Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium

Abstract

At least either of the electrical characteristics and the productivity of a metal-containing film can be improved. The present invention has: (a) a step of housing a substrate in a processing container; (b) a step of supplying a metal-containing gas to the substrate; (c) a step of supplying a first reducing gas to the substrate; (d) a step of supplying a second reducing gas different from the first reducing gas to the substrate, and a metal-containing film is formed on the substrate by performing (b), (c), and (d) one or more times.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a substrate processing method, a manufacturing method of a semiconductor device, a substrate processing apparatus, and a recording medium. BACKGROUND

[0002] As a word line of a NAND type flash memory or a DRAM having a 3-dimensional configuration, for example, a tungsten (W) film of low resistance is used. In addition, for example, a titanium nitride (TiN) film is sometimes used as a barrier film between the W film and an insulating film (see, for example, Patent Document 1 and Patent Document 2).

[0003] PRIOR ART DOCUMENTS

[0004] Patent Document 1: Japanese Patent Application Publication No. 2011-66263

[0005] Patent Document 2: International Publication No. 2019 / 058608 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] However, as the NAND type flash memory of the 3-dimensional configuration is made higher, etching becomes difficult, and thus, thinning of the word line becomes a problem.

[0008] To solve this problem, a molybdenum (Mo) film is sometimes formed instead of using the TiN film and the W film described above. However, to form a Mo film of low resistance and less foreign matter, a large flow of H2 gas needs to be flown for a long time. Thus, reduction of productivity becomes a problem.

[0009] An object of the present disclosure is to provide a technology capable of improving at least any one of an electrical characteristic of a metal-containing film and productivity.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] According to one embodiment of the present disclosure, a technology is provided, having:

[0012] (a) a step of housing a substrate in a processing container;

[0013] (b) a step of supplying a metal-containing gas to the substrate;

[0014] (c) a step of supplying a first reducing gas to the substrate;

[0015] (d) a step of supplying a second reducing gas different from the first reducing gas to the substrate,

[0016] The metal-containing film is formed on the substrate by performing (b), (c), and (d) one or more times.

[0017] EFFECTS OF THE INVENTION

[0018] According to the present disclosure, at least either of the electrical characteristics of the metal-containing film or the productivity can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is a schematic longitudinal sectional view showing a vertical processing furnace of a substrate processing apparatus in an embodiment of the present disclosure.

[0020] Figure 2 is a schematic cross-sectional view of the A-A line in Figure 1

[0021] Figure 3 is a schematic configuration view of a controller of a substrate processing apparatus in an embodiment of the present disclosure, and is a view showing a control system of the controller in a block diagram.

[0022] Figure 4 is a view showing a substrate processing procedure in an embodiment of the present disclosure.

[0023] Figure 5 is a view showing a modification example of a substrate processing procedure in an embodiment of the present disclosure.

[0024] Figure 6 is a view showing a modification example of a substrate processing procedure in an embodiment of the present disclosure.

[0025] Figure 7 (A) and Figure 7 (B) in

[0026] Figure 8 is a view showing a modification example of a substrate processing procedure in an embodiment of the present disclosure.

[0027] Figure 9 (A) and Figure 9 (B) in DETAILED DESCRIPTION

[0028] Hereinafter, description will be made while referring to Figures 1 to 4 In addition, the drawings used in the following description are schematic views, and the dimensional relationship of each element, the ratio of each element, and the like shown in the drawings can not necessarily be consistent with reality. In addition, the dimensional relationship of each element, the ratio of each element, and the like can not necessarily be consistent among a plurality of drawings.

[0029] (1) Structure of Substrate Processing Apparatus

[0030] ​The substrate processing apparatus 10 has a processing furnace 202 provided with a heater 207 as a heating unit (heating mechanism, heating system). The heater 207 is in a cylindrical shape and is vertically installed by being supported by a heater pedestal (not shown) as a holding plate.

[0031] An outer tube 203 that constitutes a reaction tube (reaction container, processing container) in a concentric circle shape with the heater 207 is provided inside the heater 207. The outer tube 203 is constituted of, for example, a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed in a cylindrical shape with an upper end closed and a lower end open. A manifold (inlet flange) 209 is provided in a concentric circle shape with the outer tube 203 below the outer tube 203. The manifold 209 is constituted of, for example, a metal such as stainless steel (SUS) and is formed in a cylindrical shape with upper and lower ends open. An O-ring 220a as a sealing member is provided between the upper end portion of the manifold 209 and the outer tube 203. The outer tube 203 is in a vertically installed state by being supported by the heater pedestal.

[0032] An inner tube 204 that constitutes a reaction container is provided inside the outer tube 203. The inner tube 204 is constituted of, for example, a heat-resistant material such as quartz or SiC and is formed in a cylindrical shape with an upper end closed and a lower end open. The processing container (reaction container) is mainly constituted of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing container (inside the inner tube 204).

[0033] The processing chamber 201 is constituted so as to be capable of housing wafers 200 as substrates in a state of being arranged in multiple stages in a vertical direction in a horizontal posture by a boat 217 as a support member.

[0034] Inside the processing chamber 201, nozzles 410, 420, 430 are provided to penetrate the side wall of the manifold 209 and the inner tube 204. The nozzles 410, 420, 430 are connected to gas supply tubes 310, 320, 330, respectively. However, the processing furnace 202 of the present embodiment is not limited to the above-described manner.

[0035] Mass flow controllers (MFCs) 312, 322, 332 as flow controllers (flow control sections) are provided in the gas supply pipes 310, 320, 330, respectively, in order from the upstream side. Valves 314, 324, 334 as on-off valves are provided in the gas supply pipes 310, 320, 330, respectively. Gas supply pipes 510, 520, 530 that supply non-reactive gas are connected to the downstream sides of the valves 314, 324, 334 of the gas supply pipes 310, 320, 330, respectively. MFCs 512, 522, 532 as flow controllers (flow control sections) and valves 514, 524, 534 as on-off valves are provided in the gas supply pipes 510, 520, 530, respectively, in order from the upstream side.

[0036] The nozzles 410, 420, 430 are connected to the front ends of the gas supply pipes 310, 320, 330, respectively. The nozzles 410, 420, 430 are L-shaped nozzles whose horizontal portions are provided to penetrate the side wall of the manifold 209 and the inner pipe 204. The vertical portions of the nozzles 410, 420, 430 are provided inside the preliminary chamber 201a of a channel shape (groove shape) formed so as to protrude to the radially outer side of the inner pipe 204 and extend in the vertical direction, and are provided in the preliminary chamber 201a so as to face upward along the inner wall of the inner pipe 204.

[0037] The nozzles 410, 420, 430 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, 420a, 430a are provided in the nozzles 410, 420, 430, respectively, at positions opposite the wafer 200. Thus, the processing gas is supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 to the wafer 200, respectively. The gas supply holes 410a, 420a, 430a are provided in a plurality of numbers from the lower portion to the upper portion of the inner pipe 204, have the same opening area, and are provided at the same opening pitch. However, the gas supply holes 410a, 420a, 430a are not limited to the above-described manner. For example, the opening area can be made to gradually increase from the lower portion to the upper portion of the inner pipe 204. Thus, the flow rate of the gas supplied from the gas supply holes 410a, 420a, 430a can be made more uniform.

[0038] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in multiple numbers at positions from the lower portion to the upper portion of the boat 217 described later. Therefore, the process gas supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 into the processing chamber 201 is supplied to the entire area of the wafer 200 housed in the lower portion to the upper portion of the boat 217. The nozzles 410, 420, 430 can be provided so as to extend from the lower portion area to the upper portion area of the processing chamber 201, but are preferably provided so as to extend to the vicinity of the top of the boat 217.

[0039] A raw material gas containing a metal element (metal-containing gas) is supplied as a process gas into the processing chamber 201 from the gas supply pipe 310 via the MFC 312, the valve 314, and the nozzle 410.

[0040] A first reducing gas is supplied as a process gas into the processing chamber 201 from the gas supply pipe 320 via the MFC 322, the valve 324, and the nozzle 420.

[0041] A second reducing gas different from the first reducing gas is supplied as a process gas into the processing chamber 201 from the gas supply pipe 330 via the MFC 332, the valve 334, and the nozzle 430.

[0042] A non-active gas such as nitrogen (N2) gas is supplied into the processing chamber 201 from the gas supply pipes 510, 520, 530 via the MFCs 512, 522, 532, the valves 514, 524, 534, and the nozzles 410, 420, 430. Hereinafter, an example in which N2 gas is used as the non-active gas will be described, but in addition to N2 gas, for example, a noble gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, or the like can be used as the non-active gas.

[0043] In a case where the raw material gas is caused to flow mainly from the gas supply pipe 310, a raw material gas supply system is mainly constituted by the gas supply pipe 310, the MFC 312, and the valve 314, but it is also possible to consider that the nozzle 410 is included in the raw material gas supply system. The raw material gas supply system can also be referred to as a metal-containing gas supply system. In addition, in a case where the first reducing gas is caused to flow from the gas supply pipe 320, a first reducing gas supply system is mainly constituted by the gas supply pipe 320, the MFC 322, and the valve 324, but it is also possible to consider that the nozzle 420 is included in the first reducing gas supply system. In addition, in a case where the second reducing gas is caused to flow from the gas supply pipe 330, a second reducing gas supply system is mainly constituted by the gas supply pipe 330, the MFC 332, and the valve 334, but it is also possible to consider that the nozzle 430 is included in the second reducing gas supply system. In addition, the metal-containing gas supply system, the first reducing gas supply system, and the second reducing gas supply system can also be referred to as a process gas supply system. In addition, it is also possible to consider that the nozzles 410, 420, and 430 are included in the process gas supply system. In addition, a non-reactive gas supply system is mainly constituted by the gas supply pipes 510, 520, and 530, the MFCs 512, 522, and 532, and the valves 514, 524, and 534.

[0044] The method of gas supply in the present embodiment transports gas via the nozzles 410, 420, and 430 disposed in the preliminary chamber 201a defined by the inner wall of the inner pipe 204 and the end portions of the plurality of wafers 200. Further, gas is ejected into the inner pipe 204 from the plurality of gas supply holes 410a, 420a, and 430a provided at positions of the nozzles 410, 420, and 430 opposite the wafers. More specifically, the gas supply holes 410a of the nozzle 410, the gas supply holes 420a of the nozzle 420, and the gas supply holes 430a of the nozzle 430 are used to eject the raw material gas and the like in a direction parallel to the surfaces of the wafers 200.

[0045] The exhaust hole (exhaust port) 204a is a through hole formed at a position of the side wall of the inner pipe 204 opposite the nozzles 410, 420, and 430, and is, for example, a slit-shaped through hole elongated in the vertical direction. Gas supplied from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 into the processing chamber 201 and flowing on the surfaces of the wafers 200 flows via the exhaust hole 204a to the gap (in the exhaust passage 206) formed between the inner pipe 204 and the outer pipe 203. Further, the gas flowing into the exhaust passage 206 flows in the exhaust pipe 231 and is exhausted to the outside of the processing furnace 202.

[0046] The exhaust hole 204a is provided at a position opposite to the plurality of wafers 200. The gas supplied from the gas supply holes 410a, 420a, 430a to the vicinity of the wafers 200 in the processing chamber 201 flows toward the horizontal direction, and then flows into the exhaust passage 206 via the exhaust hole 204a. The exhaust hole 204a is not limited to a through hole in the form of a slit, but can be composed of a plurality of holes.

[0047] The manifold 209 is provided with an exhaust pipe 231 that exhausts the atmosphere in the processing chamber 201. The pressure sensor 245 that detects the pressure in the processing chamber 201 as a pressure detector (pressure detection unit), the APC (Auto Pressure Controller) valve 243, and the vacuum pump 246 that is a vacuum exhaust device are connected in this order from the upstream side of the exhaust pipe 231. The APC valve 243 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve in a state in which the vacuum pump 246 is operated, and can adjust the pressure in the processing chamber 201 by adjusting the valve opening degree in a state in which the vacuum pump 246 is operated. The exhaust system is mainly composed of the exhaust hole 204a, the exhaust passage 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. It can be considered that the vacuum pump 246 is included in the exhaust system.

[0048] A seal cover 219 that is a furnace port cover that can hermetically seal the lower end opening of the manifold 209 is provided below the manifold 209. The seal cover 219 is configured to abut against the lower end of the manifold 209 from the vertical direction lower side. The seal cover 219 is composed of, for example, a metal such as SUS, and is formed in a disc shape. An O-ring 220b that is a seal member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cover 219. On the side of the seal cover 219 opposite to the processing chamber 201, a rotation mechanism 267 that rotates the boat 217 that accommodates the wafers 200 is provided. The rotation shaft 255 of the rotation mechanism 267 penetrates the seal cover 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cover 219 is configured to be raised and lowered in the vertical direction by the boat elevator 115 that is a lifting mechanism provided vertically outside the outer tube 203. The boat elevator 115 is configured to be able to carry the boat 217 in and out of the processing chamber 201 by raising and lowering the seal cover 219. The boat elevator 115 is a conveyance device (conveyance mechanism, conveyance system) that conveys the boat 217 and the wafers 200 accommodated in the boat 217 to and from the processing chamber 201.

[0049] The boat 217 is configured to arrange a plurality of, for example, 25 to 200, wafers 200 in a horizontal posture and in a state of center alignment with each other at intervals in the vertical direction. The boat 217 is configured, for example, of a heat-resistant material such as quartz, SiC, or the like. In the lower portion of the boat 217, a dummy substrate 218 configured of a heat-resistant material such as quartz, SiC, or the like is supported in a horizontal posture in multiple stages. According to this configuration, heat from the heater 207 is less likely to be transmitted to the side of the seal cap 219. However, the present embodiment is not limited to the above-described manner. For example, instead of providing the dummy substrate 218 in the lower portion of the boat 217, a heat-insulating cylinder configured of a cylindrical member of a heat-resistant material such as quartz, SiC, or the like can be provided.

[0050] As shown in FIG. 2, the temperature sensor 263 as a temperature detector is provided in the inner tube 204. The amount of power supplied to the heater 207 is adjusted in accordance with the temperature information detected by the temperature sensor 263, whereby the temperature in the processing chamber 201 is made to be a desired temperature distribution. Figure 2 As shown in FIG. 2, the temperature sensor 263 as a temperature detector is provided in the inner tube 204. The amount of power supplied to the heater 207 is adjusted in accordance with the temperature information detected by the temperature sensor 263, whereby the temperature in the processing chamber 201 is made to be a desired temperature distribution.

[0051] As shown in FIG. 2, the temperature sensor 263 as a temperature detector is provided in the inner tube 204. The amount of power supplied to the heater 207 is adjusted in accordance with the temperature information detected by the temperature sensor 263, whereby the temperature in the processing chamber 201 is made to be a desired temperature distribution. Figure 3 As shown in FIG. 2, the temperature sensor 263 as a temperature detector is provided in the inner tube 204. The amount of power supplied to the heater 207 is adjusted in accordance with the temperature information detected by the temperature sensor 263, whereby the temperature in the processing chamber 201 is made to be a desired temperature distribution.

[0052] The storage device 121c is configured, for example, of a flash memory, a HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the processes, conditions, and the like of the manufacturing method of the semiconductor device described later, and the like are stored in a readable manner. The process recipe is composed in such a manner that the controller 121 can obtain a prescribed result by executing each process (each step) in the manufacturing method of the semiconductor device described later, and functions as a program. Hereinafter, the process recipe, the control program, and the like will be simply referred to as a program. In the case where the term program is used in the present specification, only the process recipe alone, only the control program alone, or a combination of the process recipe and the control program can be included. The RAM 121b is configured as a memory area (work area) that temporarily holds the program, data, and the like read out by the CPU 121a.

[0053] The I / O port 121d is connected to the above-described MFC 312, 322, 332, 512, 522, 532, valve 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, and the like.

[0054] The CPU 121a is configured to read and execute a control program from the storage device 121c, and read a process and the like from the storage device 121c in accordance with input of an operation command from the input / output device 122 or the like. The CPU 121a is configured to control, in accordance with the content of the read process, a flow rate adjustment operation of various gases using the MFC 312, 322, 332, 512, 522, 532, an opening / closing operation of the valve 314, 324, 334, 514, 524, 534, an opening / closing operation of the APC valve 243, and a pressure adjustment operation using the APC valve 243 based on the pressure sensor 245, a temperature adjustment operation of the heater 207 based on the temperature sensor 263, start and stop of the vacuum pump 246, rotation and rotation speed adjustment operation of the boat 217 using the rotation mechanism 267, raising and lowering operation of the boat 217 using the boat elevator 115, accommodation operation of the wafer 200 to the boat 217, and the like.

[0055] The controller 121 can be configured by installing the above-described program stored in an external storage device (for example, a magnetic tape, a floppy disk, a hard disk, an optical disk such as a CD, a DVD, an optical magnetic disk such as an MO, a USB memory, a memory card, and the like) 123 to a computer. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they will be collectively and simply referred to as a recording medium. In the present specification, the recording medium sometimes contains only the storage device 121c alone, sometimes contains only the external storage device 123 alone, or sometimes contains both. The provision of the program to the computer can be performed using a communication unit such as the Internet, a dedicated line, or the like, instead of using the external storage device 123.

[0056] (2) Substrate Processing Step

[0057] As one step of a manufacturing step of a semiconductor device (device), a process of forming a Mo-containing film containing molybdenum (Mo) which is used as a control gate electrode of a 3D NAND, for example, is used. Figure 4 An example of a process of forming a Mo-containing film containing molybdenum (Mo) which is used as a control gate electrode of a 3D NAND, for example, is described. The process of forming the Mo-containing film is performed using the processing furnace 202 of the above-described substrate processing apparatus 10. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121.

[0058] In the substrate processing procedure (manufacturing procedure of a semiconductor device) of the present embodiment, there are:

[0059] (a) a procedure of housing the wafer 200 in the processing container, i.e., the processing chamber 201;

[0060] (b) a procedure of supplying a metal-containing gas to the wafer 200;

[0061] (c) a procedure of supplying a first reducing gas to the wafer 200;

[0062] (d) a procedure of supplying a second reducing gas to the wafer 200,

[0063] (b), (c), and (d) are performed one or more times, whereby a Mo-containing film is formed on the wafer 200 as a metal-containing film.

[0064] In the present specification, in the case where the term "wafer" is used, there are cases where the "wafer itself" is meant, and cases where a "wafer and a layer or layers, such as a prescribed layer or film, formed on the surface thereof" are meant. In the present specification, in the case where the term "surface of a wafer" is used, there are cases where the "surface of the wafer itself" is meant, and cases where the "surface of a prescribed layer or layers, such as a layer or layers, formed on the wafer" are meant. In the present specification, the case where the term "substrate" is used is synonymous with the case where the term "wafer" is used.

[0065] (Wafer loading)

[0066] When a plurality of wafers 200 are loaded into the boat 217 (wafer loading), as shown in FIG. 2, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115, and is loaded into the processing chamber 201 (boat loading), and is housed in the processing container. In this state, the seal cap 219 is in a state of closing the lower end opening of the outer tube 203 via the O-ring 220. Figure 1

[0067] (Pressure adjustment and temperature adjustment)

[0068] ​The vacuum pump 246 is used for vacuum exhaust to make the space in the processing chamber 201, i.e., the space where the wafer 200 exists, have a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 performs feedback control (pressure adjustment) based on the measured pressure information. The vacuum pump 246 is kept in an always-on state at least during the period until the processing of the wafer 200 is completed. In addition, the heater 207 is used for heating to make the processing chamber 201 have a desired temperature. At this time, the power supplied to the heater 207 is controlled based on the temperature information detected by the temperature sensor 263 to make the processing chamber 201 have a desired temperature distribution (temperature adjustment). The heating of the processing chamber 201 by the heater 207 is continued at least during the period until the processing of the wafer 200 is completed.

[0069] [First Process]

[0070] (Metal-containing gas supply)

[0071] The valve 314 is opened to make the metal-containing gas as a raw material gas flow in the gas supply pipe 310. The metal-containing gas is flow-adjusted by the MFC 312, supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410, and discharged from the exhaust pipe 231. At this time, the wafer 200 is supplied with the metal-containing gas. At this time, the valve 514 is also opened to make the non-active gas such as N2 gas flow in the gas supply pipe 510. The non-active gas flowing in the gas supply pipe 510 is flow-adjusted by the MFC 512, supplied into the processing chamber 201 together with the metal-containing gas, and discharged from the exhaust pipe 231. At this time, in order to prevent the metal-containing gas from intruding into the nozzles 420, 430, the valves 524, 534 are opened to make the non-active gas flow in the gas supply pipes 520, 530. The non-active gas is supplied into the processing chamber 201 via the gas supply pipes 320, 330, the nozzles 420, 430, and discharged from the exhaust pipe 231.

[0072] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is a pressure in the range of, for example, 1 to 3990 Pa, for example, 1000 Pa. The supply flow rate of the metal-containing gas controlled by the MFC 312 is, for example, a flow rate in the range of 0.1 to 1.0 slm, preferably, 0.3 to 0.9 slm. The supply flow rates of the non-reactive gases controlled by the MFCs 512, 522, 532 are respectively set to, for example, flow rates in the range of 0.1 to 20 slm. At this time, the temperature of the heater 207 is set to a temperature at which the temperature of the wafer 200 is, for example, a temperature in the range of 300 to 650°C. Further, the expression of the numerical range such as "1 to 3990 Pa" in the present disclosure indicates that the lower limit value and the upper limit value are included in the range. Therefore, for example, "1 to 3990 Pa" indicates "1 Pa or more and 3990 Pa or less". The same applies to other numerical ranges.

[0073] At this time, the gas flowing in the processing chamber 201 is only the metal-containing gas and the non-reactive gas. Here, as the metal-containing gas, for example, a molybdenum (Mo)-containing gas containing Mo as a metal element can be used. As the Mo-containing gas, for example, a molybdenum dioxide dichloride (MoO2Cl2) gas, a molybdenum oxychloride (MoOCl4) gas containing Mo, oxygen (O), and chlorine (Cl) can be used. By the supply of the Mo-containing gas, a Mo-containing layer is formed on the wafer 200 (the surface of the base film). The Mo-containing layer can be a Mo layer containing Cl and O, can be an adsorption layer of MoO2Cl2 (or MoOCl4), or can contain both.

[0074] [Second Process]

[0075] (Removing of Residual Gas)

[0076] After a prescribed time, for example, 1 to 60 seconds, elapses from the start of the supply of the metal-containing gas, the valve 314 of the gas supply pipe 310 is closed, and the supply of the metal-containing gas is stopped. That is, the time for which the metal-containing gas is supplied to the wafer 200 is set to, for example, a time in the range of 1 to 60 seconds. At this time, the APC valve 243 of the exhaust pipe 231 is kept in an open state, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246, and the metal-containing gas which is not reacted or which contributes to the formation of the metal-containing layer and which remains in the processing chamber 201 is removed from the processing chamber 201. That is, the processing chamber 201 is purged. At this time, the valves 514, 524, 534 are kept in an open state, and the supply of the non-reactive gas into the processing chamber 201 is maintained. The non-reactive gas functions as a purge gas, and can improve the effect of removing the metal-containing gas which is not reacted or which contributes to the formation of the metal-containing layer and which remains in the processing chamber 201 from the processing chamber 201.

[0077] [Third Process]

[0078] (Simultaneous supply of first and second reducing gases)

[0079] After the removal of the residual gas in the processing chamber 201, the valves 324, 334 are simultaneously opened, and the first and second reducing gases are caused to flow in the gas supply pipes 320, 330, respectively. The first reducing gas is flow-adjusted by the MFC 322, supplied from the gas supply hole 420a of the nozzle 420 into the processing chamber 201, and discharged from the exhaust pipe 231. The second reducing gas is flow-adjusted by the MFC 332, supplied from the gas supply hole 430a of the nozzle 430 into the processing chamber 201, and discharged from the exhaust pipe 231. At this time, the first and second reducing gases are simultaneously supplied to the wafer 200. At this time, the valves 514, 524, 534 are kept in the open state, and the supply of the non-reactive gas into the gas supply pipes 510, 520, 530 is maintained. The non-reactive gas flowing in the gas supply pipes 510, 520, 530 is flow-adjusted by the MFCs 512, 522, 532, respectively. The non-reactive gas flowing in the gas supply pipe 520 is supplied together with the first reducing gas into the processing chamber 201 via the gas supply pipe 320, the nozzle 420, and discharged from the exhaust pipe 231. In addition, the non-reactive gas flowing in the gas supply pipe 530 is supplied together with the second reducing gas into the processing chamber 201 via the gas supply pipe 330, the nozzle 430, and discharged from the exhaust pipe 231. In addition, the non-reactive gas flowing in the gas supply pipe 510 is supplied into the processing chamber 201 via the gas supply pipe 310, the nozzle 410, and discharged from the exhaust pipe 231, preventing the first and second reducing gases from intruding into the nozzle 410.

[0080] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 13,300 Pa, for example, 10,000 Pa. The supply flow rate of the first reducing gas controlled by the MFC 322 is, for example, a flow rate in the range of 1 to 50 slm, preferably 15 to 30 slm. The supply flow rate of the second reducing gas controlled by the MFC 332 is, for example, a flow rate in the range of 0.1 to 1.0 slm, preferably 0.1 to 0.5 slm. The supply flow rates of the non-reactive gases controlled by the MFCs 512, 522, 532 are set to, for example, flow rates in the range of 0.1 to 30 slm, respectively. At this time, the temperature of the heater 207 is set to a temperature at which the temperature of the wafer 200 is, for example, a temperature in the range of 300 to 650°C.

[0081] At this time, the gas flowing in the processing chamber 201 is the first and second reducing gases and the non-reactive gas. That is, the first and second reducing gases are simultaneously supplied to the wafer 200. In other words, there is a timing at which the first and second reducing gases are simultaneously supplied.

[0082] Here, as the first reducing gas, for example, a gas composed of hydrogen (H), that is, hydrogen (H2) gas, deuterium (D2) can be used. In addition, as the second reducing gas, for example, a gas containing hydrogen (H) and other elements, that is, phosphine (PH3) gas can be used. As the second reducing gas, a gas having a higher reducing action than the first reducing gas is used. In addition, the second reducing gas is a gas of a compound having a larger negative value of the standard Gibbs energy of formation than the first reducing gas. Hereinafter, a case where H2 gas is used as the first reducing gas and PH3 gas is used as the second reducing gas will be described as an example. The wafer 200 is simultaneously supplied with the two different reducing gases, H2 gas and PH3 gas, whereby the adsorption layers of oxygen (O), chlorine (Cl), and MoO2Cl2 contained in the Mo-containing layer as the metal-containing layer on the wafer 200 react with H2 and PH3, and O and Cl are reduced from the Mo-containing layer and the adsorption layers of MoO2Cl2, and O and Cl are removed, and reaction by-products such as water vapor (H2O), hydrogen chloride (HCl), chlorine (Cl2), and phosphorus oxychloride (POCl4) are discharged from the processing chamber 201.

[0083] Here, the MoO2Cl2 gas easily causes a chemical reaction with the PH3 gas. That is, the larger the negative value of the standard Gibbs energy of formation, the more easily a reaction occurs, and the more easily a gas such as POCl4 is generated. POCl4 has properties of easily desorbing and being difficult to adsorb on a film. That is, by supplying the PH3 gas, as a reaction by-product, POCl4 that easily desorbs from a film and is difficult to adsorb on a film can be generated.

[0084] That is, O and Cl of the Mo-containing layer and the adsorption layers of MoO2Cl2 react with H2 and PH3, and a MoCl terminal is formed on the wafer 200, and reaction by-products such as H2O, HCl, and POCl4 are discharged from the processing chamber 201. In addition, a Mo-containing layer containing Mo and substantially not containing Cl and O is formed on the wafer 200.

[0085] [Fourth Step]

[0086] (Supply of First Reducing Gas)

[0087] After a predetermined time, for example, 1 to 1200 seconds, elapses from the start of the simultaneous supply of the first reducing gas and the second reducing gas, the valve 334 of the gas supply pipe 330 is closed, and the supply of the second reducing gas is stopped. That is, the time during which the wafer 200 is simultaneously supplied with the first reducing gas and the second reducing gas is, for example, a time within the range of 1 to 1200 seconds. At this time, the valves 514, 524, 534 are kept in the open state, and the supply of the inert gas into the gas supply pipes 510, 520, 530 is maintained. The inert gas flowing in the gas supply pipes 510, 520, 530 is subjected to flow rate adjustment by the MFCs 512, 522, 532, respectively. The inert gas flowing in the gas supply pipe 520 is supplied together with the first reducing gas into the processing chamber 201 via the gas supply pipe 320, the nozzle 420, and is discharged from the exhaust pipe 231. In addition, the inert gases flowing in the gas supply pipes 510, 530 are supplied into the processing chamber 201 via the gas supply pipes 310, 330, the nozzles 410, 430, respectively, and are discharged from the exhaust pipe 231, and the intrusion of the first reducing gas into the nozzles 410, 430 is prevented.

[0088] At this time, the gas flowing in the processing chamber 201 is the first reducing gas and the inert gas. That is, the wafer 200 is supplied with the first reducing gas and the inert gas.

[0089] [Fourth process]

[0090] (Removal of residual gas)

[0091] After a predetermined time, for example, 1 to 1200 seconds, elapses from the start of the supply of the first reducing gas, the valve 324 of the gas supply pipe 320 is closed, and the supply of the first reducing gas is stopped. Also, by the same processing procedure as in the second process described above, the first reducing gas which has not reacted or which has contributed to the formation of the metal-containing layer, reaction by-products, and the like remaining in the processing chamber 201 are removed from the processing chamber 201. That is, the processing chamber 201 is purged.

[0092] That is, the supply of the first reducing gas and the supply of the second reducing gas are started simultaneously, and after the supply of the second reducing gas is stopped, the supply of the first reducing gas is stopped.

[0093] That is, the supply of the first reducing gas and the supply of the second reducing gas are performed in partial parallel, and the supply time of the second reducing gas with respect to the wafer 200 is shorter than the supply time of the first reducing gas. In other words, the supply time of the first reducing gas is longer than the supply time of the second reducing gas.

[0094] Here, in the case where PH3 gas is used as the second reducing gas, if the supply time of the PH3 gas is made long, the amount of POCl4, which is a reaction by-product, is increased, and the P content in the Mo-containing layer is increased. Therefore, the supply time of the H2 gas is set to be longer than the supply time of the PH3 gas. Thus, POCl4, which is a reaction by-product, can be removed, the remaining of POCl4 is suppressed, and the phosphorus (P) content in the Mo-containing layer is reduced.

[0095] (Implementation of a predetermined number of times)

[0096] The above-described first process to fifth process are sequentially performed at least once or more (a predetermined number of times (n times)), whereby a metal-containing film of a predetermined thickness is formed on the wafer 200. The above-described cycle is preferably repeated a plurality of times. Here, in the case where the metal-containing gas is a Mo-containing gas, a Mo-containing film is formed as the metal-containing film. Further, the Mo-containing film is a film in which molybdenum is a main component.

[0097] (Post-purge and atmospheric pressure recovery)

[0098] The non-reactive gas is supplied from the gas supply pipes 510, 520, 530 into the processing chamber 201 and is exhausted from the exhaust pipe 231. The non-reactive gas functions as a purge gas, whereby the processing chamber 201 is purged with the non-reactive gas, and the gas and the reaction by-product remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the non-reactive gas (non-reactive gas replacement), and the pressure in the processing chamber 201 is returned to the normal pressure (atmospheric pressure recovery).

[0099] (Wafer unloading)

[0100] Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the outer pipe 203 is opened. Further, the processed wafer 200 is unloaded from the lower end of the outer pipe 203 to the outside of the outer pipe 203 in a state where the wafer 217 supports the processed wafer 200 (boat unloading). Thereafter, the processed wafer 200 is taken out from the wafer 217 (wafer take-out).

[0101] (3) Effects based on the present embodiment

[0102] According to the present embodiment, one or more of the following effects can be obtained.

[0103] (a) The electrical characteristics of the Mo-containing film can be improved.

[0104] (b) A low-resistance Mo-containing film in which foreign matter (by-products, etc.) is reduced can be formed.

[0105] (c) The productivity can be improved.

[0106] (4) Other implementation methods

[0107] Next, a detailed description of a variation of the substrate processing step in the above embodiment will be provided. In the following variations, the timing of the supply of the first reducing gas and the second reducing gas differs from that in the above embodiment. In the following variations, only the differences from the above embodiment will be described in detail.

[0108] (Variation Example 1)

[0109] In this variation, such as Figure 5 As shown, after the metal-containing gas supply as the first step and the residual gas removal as the second step, the supply of the second reducing gas begins as the third step. After a predetermined time, for example, 1 to 20 seconds, following the start of the second reducing gas supply, the supply of the first reducing gas begins as the fourth step. After a predetermined time, for example, 1 to 20 seconds, following the simultaneous supply of the first and second reducing gases, the supply of the second reducing gas is stopped as the fifth step. After a predetermined time, for example, 1 to 120 seconds, following the cessation of the second reducing gas supply, the supply of the first reducing gas is stopped. Furthermore, as the sixth step, the residual gas is removed. This cycle of the first to sixth steps is performed at least once (a predetermined number of times (n times)), thereby forming a metal-containing film of a predetermined thickness on the wafer 200. In this modified example, the supply time of the second reducing gas relative to the wafer 200 is also shorter than the supply time of the first reducing gas.

[0110] That is, the supply of the first reducing gas begins after the supply of the second reducing gas, and the supply of the first and second reducing gases is carried out locally in parallel. The supply of the first reducing gas is stopped after the supply of the second reducing gas is stopped. In this way, by supplying the second reducing gas before the first reducing gas, elements other than the metal can be removed from the adsorption layer containing metal gas molecules and the metal-containing layer containing elements other than the metal contained in the metal gas, forming a film that is easily reduced by the first reducing gas. In other words, since the second reducing gas, which is not diluted by the first reducing gas, is supplied, the contact probability between the adsorption layer containing metal gas molecules and the second reducing gas molecules can be increased, and a film that is easily reduced by the first reducing gas can be formed. Furthermore, by stopping the supply of the first reducing gas after stopping the supply of the second reducing gas, the residue of reaction byproducts can be suppressed. Even in this case, the same as described above can be obtained. Figure 4 The same effect is achieved in the order shown. Here, when the metal-containing gas is MoO2Cl2 gas, O and Cl can be removed from the MoO2Cl2 adsorption layer and the Mo-containing layer containing Cl and O, forming a membrane that is easily reduced by the first reducing gas.

[0111] (Modified example 2)

[0112] In the present modified example, as shown in Figure 6 the supply of the first reducing gas is started as a third process after the supply of the metal-containing gas as the first process and the removal of the residual gas as the second process. After a lapse of a predetermined time, for example, 1 to 60 seconds, from the start of the supply of the first reducing gas, the supply of the second reducing gas is started as a fourth process. Further, after a lapse of a predetermined time, for example, 1 to 60 seconds, from the simultaneous supply of the first reducing gas and the second reducing gas, the supply of the second reducing gas is stopped. As a fifth process, after a lapse of a predetermined time, for example, 1 to 60 seconds, from the stop of the supply of the second reducing gas, the supply of the first reducing gas is stopped. That is, the supply of the second reducing gas is started in the supply of the first reducing gas, and the supply of the second reducing gas is stopped. That is, the supply of the second reducing gas is performed during the supply of the first reducing gas. In other words, the supply of the second reducing gas is started after the start of the supply of the first reducing gas, and the supply of the first reducing gas is stopped after the stop of the supply of the second reducing gas. Further, as a sixth process, the removal of the residual gas is performed, and the cycle of the first to sixth processes is performed at least once or more (n times), whereby a metal-containing film of a predetermined thickness is formed on the wafer 200. Further, in the present modified example, the supply time of the second reducing gas with respect to the wafer 200 is also shorter than the supply time of the first reducing gas.

[0113] That is, the supply of the second reducing gas is started after the start of the supply of the first reducing gas, the supply of the first reducing gas and the supply of the second reducing gas are performed partially in parallel, and the supply of the first reducing gas is stopped after the stop of the supply of the second reducing gas. In this way, the supply of the first reducing gas is stopped after the stop of the supply of the second reducing gas, whereby the remaining of the reaction by-products can be suppressed. Even in this case, the same effects as the sequence shown in Figure 4 can be obtained.

[0114] (Modified example 3)

[0115] In the present modified example, as shown in Figure 7 (A) and Figure 7(B) of FIG. 6, after the supply of the metal-containing gas as the first process, the removal of the residual gas as the second process, and the supply of the second reducing gas as the third process, the supply of the first reducing gas as the fourth process and the removal of the residual gas as the fifth process are performed. Further, the cycle of sequentially performing the first to fifth processes is performed at least once or more (a predetermined number of times (n times)), whereby a metal-containing film of a predetermined thickness is formed on the wafer 200. That is, the supply of the second reducing gas and the supply of the first reducing gas are not performed in parallel but are performed separately. Further, as shown in Figure 7 (A) of FIG. 6, the supply of the second reducing gas and the supply of the first reducing gas can be performed continuously, or as shown in Figure 7 (B) of FIG. 6, the removal of the residual gas and the purge of the processing chamber 201 are performed between the supply of the second reducing gas and the supply of the first reducing gas. Further, in the present modification example, the supply time of the second reducing gas with respect to the wafer 200 is also made shorter than the supply time of the first reducing gas.

[0116] That is, the supply of the second reducing gas is started before the supply of the first reducing gas, and after the supply of the second reducing gas is performed, the supply of the first reducing gas is performed. Here, a case where H2gas is used as the first reducing gas and PH3gas is used as the second reducing gas is described. In this way, after the supply of the PH3gas is performed, the supply of the H2gas is performed, whereby O and Cl can be removed from the adsorption layer of MoO2Cl2, the Mo-containing layer containing Cl and O, and a film in a state that is easily reduced by the H2gas is formed. In addition, the PH3gas can be diluted by the H2gas to suppress the above reaction. In addition, after the supply of the PH3gas is stopped, the supply of the H2gas is stopped, whereby the residual of POCl4as a reaction by-product can be suppressed. In addition, as shown in Figure 7 (B), a timing (exhaust process) where no gas is supplied is provided between the supply of the second reducing gas and the supply of the first reducing gas, whereby the by-products and the excessive second reducing gas present in the processing chamber can be removed, and the reaction probability of the Mo-containing layer with the H2molecule can be increased. Even in this case, the same effects as the sequence shown in Figure 4 can be obtained.

[0117] (Modification Example 4)

[0118] In the present modification example, as shown in Figure 8As shown, after the metal-containing gas supply as the first process and the residual gas removal as the second process are performed, a process of supplying a second reducing gas as a third process and a process of removing a residual gas as a fourth process are performed, and the cycle of sequentially performing the first process to the fourth process is performed at least once or more (a predetermined number of times (n times)), whereby a metal-containing film of a predetermined thickness is formed on the wafer 200. That is, the supply of the first reducing gas is not performed. In a case where MoO2Cl2is used as the metal-containing gas and PH3is used as the second reducing gas, O and Cl are removed from the adsorption layer of MoO2Cl2, the Mo-containing layer containing Cl and O, by supplying PH3gas, and a Mo film is obtained as described above. Figure 4 The same effects as the sequence shown above are obtained.

[0119] Further, in the above embodiment, a case where MoO2Cl2gas is used as the metal-containing gas (Mo-containing gas) is described as an example, but the present disclosure is not limited thereto.

[0120] Further, in the above embodiment, a case where H2gas is used as the first reducing gas is described as an example, but the present disclosure is not limited thereto, and for example, other reducing gases such as deuterium (D2), hydrogen gas containing activated hydrogen, or the like can be used.

[0121] Further, in the above embodiment, a case where PH3gas is used as the second reducing gas is described as an example, but the present disclosure is not limited thereto, and for example, other reducing gases such as monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, tetrasilane (Si4H 10 ) gas, borane (BH3), diborane (B2H6), or the like can be used. By using these gases, the reducing power of the Mo-containing gas can also be improved. On the other hand, a by-product that is easily detached such as POCl4that is generated in a case where PH3gas is used cannot be obtained, and the characteristics of the Mo film can deteriorate. Therefore, as the second reducing gas, PH3gas is preferable.

[0122] Further, in the above embodiment, an example in which film formation is performed using a batch-type vertical device, that is, a substrate processing device that processes a plurality of substrates at a time is described, but the present disclosure is not limited thereto, and can be appropriately applied to a case where film formation is performed using a single-type substrate processing device that processes one or more substrates at a time.

[0123] For example, in a case where a substrate processing device that processes a plurality of substrates at a time is used, the substrate processing device can be used as it is, or the substrate processing device can be modified so that the substrate processing device can be used as a substrate processing device that processes one or more substrates at a time. Figure 9The present disclosure can also be appropriately applied when forming a film using the substrate processing apparatus of the processing furnace 302 shown in (A). The processing furnace 302 includes: a processing container 303 forming a processing chamber 301; a spray head 303s supplying gas into the processing chamber 301 in a spray pattern; a support platform 317 supporting one or more wafers 200 in a horizontal position; a rotation shaft 355 supporting the support platform 317 from below; and a heater 307 provided on the support platform 317. A gas supply port 332a for supplying the aforementioned metal-containing gas, a gas supply port 332b for supplying the aforementioned first reducing gas, and a gas supply port 332c for supplying the aforementioned second reducing gas are connected to the inlet (gas inlet) of the spray head 303s. A gas supply system similar to the metal-containing gas supply system of the above embodiment is connected to the gas supply port 332a. A gas supply system similar to the first reducing gas supply system of the above embodiment is connected to the gas supply port 332b. A gas supply system identical to the second reducing gas supply system described above is connected to the gas supply port 332c. A gas dispersion plate is provided at the outlet (gas outlet) of the spray head 303s to supply gas into the processing chamber 301 in a spray pattern. An exhaust port 331 is provided in the processing container 303 to exhaust gas from the processing chamber 301. An exhaust system identical to the exhaust system in the above embodiment is connected to the exhaust port 331.

[0124] Additionally, for example, when using with Figure 9 The present disclosure can also be appropriately applied when forming a film using the substrate processing apparatus of the processing furnace 402 shown in (B). The processing furnace 402 includes: a processing container 403 for forming a processing chamber 401; a support platform 417 that horizontally supports one or more wafers 200; a rotation shaft 455 that supports the support platform 417 from below; a lamp heater 407 that irradiates the wafers 200 in the processing container 403; and a quartz window 403w through which light from the lamp heater 407 passes. The processing container 403 is connected to a gas supply port 432a for supplying the aforementioned metal-containing gas, a gas supply port 432b for supplying the aforementioned first reducing gas, and a gas supply port 432c for supplying the aforementioned second reducing gas. A gas supply system identical to the metal-containing gas supply system of the above embodiment is connected to gas supply port 432a. A gas supply system identical to the first reducing gas supply system of the above embodiment is connected to gas supply port 432b. A gas supply system identical to the second reducing gas supply system of the above embodiment is connected to the gas supply port 432c. An exhaust port 431 for venting exhaust from the processing chamber 401 is provided in the processing container 403. An exhaust system identical to the exhaust system of the above embodiment is connected to the exhaust port 431.

[0125] In the case of using these substrate processing apparatuses, film formation can be performed in the same order and processing conditions as in the above-described embodiments.

[0126] The process recipe (a program in which a processing procedure, a processing condition, and the like are described) used in the formation of these various films is preferably prepared (prepared plural) individually according to the content of the substrate processing (a film type, a composition ratio, a film quality, a film thickness, a processing procedure, a processing condition, and the like of the film to be formed). Also, at the start of the substrate processing, the appropriate process recipe is preferably selected from among the plural process recipes according to the content of the substrate processing. Specifically, the plural process recipes prepared individually according to the content of the substrate processing are preferably stored (installed) in advance in the storage device 121c possessed by the substrate processing apparatus via an electric communication line or a recording medium (the external storage device 123) in which the process recipe is recorded. Also, at the start of the substrate processing, the CPU 121a possessed by the substrate processing apparatus is preferably adapted to select the appropriate process recipe from among the plural process recipes stored in the storage device 121c according to the content of the substrate processing. By being configured in this way, various film types, composition ratios, film qualities, and film thicknesses of the films can be formed with good reproducibility in one substrate processing apparatus. In addition, the operation burden (input burden of a processing procedure, a processing condition, and the like) of the operator can be reduced, the operation mistake can be avoided, and the substrate processing can be started quickly.

[0127] In addition, the present disclosure can be implemented, for example, by changing the process recipe of the existing substrate processing apparatus. In the case of changing the process recipe, the process recipe of the present disclosure can be installed in the existing substrate processing apparatus via an electric communication line or a recording medium in which the process recipe is recorded, or the input / output device of the existing substrate processing apparatus can be operated to change the process recipe itself to the process recipe of the present disclosure.

[0128] The embodiments of the present disclosure are specifically described above. However, the present disclosure is not limited to the above-described embodiments, and various changes can be made without departing from the gist thereof.

[0129] Explanation of Reference Numerals

[0130] 10 substrate processing apparatus

[0131] 121 controller

[0132] 200 wafer (substrate)

[0133] 201 processing chamber

Claims

1. A substrate processing method characterized by, has: (a) a step of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a step of supplying a first reducing gas consisting of hydrogen to the substrate; (c) a step of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) after (c) ends, ending (b), forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times.

2. The substrate processing method according to claim 1, wherein (b) and (c) are performed locally in parallel.

3. The substrate processing method according to claim 1, wherein (b) and (c) are started at the same time.

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

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

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

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

8. The substrate processing method according to claim 1, wherein the molybdenum-containing gas is a molybdenum dichloride dioxide gas or a molybdenum tetrachloride oxide gas.

9. The substrate processing method according to claim 1, wherein the first reducing gas is hydrogen gas.

10. The substrate processing method according to claim 1, wherein the second reducing gas is a phosphine gas.

11. The substrate processing method according to claim 1, wherein the second reducing gas is a gas having a higher reduction action than the first reducing gas.

12. The substrate processing method according to claim 1, wherein the second reducing gas is a gas of a compound having a larger negative value of a standard Gibbs energy of formation than the first reducing gas.

13. A substrate processing method, characterized by, has: (a) a step of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a step of supplying a first reducing gas consisting of hydrogen to the substrate; (c) a step of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) making the time of (b) longer than the time of (c), forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times.

14. The substrate processing method according to claim 13, wherein the molybdenum-containing gas is a molybdenum dichloride dioxide gas or a molybdenum tetrachloride oxide gas.

15. The substrate processing method according to claim 13, wherein the first reducing gas is hydrogen gas.

16. The substrate processing method according to claim 13, wherein the second reducing gas is a phosphine gas.

17. The substrate processing method according to claim 13, wherein the second reducing gas is a gas having a higher reduction action than the first reducing gas.

18. The substrate processing method according to claim 13, wherein The second reducing gas is a gas of a compound having a standard formation Gibbs energy that is more negative than that of the first reducing gas.

19. A method of manufacturing a semiconductor device, characterized by The manufacturing method has: (a) a step of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a step of supplying a first reducing gas composed of hydrogen to the substrate; (c) a step of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) after the end of (c), ending (b), a step of forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times.

20. A method of manufacturing a semiconductor device, characterized by The manufacturing method has: (a) a step of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a step of supplying a first reducing gas composed of hydrogen to the substrate; (c) a step of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) a step of forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times, with the time of (b) being longer than that of (c).

21. A computer-readable recording medium having a program recorded thereon, characterized by comprising: The program causes a substrate processing apparatus to execute the following processes by a computer: (a) a process of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a process of supplying a first reducing gas composed of hydrogen to the substrate; (c) a process of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) after the end of (c), ending (b), a process of forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times.

22. A computer-readable recording medium having a program recorded thereon, characterized by comprising: The program causes a substrate processing apparatus to execute the following processes by a computer: (a) a process of supplying a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; (b) a process of supplying a first reducing gas composed of hydrogen to the substrate; (c) a process of supplying a second reducing gas containing hydrogen and another element to the substrate; (d) a process of forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times, with the time of (b) being longer than that of (c).

23. A substrate processing apparatus, characterized by comprising: having: a molybdenum-containing gas supply system that supplies a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; a first reducing gas supply system that supplies a first reducing gas composed of hydrogen to the substrate; a second reducing gas supply system that supplies a second reducing gas containing hydrogen and another element to the substrate; a control section configured to control the molybdenum-containing gas supply system, the first reducing gas supply system, and the second reducing gas supply system so as to perform the following processes: (a) a process of supplying the molybdenum-containing gas to the substrate; (b) a process of supplying the first reducing gas to the substrate; (c) a process of supplying the second reducing gas to the substrate; (d) after the end of (c), ending (b), a process of forming a molybdenum-containing film on the substrate by performing (a), (b), and (c) one or more times.

24. A substrate processing apparatus, characterized by, having: a molybdenum-containing gas supply system that supplies a molybdenum-containing gas containing molybdenum, oxygen, and chlorine to a substrate; a first reducing gas supply system that supplies a first reducing gas composed of hydrogen to the substrate; a second reducing gas supply system that supplies a second reducing gas containing hydrogen and other elements to the substrate; a control section configured to control the metal-containing gas supply system, the first reducing gas supply system, and the second reducing gas supply system so as to perform the following processes: (a) a process of supplying the molybdenum-containing gas to the substrate; (b) a process of supplying the first reducing gas to the substrate; (c) a process of supplying the second reducing gas to the substrate; (d) a process of forming a molybdenum-containing film on the substrate by performing the processes of (a), (b), and (c) one or more times, with the time of (b) being longer than the time of (c).

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