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]

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

[0002] Metal films are used as word lines of a three-dimensional NAND flash memory. As the metal film, for example, a Mo-containing film containing molybdenum (Mo) may be used (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022-064549 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when forming a metal film on a substrate, the electrical resistance (or resistivity) of the metal film may become high depending on the temperature when the substrate is unloaded from a processing chamber.

[0005] The present disclosure provides techniques that can improve the electrical properties of metal films. [Means for solving the problem]

[0006] According to a representative aspect of the present disclosure, there is provided a technique comprising the steps of: (a) loading a substrate into a processing vessel at a loading temperature; (b) heating the processing vessel to a film formation temperature; (c) supplying a processing gas into the processing vessel to form a metal film on a surface of the substrate; (d) heating the processing vessel to an unloading temperature lower than the loading temperature; and (e) unloading the substrate from the processing vessel. Effect of the Invention

[0007] The present disclosure provides techniques that can improve the electrical properties of metal films. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic vertical cross-sectional view of a substrate processing apparatus according to an embodiment of the present disclosure. [Diagram 2] FIG. 2 is a schematic configuration diagram of a controller of the substrate processing apparatus according to an embodiment of the present disclosure, and is a block diagram showing a control system of the controller. [Diagram 3] FIG. 3 is a flow diagram illustrating a method for manufacturing a semiconductor device according to a first example of steps of the substrate processing method of the present disclosure. [Figure 4] FIG. 4 is a flow diagram illustrating a method for manufacturing a semiconductor device according to a second example of the steps of the substrate processing method of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The following description will be given with reference to the drawings. However, in the following description, the same components may be given the same reference numerals and repeated description may be omitted. Note that the drawings may be shown in a schematic manner compared to the actual embodiment in order to make the description clearer, but they are merely examples and do not limit the interpretation of the present disclosure. In addition, all of the drawings used in the following description are schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings may not necessarily match the actual ones. In addition, the dimensional relationship of each element, the ratio of each element, etc. may not necessarily match between multiple drawings.

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

[0011] An outer tube 203 constituting a reaction vessel (processing vessel) is disposed inside the heater 207 concentrically with the heater 207. 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. A manifold (inlet flange) 209 is disposed below the outer tube 203 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 seal member. The manifold 209 is supported by a heater base, so that the outer tube 203 is installed vertically.

[0012] An inner tube 204 constituting a processing vessel is disposed 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 vessel is mainly constituted by the outer tube 203, the inner tube 204, and a manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel (inside the inner tube 204).

[0013] The processing chamber 201 is configured so as to be capable of accommodating wafers 200 as substrates in a boat 217 (described later) in a horizontal position and in a state in which the wafers are arranged in multiple stages in the vertical direction.

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

[0015] Mass flow controllers (MFCs) 312 and 322, which are flow rate controllers (flow rate control parts), are provided in the gas supply pipes 310 and 320, respectively, in that order from the upstream side. Valves 314 and 324, which are on-off valves, are also provided in the gas supply pipes 310 and 320, respectively. Gas supply pipes 510 and 520, which supply inert gas, are connected to the downstream sides of the valves 314 and 324 of the gas supply pipes 310 and 320, respectively. MFCs 512 and 522, which are flow rate controllers (flow rate control parts), and valves 514 and 524, which are on-off valves, are provided in the gas supply pipes 510 and 520, respectively, in that order from the upstream side.

[0016] Nozzles 410, 420 are respectively connected to the tips of the gas supply pipes 310, 320. The nozzles 410, 420 are configured as L-shaped nozzles, and their horizontal parts are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical parts of the nozzles 410, 420 are provided inside the preliminary chamber 201a having a channel shape (groove shape) that protrudes radially outward from the inner tube 204 and is formed so as to extend in the vertical direction, and are provided in the preliminary chamber 201a facing upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

[0017] The nozzles 410 and 420 are provided so as to extend from the lower region of the processing chamber 201 to the upper region of the processing chamber 201, and a plurality of gas supply holes 410a and 420a are provided at positions facing the wafer 200. As a result, the processing gas is supplied to the wafer 200 from the gas supply holes 410a and 420a of the nozzles 410 and 420, respectively. The gas supply holes 410a and 420a are provided from the lower part to the upper part of the inner tube 204, each having the same opening area, and further provided at the same opening pitch. However, the gas supply holes 410a and 420a are not limited to the above-mentioned form. For example, the opening area may be gradually increased from the lower part to the upper part of the inner tube 204. As a result, the flow rate of the gas supplied from the gas supply holes 410a and 420a can be made more uniform.

[0018] The gas supply holes 410a, 420a of the nozzles 410, 420 are provided at a height from the bottom to the top of the boat 217 described later. Therefore, the process gas supplied from the gas supply holes 410a, 420a of the nozzles 410, 420 into the process chamber 201 is supplied to the entire area of ​​the wafers 200 accommodated from the bottom to the top of the boat 217. The nozzles 410, 420 may be provided so as to extend from the bottom region to the top region of the process chamber 201, but are preferably provided so as to extend to the vicinity of the ceiling of the boat 217.

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

[0020] A reducing gas is supplied as a processing gas from the gas supply pipe 320 into the processing chamber 201 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. The inert gas can also be called a carrier gas.

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

[0023] A highly thermally conductive gas is supplied from the gas supply pipe 330 into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 420. A highly thermally conductive gas supply system is mainly configured by the gas supply pipe 330, the MFC 332, and the valve 334. The nozzle 420 may be included in the highly thermally conductive gas supply system. The gas supply pipe 330, the MFC 332, and the valve 334 may be included in the processing gas supply system 300.

[0024] Furthermore, when a highly thermally conductive gas having reducing properties is flowed as the reducing gas from the gas supply pipe 320, the gas supply pipe 330, the MFC 332, and the valve 334 may be omitted. In this case, the gas supply pipe 320, the MFC 322, and the valve 324 may mainly constitute a reducing gas supply system, a highly thermally conductive gas supply system, or a highly thermally conductive gas supply system having reducing properties. The nozzle 420 may be included in the reducing gas supply system, the highly thermally conductive gas supply system, or the highly thermally conductive gas supply system having reducing properties. By using a highly thermally conductive gas having reducing properties, the supply system can be simplified compared to the case where a reducing gas and a highly thermally conductive gas are supplied separately.

[0025] In the method of supplying gas in this embodiment, gas is transported via nozzles 410, 420 arranged in a preliminary chamber 201a in a vertically elongated space in an annular shape defined by the inner wall of the inner tube 204 and the ends of the multiple wafers 200. Then, gas is ejected into the inner tube 204 from multiple gas supply holes 410a, 420a provided in positions of the nozzles 410, 420 facing the wafers. More specifically, the process gas and the like are ejected in a direction parallel to the surface of the wafer 200 from the gas supply hole 410a of the nozzle 410 and the gas supply hole 420a of the nozzle 420.

[0026] The exhaust hole (exhaust port) 204a is a through hole formed in the side wall of the inner tube 204 at a position facing the nozzles 410, 420, and is, for example, a slit-shaped through hole that is elongated in the vertical direction. The gas that is supplied from the gas supply holes 410a, 420a of the nozzles 410, 420 into the processing chamber 201 and flows over the surface of the wafer 200 flows into the exhaust path 206 constituted by a gap formed between the inner tube 204 and the outer tube 203 via the exhaust hole 204a. The gas that has flowed into the exhaust path 206 then flows into the exhaust pipe 231 and is exhausted to the outside of the processing furnace 202.

[0027] The exhaust hole 204a is provided at a position facing the multiple wafers 200, and the gas supplied from the gas supply holes 410a, 420a to the vicinity of the wafers 200 in the processing chamber 201 flows in the horizontal direction and then flows into the exhaust path 206 via the exhaust hole 204a. The exhaust hole 204a is not limited to being configured as a slit-shaped through hole, and may be configured as a multiple hole.

[0028] The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is connected to a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum exhaust device, in this order from the upstream side. The APC valve 243 can evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0029] Below the manifold 209, a seal cap 219 is provided as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is configured to abut against the lower end of the manifold 209 from below in the vertical direction. The seal cap 219 is made of a metal such as SUS and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. On the opposite side of the seal cap 219 to the processing chamber 201, a rotation mechanism 267 is installed to rotate the boat 217 that accommodates the wafers 200. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafers 200. The seal cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 serving as a loading / unloading mechanism (lifting mechanism) vertically installed outside the outer tube 203. The boat elevator 115 is configured to be able 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 transfer device (transfer system) that transfers the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

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

[0031] In this disclosure, a numerical range such as "25 sheets to 200 sheets" means that the lower limit and the upper limit are included in the range. Therefore, for example, "25 sheets 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 serving as a temperature detector is installed in the inner tube 204, and a desired temperature distribution is achieved in the process chamber 201 by adjusting the amount of power supplied to the heater 207 based on temperature information detected by the temperature sensor 263. The temperature sensor 263 is configured in an L-shape similar to the nozzles 410 and 420, and is provided along the inner wall of the inner tube 204.

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

[0034] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. A control program for controlling the operation of the substrate processing apparatus, a process recipe describing the procedure and conditions of a manufacturing method for a semiconductor device described later, etc. are readably stored in the storage device 121c. The process recipe is a combination of processes (steps) in a manufacturing method for a semiconductor device described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. When the word program is used in this specification, it may include only a process recipe, only a control program, or a combination of a process recipe and a control program. The RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily stored.

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

[0036] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe or the like from the storage device 121c in response to an input of an operation command from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 312, 322, 512, and 522, the opening and closing operations of the valves 314, 324, 514, and 524, the opening and closing operation of the APC valve 243 and the pressure adjustment operation based on the pressure sensor 245 by the APC valve 243, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the start and stop of the vacuum pump 246, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the accommodation operation of the wafers 200 in the boat 217, and the like, 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, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, or a semiconductor memory such as a USB memory or a memory card) 123 into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. In this specification, the recording medium may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0038] (2) Substrate processing (First example of a process for a substrate processing method) As one step in the manufacturing process of a semiconductor device, an example of a substrate processing method for forming a metal film, i.e., a Mo-containing film that is a transition metal element-containing film and is a Group 6 element-containing film containing molybdenum (Mo), on a wafer 200 on which a metal insulating film, i.e., an aluminum oxide film (Al2O3 film, hereinafter also referred to as an AlO film) as a metal oxide film, has been formed will be described with reference to Fig. 3. In Fig. 3, the vertical axis indicates temperature and the horizontal axis indicates time. The step of forming the Mo-containing film is performed using the processing furnace 202 of the above-mentioned substrate processing apparatus 10. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by a controller 121.

[0039] The substrate processing process (semiconductor device manufacturing process) according to this embodiment includes, for example, (a) a step of loading a wafer 200 into a processing chamber 201 in a processing vessel having a loading temperature (T1) (loading step); (b) a step of setting the temperature of the processing chamber 201 to a film formation temperature (T2) (first temperature adjustment step); (c) 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 step of lowering the temperature inside the processing chamber 201 to an unloading temperature (T3) lower than the load-in temperature (T1); (e) a step of unloading the wafer 200 from the processing chamber 201 (unloading step); has.

[0040] In this specification, the term "wafer" may mean "the wafer itself" or "a laminate of a wafer and a predetermined layer, film, etc. 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, film, etc. formed on the wafer." In this specification, the phrase "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer, etc. formed on the wafer. In this specification, the term "substrate" is synonymous with the term "wafer."

[0041] In this specification, the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201 (processing container), and the processing pressure means the pressure inside the processing chamber 201. Furthermore, the processing time means the time the processing continues. These terms are the same in the following explanations.

[0042] (a) Delivery process 1, when a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115, carried into the processing chamber 201 (boat load), and accommodated in the processing vessel. 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 a carry-in temperature T1. The carry-in temperature T1 is set, for example, to be 150° C. or more and 500° C. or less, preferably 200° C. or more and 450° C. or less, and more preferably 300° C. or more and 450° C. or less.

[0043] (b) First temperature adjustment process (first temperature adjustment process) The inside of the processing chamber 201 is heated by the heater 207 so that the inside of the processing chamber 201 becomes a film formation temperature T2. At this time, the amount of electricity supplied to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment or temperature regulation). The temperature of the heater 207 is increased from the carry-in temperature T1 to the film formation temperature T2, for example, the temperature inside the processing chamber 201, that is, the temperature of the wafer 200. The film formation temperature T2 is set to, for example, 300° C. or more and 600° C. or less, preferably 350 to 550° C., and more preferably 400 to 500° C. The 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, at least one of hydrogen (H2) gas, which is a hydrogen (H)-containing gas, and an inert gas may be supplied into the processing chamber 201. For example, there are cases where only H2 gas is supplied, where only an inert gas is supplied, and where both are supplied. Hereinafter, 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, the MFC 322, the valve 324, and the nozzle 420. Also, Ar gas is supplied into the processing chamber 201 mainly via the gas supply pipe 520, the MFC 522, the valve 524, and the nozzle 420.

[0045] Here, H2 gas can be regarded as a reducing gas. That is, in at least a part of the first temperature adjustment process, a reducing gas is supplied into the processing vessel. This allows the temperature to be adjusted while reducing the surface of the wafer 200, so that the impurity concentration in the metal film formed on the wafer 200 can be reduced. Here, the impurities in the film refer to elements that are not included in the chemical composition of the target film. In the case where the film is a film of a simple metal element, elements other than the metal element can be impurities. Specifically, in the case of a Mo film, elements other than Mo, for example, at least one of H, chlorine (Cl) and oxygen (O) are impurities.

[0046] Also, H2 gas can be regarded as a gas with high thermal conductivity. That is, in at least a part of the first temperature adjustment process, a gas with high thermal conductivity is supplied into the processing vessel. When a gas with high thermal conductivity is supplied into the processing chamber 201, the amount of heat transferred from the heater 207 to the gas in the processing chamber 201 per unit time increases. Also, when a gas with high thermal conductivity is supplied into the processing chamber 201, the amount of heat transferred from the gas in the processing chamber 201 to the wafer 200 per unit time increases. For these reasons, 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 gas with high thermal conductivity is not supplied into the processing chamber 201. That is, the time required for temperature adjustment in the processing chamber 201 is shortened.

[0047] In addition, H2 gas can be regarded as a highly thermally conductive gas having reducing properties. That is, in at least a part of the first temperature adjustment process, a highly thermally conductive gas having reducing properties is supplied into the processing vessel. This allows the temperature in the processing chamber 201 to be adjusted in a short time while reducing the surface of the wafer 200.

[0048] Also, in at least a part of the first temperature adjustment process, for example, in the latter half of the first temperature adjustment process, the flow rate of the reducing gas (H2 gas) may be gradually increased. By increasing the concentration of the reducing gas in the processing chamber 201, the temperature in the processing chamber 201 can be adjusted in a short time while further promoting the reduction reaction. Also, in at least a part of the first temperature adjustment process, for example, in the latter half of the first temperature adjustment process, the flow rate of the highly thermally conductive gas may be gradually increased. This makes it possible to prevent the temperature in the processing chamber 201 and the wafer 200 from changing suddenly. Therefore, the thermal stress on the surface of the wafer 200 is reduced, and the pattern collapse of the wafer 200 can be suppressed.

[0049] In addition, when the first temperature adjustment step is performed by supplying H2 gas into the processing chamber 201, if the pressure in the processing chamber 201 is less than 4000 Pa, it may be difficult to obtain a shortening effect of the temperature adjustment time, and if it is 4000 Pa or more, the temperature adjustment time can be sufficiently shortened. Furthermore, if it is 6000 Pa or more, the temperature adjustment time can be further shortened. Furthermore, if it is higher than 13000 Pa, the wafer 200 may be etched by by-products generated by the reduction of the wafer 200 by the H2 gas, and if it is 13000 Pa or less, etching by the by-products can be suppressed. Furthermore, if it is 11000 Pa or less, etching by the by-products can be sufficiently suppressed. Therefore, the pressure in the processing chamber 201 is preferably 4000 Pa or more and 13000 Pa or less, and more preferably 6000 Pa or more and 11000 Pa or less.

[0050] When H2 gas is supplied in the first temperature adjustment step, the substrate is reduced during heating, and an unintended reduction reaction may occur depending on the substrate, resulting in a difference in the amount of reduction for each substrate. To suppress such an effect, only an inert gas may be supplied in the first temperature adjustment step, only a non-reducing highly thermally conductive gas may be supplied, or both may be supplied.

[0051] The inside of the processing chamber 201, i.e., the space in which the wafer 200 exists, is evacuated by the vacuum pump 246 so as to reach a 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 the measured pressure information. The vacuum pump 246 is kept in a constantly operating state 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 reducing gas, which is a high thermal conductivity gas having reducibility (for example, H2 gas), is supplied to the wafer 200. 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 be generated 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, a rapid temperature change of the wafer 200 is suppressed, and the thermal stress is reduced, so that 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 inside of the processing chamber 201 is heated by the heater 207 so as to reach the film formation temperature T2. The film formation temperature T2 is set to a temperature higher than the carry-in temperature T1 (T1 < T2). The film formation temperature T2 is, for example, a temperature in the range of 300°C or higher and 600°C or lower, preferably 350°C or higher and 550°C or lower, and more preferably 400°C or higher and 500°C or lower.

[0056] The film forming process includes (c1) a metal-containing gas supplying step, (c2) a residual gas removing step, (c3) a reducing gas supplying step, (c4) a residual gas removing step, and (c5) a step of performing the process a predetermined number of times, which are described below.

[0057] (c1) Metal-containing gas supply process The valve 314 is opened, and a metal-containing gas, which is a raw material gas serving as a processing gas, is flowed into the gas supply pipe 310. An example in which a Mo-containing gas is used as the metal-containing gas will be described below. The Mo-containing gas is adjusted in flow rate by the MFC 312, 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 this time, the valve 514 is opened at the same time, and Ar gas is flowed into the gas supply pipe 510. The Ar gas flowing through the gas supply pipe 510 is adjusted in flow rate by the MFC 512, supplied into the processing chamber 201 together with the Mo-containing gas, and exhausted from the exhaust pipe 231. At this time, in order to prevent the Mo-containing gas from entering the nozzle 420, the valve 524 is opened, and Ar gas is flowed into the gas supply pipe 520. The Ar gas is supplied into the processing chamber 201 through the gas supply pipe 320 and the 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 inside the processing chamber 201 to, for example, a pressure in the range of 4000 Pa to 11000 Pa. The supply flow rate of the metal-containing gas controlled by the MFC 312 is, 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 each, for example, in the range of 0.1 to 20 slm.

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

[0060] (c2) Residual gas removal process After a predetermined time has elapsed since the start of the supply of 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. That is, the time for supplying the Mo-containing gas to the wafer 200 is set to, for example, a time in the range of 0.01 to 60 seconds. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. That is, the inside of the processing chamber 201 is purged. At this time, the valves 514 and 524 are kept open to maintain the supply of the Ar gas into the processing chamber 201. The Ar gas acts as a purge gas, and can enhance the effect of removing the Mo-containing gas remaining in the processing chamber 201, which has not reacted or has contributed to the formation of the metal-containing layer, from the inside of the processing chamber 201.

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

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

[0063] At this time, only H2 gas and Ar gas are flowing into the processing chamber 201. Here, the H2 gas undergoes a substitution reaction with at least a part of the Mo-containing layer formed on the wafer 200 in the metal-containing gas supply process. That is, O and chlorine in the Mo-containing layer react with the H2 gas, are desorbed from the Mo layer, and are discharged from the processing chamber 201 as reaction by-products such as water vapor (H2O), hydrogen chloride (HCl), and chlorine (Cl2). That is, the surface of the wafer 200 and the formed film can be reduced by the H2 gas while the film is being formed, so that the impurity concentration in the metal film can be reduced.

[0064] In addition, when H2 gas is supplied into the processing chamber 201 to perform the film forming process, if the pressure in the processing chamber 201 is less than 4000 Pa, the effect of reducing the impurity concentration due to the reduction of the wafer 200 and the metal film by H2 gas may not be obtained, and if the pressure is 4000 Pa or more, the effect of the reduction can be obtained. If the pressure is 6000 Pa or more, the effect of the reduction can be obtained sufficiently. If the pressure in 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, and if the pressure is 13000 Pa or less, the etching by the by-products can be suppressed. If the pressure is 11000 Pa or less, the etching by the by-products can be sufficiently suppressed. Therefore, the pressure in the processing chamber 201 is preferably 4000 Pa or more and 13000 Pa or less, and more preferably 6000 Pa or more and 11000 Pa or less.

[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 the above-described step (c2: residual gas removal), unreacted or H2 gas and reaction by-products remaining in the processing chamber 201 after contributing to the formation of the metal layer are removed from the processing chamber 201. That is, the inside of the processing chamber 201 is purged.

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

[0067] (d) Cooling step After the film formation step, a cooling step is performed. In the cooling step, the heating of the heater 207 is controlled so that the temperature of the processing chamber 201 becomes the carry-out temperature T3 from the film formation temperature T2. The carry-out temperature T3 is set to a temperature lower than the carry-in temperature T1 (T3 < T1). For example, the carry-out 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. The inside of the processing chamber 201, that is, the space where the wafer 200 exists, is evacuated by the vacuum pump 246 so as to reach a desired pressure (vacuum degree).

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

[0069] Also, H2 gas can be regarded as a gas with high thermal conductivity. That is, a gas with high thermal conductivity is supplied into the processing chamber 201 in at least a part of the temperature lowering process. This shortens the temperature lowering time. Furthermore, the difference between the actual temperature of the wafer 200 and the temperature inside the furnace of the processing vessel becomes smaller than when the temperature is lowered in an atmosphere other than the high thermal conductivity gas atmosphere, so that the controllability of the substrate temperature of the wafer 200 is improved.

[0070] In addition, when H2 gas is supplied into the processing chamber 201 to perform the temperature lowering process, if the pressure in the processing chamber 201 is less than 4000 Pa, the effect of shortening the temperature control time may be difficult to obtain, and if it is 4000 Pa or more, the effect of shortening the temperature control time can be obtained. If it is 6000 Pa or more, the effect of shortening the temperature control time can be obtained sufficiently. 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, and if it is 13000 Pa or less, etching by the by-products can be suppressed. If it is 11000 Pa or less, etching by the by-products can be sufficiently suppressed. Therefore, when H2 gas is supplied into the processing chamber 201 to perform the temperature lowering process, the pressure in the processing chamber 201 is preferably 4000 Pa or more and 13000 Pa or less, and more preferably 6000 Pa or more and 11000 Pa or less.

[0071] In addition, H2 gas can be regarded as a highly thermally conductive gas having reducing properties. That is, in at least a part of the temperature lowering process, a highly thermally conductive gas having reducing properties is supplied into the processing chamber 201. This makes it possible to reduce the temperature lowering time while reducing the metal film.

[0072] Also, the temperature in the processing chamber 201 may be lowered while maintaining the state in which the processing chamber 201 is evacuated. That is, the processing chamber 201 may be kept in a vacuum state at least in a part of the temperature lowering process. Specifically, the temperature in the processing chamber 201 may be lowered to 250°C or less, more preferably 100°C or less, with the pressure in the processing chamber 201 set to 1 Pa to 100 Pa. In this case, the thermal conduction between the wafer 200 and the gas around it is difficult to occur, so the temperature lowering rate of the wafer 200 and the metal film is reduced. This lengthens the time that the wafer 200 is in a high temperature state, and the wafer 200 is in a state where it is heat-treated. As a result of this heat treatment, the crystallinity of the metal film is improved. Also, since the pressure around the wafer 200 is low, impurities in the metal film are easily desorbed, and the impurity concentration in the metal film is reduced. From the above, the electrical characteristics of the metal film can be improved. In addition, if the pressure inside the processing chamber 201 is made greater than 100 Pa, it may become difficult to obtain the above-mentioned effect due to at least one of the following: thermal conduction between the wafer 200 and the gas surrounding it may become easier to occur, and impurities in the metal film may become more difficult to desorb.

[0073] (e) Unloading process After the temperature lowering process, a carrying-out process is performed. Ar gas is supplied into the processing chamber 201 from each of the gas supply pipes 510 and 520, the atmosphere in the processing chamber 201 is replaced with Ar gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure) (return to atmospheric pressure). The seal cap 219 is lowered by the boat elevator 115, and the lower end of the outer tube 203 is opened. Then, the wafers 200 are carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 while being supported by the boat 217 (boat unloading). Thereafter, the processed wafers 200 are taken out of the boat 217 (wafer discharging).

[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 a 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 inside 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 nitridation, oxidation, etc. 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 the substrate processing method. FIG. 4 is, like FIG. 3, an example of a step of forming a Mo-containing film on the wafer 200, showing 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 the elements 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 adjustment process, for example, the inside of the processing chamber 201, that is, the space in which the wafer 200 exists, is evacuated by the vacuum pump 246 so as to reach a desired pressure (degree of vacuum).

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

[0080] Here, H2 gas can be regarded as a reducing gas. That is, in at least a part of the second temperature adjustment process, a reducing gas is supplied into the processing chamber 201. As a result, the temperature can be adjusted while reducing the metal film, and the impurity concentration in the metal film can be reduced. Therefore, the electrical characteristics of the metal film are improved. Also, H2 gas can be regarded as a highly thermally conductive gas. That is, in at least a part of the second temperature adjustment process, a highly thermally conductive gas is supplied into the processing chamber 201. As a result, the time for temperature adjustment can be shortened. Also, H2 gas can be regarded as a highly thermally conductive gas having reducing properties. That is, in at least a part of the second temperature adjustment process, a highly thermally conductive gas having reducing properties is supplied into the processing vessel. As a result, the temperature in the processing chamber 201 can be adjusted in a short time while reducing the surface of the wafer 200 with H2 gas.

[0081] Here, consider a case where a highly thermally conductive gas having reducing properties (e.g., H2 gas) is supplied to the processing chamber 201 as a reducing gas in the film formation process. If a highly thermally conductive gas is supplied to the processing chamber 201 at the start of the second temperature adjustment process, the difference in thermal conductivity between the gases supplied in the film formation process and the second temperature adjustment process becomes small, so that the temperature change of the wafer 200 decreases. This reduces the thermal stress on the surface of the wafer 200, and suppresses pattern collapse.

[0082] In addition, when the second temperature control step is performed by supplying H2 gas into the processing chamber 201, if the pressure in the processing chamber 201 is less than 4000 Pa, the effect of shortening the temperature control time is difficult to obtain, and if it is 4000 Pa or more, the effect of shortening the temperature control time can be obtained. If it is 6000 Pa or more, the effect of shortening the temperature control time can be obtained sufficiently. If it is higher than 13000 Pa, the wafer 200 is etched by by-products generated by the reduction of the wafer 200 by the H2 gas, and if it is 13000 Pa or less, the etching by the by-products can be suppressed. If it is 11000 Pa or less, the etching by the by-products can be sufficiently suppressed. Therefore, the pressure in the processing chamber 201 is 4000 Pa or more and 13000 Pa or less, and preferably 6000 Pa or more and 11000 Pa or less.

[0083] The inside of the processing chamber 201 may be set to the holding temperature while maintaining the state in which the inside of the processing chamber 201 is evacuated to vacuum. In this case, the impurities in the metal film are easily desorbed due to the low pressure around the wafer 200, and therefore the impurity concentration in the metal film is reduced.

[0084] (h) Holding process (annealing process, heat treatment process) After the second temperature adjustment step, a holding step is performed. In the holding step, the wafer 200 on which the metal film is formed in the film formation step is held in the processing chamber 201 at a holding temperature T4 (T4>T3) higher than the film formation temperature T3. That is, the wafer 200 is annealed (heat treated) at the holding temperature T4. This increases the diameter (grain size) of the crystal grains forming the metal film, improving the electrical characteristics of the metal film. The holding temperature T4 is set to a temperature in the range of, for example, 500°C to 650°C, and preferably 550°C to 600°C.

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

[0086] In addition, when H2 gas is supplied into the processing chamber 201 to perform the holding process, if the pressure in the processing chamber 201 is less than 4000 Pa, it may be difficult to obtain the effect of reducing the impurity concentration due to the reduction of the wafer 200 and the metal film, and if it is 4000 Pa or more, the effect of the reduction can be obtained. If it is 6000 Pa or more, 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, and if it is 13000 Pa or less, the etching by the by-products can be suppressed. Furthermore, if it is 11000 Pa or less, the etching by the by-products can be sufficiently suppressed. Therefore, the pressure in the processing chamber 201 is preferably 4000 Pa or more and 13000 Pa or less, and more preferably 6000 Pa or more and 11000 Pa or less.

[0087] According to the second embodiment, in addition to the effects of the second temperature adjustment step and the holding step described above, the same effects as those of the first embodiment can be obtained.

[0088] The gas will now be described.

[0089] As the inert gas, it is preferable to use a gas that does not easily react with the metal film formed in the substrate processing process. For example, it may be appropriately selected from rare gases such as helium (He) gas, neon (Ne) argon (Ar) gas, xenon (Xe) gas, and nitrogen (N2) gas. Note that, depending on the film to be formed, it may be altered by N2 gas. In that case, a gas other than N2 gas is used. For example, when a Mo film is formed as the metal film, it is preferable to use an inert gas other than N2 gas because the Mo film is altered by 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] The high thermal conductivity gas in the present disclosure is a gas having a higher thermal conductivity than the gas used as the inert gas. Here, the thermal conductivity of the gas is higher as the molecular weight of the molecules (gas molecules) that mainly constitute the gas is smaller. Therefore, for example, when Ar gas is used as the inert gas, H2 gas, D2 gas, He gas, BH3 gas, B2H6 gas, NH3 gas, N2 gas, Ne gas, SiH4 gas, and CO gas, which are gases having a molecular weight smaller than Ar, may be used as the high thermal conductivity gas. Also, for example, when N2 gas is used as the inert gas, H2 gas, D2 gas, He gas, BH3 gas, and Ne gas, which are gases having a molecular weight smaller than N2, may be used. Also, for example, when He gas is used as the inert gas, H2 gas and D2 gas, which are gases having a molecular weight smaller than He, may be used.

[0092] The highly thermally conductive gas having reducing properties in the present disclosure is a gas that belongs to both the reducing gas and the highly thermally conductive gas described above. Therefore, for example, when Ar gas is used as the inert gas, the highly thermally conductive gas having reducing properties can be H2 gas, D2 gas, BH3 gas, B2H6 gas, NH3 gas, SiH4 gas, or CO gas. It is preferable to use H2 gas or D2 gas as the highly thermally conductive gas having reducing properties.

[0093] Since D2 is more active 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 more than when H2 gas is used.

[0094] When H2 gas as a reducing gas or a highly heat conductive gas, or a highly heat conductive gas having reducing properties is supplied into 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 reduction action may not be sufficiently obtained, and the electrical resistance of the metal film may not reach the target value. By making the mass fraction of H2 in the mixed gas 70% or more, the reduction action can be sufficiently obtained, and the electrical resistance of the metal film can reach the target value. Furthermore, by making the mass fraction of H2 in the mixed gas 90% or more, the electrical resistance of the metal film can be improved to the target value or more. In other words, a metal film having electrical properties exceeding the target value can be obtained. For these reasons, it is preferable to make the mass fraction of H2 in the mixed gas 70% or more, and more preferably 90% or more. Since the mixed gas contains hydrogen, the mixed gas can also be called a hydrogen-containing gas.

[0095] Here, at least a part of the gas molecules in the processing chamber 201 may be radicalized or excited by a plasma generating unit not shown in Fig. 1. By using the gas activated by plasma in this manner, impurities in the metal film can be removed.

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

[0097] As the metal-containing gas, for example, a gas containing the above-mentioned metal element can be used. As the metal-containing gas, for example, a halogen-based metal-containing gas containing the above-mentioned metal element and a halogen element (for example, fluorine (F), Cl, bromine (Br), iodine (I)) can be used. In addition, as the halogen-based metal-containing gas, for example, a halogen-based transition metal-containing gas containing a transition metal element can be used. In addition, as the halogen-based transition metal-containing gas, for example, a halogen-containing Mo-containing gas containing Mo can be used. In addition, as the halogen-containing Mo-containing gas, for example, molybdenum dioxide dichloride (MoO2Cl2) gas, molybdenum oxide tetrachloride (MoOCl4) gas, molybdenum pentachloride (MoCl5), etc. can be used. Since halogen elements are unlikely to remain as impurities in the metal film, by forming the metal film using a metal-containing gas containing a halogen element, it is possible to suppress deterioration of the electrical characteristics (for example, electrical resistance) of the metal film. Furthermore, when an O-free metal-containing gas (Mo-containing gas) such as MoCl5 gas is used, oxidation of the wafer 200 and the metal film can be suppressed, and therefore deterioration of the electrical characteristics of the metal film can be suppressed.

[0098] In the above-mentioned embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace. Even when using these substrate processing apparatuses, each process can be performed with the same process procedure and process conditions as the above-mentioned embodiment and modified example, and the same effects as the above-mentioned embodiment and modified example can be obtained.

[0099] The disclosure made by the present disclosure has been specifically described above based on the embodiment, but it goes without saying that the present disclosure is not limited to the above embodiment and can be modified in various ways. In addition, the above-mentioned aspects and modifications can be used in appropriate combination. The processing procedures and processing conditions in this case can be, for example, the same as the processing procedures and processing conditions of the above-mentioned aspects 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) loading a substrate into a processing chamber at an entry temperature; (b) setting the inside of the processing vessel at a film formation temperature; (f) supplying a high thermal conductivity gas into the processing vessel; (c) after (f), supplying a metal-containing gas and a highly thermally conductive gas having reducing properties as processing gases into the processing vessel to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (f) at least in part, increasing the supply amount of the reducing, highly thermally conductive gas; A method for processing a substrate.

2. In (c), a cycle of supplying the metal-containing gas and the highly thermally conductive gas having reducing properties non-simultaneously into the processing vessel is performed a predetermined number of times. The method for processing a substrate according to claim 1 .

3. (a) loading a substrate into a processing vessel having an entry temperature; (b) at least in part of the step of heating the inside of the processing vessel to a film formation temperature while supplying a reducing gas into the processing vessel; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (b) increasing the amount of the reducing gas supplied into the processing vessel; A method for processing a substrate.

4. (a) loading a substrate into a processing vessel having an entry temperature; (b) at least in part of the step of heating the inside of the processing vessel to a film formation temperature while supplying a highly thermally conductive gas into the processing vessel; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (b) increasing the amount of the highly thermally conductive gas supplied into the processing vessel; A method for processing a substrate.

5. 5. The substrate processing method according to claim 1, wherein in at least a part of (d), the inside of the processing vessel is kept in a vacuum state and the temperature inside the processing vessel is changed.

6. 5. The substrate processing method according to claim 1, wherein a reducing gas is supplied into the processing vessel in at least a portion of (d).

7. 5. The substrate processing method according to claim 1, wherein in at least a part of (d), a highly thermally conductive gas is supplied into the processing vessel.

8. (d), before (g) bringing the inside of the treatment vessel to a holding temperature; (h) maintaining the inside of the treatment vessel at a holding temperature; The substrate processing method according to any one of claims 1 to 4, further comprising:

9. The substrate processing method according to claim 8 , wherein the inside of the processing vessel is maintained in a vacuum state during at least a part of (g).

10. 9. The substrate processing method of claim 8, further comprising: supplying a reducing gas into the processing vessel in at least a portion of (g).

11. 9. The substrate processing method according to claim 8, further comprising: supplying a highly thermally conductive gas into the processing vessel in at least a portion of (g).

12. 9. The substrate processing method of claim 8, further comprising: supplying a reducing gas into the processing vessel in at least a portion of (h).

13. 5. The substrate processing method according to claim 1, wherein at least a part of gas molecules in the gas inside the processing vessel is in a radicalized or excited state.

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

15. The substrate processing method according to claim 1 , wherein the metal-containing gas contains a halogen element.

16. (a) loading a substrate into a processing chamber at an entry temperature; (b) setting the inside of the processing vessel at a film formation temperature; (f) supplying a high thermal conductivity gas into the processing vessel; (c) after (f), supplying a metal-containing gas and a highly thermally conductive gas having reducing properties as processing gases into the processing vessel to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having In at least a part of (f), increasing the supply amount of the high thermal conductivity gas. A method for manufacturing a semiconductor device.

17. A processing vessel for processing a substrate therein; A heating system for controlling a temperature inside the processing vessel; a transfer mechanism for transferring the substrate into the processing chamber and transferring the substrate out of the processing chamber; a processing gas supply system for supplying a metal-containing gas and a highly thermally conductive gas having reducing properties as processing gases into the processing vessel; a high thermal conductivity gas supply system for supplying a high thermal conductivity gas into the processing vessel; (a) loading the substrate into the processing vessel at a loading temperature; (b) heating the inside of the processing vessel to a film formation temperature; (f) supplying the high thermal conductivity gas into the processing vessel; and (c) after (f), supplying the metal-containing gas and the reducing, highly thermally conductive gas into the processing vessel to form a metal film on the surface of the substrate; (d) subjecting the inside of the processing vessel to an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; and having (f) at least in part, a process of increasing the supply amount of the high thermal conductivity gas; a control unit configured to be able to control the heating system, the carry-in / out mechanism, the process gas supply system, and the high thermal conductive gas supply system so that A substrate processing apparatus comprising:

18. (a) loading a substrate into a process vessel having a process vessel interior at an entry temperature; (b) setting the inside of the processing vessel at a film formation temperature; (f) supplying a high thermal conductivity gas into the processing vessel; (c) after (f), supplying a metal-containing gas and a highly thermally conductive gas having reducing properties as processing gases into the processing vessel to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (f) at least in part, a method for increasing the supply amount of the high thermal conductivity gas, A program that is executed by a computer in a substrate processing apparatus.

19. The method of claim 19, further comprising: (a) loading a substrate into a processing chamber at a loading temperature; (b) at least in a portion of the processing vessel, while supplying a reducing gas into the processing vessel, the processing vessel being heated to a film formation temperature; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (b) increasing the amount of the reducing gas supplied into the processing vessel; A method for manufacturing a semiconductor device.

20. A process vessel for processing a substrate therein; A heating system for controlling a temperature inside the processing vessel; a transfer mechanism for transferring the substrate into the processing chamber and transferring the substrate out of the processing chamber; a processing gas supply system for supplying a processing gas into the processing vessel; a reducing gas supply system for supplying a reducing gas into the processing vessel; (a) loading a substrate into the processing vessel at a loading temperature; (b) at least in a portion of the process, a process of heating the inside of the process vessel to a film formation temperature while supplying the reducing gas into the process vessel; (c) supplying the processing gas into the processing vessel to form a metal film on the surface of the substrate; (d) subjecting the inside of the processing vessel to an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; and having (b) at least in part, increasing the supply amount of the reducing gas into the processing vessel; a control unit configured to be able to control the heating system, the carry-in / out mechanism, the process gas supply system, and the reduction gas supply system so that A substrate processing apparatus comprising: (a) loading a substrate into a processing vessel having an entry temperature; (b) at least in part, supplying a reducing gas into the processing vessel while maintaining the processing vessel at a film formation temperature; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having In at least a part of (b), a step of increasing a supply amount of the reducing gas into the processing vessel is performed, A program that is executed by a computer in a substrate processing apparatus.

22. (a) loading a substrate into a processing vessel at a loading temperature; (b) heating the inside of the processing vessel to a film formation temperature while supplying a high thermal conductivity gas into the processing vessel at least in a portion of the processing vessel; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having (b) increasing the amount of the high thermal conductivity gas supplied into the processing vessel; A method for manufacturing a semiconductor device.

23. A process vessel for processing a substrate therein; A heating system for controlling a temperature inside the processing vessel; a transfer mechanism for transferring the substrate into the processing chamber and transferring the substrate out of the processing chamber; a processing gas supply system for supplying a processing gas into the processing vessel; a high thermal conductivity gas supply system for supplying a high thermal conductivity gas into the processing vessel; (a) loading the substrate into the processing vessel at a loading temperature; (b) at least in a portion of the process, heating the inside of the process vessel to a film formation temperature while supplying the high thermal conductivity gas into the process vessel; (c) supplying the processing gas into the processing vessel to form a metal film on the surface of the substrate; (d) subjecting the inside of the processing vessel to an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; and having (b) at least in part, increasing the amount of the high thermal conductivity gas supplied into the processing vessel; a control unit configured to be able to control the heating system, the carry-in / out mechanism, the process gas supply system, and the high thermal conductive gas supply system so that A substrate processing apparatus comprising:

24. (a) loading a substrate into a processing vessel having an entry temperature; (b) at least in a portion of the processing vessel, supplying a high thermal conductivity gas into the processing vessel while maintaining the interior of the processing vessel at a film formation temperature; (c) supplying a processing gas into the processing chamber to form a metal film on the surface of the substrate; (d) setting the inside of the processing vessel at an unloading temperature that is lower than the loading temperature; (e) removing the substrate from the processing chamber; having In at least a part of (b), a step of increasing a supply amount of the high thermal conductivity gas into the processing vessel, A program that is executed by a computer in a substrate processing apparatus.

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