Patent Publication Number: US-2022216061-A1

Title: Substrate processing method, method of manufacturing semiconductor device, non-transitory computer-readable recording medium and substrate processing apparatus

Description:
CROSS-REFERENCE TO RELATED PATENT APPLICATION 
     This application is a bypass continuation application of PCT International Application No. PCT/JP2019/036603, filed on Sep. 18, 2019, in the WIPO, the entire contents of which are hereby incorporated by reference. 
    
    
     BACKGROUND 
     1. Field 
     The present disclosure relates to a substrate processing method, a method of manufacturing a semiconductor device, a non-transitory computer-readable recording medium and a substrate processing apparatus. 
     2. Related Art 
     For example, a tungsten film (also simply referred to as a “W film”) whose resistance is low is used as a word line of a DRAM or a NAND flash memory of a three-dimensional structure. In addition, according to some related arts, a titanium nitride film (also simply referred to as a “TiN film”) serving as a barrier film may be provided between the W film and an insulating film. The TiN film serves to improve the adhesion between the W film and the insulating film, and a nucleation film of growing the W film may be formed on the TiN film. 
     However, an embedding width of a groove in which the W film is formed is small. Therefore, when the TiN film is not flat, a volume of the W film may decrease. Thereby, it may be difficult to reduce the resistance of the W film. 
     SUMMARY 
     According to the present disclosure, there is provided a technique capable of forming a sufficiently flat film. 
     According to one or more embodiments of the present disclosure, there is provided a technique a substrate processing method including: forming a metal-containing multi-layer film structure on a substrate by alternately performing: (a) forming a metal-containing film on the substrate; and (b) supplying a process gas to the substrate so as to perform one or both of (b-1) forming a crystal layer separation film to a surface of the metal-containing film and (b-2) removing abnormal growth nuclei at the surface of the metal-containing film. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a diagram schematically illustrating a vertical cross-section of a vertical type process furnace of a substrate processing apparatus according to one or more embodiments of the present disclosure. 
         FIG. 2  is a diagram schematically illustrating a horizontal cross-section, taken along the line A-A shown in  FIG. 1 , of the vertical type process furnace of the substrate processing apparatus according to the embodiments of the present disclosure. 
         FIG. 3  is a block diagram schematically illustrating a configuration of a controller and related components of the substrate processing apparatus according to the embodiments of the present disclosure. 
         FIG. 4  is a diagram schematically illustrating a film-forming sequence according to a first embodiment of the present disclosure. 
         FIG. 5  is a diagram schematically illustrating a film-forming sequence according to a second embodiment of the present disclosure. 
         FIG. 6  is a diagram schematically illustrating a film-forming sequence according to a third embodiment of the present disclosure. 
         FIG. 7  is a diagram schematically illustrating a film-forming sequence according to a fourth embodiment of the present disclosure. p  FIG. 8  is a diagram schematically illustrating a modified example of a film-forming step in the film-forming sequences according to the embodiments of the present disclosure. 
         FIG. 9A  is a diagram schematically illustrating a vertical cross-section of a process furnace of a substrate processing apparatus according to another embodiment of the present disclosure, and  FIG. 9B  is a diagram schematically illustrating a vertical cross-section of a process furnace of a substrate processing apparatus according to still another embodiment of the present disclosure. 
         FIG. 10  is a diagram schematically illustrating a comparison of cross-sections of TiN films formed on a substrate according to a comparative example and first through third examples. 
     
    
    
     DETAILED DESCRIPTION 
     Embodiments 
     Hereinafter, one or more embodiments (also simply referred to as “embodiments”) according to the technique of the present disclosure will be described with reference to  FIGS. 1 through 4 . 
     (1) Configuration of Substrate Processing Apparatus 
     A substrate processing apparatus  10  includes a process furnace  202 . The process furnace  202  is provided with a heater  207  serving as a heating apparatus (which is a heating structure or a heating system). The heater  207  is of a cylindrical shape, and is vertically installed while being supported by a heater base (not shown) serving as a support plate. 
     An outer tube  203  constituting a reaction vessel (which is a process vessel) is provided in an inner side of the heater  207  to be aligned in a manner concentric with the heater  207 . For example, the outer tube  203  is made of a heat resistant material such as quartz (SiO 2 ) and silicon carbide (SiC). For example, the outer tube  203  is of a cylindrical shape with a closed upper end and an open lower end. A manifold (which is an inlet flange)  209  is provided under the outer tube  203  to be aligned in a manner concentric with the outer tube  203 . For example, the manifold  209  is made of a metal such as stainless steel (SUS). The manifold  209  is of a cylindrical shape with open upper and lower ends. An O-ring  220   a  serving as a seal is provided between the upper end of the manifold  209  and the outer tube  203 . As the manifold  209  is supported by the heater base (not shown), the outer tube  203  is installed vertically. 
     An inner tube  204  constituting the reaction vessel is provided in an inner side of the outer tube  203 . For example, the inner tube  204  is made of a heat resistant material such as quartz (SiO 2 ) and silicon carbide (SiC). For example, the inner tube  204  is of a cylindrical shape with a closed upper end and an open lower end. The process vessel (reaction vessel) is constituted mainly by the outer tube  203 , the inner tube  204  and the manifold  209 . A process chamber  201  is provided in (or defined by) a hollow cylindrical portion of the process vessel (that is, an inner side of the inner tube  204 ). 
     The process chamber  201  is configured to stack and accommodate a plurality of wafers including a wafer  200  serving as a substrate in a horizontal orientation in a multistage manner along a vertical direction by a boat  217  described later. Hereinafter, the plurality of wafers including the wafer  200  may also be simply referred to as wafers  200 . 
     Nozzles  410 ,  420 ,  430 ,  440  and  450  are installed in the process chamber  201  so as to penetrate a side wall of the manifold  209  and the inner tube  204 . Gas supply pipes  310 ,  320 ,  330 ,  340  and  350  are connected to the nozzles  410 ,  420 ,  430 ,  440  and  450 , respectively. However, the process furnace  202  according to the present embodiments is not limited thereto. 
     Mass flow controllers (MFCs)  312 ,  322 ,  332 ,  342  and  352  serving as flow rate controllers (flow rate control structures) and valves  314 ,  324 ,  334 ,  344  and  354  serving as opening/closing valves are sequentially installed at the gas supply pipes  310 ,  320 ,  330 ,  340  and  350  in this order from upstream sides to downstream sides of the gas supply pipes  310 ,  320 ,  330 ,  340  and  350 , respectively, in a gas flow direction. Gas supply pipes  510 ,  520 ,  530 ,  540  and  550  through which an inert gas is supplied are connected to the gas supply pipes  310 ,  320 ,  330 ,  340  and  350  at downstream sides of the valves  314 ,  324 ,  334 ,  344  and  354 , respectively. Mass flow controllers (MFCs)  512 ,  522 ,  532 ,  542  and  552  serving as flow rate controllers (flow rate control structures) and valves  514 ,  524 ,  534 ,  544  and  554  serving as opening/closing valves are sequentially installed at the gas supply pipes  510 ,  520 ,  530 ,  540  and  550  in this order from upstream sides to downstream sides of the gas supply pipes  510 ,  520 ,  530 ,  540  and  550  respectively, in the gas flow direction. 
     The nozzles  410 ,  420 ,  430 ,  440  and  450  are connected to front ends (tips) of the gas supply pipes  310 ,  320 ,  330 ,  340  and  350 , respectively. Each of the nozzles  410 ,  420 ,  430 ,  440  and  450  may be implemented as an L-shaped nozzle, and a horizontal portion of each of the nozzles  410 ,  420 ,  430 ,  440  and  450  is installed so as to penetrate the side wall of the manifold  209  and the inner tube  204 . A vertical portion of each of the nozzles  410 ,  420 ,  430 ,  440  and  450  is installed in a spare chamber  201   a  of a channel shape (a groove shape) protruding outward in a radial direction of the inner tube  204  and extending in the vertical direction. That is, the vertical portion of each of the nozzles  410 ,  420 ,  430 ,  440  and  450  is installed in the spare chamber  201   a  along an inner wall of the inner tube  204  toward an upper portion of the inner tube  204  (in an upward direction in which the wafers  200  are arranged). 
     The nozzles  410 ,  420 ,  430 ,  440  and  450  are provided so as to extend from a lower region of the process chamber  201  to an upper region of the process chamber  201 , and are provided with a plurality of gas supply holes  410   a , a plurality of gas supply holes  420   a , a plurality of gas supply holes  430   a , a plurality of gas supply holes  440   a  and a plurality of gas supply holes  450   a , respectively, at positions facing the wafers  200 . Thereby, a gas such as a process gas is supplied to the wafers  200  through the gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450 . The gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a  are provided from a lower portion to the upper portion of the inner tube  204 . An opening area of each of the gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a  is the same, and each of the gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a  is provided at the same pitch. However, the gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a  are not limited thereto. For example, the opening area of each of the gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a  may gradually increase from the lower portion to the upper portion of the inner tube  204  to further uniformize a flow rate of the gas supplied through the gas supply holes  410   a , the gas supply holes  420   a , the gas supply holes  430   a , the gas supply holes  440   a  and the gas supply holes  450   a.    
     The gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450  are provided from a lower portion to an upper portion of the boat  217  described later. Therefore, the process gas supplied into the process chamber  201  through the gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450  can be supplied onto the wafers  200  accommodated in the boat  217  from the lower portion to the upper portion thereof, that is, an entirety of the wafers  200  accommodated in the boat  217 . The nozzles  410 ,  420 ,  430 ,  440  and  450  may extend from the lower region to the upper region of the process chamber  201 . However, it is preferable that the nozzles  410 ,  420 ,  430 ,  440  and  450  may extend to the vicinity of a ceiling of the boat  217 . 
     A source gas containing a metal element (which is a metal-containing gas) serving as the process gas is supplied into the process chamber  201  through the gas supply pipe  310  provided with the MFC  312  and the valve  314  and the nozzle  410 . As a source material of the source gas, for example, the source gas contains titanium (Ti) serving as the metal element. For example, as the source material, titanium tetrachloride (TiCl 4 ) serving as a halogen-based source (which is a halide or a halogen-based titanium source material) may be used. 
     A silicon-containing gas serving as the process gas is supplied into the process chamber  201  through the gas supply pipe  320  provided with the MFC  322  and the valve  324  and the nozzle  420 . For example, a silane-based gas or a chlorosilane-based gas may be used as the silicon-containing gas. For example, silane (SiH 4 ) gas may be used as the silane-based gas. For example, hexachlorodisilane (Si 2 Cl 6 ) gas may be used as the chlorosilane-based gas. According to the present embodiments, the terms “silane-based gas” or “chlorosilane-based gas” may also refer to a gas constituted by a chemical compound wherein the number of silicon (Si), hydrogen (H) or chlorine (Cl) in its chemical formula is different from that of silane or hexachlorodisilane. 
     A reactive gas serving as the process gas is supplied into the process chamber  201  through the gas supply pipe  330  provided with the MFC  332  and the valve  334  and the nozzle  430 . As the reactive gas, for example, a nitrogen-containing gas containing nitrogen (N) such as ammonia (NH 3 ) gas may be used. 
     An oxygen-containing gas serving as the process gas is supplied into the process chamber  201  through the gas supply pipe  340  provided with the MFC  342  and the valve  344  and the nozzle  440 . For example, a gas such as oxygen (O 2 ) gas, ozone (O 3 ) gas, nitric oxide (NO) gas and nitrous oxide (N 2 O) gas may be used as the oxygen-containing gas. 
     A halogen-containing gas serving as the process gas is supplied into the process chamber  201  through the gas supply pipe  350  provided with the MFC  352  and the valve  354  and the nozzle  450 . For example, a gas containing a metal element may be used as the halogen-containing gas. For example, tungsten hexafluoride (WF 6 ) gas may be used as the halogen-containing gas. However, a gas such as nitrogen trifluoride (NF 3 ) gas, chlorine trifluoride (ClF 3 ) gas, fluorine (F 2 ) gas and hydrogen fluoride (HF) gas may be used as the halogen-containing gas. 
     The inert gas such as nitrogen (N 2 ) gas is supplied into the process chamber  201  through the gas supply pipes  510 ,  520 ,  530 ,  540  and  550  provided with the MFCs  512 ,  522 ,  532 ,  542  and  552  and the valves  514 ,  524 ,  534 ,  544  and  554 , respectively, and the nozzles  410 ,  420 ,  430 ,  440  and  450 . While the present embodiments will be described by way of an example in which the N 2  gas is used as the inert gas, the inert gas according to the present embodiments is not limited thereto. For example, instead of the N 2  gas, a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas and xenon (Xe) gas may be used as the inert gas. 
     A process gas supplier (also referred to as a process gas supply structure or a process gas supply system) is constituted mainly by the gas supply pipes  310 ,  320 ,  330 ,  340  and  350 , the MFCs  312 ,  322 ,  332 ,  342  and  352 , the valves  314 ,  324 ,  334 ,  344  and  354  and the nozzles  410 ,  420 ,  430 ,  440  and  450 . However, only the nozzles  410 ,  420 ,  430 ,  440  and  450  may be considered as the process gas supplier. The process gas supplier may also be simply referred to as a “gas supplier” (which is a gas supply structure or a gas supply system). When the source gas is supplied through the gas supply pipe  310 , a source gas supplier (which is a source gas supply structure or a source gas supply system) is constituted mainly by the gas supply pipe  310 , the MFC  312  and the valve  314 . The source gas supplier may further include the nozzle  410 . In addition, when the silicon-containing gas is supplied through the gas supply pipe  320 , a silicon-containing gas supplier (which is a silicon-containing gas supply structure or a silicon-containing gas supply system) is constituted mainly by the gas supply pipe  320 , the MFC  322  and the valve  324 . The silicon-containing gas supplier may further include the nozzle  420 . In addition, when the reactive gas is supplied through the gas supply pipe  330 , a reactive gas supplier (which is a reactive gas supply structure or a reactive gas supply system) is constituted mainly by the gas supply pipe  330 , the MFC  332  and the valve  334 . The reactive gas supplier may further include the nozzle  430 . When the nitrogen-containing gas serving as the reactive gas is supplied through the gas supply pipe  330 , the reactive gas supplier may also be referred to as a nitrogen-containing gas supplier (which is a nitrogen-containing gas supply structure or a nitrogen-containing gas supply system). In addition, when the oxygen-containing gas is supplied through the gas supply pipe  340 , an oxygen-containing gas supplier (which is an oxygen-containing gas supply structure or an oxygen-containing gas supply system) is constituted mainly by the gas supply pipe  340 , the MFC  342  and the valve  344 . The oxygen-containing gas supplier may further include the nozzle  440 . In addition, when the halogen-containing gas is supplied through the gas supply pipe  350 , a halogen-containing gas supplier (which is a halogen-containing gas supply structure or a halogen-containing gas supply system) is constituted mainly by the gas supply pipe  350 , the MFC  352  and the valve  354 . The halogen-containing gas supplier may further include the nozzle  450 . In addition, an inert gas supplier (which is an inert gas supply structure or an inert gas supply system) is constituted mainly by the gas supply pipes  510 ,  520 ,  530 ,  540  and  550 , the MFCs  512 ,  522 ,  532 ,  542  and  552  and the valves  514 ,  524 ,  534 ,  544  and  554 . 
     According to the present embodiments, the gas is supplied through the nozzles  410 ,  420 ,  430 ,  440  and  450  provided in a vertically long annular space (which is defined by the inner wall of the inner tube  204  and edges (peripheries) of the wafers  200 ) in the spare chamber  201 a. Then, the gas is ejected into the inner tube  204  through the gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450  provided at the positions facing the wafers  200 . More specifically, the gas such as the source gas and the reactive gas is ejected into the inner tube  204  in a direction parallel to surfaces of the wafers  200  through the gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450 . 
     An exhaust hole (exhaust port)  204   a  is a through-hole facing the nozzles  410 ,  420 ,  430 ,  440  and  450 , and is provided at a side wall of the inner tube  204 . For example, the exhaust hole  204   a  may be of a narrow slit-shaped through-hole elongating vertically. The gas supplied into the process chamber  201  through the gas supply holes  410   a  of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450  flows over the surfaces of the wafers  200 . Then, the gas that has flowed over the surfaces of the wafers  200  is exhausted through the exhaust hole  204   a  into an exhaust path  206  constituted by a gap provided between the inner tube  204  and the outer tube  203 . Then, the gas flowing in the exhaust path  206  flows into an exhaust pipe  231  and is then discharged (exhausted) out of the process furnace  202 . 
     The exhaust hole  204   a  is provided at a location facing the wafers  200 . The gas supplied into the vicinity of the wafers  200  in the process chamber  201  through the gas supply holes  410 a of the nozzle  410 , the gas supply holes  420   a  of the nozzle  420 , the gas supply holes  430   a  of the nozzle  430 , the gas supply holes  440   a  of the nozzle  440  and the gas supply holes  450   a  of the nozzle  450  flows in a horizontal direction. The gas that has flowed in the horizontal direction is exhausted through the exhaust hole  204   a  into the exhaust path  206 . The exhaust hole  204   a  is not limited to the slit-shaped through-hole. For example, the exhaust hole  204   a  may be configured as a plurality of holes. 
     The exhaust pipe  231  through which an inner atmosphere of the process chamber  201  is exhausted is installed at the manifold  209 . A pressure sensor  245  serving as a pressure detector (pressure detecting structure) configured to detect an inner pressure of the process chamber  201 , an APC (Automatic Pressure Controller) valve  243  and a vacuum pump  246  serving as a vacuum exhaust apparatus are sequentially connected to the exhaust pipe  231  in this order from an upstream side to a downstream side of the exhaust pipe  231 . With the vacuum pump  246  in operation, the APC valve  243  may be opened or closed to perform a vacuum exhaust of the process chamber  201  or stop the vacuum exhaust. In addition, with the vacuum pump  246  in operation, an opening degree of the APC valve  243  may be adjusted in order to adjust the inner pressure of the process chamber  201 . An exhauster (also referred to as an exhaust structure or an exhaust system) is constituted mainly by the exhaust hole  204   a , the exhaust path  206 , the exhaust pipe  231 , the APC valve  243  and the pressure sensor  245 . The exhauster may further include the vacuum pump  246 . 
     A seal cap  219  serving as a furnace opening lid capable of airtightly sealing a lower end opening of the manifold  209  is provided under the manifold  209 . The seal cap  219  is in contact with the lower end of the manifold  209  from vertically thereunder. For example, the seal cap  219  is made of a metal such as SUS, and is of a disk shape. An  0 -ring  220 b serving as a seal is provided on an upper surface of the seal cap  219  so as to be in contact with the lower end of the manifold  209 . A rotator  267  configured to rotate the boat  217  accommodating the wafers  200  is provided at the seal cap  219  opposite to the process chamber  201 . A rotating shaft  255  of the rotator  267  is connected to the boat  217  through the seal cap  219 . As the rotator  267  rotates the boat  217 , the wafers  200  accommodated in the boat  217  are rotated. The seal cap  219  may be elevated or lowered in the vertical direction by a boat elevator  115  serving as an elevating structure vertically provided outside the outer tube  203 . When the seal cap  219  is elevated or lowered in the vertical direction by the boat elevator  115 , the boat  217  may be transferred (loaded) into the process chamber  201  or transferred (unloaded) out of the process chamber  201 . The boat elevator  115  serves as a transfer device (which is a transfer structure or a transfer system) that loads the boat  217  and the wafers  200  accommodated in the boat  217  into the process chamber  201  or unloads the boat  217  and the wafers  200  accommodated in the boat  217  out of the process chamber  201 . 
     The boat  217  serving as a substrate retainer is configured to accommodate (support) the wafers  200  (for example,  25  wafers to  200  wafers) while the wafers  200  are horizontally oriented with their centers aligned with each other with a predetermined interval therebetween in the vertical direction. For example, the boat  217  is made of a heat resistant material such as quartz and SiC. A plurality of heat insulating plates including a heat insulating plate  218  horizontally oriented are provided under the boat  217  in a multistage manner (not shown). The heat insulating plate  218  is made of a heat resistant material such as quartz and SiC. With such a configuration, the heat insulating plate  218  suppresses the transmission of the heat from the heater  207  to the seal cap  219 . However, the present embodiments are not limited thereto. For example, instead of the heat insulating plate  218 , a heat insulating cylinder (not shown) such as a cylinder made of a heat resistant material such as quartz and SiC may be provided under the boat  217 . 
     As shown in  FIG. 2 , a temperature sensor  263  serving as a temperature detector is installed in the inner tube  204 . An amount of the current supplied to the heater  207  is adjusted based on temperature information detected by the temperature sensor  263  such that a desired temperature distribution of an inner temperature of the process chamber  201  can be obtained. Similar to the nozzles  410 ,  420 ,  430 ,  440  and  450 , the temperature sensor  263  is L-shaped, and is provided along the inner wall of the inner tube  204 . 
     As shown in  FIG. 3 , a controller  121  serving as a control device (control structure) is constituted by a computer including a CPU (Central Processing Unit)  121   a , a RAM (Random Access Memory)  121   b , a memory  121   c  and an I/O port  121 d. The RAM  121   b , the memory  121   c  and the I/O port  121   d  may exchange data with the CPU  121   a  through an internal bus. For example, an input/output device  122  such as a touch panel is connected to the controller  121 . 
     The memory  121   c  is configured by a component such as a flash memory and a hard disk drive (HDD). For example, a control program configured to control the operation of the substrate processing apparatus  10  or a process recipe containing information on sequences and conditions of a method of manufacturing a semiconductor device described later is readably stored in the memory  121   c . The process recipe is obtained by combining steps (processes) of the method of manufacturing the semiconductor device described later such that the controller  121  can execute the steps to acquire a predetermined result, and functions as a program. Hereafter, the process recipe and the control program may be collectively or individually referred to as a “program”. In the present specification, the term “program” may refer to the process recipe alone, may refer to the control program alone, or may refer to a combination of the process recipe and the control program. The RAM  121   b  functions as a memory area (work area) where a program or data read by the CPU  121   a  is temporarily stored. 
     The I/O port  121   d  is connected to the above-described components such as the MFCs  312 ,  322 ,  332 ,  342 ,  352 ,  512 ,  522 ,  532 ,  542  and  552 , the valves  314 ,  324 ,  334 ,  344 ,  354 ,  514 ,  524 ,  534 ,  544  and  554 , the pressure sensor  245 , the APC valve  243 , the vacuum pump  246 , the heater  207 , the temperature sensor  263 , the rotator  267  and the boat elevator  115 . 
     The CPU  121   a  is configured to read the control program from the memory  121   c  and execute the read control program. In addition, the CPU  121   a  is configured to read a recipe such as the process recipe from the memory  121   c  in accordance with an operation command inputted from the input/output device  122 . According to the contents of the read recipe, the CPU  121   a  may be configured to be capable of controlling various operations such as flow rate adjusting operations for various gases by the MFCs  312 ,  322 ,  332 ,  342 ,  352 ,  512 ,  522 ,  532 ,  542  and  552 , opening and closing operations of the valves  314 ,  324 ,  334 ,  344 ,  354 ,  514 ,  524 ,  534 ,  544  and  554 , an opening and closing operation of the APC valve  243 , a pressure adjusting operation by the APC valve  243  based on the pressure sensor  245 , a temperature adjusting operation by the heater  207  based on the temperature sensor  263 , a start and stop of the vacuum pump  246 , an operation of adjusting the rotation and the rotation speed of the boat  217  by the rotator  267 , an elevating and lowering operation of the boat  217  by the boat elevator  115  and an operation of transferring and accommodating the wafer  200  into the boat  217 . 
     The controller  121  may be embodied by installing the above-described program stored in an external memory  123  into a computer. For example, the external memory  123  may include a magnetic tape, a magnetic disk such as a flexible disk and a hard disk, an optical disk such as a CD and a DVD, a magneto-optical disk such as an MO and a semiconductor memory such as a USB memory and a memory card. The memory  121   c  or the external memory  123  may be embodied by a non-transitory computer readable recording medium. Hereafter, the memory  121   c  and the external memory  123  are collectively or individually referred to as a “recording medium”. In the present specification, the term “recording medium” may refer to the memory  121   c  alone, may refer to the external memory  123  alone, and may refer to both of the memory  121   c  and the external memory  123 . Instead of the external memory  123 , a communication means such as the Internet and a dedicated line may be used for providing the program to the computer. 
     (2) Substrate Processing (Film-forming Process) 
     Hereinafter, as a part of a manufacturing process of the semiconductor device, an example of a substrate processing of forming a titanium nitride film (also simply referred to as a “TiN film”) on the wafers  200  will be described with reference to  FIG. 4 . The substrate processing of forming the TiN film is performed using the process furnace  202  of the substrate processing apparatus  10  described above. In the following description, the operations of the components constituting the substrate processing apparatus  10  are controlled by the controller  121 . 
     First Embodiment 
     A first embodiment will be described with reference to  FIG. 4 . In the substrate processing (the manufacturing process of the semiconductor device) according to the present embodiment, a multi-layer film structure including a plurality of TiN films is formed on the wafers  200  by alternately performing: 
     (a) a step of forming the TiN film serving as a metal-containing film on the wafer  200 ; and 
     (b) a step of supplying the process gas to the wafer  200  so as to perform one or both of (b-1) a crystal layer separation film forming step of forming the crystal layer separation film to a surface of the TiN film and (b-2) an abnormal growth nuclei removing step of removing the abnormal growth nuclei at the surface of the TiN film. 
     In addition, a cycle comprising (a) and (b) may be repeatedly performed. In the crystal layer separation film forming step, the O 2  gas serving as the oxygen-containing gas is supplied as the process gas. A pressure when supplying the O 2  gas may be set to be different for each execution of the cycle, or the SiH 4  gas serving as the silicon-containing gas may be supplied. 
     In addition, in the abnormal growth nuclei removing step, the WF 6  gas serving as the halogen-containing gas and also serving the gas containing the metal element may be supplied as the process gas. 
     When the TiN film is formed, the abnormal growth nuclei may grow with a crystal growth of the TiN film. According to the present embodiment, it is possible to stop the crystal growth of the TiN film by forming the crystal layer separation film on the surface of the TiN film each time the TiN film of a predetermined thickness is formed. As a result, it is possible to stop a growth of the abnormal growth nuclei. Thereby, the surface of the TiN film is flattened. In addition, by removing (etching) the abnormal growth nuclei formed on the surface of the TiN film each time the TiN film of the predetermined thickness is formed, the surface of the TiN film is flattened. When the abnormal growth nuclei is removed, the surface of the TiN film is also etched. The “crystal growth of the TiN film” may also refer to a growth of TiN crystal grains. When the TiN film is formed, a plurality of crystals (crystal grains) may usually grow. The abnormal growth nuclei may be formed in the plurality of crystals. 
     In the present specification, the term “wafer” may refer to “a wafer itself”, or may refer to “a wafer and a stacked structure (aggregated structure) of a predetermined layer (or layers) or a film (or films) formed on a surface of the wafer”. In the present specification, the term “a surface of a wafer” may refer to “a surface of a wafer itself”, or may refer to “a surface of a predetermined layer or a film formed on a wafer”. In the present specification, the terms “substrate” and “wafer” may be used as substantially the same meaning. That is, the term “substrate” may be substituted by “wafer” and vice versa. 
     Wafer Loading Step 
     The wafers  200  are charged (transferred) into the boat  217  (wafer charging step). After the boat  217  is charged with the wafers  200 , as shown in  FIG. 1 , the boat  217  charged with the wafers  200  is elevated by the boat elevator  115  and loaded (transferred) into the process chamber  201  (boat loading step). With the boat  217  loaded, the seal cap  219  seals a lower end opening of the outer tube  203  (that is, the lower end opening of the manifold  209 ) via the O-ring  220   b.    
     &lt;Pressure Adjusting Step and Temperature Adjusting Step&gt; 
     The vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  until the inner pressure of the process chamber  201  (that is, a space in which the wafers  200  are accommodated) reaches and is maintained at a desired pressure (vacuum degree). When the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201 , the inner pressure of the process chamber  201  is measured by the pressure sensor  245 , and the APC valve  243  is feedback-controlled based on pressure information measured by the pressure sensor  245  (pressure adjusting step). The vacuum pump  246  continuously vacuum-exhausts the inner atmosphere of the process chamber  201  until at least a processing (that is, the substrate processing) of the wafer  200  is completed. In addition, the heater  207  heats the process chamber  201  until the inner temperature of the process chamber  201  reaches and is maintained at a desired temperature. When the heater  207  heats the process chamber  201 , the amount of the current supplied to the heater  207  is feedback-controlled based on the temperature information detected by the temperature sensor  263  such that the desired temperature distribution of the inner temperature of the process chamber  201  is obtained (temperature adjusting step). The heater  207  continuously heats the process chamber  201  until at least the processing of the wafer  200  is completed. 
     &lt;Film-Forming Step&gt; 
     A film-forming step is performed by performing a cycle including a first step, a second step, a third step and a fourth step described below a predetermined number of times (n times). 
     &lt;TiCl 4  Gas Supply Step, First Step&gt; 
     The valve  314  is opened to supply the TiCl 4  gas serving as the source gas into the gas supply pipe  310 . A flow rate of the TiCl 4  gas supplied into the gas supply pipe  310  is adjusted by the MFC  312 . The TiCl 4  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  410   a  of the nozzle  410 , and is exhausted through the exhaust pipe  231 . Thereby, the TiCl 4  gas is supplied to the wafers  200 . When the TiCl 4  gas is supplied, simultaneously, the valve  514  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  510 . A flow rate of the N 2  gas supplied into the gas supply pipe  510  is adjusted by the MFC  512 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the TiCl 4  gas, and is exhausted through the exhaust pipe  231 . In the first step, in order to prevent the TiCl 4  gas from entering the nozzles  420 ,  430 ,  440  and  450 , the valves  524 ,  534 ,  544  and  554  may be opened to supply the N 2  gas into the gas supply pipes  520 ,  530 ,  540  and  550 . The N 2  gas is then supplied into the process chamber  201  through the gas supply pipes  320 ,  330 ,  340  and  350  and the nozzles  420 ,  430 ,  440  and  450 , and is exhausted through the exhaust pipe  231 . 
     In the first step, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 1 Pa to 3,990 Pa. For example, a supply flow rate of the TiCl 4  gas controlled by the MFC  312  may be set to a flow rate within a range from 0.1 slm to 2.0 slm. For example, supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522 ,  532 ,  542  and  552  may be set to flow rates within a range from 0.1 slm to 20 slm, respectively. In the first step, for example, a temperature of the heater  207  may be set such that a temperature of the wafer  200  reaches and is maintained at a temperature within a range from 300° C. to 500° C. 
     In the first step, the TiCl 4  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the TiCl 4  gas and the N 2  gas. By supplying the TiCl 4  gas, a titanium-containing layer is formed on the wafer  200  (that is, on a base film on the surface of the wafer  200 ). The titanium-containing layer may refer to a titanium layer containing chlorine (Cl), may refer to an adsorption layer of the TiCl 4  gas, or may refer to both of the titanium layer containing chlorine and the adsorption layer of the TiCl 4  gas. 
     &lt;Residual Gas Removing Step, Second Step&gt; 
     After a predetermined time (for example, from 0.01 second to 10 seconds) has elapsed from a supply of the TiCl 4  gas, the valve  314  is closed to stop the supply of the TiCl 4  gas. In the second step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the TiCl 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the titanium-containing layer out of the process chamber  201 . In the second step, with the valves  514 ,  524 ,  534 ,  544  and  554  open, the N 2  gas is continuously supplied into the process chamber  201 . The N 2  gas serves as a purge gas, which improves the efficiency of removing the TiCl 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the titanium-containing layer out of the process chamber  201 . 
     &lt;NH 3  Gas Supply Step, Third Step&gt; 
     After the residual gas in the process chamber  201  is removed, the valve  334  is opened to supply the NH 3  gas serving as the reactive gas into the gas supply pipe  330 . A flow rate of the NH 3  gas supplied into the gas supply pipe  330  is adjusted by the MFC  332 . The NH 3  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  430   a  of the nozzle  430 , and is exhausted through the exhaust pipe  231 . Thereby, the NH 3  gas is supplied to the wafers  200 . When the NH 3  gas is supplied, simultaneously, the valve  534  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  530 . A flow rate of the N 2  gas supplied into the gas supply pipe  530  is adjusted by the MFC  532 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the NH 3  gas, and is exhausted through the exhaust pipe  231 . In the third step, in order to prevent the NH 3  gas from entering the nozzles  410 ,  420 ,  440  and  450 , the valves  514 ,  524 ,  544  and  554  may be opened to supply the N 2  gas into the gas supply pipes  510 ,  520 ,  540  and  550 . The N 2  gas is then supplied into the process chamber  201  through the gas supply pipes  310 ,  320 ,  340  and  350  and the nozzles  410 ,  420 ,  440  and  450 , and is exhausted through the exhaust pipe  231 . 
     In the third step, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 1 Pa to 3,990 Pa. For example, a supply flow rate of the NH 3  gas controlled by the MFC  332  may be set to a flow rate within a range from 0.1 slm to 30.0 slm. For example, the supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522 ,  532 ,  542  and  552  may be set to flow rates within a range from 0.1 slm to 30 slm, respectively. For example, a supply time (time duration) of supplying the NH 3  gas to the wafer  200  may be set to a time within a range from 0.01 second to 30 seconds. In the third step, for example, the temperature of the heater  207  may be set to substantially the same temperature as in the TiCl 4  gas supply step. 
     In the third step, the NH 3  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the NH 3  gas and the N 2  gas. A substitution reaction occurs between the NH 3  gas and at least a portion of the titanium-containing layer formed on the wafer  200  in the first step. During the substitution reaction, titanium (Ti) contained in the titanium-containing layer and nitrogen (N) contained in the NH 3  gas are bonded together. As a result, a TiN layer is formed on the wafer  200 . 
     &lt;Residual Gas Removing Step, Fourth Step&gt; 
     After the TiN layer is formed, the valve  334  is closed to stop a supply of the NH 3  gas. Then, a residual gas in the process chamber  201  such as the NH 3  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiN layer and reaction byproducts are removed out of the process chamber  201  in substantially the same manners as in the residual gas removing step (that is, the second step) described above. 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing the cycle wherein the first step, the second step, the third step and the fourth step described above are sequentially performed in this order the predetermined number of times (n times), the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 . 
     &lt;Crystal Layer Separation Film Forming Step&gt; 
     As the crystal layer separation film forming step according to the first embodiment, an O 2  gas supply step is performed. 
     &lt;O 2  Gas Supply Step, Fifth Step of First Embodiment&gt; 
     After the TiN film of the predetermined thickness is formed, the valve  344  is opened to supply the O 2  gas serving as the oxygen-containing gas into the gas supply pipe  340 . A flow rate of the O 2  gas supplied into the gas supply pipe  340  is adjusted by the MFC  342 . The O 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  440   a  of the nozzle  440 , and is exhausted through the exhaust pipe  231 . Thereby, the O 2  gas is supplied to the wafers  200 . When the O 2  gas is supplied, simultaneously, the valve  544  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  540 . A flow rate of the N 2  gas supplied into the gas supply pipe  540  is adjusted by the MFC  542 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the O 2  gas, and is exhausted through the exhaust pipe  231 . In the fifth step of the first embodiment, the valves  514 ,  524 ,  534  and  554  are closed to stop the supply of the N 2  gas through the nozzles  410 ,  420 ,  430  and  450 . 
     In the fifth step of the first embodiment, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 0.1 Pa to 3,990 Pa, and the inner pressure of the process chamber  201  is adjusted differently each time the fifth step of the first embodiment is performed. In addition, for example, a supply flow rate of the O 2  gas controlled by the MFC  342  may be set to a flow rate within a range from 0.1 slm to 10 slm. For example, a supply flow rate of the N 2  gas controlled by the MFC  542  may be set to a flow rate within a range from 0.1 slm to 20 slm. In the fifth step of the first embodiment, for example, the temperature of the heater  207  may be set such that the temperature of the wafer  200  is constantly maintained at substantially the same temperature as a film-forming temperature (which is the temperature of the wafer  200  in the film-forming step), for example, a temperature within a range from 300° C. to 500° C. However, the temperature of the wafer  200  in the fifth step of the first embodiment may be set to be different from the film-forming temperature. 
     In the fifth step of the first embodiment, the O 2  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the O 2  gas and the N 2  gas. By supplying the O 2  gas, the TiN film on the wafer  200  (that is, on the base film on the surface of the wafer  200 ) is oxidized, and oxygen atoms are diffused in the TiN film so as to change a crystallinity of the TiN film. As a result, a titanium oxynitride film (also referred to as a “TiNO film”) or a titanium oxide film (also referred to as a “TiO film”) serving as a crystal layer separation film is formed on the surface of the TiN film, and the surface of the TiN film is flattened. 
     In addition, the pressure (that is, the inner pressure of the process chamber  201 ) in the fifth step of the first embodiment may be adjusted to a pressure closer to the atmospheric pressure rather than the pressure described above. By adjusting the pressure closer to the atmospheric pressure, it is possible to improve a contact probability between molecules of the O 2  gas and the film to be processed (in the present embodiment, the TiN film), and it is also possible to improve an oxygen adsorption rate on the surface of the film to be processed. That is, it is possible to improve a uniformity of an oxidation process. 
     &lt;Purge Step&gt; 
     &lt;Residual Gas Removing Step, Sixth Step&gt; 
     After a predetermined time has elapsed from a supply of the O 2  gas, the valve  344  is closed to stop the supply of the O 2  gas. In the sixth step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the O 2  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiNO film or the TiO film out of the process chamber  201 . In the sixth step, with the valve  544  open, the valves  514 ,  524 ,  534  and  554  are opened to supply the N 2  gas into the process chamber  201 . The N 2  gas serves as the purge gas, which improves the efficiency of removing the O 2  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiNO film or the TiO film out of the process chamber  201 . 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing a cycle wherein (a) the predetermined number of executions (n times) of the film-forming step, (b) the crystal layer separation film forming step by supplying the O 2  gas and (c) the purge step (that is, the sixth step) described above are sequentially performed in this order at least once (a predetermined number of times: m times), a multi-layer TiN film structure of a predetermined thickness (for example, 250 Å) constituted by the plurality of TiN films (each of which has the predetermined thickness, for example, 100 Å) separated by the TiNO film or the TiO film serving as the crystal layer separation film can be formed on the wafer  200 . 
     As described above, the pressure when the O 2  gas is supplied in the crystal layer separation film forming step (that is, the fifth step of the first embodiment) is controlled to be different for each execution of the cycle. Specifically, the pressure when the O 2  gas is supplied in the crystal layer separation film forming step described above is controlled to increase as the number of executions of the cycle increases (that is, the pressure during a later execution of the cycle is controlled to be higher than the pressure during an earlier execution of the cycle). Further, the pressure when the O 2  gas is supplied in the crystal layer separation film forming step described above is set to be smaller than a pressure during a final supply of the O 2  gas after, for example, a thickness of the TiN film reaches 250 Å in a case where a target thickness of the TiN film is 250 Å. As the inner pressure of the process chamber  201  becomes higher, the surface of the TiN film is more likely to be oxidized. Therefore, the surface of the TiN film is reoxidized by setting the pressure to be smaller than the pressure during the final supply of the O 2  gas (which is, for example, close to the atmospheric pressure) while controlling the pressure to increase as the number of the executions of the cycle increases. 
     &lt;After-Purge Step and Returning to Atmospheric Pressure Step&gt; 
     The N 2  gas is supplied into the process chamber  201  through each of the gas supply pipes  510 ,  520 ,  530 ,  540  and  550 , and is exhausted through the exhaust pipe  231 . The N 2  gas serves as the purge gas, and the inner atmosphere of the process chamber  201  is purged with the inert gas. Thereby, the residual gas in the process chamber  201  and by-products remaining in the process chamber  201  are removed from the process chamber  201  (after-purge step). Thereafter, the inner atmosphere of the process chamber  201  is replaced with the inert gas (substitution by the inert gas), and the inner pressure of the process chamber  201  is returned to the normal pressure (atmospheric pressure) (returning to atmospheric pressure step). 
     &lt;Wafer Unloading Step&gt; 
     Thereafter, the seal cap  219  is lowered by the boat elevator  115  and the lower end of the outer tube  203  is opened. Then, the boat  217  with the processed wafers  200  charged therein is unloaded out of the inner tube  204  through the lower end of the inner tube  204  (boat unloading step). Then, the processed wafers  200  are transferred (discharged) from the boat  217  (wafer discharging step). 
     That is, according to the present embodiment, each time the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 , the crystal layer separation film is formed on the surface of the TiN film. Thereby, the surface of the TiN film is oxidized so as to change the crystallinity of the TiN film, and the crystal growth of the TiN film can be suppressed. As a result, it is possible to suppress the formation of the abnormal growth nuclei, and it is also possible to form a flattened TiN film of a predetermined thickness (for example, 250 Å). That is, it is possible to reduce a resistance of the W film formed on the surface of the TiN film. 
     (3) Effects According to Present Embodiment 
     According to the present embodiment described above, it is possible to obtain at least one among the following effects. 
     (a) By suppressing the formation of the abnormal growth nuclei, it is possible to form a sufficiently flat TiN film. 
     (b) It is possible to reduce the resistance of the W film formed on the TiN film. 
     (4) Other Embodiments 
     Subsequently, other embodiments of the embodiment described above will be described in detail. In the following embodiments, detailed description will be given only on their features different from those of the embodiment described above. 
     Second Embodiment 
       FIG. 5  is a diagram schematically illustrating a film-forming sequence according to a second embodiment. The crystal layer separation film forming step of the present embodiment is different from that of the embodiment described above. Specifically, using the substrate processing apparatus  10  described above, the SiH 4  gas serving as the silicon-containing gas is supplied in the crystal layer separation film forming step of the present embodiment instead of the O 2  gas supply in the crystal layer separation film forming step of the embodiment described above. 
     &lt;Crystal Layer Separation Film Forming Step&gt; 
     As the crystal layer separation film forming step according to the second embodiment, a SiH 4  gas supply step is performed. 
     &lt;SiH 4  Gas Supply Step, Fifth Step of Second Embodiment&gt; 
     After the TiN film of the predetermined thickness is formed, the valve  324  is opened to supply the SiH 4  gas serving as the silicon-containing gas into the gas supply pipe  320 . A flow rate of the SiH 4  gas supplied into the gas supply pipe  320  is adjusted by the MFC  322 . The SiH 4  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  420   a  of the nozzle  420 , and is exhausted through the exhaust pipe  231 . Thereby, the SiH 4  gas is supplied to the wafers  200 . When the SiH 4  gas is supplied, simultaneously, the valve  524  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  520 . A flow rate of the N 2  gas supplied into the gas supply pipe  520  is adjusted by the MFC  522 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the SiH 4  gas, and is exhausted through the exhaust pipe  231 . In the fifth step of the first embodiment, the valves  514 ,  534 ,  544  and  554  are closed to stop the supply of the N 2  gas through the nozzles  410 ,  430 ,  440  and  450 . 
     In the fifth step of the second embodiment, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 0.1 Pa to 3,990 Pa. In addition, for example, a supply flow rate of the SiH 4  gas controlled by the MFC  322  may be set to a flow rate within a range from 0.1 slm to 10 slm. For example, a supply flow rate of the N 2  gas controlled by the MFC  522  may be set to a flow rate within a range from 0.1 slm to 20 slm. In the fifth step of the second embodiment, for example, the temperature of the heater  207  may be set such that the temperature of the wafer  200  is constantly maintained at substantially the same temperature as the film-forming temperature (which is the temperature of the wafer  200  in the film-forming step), for example, a temperature within a range from 300° C. to 500° C. However, the temperature of the wafer  200  in the fifth step of the second embodiment may be set to be different from the film-forming temperature. 
     In the fifth step of the second embodiment, the SiH 4  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the SiH 4  gas and the N 2  gas. By supplying the SiH 4  gas, a titanium silicon nitride film (also referred to as a “TiSiN film”) serving as the crystal layer separation film is formed on the surface of the TiN film, and the surface of the TiN film is flattened. 
     &lt;Purge Step&gt; 
     &lt;Residual Gas Removing Step, Sixth Step&gt; 
     After a predetermined time has elapsed from a supply of the SiH 4  gas, the valve  324  is closed to stop the supply of the SiH 4  gas. In the sixth step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the SiH 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiSiN film out of the process chamber  201 . In the sixth step, with the valve  524  open, the valves  514 ,  534 ,  544  and  554  are opened to supply the N 2  gas into the process chamber  201 . The N 2  gas serves as the purge gas, which improves the efficiency of removing the SiH 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiSiN film out of the process chamber  201 . 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing a cycle wherein (a) the predetermined number of executions (n times) of the film-forming step, (b) the crystal layer separation film forming step by supplying the SiH 4  gas and (c) the purge step (that is, the sixth step) described above are sequentially performed in this order at least once (a predetermined number of times: m times), a multi-layer TiN film structure of a predetermined thickness (for example, 250 Å) constituted by the plurality of TiN films (each of which has the predetermined thickness of, for example, 100 Å) separated by the TiSiN film serving as the crystal layer separation film can be formed on the wafer  200 . 
     That is, according to the present embodiment, each time the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 , the crystal layer separation film is formed on the surface of the TiN film. Thereby, the crystals on the surface of the TiN film can be separated from one another, and the crystal growth of the TiN film can be suppressed. As a result, it is possible to suppress the formation of the abnormal growth nuclei, and it is also possible to form a flattened TiN film of a predetermined thickness (for example, 250 Å). That is, it is possible to reduce the resistance of the W film formed on the surface of the TiN film. 
     Third Embodiment 
       FIG. 6  is a diagram schematically illustrating a film-forming sequence according to a third embodiment. According to the present embodiment, the WF 6  gas serving as the halogen-containing gas and also serving as the gas containing the metal element is supplied in the abnormal growth nuclei removing step of the present embodiment instead of the O 2  gas or the SiH 4  gas in the crystal layer separation film forming step of the embodiment described above. 
     &lt;Abnormal Growth Nuclei Removing Step&gt; 
     As the abnormal growth nuclei removing step according to the second embodiment, a WF 6  gas supply step is performed. 
     &lt;WF 6  Gas Supply Step, Fifth Step of Third Embodiment&gt; 
     After the TiN film of the predetermined thickness is formed, the valve  354  is opened to supply the WF 6  gas serving as the halogen-containing gas into the gas supply pipe  350 . A flow rate of the WF 6  gas supplied into the gas supply pipe  350  is adjusted by the MFC  352 . The WF 6  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  450   a  of the nozzle  450 , and is exhausted through the exhaust pipe  231 . Thereby, the WF 6  gas is supplied to the wafers  200 . When the WF 6  gas is supplied, simultaneously, the valve  554  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  550 . A flow rate of the N 2  gas supplied into the gas supply pipe  550  is adjusted by the MFC  552 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the WF 6  gas, and is exhausted through the exhaust pipe  231 . In the fifth step of the third embodiment, the valves  514 ,  524 ,  534  and  544  are closed to stop the supply of the N 2  gas through the nozzles  410 ,  420 ,  430  and  440 . 
     In the fifth step of the third embodiment, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 0.1 Pa to 6,650 Pa. In addition, for example, a supply flow rate of the WF 6  gas controlled by the MFC  352  may be set to a flow rate within a range from 0.01 slm to 10 slm. For example, a supply flow rate of the N 2  gas controlled by the MFC  552  may be set to a flow rate within a range from 0.1 slm to 30 slm. For example, a supply time (time duration) of supplying the WF 6  gas to the wafer  200  may be set to a time within a range from 0.01 second to 30 seconds. In the fifth step of the third embodiment, for example, the temperature of the heater  207  may be set such that the temperature of the wafer  200  is constantly maintained at substantially the same temperature as the film-forming temperature (which is the temperature of the wafer  200  in the film-forming step), for example, a temperature within a range from 300° C. to 500° C. However, the temperature of the wafer  200  in the fifth step of the third embodiment may be set to be different from the film-forming temperature. 
     In the fifth step of the third embodiment, the WF 6  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the WF 6  gas and the N 2  gas. By supplying the WF 6  gas, it is possible to remove (etch) the abnormal growth nuclei formed on the surface of the TiN film on the wafer  200 . As a result, the surface of the TiN film is flattened. 
     &lt;Purge Step&gt; 
     &lt;Residual Gas Removing Step, Sixth Step&gt; 
     After a predetermined time has elapsed from a supply of the WF 6  gas, the valve  354  is closed to stop the supply of the WF 6  gas. In the sixth step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the WF 6  gas remaining in the process chamber  201  which did not react or which contributed to the removal of the abnormal growth nuclei and reaction by-products such as TiWFx out of the process chamber  201 . In the sixth step, with the valve  554  open, the valves  514 ,  524 ,  534  and  544  are opened to supply the N 2  gas into the process chamber  201 . The N 2  gas serves as the purge gas, which improves the efficiency of removing the WF 6  gas remaining in the process chamber  201  which did not react or which contributed to the removal of the abnormal growth nuclei and the reaction by-products such as the TiWFx out of the process chamber  201 . 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing a cycle wherein (a) the predetermined number of executions (n times) of the film-forming step, (b) the abnormal growth nuclei removing step and (c) the purge step (that is, the sixth step) described above are sequentially performed in this order at least once (a predetermined number of times: m times), the abnormal growth nuclei formed on the wafer  200  are removed. Thereby, a multi-layer TiN film structure of a predetermined thickness (for example, 250 Å) constituted by the plurality of TiN films (each of which has the predetermined thickness of, for example, 100 Å) separated by an amorphous TiN film can be formed on the wafer  200 . 
     That is, according to the present embodiment, each time the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 , the abnormal growth nuclei formed on the wafer  200  are removed (etched). By removing the abnormal growth nuclei formed on the wafer  200 , it is also possible to form a flattened TiN film of a predetermined thickness (for example, 250 Å). That is, it is possible to reduce the resistance of the W film formed on the surface of the TiN film. 
     Fourth Embodiment 
       FIG. 7  is a diagram schematically illustrating a film-forming sequence according to a fourth embodiment. According to the present embodiment, after the abnormal growth nuclei removing step of the third embodiment, the crystal layer separation film forming step described above is performed. That is, according to the present embodiment, both of the abnormal growth nuclei removing step and the crystal layer separation film forming step are performed. Specifically, using the substrate processing apparatus  10  described above, the WF 6  gas supply step serving as the abnormal growth nuclei removing step of the third embodiment is performed, and thereafter, the O 2  gas supply step serving as the crystal layer separation film forming step of the first embodiment described above or the SiH 4  gas supply step serving as the crystal layer separation film forming step of the second embodiment described above is performed. 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing a cycle wherein (a) the predetermined number of executions (n times) of the film-forming step, (b) the abnormal growth nuclei removing step, (c) the crystal layer separation film forming step and (d) the purge step (that is, the sixth step) described above are sequentially performed in this order at least once (a predetermined number of times: m times), the abnormal growth nuclei formed on the wafer  200  are removed. Thereby, a multi-layer TiN film structure of a predetermined thickness (for example, 250 Å) constituted by the plurality of TiN films (each of which has the predetermined thickness of, for example, 100 Å) separated by the crystal layer separation film can be formed on the wafer  200 . 
     That is, according to the present embodiment, each time the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 , the abnormal growth nuclei formed on the wafer  200  are removed and the crystal layer separation film is formed. Thereby, the crystal growth on the surface of the TiN film can be suppressed after the abnormal growth nuclei formed on the surface of the wafer  200  are removed. As a result, it is possible to suppress the formation of the abnormal growth nuclei, and it is also possible to form a flattened TiN film of a predetermined thickness (for example, 250 Å). That is, it is possible to reduce the resistance of the W film formed on the surface of the TiN film. 
     &lt;Modified Example&gt; 
     Subsequently, a modified example of the film-forming step in the film-forming sequences according to the embodiments of the present disclosure will be described with reference to  FIG. 8 . 
     The film-forming step of the present modified example is different from that in the film-forming sequences of the embodiments described above. Specifically, according to the present modified example, the SiH 4  gas is supplied during the TiCl 4  gas supply step (that is, the first step) in the film-forming step of the embodiments described above. 
     &lt;Film-forming Step&gt; 
     The film-forming step is performed by performing a cycle including a first step, a second step, a third step and a fourth step described below a predetermined number of times (n times). 
     &lt;TiCl 4  Gas Supply Step, First Sub-step of First Step&gt; 
     The TiCl 4  gas is supplied into the process chamber  201  in substantially the same manners as in the TiCl 4  gas supply step (that is, the first step) in the film-forming step of the embodiments described above. In the first sub-step of the first step, the TiCl 4  gas and the N 2  gas are supplied into the process chamber  201  without any other gas being supplied into the process chamber  201  together with the TiCl 4  gas and the N 2  gas. By supplying the TiCl 4  gas, the titanium-containing layer is formed on the wafer  200  (that is, on the base film on the surface of the wafer  200 ). 
     &lt;SiH 4  Gas Supply Step, Second Sub-step of First Step&gt; 
     After a predetermined time (for example, from 0.01 second to 5 seconds) has elapsed from the supply of the TiCl 4  gas, the valve  324  is opened to supply the SiH 4  gas serving as the silicon-containing gas and also serving as a reducing gas into the gas supply pipe  320 . The flow rate of the SiH 4  gas supplied into the gas supply pipe  320  is adjusted by the MFC  322 . The SiH 4  gas whose flow rate is adjusted is then supplied into the process chamber  201  through the gas supply holes  420   a  of the nozzle  420 , and is exhausted through the exhaust pipe  231 . When the SiH 4  gas is supplied, simultaneously, the valve  524  may be opened to supply the inert gas such as the N 2  gas into the gas supply pipe  520 . The flow rate of the N 2  gas supplied into the gas supply pipe  520  is adjusted by the MFC  522 . The N 2  gas whose flow rate is adjusted is then supplied into the process chamber  201  together with the SiH 4  gas, and is exhausted through the exhaust pipe  231 . In addition, in order to prevent the TiCl 4  gas and the SiH 4  gas from entering the nozzles  430 ,  440  and  450 , the valves  534 ,  544  and  554  may be opened to supply the N 2  gas into the gas supply pipes  530 ,  540  and  550 . Thereby, the TiCl 4  gas, the SiH 4  gas and the N 2  gas are simultaneously supplied to the wafers  200 . That is, in the second sub-step of the first step, there is a timing at which at least the TiCl 4  gas and the SiH 4  gas are simultaneously supplied. 
     In the second sub-step of the first step, for example, the APC valve  243  is appropriately controlled to adjust the inner pressure of the process chamber  201  to a pressure within a range from 130 Pa to 3,990 Pa. When the inner pressure of the process chamber  201  is lower than 130 Pa, silicon contained in the SiH 4  gas may enter the titanium-containing layer so as to increase the silicon content in the TiN film to be formed. Thereby, a titanium silicon nitride film (TiSiN film) may be formed instead of the TiN film. Similarly, when the inner pressure of the process chamber  201  is higher than 3,990 Pa, silicon contained in the SiH 4  gas may enter the titanium-containing layer so as to increase the silicon content in the TiN film to be formed. Thereby, the titanium silicon nitride film (TiSiN film) may be formed instead of the TiN film. As described above, when the inner pressure of the process chamber  201  is too low or too high, an elemental composition of the film to be formed may change. For example, the supply flow rate of the SiH 4  controlled by the MFC  322  may be set to a flow rate within a range from 0.1 slm to 5 slm. For example, the supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522 ,  532 ,  542  and  552  may be set to flow rates within a range from 0.01 slm to 20 slm, respectively. In the second sub-step of the first step, for example, the temperature of the heater  207  may be set to substantially the same temperature as that of the TiCl 4  gas supply step. 
     After a predetermined time (for example, from 0.01 second to 10 seconds) has elapsed from the supply of the TiCl 4  gas, the valve  314  of the gas supply pipe  310  is closed to stop the supply of the TiCl 4  gas. In addition, in order to prevent the SiH 4  gas from entering the nozzle  410 , with the valve  514  open, the N 2  gas is supplied into the gas supply pipes  510 ,  530 ,  540  and  550 . The N 2  gas is then supplied into the process chamber  201  through the gas supply pipes  320 ,  330 ,  340  and  350 , the nozzles  410 ,  430 ,  440  and  450 , and is exhausted through the exhaust pipe  231 . Thereby, the SiH 4  gas and the N 2  gas are supplied to the wafers  200 . 
     &lt;Residual Gas Removing Step, Second Step&gt; 
     After a predetermined time (for example, from 0.01 second to 60 seconds) has elapsed from the supply of the SiH 4  gas, the valve  324  is closed to stop the supply of the SiH 4  gas. In the second step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the TiCl 4  gas and the SiH 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the titanium-containing layer out of the process chamber  201 . In the second step, with the valves  514 ,  524 ,  534 ,  544  and  554  open, the N 2  gas is continuously supplied into the process chamber  201 . The N 2  gas serves as the purge gas, which improves the efficiency of removing the TiCl 4  gas and the SiH 4  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the titanium-containing layer out of the process chamber  201 . In the second step, HCl (which is a growth inhibitor) reacts with the SiH 4  gas and is discharged from the process chamber  201  as silicon tetrachloride (SiCl 4 ) and hydrogen (H 2 ) gas. 
     &lt;NH 3  Gas Supply Step, Third Step&gt; 
     After the residual gas in the process chamber  201  is removed, the NH 3  gas is supplied into the process chamber  201  in substantially the same manners as in the third step in the film-forming step of the embodiments described above. 
     &lt;Residual Gas Removing Step, Fourth Step&gt; 
     After a predetermined time has elapsed from the supply of the NH 3  gas, the valve  334  is closed to stop the supply of the NH 3  gas. In the fourth step, with the APC valve  243  of the exhaust pipe  231  open, the vacuum pump  246  vacuum-exhausts the inner atmosphere of the process chamber  201  to remove a residual gas in the process chamber  201  such as the NH 3  gas remaining in the process chamber  201  which did not react or which contributed to the formation of the TiN layer and the reaction byproducts out of the process chamber  201  in substantially the same manners as in the fourth step in the film-forming step of the embodiments described above. 
     &lt;Performing a Predetermined Number of Times&gt; 
     By performing the cycle wherein the first step, the second step, the third step and the fourth step of the modified example described above are sequentially performed in this order the predetermined number of times (n times), the TiN film of a predetermined thickness (for example, 100 Å) is formed on the wafer  200 . 
     According to the present modified example, by performing one or both of the crystal layer separation film forming step and the abnormal growth nuclei removing step similar to the embodiments described above, it is possible to obtain substantially the same effects as those of the film-forming sequences shown in  FIGS. 4 through 7 . 
     In addition, while the embodiments described above are described by way of an example in which the TiN film is formed, the technique of the present disclosure is not limited thereto. For example, the technique of the present disclosure may also be applied to form another metal film other than the TiN film. For example, as a metal element, an element such as tungsten (W), tantalum (Ta), ruthenium (Ru), molybdenum (Mo), zirconium (Zr), hafnium (Hf), aluminum (Al), silicon (Si), germanium (Ge) and gallium (Ga), an element of the same family as the elements described above, or a transition metal may be used. For example, the technique of the present disclosure may also be applied to form a film containing one of the elements described above alone, a compound film of the elements described above and nitrogen (that is, a nitride film) or a compound film of the elements described above and oxygen (that is, an oxide film). When forming the films described above, the halogen-containing gas described above or a gas containing at least one of the halogen element, an amino group, a cyclopentane group or oxygen (O) may be used. 
     In addition, while the embodiments described above are described by way of an example in which the O 2  gas is used as the oxygen-containing gas in the crystal layer separation film forming step, the technique of the present disclosure is not limited thereto. For example, the technique of the present disclosure may also be applied when a gas such as the ozone (O 3 ) gas, the nitric oxide (NO) gas and the nitrous oxide (N 2 O) gas is used as the oxygen-containing gas. In addition, in the crystal layer separation film forming step using the oxygen-containing gas, it is preferable to diffuse the oxygen atoms into the TiN film. Therefore, it is preferable to use the oxygen-containing gas such as the O 2  gas, the O 3  gas, the NO gas and the N 2 O gas rather than water vapor (H 2 O) containing hydrogen atoms. 
     In addition, while the embodiments described above are described by way of an example in which the oxidation process using the oxygen-containing gas is performed as a process of the crystal layer separation film forming step, the technique of the present disclosure is not limited thereto. For example, by performing a nitriding process using the nitrogen-containing gas, it is also possible to separate the crystal layer. For example, a gas such as the ammonia (NH 3 ) gas and a mixed gas of nitrogen (N 2 ) gas and the hydrogen (H 2 ) gas may be used as the nitrogen-containing gas. In addition, active species of the gases described above may be used as the nitrogen-containing gas. 
     In addition, while the embodiments described above are described by way of an example in which the SiH 4  gas is used as the silicon-containing gas in the crystal layer separation film forming step, the technique of the present disclosure is not limited thereto. For example, the technique of the present disclosure may also be applied when the silane-based gas or the chlorosilane-based gas such as the hexachlorodisilane (Si 2 Cl 6 ) gas is used as the silicon-containing gas. 
     In addition, while the embodiments described above are described by way of an example in which the WF 6  gas (which contains a halogen element and a metal element) is used as the halogen-containing gas in the abnormal growth nuclei removing step, the technique of the present disclosure is not limited thereto. For example, the technique of the present disclosure may also be applied when a halogen-containing gas free of a metal element is used. As the halogen-containing gas free of the metal element, for example, a gas such as the NF 3  gas, the C 1 F 3  gas, the F 2  gas and the HF gas may be used. For example, as the halogen element, an element such as chlorine (Cl), fluorine (F) and bromine (Br) may be used, and as the metal element, an element such as W, Ti, Ta, Mo, Zr, Hf, Al, Si, Ge and Ga may be used. That is, the technique of the present disclosure may also be applied when a gas containing at least one among the elements described above is used as the halogen-containing gas. In addition, the halogen-containing gas may further contain oxygen (O) atom. For example, a gas such as molybdenum dichloride dioxide (MoO 2 Cl 2 ) gas and molybdenum oxytetrachloride (Mo 0 Cl 4 s may be used as the halogen-containing gas. 
     In addition, while the embodiments described above are described by way of an example in which a vertical batch type substrate processing apparatus configured to simultaneously process a plurality of substrates is used to form the film, the technique of the present disclosure is not limited thereto. For example, the technique of the present disclosure may also be preferably applied when a single wafer type substrate processing apparatus configured to simultaneously process one or several substrates is used to form the film. 
     For example, the technique of the present disclosure may also be preferably applied when a film is formed by using a substrate processing apparatus including a process furnace  302  shown in  FIG. 9A . The process furnace  302  may include: a process vessel  303  defining a process chamber  301  therein; a shower head  303   s  through which a gas is supplied in a shower-like manner into the process chamber  301 ; a support plate  317  configured to support one or several wafers  200  in a horizontal orientation; a rotating shaft  355  configured to support the support plate  317  from thereunder; and a heater  307  provided in the support plate  317 . A gas supply port  332   a  through which the source gas described above is supplied, a gas supply port  332   b  through which the reactive gas described above is supplied and a gas supply port  332   c  through which a gas such as the oxygen-containing gas, the silicon-containing gas and the halogen-containing gas is supplied are connected to an inlet (gas introduction port) of the shower head  303   s . A source gas supplier similar to the source gas supplier of the embodiments described above is connected to the gas supply port  332   a . A reactive gas supplier similar to the reactive gas supplier of the embodiments described above is connected to the gas supply port  332   b . A gas supplier similar to the oxygen-containing gas supplier, the silicon-containing gas supplier or the halogen-containing gas supplier of the embodiments described above is connected to the gas supply port  332   c . A gas distribution plate (not shown) through which the gas is supplied in a shower-like manner into the process chamber  301  is provided at an outlet (gas discharge port) of the shower head  303   s . An exhaust port  331  through which an inner atmosphere of the process chamber  301  is exhausted is provided at the process vessel  303 . An exhauster (not shown) similar to the exhauster of the embodiments described above is connected to the exhaust port  331 . 
     For example, the technique of the present disclosure may also be preferably applied when a film is formed by using a substrate processing apparatus including a process furnace  402  shown in  FIG. 9B . The process furnace  402  may include: a process vessel  403  defining a process chamber  401 ; a support plate  417  configured to support one or several wafers  200  in a horizontal orientation; a rotating shaft  455  configured to support the support plate  417  from thereunder; a lamp heater  407  configured to irradiate light to the wafer  200  or the wafers  200  in the process vessel  403 ; and a quartz window  403   w  through which the light of the lamp heater  407  is transmitted. A gas supply port  432   a  through which the source gas described above is supplied, a gas supply port  432   b  through which the reactive gas described above is supplied and a gas supply port  432   c  through which a gas such as the oxygen-containing gas, the silicon-containing gas and the halogen-containing gas is supplied are connected to the process vessel  403 . A source gas supplier similar to the source gas supplier of the embodiments described above is connected to the gas supply port  432   a . A reactive gas supplier similar to the reactive gas supplier of the embodiments described above is connected to the gas supply port  432   b . A gas supplier similar to the oxygen-containing gas supplier, the silicon-containing gas supplier or the halogen-containing gas supplier of the embodiments described above is connected to the gas supply port  432   c . An exhaust port  431  through which an inner atmosphere of the process chamber  401  is exhausted is provided at the process vessel  403 . An exhauster (not shown) similar to the exhauster of the embodiments described above is connected to the exhaust port  431 . 
     When the substrate processing apparatuses described above are used to perform the film-forming step, process sequences and process conditions may be substantially the same as those of the embodiments described above. 
     It is preferable that the process recipe (that is, a program defining parameters such as the process sequences and the process conditions of the substrate processing) used to form the above-described various films is prepared individually according to the contents of the substrate processing such as a type of the film to be formed, a composition ratio of the film, a quality of the film, a thickness of the film, the process sequences and the process conditions of the substrate processing. That is, a plurality of process recipes are prepared individually. When starting the substrate processing, an appropriate process recipe is preferably selected among the plurality of process recipes in accordance with the contents of the substrate processing. Specifically, it is preferable that the plurality of process recipes are stored (installed) in the memory  121   c  of the substrate processing apparatus  10  in advance via an electric communication line or the recording medium (the external memory  123 ) storing the plurality of process recipes. Then, when starting the substrate processing, the CPU  121   a  preferably selects the appropriate process recipe among the plurality of process recipes stored in the memory  121   c  of the substrate processing apparatus  10  in accordance with the contents of the substrate processing. Thus, various films of different types, composition ratios, different qualities and different thicknesses may be universally formed with a high reproducibility using a single substrate processing apparatus. In addition, since a burden on an operator such as inputting the process sequences and the process conditions may be reduced, various substrate processes may be performed quickly while avoiding a malfunction of the apparatus. 
     The technique of the present disclosure may also be implemented by changing an existing process recipe stored in the substrate processing apparatus to a new process recipe. When changing the existing process recipe to the new process recipe, the new process recipe according to the technique of the present disclosure may be installed in the substrate processing apparatus via the electric communication line or the recording medium storing the plurality of process recipes. The existing process recipe itself already stored in the substrate processing apparatus may also be directly changed to the new process recipe according to the technique of the present disclosure by operating the input/output device of the substrate processing apparatus. 
     The technique of the present disclosure may be applied to, for example, a word line of a DRAM or a NAND flash memory of a three-dimensional structure. 
     As described above, the technique of the present disclosure is described in detail by way of the embodiments and the modified example. However, the technique of the present disclosure is not limited thereto. The embodiments and the modified example described above may be appropriately combined. 
     (4) Examples of Embodiments 
     In a comparative example shown in  FIG. 10 , a cross-section of the wafer  200  when the TiN film of a thickness of 250 Å is formed on the wafer  200  by performing the film-forming step shown in  FIG. 4  by using the substrate processing apparatus  10  described above is illustrated. In a first example shown in  FIG. 10 , a cross-section of the wafer  200  when the TiN film of a thickness of 250 Å is formed on the wafer  200  by performing the film-forming sequence (in which the O 2  gas supply step is performed each time the TiN film of a thickness of 100 Å is formed) shown in  FIG. 4  by using the substrate processing apparatus  10  described above is illustrated. In a second example shown in  FIG. 10 , a cross-section of the wafer  200  when the TiN film of a thickness of 250 Å is formed on the wafer  200  by performing the film-forming sequence (in which the SiH 4  gas supply step is performed each time the TiN film of a thickness of 100 Å is formed) shown in  FIG. 5  by using the substrate processing apparatus  10  described above is illustrated. In a third example shown in  FIG. 10 , a cross-section of the wafer  200  when the TiN film of a thickness of 250 Å is formed on the wafer  200  by performing the film-forming sequence (in which the WF 6  gas supply step is performed each time the TiN film of a thickness of 100 Å is formed) shown in  FIG. 6  by using the substrate processing apparatus  10  described above is illustrated. 
     Then, the cross-sections of the TiN films formed in the comparative example and the first through third examples are observed using an atomic force microscope. As shown in  FIG. 10 , it is confirmed that the abnormal growth nuclei are formed on the surface of the TiN film of the comparative example. A root mean square roughness (“Rms”) of the TiN film is 1.62 nm, and a maximum height difference (“Rmax”) is 25.7 nm in the comparative example. On the other hand, it is confirmed that the surface of the TiN film of the first example is flattened. It is confirmed that three TiN layers are stacked in the TiN film of the first example, and the crystal layer separation film is formed between the three TiN layers of the first example. The root mean square roughness (Rms) of the TiN film is 0.91 nm, and the maximum height difference (Rmax) is 9.79 nm in the first example. In addition, it is confirmed that the surface of the TiN film of the second example is flattened. It is confirmed that three TiN layers are stacked in the TiN film of the second example, and the crystal layer separation film is formed between the three TiN layers of the second example. The root mean square roughness (Rms) of the TiN film is 0.80 nm, and the maximum height difference (Rmax) is 9.56 nm in the second example. In addition, it is confirmed that the surface of the TiN film of the third example is flattened. It is confirmed that three TiN layers separated by the amorphous TiN film are stacked in the TiN film of the third example. The root mean square roughness (Rms) of the TiN film is 1.00 nm, and the maximum height difference (Rmax) is 11.3 nm in the third example. 
     That is, it is confirmed that, by performing one or both of the crystal layer separation film forming step and the abnormal growth nuclei removing step each time the TiN film of a thickness of 100 Å is formed on the wafer  200  by performing the film-forming step of the TiN film, it is possible to form a sufficiently flat TiN film of a thickness of 250 Å. 
     According to some embodiments of the present disclosure, it is possible to form the sufficiently flat film.