Tabernacle Method and Tabernacle Device

Abstract

A film deposition method is a film deposition method for depositing a graphene film, comprising a step of introducing a substrate into a processing vessel, a first step of forming a graphene film on a substrate using a plasma of a first processing gas containing a carbon-containing gas, and a second step of forming a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second processing gas containing a dopant gas.

Description

Technology Field

[0001] The present disclosure relates to a tabernacle method and a tabernacle apparatus. Background Technology

[0002] In recent years, graphene films have been proposed as new thin-film barrier layer materials to replace metal nitride films. In graphene film deposition technology, it has been proposed to form a graphene film directly on a silicon substrate or an insulating film by performing graphene deposition at high radical density and low electron temperature, for example, using a microwave plasma CVD (Chemical Vapor Deposition) device (e.g., Patent Document 1). In addition, it has been proposed to irradiate a substrate with a plasma containing CH4 and N2 to generate a nitrogen-doped graphene film on the substrate (e.g., Patent Document 2). Prior art literature

[0003] Japanese Patent Publication No. 2019-055887, International Publication No. 2017 / 213045 The problem to be solved

[0004] The present disclosure provides a film deposition method and a film deposition apparatus capable of controlling the position ratio of nitrogen dope to a graphene film. means of solving the problem

[0005] A film deposition method according to one embodiment of the present disclosure is a film deposition method for depositing a graphene film, comprising: a loading process for bringing a substrate into a processing vessel; a first process for forming a graphene film on a substrate using a plasma of a first processing gas containing a carbon-containing gas; and a second process for forming a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second processing gas containing a dopant gas. Effects of the invention

[0006] According to the present disclosure, the position ratio of nitrogen dope to a graphene film can be controlled. Brief explanation of the drawing

[0007] FIG. 1 is a schematic cross-sectional view illustrating an example of a membrane forming device in one embodiment of the present disclosure. Figure 2 is a drawing illustrating an example of a grain boundary. Figure 3 is a diagram illustrating the location of the nitrogen dope in the grain. FIG. 4 is a drawing illustrating an example of a combination of each process for each sequence in the present embodiment. FIG. 5 is a flowchart illustrating an example of the tabernacle treatment in the present embodiment. FIG. 6 is a flowchart illustrating an example of a partial film formation process of sequence SE3 in the present embodiment. FIG. 7 is a flowchart illustrating an example of the tabernacle treatment in the present embodiment. FIG. 8 is a flowchart illustrating an example of the tabernacle treatment in the present embodiment. Figure 9 is a diagram illustrating an example of the experimental results of sequence SE1. Figure 10 is a diagram illustrating an example of the experimental results of sequence SE2. Figure 11 is a diagram illustrating an example of a comparison of experimental results between sequence SE1 and sequence SE2. Figure 12 is a diagram illustrating an example of the experimental results of sequence SE3. Figure 13 is a diagram illustrating an example of the experimental results of sequence SE4. Figure 14 is a diagram illustrating an example of the experimental results of sequence SE4. Figure 15 is a diagram illustrating an example of the experimental results of sequence SE4. Figure 16 is a diagram illustrating an example of a comparison of experimental results between sequence SE4 and sequence SE8. Figure 17 is a diagram illustrating an example of a comparison of experimental results between sequence SE9 and sequence SE10. Specific details for implementing the invention

[0008] Hereinafter, embodiments of the disclosed membrane formation method and membrane formation device will be described in detail based on the drawings. Furthermore, the disclosed technology is not limited by the following embodiments.

[0009] In nitrogen-doped graphene films, the substitution positions of nitrogen atoms can be broadly classified into three types. The first is the graphitic type, in which the central carbon atoms of the three six-membered rings are substituted with nitrogen atoms. The second is the pyridinic type, in which the carbon atoms of the six-membered ring groups at the grain ends are substituted with nitrogen atoms. The third is the pyrrolic type, in which the carbon atoms of the six-membered ring groups are substituted with nitrogen atoms and also form five-membered rings. It is difficult to control the ratio of these graphitic, pyridinic, and pyrrolic types—that is, the ratio of nitrogen doping positions to the graphene film. Therefore, controlling the ratio of nitrogen doping positions to the graphene film is expected.

[0010] [Composition of the Tabernacle Device (1)]

[0011] FIG. 1 is a schematic cross-sectional view illustrating an example of a film deposition apparatus according to one embodiment of the present disclosure. The film deposition apparatus (1) exemplified in FIG. 1 is configured, for example, as a plasma processing apparatus of the RLSA (registered trademark) microwave plasma type. In addition, the film deposition apparatus (1) is an example of a substrate processing apparatus.

[0012] The membrane device (1) comprises a device body (10) and a control unit (11) that controls the device body (10). The device body (10) comprises a chamber (101), a stage (102), a microwave introduction mechanism (103), a gas supply mechanism (104), and an exhaust mechanism (105).

[0013] The chamber (101) is formed in a roughly cylindrical shape, and an opening (110) is formed in the roughly central part of the bottom wall (101a) of the chamber (101). An exhaust chamber (111) is provided in the bottom wall (101a) that communicates with the opening (110) and protrudes downward. An opening (117) through which a substrate (hereinafter also referred to as a wafer) (W) passes is formed in the side wall (101s) of the chamber (101), and the opening (117) is opened and closed by a gate valve (118). Additionally, the chamber (101) is an example of a processing vessel.

[0014] A substrate (W) to be processed is loaded onto the stage (102). The stage (102) is approximately circular in shape and is formed of ceramics such as AlN. The stage (102) is supported by a cylindrical support member (112) made of ceramics such as AlN that extends upward from approximately the center of the bottom of the exhaust chamber (111). An edge ring (113) is provided on the outer edge of the stage (102) to surround the substrate (W) loaded on the stage (102). Additionally, a lifting pin (not shown) for lifting the substrate (W) is provided inside the stage (102) so as to protrude and recess with respect to the upper surface of the stage (102).

[0015] Additionally, a resistance heating type heater (114) is embedded inside the stage (102), and the heater (114) heats the substrate (W) loaded on the stage (102) according to the power supplied from the heater power source (115). Additionally, a thermocouple (not shown) is inserted into the stage (102), and based on a signal from the thermocouple, the temperature of the substrate (W) can be controlled to, for example, 350 to 850°C. Furthermore, within the stage (102), an electrode (116) of the same size as the substrate (W) is embedded above the heater (114), and a bias power source (119) is electrically connected to the electrode (116). The bias power source (119) supplies bias power of a predetermined frequency and size to the electrode (116). Ions are introduced into the substrate (W) loaded on the stage (102) by the bias power supplied to the electrode (116). Additionally, the bias power supply (119) may not need to be provided depending on the characteristics of the plasma treatment.

[0016] A microwave introduction mechanism (103) is provided at the top of a chamber (101) and has an antenna (121), a microwave output unit (122), and a microwave transmission mechanism (123). A plurality of slots (121a), which are through holes, are formed in the antenna (121). The microwave output unit (122) outputs microwaves. The microwave transmission mechanism (123) guides the microwaves output from the microwave output unit (122) to the antenna (121).

[0017] A dielectric window (124) formed of dielectric material is provided below the antenna (121). The dielectric window (124) is supported by a support member (132) provided in a ring shape on the upper part of the chamber (101). A wave plate (126) is provided above the antenna (121). A shield member (125) is provided above the antenna (121). An unillustrated fluid path is provided inside the shield member (125), and the shield member (125) cools the antenna (121), the dielectric window (124), and the wave plate (126) by a fluid, such as water, flowing through the fluid path.

[0018] The antenna (121) is formed, for example, with a surface made of silver or plated copper or aluminum, and has a plurality of slots (121a) for radiating microwaves arranged in a predetermined pattern. The arrangement pattern of the slots (121a) is appropriately set so that microwaves are radiated evenly. An example of a suitable pattern is a radial line slot in which a plurality of pairs of slots (121a) are arranged concentrically, with two slots (121a) arranged in a T-shape forming a pair. The length or spacing of the slots (121a) is appropriately determined according to the effective wavelength (λg) of the microwave. Additionally, the slots (121a) may have other shapes, such as a circular shape or an arc shape. Furthermore, the arrangement shape of the slots (121a) is not particularly limited and may be arranged in a spiral shape or a radial shape, in addition to a concentric shape. The pattern of the slot (121a) is appropriately set so that the microwave radiation characteristics obtain a desired plasma density distribution.

[0019] The wave plate (126) is formed from a dielectric material having a dielectric constant greater than that of a vacuum, such as quartz, ceramics (Al2O3), polytetrafluoroethylene, or polyimide. The wave plate (126) has the function of making the antenna (121) smaller by shortening the wavelength of the microwave compared to that of a vacuum. In addition, the dielectric window (124) is also composed of the same dielectric material.

[0020] The thickness of the dielectric window (124) and the wave plate (126) is adjusted so that the wave plate (126), antenna (121), dielectric window (124), and the equivalent circuit formed by the plasma satisfy the resonance condition. By adjusting the thickness of the wave plate (126), the phase of the microwave can be adjusted. By adjusting the thickness of the wave plate (126) so that the junction of the antenna (121) becomes an "antinode" of the standing wave, the reflection of the microwave is minimized, and the radiation energy of the microwave can be maximized. In addition, by making the wave plate (126) and the dielectric window (124) of the same material, interfacial reflection of the microwave can be prevented.

[0021] The microwave output unit (122) has a microwave oscillator. The microwave oscillator may be of the magnetron type or the solid-state type. The frequency of the microwave generated by the microwave oscillator is, for example, a frequency of 300 MHz to 10 GHz. As an example, the microwave output unit (122) outputs a microwave of 2.45 GHz by a magnetron-type microwave oscillator. Microwaves are an example of electromagnetic waves.

[0022] The microwave transmission mechanism (123) has a waveguide (127) and a coaxial waveguide (128). Additionally, it may have a mode conversion mechanism. The waveguide (127) guides microwaves output from a microwave output unit (122). The coaxial waveguide (128) includes an inner conductor connected to the center of the antenna (121) and an outer conductor on the outside thereof. A mode conversion mechanism is provided between the waveguide (127) and the coaxial waveguide (128). Microwaves output from the microwave output unit (122) propagate through the waveguide (127) in TE mode and are converted from TE mode to TEM mode by the mode conversion mechanism. The microwave converted to TEM mode is transmitted to the wave plate (126) via the coaxial waveguide (128) and radiated from the wave plate (126) into the chamber (101) via the slot (121a) of the antenna (121) and the dielectric window (124). Additionally, a tuner (not shown) is provided in the middle of the waveguide (127) to match the impedance of the load (plasma) inside the chamber (101) to the output impedance of the microwave output section (122).

[0023] The gas supply mechanism (104) has a shower ring (142) provided on a ring along the inner wall of the chamber (101). The shower ring (142) has a ring-shaped flow path (166) provided inside and a plurality of discharge ports (167) connected to the flow path (166) and opened on the inside. A gas supply unit (163) is connected to the flow path (166) via a pipe (161). The gas supply unit (163) is provided with a plurality of gas sources and a plurality of flow rate controllers. In one embodiment, the gas supply unit (163) is configured to supply at least one processing gas from a corresponding gas source to the shower ring (142) via a corresponding flow rate controller. The gas supplied to the shower ring (142) is supplied into the chamber (101) from the plurality of discharge ports (167).

[0024] Additionally, when a graphene film is formed on the substrate (W), the gas supply unit (163) supplies carbon-containing gas, hydrogen-containing gas, and noble gas, controlled at a predetermined flow rate, into the chamber (101) via a shower (142). In this embodiment, the carbon-containing gas is, for example, C2H2 gas. In addition, C2H4 gas, CH4 gas, C2H6 gas, C3H8 gas, or C3H6 gas may be used instead of or in addition to C2H2 gas. In addition, in this embodiment, the hydrogen-containing gas is, for example, hydrogen gas. In addition, halogen-based gases such as F2 (fluorine) gas, Cl2 (chlorine) gas, or Br2 (bromine) gas may be used instead of or in addition to hydrogen gas. In addition, in this embodiment, the noble gas is, for example, Ar gas. In addition to Ar gas, other noble gases such as He gas may be used.

[0025] The exhaust mechanism (105) has an exhaust chamber (111), an exhaust pipe (181) provided on the side wall of the exhaust chamber (111), and an exhaust device (182) connected to the exhaust pipe (181). The exhaust device (182) has a vacuum pump and a pressure control valve, etc.

[0026] The control unit (11) has a memory, a processor, and an input / output interface. The memory stores a recipe including a program executed by the processor and conditions for each process. The processor executes the program read from the memory and controls each part of the device body (10) via the input / output interface based on the recipe stored in the memory.

[0027] For example, the control unit (11) controls each part of the film-forming device (1) to perform the film-forming method described below. As a detailed example, the control unit (11) performs a loading process of bringing a substrate (wafer) (W) into the chamber (101). The control unit (11) performs a first process of forming a graphene film on the substrate using a plasma of a first processing gas containing a carbon-containing gas. The control unit (11) performs a second process of forming a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second processing gas containing a dopant gas. Here, the carbon-containing gas may be acetylene (C2H2) gas supplied from the gas supply unit (163). Also, the dopant gas may be N2 gas supplied from the gas supply unit (163). Also, the carbon-containing gas is not limited to acetylene. For example, hydrocarbon gases such as ethylene (C2H4), methane (CH4), ethane (C2H6), propane (C3H8), propylene (C3H6), and acetylene (C2H2), benzene (C6H6), toluene (C7H8), and ethylbenzene (C8H 10 ), styrene (C8H8), cyclohexane (C6H 12 Cyclic hydrocarbon gases such as ) and furthermore, as carbon-containing gases, alcohols such as methanol (CH3OH) and ethanol (C2H5OH) may be used. In addition, the dopant gas is not limited to N2. For example, ammonia (NH3) may be used. In addition, the dopant gas is not limited to nitrogen-containing gases. For example, it may be a boron-containing gas.

[0028] [Grain Boundary]

[0029] Next, grain boundaries in a graphene film are explained using FIG. 2. FIG. 2 is a drawing illustrating an example of grain boundaries. The wafer (12) shown in FIG. 2 represents a state in which a graphene film (14) is deposited on a silicon substrate (13). At this time, grain boundaries (grain boundaries) (15) may occur in the graphene film (14). When grain boundaries (15) occur in the graphene film (14), it may become difficult to secure barrier properties in the graphene film. That is, the grain boundaries (15) become diffusion paths, causing elements to diffuse from the silicon substrate (13) or to diffuse from a metal-containing film further deposited on the graphene film (14) toward the silicon substrate (13). To suppress the occurrence of grain boundaries (15), it is possible to reduce the diffusion pass by doping the graphene with other elements. Thus, in this embodiment, a nitrogen-doped graphene film is produced. Additionally, as for the doping of other elements on the graphene film, boron may be doped instead of nitrogen, or nitrogen and boron may be doped.

[0030] [Location of Nitrogen Dope]

[0031] Next, the location of the nitrogen dope is explained using FIG. 3. FIG. 3 is a diagram illustrating the location of the nitrogen dope in the grain. As shown in FIG. 3, the grain (20) includes a graphic type (21), a pyrroleic type (22), a pyridinic type (23), and a pyridinic oxide type (24). As described above, the graphic type (21) is a type in which the central carbon atom of three six-membered rings is substituted with a nitrogen atom. The pyrroleic type (22) is a type in which the carbon atom of a six-membered ring is substituted with a nitrogen atom and also becomes a five-membered ring. The pyridinic type (23) is a type in which, in the six-membered ring at the end of the grain (20), the carbon atom of the six-membered ring is substituted with a nitrogen atom. The pyridinic oxide type (24) is a type in which the nitrogen atom of the pyridinic type (23) becomes an oxide accompanied by an oxygen atom. In addition, in the following description, the graphic type (21) may be referred to as “N-Graphitic,” the pyrrolic type (22) as “N-pyrrolic,” the pyridinic type (23) as “N-pyridinic,” and the pyridinic oxide type (24) as “N-Pyridine oxide.”

[0032] [Sequence List]

[0033] Next, using FIG. 4, the combination of each process of the film formation treatment is described as a sequence list. FIG. 4 is a diagram illustrating an example of the combination of each process for each sequence in the present embodiment. The table (30) shown in FIG. 4 represents the combination of the first to fourth processes of the film formation treatment as sequences SE1 to SE11. In the table (30), the process marked with a √ is executed. Furthermore, the following description describes the case where N2 gas is used as the dopant gas.

[0034] The first process is a process of forming a graphene film on a substrate (W) using a plasma of a first treatment gas containing a carbon-containing gas. The second process is a process of forming a doped graphene film on one or more of the substrate (W) and the graphene film using a plasma of a second treatment gas containing N2 gas.

[0035] The third process is a process of treating one or more of the graphene film and doped graphene film with a plasma of a third treatment gas containing N2 gas and Ar gas. The fourth process is a process of treating one or more of the graphene film and doped graphene film with a plasma of a fourth treatment gas containing N2 gas and not Ar gas. Additionally, the third and fourth processes are processes of modifying the surface of one or more of the graphene film and doped graphene film on the substrate (W). By performing modification, nitrogen can be doped into the graphene film and doped graphene film on the substrate (W).

[0036] Sequence SE1 is a sequence in which a substrate (W) is introduced into a chamber (101), a second process is performed to form a doped graphene film on the substrate (W), and then the substrate (W) is removed.

[0037] Sequence SE2 is a sequence in which a substrate (W) is introduced into a chamber (101), a first process is performed to form a graphene film on the substrate (W), a second process is performed to form a doped graphene film on the graphene film, and the substrate (W) is removed.

[0038] Sequence SE3 is a sequence in which, after bringing a substrate (W) into the chamber (101), a cycle treatment is performed as a second process to form a doped graphene film on the substrate (W) using a plasma of a second treatment gas that intermittently supplies a first dopant gas (N2 gas), and the substrate (W) is removed. Additionally, in Sequence SE3, the cycle treatment of the second process may be performed after the first process is completed following the introduction of the substrate (W) into the chamber (101).

[0039] Sequence SE4 is a sequence in which a substrate (W) is introduced into a chamber (101), a first process is performed to form a graphene film on the substrate (W), a third process is performed to dope the graphene film with nitrogen to form a doped graphene film, and the substrate (W) is removed.

[0040] Sequence SE5 is a sequence in which a substrate (W) is introduced into a chamber (101), a second process is performed to form a doped graphene film on the substrate (W), a third process is performed to also dope nitrogen onto the doped graphene film, and the substrate (W) is removed.

[0041] Sequence SE6 is a sequence in which, after bringing a substrate (W) into a chamber (101), a first process is performed to form a graphene film on the substrate (W), a second process is performed to form a doped graphene film on the graphene film, a third process is performed to also dope nitrogen onto the doped graphene film, and the substrate (W) is removed.

[0042] Sequence SE7 is a sequence in which, after bringing the substrate (W) into the chamber (101), a cycle treatment of sequence SE3 is performed as a second process to form a doped graphene film on the substrate (W), a third process is performed to dope nitrogen onto the doped graphene film, and the substrate (W) is removed. Additionally, in sequence SE7, after bringing the substrate (W) into the chamber (101) and completing the first process, a cycle treatment of sequence SE3 may be performed as a second process.

[0043] Sequence SE8 is a sequence in which, after the third process of sequence SE4, a fourth process is performed to dope nitrogen onto one or more of the graphene film and doped graphene film to form a doped graphene film, and the substrate (W) is removed. Additionally, the third process in sequence SE8 may proceed to the fourth process while maintaining the plasma from the first process.

[0044] Sequence SE9 is a sequence in which, after the third process of sequence SE5, a fourth process is performed to further dope nitrogen onto the doped graphene film to form a doped graphene film, and the substrate (W) is removed. Additionally, in the third process of sequence SE9, it is acceptable to proceed to the fourth process while maintaining the plasma from the second process.

[0045] Sequence SE10 is a sequence in which, after the third process of sequence SE6, a fourth process is performed to further dope nitrogen onto the doped graphene film to form a doped graphene film, and the substrate (W) is removed. Additionally, in the third process of sequence SE10, it is acceptable to proceed to the fourth process while maintaining the plasma from the second process.

[0046] Sequence SE11 is a sequence in which, after the third process of sequence SE7, a fourth process is performed to further dope nitrogen onto the doped graphene film to form a doped graphene film, and the substrate (W) is removed. Additionally, in the third process of sequence SE11, it is acceptable to proceed to the fourth process while maintaining the plasma from the second process.

[0047] [The Tabernacle Method]

[0048] Sequence SE2

[0049] Next, the membrane formation process according to the present embodiment will be described. FIG. 5 is a flowchart illustrating an example of the membrane formation process in the present embodiment. In the membrane formation process of FIG. 5, sequence SE2 is described as an example.

[0050] In the film formation process according to the present embodiment, first, the control unit (11) opens the opening (117) by controlling the gate valve (118). When the opening (117) is open, the substrate (W) is brought into the processing space of the chamber (101) through the opening (117) and loaded onto the stage (102). That is, the control unit (11) brings the substrate (W) into the chamber (101) (step S1). The control unit (11) closes the opening (117) by controlling the gate valve (118).

[0051] The control unit (11) reduces the pressure inside the chamber (101) to a first pressure (e.g., 5 mTorr to 1 Torr). Additionally, the control unit (11) controls the temperature of the substrate (W) to a predetermined temperature (e.g., 300°C or higher). The control unit (11) controls the supply of a first treatment gas, which is a plasma generating gas, to the chamber (101) from the discharge port (167). The first treatment gas is a gas containing a carbon-containing gas. The carbon-containing gas is, for example, a gas containing acetylene (C2H2). Additionally, the first treatment gas may contain hydrogen gas or argon gas. Furthermore, the control unit (11) guides the microwave output from the microwave output unit (122) of the microwave introduction mechanism (103) to the antenna (121) and radiates it from the antenna (121) to ignite the plasma. The control unit (11) performs a first process with a plasma of a first processing gas for a predetermined time (e.g., 5 seconds to 60 minutes) (step S2). In the first process, a graphene film is formed on a substrate (W).

[0052] When the first process is completed, the control unit (11) controls the supply of a second treatment gas, which is a plasma generating gas, to the chamber (101) from the discharge port (167) while maintaining the plasma of the first treatment gas. The second treatment gas is, for example, a mixed gas containing the first treatment gas and N2 gas. That is, the control unit (11) controls the supply of N2 gas to the chamber (101) while supplying the first treatment gas to the chamber (101) from the discharge port (167). The control unit (11) executes the second process with the plasma of the second treatment gas for a predetermined time (for example, 5 seconds to 60 minutes) (Step S3). In addition, the flow rate of the second treatment gas in the second process is different from the flow rate of the first treatment gas in the first process. In addition, in the second process, the pressure inside the chamber (101) may be changed to a second pressure (e.g., 5 mTorr to 1 Torr). In the second process, a doped graphene film is formed on the graphene film.

[0053] When the second process is completed, the control unit (11) opens the opening (117) by controlling the gate valve (118). The control unit (11) lifts the substrate (W) by protruding an unillustrated lifting pin from the upper surface of the stage (102). When the opening (117) is open, the substrate (W) is removed from the chamber (101) by an arm of an unillustrated return chamber through the opening (117). That is, the control unit (11) controls the removal of the substrate (W) from the chamber (101) (step S4). When the removal of the substrate (W) is completed, the control unit (11) terminates the film deposition process. Additionally, in the film deposition process of FIG. 5, the case where the first process is omitted becomes sequence SE1.

[0054] The control unit (11) may perform a cleaning process to clean the inside of the chamber (101) after removing the substrate (W). In the cleaning process, a dummy wafer is loaded onto the stage (102), and a cleaning gas is supplied into the chamber (101) to clean a carbon film, such as an amorphous carbon film, attached to the inner wall of the chamber (101). Additionally, O2 gas may be used as the cleaning gas, but it may also be a gas containing oxygen, such as CO gas or CO2 gas. Additionally, the cleaning gas may contain a noble gas, such as Ar gas. Also, a dummy wafer may not be used. The cleaning process may be performed for each process or for each specific number of processes.

[0055] Sequence SE3

[0056] Next, sequence SE3 will be described using FIG. 6. FIG. 6 is a flowchart illustrating an example of a partial film deposition process of sequence SE3 in the present embodiment. Sequence SE3 differs in that it undergoes a cycle process during step 3 (second process) of the film deposition process of sequence SE2. Here, the different cycle process is described, and since the other steps are the same as those of sequence SE2, their description is omitted.

[0057] When the first process of step S2 is completed, the control unit (11) performs plasma treatment for a predetermined time (e.g., 5 seconds) while maintaining a plasma of a first treatment gas containing carbon-containing gas and a first flow rate of H2 gas from the discharge port (167) (step S31). Subsequently, the control unit (11) changes the flow rate of the H2 gas of the first treatment gas from the discharge port (167) from the first flow rate to a second flow rate (e.g., changes it to a second flow rate greater than the first flow rate), and performs plasma treatment for a predetermined time (e.g., 5 seconds) with the plasma of the first treatment gas with the changed flow rate of H2 gas (step S32). The first flow rate of H2 gas is, for example, 0 to 100 sccm, and the second flow rate of H2 gas is, for example, 0 to 100 sccm.

[0058] Next, the control unit (11) changes the flow rate of the H2 gas of the first treatment gas from the discharge port (167) to the first flow rate and controls the supply of a mixed gas containing the first treatment gas and N2 gas to the chamber (101). That is, the control unit (11) controls the supply of N2 gas to the chamber (101) while supplying the first treatment gas from the discharge port (167). At this time, the flow rate of N2 gas is, for example, 100 sccm. The control unit (11) performs plasma treatment for a predetermined time (for example, 5 seconds) with the plasma of the mixed gas containing the first treatment gas and N2 gas. Then, after the predetermined time has elapsed, the supply of N2 gas is stopped (step S33).

[0059] The control unit (11) determines whether the processing of steps S31 to S33 has elapsed a predetermined cycle (e.g., 6 cycles) (step S34). If the control unit (11) determines that a predetermined cycle has not elapsed (step S34: "No"), it returns to step S31. If the control unit (11) determines that a predetermined cycle has elapsed (step S34: "Yes"), it terminates the cycle processing. Additionally, in the following description, the pattern of this cycle processing is represented as sequence SE3-C.

[0060] Additionally, in the cycle process, the plasma treatment with the first treatment gas with the changed H2 gas flow rate in Step S32 may be omitted, and Steps S31 and S33 may be repeated. In the following description, the pattern of this cycle process is shown as sequence SE3-B.

[0061] In addition, among the processing steps similar to Sequence SE2, the first process of Step S2 and the plasma treatment with H2 gas in Step S32 of the cycle processing may be omitted. That is, only the cycle processing repeating Steps S31 and S33 is performed. In the following description, the pattern of this cycle processing is represented as Sequence SE3-A.

[0062] Sequence SE6

[0063] Next, using FIG. 7, the film formation process in sequence SE6 will be described. FIG. 7 is a flowchart illustrating an example of the film formation process in the present embodiment. In addition, in sequence SE6, the process of steps S1 to S4 of the film formation process is the same as in sequence SE2, so the description thereof is omitted.

[0064] When the second process of step S3 is completed, the control unit (11) controls the supply of a third treatment gas, which is a plasma generating gas, to the chamber (101) from the discharge port (167) while maintaining the plasma of the second treatment gas. The third treatment gas is a mixed gas containing, for example, N2 gas and Ar gas. The control unit (11) executes the third process with the plasma of the third treatment gas for a predetermined time (e.g., 5 seconds to 60 minutes) (step S11). In the third process, treatment is performed on the surface of the doped graphene film and nitrogen is doped. Additionally, in the third process, the pressure inside the chamber (101) may be changed to a third pressure (e.g., 5 mTorr to 5 Torr). When the third process is completed, the control unit (11) proceeds to step S4.

[0065] Additionally, in sequence SE6, the second process (step S3) may be omitted, and the process may proceed from the first process (step S2) to the third process (step S11), which corresponds to sequence SE4. In this case, in the third process, a modification treatment is performed on the surface of the graphene film, and nitrogen is doped.

[0066] Additionally, in sequence SE6, the first process (step S2) may be omitted, and after bringing the substrate (W) into the chamber (101), proceed to the second process (step S3), which corresponds to sequence SE5. In this case, in the third process (step S11), a modification treatment is performed on the surface of the doped graphene film, and nitrogen is doped.

[0067] Additionally, in sequence SE6, the first process (step S2) may be omitted, and the second process (step S3) may be performed as a cycle process in the same way as the second process of sequence SE3, and this case corresponds to sequence SE7. In this case, in the third process (step S11), a modification treatment is performed on the surface of the doped graphene film, and nitrogen is doped.

[0068] Sequence SE10

[0069] Next, using FIG. 8, the film formation process in sequence SE10 will be described. FIG. 8 is a flowchart illustrating an example of the film formation process in the present embodiment. In addition, in sequence SE10, the process of steps S1 to S5 and S11 of the film formation process is the same as in sequence SE6, so the description thereof is omitted.

[0070] When the third process of step S11 is completed, the control unit (11) controls the supply of a fourth treatment gas, which is a plasma generating gas, to the chamber (101) from the discharge port (167) while maintaining the plasma of the third treatment gas. The fourth treatment gas is a mixed gas that includes, for example, N2 gas and does not include Ar gas. The control unit (11) executes the fourth process with the plasma of the fourth treatment gas for a predetermined time (for example, 5 seconds to 60 minutes) (step S12). In the fourth process, a modification treatment is performed on the surface of the doped graphene film, and nitrogen is doped. Additionally, in the fourth process, the pressure inside the chamber (101) may be changed to a fourth pressure (for example, 5 mTorr to 5 Torr). When the fourth process is completed, the control unit (11) proceeds to step S4. In addition, the processing time of the third process of step S11 in sequence SE10 may be a time that allows transition to the fourth process while maintaining the plasma from the second process (e.g., 1 second to 60 minutes).

[0071] In addition, in sequence SE10, the second process (step S3) may be omitted, and the process may proceed from the first process (step S2) to the third process (step S11), which corresponds to sequence SE8. In this case, in the third process (step S11) and the fourth process (step S12), a modification treatment is performed on the surface of one or more of the graphene film and the doped graphene film, and nitrogen is doped. Also, if the processing time of the third process is short, the doped graphene film is not formed in the third process, and nitrogen is doped into the graphene film in the fourth process.

[0072] Additionally, in sequence SE10, the first process (step S2) may be omitted, and after bringing the substrate (W) into the chamber (101), proceed to the second process (step S3); this case corresponds to sequence SE9. In this case, in the third process (step S11) and the fourth process (step S12), a modification treatment is performed on the surface of the doped graphene film, and nitrogen is doped. Furthermore, if the processing time of the third process is short, the doped graphene film is not formed in the third process, and nitrogen is doped into the graphene film in the fourth process.

[0073] Additionally, in sequence SE10, the first process (step S2) may be omitted, and the second process (step S3) may be performed as a cycle process similar to the second process of sequence SE3, and this case corresponds to sequence SE11. In this case, in the third process (step S11) and the fourth process (step S12), a modification treatment is performed on the surface of the doped graphene film, and nitrogen is doped. Furthermore, if the processing time of the third process is short, the doped graphene film is not formed in the third process, and nitrogen is doped into the graphene film in the fourth process.

[0074] [Experimental Results]

[0075] Next, the experimental results will be explained using Figures 9 to 17.

[0076] Sequence SE1

[0077] FIG. 9 is a diagram illustrating an example of the experimental results of sequence SE1. Graph (31) shown in FIG. 9 represents the result of an XPS (X-ray Photoelectron Spectroscopy) measurement performed on the edge portion of the substrate (W) that underwent sequence SE1. Additionally, graph (31) is data excluding background components. In sequence SE1, the ratio of nitrogen (N) doped into graphene to carbon (C) (N / C ratio) was 5.6%. Graph (32) represents the N (nitrogen) that reacted with the Si (silicon) of the substrate (W). Graph (33) represents the pyridinic type (23). Graph (34) represents the pyrroleic type (22). Graph (35) represents the pyridinic oxide type (24). Graph (36) is the sum of graphs (32 to 35).

[0078] Table (37) summarizes the results of graph (31). In sequence SE1, the flow rate of N2 gas was set to 100 sccm. At this time, the total amount of nitrogen (N atm%) in the observation range of XPS measurement was 4.30 atm%. The nitrogen (N) corresponding to graph (32) was 44.68% of the total amount. The pyridinic type (23) (N-pyridinic) corresponding to graph (33) was 27.46% of the total amount. The pyrrolic type (22) (N-pyrrolic) corresponding to graph (34) was 19.15% of the total amount. The graphic type (21) (N-Graphitic) was 0.00% of the total amount. The pyridinic oxide type (24) (N-Pyridine oxide) corresponding to graph (35) was 10.72% of the total amount. In addition, the ratio of the total amount corresponds to the area ratio in graph (31). From graph (31) and table (37), in sequence SE1, the peak of graph (32) corresponding to the total amount of nitrogen is large, but the peaks of the pyridinic type (23), pyrroleic type (22), and pyridinic oxide type (24) can be confirmed by fitting.

[0079] Sequence SE2

[0080] FIG. 10 is a diagram illustrating an example of the experimental results of sequence SE2. Graph (40) shown in FIG. 10 represents the result of an XPS measurement fitted at the edge portion of the substrate (W) that underwent sequence SE2. Additionally, graph (40) is data excluding background components. Furthermore, in sequence SE2, when the flow rate of N2 gas is 100 sccm, the ratio of nitrogen (N) to carbon (C) (N / C ratio) was 2.1%. Graph (41) represents N (nitrogen) that reacted with Si (silicon) of the substrate (W). Graph (42) represents the pyridinic type (23). Graph (43) represents the pyrroleic type (22). Graph (44) represents the graphic type (21). Graph (45) represents the pyridinic oxide type (24). Graph (46) is the sum of graphs (41 to 45).

[0081] Table (47) summarizes the results of graph (40) with an N2 gas flow rate of 100 sccm (in the bold frame) and integrates the same results when the N2 gas flow rates are 200 sccm and 300 sccm, respectively. As shown in Table (47), when the N2 gas flow rate is 100 sccm, the total amount of nitrogen (N atm%) in the observation range of XPS measurement was 1.75 atm%. The nitrogen (N) corresponding to graph (41) was 24.09% of the total amount. The pyridinic type (23) corresponding to graph (42) was 43.66% of the total amount. The pyrroleic type (22) corresponding to graph (43) was 32.78% of the total amount. The graphic type (21) corresponding to graph (44) was 16.79% of the total amount. The pyridinic oxide type (24) corresponding to graph (45) was 7.69% of the total amount. Also, the ratio of the total amount corresponds to the area ratio in graph (40).

[0082] When the flow rate of N2 gas is 200 sccm, the total amount of nitrogen in the observation range of the XPS measurement was 4.35 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 21.13% of the total amount. The pyridinic type (23) was 36.47% of the total amount. The pyrrolitic type (22) was 32.15% of the total amount. The graphitic type (21) was 11.91% of the total amount. The pyridinic oxide type (24) was 4.42% of the total amount.

[0083] When the flow rate of N2 gas was 300 sccm, the total amount of nitrogen in the observation range of the XPS measurement was 5.34 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 21.12% of the total amount. The pyridinic type (23) was 30.19% of the total amount. The pyrroleic type (22) was 31.66% of the total amount. The graphic type (21) was 21.95% of the total amount. The pyridinic oxide type (24) was 9.90% of the total amount. From the graph (40) and table (47), in sequence SE2, the total amount of nitrogen and the graphic type (21) increased as the flow rate of N2 gas was increased. In addition, regardless of the flow rate of N2 gas, nitrogen (N), pyridinic type (23), pyrroleic type (22), and pyridinic oxide type (24) did not undergo significant changes.

[0084] <Comparison of Sequence SE1 and SE2>

[0085] FIG. 11 is a diagram illustrating an example of a comparison of experimental results between sequence SE1 and sequence SE2. Table (48) shown in FIG. 11 summarizes the experimental results of sequence SE1 and sequence SE2. As shown in Table (48), the processing time of the second process for sequence SE1 was set to 80 seconds, and for sequence SE2, the processing time of the first process was set to 48 seconds and the processing time of the second process was set to 30 seconds. In addition, the flow rate of N2 gas was set to 100 sccm for both. When comparing the experimental results of sequence SE1 and sequence SE2, it can be seen that the amount of nitrogen doping is different and the location where nitrogen is easily substituted is different. In sequence SE2, compared to sequence SE1, the nitrogen (N) that reacted with the Si of the substrate (W) and the pyridinic oxide type (24) are small, and the pyridinic type (23), pyrroleic type (22), and graphitic type (21) are large.

[0086] Sequence SE3

[0087] FIG. 12 is a diagram illustrating an example of experimental results for sequence SE3. The table (50) shown in FIG. 12 is a combined table for the first and second processes of sequences SE3-A, SE3-B, and SE3-C. The processing time for the first process is set to 20 seconds, and the processing time for cycles CY1 to CY3 of the second process is set to 5 seconds each. Additionally, the flow rate of H2 gas in cycle CY2 is set to 60 sccm, and the flow rate of N2 gas in cycle CY3 is set to 100 sccm. In the table (50), ○ indicates that the corresponding process or cycle is executed, and × indicates that the corresponding process or cycle is not executed. Additionally, the predetermined number of cycles for the second process is set to 8 cycles for sequence SE3-A and 6 cycles for sequences SE3-B and SE3-C.

[0088] Graph (51) shows the results of XPS measurements of a substrate (W) that has undergone sequences SE3-A, SE3-B, and SE3-C, respectively. Table (52) summarizes the results of Graph (51). As shown in Table (52), in the case of sequence SE3-A, the total amount of nitrogen (N atm%) in the observation range of the XPS measurement was 25.09 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 72.99% of the total amount. The pyridinic type (23) was 27.66% of the total amount. The pyrroleic type (22) was 0.09% of the total amount. The graphic type (21) was 0.00% of the total amount. The pyridinic oxide type (24) was 0.00% of the total amount. In sequence SE3-A, N is easily introduced into the film (it is not substituted), most of which is nitrogen (N) that reacted with Si of the substrate (W), and the difference was pyridinic type (23).

[0089] In the case of sequence SE3-B, the total amount of nitrogen in the observation range of the XPS measurement was 4.75 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 41.76% of the total amount. The pyridinic type (23) was 27.65% of the total amount. The pyrroleic type (22) was 8.75% of the total amount. The graphic type (21) was 9.27% ​​of the total amount. The pyridinic oxide type (24) was 12.10% of the total amount. Sequence SE3-B had more pyridinic oxide type (24) than sequences SE3-A and SE3-C.

[0090] In the case of sequence SE3-C, the total amount of nitrogen in the observation range of the XPS measurement was 3.16 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 22.59% of the total amount. The pyridinic type (23) was 26.86% of the total amount. The pyrroleic type (22) was 23.25% of the total amount. The graphic type (21) was 22.39% of the total amount. The pyridinic oxide type (24) was 4.45% of the total amount. Sequence SE3-C had more of the graphic type (21) than sequences SE3-A and SE3-B.

[0091] Sequence SE4

[0092] FIGS. 13 to 15 are drawings illustrating an example of the experimental results of sequence SE4. Graph (53) shown in FIG. 13 shows the results of XPS measurements of a substrate (W) that has undergone sequence SE4 with the processing time of the first process set to 50 seconds and the pressure inside the chamber (101) of the third process set to 1.0 Torr. Additionally, graph (53) is data excluding background components. Graph (54) shows N (nitrogen) that has reacted with Si (silicon) of the substrate (W). Graph (55) shows the pyridinic type (23). Graph (56) shows the pyrroleic type (22). Graph (57) shows the graphic type (21). Graph (58) shows the pyridinic oxide type (24). Graph (59) is the sum of graphs (54 to 58).

[0093] Table (60) summarizes the results of graph (53). As shown in Table (60), in sequence SE4, the flow rate of N2 gas was set to 100 sccm. At this time, the total amount of nitrogen (N atm%) in the observation range of XPS measurement was 8.7 atm%. The nitrogen (N) corresponding to graph (54) was 13.8% of the total amount. The pyridinic type (23) corresponding to graph (55) was 57.3% of the total amount. The pyrroleic type (22) corresponding to graph (56) was 24.4% of the total amount. The graphic type (21) corresponding to graph (57) was 2.1% of the total amount. The pyridinic oxide type (24) corresponding to graph (58) was 3.5% of the total amount. In addition, the ratio of the total amount corresponds to the area ratio in graph (53). From the graph (53) and table (60), in sequence SE4, the pyridinic type (23) is dominant, followed by the pyrroleic type (22).

[0094] The graph (61) shown in FIG. 14 shows the results of XPS measurements at the center portion of the substrate (W) in which sequence SE4 is performed, with the pressure inside the chamber (101) of the third process being varied to 0.1 Torr, 0.2 Torr, 0.4 Torr, and 1.0 Torr, respectively. Additionally, a third processing gas, which is a mixture of Ar gas and N2 gas, is supplied into the chamber (101) of the third process. Also, the processing time of the third process is set to 50 seconds, as in FIG. 13.

[0095] Table (62) summarizes the results of fitting the graph (61). As shown in Table (62), when the pressure is 0.1 Torr, the total amount of nitrogen (N atm%) in the observation range of the XPS measurement was 8.8 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 5.92% of the total amount. The pyridinic type (23) was 67.24% of the total amount. The pyrroleic type (22) was 10.91% of the total amount. The graphic type (21) was 7.53% of the total amount. The pyridinic oxide type (24) was 9.39% of the total amount. The ratio of nitrogen (N) to carbon (C) (N / C ratio) was 11.1%.

[0096] When the pressure was 0.2 Torr, the total amount of nitrogen in the observation range of the XPS measurement was 7.1 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 0.56% of the total amount. The pyridinic type (23) was 66.01% of the total amount. The pyrroleic type (22) was 21.02% of the total amount. The graphic type (21) was 10.96% of the total amount. The pyridinic oxide type (24) was 3.56% of the total amount. The ratio of nitrogen (N) to carbon (C) (N / C ratio) was 8.6%.

[0097] When the pressure was 0.4 Torr, the total amount of nitrogen in the observation range of the XPS measurement was 6.8 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 4.73% of the total amount. The pyridinic type (23) was 59.92% of the total amount. The pyrroleic type (22) was 23.41% of the total amount. The graphic type (21) was 13.33% of the total amount. The pyridinic oxide type (24) was 0.78% of the total amount. The ratio of nitrogen (N) to carbon (C) (N / C ratio) was 8.2%.

[0098] When the pressure was 1.0 Torr, the total amount of nitrogen in the observation range of the XPS measurement was 8.7 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 13.76% of the total amount. The pyridinic type (23) was 57.31% of the total amount. The pyrrotic type (22) was 24.39% of the total amount. The graphic type (21) was 2.12% of the total amount. The pyridinic oxide type (24) was 3.53% of the total amount. The ratio of nitrogen (N) to carbon (C) (N / C ratio) was 11.7%.

[0099] Graph (63) graphs the ratio of nitrogen (N) to carbon (C) (N / C ratio). As shown in graph (63), with respect to pressure changes in the chamber (101) of the third process, the ratio of nitrogen (N) to carbon (C) (N / C atm% ratio) does not change significantly, and it can be said that there is not much pressure dependence. In addition, from table (62), it can be said that the total amount of nitrogen also does not change significantly and has not much pressure dependence.

[0100] From the table (62), it can be seen that the pyridinic type (23) and the pyrroleic type (22) are dominant regardless of the pressure. Additionally, the proportion of the pyrroleic type (22) increases as the pressure rises.

[0101] The graph (64) shown in FIG. 15 is the measurement result of Raman spectroscopy of the substrate (W) when only the first process is performed (Ref) and when the pressure inside the chamber (101) of the third process is changed to 0.1 Torr, 0.2 Torr, 0.4 Torr, and 1.0 Torr. Peak (65) represents the G-band, and peak (66) represents the D-band. Graph (67) shows the change in the peak (65) according to each pressure. If the peak (65) in the case where only the first process is performed (Ref) is set as the reference value 68, it can be seen that the measurement result 69 of the third process at each pressure shows that the peak shifts with increasing pressure. That is, at each pressure, it can be seen that the graphene reacts with nitrogen and the state of the graphene changes. Graph (70) shows the reference value 68, the G / D ratio at each pressure, and the film thickness (Thickness of CTR) of the center portion of the substrate (W). Also, the G / D ratio is the ratio of the G-band to the D-band. From Graph (70), the G / D ratio appears good in nitrogen-doped graphene, but it is thought to be due to the film thickness. Additionally, no clear damage was observed on the surface of the doped graphene film.

[0102] <Comparison of Sequence SE4 and SE8>

[0103] FIG. 16 is a diagram illustrating an example of a comparison of experimental results between sequence SE4 and sequence SE8. Graph (71) shown in FIG. 16 represents the results of XPS measurements of a substrate (W) that has undergone sequence SE8, with the processing time of the first process set to 75 seconds and the pressure inside the chamber (101) of the third and fourth processes set to 1.0 Torr. Additionally, graph (71) is data excluding background components. Graph (72) represents N (nitrogen) that has reacted with Si (silicon) of the substrate (W). Graph (73) represents the pyridinic type (23). Graph (74) represents the pyrroleic type (22). Graph (75) represents the graphic type (21). Graph (76) represents the pyridinic oxide type (24). Graph (77) is the sum of graphs (72 to 76). In addition, the graph of the XPS measurement result of sequence SE4 is omitted because it is the same as the graph (53) of FIG. 13.

[0104] Table (78) summarizes the results of sequence SE4 and sequence SE8. As shown in Table (78), for sequence SE4, the total amount of nitrogen (N atm%) in the observation range of XPS measurement was 8.7 atm%. The nitrogen (N) that reacted with the Si of the substrate (W) was 13.8% of the total amount. The pyridinic type (23) was 57.3% of the total amount. The pyrroleic type (22) was 24.4% of the total amount. The graphitic type (21) was 2.1% of the total amount. The pyridinic oxide type (24) was 3.5% of the total amount. Additionally, for sequence SE4, the processing time of the first process is set to 75 seconds, and the pressure inside the chamber (101) of the third process is set to 1.0 Torr.

[0105] In the case of sequence SE8, the total amount of nitrogen in the observation range of the XPS measurement was 5.2 atm%. The nitrogen (N) corresponding to graph (72) was 9.9% of the total amount. The pyridinic type (23) corresponding to graph (73) was 50.7% of the total amount. The pyrroleic type (22) corresponding to graph (74) was 29.7% of the total amount. The graphic type (21) corresponding to graph (75) was 14.5% of the total amount. The pyridinic oxide type (24) corresponding to graph (76) was 1.6% of the total amount. Additionally, the ratio of the total amount corresponds to the area ratio in graph (71).

[0106] When comparing the results of sequence SE4 and sequence SE8, the proportion of the graphical type (21) increases in sequence SE8. Also, it can be seen that there is no change in sequence SE4 and sequence SE8 in that the pyridinic type (23) and pyrroleic type (22) are dominant.

[0107] <Comparison of Sequence SE9 and SE10>

[0108] FIG. 17 is a diagram illustrating an example of a comparison of experimental results between sequence SE9 and sequence SE10. Graph (79) shown in FIG. 17 represents the results of XPS measurements of a substrate (W) that has undergone sequence SE9, with the processing time of the second process set to 80 seconds and the pressure inside the chamber (101) of the third and fourth processes set to 1.0 Torr. Additionally, graph (79) is data excluding background components. Graph (80) represents N (nitrogen) that has reacted with Si (silicon) of the substrate (W). Graph (81) represents the pyridinic type (23). Graph (82) represents the pyrroleic type (22). Graph (83) represents the graphic type (21). Graph (84) represents the pyridinic oxide type (24). Graph (85) is the sum of graphs (80 to 84).

[0109] Graph (86) shows the results of XPS measurements of a substrate (W) that has undergone sequence SE10 with the processing time of the first process set to 48 seconds, the processing time of the second process set to 30 seconds, and the pressure inside the chamber (101) of the third and fourth processes set to 1.0 Torr. Additionally, Graph (86) is data excluding background components. Graph (87) shows N (nitrogen) that has reacted with Si (silicon) of the substrate (W). Graph (88) shows the pyridinic type (23). Graph (89) shows the pyrroleic type (22). Graph (90) shows the graphic type (21). Graph (91) shows the pyridinic oxide type (24). Graph (92) is the sum of Graphs (87 to 91).

[0110] Table (93) summarizes the results of sequence SE9 and sequence SE10. As shown in Table (93), for sequence SE9, the total amount of nitrogen (N atm%) in the observation range of XPS measurement was 9.36 atm%. The nitrogen (N) corresponding to graph (80) was 19.44% of the total amount. The pyridinic type (23) corresponding to graph (81) was 64.45% of the total amount. The pyrroleic type (22) corresponding to graph (82) was 8.97% of the total amount. The graphic type (21) corresponding to graph (83) was 3.59% of the total amount. The pyridinic oxide type (24) corresponding to graph (84) was 2.29% of the total amount. Additionally, the ratio of the total amount corresponds to the area ratio in graph (79).

[0111] In the case of sequence SE10, the total amount of nitrogen in the observation range of the XPS measurement was 9.88 atm%. The nitrogen (N) corresponding to graph (87) was 32.07% of the total amount. The pyridinic type (23) corresponding to graph (88) was 37.51% of the total amount. The pyrroleic type (22) corresponding to graph (89) was 15.38% of the total amount. The graphic type (21) corresponding to graph (90) was 12.00% of the total amount. The pyridinic oxide type (24) corresponding to graph (91) was 3.31% of the total amount. Additionally, the ratio of the total amount corresponds to the area ratio in graph (86).

[0112] When comparing the results of sequence SE9 and sequence SE10, it can be seen that sequence SE10 has a relatively higher proportion of graphic type (21). Also, in sequence SE9, it can be seen that the proportion of pyridinic type (23) is particularly high. As shown in the experimental results described above, the positional ratio of nitrogen dope to the graphene film can be controlled by using each sequence.

[0113] In addition, in the above-described embodiment, the cleaning process was performed for each wafer of the substrate (W) to be processed, but the cleaning process may also be performed after processing multiple substrates (W) for each lot, for example.

[0114] According to the above embodiment, the film formation device (1) has a processing vessel (chamber (101)) capable of receiving a substrate (W) and a control unit (11). The control unit (11) performs a process of bringing the substrate (W) into the processing vessel, a first process of forming a graphene film on the substrate (W) using a plasma of a first processing gas containing a carbon-containing gas, and a second process of forming a doped graphene film on one or more of the substrate (W) and the graphene film using a plasma of a second processing gas containing a dopant gas. As a result, the positional ratio of the nitrogen dope to the graphene film can be controlled.

[0115] In addition, according to the present embodiment, the first treatment gas includes a hydrogen-containing gas of a first flow rate. As a result, the formation of the graphene film can be controlled.

[0116] In addition, according to the present embodiment, the second treatment gas includes the first treatment gas. As a result, the plasma can be transferred from the first process to the second process while being maintained.

[0117] In addition, according to the present embodiment, the second process forms a doped graphene film with a plasma of a second treatment gas that intermittently supplies a dopant gas. As a result, the proportion of the pyridinic type (23) can be increased.

[0118] In addition, according to the present embodiment, the second process supplies a second flow rate of hydrogen-containing gas before the supply of intermittently supplied dopant gas. As a result, the ratio of graphic type (21) and pyridinic type (23) can be increased.

[0119] In addition, according to the present embodiment, there is also a third process for treating one or more films among a graphene film and a doped graphene film with a plasma of a third treatment gas comprising a dopant gas and an argon gas. As a result, the positional ratio of the nitrogen dope to the graphene film can be controlled.

[0120] In addition, according to the present embodiment, the first treatment gas includes a dopant gas, and the second treatment gas includes argon gas. As a result, the position ratio of the nitrogen dope to the graphene film can be controlled.

[0121] In addition, according to the present embodiment, there is also a fourth process for treating one or more films among a graphene film and a doped graphene film with a plasma of a fourth treatment gas that includes a dopant gas and does not include argon gas. As a result, the positional ratio of the nitrogen dope to the graphene film can be controlled.

[0122] In addition, according to the present embodiment, the dopant gas comprises one or more of nitrogen and boron. As a result, the positional ratio of one or more of the dopes of nitrogen and boron to the graphene film can be controlled.

[0123] In addition, according to the present embodiment, the flow rate of the second treatment gas in the second process is different from the flow rate of the first treatment gas in the first process. As a result, the positional ratio of the nitrogen dope to the graphene film can be controlled.

[0124] In addition, according to the present embodiment, the plasma is a microwave plasma. As a result, by using N2 gas as the dopant gas, nitrogen doping with low ion energy and low damage can be realized. Furthermore, the positional ratio of the nitrogen doping to the graphene film can be controlled.

[0125] The embodiments disclosed herein are illustrative in all respects and should not be considered restrictive. The above-described embodiments may be omitted, substituted, or modified in various forms without departing from the appended claims and their common knowledge.

[0126] In addition, in the above-described embodiment, a film deposition apparatus (1) that performs etching or film deposition on a substrate (W) using microwave plasma as a plasma source has been described as an example, but the disclosed technology is not limited to this. If the apparatus performs treatment on a 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, magnetron plasma, etc., can be used.

[0127] In addition, the present disclosure may also have the following configuration.

[0128] (1)

[0129] As a method for forming a graphene film,

[0130] A loading process for bringing a substrate into a processing container, and

[0131] A first process for forming the graphene film on the substrate using a plasma of a first treatment gas containing a carbon-containing gas, and

[0132] A second process for forming a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second treatment gas containing a dopant gas.

[0133] The tabernacle method having

[0134] (2)

[0135] The above first treatment gas comprises a hydrogen-containing gas of a first flow rate,

[0136] The tabernacle method described in (1) above.

[0137] (3)

[0138] The second treatment gas above comprises the first treatment gas,

[0139] The tabernacle method described in (1) or (2) above.

[0140] (4)

[0141] The second process above forms the doped graphene film using a plasma of the second treatment gas that intermittently supplies the dopant gas.

[0142] The tabernacle method described in any one of (1) to (3) above.

[0143] (5)

[0144] The second process above supplies a hydrogen-containing gas of a second flow rate before supplying the dopant gas that is supplied intermittently.

[0145] The tabernacle method described in (4) above.

[0146] (6)

[0147] Additionally, having a third process for treating one or more films among the graphene film and the doped graphene film with a plasma of a third treatment gas comprising the dopant gas and argon gas,

[0148] The tabernacle method described in any one of (1) to (5) above.

[0149] (7)

[0150] The first treatment gas above includes the dopant gas, and

[0151] The above second treatment gas includes argon gas.

[0152] The tabernacle method described in (1) above.

[0153] (8)

[0154] Additionally, having a fourth process for treating one or more of the graphene film and the doped graphene film with a plasma of a fourth treatment gas that includes the dopant gas and does not include argon gas,

[0155] The tabernacle method described in any one of (1) to (7) above.

[0156] (9)

[0157] The above dopant gas comprises one or more of nitrogen and boron,

[0158] The tabernacle method described in any one of (1) to (8) above.

[0159] (10)

[0160] The flow rate of the second treatment gas in the second process is a flow rate different from the flow rate of the first treatment gas in the first process,

[0161] The tabernacle method described in any one of (1) to (9) above.

[0162] (11)

[0163] The above plasma is a microwave plasma.

[0164] The tabernacle method described in any one of (1) to (10) above.

[0165] (12)

[0166] As a tabernacle apparatus,

[0167] A processing container capable of accommodating a substrate, and

[0168] Having a control unit,

[0169] The above control unit is configured to control the film formation device to bring the substrate into the processing vessel, and

[0170] The above control unit is configured to control the film formation device to form a graphene film on the substrate using a plasma of a first treatment gas containing a carbon-containing gas, and

[0171] The above control unit is configured to control the film formation device to form a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second treatment gas containing a dopant gas.

[0172] Tabernacle apparatus. Explanation of the symbols

[0173] 1: Tabernacle Equipment 11: Control unit 20: Grain 21: Graphic type 22: Pyrrolic type 23: Pyridinic type 24: Pyridinic oxide type 101: Chamber 102: Stage 103: Microwave introduction mechanism 104: Gas supply equipment 105: Exhaust device SE1 to SE11: Sequence W: Substrate

Claims

Claim 1 A film deposition method for forming a graphene film, comprising: a step of introducing a substrate into a processing vessel; a first step of forming the graphene film on the substrate using a plasma of a first processing gas containing a carbon-containing gas; and a second step of forming a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second processing gas containing a dopant gas while maintaining the plasma of the first processing gas after the first step. Claim 2 A film formation method according to claim 1, wherein the first treatment gas comprises a hydrogen-containing gas of a first flow rate. Claim 3 A film formation method according to claim 1 or 2, wherein the second treatment gas comprises the first treatment gas. Claim 4 In claim 1, the second process is a film formation method in which the doped graphene film is formed using a plasma of the second treatment gas that intermittently supplies the dopant gas. Claim 5 In paragraph 4, the second process is a film formation method in which a second flow rate of hydrogen-containing gas is supplied before the supply of the dopant gas that is supplied intermittently. Claim 6 A film formation method according to claim 1, further comprising a third process of treating one or more films among the graphene film and the doped graphene film with a plasma of a third treatment gas including the dopant gas and argon gas. Claim 7 A film formation method according to claim 1, wherein the first treatment gas comprises the dopant gas and the second treatment gas comprises argon gas. Claim 8 A film formation method according to claim 1, further comprising a fourth process of treating one or more of the graphene film and the doped graphene film with a plasma of a fourth treatment gas that includes the dopant gas and does not include argon gas. Claim 9 A film formation method according to claim 1, wherein the dopant gas comprises one or more of nitrogen and boron. Claim 10 A film formation method according to claim 1, wherein the flow rate of the second treatment gas in the second process is a different flow rate from the flow rate of the first treatment gas in the first process. Claim 11 In claim 1, the plasma is a microwave plasma, a film formation method. Claim 12 A film deposition device comprising a processing vessel capable of receiving a substrate and a control unit, wherein the control unit is configured to control the film deposition device to bring the substrate into the processing vessel, wherein the control unit is configured to control the film deposition device to form a graphene film on the substrate using a plasma of a first processing gas containing a carbon-containing gas, and wherein the control unit is configured to control the film deposition device to form a doped graphene film on one or more of the substrate and the graphene film using a plasma of a second processing gas containing a dopant gas while maintaining the plasma of the first processing gas after the graphene film is formed.

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