Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus and program

Abstract

To provide a technology capable of improving the electrical properties of metallic films.SOLUTION: According to an aspect of the present disclosure, there is provided a technology comprising the steps of (a) carrying a substrate into a processing vessel at a carrying-in temperature, (b) bringing the processing vessel to a deposition temperature, (c) supplying a processing gas into the processing vessel to form a metal film on a surface of the substrate, (d) bringing the processing vessel to a carry-out temperature lower than the carrying-in temperature and (e) removing the substrate from the processing vessel.SELECTED DRAWING: Figure 3

Description

Technical Field

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[0001] The present disclosure is a technology effective when applied to a substrate processing method, a method for manufacturing a semiconductor device, a substrate processing apparatus, and a program.

Background Art

[0002] A metal film is used as a word line of a three-dimensional structure NAND type flash memory. In addition, as the metal film, for example, a Mo-containing film containing molybdenum (Mo) may be used (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] This disclosure provides a technology capable of improving the electrical properties of a metal film. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a longitudinal cross-sectional view showing a schematic of a substrate processing apparatus in one embodiment of the present disclosure. [Figure 2] Figure 2 is a schematic diagram of the controller of a substrate processing apparatus in one embodiment of the present disclosure, and shows the controller's control system in block diagram form. [Figure 3] Figure 3 is a flowchart illustrating a first example of a semiconductor device manufacturing method according to the substrate processing method of this disclosure. [Figure 4] Figure 4 is a flowchart illustrating a method for manufacturing a semiconductor device according to a second example of the substrate processing method of the present disclosure. [Modes for carrying out the invention]

[0009] The following explanation will be based on drawings. However, in the following explanation, the same reference numerals will be used for identical components, and repeated explanations may be omitted. In addition, the drawings may be more schematic than the actual embodiments in order to make the explanation clearer, but they are merely examples and do not limit the interpretation of this disclosure. Furthermore, all drawings used in the following explanation are schematic, and the dimensional relationships and ratios of each element shown in the drawings may not necessarily match those of reality. Also, the dimensional relationships and ratios of each element may not necessarily match between multiple drawings.

[0010] (1) Configuration of substrate processing apparatus The substrate processing apparatus 10 includes a processing furnace 202 equipped with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 is cylindrical in shape and is mounted vertically by being supported by a heater base (not shown) which serves as a holding plate.

[0011] Inside the heater 207, an outer tube 203 is arranged concentrically with the heater 207 to form a reaction vessel (processing vessel). The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (inlet flange) 209 is arranged concentrically with the outer tube 203. The manifold 209 is made of a metal such as stainless steel (SUS) and is formed in a cylindrical shape with open upper and lower ends. An O-ring 220a is provided between the upper end of the manifold 209 and the outer tube 203 as a sealing member. The manifold 209 is supported by the heater base, so that the outer tube 203 is installed vertically.

[0012] An inner tube 204, which constitutes the processing container, is arranged inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. The processing container is mainly composed of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical part of the processing container (inside the inner tube 204).

[0013] The processing chamber 201 is configured to accommodate wafers 200 as substrates, arranged in a horizontal position in multiple vertical layers by boats 217, which will be described later.

[0014] Within the processing chamber 201, nozzles 410 and 420 are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. Gas supply pipes 310 and 320 are connected to the nozzles 410 and 420, respectively. However, the processing furnace 202 of this embodiment is not limited to the above configuration.

[0015] Gas supply pipes 310 and 320 are equipped with flow controllers (flow control units), namely mass flow controllers (MFCs) 312 and 322, respectively, from upstream to downstream. Gas supply pipes 310 and 320 are also equipped with on-off valves, namely valves 314 and 324, respectively. Downstream of valves 314 and 324 on gas supply pipes 310 and 320, gas supply pipes 510 and 520, respectively, which supply inert gas. Gas supply pipes 510 and 520 are equipped with flow controllers (flow control units), namely MFCs 512 and 522, and on-off valves, namely valves 514 and 524, respectively, from upstream to downstream.

[0016] Nozzles 410 and 420 are connected to the ends of the gas supply pipes 310 and 320, respectively. The nozzles 410 and 420 are configured as L-shaped nozzles, with their horizontal portions penetrating the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410 and 420 are located inside a channel-shaped (groove-shaped) spare chamber 201a that protrudes radially outward from the inner tube 204 and extends vertically. Within the spare chamber 201a, the nozzles are positioned upward (upward in the direction of wafer 200 arrangement) along the inner wall of the inner tube 204.

[0017] The nozzles 410 and 420 are provided to extend from the lower region to the upper region of the processing chamber 201, and each has multiple gas supply holes 410a and 420a located opposite the wafer 200. This allows processing gas to be supplied to the wafer 200 from the gas supply holes 410a and 420a of the nozzles 410 and 420, respectively. These gas supply holes 410a and 420a are provided in multiple locations extending from the lower to the upper part of the inner tube 204, each having the same opening area and the same opening pitch. However, the gas supply holes 410a and 420a are not limited to the above configuration. For example, the opening area may be gradually increased from the lower to the upper part of the inner tube 204. This makes it possible to more uniformly distribute the flow rate of the gas supplied from the gas supply holes 410a and 420a.

[0018] The gas supply holes 410a and 420a of the nozzles 410 and 420 are provided in plurality at positions corresponding to the height from the lower part to the upper part of the boat 217 described later. Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410a and 420a of the nozzles 410 and 420 is supplied to the entire area of the wafer 200 accommodated from the lower part to the upper part of the boat 217. The nozzles 410 and 420 may be provided so as to extend from the lower region to the upper region of the processing chamber 201, but it is preferable that they are provided so as to extend up to near the ceiling of the boat 217.

[0019] From the gas supply pipe 310, a raw material gas is supplied into the processing chamber 201 as a processing gas via the MFC 312, the valve 314, and the nozzle 410.

[0020] From the gas supply pipe 320, a reducing gas is supplied into the processing chamber 201 as a processing gas via the MFC 322, the valve 324, and the nozzle 420.

[0021] From the gas supply pipes 510 and 520, an inert gas is supplied into the processing chamber 201 via the MFCs 512 and 522, the valves 514 and 524, and the nozzles 410 and 420, respectively. The inert gas can also be referred to as a carrier gas.

[0022] Mainly, the processing gas supply system 300 is constituted by the gas supply pipes 310 and 320, the MFCs 312 and 322, and the valves 314 and 324. Also, the nozzles 410 and 420 may be considered to be included in the processing gas supply system 300. The processing gas supply system 300 may simply be referred to as a gas supply system. When flowing a Mo-containing gas from the gas supply pipe 310, mainly, a Mo-containing gas supply system is constituted by the gas supply pipe 310, the MFC 312, and the valve 314. Also, the nozzle 410 may be considered to be included in the Mo-containing gas supply system. When flowing a reducing gas from the gas supply pipe 320, mainly, a reducing gas supply system is constituted by the gas supply pipe 320, the MFC 322, and the valve 324. Also, the nozzle 420 may be considered to be included in the reducing gas supply system. Also, mainly, the inert gas supply system is constituted by the gas supply pipes 510 and 520, the MFCs 512 and 522, and the valves 514 and 524.

[0023] High thermal conductivity gas is supplied from the gas supply pipe 330 into the processing chamber 201 via the MFC 332, valve 334, and nozzle 420. The high thermal conductivity gas supply system mainly consists of the gas supply pipe 330, MFC 332, and valve 334. Alternatively, the nozzle 420 may be considered as part of the high thermal conductivity gas supply system. Alternatively, the gas supply pipe 330, MFC 332, and valve 334 may be considered as part of the processing gas supply system 300.

[0024] Furthermore, if a reducing gas with high thermal conductivity is supplied as a reducing gas from the gas supply pipe 320, the gas supply pipe 330, MFC 332, and valve 334 may be omitted. In this case, the reducing gas supply system may be mainly composed of the gas supply pipe 320, MFC 322, and valve 324, or it may be composed of a high thermal conductivity gas supply system, or it may be composed of a reducing gas with high thermal conductivity. The nozzle 420 may also be considered as part of the reducing gas supply system, the high thermal conductivity gas supply system, or the reducing gas with high thermal conductivity supply system. By using a reducing gas with high thermal conductivity, the supply system can be simplified compared to supplying the reducing gas and the high thermal conductivity gas separately.

[0025] In this embodiment, the gas supply method involves transporting gas through nozzles 410 and 420 located in a preliminary chamber 201a within a vertically elongated, annular space defined by the inner wall of the inner tube 204 and the edges of multiple wafers 200. The gas is then ejected into the inner tube 204 from multiple gas supply holes 410a and 420a located on the nozzles 410 and 420, facing the wafers. More specifically, the gas supply holes 410a of nozzle 410 and 420a of nozzle 420 eject the processing gas in a direction parallel to the surface of the wafers 200.

[0026] The exhaust port (exhaust vent) 204a is a through-hole formed in the side wall of the inner tube 204, opposite the nozzles 410 and 420, and is, for example, a slit-shaped through-hole that is elongated vertically. The gas supplied into the processing chamber 201 from the gas supply holes 410a and 420a of the nozzles 410 and 420, and flowing over the surface of the wafer 200, flows through the exhaust port 204a into the exhaust passage 206, which is formed in the gap between the inner tube 204 and the outer tube 203. The gas that has flowed into the exhaust passage 206 then flows into the exhaust pipe 231 and is discharged outside the processing furnace 202.

[0027] The exhaust port 204a is located opposite to the multiple wafers 200, and the gas supplied from the gas supply ports 410a and 420a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally before flowing into the exhaust passage 206 through the exhaust port 204a. The exhaust port 204a is not limited to being a slit-shaped through-hole, but may also be composed of multiple holes.

[0028] The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere inside the processing chamber 201. Connected to the exhaust pipe 231, in order from upstream, are a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum evacuation device. The APC valve 243 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation inside the processing chamber 201, and furthermore, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening while the vacuum pump 246 is operating. The exhaust system mainly consists of the exhaust port 204a, exhaust passage 206, exhaust pipe 231, APC valve 243, and pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0029] Below the manifold 209, a seal cap 219 is provided, which serves as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is configured to abut the lower end of the manifold 209 from the vertically downward side. The seal cap 219 is made of a metal such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that abuts the lower end of the manifold 209. On the opposite side of the processing chamber 201 in the seal cap 219, a rotating mechanism 267 is installed to rotate a boat 217 that houses the wafers 200. The rotating shaft 255 of the rotating mechanism 267 is connected to the boat 217 by passing through the seal cap 219. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed vertically outside the outer tube 203 as an loading / unloading mechanism (lifting mechanism). The boat elevator 115 is configured to load and unload the boat 217 into and out of the processing chamber 201 by raising and lowering the seal cap 219. The boat elevator 115 is configured as a transport device (transport system) that transports the boat 217 and the wafer 200 contained in the boat 217 into and out of the processing chamber 201.

[0030] The boat 217, which serves as a substrate support, is configured to hold multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position, with their centers aligned and spaced apart vertically. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, a heat-insulating plate 218, also made of a heat-resistant material such as quartz or SiC, is supported in multiple stages (not shown) in a horizontal position. This configuration makes it difficult for heat from the heater 207 to be transferred to the seal cap 219. However, this embodiment is not limited to the above configuration. For example, instead of providing a heat-insulating plate 218 at the bottom of the boat 217, a heat-insulating cylinder, which is a cylindrical member made of a heat-resistant material such as quartz or SiC, may be provided.

[0031] In this disclosure, numerical ranges such as "25 to 200 sheets" mean that the lower and upper limits are included within that range. Therefore, for example, "25 to 200 sheets" means "25 sheets or more and 200 sheets or less." The same applies to other numerical ranges.

[0032] A temperature sensor 263 is installed inside the inner tube 204 as a temperature detector. The amount of current supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263 so that the temperature inside the processing chamber 201 reaches a desired temperature distribution. The temperature sensor 263 is configured in an L-shape, similar to the nozzles 410 and 420, and is installed along the inner wall of the inner tube 204.

[0033] As shown in Figure 2, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121.

[0034] The storage device 121c is composed of, for example, flash memory, an HDD (Hard Disk Drive), etc. The storage device 121c contains, in a readable format, a control program that controls the operation of the substrate processing device, and a process recipe that describes the procedures and conditions for the semiconductor device manufacturing method, which will be described later. The process recipe is a combination of steps that cause the controller 121 to execute each step in the semiconductor device manufacturing method, which will be described later, and to obtain a predetermined result; it functions as a program. Hereinafter, this process recipe, control program, etc., will be collectively referred to simply as a program. In this specification, the term "program" may include only the process recipe, only the control program, or a combination of the process recipe and the control program. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0035] I / O port 121d is connected to the aforementioned MFCs 312, 322, 332, 512, 522, valves 314, 324, 334, 514, 524, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotary mechanism 267, boat elevator 115, etc.

[0036] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read recipes and other information from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control operations such as adjusting the flow rate of various gases by MFCs 312, 322, 512, and 522, opening and closing valves 314, 324, 514, and 524, opening and closing APC valve 243 and pressure adjustment operation based on pressure sensor 245 by APC valve 243, temperature adjustment operation of heater 207 based on temperature sensor 263, starting and stopping vacuum pump 246, rotating mechanism 267 for rotation and rotation speed adjustment operation of boat 217, raising and lowering operation of boat 217 by boat elevator 115, and loading wafers 200 into boat 217, in accordance with the contents of the read recipe.

[0037] The controller 121 can be configured by installing the above-mentioned program, stored in an external storage device (for example, magnetic tape, magnetic disks such as flexible disks or hard disks, optical disks such as CDs or DVDs, magneto-optical disks such as MOs, or semiconductor memory such as USB memory or memory cards) 123, into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, a recording media may include only the storage device 121c, only the external storage device 123, or both. The program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0038] (2) Substrate processing process (Example of a substrate processing method) As one step in the manufacturing process of semiconductor devices, an example of a substrate processing method for forming a metal film, specifically a transition metal element-containing film containing molybdenum (Mo), a group 6 element-containing film, on a wafer 200 on which a metal insulating film, specifically an aluminum oxide film (Al2O3 film, hereinafter also referred to as an AlO film), has been formed, will be explained with reference to Figure 3. In Figure 3, the vertical axis shows temperature and the horizontal axis shows time. The process of forming the Mo-containing film is carried out using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following explanation, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121.

[0039] The substrate processing step (semiconductor manufacturing step) according to this embodiment is, for example, (a) A process of loading the wafer 200 into the processing chamber 201, which is a processing container at the loading temperature (T1) (loading process), (b) A step to bring the processing chamber 201 to the film deposition temperature (T2) (first temperature control step), (c) A process of supplying a processing gas into the processing chamber 201 and forming a metal film on the surface of the wafer 200 (film formation process), (d) A process to bring the temperature inside the processing chamber 201 to an outlet temperature (T3) that is lower than the input temperature (T1) (cooling process), (e) A process of removing the wafer 200 from the processing room 201 (removal process), It has.

[0040] In this specification, the term "wafer" may mean "the wafer itself" or "a laminate of a wafer and a predetermined layer or film formed on its surface." In this specification, the term "surface of a wafer" may mean "the surface of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer." In this specification, the phrase "form a predetermined layer on a wafer" may mean directly forming a predetermined layer on the surface of the wafer itself or forming a predetermined layer on top of a layer already formed on the wafer. In this specification, the term "substrate" has the same meaning as the term "wafer."

[0041] In this specification, processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201 (processing container), and processing pressure refers to the pressure inside the processing chamber 201. Processing time refers to the duration for which the processing is continued. These terms also apply in the following descriptions.

[0042] (a) Delivery process Once multiple wafers 200 are loaded into the boat 217 (wafer charging), as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading), and then placed in the processing container. In this state, the seal cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220. At this time, the processing chamber 201 is heated by the heater 207 to reach the loading temperature T1. The loading temperature T1 is set to, for example, 150°C to 500°C, preferably 200°C to 450°C, and more preferably 300°C to 450°C.

[0043] (b) First temperature adjustment process (first temperature adjustment process) The processing chamber 201 is heated by the heater 207 so that the inside reaches the film deposition temperature T2. At this time, the amount of power supplied to the heater 207 is feedback-controlled (temperature adjustment or temperature control) based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has a desired temperature distribution. The temperature of the heater 207 is raised so that the temperature inside the processing chamber 201, that is, the temperature of the wafer 200, is raised from, for example, the input temperature T1 to the film deposition temperature T2. The film deposition temperature T2 is set to, for example, 300°C to 600°C, preferably 350 to 550°C, and more preferably 400 to 500°C. Furthermore, heating inside the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.

[0044] At this time, hydrogen (H2) gas, which is a hydrogen (H)-containing gas, and at least one inert gas may be supplied into the processing chamber 201. For example, only H2 gas may be supplied, only an inert gas may be supplied, or both may be supplied. Below, an example in which argon (Ar) gas is used as the inert gas will be described. In this example, H2 gas is supplied into the processing chamber 201 mainly via the gas supply pipe 320, MFC 322, valve 324, and nozzle 420. Ar gas is supplied into the processing chamber 201 mainly via the gas supply pipe 520, MFC 522, valve 524, and nozzle 420.

[0045] Here, H2 gas can be considered a reducing gas. That is, in at least a part of the first temperature control process, a reducing gas is supplied into the processing container. This allows the surface of the wafer 200 to be reduced while the temperature is controlled, thereby reducing the concentration of impurities in the metal film formed on the wafer 200. Here, impurities in the film refer to elements that are not included in the chemical composition of the target film. If the film is a film of a single metal element, elements other than the metal element may be impurities. Specifically, in the case of a Mo film, elements other than Mo are impurities, such as H, chlorine (Cl), and oxygen (O), or at least one of these.

[0046] Furthermore, H2 gas can be considered a highly thermally conductive gas. That is, a highly thermally conductive gas is supplied into the processing chamber in at least part of the first temperature control process. When a highly thermally conductive gas is supplied into the processing chamber 201, the amount of heat conducted per unit time from the heater 207 to the gas in the processing chamber 201 increases. Also, when a highly thermally conductive gas is supplied into the processing chamber 201, the amount of heat conducted per unit time from the gas in the processing chamber 201 to the wafer 200 increases. As a result, the temperature of the gas in the processing chamber 201 and the temperature of the wafer 200 rise in a shorter time than when a highly thermally conductive gas is not supplied into the processing chamber 201. In other words, the time required for temperature control in the processing chamber 201 is shortened.

[0047] Furthermore, H2 gas can be considered a highly thermally conductive gas with reducing properties. In other words, a highly thermally conductive gas with reducing properties is supplied into the processing container in at least a part of the first temperature control process. This allows the temperature inside the processing chamber 201 to be controlled in a short time while reducing the surface of the wafer 200.

[0048] Furthermore, the flow rate of the reducing gas (H2 gas) may be gradually increased in at least a portion of the first temperature control process, for example, in the latter half of the first temperature control process. By increasing the concentration of the reducing gas in the processing chamber 201, the reduction reaction can be further promoted while the temperature inside the processing chamber 201 can be controlled in a short time. Also, the flow rate of the high thermal conductivity gas may be gradually increased in at least a portion of the first temperature control process, for example, in the latter half of the first temperature control process. This prevents abrupt changes in the temperature inside the processing chamber 201 and the wafer 200. Therefore, the thermal stress on the surface of the wafer 200 is reduced, and pattern deformation of the wafer 200 can be suppressed.

[0049] When supplying H2 gas into the processing chamber 201 to perform the first temperature control process, if the pressure inside the processing chamber 201 is less than 4000 Pa, it may be difficult to obtain the effect of shortening the temperature control time. If it is 4000 Pa or higher, a sufficient effect of shortening the temperature control time can be obtained. Furthermore, if it is 6000 Pa or higher, an even greater effect of shortening the temperature control time can be obtained. In addition, if it is higher than 13000 Pa, the wafer 200 may be etched by by-products generated when the H2 gas reduces the wafer 200. If it is 13000 Pa or lower, etching by by-products can be suppressed. Furthermore, if it is 11000 Pa or lower, etching by by-products can be sufficiently suppressed. Therefore, it is preferable that the pressure inside the processing chamber 201 be between 4000 Pa and 13000 Pa, and more preferably between 6000 Pa and 11000 Pa.

[0050] When H2 gas is supplied in the first temperature control process, the substrate is reduced during the heating process, which may cause unintended reduction reactions in some substrates, resulting in differences in the amount of reduction between substrates. To suppress such effects, only an inert gas may be supplied in the first temperature control process, only a highly thermally conductive gas without reducing properties may be supplied, or both may be supplied.

[0051] Furthermore, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated by the vacuum pump 246 to the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled (pressure adjustment) based on this measured pressure information. The vacuum pump 246 is kept running continuously, at least until the processing of the wafer 200 is completed.

[0052] (f) Film deposition preparation process Next, a step of supplying a high thermal conductivity gas into the processing chamber 201 (film formation preparation step) may be performed. That is, the high thermal conductivity gas may be supplied into the processing container. As the high thermal conductivity gas, for example, H2 gas can be used. Note that the film formation preparation step is preferably performed when a gas other than the high thermal conductivity gas is supplied in the first temperature control step.

[0053] Here, consider a case where, in the first temperature control step, a gas other than the high thermal conductivity gas, such as Ar gas, is supplied, and then, in the film formation step described later, a high thermal conductivity gas having reducibility (for example, H2 gas) is supplied to the wafer 200 as a reducing gas. In this case, due to the difference in the thermal conductivity of the gas supplied into the processing chamber 201 in the first temperature control step and the film formation step, the substrate temperature of the wafer 200 may change rapidly. As a result, thermal stress may occur on the surface of the wafer 200, and the pattern formed on the surface of the wafer 200 may be damaged (pattern collapse may occur). By performing the film formation preparation step, the difference in the thermal conductivity of the gas supplied into the processing chamber 201 in the first temperature control step and the film formation step can be reduced. Therefore, the thermal stress on the surface of the wafer 200 as described above can be reduced, and pattern collapse can be suppressed.

[0054] Also, in at least a part of the film formation preparation step, the supply amount of the high thermal conductivity gas may be increased. Thereby, the rapid temperature change of the wafer 200 is suppressed, and the thermal stress is reduced, so that the pattern collapse of the wafer 200 can be suppressed.

[0055] (c) Film formation step In the film formation step, a processing gas is supplied into the processing chamber 201, and a metal film is formed on the surface of the wafer 200. At this time, the processing chamber 201 is heated by the heater 207 so that the film formation temperature T2 is reached. The film formation temperature T2 is set to a temperature higher than the loading temperature T1 (T1 < T2). The film formation temperature T2 is, for example, a temperature within the range of 300°C or higher and 600°C or lower, preferably set to a temperature of 350°C or higher and 550°C or lower, more preferably 400°C or higher and 500°C or lower.

[0056] The film formation process is carried out including the following steps: (c1) supplying a metal-containing gas, (c2) removing residual gas, (c3) supplying a reducing gas, (c4) removing residual gas, and (c5) performing the process a predetermined number of times.

[0057] (c1) Metal-containing gas supply process Valve 314 is opened, and the metal-containing gas, which is the raw material gas used as the processing gas, flows into the gas supply pipe 310. The following describes an example in which Mo-containing gas is used as the metal-containing gas. The flow rate of the Mo-containing gas is adjusted by MFC 312 and supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410, and exhausted from the exhaust pipe 231. At this time, the Mo-containing gas is supplied to the wafer 200. At the same time, valve 514 is opened, and Ar gas flows into the gas supply pipe 510. The Ar gas that has flowed through the gas supply pipe 510 is adjusted by MFC 512, supplied into the processing chamber 201 together with the Mo-containing gas, and exhausted from the exhaust pipe 231. Also at this time, in order to prevent the Mo-containing gas from entering the nozzle 420, valve 524 is opened, and Ar gas flows into the gas supply pipe 520. The Ar gas is supplied into the processing chamber 201 via the gas supply pipe 320 and nozzle 420, and exhausted from the exhaust pipe 231.

[0058] At this time, it is preferable to adjust the APC valve 243 to set the pressure in the processing chamber 201 to a pressure within the range of, for example, 4000 Pa to 11000 Pa. The supply flow rate of the metal-containing gas controlled by the MFC 312 is set to a flow rate within the range of, for example, 0.1 to 1.0 slm, preferably 0.3 to 0.9 slm. The supply flow rates of the Ar gas controlled by the MFCs 512 and 522 are set to a flow rate within the range of, for example, 0.1 to 20 slm, respectively.

[0059] By supplying Mo-containing gas, a Mo-containing layer is formed as a metal-containing layer on the wafer 200 (the AlO film which is the underlying surface film). The Mo-containing layer may be a Mo layer containing Cl, O, and H, or it may be an adsorbed layer of Mo-containing gas, or it may contain both.

[0060] (c2) Residual gas removal process After a predetermined time has elapsed since the start of supplying the Mo-containing gas, for example, 0.01 to 60 seconds, the valve 314 of the gas supply pipe 310 is closed to stop the supply of the Mo-containing gas. In other words, the time for which the Mo-containing gas is supplied to the wafer 200 is, for example, within the range of 0.01 to 60 seconds. At this time, the APC valve 243 of the exhaust pipe 231 is left open, and the processing chamber 201 is evacuated using the vacuum pump 246. That is, the processing chamber 201 is purged. At this time, valves 514 and 524 are left open to maintain the supply of Ar gas into the processing chamber 201. The Ar gas acts as a purge gas and can enhance the effect of removing unreacted or metal-containing gas that has contributed to the formation of the metal layer remaining in the processing chamber 201.

[0061] (c3) Reducing gas supply process After removing residual gas from the processing chamber 201, valve 324 is opened, and H2 gas is supplied into the gas supply pipe 320 as a reducing gas for processing. The H2 gas flow rate is regulated by MFC 322, and it is supplied into the processing chamber 201 through the gas supply hole 420a of the nozzle 420 and exhausted through the exhaust pipe 231. At this time, H2 gas is supplied to the wafer 200. Simultaneously, valve 524 is opened, and Ar gas is allowed to flow into the gas supply pipe 520. The Ar gas flowing through the gas supply pipe 520 is regulated by MFC 522. The Ar gas is supplied into the processing chamber 201 together with the H2 gas and exhausted through the exhaust pipe 231. At this time, in order to prevent H2 gas from entering the nozzle 410, valve 514 is opened, and Ar gas is allowed to flow into the gas supply pipe 510. The Ar gas is supplied into the processing chamber 201 via the gas supply pipe 310 and nozzle 410 and exhausted through the exhaust pipe 231.

[0062] At this time, the APC valve 243 is adjusted to set the pressure in the processing chamber 201 to a pressure within the range of, for example, 4000 Pa to 13000 Pa. The supply flow rate of H2 gas controlled by MFC 322 is set to a flow rate within the range of, for example, 1 to 60 slm, preferably 15 to 35 slm. The supply flow rates of Ar gas controlled by MFC 512 and 522 are set to a flow rate within the range of, for example, 0.1 to 30 slm, respectively. The time for supplying H2 gas to the wafer 200 is set to a time within the range of, for example, 0.01 to 600 seconds.

[0063] At this time, the only gases flowing into the processing chamber 201 are H2 gas and Ar gas. Here, the H2 gas undergoes a substitution reaction with at least a portion of the Mo-containing layer formed on the wafer 200 during the metal-containing gas supply process. That is, the O and chlorine in the Mo-containing layer react with the H2 gas, desorb from the Mo layer, and are discharged from the processing chamber 201 as reaction byproducts such as water vapor (H2O), hydrogen chloride (HCl), and chlorine (Cl2). In other words, since the film can be formed while reducing the surface of the wafer 200 and the formed film with H2 gas, the concentration of impurities in the metal film can be reduced.

[0064] Furthermore, when supplying H2 gas into the processing chamber 201 to perform the film deposition process, if the pressure inside the processing chamber 201 is less than 4000 Pa, the effect of reducing impurity concentration by the reduction of the wafer 200 and metal film by the H2 gas may not be obtained. If the pressure is 4000 Pa or higher, the reduction effect can be obtained. If the pressure is 6000 Pa or higher, the reduction effect can be obtained sufficiently. Also, if the pressure inside the processing chamber 201 is higher than 13000 Pa, the wafer 200 may be etched by by-products generated when the H2 gas reduces the wafer 200. If the pressure is 13000 Pa or lower, etching by by-products can be suppressed. If the pressure is 11000 Pa or lower, etching by by-products can be sufficiently suppressed. Therefore, it is preferable that the pressure inside the processing chamber 201 be between 4000 Pa and 13000 Pa, and more preferably between 6000 Pa and 11000 Pa.

[0065] (c4) Residual gas removal process After forming the metal layer, close valve 324 to stop the supply of H2 gas. Then, by the same processing procedure as in the above step (c2: residual gas removal), unreacted H2 gas or reaction by-products remaining in processing chamber 201 after contributing to the formation of the metal layer are removed from processing chamber 201. That is, processing chamber 201 is purged.

[0066] (c5) Predetermined number of cycles implementation step By performing the cycles of sequentially performing the above steps (c1) to (c4) a predetermined number of times (n times, where n is an integer of 1 or more), a metal-containing film with a predetermined thickness (for example, 0.5 to 40.0 nm) is formed on wafer 200. It is preferable to repeat the above cycles a plurality of times. Also, each of the steps (c1) to (c4) may be performed at least once or more. That is, the cycles of supplying the metal-containing gas and the hydrogen-containing gas into the processing vessel non-simultaneously are executed a predetermined number of times.

[0067] (d) Temperature reduction step After the film formation step, a temperature reduction step is implemented. In the temperature reduction step, the heating of heater 207 is controlled so that the temperature of processing chamber 201 becomes the unloading temperature T3 from the film formation temperature T2. The unloading temperature T3 is set to a temperature lower than the loading temperature T1 (T3 < T1). For example, the unloading temperature T3 is a temperature within the range of 400 °C or lower, preferably 250 °C or lower, and more preferably 100 °C or lower. Vacuum evacuation is performed by vacuum pump 246 so that the inside of processing chamber 201, that is, the space where wafer 200 exists, reaches a desired pressure (degree of vacuum).

[0068] At this time, H2 gas is supplied to processing chamber 201 as a reducing gas. That is, in at least a part of the temperature reduction step, a reducing gas is supplied into processing chamber 201. Thereby, while reducing the metal film, the temperature inside processing chamber 201 can be lowered, so the impurity concentration in the metal film is reduced and the electrical characteristics of the metal film are improved. Here, the impurities in the temperature reduction step may mean, for example, nitrogen (N) in addition to the above-mentioned impurities.

[0069] Furthermore, H2 gas can be considered a highly thermally conductive gas. In other words, a highly thermally conductive gas is supplied into the processing chamber 201 for at least a portion of the cooling process. This shortens the cooling time. In addition, the temperature difference between the actual temperature of the wafer 200 and the temperature inside the furnace of the processing vessel becomes smaller than when cooling in an atmosphere that is not a highly thermally conductive gas atmosphere, thus improving the controllability of the substrate temperature of the wafer 200.

[0070] Furthermore, when supplying H2 gas into the processing chamber 201 to perform the cooling process, if the pressure inside the processing chamber 201 is less than 4000 Pa, the effect of shortening the temperature control time may not be obtained, but if it is 4000 Pa or higher, the effect of shortening the temperature control time can be obtained. If it is 6000 Pa or higher, the effect of shortening the temperature control time can be sufficiently obtained. Also, if it is higher than 13000 Pa, the wafer 200 may be etched by by-products generated when the H2 gas reduces the wafer 200, but etching by by-products can be suppressed if it is 13000 Pa or lower. Furthermore, etching by by-products can be sufficiently suppressed if it is 11000 Pa or lower. Therefore, when supplying H2 gas into the processing chamber 201 to perform the cooling process, it is preferable to set the pressure inside the processing chamber 201 to 4000 Pa or more and 13000 Pa or less, and it is even more preferable to set it to 6000 Pa or more and 11000 Pa or less.

[0071] Furthermore, H2 gas can be considered a highly thermally conductive gas with reducing properties. In other words, a highly thermally conductive gas with reducing properties is supplied into the processing chamber 201 for at least a portion of the cooling process. This allows the cooling time to be shortened while reducing the metal film.

[0072] Alternatively, the temperature inside the processing chamber 201 may be lowered while maintaining a vacuum inside the processing chamber 201. In other words, the processing chamber 201 may be kept under vacuum for at least a portion of the cooling process. Specifically, the temperature inside the processing chamber 201 may be lowered to 250°C or less, more preferably 100°C or less, while the pressure inside the processing chamber 201 is set to 1 Pa to 100 Pa. In this case, heat conduction between the wafer 200 and the surrounding gas becomes less likely, thus reducing the cooling rate of the wafer 200 and the metal film. As a result, the time that the wafer 200 remains at a high temperature increases, and the wafer 200 is subjected to heat treatment. As a result of this heat treatment, the crystallinity of the metal film is improved. In addition, because the pressure around the wafer 200 is low, impurities in the metal film are more easily removed, thus reducing the impurity concentration in the metal film. From the above, the electrical properties of the metal film can be improved. Furthermore, if the pressure inside the processing chamber 201 is increased to more than 100 Pa, the above-mentioned effects may become less likely to be obtained due to at least one of the following: increased heat conduction between the wafer 200 and the surrounding gas, or difficulty in removing impurities from the metal film.

[0073] (e) Unloading process After the cooling process, the unloading process is carried out. Ar gas is supplied into the processing chamber 201 from gas supply pipes 510 and 520, respectively, replacing the atmosphere in the processing chamber 201 with Ar gas (inert gas replacement) and returning the pressure in the processing chamber 201 to normal pressure (atmospheric pressure return). The seal cap 219 is lowered by the boat elevator 115, opening the lower end of the outer tube 203. Then, with the wafer 200 supported by the boat 217, it is unloaded from the lower end of the outer tube 203 to the outside of the outer tube 203 (boat unloading). After that, the processed wafer 200 is removed from the boat 217 (wafer discharge).

[0074] As described above, in the substrate processing step in the present disclosure, after the step of setting the temperature inside the processing chamber 201 to the carry-out temperature T3 (T3 < T1) lower than the carry-in temperature T1 (temperature reduction step), the step of carrying out the wafer 200 from the inside of the processing chamber 201 (carry-out step) is performed. That is, after forming the metal film, the wafer 200 is cooled to the carry-out temperature T3 lower than the carry-in temperature T1 and then carried out to the outside of the outer tube 203. As a result, since the temperature of the wafer 200 at the time of carry-out decreases, deterioration of the metal film at the time of carry-out is suppressed. Therefore, the electrical characteristics of the metal film are improved. Here, the deterioration of the metal film that occurs during the carry-out step means that at least one of, for example, nitridation and oxidation occurs in the metal film due to the atmosphere inside the processing chamber 201 or the atmosphere outside the processing chamber 201.

[0075] (Second Example of Steps of Substrate Processing Method) FIG. 4 is a flowchart for explaining a method of manufacturing a semiconductor device according to a second example of the steps of a substrate processing method. Similar to FIG. 3, FIG. 4 shows an example of the step of forming a Mo-containing film on the wafer 200, with temperature on the vertical axis and time on the horizontal axis. In the description of FIG. 4, mainly the parts different from the manufacturing process of FIG. 3 will be described, and the same reference numerals will be given to the elements substantially the same as those described in FIG. 3, and the description thereof will be omitted.

[0076] The main difference between FIG. 4 and FIG. 3 is that a second temperature adjustment step and a holding step are added between the film forming step and the temperature reduction step. Hereinafter, the second temperature adjustment step and the holding step will be described.

[0077] (g) Second Temperature Adjustment Step (Second Temperature Adjustment Process) After the film forming step, the second temperature adjustment step is executed. In the second temperature adjustment step, the temperature inside the processing chamber 201 or the temperature of the wafer 200 is raised from the film forming temperature T2 to a holding temperature T4 (T4 > T2) higher than the film forming temperature T2. In the second temperature adjustment step, the temperature inside the processing chamber 201 or the temperature of the wafer 200 is raised from the film forming temperature T2 to the holding temperature T4. Here, the heating of the heater 207 is controlled so that the temperature inside the processing chamber 201 is raised from the film forming temperature T2 to the holding temperature T4.

[0078] In the second temperature control process, for example, the processing chamber 201, that is, the space where the wafer 200 is located, is evacuated by a vacuum pump 246 so that it reaches a desired pressure (vacuum level).

[0079] At this time, H2 gas is supplied from the gas supply pipe 320 into the processing chamber 201 via the MFC 322, valve 324, and nozzle 420. In addition, Ar gas is supplied from the gas supply pipe 520 as an inert gas into the processing chamber 201 via the MFC 522, valve 524, and nozzle 420.

[0080] Here, H2 gas can be considered a reducing gas. That is, in at least a portion of the second temperature control process, a reducing gas is supplied into the processing chamber 201. This allows the metal film to be reduced while the temperature is controlled, thereby reducing the impurity concentration in the metal film. Consequently, the electrical properties of the metal film are improved. Furthermore, H2 gas can be considered a high thermal conductivity gas. That is, in at least a portion of the second temperature control process, a high thermal conductivity gas is supplied into the processing chamber 201. This allows the temperature control time to be shortened. Furthermore, H2 gas can be considered a high thermal conductivity gas with reducing properties. That is, in at least a portion of the second temperature control process, a high thermal conductivity gas with reducing properties is supplied into the processing container. This allows the temperature inside the processing chamber 201 to be controlled in a short time while the surface of the wafer 200 is reduced with H2 gas.

[0081] Here, consider the case where a highly thermally conductive gas with reducing properties (for example, H2 gas) is supplied to the processing chamber 201 as a reducing gas during the film deposition process. When a highly thermally conductive gas is supplied to the processing chamber 201 at the start of the second temperature control process, the difference in thermal conductivity between the gas supplied during the film deposition process and the second temperature control process becomes smaller, thus reducing the temperature change of the wafer 200. This reduces thermal stress on the surface of the wafer 200 and suppresses pattern deformation.

[0082] When supplying H2 gas into the processing chamber 201 to perform the second temperature control process, if the pressure inside the processing chamber 201 is less than 4000 Pa, it is difficult to shorten the temperature control time, but if it is 4000 Pa or higher, it is possible to shorten the temperature control time. If it is 6000 Pa or higher, a sufficient reduction in temperature control time can be obtained. Furthermore, if it is higher than 13000 Pa, the wafer 200 will be etched by by-products generated when the H2 gas reduces the wafer 200, but if it is 13000 Pa or lower, etching by by-products can be suppressed. Furthermore, if it is 11000 Pa or lower, etching by by-products can be sufficiently suppressed. Therefore, the pressure inside the processing chamber 201 should be 4000 Pa or higher and 13000 Pa or lower, preferably 6000 Pa or higher and 11000 Pa or lower.

[0083] Alternatively, the processing chamber 201 may be kept under vacuum while maintaining a constant temperature inside the chamber. In this case, the lower pressure around the wafer 200 makes it easier for impurities in the metal film to detach, thus reducing the impurity concentration in the metal film.

[0084] (h) Holding process (annealing process, heat treatment process) After the second temperature control process, a holding process is performed. In the holding process, the wafer 200, on which the metal film has been formed in the film deposition process, is held in a processing chamber 201 at a holding temperature T4 (T4 > T3) that is higher than the film deposition temperature T3. In other words, the wafer 200 is annealed (heat treated) at the holding temperature T4. This increases the diameter (particle size) of the crystal grains that form the metal film, improving the electrical properties of the metal film. The holding temperature T4 is set to a temperature in the range of 500°C to 650°C, preferably 550°C to 600°C.

[0085] At this time, H2 gas is supplied from the gas supply pipe 320 as a reducing gas into the processing chamber 201 via the MFC 322, valve 324, and nozzle 420. In addition, Ar gas is supplied from the gas supply pipe 520 as an inert gas into the processing chamber 201 via the MFC 522, valve 524, and nozzle 420. In other words, a reducing gas is supplied into the processing chamber 201 for at least a part of the holding process. Since heat treatment can be performed while reducing the metal film, the concentration of impurities in the metal film can be reduced, and thus the electrical properties of the metal film are improved.

[0086] When supplying H2 gas into the processing chamber 201 for the holding process, if the pressure inside the processing chamber 201 is less than 4000 Pa, it may be difficult to obtain the effect of reducing the impurity concentration by reducing the wafer 200 and metal film. If it is 4000 Pa or higher, the effect of reduction can be obtained. If it is 6000 Pa or higher, the effect of shortening the temperature control time can be sufficiently obtained. Furthermore, if it is higher than 13000 Pa, the wafer 200 may be etched by by-products generated when the H2 gas reduces the wafer 200. If it is 13000 Pa or lower, etching by by-products can be suppressed. Furthermore, if it is 11000 Pa or lower, etching by by-products can be sufficiently suppressed. Therefore, it is preferable that the pressure inside the processing chamber 201 be 4000 Pa or more and 13000 Pa or less, and more preferably 6000 Pa or more and 11000 Pa or less.

[0087] According to Embodiment Example 2, in addition to the effects of the second temperature control step and the holding step described above, the same effects as in Embodiment 1 can be obtained.

[0088] The following explains gas.

[0089] As the inert gas, it is preferable to use a gas that does not react easily with the metal film formed in the substrate processing process. For example, helium (He) gas, neon (Ne) gas, argon (Ar) gas, xenon (Xe) gas, and other noble gases or nitrogen (N2) gas may be appropriately selected and used. However, depending on the film to be formed, it may be altered by N2 gas. In that case, a gas other than N2 gas should be used. For example, when forming a molybdenum (Mo) film as the metal film, the Mo film will be altered by N2 gas, so it is preferable to use an inert gas other than N2 gas.

[0090] Examples of reducing gases that can be used include H2 gas, deuterium (D2) gas, borane (BH3) gas, diborane (B2H6) gas, carbon monoxide (CO) gas, ammonia (NH3) gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monogermane (GeH4) gas, and digermane (Ge2H6).

[0091] In this disclosure, a high thermal conductivity gas is a gas with a higher thermal conductivity than the gas used as an inert gas. Here, the thermal conductivity of a gas is higher the smaller the molecular weight of the molecules that mainly constitute the gas (gas molecules). Therefore, for example, when Ar gas is used as the inert gas, gases with a smaller molecular weight than Ar, such as H2 gas, D2 gas, He gas, BH3 gas, B2H6 gas, NH3 gas, N2 gas, Ne gas, SiH4 gas, and CO gas, may be used as the high thermal conductivity gas. Also, for example, when N2 gas is used as the inert gas, gases with a smaller molecular weight than N2, such as H2 gas, D2 gas, He gas, BH3 gas, and Ne gas, may be used. Also, for example, when He gas is used as the inert gas, gases with a smaller molecular weight than He, such as H2 gas and D2 gas, may be used.

[0092] In this disclosure, a reducing, high-thermal-conductivity gas refers to a gas that belongs to both the reducing gas and high-thermal-conductivity gas categories described above. Therefore, for example, when Ar gas is used as the inert gas, H2 gas, D2 gas, BH3 gas, B2H6 gas, NH3 gas, SiH4 gas, and CO gas can be used as the reducing, high-thermal-conductivity gas. It is preferable to use H2 gas or D2 gas as the reducing, high-thermal-conductivity gas.

[0093] Since D2 is more reactive than H2, D2 gas has a greater reducing effect than H2 gas. Therefore, when D2 gas is used as a reducing gas, the impurity concentration in the metal film can be reduced even more effectively than with H2 gas.

[0094] When a reducing gas or a highly thermally conductive gas, or H2 gas as a highly thermally conductive gas with reducing properties, is supplied to the processing chamber 201 as a mixed gas of H2 and other gases, if the mass fraction of H2 in the mixed gas is less than 70%, the reducing effect may not be sufficiently obtained, and the electrical resistance of the metal film may not reach the target value. By setting the mass fraction of H2 in the mixed gas to 70% or more, the reducing effect can be sufficiently obtained, and the electrical resistance of the metal film can reach the target value. Furthermore, by setting the mass fraction of H2 in the mixed gas to 90% or more, the electrical resistance of the metal film can be improved to a value beyond the target value. In other words, a metal film with electrical properties exceeding the target value can be obtained. For these reasons, it is preferable to set the mass fraction of H2 in the mixed gas to 70% or more, and more preferable to set it to 90% or more. Since the mixed gas contains hydrogen, it can also be called a hydrogen-containing gas.

[0095] Here, at least some of the gas molecules in the processing chamber 201 may be radicalized or excited by a plasma generation unit (not shown in Figure 1). By utilizing the gas activated by the plasma in this way, impurities in the metal film can be removed.

[0096] In this disclosure, a metal film is a film containing a metal element as its main element. The metal element is preferably a transition metal element. Examples of transition metal elements include Group 4 elements such as zirconium (Zr), hafnium (Hf), and titanium (Ti). There are also Group 6 elements such as molybdenum (Mo) and tungsten (W), and Group 8 elements such as ruthenium (Ru). Furthermore, there are Group 5 elements such as vanadium (V), niobium (Nb), and tantalum (Ta). In addition to transition metals, there are also Group 13 elements such as aluminum (Al), gallium (Ga), and indium (In).

[0097] As a metal-containing gas, for example, a gas containing the metal elements described above can be used. As a metal-containing gas, for example, a halogen-based metal-containing gas containing the metal elements described above and halogen elements (e.g., fluorine (F), Cl, bromine (Br), iodine (I)) can be used. As a halogen-based metal-containing gas, for example, a halogen-based transition metal-containing gas containing transition metal elements can be used. As a halogen-based transition metal-containing gas, for example, a halogen-containing Mo-containing gas containing Mo can be used. As a halogen-containing Mo-containing gas, for example, molybdenum chloride dichloride (MoO2Cl2) gas, molybdenum tetrachloride (MoOCl4) gas, molybdenum pentachloride (MoCl5), etc. can be used. Since halogen elements are less likely to remain as impurities in the metal film, forming a metal film using a metal-containing gas containing halogen elements can suppress deterioration of the electrical properties (e.g., electrical resistance) of the metal film. Furthermore, when using an oxygen-free metal-containing gas (Mo-containing gas) such as MoCl5 gas, oxidation of the wafer 200 and the metal film can be suppressed, thereby preventing deterioration of the electrical properties of the metal film.

[0098] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above-described embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace. Even when using these substrate processing apparatuses, each process can be carried out using the same processing procedures and processing conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0099] The disclosure made by the Discloser has been described in detail based on embodiments, but it goes without saying that the disclosure is not limited to the embodiments described above and can be modified in various ways. Furthermore, the above embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above embodiments and modifications. [Explanation of symbols]

[0100] 10: Substrate processing equipment 200: Substrate (wafer) 204: Processing container (inner tube) 115: Loading / unloading mechanism (boat elevator) 300: Processing gas supply system

Claims

1. (a) A step of supplying an inert gas into the space in which the substrate is placed, (b) A step of raising the temperature of the substrate to a second temperature higher than the first temperature, (c) A step of supplying a high thermal conductivity gas, which has a higher thermal conductivity than the inert gas, into the space after the start of (b), (d)(c) followed by, (d1) A step of supplying a raw material gas containing a metal element to the substrate at the second temperature and forming a layer containing the metal element on the substrate, (d2) A step of supplying a reducing gas with a higher thermal conductivity than the inert gas to the substrate at the second temperature, and reacting the reducing gas with the layer, A step of forming a metal film containing the metal element as the main element on the substrate, It has and performs (a) before the end of (d), Substrate processing method.

2. The substrate processing method according to claim 1, wherein (c) is performed simultaneously with (b).

3. The substrate processing method according to claim 1, wherein (c) is performed after (b).

4. (a) (a1)(b) The step of supplying the inert gas into the space, The substrate processing method according to claim 3, wherein the process is carried out.

5. The substrate processing method according to claim 1, wherein in at least a portion of (b), the amount of the high thermal conductivity gas supplied into the space is increased.

6. (d) The substrate processing method according to claim 1, wherein (d1) and (d2) are performed non-simultaneously.

7. (a) (a2) Between (d1) and (d2), a step of purging the space using the inert gas, The substrate processing method according to claim 1, wherein the process is carried out.

8. The substrate processing method according to claim 1, wherein the high thermal conductivity gas has reducing properties.

9. The substrate processing method according to claim 1, wherein the high thermal conductivity gas is a hydrogen-containing gas.

10. The hydrogen-containing gas includes hydrogen gas. The substrate processing method according to claim 9, wherein the mass fraction of the hydrogen gas in the hydrogen-containing gas is 70% or more.

11. The substrate processing method according to claim 1, wherein the inert gas is argon gas.

12. The substrate processing method according to claim 1, wherein the metal film is a molybdenum film.

13. (a) A step of supplying an inert gas into the space in which the substrate is placed, (b) A step of raising the temperature of the substrate to a second temperature higher than the first temperature, (c) A step of supplying a high thermal conductivity gas, which has a higher thermal conductivity than the inert gas, into the space after the start of (b), (d)(c) followed by, (d1) A step of supplying a raw material gas containing a metal element to the substrate at the second temperature and forming a layer containing the metal element on the substrate, (d2) A step of supplying a reducing gas with a higher thermal conductivity than the inert gas to the substrate at the second temperature, and reacting the reducing gas with the layer, A step of forming a metal film containing the metal element as the main element on the substrate, It has and performs (a) before the end of (d), A method for manufacturing a semiconductor device.

14. An inert gas supply system that supplies inert gas into the space in which the substrate is placed, A high thermal conductivity gas supply system that supplies a high thermal conductivity gas with a higher thermal conductivity than the inert gas into the space, A raw material gas supply system that supplies a raw material gas containing a metal element into the aforementioned space, A reducing gas supply system that supplies a reducing gas with a higher thermal conductivity than the inert gas into the aforementioned space, A heating system for heating the aforementioned substrate, (a) A process of supplying the inert gas into the space, (b) A process to raise the temperature of the substrate to a second temperature higher than the first temperature, (c) After the start of (b), the process of supplying the high thermal conductivity gas into the space, (d)(c) followed by, (d1) A process of supplying the raw material gas to the substrate at the second temperature and forming a layer containing the metal element on the substrate, (d2) A process of supplying the reducing gas to the substrate at the second temperature and reacting the reducing gas with the layer, A process to form a metal film containing the metal element as the main element on the substrate, The process includes, and (a) is performed before the completion of (d), A control unit is configured to control the inert gas supply system, the high thermal conductivity gas supply system, the raw material gas supply system, the reducing gas supply system, and the heating system so that the following can be performed: A substrate processing apparatus having

15. (a) A procedure for supplying an inert gas into the space in which a substrate is placed, (b) A procedure for raising the temperature of the substrate to a second temperature higher than the first temperature, (c) A procedure to supply a high thermal conductivity gas with a higher thermal conductivity than the inert gas into the space after the start of (b), (d)(c) followed by, (d1) A procedure to supply a raw material gas containing a metal element to the substrate at the second temperature and to form a layer containing the metal element on the substrate, (d2) A procedure to supply a reducing gas with a higher thermal conductivity than the inert gas to the substrate at the second temperature, and to react the reducing gas with the layer, A procedure to form a metal film containing the metal element as the main element on the substrate, The procedure includes having (a) before the completion of (d), A program that a computer instructs a circuit board processing unit to execute.

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