Substrate processing method, method for manufacturing semiconductor device, 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 in three-dimensional NAND flash memory. Furthermore, 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] 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, for example, quartz (SiO 2 The outer tube 203 is made of a heat-resistant material such as silicon carbide (SiC) or the like, 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 and 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 an open upper end and lower end. An O-ring 220a is provided as a seal member between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported by the 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, for example, quartz (SiO 2 The processing vessel is made of a heat-resistant material such as silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. The processing vessel is mainly composed of an outer tube 203, an 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 air-tightly 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. A rotation mechanism 267 that rotates a boat 217 that accommodates wafers 200 is provided on the opposite side of the seal cap 219 to the processing chamber 201. 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 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 lifting 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, hydrogen (H) containing gas is introduced into the processing chamber 201. 2 At least one of the following gases may be supplied: H 2 There are cases where only gas is supplied, cases where only inert gas is supplied, and cases where both are supplied. Below, an example where argon (Ar) gas is used as the inert gas will be explained. In this example, H 2 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. In addition, 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, H 2 The 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, H 2 The gas can be regarded as a highly thermally conductive gas. That is, in at least a part of the first temperature adjustment process, a highly thermally conductive gas is supplied into the processing vessel. When a highly thermally conductive gas 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. In addition, when a highly thermally conductive gas 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 highly thermally conductive gas is not supplied into the processing chamber 201. That is, the time required for temperature adjustment in the processing chamber 201 is shortened.

[0047] Also, H 2 The 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 step, 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] In addition, in at least a part of the first temperature control step, for example in the latter half of the first temperature control step, a reducing gas (H 2 The flow rate of the highly thermally conductive gas may be gradually increased. By increasing the concentration of the reducing gas in the processing chamber 201, the reduction reaction is further promoted and the temperature in the processing chamber 201 can be adjusted in a short time. In addition, the flow rate of the highly thermally conductive gas may be gradually increased in at least a part of the first temperature adjustment process, for example, in the latter half of the first temperature adjustment process. 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, H 2When the gas is supplied into the processing chamber 201 to perform the first temperature adjustment step, if the pressure inside the processing chamber 201 is less than 4000 Pa, it may be difficult to obtain a reduction in the temperature adjustment time, whereas if it is 4000 Pa or more, it is possible to obtain a sufficient reduction in the temperature adjustment time. Furthermore, if it is 6000 Pa or more, it is possible to obtain an even greater reduction in the temperature adjustment time. Furthermore, if it is higher than 13000 Pa, H 2 The wafer 200 may be etched by by-products generated by the gas reducing the wafer 200, and etching by the by-products can be suppressed by setting the pressure at 13000 Pa or less. Also, etching by the by-products can be sufficiently suppressed by setting the pressure at 11000 Pa or less. Therefore, the pressure inside the processing chamber 201 is preferably set to 4000 Pa or more and 13000 Pa or less, and more preferably set to 6000 Pa or more and 11000 Pa or less.

[0050] In the first temperature control process, H 2 When gas is supplied, the substrate is reduced during heating, and therefore, depending on the substrate, an unintended reduction reaction may occur, 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, or 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 process of supplying a highly thermally conductive gas into the processing chamber 201 (a film formation preparation process) may be performed. That is, a highly thermally conductive gas may be supplied into the processing vessel. As the highly thermally conductive gas, for example, H 2Gas can be utilized. Note that the film formation preparation step is preferably performed when a gas that is not a high thermal conductivity gas is supplied in the first temperature control step.

[0053] Here, in the first temperature control step, after supplying a gas that is not a high thermal conductivity gas, such as Ar gas for example, in the film formation step described later, as a reducing gas, a high thermal conductivity gas having reducibility (e.g., H 2 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 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 in 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 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 from the processing chamber 201, the valve 324 is opened and H is introduced into the gas supply pipe 320 as a reducing gas as a processing gas. 2 Supply gas. H 2 The gas is adjusted in flow rate by the MFC 322, supplied from the gas supply holes 420a of the nozzle 420 into the processing chamber 201, and exhausted from the exhaust pipe 231. 2 At the same time, the valve 524 is opened to allow Ar gas to flow 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 H 2 The gas is supplied into the processing chamber 201 together with the gas and exhausted from the exhaust pipe 231. 2 In order to prevent the intrusion of gas, the valve 514 is opened to allow Ar gas 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 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, for example, a pressure in the range of 4000 Pa to 13000 Pa. 2The supply flow rate of the gas is, for example, 1 to 60 slm, preferably 15 to 35 slm. The supply flow rate of the Ar gas controlled by the MFCs 512 and 522 is, for example, 0.1 to 30 slm. 2 The time for which the gas is supplied to the wafer 200 is set within a range of, for example, 0.01 to 600 seconds.

[0063] At this time, the gas flowing in the processing chamber 201 is H 2 Gas and Ar only. Here, H 2 The 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 step. That is, O and chlorine in the Mo-containing layer are replaced by H 2 It reacts with the gas, desorbs from the Mo layer, and becomes water vapor (H 2 O), hydrogen chloride (HCl), and chlorine (Cl 2 ) and other reaction by-products are discharged from the processing chamber 201. 2 Since the film can be formed while reducing with gas, the impurity concentration in the metal film can be reduced.

[0064] In addition, H 2 When a gas is supplied into the processing chamber 201 to perform a film formation process, if the pressure inside the processing chamber 201 is set to less than 4000 Pa, H 2 In some cases, the effect of reducing the impurity concentration of the wafer 200 and the metal film by the reduction gas may not be obtained easily. 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. Also, if the pressure inside the processing chamber 201 is made higher than 13000 Pa, the H 2 The wafer 200 may be etched by by-products generated when the gas reduces the wafer 200, and etching by the by-products can be suppressed by setting the pressure at 13000 Pa or less. Etching by the by-products can be sufficiently suppressed by setting the pressure at 11000 Pa or less. Therefore, the pressure inside the processing chamber 201 is preferably set to 4000 Pa or more and 13000 Pa or less, and more preferably set to 6000 Pa or more and 11000 Pa or less.

[0065] (c4) Residual gas removal step After forming the metal layer, close valve 324 to stop the supply of H 2 gas. Then, in the same processing procedure as the above-described step (c2: residual gas removal), unreacted H remaining in processing chamber 201 or H after contributing to the formation of the metal layer 2 gas and reaction by-products are removed from processing chamber 201. That is, 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 wafer 200. The above cycle is preferably repeated a plurality of times. Also, each of the steps of steps (c1) to (c4) may be performed at least once or more. That is, a cycle of supplying a metal-containing gas and a hydrogen-containing gas into the processing container non-simultaneously is executed a predetermined number of times.

[0067] (d) Temperature reduction step After the film formation step, a temperature reduction step is performed. In the temperature reduction step, the heating of heater 207 is controlled so that the temperature of 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 set to a temperature within the range of 400°C or lower, preferably 250°C or lower, and more preferably 100°C or lower. Processing chamber 201, that is, the space where wafer 200 exists is evacuated by vacuum pump 246 so as to reach a desired pressure (degree of vacuum).

[0068] At this time, H is used as a reducing gas to processing chamber 201 2In other words, a reducing gas is supplied into the processing chamber 201 during at least a part of the temperature lowering process. This allows the temperature in the processing chamber 201 to be lowered while reducing the metal film, thereby reducing the impurity concentration in the metal film and improving the electrical properties of the metal film. Here, the impurities in the temperature lowering process may refer to, for example, nitrogen (N) in addition to the above-mentioned impurities.

[0069] Also, H 2 The gas can be regarded as a highly thermally conductive gas. That is, a highly thermally conductive gas 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 highly thermally conductive gas atmosphere, so that the controllability of the substrate temperature of the wafer 200 is improved.

[0070] In addition, H 2 When gas is supplied into the processing chamber 201 to perform the temperature lowering 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, but 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. Also, if it is higher than 13000 Pa, H 2 When the gas reduces the wafer 200, by-products are generated, which may etch the wafer 200. If the pressure is set to 13,000 Pa or less, etching by the by-products can be suppressed. If the pressure is set to 11,000 Pa or less, etching by the by-products can be sufficiently suppressed. 2 When the temperature lowering step is performed by supplying gas into the processing chamber 201, the pressure inside the processing chamber 201 is preferably set to 4000 Pa or more and 13000 Pa or less, and more preferably set to 6000 Pa or more and 11000 Pa or less.

[0071] Also, H 2The 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 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 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 and oxidation, for example, 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 the steps of the 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, with temperature shown on the vertical axis and time shown 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 formation 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 formation 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 formation temperature T2 to a holding temperature T4 (T4 > T2) higher than the film formation 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 formation 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 formation 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, H 2 Gas is supplied 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 a gas supply pipe 520 into the processing chamber 201 via the MFC 522, the valve 524, and the nozzle 420.

[0080] Here, H 2 The 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. This allows the temperature to be adjusted while reducing the metal film, thereby reducing the impurity concentration in the metal film. Therefore, the electrical properties of the metal film are improved. In addition, H 2 The gas can be regarded as a gas with high thermal conductivity. That is, in at least a part of the second temperature adjustment process, a gas with high thermal conductivity is supplied into the processing chamber 201. This can shorten the time for temperature adjustment. 2 The gas can be regarded as a highly thermally conductive gas having reducing properties. That is, in at least a part of the second temperature control step, a highly thermally conductive gas having reducing properties is supplied into the processing vessel. As a result, the surface of the wafer 200 is heated to H 2 The temperature inside the processing chamber 201 can be adjusted in a short time while performing reduction with gas.

[0081] In the film formation process, a reducing gas having high thermal conductivity (e.g., H 2 Consider the case where a highly thermally conductive gas (gas) is supplied to the processing chamber 201. 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, H 2When the gas is supplied into the processing chamber 201 to perform the second temperature control step, if the pressure inside the processing chamber 201 is less than 4000 Pa, it is difficult to obtain a reduction in the temperature control time, but if it is 4000 Pa or more, the temperature control time can be reduced. If it is 6000 Pa or more, the temperature control time can be reduced sufficiently. If it is higher than 13000 Pa, the H 2 The wafer 200 is etched by by-products generated by the gas reducing the wafer 200, and etching by the by-products can be suppressed by setting the pressure at 13000 Pa or less. Also, etching by the by-products can be sufficiently suppressed by setting the pressure at 11000 Pa or less. Therefore, the pressure inside the processing chamber 201 is set to 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, H is supplied from the gas supply pipe 320 as a reducing gas. 2Gas is supplied 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, H 2 When gas is supplied into the processing chamber 201 to perform the holding step, 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 the metal film, but if it is 4000 Pa or more, the effect of reduction can be obtained. If it is 6000 Pa or more, the effect of shortening the temperature control time can be sufficiently obtained. Also, if it is higher than 13000 Pa, H 2 The wafer 200 may be etched by by-products generated when the gas reduces the wafer 200, and etching by the by-products can be suppressed by setting the pressure at 13000 Pa or less. Also, etching by the by-products can be sufficiently suppressed by setting the pressure at 11000 Pa or less. Therefore, the pressure inside the processing chamber 201 is preferably set to 4000 Pa or more and 13000 Pa or less, and more preferably set to 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] It is preferable to use an inert gas that does not easily react with the metal film formed in the substrate processing step. For example, rare gases such as helium (He) gas, neon (Ne) gas, argon (Ar) gas, xenon (Xe) gas, and nitrogen (N 2 ) gas may be appropriately selected and used.2 It may be altered by gas. In that case, 2 For example, when forming a Mo film as a metal film, the Mo film is 2 Because it is altered by gas, N 2 It is preferable to use an inert gas other than gas.

[0090] The reducing gas is, for example, H 2 Gas, Deuterium (D 2 ) gas, borane (BH 3 ) gas, diborane (B 2 H 6 ) gas, carbon monoxide (CO) gas, ammonia (NH 3 ) gas, monosilane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas, trisilane (Si 3 H 8 ) gas, monogermane (GeH 4 ) gas, digermane (Ge 2 H 6 ) is available.

[0091] In the present disclosure, the highly thermally conductive gas 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, H 2 Gas, D 2 Gas, He gas, BH 3 Gas, B. 2 H 6 Gas, NH 3 Gas, N 2 Gas, Ne gas, SiH 4 Gas such as N2 gas or CO2 gas may be used. 2 If gas is used, N 2 H, a gas with a smaller molecular weight than 2 Gas, D 2 Gas, He gas, BH 3For example, when He gas is used as the inert gas, H gas, which has a smaller molecular weight than He, may be used. 2 Gas, D 2 Gas may also 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, H 2 Gas, D 2 Gas, BH 3 Gas, B. 2 H 6 Gas, NH 3 Gas, SiH 4 Gases with high thermal conductivity and reducing properties include H 2 Gas or D 2 It is preferable to use a gas.

[0093] D 2 H 2 Since it is more active than D 2 Gas is H 2 The reducing effect is greater than that of gas. Therefore, D is used as a reducing gas. 2 When gas is used, H 2 It is possible to reduce the impurity concentration in the metal film more effectively than with gas.

[0094] Reducing gas or high thermal conductivity gas, H as a reducing and high thermal conductivity gas 2 Gas, H 2 When the mixed gas containing H and other gas is supplied to the processing chamber 201, the H 2 If the mass fraction of H is less than 70%, the reduction effect may not be sufficient, and the electrical resistance of the metal film may not reach the target value. 2 By making the mass fraction of H 70% or more, the reduction effect can be sufficiently obtained, and the electrical resistance of the metal film can reach the target value. 2By making the mass fraction of H 90% or more, the electrical resistance of the metal film can be improved to a target value or higher. In other words, it is possible to obtain a metal film having electrical properties that exceed the target value. 2 The mass fraction of is preferably 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 (e.g., fluorine (F), Cl, bromine (Br), iodine (I)) can be used. Furthermore, as the halogen-based metal-containing gas, for example, a halogen-based transition metal-containing gas containing a transition metal element can be used. Furthermore, as the halogen-based transition metal-containing gas, for example, a halogen-containing Mo-containing gas containing Mo can be used. Furthermore, as the halogen-containing Mo-containing gas, for example, molybdenum dioxide dichloride (MoO 2 Cl 2) gas, molybdenum oxide tetrachloride (MoOCl 4 ) gas, molybdenum pentachloride (MoCl 5 ) 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 halogen elements, it is possible to suppress deterioration of the electrical properties (e.g., electrical resistance) of the metal film. In addition, MoCl 5 When an O-free metal-containing gas (Mo-containing gas) such as the above 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 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. A substrate processing method comprising the steps of:

2. the treatment gas is a metal-containing gas and a reducing gas; (c) performing a cycle of supplying the metal-containing gas and the reducing gas non-simultaneously into the processing vessel a predetermined number of times; The method for processing a substrate according to claim 1 .

3. The substrate processing method according to claim 1 , further comprising: supplying a reducing gas into the processing vessel in at least a portion of (b).

4. 2. The substrate processing method according to claim 1, further comprising: supplying a highly thermally conductive gas into the processing vessel in at least a portion of (b).

5. The substrate processing method according to claim 3 , further comprising increasing an amount of the reducing gas supplied into the processing vessel in at least a portion of (b).

6. 5. The substrate processing method according to claim 4, further comprising increasing an amount of the highly thermally conductive gas supplied into the processing vessel in at least a portion of (b).

7. The reducing gas supplied in (c) is a highly heat-conductive gas having reducing properties; (c), (f) supplying a highly thermally conductive gas into the processing vessel; The method of claim 2 further comprising:

8. The substrate processing method according to claim 7 , further comprising increasing a supply amount of the highly thermally conductive gas in at least a portion of (f).

9. 2. 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 a temperature inside the processing vessel is changed.

10. The substrate processing method according to claim 1 , further comprising: supplying a reducing gas into the processing vessel in at least a portion of (d).

11. 2. The substrate processing method according to claim 1, further comprising: supplying a highly thermally conductive gas into the processing vessel in at least a portion of (d).

12. (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 method of claim 1 , further comprising:

13. 13. The substrate processing method of claim 12, wherein the inside of the processing vessel is maintained in a vacuum state during at least a part of (g), and the temperature inside the processing vessel is reduced to the unloading temperature.

14. The substrate processing method of claim 12 , further comprising: supplying a reducing gas into the processing vessel during at least a portion of (g).

15. The substrate processing method according to claim 12 , further comprising: supplying a highly thermally conductive gas into the processing vessel in at least a portion of (g).

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

17. 17. The substrate processing method according to claim 3, wherein the reducing gas is a highly heat conductive gas having reducing properties.

18. The substrate processing method according to claim 3 , wherein the reducing gas is a hydrogen-containing gas.

19. 17. The substrate processing method according to claim 3, wherein the reducing gas is a deuterium-containing gas.

20. the hydrogen-containing gas comprises hydrogen gas; The substrate processing method according to claim 18 , wherein a mass fraction of hydrogen gas in the hydrogen-containing gas is 70% or more.

21. the hydrogen-containing gas comprises hydrogen gas; The substrate processing method according to claim 18 , wherein a mass fraction of hydrogen gas in the hydrogen-containing gas is 90% or more.

22. 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.

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

24. The substrate processing method according to claim 2 , wherein the metal-containing gas contains a halogen element.

25. (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; (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; A method for manufacturing a semiconductor device having the above structure.

26. a processing vessel whose interior is controlled to a carry-in temperature, a film forming temperature, and an unloading temperature lower than the carry-in temperature, and in which a substrate is processed; 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 chamber to form a metal film on the surface of the substrate; A substrate processing apparatus comprising:

27. (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; (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; A program for causing a substrate processing apparatus to execute the method comprising the steps of:

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