to modify the sidewalls of each metal-containing layer 71. In step S101, the pretreatment is performed by the film forming apparatus 20 under the following processing conditions, for example: Pressure in the chamber 201: 50 mTorr to 1 Torr (6.7 to 133 Pa) Flow rate ratio of gases contained in the modifying gas: H2:Ar = 200:2 to 50:50 Temperature of the substrate W: 250 to 550°C Processing time: 5 seconds to 15 minutes

[0056] The pretreatment in step S101 reduces an oxide film unintentionally formed on the surface of the sidewall of the metal-containing layer 71 during transport of the substrate W. The modifying gas used in the pretreatment in step S101 includes an inert gas and a hydrogen-containing gas. In this embodiment, the inert gas includes at least one of a rare gas such as He gas or Ar gas, or N gas, and the hydrogen-containing gas includes at least one of H gas or NH gas.

[0057] In addition, plasma may be used in the pretreatment of step S101. The pretreatment using plasma is performed, for example, under the following treatment conditions: Pressure in the chamber 201: 50 mTorr to 1 Torr (6.7 to 133 Pa) Flow rate of hydrogen-containing gas (e.g., H2 gas): 250 to 1000 sccm (0.42 to 1.69 Pa·m 3 / s) Microwave power: 100 to 1500 W Temperature of substrate W: 250 to 550°C Processing time: 5 seconds to 15 minutes

[0058] Next, a graphene film is formed on the sidewall of the metal-containing layer 71 (step S102). Step S102 is an example of process c). In step S102, plasma is generated from a first process gas containing a carbon-containing gas in the chamber 201, and the graphene film 73 is formed on the sidewall of the metal-containing layer 71 using the generated plasma. In step S102, the graphene film 73 is formed by the film formation apparatus 20 under the following process conditions, for example: Pressure in the chamber 201: 1 to 100 mTorr (0.133 to 13.3 Pa) First process gas: C2H2 / Ar=5 to 100 sccm / 50 to 1000 sccm (0.00845 to 0.17 Pa m 3 / s / 0.0845 to 1.7 Pa·m 3 / s) Microwave power: 300 to 3000 W Temperature of substrate W: 250 to 550°C Processing time: 5 seconds to 15 minutes

[0059] By the process of step S102, a graphene film 73 is formed on the sidewall of the metal-containing layer 71, as shown in FIG. 8B . In step S102, the pressure inside the chamber 201 is preferably 50 mTorr to 100 mTorr (6.67 Pa to 13.3 Pa). The microwave power is preferably 300 W to 1500 W. The first process gas contains a carbon-containing gas and an inert gas. The first process gas may contain a hydrogen-containing gas such as H gas or NH gas. In this embodiment, the carbon-containing gas is a hydrocarbon gas (e.g., C2H2 gas or C2H4 gas) represented by CxHy (x and y are natural numbers), and the inert gas is a rare gas such as He gas or Ar gas.

[0060] Next, the substrate W is transferred from the film formation apparatus 20 to the film formation apparatus 30 (step S103). In step S103, the transfer robot 110 in the VTM 11 transfers the substrate W from the chamber 201 of the film formation apparatus 20 and transfers it into the chamber 31 of the film formation apparatus 30.

[0061] Next, a thermally decomposable organic film is embedded in the grooves formed by adjacent metal-containing layers 71 on the substrate W (step S104). Step S104 is an example of process d). In step S104, a first monomer and a second monomer are supplied into the chamber 31, and a vapor deposition polymerization reaction of the first monomer and the second monomer occurs on the surface of the substrate W, thereby forming a thermally decomposable polymer organic film on the surface of the substrate W. In this embodiment, the first monomer is, for example, an isocyanate, the second monomer is, for example, an amine, and the polymer organic film has a polyurea bond. As a result, the organic film 74 is embedded in the grooves formed by adjacent metal-containing layers 71, as shown in FIG. 8C , for example.

[0062] In step S104, the organic film 74 is formed on the surface of the substrate W under the following processing conditions, for example: Pressure in the chamber 31: 0.5 to 20 Torr (66.7 to 2666 Pa) Flow rate of isocyanate vapor: 1 to 20 sccm (0.0017 to 0.034 Pa·m 3 / s) Flow rate of amine vapor: 1 to 20 sccm (0.0017 to 0.034 Pa m 3 / s) Temperature of substrate W: 40 to 150°C

[0063] Next, the substrate W is transferred from the film forming apparatus 30 to the plasma processing apparatus 40 (step S105). In step S105, the substrate W is transferred from the chamber 31 of the film forming apparatus 30 to the chamber 41 of the plasma processing apparatus 40 by the transfer robot 110 in the VTM 11.

[0064] Next, the unnecessary organic film 74 on the substrate W is removed (step S106). Step S106 is an example of process h). In step S106, plasma is generated from the processing gas in the chamber 41. Then, the unnecessary organic film 74 formed on the dielectric layer 72 is removed by the generated plasma, for example, as shown in FIG. 8D. In other words, the organic film 74 is removed so as to expose the dielectric layer 72. In step S106, the unnecessary organic film 74 is removed by the plasma processing apparatus 40 under the following processing conditions, for example: Pressure in the chamber 41: 0.05 to 1.0 Torr (6.67 to 133 Pa) Processing gas: H2 / N2=100 to 300 sccm / 100 to 300 sccm (0.17 to 0.51 Pa·m 3 / s / 0.17 to 0.51 Pa·m 3 / s) High frequency power: 100 to 400 W Temperature of substrate W: 40 to 80°C

[0065] Next, the substrate W is transferred from the plasma processing apparatus 40 to the film forming apparatus 50 (step S107). In step S107, the substrate W is transferred from the chamber 41 of the plasma processing apparatus 40 by the transfer robot 110 in the VTM 11 and transferred into the chamber 201 of the film forming apparatus 50.

[0066] Next, a sealing film is formed on the organic film 74 (step S108). Step S108 is an example of process e). In step S108, plasma is generated in the chamber 201 from a process gas containing, for example, organic aminosilane. Then, by the generated plasma, a sealing film 75 is formed on the organic film 74, as shown in FIG. 8E, for example. In this embodiment, the sealing film 75 is, for example, a silicon oxide film. Note that the sealing film 75 may be another silicon-containing film, such as a silicon nitride film. In step S108, the sealing film 75 is formed by the film forming apparatus 50 under the following process conditions, for example: Pressure in the chamber 201: 0.1 to 10 Torr (13.3 to 1333 Pa) Process gas: organic aminosilane = 10 to 50 sccm (0.017 to 0.085 Pa m 3 / s) Microwave power: 50 to 200 W Temperature of substrate W: 20 to 100°C

[0067] Next, the substrate W is transferred from the film forming apparatus 50 to the heating apparatus 60 (step S109). In step S109, the substrate W is transferred from the chamber 201 of the film forming apparatus 50 to the chamber 61 of the heating apparatus 60 by the transfer robot 110 in the VTM 11.

[0068] Next, the substrate W is heated (step S110). Step S110 is an example of process f). In step S110, the substrate W is heated, whereby the organic film 74 is thermally decomposed and the organic film 74 is detached through the sealing film 75. As a result, as shown in FIG. 8F, for example, an air gap 74a is formed between the groove formed by the adjacent metal-containing layers 71 and the sealing film 75. In step S110, the substrate W is heated under the following processing conditions, for example: Pressure in the chamber 61: 0.5 to 20 Torr (66.7 to 2666 Pa) Gas supplied into the chamber 61: N2=200 to 2000 sccm (0.34 to 3.4 Pa·m 3 / s) Temperature of substrate W: 350 to 450°C

[0069] Next, the substrate W is transferred from the heating device 60 to the film forming device 50 (step S111). In step S111, the substrate W is transferred out of the chamber 61 of the heating device 60 by the transfer robot 110 in the VTM 11 and transferred back into the chamber 201 of the film forming device 50.

[0070] Next, a protective film is formed on the sealing film 75 (step S112). In step S112, plasma is generated in the chamber 201 from a process gas containing, for example, organic aminosilane. Then, by the generated plasma, a protective film 76 is formed on the sealing film 75, as shown in FIG. 8G, for example. In this embodiment, the protective film 76 is, for example, a silicon nitride film. In step S112, the protective film 76 is formed by the film forming apparatus 50 under, for example, the following process conditions: Pressure in the chamber 201: 0.1 to 10 Torr (13.3 to 1333 Pa) Process gas: organic aminosilane = 10 to 50 sccm (0.017 to 0.085 Pa m 3 / s) Microwave power: 50 to 200 W Temperature of substrate W: 20 to 100°C

[0071] Next, the substrate W is unloaded from the film forming apparatus 50 (step S113), and the method for manufacturing a semiconductor device shown in this flowchart is then completed.

[0072] [Thickness of Sealing Film 75] Fig. 9 is a diagram showing an example of the state of the air gap 74a for each thickness of the sealing film 75. For example, as shown in Fig. 9, when the thickness of the sealing film 75 is 1.2 nm, the sealing film 75 is torn in places, as shown in Fig. 9. Therefore, it is preferable that the thickness of the sealing film 75 is thicker than 1.2 nm.

[0073] 9, for example, when the thickness of the sealing film 75 is 2.4 nm, the organic film 74 in the groove formed by the adjacent metal-containing layers 71 is not completely detached and remains even after the substrate W is heated. Therefore, it is preferable that the thickness of the sealing film 75 is thinner than 2.4 nm.

[0074] On the other hand, when the thickness of the sealing film 75 was 1.6 nm and 2.0 nm, as shown in Fig. 9, for example, the organic film 74 was not observed in the groove formed by the adjacent metal-containing layers 71. Furthermore, the sealing film 75 was not torn. Therefore, it is preferable that the thickness of the sealing film 75 be 1.2 nm or more and 2.0 nm or less.

[0075] [Resistance Value of Metal-Containing Layer 71] As a comparative example, the resistance value of the metal-containing layer 71 was measured when the air gap 74a was formed on the sidewall of the metal-containing layer 71 without forming the graphene film 73. The results shown in Figures 10A and 10B were obtained. In the comparative example, the metal-containing layer 71 was heated to remove the organic film 74, which expanded the crystal grains of the metal-containing layer 71 and reduced the resistance value of the metal-containing layer 71. Referring to Figure 10B, in the comparative example, the resistance value of the metal-containing layer 71 after the air gap 74a was formed was reduced by approximately 9% from the initial state.

[0076] On the other hand, in this embodiment, in which the graphene film 73 is formed on the sidewall of the metal-containing layer 71 before the air gap 74a is formed, results such as those shown in FIGS. 11A and 11B were obtained. In this embodiment, the resistance of the metal-containing layer 71 was reduced by approximately 14% from the initial state when the graphene film 73 was formed on the sidewall of the metal-containing layer 71. This reduction in resistance was maintained even after the air gap 74a was formed. Comparing FIGS. 10B and 11B , by forming the graphene film 73 on the sidewall of the metal-containing layer 71, the reduction in the resistance of the metal-containing layer 71 was increased by approximately 5% compared to when the graphene film 73 was not formed on the sidewall of the metal-containing layer 71. Therefore, in this embodiment, by forming the graphene film 73 on the sidewall of the metal-containing layer 71, the resistance of the metal-containing layer 71 used as wiring in a semiconductor device can be further reduced.

[0077] FIG. 12A is a diagram showing an example of capacitance between metal-containing layers 71 in the comparative example. FIG. 12B is a diagram showing an example of capacitance between metal-containing layers 71 in the first embodiment. Referring to FIGS. 12A and 12B , in both the comparative example and the first embodiment, the capacitance between the metal-containing layers 71 hardly changes between the initial state and after the formation of the air gap 74a. In the initial state, as shown in FIG. 8A , for example, there is a space between adjacent metal-containing layers 71. The fact that the capacitance between the metal-containing layers 71 is almost the same in the initial state and after the formation of the air gap 74a suggests that a sufficiently large air gap 74a is formed between the adjacent metal-containing layers 71. By forming a sufficiently large air gap 74a between the adjacent metal-containing layers 71, the capacitance between the adjacent metal-containing layers 71 can be reduced.

[0078] In this way, in this embodiment, the resistance value of the metal-containing layer 71 can be reduced, and the capacitance between the metal-containing layers 71 can be reduced by forming the air gap 74a between adjacent metal-containing layers 71. This reduces the delay of signals flowing through the metal-containing layer 71 used as wiring within the semiconductor device.

[0079] The first embodiment has been described above. As described above, the method for manufacturing a semiconductor device according to the first embodiment includes steps a), b), c), d), e), and f). In step a), a substrate (substrate W) having a pattern including a plurality of metal-containing layers (metal-containing layers 71) formed on an underlayer (underlayer 70) and dielectric layers (dielectric layers 72) formed on each of the metal-containing layers is prepared in a chamber (chamber 201). In step b), a modifying gas is supplied into the chamber to modify the sidewalls of each metal-containing layer. In step c), plasma is generated from a first process gas including a carbon-containing gas in the chamber, and a graphene film (graphene film 73) is formed on the sidewall of the metal-containing layer using the generated plasma. In step d), a thermally decomposable organic film (organic film 74) is embedded in a groove formed between adjacent metal-containing layers. In step e), a sealing film (sealing film 75) is formed on the organic film embedded in the groove. In step f), the substrate is heated to thermally decompose the organic film, and the organic film is detached through the sealing film, thereby forming an air gap (air gap 74 a) between the groove and the sealing film, thereby manufacturing a semiconductor device with little signal delay.

[0080] The method for manufacturing a semiconductor device according to the first embodiment further includes a step of removing the organic film formed on the dielectric layer, which is performed between steps d) and e), thereby forming an air gap of a desired shape between adjacent metal-containing layers 71.

[0081] In the first embodiment described above, the thickness of the sealing film is preferably 1.6 nm or more and 2.0 nm or less, which allows an air gap of a desired shape to be formed between adjacent metal-containing layers 71.

[0082] In the first embodiment described above, the sealing film may be a silicon oxide film or a silicon nitride film, which allows the organic film embedded between the adjacent metal-containing layers 71 to be removed.

[0083] In the first embodiment described above, the modifying gas preferably contains an inert gas and a hydrogen-containing gas, and the flow rate ratio of the inert gas to the hydrogen-containing gas is preferably in the range of 200:2 to 50:50, thereby modifying the sidewall of the metal-containing layer 71 so that the graphene film can be more easily attached thereto.

[0084] In the first embodiment, the inert gas contained in the modifying gas includes at least one of He gas, Ar gas, and N gas. The hydrogen-containing gas contained in the modifying gas includes at least one of H gas and NH gas. This allows the sidewall of the metal-containing layer 71 to be modified so that the graphene film can be more easily attached.

[0085] In the first embodiment described above, the temperature of the substrate in step c) is preferably 250° C. or higher and 550° C. or lower. This allows the graphene film to be efficiently formed on the sidewall of the metal-containing layer 71.

[0086] In the first embodiment described above, the temperature of the substrate in step d) is preferably 40° C. or higher and 150° C. or lower, which allows the organic film to be efficiently embedded in the grooves formed by adjacent metal-containing layers.

[0087] In the first embodiment described above, the temperature of the substrate in step e) is preferably 20° C. or higher and 100° C. or lower, which allows the sealing film to be efficiently formed on the organic film.

[0088] In the first embodiment described above, the temperature of the substrate in step f) is preferably 350° C. or higher and 450° C. or lower, so that the organic film can be efficiently removed through the sealing film.

[0089] In the first embodiment, the surface of the underlayer is made of TiN or TaN, which can suppress the formation of a graphene film on the underlayer.

[0090] In the first embodiment, the metal-containing layer contains at least one of Ru, Co, and Cu, which allows a graphene film to be efficiently formed on the metal-containing layer.

[0091] In the first embodiment, in step d), gases of the first monomer and the second monomer are supplied into the chamber, and the organic film is embedded in the groove by vapor deposition polymerization of the first monomer and the second monomer, thereby enabling the organic film to be embedded efficiently in the groove formed by adjacent metal-containing layers.

[0092] In the first embodiment described above, the first monomer is an isocyanate, the second monomer is an amine, and the organic film contains a urea bond, which allows the organic film to be efficiently detached through the sealing film.

[0093] The first embodiment described above is a semiconductor device manufacturing system (manufacturing system 10) including a first processing apparatus (film formation apparatus 20), a second processing apparatus (film formation apparatus 30), a third processing apparatus (film formation apparatus 50), a fourth processing apparatus (heating apparatus 60), and a control device (controller 15) that controls the first processing apparatus, the second processing apparatus, the third processing apparatus, and the fourth processing apparatus. The control device executes steps a), b), c), d), e), and f). In step a), a substrate (substrate W) having a pattern including multiple metal-containing layers (metal-containing layers 71) formed on an underlayer (underlayer 70) and dielectric layers (dielectric layers 72) formed on each of the metal-containing layers is prepared in a chamber (chamber 201) of the first processing apparatus. In step b), a modifying gas is supplied into the chamber to modify the sidewalls of each metal-containing layer. In step c), plasma is generated from a first process gas containing a carbon-containing gas in a chamber, and the generated plasma is used to form a graphene film (graphene film 73) on the sidewall of the metal-containing layer. In step d), a thermally decomposable organic film (organic film 74) is embedded in a groove formed by adjacent metal-containing layers using a second processing apparatus. In step e), a sealing film (sealing film 75) is formed on the organic film embedded in the groove using a third processing apparatus. In step f), an air gap (air gap 74a) is formed between the groove and the sealing film by heating the substrate using a fourth processing apparatus and desorbing the organic film through the sealing film. This allows for the manufacture of a semiconductor device with minimal signal delay.

[0094] Second Embodiment When the substrate W is heated in step S110 of the first embodiment, depending on the conditions, the organic film 74 in the grooves formed by the adjacent metal-containing layers 71 may not be completely removed and may remain as residue. The residue in the grooves may become conductive due to heating. Therefore, as shown in FIG. 13 , the leakage current after the air gaps 74 a are formed may be larger than the leakage current at the stage when the graphene film 73 is formed. Therefore, in the second embodiment, in order to remove the residue after the air gaps 74 a are formed, a process for removing the organic film 74 is performed after the substrate W is heated to form the air gaps 74 a.

[0095] [Method of Manufacturing Semiconductor Device] Fig. 14 is a flowchart showing an example of a method of manufacturing a semiconductor device according to the second embodiment. The manufacturing method illustrated in Fig. 14 is realized by the control device 15 controlling each part of the manufacturing system 10. Note that processes in Fig. 14 that are assigned the same reference numerals as those in Fig. 7 are the same as the processes described using Fig. 7 except for the points described below, and therefore redundant description will be omitted.

[0096] After the substrate W is heated by the heating device 60, the substrate W is transferred from the heating device 60 to the plasma processing device 40 (step S120). In step S120, the transfer robot 110 in the VTM 11 transfers the substrate W from the chamber 61 of the heating device 60 and transfers it into the chamber 41 of the plasma processing device 40.

[0097] Next, the substrate W is irradiated with plasma (step S121). Step S121 is an example of process g). In step S121, plasma is generated from a processing gas in the chamber 41. In this embodiment, the processing gas is Ar gas. The processing gas used in step S121 is an example of a third processing gas that does not contain oxygen. Note that the processing gas used in step S121 may be a rare gas other than Ar, or may be a gas containing at least one of a rare gas, N2 gas, or H2 gas.

[0098] In step S121, plasma is generated under the following processing conditions, for example: Pressure in chamber 41: 0.5 to 5 Torr (66.7 to 667 Pa) Processing gas: Ar=200 to 2000 sccm (0.34 to 3.4 Pa·m 3 / s) High frequency power: 50 to 500 W Temperature of substrate W: 300 to 400°C

[0099] 15 , the generated plasma is irradiated onto the substrate W. As a result, activated species and the like contained in the plasma are supplied to the residue 77 remaining in the air gap 74 a, decomposing the residue 77. The decomposed residue 77 is detached through the sealing film 75.

[0100] Next, the substrate W is transferred from the plasma processing apparatus 40 to the film forming apparatus 50 (step S122). In step S122, the substrate W is transferred from the chamber 41 of the plasma processing apparatus 40 by the transfer robot 110 in the VTM 11 and transferred into the chamber 201 of the film forming apparatus 50. Then, the processes from step S112 onwards are executed.

[0101] 16 is a diagram showing an example of leakage current in the second embodiment. The leakage current when plasma is applied after the air gap 74a is formed is reduced compared to the leakage current before plasma application, as shown in FIG. 16. Therefore, by applying plasma after the air gap 74a is formed, the leakage current between adjacent metal-containing layers 71 can be reduced.

[0102] The second embodiment has been described above. As described above, the method for manufacturing a semiconductor device according to the second embodiment further includes step g). In step g), plasma is irradiated into the trench through the sealing film after the air gap is formed in step f). This reduces leakage current between adjacent metal-containing layers 71.

[0103] In step g) of the second embodiment, plasma generated from a third process gas containing no oxygen is irradiated into the groove through the sealing film. The third process gas contains at least one of a rare gas, N2 gas, and H2 gas. This reduces leakage current between adjacent metal-containing layers 71.

[0104] [Others] The technology disclosed in the present application is not limited to the above-described embodiment, and various modifications are possible within the scope of the gist thereof.

[0105] For example, in the second embodiment described above, after the substrate W is heated to form the air gap 74a, the substrate W is irradiated with plasma generated from a processing gas that does not contain oxygen, but the disclosed technology is not limited to this. As another embodiment, after the substrate W is heated to form the air gap 74a, the substrate W may be irradiated with plasma generated from a processing gas that contains oxygen. This allows the residue 77 remaining in the air gap 74a to be more efficiently removed.

[0106] However, when plasma generated from a processing gas containing oxygen is used to remove the residue 77, depending on the conditions, the graphene film 73 may also be removed due to activated species derived from oxygen contained in the plasma. Furthermore, depending on the conditions, the activated species derived from oxygen contained in the plasma may oxidize the sidewall of the metal-containing layer 71, increasing the resistance value of the metal-containing layer 71. Therefore, when plasma generated from a processing gas containing oxygen is used to remove the residue 77, it is preferable to perform the process under the following processing conditions: Pressure in the chamber 41: 0.5 to 1 Torr (66.7 to 133 Pa) Processing gas: O2 = 10 to 50 sccm (0.017 to 0.085 Pa·m 3 / s) High frequency power: 100 to 200 W Temperature of substrate W: 200 to 400°C

[0107] In addition, in each of the above-described embodiments, the graphene film 73 is formed using the film formation apparatus 20 having a plurality of microwave radiation mechanisms 543, but the disclosed technology is not limited to this. As another embodiment, the graphene film 73 may be formed using, for example, a film formation apparatus having one microwave radiation mechanism.

[0108] Furthermore, in each of the above-described embodiments, the film formation apparatus 20 that forms the graphene film 73 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 film 73 on the substrate W 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.

[0109] In the above-described embodiments, an isocyanate is used as the first monomer and an amine is used as the second monomer to form the thermally decomposable polymer organic film 74 having a urea bond (—NH—CO—NH—) on the surface of the substrate W. However, the disclosed technology is not limited to this. For example, an epoxide may be used as the first monomer and an amine as the second monomer to form the thermally decomposable polymer organic film having a 2-aminoethanol bond (—NH—CH2-CH(OH)—) on the surface of the substrate W. Alternatively, an isocyanate may be used as the first monomer and an alcohol as the second monomer to form the thermally decomposable polymer organic film having a urethane bond (—NH—CO—O—) on the surface of the substrate W. Alternatively, an acyl halide may be used as the first monomer and an amine as the second monomer to form the thermally decomposable polymer organic film having an amide bond (—NH—CO—) on the surface of the substrate W. Alternatively, a carboxylic acid anhydride may be used as the first monomer and an amine as the second monomer to form an organic film of a thermally decomposable polymer having an imide bond (—CO—N(—)—CO—) on the surface of the substrate W.

[0110] 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.

[0111] Furthermore, the following supplementary notes are disclosed regarding the above-described embodiment.

[0112] (Supplementary Note 1) A method for manufacturing a semiconductor device, comprising: a) preparing, in a chamber, a substrate having a pattern including a plurality of metal-containing layers formed on an underlayer and a dielectric layer formed on each of the metal-containing layers; b) modifying sidewalls of each of the metal-containing layers by supplying a modifying gas into the chamber; c) generating plasma from a first process gas including a carbon-containing gas in the chamber and forming a graphene film on the sidewall of the metal-containing layer using the generated plasma; d) embedding a thermally decomposable organic film in a groove formed by adjacent the metal-containing layers; e) forming a sealing film on the organic film embedded in the groove; and f) forming an air gap between the groove and the sealing film by heating the substrate to thermally decompose the organic film and detaching the organic film through the sealing film. (Supplementary Note 2) The method for manufacturing a semiconductor device according to Supplementary Note 1, further comprising: g) irradiating plasma into the groove through the sealing film after the air gap is formed in step f). (Supplementary Note 3) The method for manufacturing a semiconductor device according to Supplementary Note 2, wherein in step g), plasma generated from a second process gas containing oxygen is irradiated into the groove through the sealing film. (Supplementary Note 4) The method for manufacturing a semiconductor device according to Supplementary Note 2, wherein in step g), plasma generated from a third process gas not containing oxygen is irradiated into the groove through the sealing film. (Supplementary Note 5) The method for manufacturing a semiconductor device according to Supplementary Note 4, wherein the third process gas contains at least one of a rare gas, N2 gas, or H2 gas. (Supplementary Note 6) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 5, further comprising the step of: h) removing the organic film formed on the dielectric layer, performed between step d) and step e). (Supplementary Note 7) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 6, wherein the thickness of the sealing film is 1.6 nm or more and 2.0 nm or less. (Supplementary Note 8) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 7, wherein the sealing film is a silicon oxide film or a silicon nitride film. (Supplementary Note 9) The method for manufacturing a semiconductor device according to any one of Supplementary Notes 1 to 8, wherein the modifying gas contains an inert gas and a hydrogen-containing gas.(Supplementary Note 10) The method for manufacturing a semiconductor device according to Supplementary Note 9, wherein the flow rate ratio of the inert gas to the hydrogen-containing gas is in the range of 200:2 to 50:50. (Supplementary Note 11) The method for manufacturing a semiconductor device according to Supplementary Note 9 or 10, wherein the inert gas contains at least one of He gas, Ar gas, or N2 gas. (Supplementary Note 12) The method for manufacturing a semiconductor device according to any one of Supplementary Notes 9 to 11, wherein the hydrogen-containing gas contains at least one of H2 gas or NH3 gas. (Supplementary Note 13) The method for manufacturing a semiconductor device according to any one of Supplementary Notes 1 to 12, wherein the temperature of the substrate in step c) is 250°C or higher and 550°C or lower. (Supplementary Note 14) The method for manufacturing a semiconductor device according to any one of Supplementary Notes 1 to 13, wherein the temperature of the substrate in step d) is 40°C or higher and 150°C or lower. (Supplementary Note 15) The method for manufacturing a semiconductor device according to any one of Supplementary Notes 1 to 14, wherein the temperature of the substrate in step e) is 20°C or higher and 100°C or lower. (Supplementary Note 16) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 15, wherein the temperature of the substrate in step f) is 350°C or higher and 450°C or lower. (Supplementary Note 17) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 16, wherein the surface of the underlayer is TiN or TaN. (Supplementary Note 18) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 17, wherein the metal-containing layer contains at least one of Ru, Co, and Cu. (Supplementary Note 19) The method for manufacturing a semiconductor device according to any one of Supplements 1 to 18, wherein in step d), gases of a first monomer and a second monomer are supplied into the chamber, and the organic film is embedded in the groove by vapor deposition polymerization of the first monomer and the second monomer. (Supplementary Note 20) The method for manufacturing a semiconductor device according to Supplementary Note 19, wherein the first monomer is isocyanate, the second monomer is amine, and the organic film contains a urea bond.(Supplementary Note 21) A method for manufacturing a semiconductor device, comprising: a first processing apparatus; a second processing apparatus; a third processing apparatus; a fourth processing apparatus; and a control apparatus for controlling the first processing apparatus, the second processing apparatus, the third processing apparatus, and the fourth processing apparatus, wherein the control apparatus performs the following steps: a) preparing, in a chamber of the first processing apparatus, a substrate having a pattern including a plurality of metal-containing layers formed on an underlayer and a dielectric layer formed on each of the metal-containing layers; b) modifying sidewalls of each of the metal-containing layers by supplying a modifying gas into the chamber; c) generating plasma from a first processing gas including a carbon-containing gas in the chamber, and forming a graphene film on the sidewalls of the metal-containing layers by using the generated plasma; d) using the second processing apparatus, filling a groove formed by adjacent metal-containing layers with a thermally decomposable organic film; and e) using the third processing apparatus, forming a sealing film on the organic film filled in the grooves. f) using the fourth processing apparatus, heating the substrate to thermally decompose the organic film and detaching the organic film through the sealing film, thereby forming an air gap between the groove and the sealing film.

[0113] G Gate valve W Substrate 10 Manufacturing system 11 VTM 110 Transfer robot 12 LLM 13 EFEM 130 Transfer robot 14 Load port 15 Control device 20 Film formation device 30 Film formation device 40 Plasma treatment device 50 Film formation device 60 Heating device 70 Underlayer 71 Metal-containing layer 72 Dielectric layer 73 Graphene film 74 Organic film 74a Air gap 75 Sealing film 76 Protective film

Claims

1. A method for manufacturing a semiconductor device, comprising the steps of: a) preparing in a chamber a substrate having a pattern including a plurality of metal-containing layers formed on an underlayer and a dielectric layer formed on each of the metal-containing layers; b) modifying a sidewall of each of the metal-containing layers by supplying a modifying gas into the chamber; c) generating plasma from a first process gas including a carbon-containing gas in the chamber, and forming a graphene film on the sidewall of the metal-containing layer using the generated plasma; d) embedding a thermally decomposable organic film in a groove formed by adjacent metal-containing layers; e) forming a sealing film on the organic film embedded in the groove; and f) forming an air gap between the groove and the sealing film by heating the substrate to thermally decompose the organic film and detaching the organic film through the sealing film.

2. The method for manufacturing a semiconductor device according to claim 1, further comprising the step of: g) irradiating plasma into the groove through the sealing film after the air gap is formed in the step f).

3. The method for manufacturing a semiconductor device according to claim 2, wherein in said step g), plasma generated from a second process gas containing oxygen is irradiated into said groove through said sealing film.

4. The method for manufacturing a semiconductor device according to claim 2, wherein in said step g), plasma generated from a third process gas not containing oxygen is irradiated into said groove through said sealing film.

5. The method for manufacturing a semiconductor device according to claim 4, wherein the third process gas contains at least one of a rare gas, N2 gas, and H2 gas.

6. The method for manufacturing a semiconductor device according to claim 1, further comprising the step of: h) removing the organic film formed on the dielectric layer, the step being performed between the step d) and the step e).

7. The method for manufacturing a semiconductor device according to claim 1, wherein the thickness of the sealing film is 1.6 nm or more and 2.0 nm or less.

8. The method for manufacturing a semiconductor device according to claim 1, wherein the sealing film is a silicon oxide film or a silicon nitride film.

9. The method for manufacturing a semiconductor device according to claim 1, wherein the modifying gas includes an inert gas and a hydrogen-containing gas.

10. The method for manufacturing a semiconductor device according to claim 9, wherein the flow rate ratio of the inert gas to the hydrogen-containing gas is in the range of 200:2 to 50:

50.

11. The method for manufacturing a semiconductor device according to claim 9 or 10, wherein the inert gas contains at least one of He gas, Ar gas, and N2 gas.

12. The method for manufacturing a semiconductor device according to claim 9, wherein the hydrogen-containing gas contains at least one of H2 gas and NH3 gas.

13. The method for manufacturing a semiconductor device according to claim 1, wherein the temperature of the substrate in step c) is 250° C. or higher and 550° C. or lower.

14. The method for manufacturing a semiconductor device according to claim 1, wherein the temperature of the substrate in step d) is 40° C. or higher and 150° C. or lower.

15. The method for manufacturing a semiconductor device according to claim 1, wherein the temperature of the substrate in step e) is 20° C. or higher and 100° C. or lower.

16. The method for manufacturing a semiconductor device according to claim 1, wherein the temperature of the substrate in step f) is 350° C. or higher and 450° C. or lower.

17. The method for manufacturing a semiconductor device according to claim 1, wherein the surface of the underlayer is made of TiN or TaN.

18. The method for manufacturing a semiconductor device according to claim 1, wherein the metal-containing layer contains at least one of Ru, Co, and Cu.

19. A method for manufacturing a semiconductor device as described in claim 1, wherein in step d), gases of a first monomer and a second monomer are supplied into the chamber, and the organic film is embedded in the groove by vapor deposition polymerization of the first monomer and the second monomer.

20. The method for manufacturing a semiconductor device according to claim 19, wherein the first monomer is an isocyanate, the second monomer is an amine, and the organic film contains a urea bond.

21. A method for manufacturing a semiconductor device, comprising: a first processing apparatus; a second processing apparatus; a third processing apparatus; a fourth processing apparatus; and a control apparatus for controlling the first processing apparatus, the second processing apparatus, the third processing apparatus, and the fourth processing apparatus, the control apparatus performing the following steps: a) preparing a substrate having a pattern including a plurality of metal-containing layers formed on an underlayer and a dielectric layer formed on each of the metal-containing layers in a chamber of the first processing apparatus; b) modifying a sidewall of each of the metal-containing layers by supplying a modifying gas into the chamber; c) generating plasma from a first processing gas including a carbon-containing gas in the chamber, and forming a graphene film on the sidewall of the metal-containing layer by using the generated plasma; d) embedding a thermally decomposable organic film in a groove formed by adjacent metal-containing layers by using the second processing apparatus; and e) forming a sealing film on the organic film embedded in the groove by using the third processing apparatus. f) using the fourth processing apparatus, heating the substrate to thermally decompose the organic film, and detaching the organic film through the sealing film, thereby forming an air gap between the groove and the sealing film.

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