Manufacturing method of semiconductor device and manufacturing system

Abstract

To manufacture a semiconductor device in which delay of a signal is reduced.SOLUTION: A manufacturing method of a semiconductor device includes a step a), a step b), a step c), a step d), a step e) and a step f). In the step a), a substrate having a pattern including a plurality of metal-containing layers formed on a ground layer and a dielectric layer formed on each metal-containing layer is prepared in a chamber. In the step b), a modification gas is supplied into the chamber, and a sidewall of each metal-containing layer is modified. In the step c), a graphene film is formed on the sidewall of the metal-containing layer using plasma generated from a first process gas including a carbon-containing gas in the chamber. In the step d), a thermally decomposable organic film is embedded in a groove formed by adjacent metal-containing layers. In the step e), an encapsulation film is formed on the organic film embedded in the groove. In the step f), the organic film is thermally decomposed by heating the substrate; the organic film is desorbed via the encapsulation film; and an air gap is formed between the groove and the encapsulation film.SELECTED DRAWING: Figure 7

Description

Technical Field

[0001] Various aspects and embodiments of the present disclosure relate to a method for manufacturing a semiconductor device and a manufacturing system.

Background Art

[0002] For example, Patent Document 1 below discloses that "one aspect of the present disclosure is a method for manufacturing a semiconductor device, including a first lamination step, a second lamination step, and a detachment 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 detachment step, the organic material is thermally decomposed by heating the substrate to a predetermined temperature, and the organic material under the silicon nitride film is detached through the silicon nitride film to form an air gap."

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0005] One aspect of the present disclosure is a method of manufacturing a semiconductor device, including step a), step b), step c), step d), step e), and step f). In step a), a substrate having a pattern including a plurality of metal-containing layers formed on an underlying layer and a dielectric layer formed on each metal-containing layer is prepared in a chamber. In step b), the sidewalls of each metal-containing layer are modified by supplying a modifying gas into the chamber. In step c), plasma is generated from a first processing gas containing a carbon-containing gas in the chamber, and a graphene film is formed on the sidewalls of the metal-containing layer using the generated plasma. In step d), a thermally decomposable 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 organic film is thermally decomposed by heating the substrate, and the organic film is desorbed through the sealing film, thereby forming an air gap between the groove and the sealing film.

Advantages of the Invention

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

Brief Description of the Drawings

[0007]

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Figure 8A

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Embodiments for Carrying Out the Invention

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

[0009] With the recent increase in functionality and density of semiconductor devices, the internal wiring has been becoming finer, and the wiring resistance has a tendency to increase. In addition, with the increase in density of semiconductor devices, the interval between internal wirings has become narrower, and the wiring capacitance has a tendency to increase. When the wiring resistance and the wiring capacitance increase, the delay of a signal flowing through the wiring increases, and the quality of the signal deteriorates. Therefore, it is required to reduce the wiring resistance and the wiring capacitance of the internal wiring of a semiconductor device.

[0010] Therefore, the present disclosure provides a technique capable of manufacturing a semiconductor device with less signal delay.

[0011] (First Embodiment) [Configuration Example of Manufacturing System 10] FIG. 1 is a system configuration diagram showing 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, a plurality of LLM (Load Lock Modules) 12, and an EFEM (Equipment Front End Module) 13. A film forming apparatus 20, a film forming apparatus 30, a plasma processing apparatus 40, a film forming apparatus 50, and a heating apparatus 60 are connected to the side wall of the VTM 11 via a gate valve G. In the example of FIG. 1, one film forming apparatus 20, one film forming apparatus 30, one plasma processing apparatus 40, one film forming apparatus 50, and one heating apparatus 60 are respectively connected to the VTM 51, but the disclosed technology is not limited thereto. As another example, a plurality of at least one of the film forming apparatus 20, the film forming apparatus 30, the plasma processing apparatus 40, the film forming apparatus 50, and the heating apparatus 60 may be connected to the VTM 11.

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

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

[0014] The plasma processing apparatus 40 removes an unnecessary organic film 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 apparatus 60 forms an air gap between the groove and the sealing film by thermally decomposing the organic film by heating the substrate W and desorbing the organic film through the sealing film. The heating apparatus 60 is an example of a fourth processing apparatus.

[0017] On the other side wall of the VTM11, a plurality of LLM12s are connected via the gate valve G. In the example of FIG. 1, two LLM12s are connected to the VTM11, but the number of LLM12s connected to the VTM11 may be more than two or may be one.

[0018] A transfer robot 110 is arranged inside the VTM11. The transfer robot 110 transfers the substrate W among the film forming apparatus 20, the film forming apparatus 30, the plasma processing apparatus 40, the film forming apparatus 50, the heating apparatus 60, and the LLM12. The inside of the VTM11 is maintained at a predetermined pressure atmosphere lower than the atmospheric pressure.

[0019] One side wall of each LLM12 is connected to the VTM11 via the gate valve G, and the other side wall is connected to the EFEM13 via the gate valve G. When the substrate W is carried into the LLM12 from the EFEM13 via the gate valve G, the gate valve G is closed, and the pressure inside the LLM12 is reduced to a pressure similar to the pressure inside the VTM11. Then, the gate valve G is opened, and the substrate W inside the LLM12 is carried out into the VTM11 by the transfer robot 110.

[0020] Also, with the pressure inside the LLM12 being similar to the pressure inside the VTM11, the substrate W is carried into the LLM12 from the VTM11 via the gate valve G by the transfer robot 110, and the gate valve G is closed. Then, the pressure inside the LLM12 is increased to a pressure similar to the pressure inside the EFEM13. Then, the gate valve G is opened, and the substrate W inside the LLM12 is carried out into the EFEM13.

[0021] A plurality of load ports 14 are provided on the side wall of the EFEM13 opposite to the side wall where the gate valve G is provided. A container such as a FOUP (Front Opening Unified Pod) capable of accommodating a plurality of substrates W is connected to each load port 14. Note that an aligner module or the like for changing the orientation of the substrate W may be provided inside the EFEM13.

[0022] Inside the EFEM 13, for example, it is at atmospheric pressure. Inside the EFEM 13, a transfer robot 130 is provided. The transfer robot 130 transfers the substrate W between the LLM 12 and the container connected to the load port 14. On the upper part of the EFEM 13, an FFU (Fan Filter Unit) or the like is provided, and dry air from which particles and the like have been removed is supplied into the EFEM 13 from above, and a downflow is formed inside the EFEM 13. In addition, in the present embodiment, the inside of the EFEM 13 is at atmospheric pressure, but as another form, the pressure inside the EFEM 13 may be controlled to be a positive pressure. Thereby, intrusion of particles and the like from the outside into the EFEM 13 can be suppressed.

[0023] The control device 15 includes a memory, a processor, and an input / output interface. Data such as a control program and a processing recipe are stored in the memory. The processor reads out the control program from the memory and executes it, and controls each part of the manufacturing system 10 via the input / output interface based on the recipe and the like stored in the memory.

[0024] [Configuration examples of the film forming apparatus 20 and the 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 introduction device 205. The chamber 201 houses the 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 the gas inside the chamber 201. The microwave introduction device 205 generates microwaves for generating plasma inside the chamber 201 and introduces the microwaves into the chamber 201.

[0025] The chamber 201 is formed of a metallic material such as aluminum or its alloy, has a substantially cylindrical shape, and includes a plate-shaped top wall portion 211, a bottom wall portion 213, and a side wall portion 212 connecting these. The microwave introducing device 205 is provided above the chamber 201 and functions as plasma generating means for introducing electromagnetic waves (microwaves) into the chamber 201 to generate plasma. The microwave introducing device 205 will be described in detail later.

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

[0027] The mounting table 202 has a substantially disc shape and is formed of ceramics such as aluminum nitride. The mounting table 202 is supported by a support member 220 and a base member 221, both of which are formed of ceramics such as cylindrical aluminum nitride extending upward from the center of the bottom of the chamber 201. A guide ring 281 for guiding the substrate W is provided at the outer edge of the mounting table 202. Further, inside the mounting table 202, lifting pins (not shown) for lifting and lowering the substrate W are provided so as to be able to protrude and retract with respect to the upper surface of the mounting table 202.

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

[0029] A plurality of gas introduction nozzles 223 are fitted into the openings formed in the top wall portion 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 supply source of the processing gas. For example, when forming a graphene film, as the processing gas, a mixed gas containing a rare gas and a carbon-containing gas is used. As the rare gas, for example, argon is used. As the carbon-containing gas, for example, a hydrocarbon gas represented by CxHy (x, y are natural numbers) such as ethylene (C2H4) is used. Also, for example, when forming a silicon-containing film as a sealing film, as the processing gas, a mixed gas containing a silicon-containing gas, a reaction gas, and a rare gas is used. As the silicon-containing gas, for example, silane (SiH4), dichlorosilane (DCS), etc. are used. Also, as the reaction gas, for example, nitrogen, ammonia, oxygen, etc. are used. Also, as the rare gas, for example, argon, helium, etc. are used. Note that the gas supply mechanism 203 is provided with a valve and a flow controller for each gas type, and the flow rate of the gas is adjusted for each gas type. Also, a hydrogen-containing gas such as hydrogen gas may be added to the processing gas.

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

[0031] The microwave introduction device 205 includes a top wall portion 211 of the chamber 201, a microwave output portion 230, and an antenna unit 240. The top wall portion 211 functions as a top plate. The microwave output portion 230 generates microwaves and distributes and outputs the microwaves to a plurality of paths. The antenna unit 240 radiates the microwaves output from the microwave output portion 230 into the chamber 201.

[0032] The microwave output portion 230 includes a microwave power supply, a microwave oscillator, an amplifier, and a distributor. The microwave oscillator is solid state and oscillates microwaves (for example, PLL oscillation) at, for example, 860 MHz. Note that the frequency of the microwaves is not limited to 860 MHz, and those in the range of 700 MHz to 10 GHz such as 2.45 GHz, 8.35 GHz, 5.8 GHz, 1.98 GHz, etc. can be used. The amplifier amplifies the microwaves oscillated by the microwave oscillator. The distributor distributes the microwaves amplified by the amplifier to a plurality of paths. The distributor distributes the microwaves while matching the impedance between the input side and the output side.

[0033] The antenna unit 240 includes a plurality of antenna modules. The plurality of antenna modules each introduce the microwaves distributed by the distributor of the microwave output portion 230 into the chamber 201. The configurations of the plurality of antenna modules are all the same. 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 includes 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 travels toward the main amplifier.

[0035] A plurality of microwave radiation mechanisms 243 are provided on the ceiling wall portion 211, as shown in FIG. 2, for example. The microwave radiation mechanism 243 has a cylindrical outer conductor and an inner conductor provided coaxially with the outer conductor inside the outer conductor. The microwave radiation mechanism 243 has a coaxial tube having a microwave transmission line between the outer conductor and the inner conductor, and an antenna unit that radiates microwaves into the chamber 201. On the lower surface side of the antenna unit, a microwave transmission plate 263 fitted into the ceiling wall portion 211 is provided, and its lower surface is exposed to the internal space of the chamber 201. The microwaves transmitted through the microwave transmission plate 263 generate plasma in the space within the chamber 201. That is, the microwave radiation mechanism 243 is an example of a plasma source.

[0036] FIG. 3 is a diagram schematically showing an example of the ceiling wall portion 211. In the present embodiment, as shown in FIG. 3 for example, seven microwave radiation mechanisms 243 are provided on the ceiling wall portion 211, and the corresponding microwave transmission plates 263 are arranged on the ceiling wall portion 211 so as to be evenly arranged in a hexagonal close-packed arrangement. That is, one of the seven microwave transmission plates 263 is arranged substantially at the center of the ceiling 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 intervals between adjacent microwave transmission plates 263 are equal. Note that the center of the ceiling wall portion 211 is an example of the central region, and the periphery of the microwave radiation mechanism 243 arranged at the center of the ceiling wall portion 211 is an example of the peripheral region. That is, one microwave radiation mechanism 243 is arranged in the central region, and six are arranged in the peripheral region. Further, the plurality of gas introduction nozzles 223 are arranged so as to surround the periphery of 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 each microwave radiation mechanism 243 arranged in the peripheral region will be referred to as the peripheral microwave radiation mechanism 243. Note that the number of microwave radiation mechanisms 243 is not limited to seven, and may be less than seven or more than seven.

[0037] [Configuration example of film forming apparatus 30] FIG. 4 is a diagram showing an example of the film forming apparatus 30. The film forming apparatus 30 includes a chamber 31, an exhaust mechanism 32, a gas supply unit 33, a shower head 35, and a stage 36. In the present embodiment, the film forming apparatus 30 is, for example, a CVD (Chemical Vapor Deposition) apparatus.

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

[0039] In the chamber 31, a gas supply unit 33 for supplying a plurality of types of raw material monomers is connected via a shower head 35. In the present embodiment, the plurality of types of raw material monomers are, for example, isocyanate and amine. Isocyanate is an example of the first monomer, and amine is an example of the second monomer. The gas supply unit 33 includes 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 stores, for example, a liquid of isocyanate. The raw material supply source 330b stores, for example, a liquid of amine.

[0040] The vaporizer 331a vaporizes the liquid of isocyanate supplied from the raw material supply source 330a. The vapor of isocyanate vaporized by the vaporizer 331a is introduced into the shower head 35 via the pipe 34a. Further, the vaporizer 331b vaporizes the liquid of amine supplied from the raw material supply source 330b. The vapor of amine 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, at the upper part of the chamber 31, and a large number of discharge ports are formed on the lower surface. The shower head 35 discharges the vapor of isocyanate introduced via the pipe 34a and the vapor of amine introduced via the pipe 34b into the chamber 31 in a shower-like manner from separate discharge ports.

[0042] In the chamber 31, a stage 36 is provided. The stage 36 has a temperature adjustment mechanism (not shown). The substrate W carried into the chamber 31 through the opening 31a formed in the side wall of the chamber 31 is placed on the stage 36. The opening 31a is opened and closed by a gate valve G. The stage 36 has a temperature adjustment mechanism, and the temperature of the substrate W is controlled by the temperature adjustment mechanism so as to be a temperature suitable for the vapor-phase polymerization of the raw material monomers supplied from the gas supply unit 33. The temperature suitable for the vapor-phase polymerization can be determined according to the type of the raw material monomers. The temperature suitable for the vapor-phase polymerization is, for example, a temperature in the range of 60°C to 100°C.

[0043] Using such a film forming apparatus 30, a polymer organic film is formed on the surface of the substrate W by causing a vapor phase polymerization reaction of two types of raw material monomers 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] [Configuration Example of Plasma Processing Apparatus 40] FIG. 5 is a diagram showing an example of the 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 gas in the chamber 41 is exhausted by the exhaust mechanism 42, and the inside of the chamber 41 is controlled to a predetermined pressure.

[0045] A stage 43 on which the substrate W is placed is provided in the chamber 41. The substrate W carried into the chamber 41 through an opening 41a formed in the side wall of the chamber 41 is 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 in the stage 43. Further, the stage 43 is electrically connected to the bottom of the chamber 41 and functions as an anode electrode. Above the stage 43, a shower head 44 is provided so as to face the upper surface of the stage 43. The shower head 44 is supported by the upper part of the chamber 41 via an insulating member 44A. A power source 45 for supplying high-frequency power for plasma generation is connected to the shower head 44. The shower head 44 functions as a cathode electrode with respect to the stage 43.

[0046] The gas supply source 46 supplies a processing gas. The flow controller 47 adjusts the flow rate of the processing gas supplied from the gas supply source 46 and supplies it into the diffusion space 44B of the shower head 44. The processing gas supplied into the diffusion space 44B diffuses within the diffusion space 44B and is supplied into the chamber 41 in a shower-like manner from a plurality of discharge ports 44C formed on the lower surface of the diffusion space 44B. In FIG. 5, one gas supply source 46 and one flow controller 47 are shown, but actually, a set of the gas supply source 46 and the flow 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 turned into plasma by the high-frequency power supplied into the chamber 41 from the power source 45. Then, the substrate W is processed such as etched by ions, active species, etc. contained in the plasma.

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

[0049] In the chamber 61, a stage 64 on which the substrate W is placed is provided. A lamp house 65 is provided at a position facing the surface of the stage 64 on which the substrate W is placed. In the lamp house 65, a lamp 65a such as an infrared lamp is arranged.

[0050] A gas supply part 63a is connected to the side wall of the chamber 61 through the supply pipe 63. The gas supply part 63a supplies an inert gas such as N2 gas into the chamber 61 through the supply pipe 63. Further, an opening 61a for loading and unloading the substrate W is formed in the side wall of the chamber 61. The opening 61a is opened and closed by a gate valve G.

[0051] At the bottom of the chamber 61, an exhaust device 66 is connected via an exhaust pipe 62. The exhaust device 66 has a pressure regulating valve. The exhaust device 66 exhausts the gas in the chamber 61 and controls the pressure regulating valve so that the pressure in the chamber 61 becomes a predetermined pressure.

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

[0053] [Method for manufacturing a semiconductor device] FIG. 7 is a flowchart showing an example of a method for 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. Hereinafter, description will be made with reference to FIGS. 8A to 8G.

[0054] First, the substrate W is carried into the chamber 201 of the film forming apparatus 20 (step S100). Step S100 is an example of step a). In step S100, for example, a substrate W having a structure as shown in FIG. 8A is carried into the plasma processing apparatus 200 by the transfer robot 110 in the VTM11. The substrate W has a pattern including a plurality of metal-containing layers 71 formed on the underlying layer 70 and dielectric layers 72 formed on each of the metal-containing layers 71. A semiconductor device is made from the substrate W. In the present embodiment, at least the surface of the underlying layer 70 is formed of, for example, TiN or TaN. The metal-containing layer 71 contains at least any one of, for example, Ru, Co, Cu, Mo, Ni, or W. The metal-containing layer 71 is used, for example, as wiring in a semiconductor device. The dielectric layer 72 is a silicon-containing film such as a silicon nitride film.

[0055] Next, a pretreatment is performed on the substrate W (step S101). Step S101 is an example of step b). In step S101, by supplying a reforming gas into the chamber 201, the side walls of each metal-containing layer 71 are reformed. In step S101, the pretreatment is performed by the film forming apparatus 20 under the following processing conditions, for example. Pressure inside the chamber 201: 50 mTorr to 1 Torr (6.7 to 133 Pa) Flow rate ratio of the gases contained in the reforming 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] By the pretreatment in step S101, on the surface of the side walls of the metal-containing layer 71, an oxide film unintentionally formed during the conveyance of the substrate W or the like is reduced. Note that the reforming gas used in the pretreatment of step S101 contains an inert gas and a hydrogen-containing gas. In the present embodiment, the inert gas contains at least one of noble gases such as He gas and Ar gas, or N2 gas, and the hydrogen-containing gas contains at least one of H2 gas or NH3 gas.

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

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

[0059] By the processing of step S102, for example, as shown in FIG. 8B, a graphene film 73 is formed on the sidewalls of the metal-containing layer 71. Note that in step S102, the pressure inside the chamber 201 is more preferably 50 mTorr - 100 mTorr (6.67 Pa - 13.3 Pa). Also, the power of the microwave is more preferably 300 W - 1500 W. Further, the first processing gas contains a carbon-containing gas and an inert gas. The first processing gas may contain a hydrogen-containing gas such as H2 gas or NH3 gas. In the present embodiment, the carbon-containing gas is a hydrocarbon gas represented by, for example, CxHy (x and y are natural numbers) (for example, C2H2 gas or C2H4 gas), 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 forming apparatus 20 to the film forming apparatus 30 (step S103). In step S103, the substrate W is carried out from the chamber 201 of the film forming apparatus 20 by the transfer robot 110 in the VTM11 and carried into the chamber 31 of the film forming apparatus 30.

[0061] Next, a thermally decomposable organic film is embedded in the grooves formed by the adjacent metal-containing layers 71 on the substrate W (step S104). Step S104 is an example of step 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 polymer organic film that is thermally decomposable on the surface of the substrate W. In the present embodiment, the first monomer is, for example, isocyanate, the second monomer is, for example, amine, and the polymer organic film has a polyurea bond. As a result, as shown in, for example, FIG. 8C, the organic film 74 is embedded in the grooves formed by the adjacent metal-containing layers 71.

[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 the 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 carried out of the chamber 31 of the film forming apparatus 30 by the transfer robot 110 in the VTM11 and carried into the chamber 41 of the plasma processing apparatus 40.

[0064] Next, the unnecessary organic film 74 on the substrate W is removed (step S106). Step S106 is an example of step 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 that the dielectric layer 72 is exposed. 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 chamber 41: 0.05 - 1.0 Torr (6.67 - 133 Pa) Processing gas: H2 / N2 = 100 - 300 sccm / 100 - 300 sccm (0.17 - 0.51 Pa·m 3 / s / 0.17 - 0.51 Pa·m 3 / s) High-frequency power: 100 - 400 W Temperature of substrate W: 40 - 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 carried out of the chamber 41 of the plasma processing apparatus 40 by the transfer robot 110 in the VTM11 and carried 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 step e). In step S108, plasma is generated from a processing gas containing, for example, organic aminosilane in the chamber 201. Then, the generated plasma forms a sealing film 75 on the organic film 74, for example, as shown in FIG. 8E. In the present 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 processing conditions, for example. Pressure in chamber 201: 0.1 - 10 Torr (13.3~1333 Pa) Processing gas: Organic aminosilane = 10~50 sccm (0.017~0.085 Pa·m 3 / s) Power of microwave: 50~200 W Temperature of substrate W: 20~100 °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 carried out of the chamber 201 of the film forming apparatus 50 by the transfer robot 110 in the VTM11 and carried into the chamber 61 of the heating apparatus 60.

[0068] Next, the substrate W is heated (step S110). Step S110 is an example of step f). In step S110, when the substrate W is heated, the organic film 74 is thermally decomposed, and the organic film 74 is desorbed through the sealing film 75. As a result, for example, as shown in FIG. 8F, 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 chamber 61: 0.5~20 Torr (66.7~2666 Pa) Gas supplied into chamber 61: N2 = 200~2000 sccm (0.34~3.4 Pa·m 3 / s) Temperature of substrate W: 350~450 °C

[0069] Next, the substrate W is transferred from the heating apparatus 60 to the film forming apparatus 50 (step S111). In step S111, the substrate W is carried out of the chamber 61 of the heating apparatus 60 by the transfer robot 110 in the VTM11 and carried into the chamber 201 of the film forming apparatus 50 again.

[0070] Next, a protective film is formed on the sealing film 75 (step S112). In step S112, for example, plasma is generated from a processing gas containing organic aminosilane in the chamber 201. Then, due to the generated plasma, a protective film 76 is formed on the sealing film 75 as shown in, for example, FIG. 8G. In the present 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 the following processing conditions, for example. Pressure in the chamber 201: 0.1 to 10 Torr (13.3 to 1333 Pa) Processing gas: organic aminosilane = 10 to 50 sccm (0.017 to 0.085 Pa·m 3 / s) Power of microwave: 50 to 200 W Temperature of the substrate W: 20 to 100 °C

[0071] Next, the substrate W is carried out of the film forming apparatus 50 (step S113). Then, the manufacturing method of the semiconductor device shown in this flowchart ends.

[0072] [Thickness of the 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, for example. Therefore, the thickness of the sealing film 75 is preferably greater than 1.2 nm.

[0073] On the other hand, when the thickness of the sealing film 75 is 2.4 nm, even after the substrate W is heated, the organic film 74 in the groove formed by the adjacent metal-containing layers 71 did not completely desorb and remained as shown in FIG. 9, for example. Therefore, the thickness of the sealing film 75 is preferably less 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, for example, as shown in FIG. 9, the organic film 74 was not seen in the groove formed by the adjacent metal-containing layers 71. Also, the sealing film 75 was not broken. Therefore, it is preferable that the thickness of the sealing film 75 is 1.2 nm or more and 2.0 nm or less.

[0075] [Resistance value of the metal-containing layer 71] As a comparative example, when measuring the resistance value of the metal-containing layer 71 in the case where the air gap 74a was formed without forming the graphene film 73 on the side wall of the metal-containing layer 71, for example, the results as shown in FIGS. 10A and 10B were obtained. In the comparative example, when the metal-containing layer 71 was heated to desorb the organic film 74, the crystal grains of the metal-containing layer 71 were enlarged and the resistance value of the metal-containing layer 71 was reduced. Referring to FIG. 10B, in the comparative example, the resistance value of the metal-containing layer 71 after the air gap 74a was formed was reduced by about 9% from the initial state.

[0076] On the other hand, in the present embodiment where the graphene film 73 is formed on the side wall of the metal-containing layer 71 before the air gap 74a is formed, for example, the results as shown in FIGS. 11A and 11B were obtained. In the present embodiment, at the stage where the graphene film 73 was formed on the side wall of the metal-containing layer 71, the resistance value of the metal-containing layer 71 was reduced by about 14% from the initial state. Such a reduction in the resistance value is maintained even after the air gap 74a is formed. Comparing FIG. 10B and FIG. 11B, by forming the graphene film 73 on the side wall of the metal-containing layer 71, the reduction rate of the resistance value of the metal-containing layer 71 is increased by about 5% compared to the case where the graphene film 73 is not formed on the side wall of the metal-containing layer 71. Therefore, in the present embodiment, by forming the graphene film 73 on the side wall of the metal-containing layer 71, the resistance value of the metal-containing layer 71 used as a wiring in the semiconductor device can be further reduced.

[0077] FIG. 12A is a diagram showing an example of the capacitance between the metal-containing layers 71 in the comparative example. FIG. 12B is a diagram showing an example of the capacitance between the 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, for example, as shown in FIG. 8A, 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 between the initial state and after the formation of the air gap 74a is considered to mean that an air gap 74a of sufficient size is formed between adjacent metal-containing layers 71. By forming an air gap 74a of sufficient size between adjacent metal-containing layers 71, the capacitance between adjacent metal-containing layers 71 can be reduced.

[0078] Thus, in this embodiment, the resistance value of the metal-containing layer 71 can be reduced, and by forming an air gap 74a between adjacent metal-containing layers 71, the capacitance between the metal-containing layers 71 can be reduced. As a result, the delay of the signal flowing through the metal-containing layer 71 used as wiring in the semiconductor device can be reduced.

[0079] The above described the first embodiment. As described above, the method for manufacturing a semiconductor device in the first embodiment includes step a), step b), step c), step d), step e), and step f). In step a), a substrate (substrate W) having a pattern including a plurality of metal-containing layers (metal-containing layer 71) formed on an underlying layer (underlying layer 70) and a dielectric layer (dielectric layer 72) formed on each metal-containing layer is prepared in a chamber (chamber 201). In step b), by supplying a modifying gas into the chamber, the sidewalls of each metal-containing layer are modified. In step c), plasma is generated from a first processing gas containing a carbon-containing gas in the chamber, and a graphene film (graphene film 73) is formed on the sidewalls of the metal-containing layer using the generated plasma. In step d), a thermally decomposable organic film (organic film 74) is embedded in the groove formed by 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), by heating the substrate to thermally decompose the organic film and desorb the organic film through the sealing film, an air gap (air gap 74a) is formed between the groove and the sealing film. Thereby, a semiconductor device with less signal delay can be manufactured.

[0080] Also, the method for manufacturing a semiconductor device in the above-described first embodiment further includes a step, which is executed between step d) and step e), of removing the organic film formed on the dielectric layer. Thereby, an air gap with a desired shape can be formed between adjacent metal-containing layers 71.

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

[0082] Also, in the above-described first embodiment, the sealing film may be a silicon oxide film or a silicon nitride film. Thereby, the organic film embedded between adjacent metal-containing layers 71 can be desorbed.

[0083] Also, in the above-described first embodiment, the reformed gas 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, the side wall of the metal-containing layer 71 can be reformed so that the graphene film easily adheres thereto.

[0084] Also, in the above-described first embodiment, the inert gas contained in the reformed gas contains at least one of He gas, Ar gas, or N2 gas. Further, the hydrogen-containing gas contained in the reformed gas contains at least one of H2 gas or NH3 gas. Thereby, the side wall of the metal-containing layer 71 can be reformed so that the graphene film easily adheres thereto.

[0085] Also, in the above-described first embodiment, the temperature of the substrate in step c) is preferably 250°C or higher and 550°C or lower. Thereby, a graphene film can be efficiently formed on the side wall of the metal-containing layer 71.

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

[0087] Also, in the above-described first embodiment, the temperature of the substrate in step e) is preferably 20°C or higher and 100°C or lower. Thereby, a sealing film can be efficiently formed on the organic film.

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

[0089] Also, in the above-described first embodiment, the surface of the underlayer is TiN or TaN. Thereby, the formation of the graphene film on the underlayer can be suppressed.

[0090] Also, in the above-described first embodiment, the metal-containing layer contains at least one of Ru, Co, or Cu. Thereby, a graphene film can be efficiently formed on the metal-containing layer.

[0091] Also, in the above-described first embodiment, in step d), a gas of a first monomer and a second monomer is supplied into the chamber, and an organic film is embedded in the groove by vapor deposition polymerization of the first monomer and the second monomer. Thereby, the organic film can be efficiently embedded in the groove formed by the adjacent metal-containing layers.

[0092] Also, in the above-described first embodiment, the first monomer is isocyanate, the second monomer is amine, and the organic film contains a urea bond. Thereby, the organic film can be efficiently desorbed through the sealing film.

[0093] Further, the above-described first embodiment is a semiconductor device manufacturing system (manufacturing system 10), which includes a first processing apparatus (film forming apparatus 20), a second processing apparatus (film forming apparatus 30), a third processing apparatus (film forming apparatus 50), a fourth processing apparatus (heating apparatus 60), and a control apparatus (control apparatus 15) for controlling the first processing apparatus, the second processing apparatus, the third processing apparatus, and the fourth processing apparatus. The control apparatus executes step a), step b), step c), step d), step e), and step f). In step a), a substrate (substrate W) having a pattern including a plurality of metal-containing layers (metal-containing layer 71) formed on an underlying layer (underlying layer 70) and dielectric layers (dielectric layer 72) formed on each of the metal-containing layers is prepared in a chamber (chamber 201) of the first processing apparatus. In step b), the sidewalls of each of the metal-containing layers are modified by supplying a modifying gas into the chamber. In step c), plasma is generated from a first processing gas containing a carbon-containing gas in the chamber, and a graphene film (graphene film 73) is formed on the sidewalls of the metal-containing layers using the generated plasma. In step d), a thermally decomposable organic film (organic film 74) is embedded in a groove formed by adjacent metal-containing layers using the second processing apparatus. In step e), a sealing film (sealing film 75) is formed on the organic film embedded in the groove using the third processing apparatus. In step f), the substrate is heated using the fourth processing apparatus to thermally decompose the organic film, and the organic film is desorbed through the sealing film, thereby forming an air gap (air gap 74a) between the groove and the sealing film. Thereby, a semiconductor device with less signal delay can be manufactured.

[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 groove formed by the adjacent metal-containing layers 71 may not all be removed and may remain as a residue. The residue in the groove may become conductive due to heating. Therefore, the leakage current after the air gap 74a is formed may be larger than the leakage current at the stage when the graphene film 73 is formed, as shown in FIG. 13, for example. Therefore, in the second embodiment, in order to remove the residue after the air gap 74a is formed, after heating the substrate W to form the air gap 74a, a process for removing the organic film 74 is performed.

[0095] [Method of manufacturing a 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. In FIG. 14, the processes denoted by the same reference numerals as those in FIG. 7 are the same as the processes described with reference to FIG. 7 except for the points described below, and thus redundant explanations are 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 substrate W is carried out of the chamber 61 of the heating device 60 by the transfer robot 110 in the VTM11 and carried 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 step g). In step S121, plasma is generated from the processing gas in the chamber 41. In the present embodiment, the processing gas is an 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 noble gas other than Ar, or may be a gas containing at least one of a noble gas, N2 gas, or H2 gas.

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

[0099] Then, as shown in FIG. 15 for example, the generated plasma is irradiated onto the substrate W. As a result, active species and the like contained in the plasma are supplied to the residue 77 remaining in the air gap 74a, and the residue 77 is decomposed. The decomposed residue 77 desorbs 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 transfer robot 110 in the VTM11 takes out the substrate W from the chamber 41 of the plasma processing apparatus 40 and transfers it into the chamber 201 of the film forming apparatus 50. Then, the processes after step S112 are executed.

[0101] FIG. 16 is a diagram showing an example of the leakage current in the second embodiment. The leakage current when plasma is irradiated after forming the air gap 74a is reduced compared to before irradiating the plasma, as shown in FIG. 16 for example. Therefore, by irradiating plasma through the sealing film after forming the air gap 74a, 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 in the second embodiment further includes step g). Step g) is to irradiate plasma into the groove through the sealing film after the air gap is formed in step f). Thereby, the leakage current between adjacent metal - containing layers 71 can be reduced.

[0103] Also, in step g) in the above-described second embodiment, plasma generated from a third processing gas containing no oxygen is irradiated into the groove through the sealing film. The third processing gas contains at least one of a rare gas, N2 gas, or H2 gas. Thereby, the leakage current between adjacent metal-containing layers 71 can be reduced.

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

[0105] For example, in the above-described second embodiment, after heating the substrate W to form the air gap 74a, the substrate W is irradiated with plasma generated from a processing gas containing no oxygen, but the disclosed technology is not limited to this. As another form, after heating the substrate W to form the air gap 74a, the substrate W may be irradiated with plasma generated from a processing gas containing oxygen. Thereby, the residue 77 remaining in the air gap 74a can be more efficiently desorbed.

[0106] However, when using plasma generated from a processing gas containing oxygen to remove the residue 77, depending on the conditions, the graphene film 73 may also be removed by active species derived from oxygen contained in the plasma. Also, depending on the conditions, the side walls of the metal-containing layer 71 may be oxidized by active species derived from oxygen contained in the plasma, and the resistance value of the metal-containing layer 71 may increase. Therefore, when using plasma generated from a processing gas containing oxygen to remove the residue 77, it is preferably performed 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 the substrate W: 200 to 400 °C

[0107] In each of the above-described embodiments, the graphene film 73 is formed using the film forming apparatus 20 having a plurality of microwave radiation mechanisms 543. However, the disclosed technology is not limited thereto. As another form, for example, the graphene film 73 may be formed using a film forming apparatus having one microwave radiation mechanism.

[0108] In each of the above-described embodiments, the film forming apparatus 20 that forms the graphene film 73 using microwave plasma as a plasma source has been described as an example. However, the disclosed technology is not limited thereto. As long as it is an apparatus that forms the graphene film 73 on the substrate W using plasma, the plasma source is not limited to microwave plasma. For example, any plasma source such as capacitively coupled plasma, inductively coupled plasma, magnetron plasma, etc. can be used.

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

[0110] It should be noted that the embodiments disclosed this time should be considered as illustrative in all respects and not restrictive. In fact, the above-described embodiments can be embodied in various forms. Also, the above embodiments may be omitted, replaced, or changed in various forms without departing from the scope and spirit of the appended claims.

[0111] Also, regarding the above embodiments, the following additional notes are disclosed.

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

Explanation of Reference Numerals

[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 forming apparatus 30 Film forming apparatus 40 Plasma processing apparatus 50 Film forming apparatus 60 Heating apparatus 70 Underlying layer 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) preparing a substrate having a pattern including a plurality of metal-containing layers formed on an underlying layer and a dielectric layer formed on each of the metal-containing layers in a chamber; 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 containing a carbon-containing gas in the chamber and forming a graphene film on the sidewalls of the metal-containing layers 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; f) forming an air gap between the groove and the sealing film by heating the substrate to thermally decompose the organic film and desorbing the organic film through the sealing film; A method of manufacturing a semiconductor device including the above steps.

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

3. In step g), the method of manufacturing a semiconductor device according to claim 2, wherein plasma generated from a second processing gas containing oxygen is irradiated into the groove through the sealing film.

4. In step g), the method of manufacturing a semiconductor device according to claim 2, wherein plasma generated from a third processing gas not containing oxygen is irradiated into the groove through the sealing film.

5. The method of manufacturing a semiconductor device according to claim 4, wherein the third processing gas contains at least one of a noble gas, N2 gas, or H2 gas.

6. h) further including a step of removing the organic film formed on the dielectric layer, which is performed between step d) and step e). The method of manufacturing a semiconductor device according to claim 1, further including the above step.

7. The method of 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 of 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 of manufacturing a semiconductor device according to claim 1, wherein the modifying gas contains an inert gas and a hydrogen-containing gas.

10. The method of manufacturing a semiconductor device according to claim 9, wherein a flow rate ratio of the inert gas to the hydrogen-containing gas is in a 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, or 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 or 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 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, or Cu.

19. In step d), a gas of a first monomer and a second monomer is 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. The method for manufacturing a semiconductor device according to claim 1.

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

21. A first processing device, A second processing device, A third processing device, A fourth processing device, And a control device for controlling the first processing device, the second processing device, the third processing device, and the fourth processing device. Comprising, The control device, a) A step of 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 device. b) A step of modifying sidewalls of each of the metal-containing layers by supplying a reforming gas into the chamber. c) A step of generating plasma from a first processing gas containing a carbon-containing gas in the chamber and forming a graphene film on the sidewalls of the metal-containing layer using the generated plasma. d) A step of embedding a thermally decomposable organic film in a groove formed by the adjacent metal-containing layers using the second processing apparatus; e) A step of forming a sealing film on the organic film embedded in the groove using the third processing apparatus; f) A step of forming an air gap between the groove and the sealing film by heating the substrate using the fourth processing apparatus to thermally decompose the organic film and desorbing the organic film through the sealing film. A semiconductor device manufacturing system that executes the above steps.

Images