Patent Publication Number: US-2021166948-A1

Title: Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     The application is a Bypass Continuation Application of PCT International Application No. PCT/JP2018/026672, filed Jul. 17, 2018, the disclosure of which is incorporated herein in its entirety by reference. 
    
    
     TECHNICAL FIELD 
     The present disclosure relates to a method of manufacturing a semiconductor device, a substrate processing apparatus, and a recording medium. 
     BACKGROUND 
     In the related art, a patterning technique is also becoming miniaturized according to miniaturization of large scale integrated circuits (hereinafter, referred to as “LSIs”). As the patterning technique, for example, a hard mask or the like is used, but it is difficult to apply a method of exposing a resist to separate an etching region and a non-etching region due to the miniaturization of the patterning technique. For this reason, an epitaxial film such as silicon (Si) or silicon germanium (SiGe) is selectively grown and formed on a substrate such as a silicon (Si) wafer. 
     SUMMARY 
     Some embodiments of the present disclosure provide a technique capable of selectively forming a film on a substrate. 
     According to embodiments of the present disclosure, there is provided a technique that includes: organically terminating a first region of a substrate by supplying an adsorption control agent containing an organic ligand to the substrate while regulating a temperature of the substrate including the first region and a second region different from the first region formed on a surface of the substrate depending on a composition of the first region; and selectively growing a film on the second region by supplying a deposition gas to the substrate. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
       The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the present disclosure. 
         FIG. 1  is a vertical cross-sectional view schematically illustrating a process furnace of a substrate processing apparatus according to embodiments of the present disclosure. 
         FIG. 2  is a schematic horizontal cross-sectional view of the process furnace taken along a line A-A in  FIG. 1 . 
         FIG. 3  is a schematic configuration diagram of a controller of a substrate processing apparatus according to embodiments of the present disclosure, in which a control system of the controller is shown in a block diagram. 
         FIG. 4  is a diagram illustrating a gas supply timing according to embodiments of the present disclosure. 
         FIG. 5A  is a model diagram illustrating a state of a surface of a wafer on which a Si layer, a SiN layer, and a SiO 2  layer are formed before exposure to a HMDSN gas,  FIG. 5B  is a model diagram illustrating a state immediately after the surface of the wafer is exposed to the HMDSN gas, and  FIG. 5C  is a model diagram illustrating a state of the surface of the wafer after exposure to the HMDSN gas. 
         FIG. 6A  is a model diagram illustrating a state of the surface of the wafer immediately after a TiCl 4  gas is supplied,  FIG. 6B  is a model diagram illustrating a state of the surface of the wafer after exposure to the TiCl 4  gas, and  FIG. 6C  is a model diagram illustrating a state of the surface of the wafer immediately after a NH 3  gas is supplied. 
         FIG. 7A  is a model diagram illustrating a state of the surface of the wafer after exposure to the NH 3  gas, and  FIG. 7B  is a diagram illustrating the surface of the wafer after substrate processing according to embodiments of the present disclosure is performed. 
         FIG. 8A  is a model diagram illustrating a state immediately after the surface of the wafer is exposed to the HMDSN gas,  FIG. 8B  is a model diagram illustrating a state of the surface of the wafer after exposure to the HMDSN gas, and  FIG. 8C  is a model diagram illustrating a state after the state of the surface of the wafer after the exposure to the HMDSN gas in  FIG. 8B . 
         FIG. 9A  is a diagram illustrating a relationship between the number of film formation cycles of the TiN film formed on each of the Si layer, the SiN layer, and the SiO 2  layer at a processing temperature of 200 degrees C. and a film thickness, and FIG. 9B is a model diagram illustrating a state of the surface of the wafer after 100 cycles of the TiN film formed on each of the Si layer, the SiN layer, and the SiO 2  layer at the processing temperature of 200 degrees C. 
         FIG. 10A  is a diagram illustrating a relationship between the number of film formation cycles of the TiN film formed on each of the Si layer, the SiN layer, and the SiO 2  layer at a processing temperature of 350 degrees C. and a film thickness, and  FIG. 10B  is a model diagram illustrating a state of the surface of the wafer after 100 cycles of the TiN film formed on each of the Si layer, the SiN layer, and the SiO 2  layer at the processing temperature of 350 degrees C. 
     
    
    
     DETAILED DESCRIPTION 
     Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the present disclosure. However, it will be apparent to one of ordinary skill in the art that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, systems, and components have not been described in detail so as not to obscure aspects of the various embodiments. 
     Exemplary embodiments of the present disclosure will now be described. 
       FIG. 1  is a vertical cross-sectional view of a substrate processing apparatus configured to perform a method of manufacturing a semiconductor device (hereinafter, simply referred to as a “substrate processing apparatus  10 ”). 
     Hereinafter, a description will be made with reference to  FIGS. 1 to 4 . The substrate processing apparatus  10  is configured as an example of an apparatus used in the processes of manufacturing a semiconductor device. Further, in the following description, a case where a titanium nitride (TiN) film as a thin film is formed on a wafer  200  in which a silicon (Si) layer, a silicon nitride (SiN) layer, and a silicon oxide (SiO 2 ) layer are formed as base films on a surface of the wafer  200  will be described. 
     (1) Configuration of the Substrate Processing Apparatus 
     The substrate processing apparatus  10  includes a process furnace  202  in which a heater  207  as a heating means (a heating mechanism or a heating system) is installed. The heater  207  has a cylindrical shape and is supported by a heater base (not shown) as a holding plate to be vertically installed. 
     An outer tube  203  constituting a reaction vessel (process vessel) is disposed inside the heater  207  to be concentric with the heater  207 . The outer tube  203  is made of a heat resistant material, e.g., quartz (SiO 2 ), silicon carbide (SiC) or the like, and has a cylindrical shape with its upper end closed and its lower end opened. A manifold (inlet flange)  209  is disposed below the outer tube  203  in a concentric relationship with the outer tube  203 . The manifold  209  is made of metal, e.g., stainless steel (SUS), and has a cylindrical shape with its upper and lower ends opened. An O-ring  220   a  as a seal member is installed between the upper end portion of the manifold  209  and the outer tube  203 . The manifold  209  is supported by the heater base. Thus, the outer tube  203  comes into a vertically mounted state. 
     An inner tube  204  constituting a reaction vessel is disposed inside the outer tube  203 . The inner tube  204  is made of a heat resistant material, e.g., quartz (SiO 2 ), silicon carbide (SiC) or the like, and has a cylindrical shape with its upper end closed and its lower end opened. The process vessel (reaction vessel) mainly includes the outer tube  203 , the inner tube  204 , and the manifold  209 . A process chamber  201  is formed in a hollow cylindrical portion of the process vessel (inside the inner tube  204 ). 
     The process chamber  201  is configured to accommodate wafers  200  as substrates, in such a state that the wafers  200  are arranged in a horizontal posture and in multiple stages along a vertical direction in a boat  217  to be described below. 
     Nozzles  410 ,  420  and  430  are installed in the process chamber  201  to penetrate a sidewall of the manifold  209  and the inner tube  204 . Gas supply pipes  310 ,  320  and  330  are respectively connected to the nozzles  410 ,  420  and  430 . However, the process furnace  202  of the present embodiment is not limited to the aforementioned configuration. 
     Mass flow controllers (MFCs)  312 ,  322 , and  332 , which are flow rate controllers (flow rate control parts), are installed at the gas supply pipes  310 ,  320  and  330  sequentially from the corresponding upstream sides, respectively. In addition, valves  314 ,  324 , and  334 , which are opening/closing valves, are installed at the gas supply pipes  310 ,  320  and  330 , respectively. Gas supply pipes  510 ,  520  and  530 , which supply an inert gas, are respectively connected to the gas supply pipes  310 ,  320 , and  330  at the downstream side of the valves  314 ,  324  and  334 . MFCs  512 ,  522  and  532 , which are flow rate controllers (flow rate control parts), and valves  514 ,  524  and  534 , which are opening/closing valves, are installed at the gas supply pipes  510 ,  520  and  530  sequentially from the corresponding upstream sides, respectively. 
     The nozzles  410 ,  420 , and  430  are connected to front end portions of the gas supply pipes  310 ,  320 , and  330  respectively. The nozzles  410 ,  420  and  430  are each configured as an L-shaped nozzle. Horizontal portions of the nozzles  410 ,  420  and  430  are formed to penetrate the sidewall of the manifold  209  and the inner tube  204 . Vertical portions of the nozzles  410 ,  420  and  430  is formed in a channel-shaped (groove-shaped) spare chamber  201   a  formed to protrude outward of the inner tube  204  in a radial direction and to extend along the vertical direction, and is also formed to extend upward along the inner wall of the inner tube  204  in the spare chamber  201   a  (upward in the arrangement direction of the wafers  200 ). 
     The nozzles  410 ,  420 , and  430  are installed to extend from a lower region of the process chamber  201  to an upper region of the process chamber  201 , and a plurality of gas supply holes  410   a,    420   a  and  430   a  are respectively formed at the opposite positions of the wafers  200 . Thus, a processing gas is supplied from each of the gas supply holes  410   a,    420   a,  and  430   a  of the nozzles  410 ,  420 , and  430  to the wafers  200 . The gas supply holes  410   a,    420   a,  and  430   a  may be installed in a plural number between the lower portion of the inner tube  204  and the upper portion of the inner tube  204 . The respective gas supply holes  410   a,    420   a,  and  430   a  may have the same aperture area and may be formed at the same aperture pitch. However, the gas supply holes  410   a,    420   a  and  430   a  are not limited to the aforementioned configuration. For example, the aperture area may be gradually enlarged from the lower portion of the inner tube  204  to the upper portion of the inner tube  204 . Thus, it is possible to make a flow rate of the gas supplied from the gas supply holes  410   a,    420   a  and  430   a  more uniform. 
     The gas supply holes  410   a,    420   a  and  430   a  of the nozzles  410 ,  420 , and  430  may be formed in a plural number at height positions from the lower portion of the boat  217  to the upper portion of the boat  217  to be described below. Therefore, the processing gas supplied from the gas supply holes  410   a,    420   a  and  430   a  of the nozzles  410 ,  420 , and  430  into the process chamber  201  is supplied to the whole region of the wafers  200  accommodated from the lower portion of the boat  217  to the upper portion of the boat  217 . The nozzles  410 ,  420 , and  430  may be installed to extend from the lower region of the process chamber  201  to the upper region of the process chamber  201  but may be installed to extend up to near the ceiling of the boat  217 . 
     A processing gas, which contains an organic ligand, as a pre-processing gas, is supplied from the gas supply pipe  310  into the process chamber  201  via the MFC  312 , the valve  314 , and the nozzle  410 . As the processing gas containing an organic ligand, a processing gas containing an alkyl group such as dialkylamine or the like and containing alkylamine in the ligand (containing an alkyl ligand) is used, and a hexamethyldisilazane (HMDSN) gas containing a methyl group may be used as an example of the processing gas. The processing gas containing the organic ligand is used as an adsorption control agent (adsorption inhibitor) that controls film formation of a deposition gas to be supplied subsequently. 
     A precursor gas as the deposition gas, as the processing gas, is supplied from the gas supply pipe  320  into the process chamber  201  via the MFC  322 , the valve  324 , and the nozzle  420 . As the precursor gas, a Cl-containing gas containing chlorine (Cl), which is a precursor molecule not adsorbed to the alkyl ligand and which contains, for example, electrically negative ligands such as halogen or the like, is used, and a titanium tetrachloride (TiCl 4 ) gas may be used as an example of the precursor gas. 
     A reaction gas reacting with the precursor gas as the deposition gas, as the processing gas, is supplied from the gas supply pipe  330  into the process chamber  201  via the MFC  332 , the valve  334 , and the nozzle  430 . As the reaction gas, for example, a N-containing gas containing nitrogen (N) is used, and an ammonia (NH 3 ) gas may be used as an example of the reaction gas. 
     An inert gas, for example, a nitrogen (N 2 ) gas, is supplied from the gas supply pipes  510 ,  520 , and  530  into the process chamber  201  via the MFCs  512 ,  522 , and  532 , the valves  514 ,  524 , and  534 , and the nozzles  410 ,  420 , and  430 . An example in which the N 2  gas is used as the inert gas will be described below, but in addition to the N 2  gas, for example, a rare gas such as an argon (Ar) gas, a helium (He) gas, a neon (Ne) gas, a xenon (Xe) gas or the like may be used as the inert gas. 
     A processing gas supply system mainly includes the gas supply pipes  310 ,  320 , and  330 , the MFCs  312 ,  322  and  332 , the valves  314 ,  324 , and  334 , and the nozzles  410 ,  420 , and  430 , but only the nozzles  410 ,  420  and  430  may be regarded as the processing gas supply system. The processing gas supply system may be simply referred to as a gas supply system. When an adsorption control agent is allowed to flow from the gas supply pipe  310 , a first gas supply system configured to supply the adsorption control agent containing the organic ligand mainly includes the gas supply pipe  310 , the MFC  312 , and the valve  314 , but the nozzle  410  may be regarded as being included in the first gas supply system. Further, a second gas supply system configured to supply the deposition gas mainly includes the gas supply pipes  320  and  330 , the MFCs  322  and  332 , the valves  324  and  334 , and the nozzles  420  and  430 , but only the nozzles  420  and  430  may be regarded as the second gas supply system. In addition, when the precursor gas is allowed to flow from the gas supply pipe  320 , a precursor gas supply system mainly includes the gas supply pipe  320 , the MFC  322 , and the valve  324 , but the nozzle  420  may be regarded as being included in the precursor gas supply system. Moreover, when a reaction gas is allowed to flow from the gas supply pipe  330 , a reaction gas supply system mainly includes the gas supply pipe  330 , the MFC  332 , and the valve  334 , but the nozzle  430  may be regarded as being included in the reaction gas supply system. When a nitrogen-containing gas as the reaction gas is supplied from the gas supply pipe  330 , the reaction gas supply system may be referred to as a nitrogen-containing gas supply system. Further, an inert gas supply system mainly includes the gas supply pipes  510 ,  520 , and  530 , the MFCs  512 ,  522 , and  532 , and the valves  514 ,  524 , and  534 . 
     In a gas supply method according to the present embodiment, a gas is transferred via the nozzles  410 ,  420 , and  430 , which are disposed in the spare chamber  201   a  in annular longitudinal space defined by the inner wall of the inner tube  204  and end portions of a plurality of wafers  200 . Then, the gas is injected from the plurality of gas supply holes  410   a,    420   a  and  430   a  formed at positions of the nozzles  410 ,  420 , and  430  facing the wafers into the inner tube  204 . More specifically, the precursor gas or the like is injected from the gas supply hole  410   a  of the nozzle  410 , the gas supply hole  420   a  of the nozzle  420 , and the gas supply hole  430   a  of the nozzle  430  in a direction parallel to the surfaces of the wafers  200 . 
     An exhaust hole (exhaust port)  204   a  is a through-hole formed on the sidewall of the inner tube  204  and at the opposite position of the nozzles  410 ,  420 , and  430 , and is, for example, a vertically-elongated slit-shaped through-hole. The gas supplied from the gas supply holes  410   a,    420   a,  and  430   a  of the nozzles  410 ,  420 , and  430  into the process chamber  201  and flowing on the surfaces of the wafers  200  flows through an exhaust passage  206  as a gap formed between the inner tube  204  and the outer tube  203  via the exhaust hole  204   a.  Then, the gas flowing through the exhaust passage  206  flows through an exhaust pipe  231  and is discharged to the outside of the process furnace  202 . 
     The exhaust hole  204   a  is formed at the opposite position of the wafers  200 , and the gas supplied from the gas supply holes  410   a,    420   a,  and  430   a  to a region near the wafers  200  in the process chamber  201  flows in the horizontal direction and then flows through the exhaust passage  206  via the exhaust hole  204   a.  The exhaust hole  204   a  is not limited to being configured as the slit-shaped through-hole but may be configured by a plurality of holes. 
     The exhaust pipe  231  configured to exhaust an internal atmosphere of the process chamber  201  is installed at the manifold  209 . A pressure sensor  245  as a pressure detector (pressure detection part) which detects the internal pressure of the process chamber  201 , an auto pressure controller (APC) valve  243 , and a vacuum pump  246  as a vacuum exhaust device are connected to the exhaust pipe  231  sequentially from the corresponding upstream side. The APC valve  243  is configured so that a vacuum exhaust and a vacuum exhaust stop of the interior of the process chamber  201  can be performed by opening and closing the APC valve  243  while operating the vacuum pump  246  and so that the internal pressure of the process chamber  201  can be regulated by adjusting an opening degree of the APC valve  243  while operating the vacuum pump  246 . An exhaust system mainly includes the exhaust hole  204   a,  the exhaust passage  206 , the exhaust pipe  231 , the APC valve  243 , and the pressure sensor  245 . The vacuum pump  246  may be regarded as being included in the exhaust system. 
     A seal cap  219 , which serves as a furnace opening lid configured to be capable of hermetically sealing a lower end opening of the manifold  209 , is installed under the manifold  209 . The seal cap  219  is configured to make contact with the lower end portion of the manifold  209  from a lower side in the vertical direction. The seal cap  219  is made of metal such as, e.g., stainless steel (SUS) or the like, and is formed in a disc shape. An O-ring  220   b,  which is a seal member making contact with the lower end portion of the manifold  209 , is installed at an upper surface of the seal cap  219 . A rotation mechanism  267  configured to rotate the boat  217  which accommodates the wafers  200  is installed at the opposite side of the seal cap  219  from the process chamber  201 . A rotary shaft  255  of the rotation mechanism  267 , which penetrates the seal cap  219 , is connected to the boat  217 . The rotation mechanism  267  is configured to rotate the wafers  200  by rotating the boat  217 . The seal cap  219  is configured to be vertically moved up or down by a boat elevator  115  which is an elevator mechanism vertically installed outside the outer tube  203 . The boat elevator  115  is configured to be capable of loading or unloading the boat  217  into or from the process chamber  201  by moving the seal cap  219  up or down. The boat elevator  115  is configured as a transfer device (transfer mechanism) which transfers the boat  217  and the wafers  200  accommodated in the boat  217  into and out of the process chamber  201 . 
     The boat  217  serving as a substrate support is configured to support a plurality of wafers  200 , e.g., 25 to 200 wafers, in such a state that the wafers  200  are arranged in a horizontal posture along a vertical direction with the centers of the wafers  200  aligned with one another. That is, the boat  217  is configured to arrange the wafers  200  in a spaced-apart relationship. The boat  217  is made of a heat resistant material such as quartz or SiC. Heat insulating plates  218  made of a heat resistant material such as quartz or SiC are installed below the boat  217  in a horizontal posture and in multiple stages (not shown). With this configuration, it may be difficult for heat generated from the heater  207  to be transferred to the seal cap  219 . However, the present embodiment is not limited to the aforementioned configuration. For example, instead of installing the heat insulating plates  218  below the boat  217 , a heat insulating tube as a tubular member made of a heat resistant material such as quartz or SiC may be installed under the boat  217 . 
     As illustrated in  FIG. 2 , a temperature sensor  263  serving as a temperature detector is installed in the inner tube  204 . Based on temperature information detected by the temperature sensor  263 , an amount of electric power supplied to the heater  207  is regulated such that the interior of the process chamber  201  has a desired temperature distribution. Similar to the nozzles  410 ,  420 , and  430 , the temperature sensor  263  is formed in an L shape. The temperature sensor  263  is installed along the inner wall of the inner tube  204 . 
     As illustrated in  FIG. 3 , a controller  121 , which is a control part (control means), may be configured as a computer including a central processing unit (CPU)  121   a,  a random access memory (RAM)  121   b,  a memory device  121   c,  and an I/O port  121   d.  The RAM  121   b,  the memory device  121   c  and the I/O port  121   d  are configured to be capable of exchanging data with the CPU  121   a  via an internal bus. An input/output device  122  formed of, e.g., a touch panel or the like, is connected to the controller  121 . 
     The memory device  121   c  includes, for example, a flash memory, a hard disk drive (HDD), or the like. A control program that controls operations of a substrate processing apparatus, a process recipe that specifies sequences and conditions of a method of manufacturing a semiconductor device to be described below, and the like are readably stored in the memory device  121   c.  The process recipe functions as a program configured to cause the controller  121  to execute each process (each step) in the method of manufacturing a semiconductor device, as described below, to obtain a predetermined result. Hereinafter, the process recipe and the control program will be generally and simply referred to as a “program.” When the term “program” is used herein, it may indicate a case of including only the process recipe, a case of including only the control program, or a case of including a combination of the process recipe and the control program. The RAM  121   b  is configured as a memory area (work area) in which a program, data or the like read by the CPU  121   a  is temporarily stored. 
     The I/O port  121   d  is connected to the MFCs  312 ,  322 ,  332 ,  512 ,  522  and  532 , the valves  314 ,  324 ,  334 ,  514 ,  524  and  534 , the pressure sensor  245 , the APC valve  243 , the vacuum pump  246 , the heater  207 , the temperature sensor  263 , the rotation mechanism  267 , the boat elevator  115 , and the like. 
     The CPU  121   a  is configured to read the control program from the memory device  121   c  and execute the same. The CPU  121   a  also reads the recipe and the like from the memory device  121   c  according to an input of an operation command and the like from the input/output device  122 . In addition, the CPU  121   a  is configured to control, according to the contents of the recipe thus read, flow rate regulating operations of various kinds of gases by the MFCs  312 ,  322 ,  332 ,  512 ,  522 , and  532 , opening/closing operations of the valves  314 ,  324 ,  334 ,  514 ,  524 , and  534 , opening/closing operations of the APC valve  243 , a pressure regulating operation performed by the APC valve  243  based on the pressure sensor  245 , a temperature regulating operation performed by the heater  207  based on the temperature sensor  263 , driving and stopping of the vacuum pump  246 , operations of rotating the boat  217  with the rotation mechanism  267  and adjusting the rotation speed of the boat  217 , an operation of moving the boat  217  up or down with the boat elevator  115 , an operation of accommodating the wafers  200  in the boat  217 , and the like. 
     The controller  121  may be configured by installing, on the computer, the aforementioned program stored in an external memory device  123  (for example, a magnetic tape, a magnetic disc such as a flexible disc or a hard disk, an optical disc such as a CD or DVD, a magneto-optical disc such as a MO, or a semiconductor memory such as a USB memory or a memory card). The memory device  121   c  or the external memory device  123  is configured as a computer-readable recording medium. Hereinafter, the memory device  121   c  and the external memory device  123  will be generally and simply referred to as a “recording medium.” In the present disclosure, the term “recording medium” may indicate a case of including only the memory device  121   c,  a case of including only the external memory device  123 , or a case of including both the memory device  121   c  and the external memory device  123 . Further, the program may be supplied to the computer by using a communication means such as the Internet or a dedicated line, instead of using the external memory device  123 . 
     (2) Substrate Processing 
     An example of selectively growing a TiN film on a SiN layer on a wafer  200  including, for example, a Si layer and a SiO 2  layer as a first region and the SiN layer as a second region, which are a plurality of regions as base films, on a surface of the wafer  200 , which is a process of manufacturing a semiconductor device, will be described with reference to  FIG. 4 . This process is performed by using the process furnace  202  of the substrate processing apparatus  10  described above. In the following descriptions, the operations of the respective parts constituting the substrate processing apparatus  10  are controlled by the controller  121 . 
     The substrate processing (the process of manufacturing a semiconductor device) according to the present embodiment includes: a step of organically terminating surfaces of a Si layer and a SiO 2  layer by supplying a HMDSN gas as an adsorption control agent containing an organic ligand to a wafer  200  while regulating a temperature of the wafer  200  including the Si layer, a SiN layer, and the SiO 2  layer on a surface of the wafer  200  depending on a composition of the Si layer and the SiO 2  layer; and a step of selectively growing a TiN film on the SiN layer by supplying a TiCl 4  gas as a precursor gas and a NH 3  gas as a reaction gas, as deposition gases, to the wafer  200 . 
     Further, the step of organically terminating the surfaces of the Si layer and the SiO 2  layer may be performed multiple times. In addition, the step of organically terminating the surfaces of the Si layer and the SiO 2  layer will be referred to as “pre-processing.” The step of selectively growing the TiN film on the SiN layer will be referred to as a film-forming process. 
     When the term “wafer” is used herein, it may refer to “a wafer itself” or “a laminated body of a wafer and a predetermined layer or film formed on a surface of the wafer.” In addition, when the phrase “a surface of a wafer” is used herein, it may refer to “a surface of a wafer itself” or “a surface of a predetermined layer or film formed on a wafer”. Further, when the term “substrate” is used herein, it may be synonymous with the term “wafer.” 
     Wafer Loading 
     When a plurality of wafers  200  is charged on the boat  217  (wafer charging), as illustrated in  FIG. 1 , the boat  217  supporting the plurality of wafers  200  is lifted up by the boat elevator  115  and is loaded into the process chamber  201  (boat loading). In this state, the seal cap  219  seals a lower end opening of the outer tube  203  via the O-ring  220 . 
     Pressure Regulation and Temperature Regulation 
     The interior of the process chamber  201  is vacuum-exhausted by the vacuum pump  246  to reach a desired pressure (degree of vacuum). In this operation, the internal pressure of the process chamber  201  is measured by the pressure sensor  245 . The APC valve  243  is feedback-controlled based on the measured pressure information (pressure regulation). The vacuum pump  246  may be continuously activated at least until the processing of the wafers  200  is completed. Further, the interior of the process chamber  201  is heated by the heater  207  to a desired temperature. In this operation, the amount of electric power supplied to the heater  207  is feedback-controlled based on the temperature information detected by the temperature sensor  263  such that the interior of the process chamber  201  has a desired temperature distribution (temperature regulation). The heating of the interior of the process chamber  201  by the heater  207  may be continuously performed at least until the processing of the wafers  200  is completed. 
     A: Organic Termination Step (Pre-Processing) 
     First, organic termination is generated on the Si layer and the SiO 2  layer of the wafer  200  as pre-processing. 
     A-1: [Adsorption Control Agent Supply Step] 
     HMDSN Gas Supply 
     The valve  314  is opened to allow a HMDSN gas as an adsorption control agent to flow through the gas supply pipe  310 . A flow rate of the HMDSN gas is regulated by the MFC  312 . The HMDSN gas is supplied from the gas supply hole  410   a  of the nozzle  410  into the process chamber  201  and is exhausted from the exhaust pipe  231 . At this time, the HMDSN gas is supplied to the wafer  200 . In parallel with this, the valve  514  is opened to allow an inert gas such as a N 2  gas or the like to flow through the gas supply pipe  510 . A flow rate of the N 2  gas flowing through the gas supply pipe  510  is regulated by the MFC  512 . The N 2  gas is supplied into the process chamber  201  together with the HMDSN gas and is exhausted from the exhaust pipe  231 . At this time, the valves  524  and  534  are opened to allow a N 2  gas to flow through the gas supply pipes  520  and  530 , thereby preventing the HMDSN gas from entering the nozzles  420  and  430 . The N 2  gas is supplied into the process chamber  201  via the gas supply pipes  320  and  330  and the nozzles  420  and  430  and is exhausted from the exhaust pipe  231 . 
     At this time, the internal pressure of the process chamber  201  may be set at a pressure which falls within a range of, for example, 10 to 1,000 Pa, by regulating the APC valve  243 . A supply flow rate of the HMDSN gas controlled by the MFC  312  may be set at a flow rate which falls within a range of, for example, 10 to 1,000 sccm. The supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522  and  532  may be set at a flow rate which falls within a range of, for example, 20 to 2,000 sccm. At this time, the temperature of the heater  207  is set such that the temperature of the wafer  200  becomes a temperature which falls within a range of, for example, 100 to 250 degrees C., specifically 150 to 250 degrees C. in some embodiments, or specifically 180 to 220 degrees C. in some embodiments. Further, in the present disclosure, an expression of the numerical range such as “100 to 250 degrees C.” may mean that a lower limit value and an upper limit value are included in that range. Therefore, “100 to 250 degrees C.” may mean “100 degrees C. or higher and 250 degrees C. or lower.” The same applies to other numerical ranges. 
     That is, the temperature of the heater  207  at this time is a temperature at which the organic ligand contained in the HMDSN gas is adsorbed on the Si layer and the SiO 2  layer but not adsorbed on the SiN layer such that the surfaces of the Si layer and the SiO 2  layer are organically terminated. 
     The gases flowing through the process chamber  201  at this time are the HMDSN gas and the N 2  gas. The organic ligand contained in the HMDSN gas is bonded to and organically terminate the surfaces of the Si layer and the SiO 2  layer of the wafer  200  by the supply of the HMDSN gas. 
     In this case, the temperature at which adsorption, desorption or decomposition of the adsorption control agent starts to occur differs depending on a kind (composition) of the Si layer, the SiO 2  layer, the SiN layer or the like on the surface of the wafer. Specifically, the adsorption control agent is more easily adsorbed on the Si layer than on the SiO 2  layer and the SiN layer, and the temperature at which the desorption or decomposition of the adsorption control agent starts to occur is high. Further, the adsorption control agent is not adsorbed on the SiO 2  layer up to 80 degrees C., but starts being adsorbed on the SiO 2  layer from around 100 degrees C. Then, as the temperature rises, an adsorption rate becomes faster, and becomes the fastest around 200 degrees C. However, when the temperature rises to around 250 degrees C., the adsorption control agent begins to be autolyzed. That is, the adsorption control agent may not be adsorbed on either the Si layer or the SiO 2  layer at a temperature lower than 100 degrees C., and the adsorption control agent may be autolyzed at a temperature higher than 250 degrees C. such that the organic ligand (the methyl group or the like) may be separated or desorbed from at least the SiO 2  layer. In other words, the temperature of the heater  207  is regulated such that the temperature of the wafer  200  becomes, for example, 100 to 250 degrees C., specifically 180 to 220 degrees C. in some embodiments, or specifically 190 to 210 degrees C. in some embodiments, thereby organically terminating the surfaces of the Si layer and the SiO 2  layer. 
     That is, since the kind of the surface of the wafer  200  on which the organic ligand contained in the adsorption control agent is adsorbed may be set different by controlling the temperature of the wafer  200  when the wafer  200  is exposed to the adsorption control agent, film formation may be performed according to the kind of the surface of the wafer. In other words, the kind of the surface of the wafer  200  to be selectively grown may be controlled. 
     Further, the temperature at which the organic ligand contained in the HMDSN gas is adsorbed on the Si layer to organically terminate the surface of the Si layer is a temperature which falls within a range of 100 to 500 degrees C., specifically 150 to 400 degrees C. in some embodiments, or specifically 180 to 350 degrees C. in some embodiments. In addition, the temperature at which the organic ligand contained in the HMDSN gas is adsorbed on the SiO 2  layer to organically terminate the surface of the SiO 2  layer is a temperature which falls within a range of 150 to 250 degrees C., specifically 180 to 220 degrees C. in some embodiments, or specifically 190 to 210 degrees C. in some embodiments. 
     After a predetermined period of time elapses from the start of the supply of the HMDSN gas, the valve  314  of the gas supply pipe  310  is closed to stop the supply of the HMDSN gas. 
     A state in which the surfaces of the Si layer and the SiO 2  layer are organically terminated is illustrated in  FIGS. 5A to 5C .  FIG. 5A  is a model diagram illustrating a state of the surface of the wafer  200  on which the Si layer, the SiN layer and the SiO 2  layer are formed before exposure to the HMDSN gas,  FIG. 5B  is a model diagram illustrating a state immediately after the surface of the wafer  200  is exposed to the HMDSN gas, and  FIG. 5C  is a model diagram illustrating a state of the surface of the wafer  200  after the exposure to the HMDSN gas. In  FIGS. 5B and 5C  and drawings illustrated subsequently, Me indicates a methyl group (CH 3 ). 
     Referring to  FIGS. 5B and 5C , on the surface of the wafer  200  after exposure to the HMDSN gas, H molecules on the Si layer and the SiO 2  layer adsorbed on the surface by the HMDSN gas are bonded to N molecules of the HMDSN gas to generate NH 3  to be desorbed. Then, Si(Me) 3  containing the methyl group as the organic ligand is adsorbed on a place from which the H molecules are desorbed, to organically terminate the surfaces of the Si layer and the SiO 2  layer. 
     A-2: [Purge Step] 
     Residual Gas Removal 
     Next, when the supply of the HMDSN gas is stopped, a purge process is performed to exhaust the gas in the process chamber  201 . At this time, the interior of the process chamber  201  is vacuum-exhausted by the vacuum pump  246  while keeping the APC valve  243  of the exhaust pipe  231  opened, and the unreacted HMDSN gas or the HMDSN gas after the surfaces of the Si layer and the SiO 2  layer is organically terminated, which remains within the process chamber  201 , is removed from the interior of the process chamber  201 . At this time, the supply of the N 2  gas into the process chamber  201  is maintained while keeping the valves  514 ,  524  and  534  opened. The N 2  gas acts as a purge gas. Thus, it is possible to further remove the unreacted HMDSN gas or the HMDSN gas remaining within the process chamber  201  from the interior of the process chamber  201 . 
     Performing a Predetermined Number of Times 
     A cycle which sequentially performs the adsorption control agent supply step and the purge step described above is performed once or more (a predetermined number of times (n times)), whereby the surfaces of the Si layer and the SiO 2  layer formed on the wafer  200  are organically terminated. 
     Further, in the pre-processing described above, the supply and exhaust of the HMDSN gas are alternately performed. In a case where a byproduct (for example, HMDSN) generated by reaction between the HMDSN gas and the Si layer and the SiO 2  layer as the base films stays on the wafer  200 , the Cl-containing gas contained in the precursor gas may be prevented from reaching a surface of the SiN layer of the wafer  200  by such a byproduct. Therefore, the byproduct is exhausted. This prevents an occurrence of harmful effects due to the byproduct. 
     B. Selective Growth Step (Film-Forming Process) 
     Subsequently, a TiN film is formed on the surface of the SiN layer on the wafer  200  in which the surfaces of the Si layer and the SiO 2  layer are organically terminated by the pre-processing. 
     B-1: [First Step] 
     TiCl 4  Gas Supply 
     The valve  324  is opened to allow a TiCl 4  gas, which is the precursor gas, to flow through the gas supply pipe  320 . The flow rate of the TiCl 4  gas is regulated by the MFC  322 . The TiCl 4  gas is supplied from the gas supply hole  420   a  of the nozzle  420  into the process chamber  201  and is exhausted from the exhaust pipe  231 . At this time, the TiCl 4  gas is supplied to the wafer  200 . In parallel with this, the valve  524  is opened to allow an inert gas such as a N 2  gas or the like to flow through the gas supply pipe  520 . The flow rate of the N 2  gas flowing through the gas supply pipe  520  is regulated by the MFC  522 . The N 2  gas is supplied into the process chamber  201  together with the TiCl 4  gas and is exhausted from the exhaust pipe  231 . At this time, the valves  514  and  534  are opened to allow a N 2  gas to flow through the gas supply pipes  510  and  530 , thereby preventing the TiCl 4  gas from entering the nozzles  410  and  430 . The N 2  gas is supplied into the process chamber  201  via the gas supply pipes  310  and  330  and the nozzles  410  and  430  and is exhausted from the exhaust pipe  231 . 
     At this time, the internal pressure of the process chamber  201  may be set at a pressure which falls within a range of, for example, 10 to 1,000 Pa, for example, 50 Pa, by regulating the APC valve  243 . The supply flow rate of the TiCl 4  gas controlled by the MFC  322  may be set at a flow rate which falls within a range of, for example, 0.01 to 1 slm. The supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522  and  532  may be respectively set at a flow rate which falls within a range of, for example, 0.1 to 2 slm. The time, during which the TiCl 4  gas is supplied to the wafer  200 , may be set at a time which falls within a range of, for example, 0.1 to 100 seconds. At this time, the temperature of the heater  207  is set such that the temperature of the wafer  200  becomes a temperature which falls within a range of, for example, 150 to 500 degrees C., specifically 200 to 400 degrees C. in some embodiments, or specifically 200 to 350 degrees C. in some embodiments. 
     The gases flowing through the process chamber  201  at this time are the TiCl 4  gas and the N 2  gas. The TiCl 4  gas is not adsorbed on the Si layer and the SiO 2  layer whose surfaces are organically terminated in the pre-processing described above, but is adsorbed on the SiN layer. Since halogen (Cl) contained in the TiCl 4  gas and the organic ligand on the Si layer and the SiO 2  layer are respectively electrically negative ligands, they become repulsive factors which may not be adsorbed easily. 
     In this case, when a thin film is selectively formed on a specific wafer surface, the precursor gas may be adsorbed on a wafer surface on which a film is not desired to be formed, causing unintended film formation. This is a breaking of selectivity. This breaking of selectivity is likely to occur when probability of adsorption of precursor gas molecules on the wafer is high. That is, lowering the probability of adsorption of precursor gas molecules on the wafer on which the film is not desired to be formed directly leads to improvement of selectivity. 
     The adsorption of the precursor gas on the wafer surface is brought about when the precursor gas stays on the wafer surface for a certain period of time due to an electrical interaction between the precursor molecules and the wafer surface. That is, the probability of adsorption depends on both an exposure density of the precursor gas or its decomposition product to the wafer and an electrochemical factor of the wafer itself. In the present disclosure, the electrochemical factor of the wafer itself often refers to, for example, surface defects at atomic levels, or electrification by polarization, electric field or the like. That is, if the electrochemical factor and the precursor gas on the wafer surface are easily attracted to each other, it can be said that adsorption is likely to occur. 
     In a related-art semiconductor film-forming process, a selective film-forming process has been realized by a method of suppressing a precursor gas from staying at a place of the wafer where an adsorption occurs easily as much as possible by lowering a pressure or raising a gas flow velocity of the precursor gas. However, as a surface area of the semiconductor device has increased according to evolution of miniaturization or three-dimensionalization, technical evolution has been achieved such that an exposure amount of the precursor gas to the wafer increases. In recent years, a method of obtaining high step coverage even for a pattern which is fine and large in the surface area by a method which alternately supplies gases has become mainstream. That is, it is difficult to selectively form a film by countermeasures on the precursor gas side. 
     Further, in semiconductor devices, various thin films such as a Si film or a SiO 2  film, a SiN film, and a metal film are used, and particularly, the control of selective growth characteristics in a SiO film, which is one of the most widely used materials, significantly contributes to increasing a margin or a degree of freedom in device processing. 
     The methyl group as the alkyl ligand contained in the HMDSN gas as the adsorption control agent in the present embodiment is electrically negative. Therefore, in a case where the precursor molecules are negative, the methyl group and the precursor molecules repel each other and may not be easily bonded with each other. For example, since the methyl group (Me—) adsorbed on the Si layer and the SiO 2  layer and the halogen (Cl—) contained in the TiCl 4  gas are negative, they may not be easily bonded with each other. That is, it can be said that the material containing the alkyl ligand has selective controllability to halogen. Thus, an incubation time is prolonged on the Si layer and the SiO 2  layer, thereby selectively growing the TiN film on the surface of the SiN layer other than the Si layer and the SiO 2  layer. The incubation time refers to a time until a film begins to grow on the wafer surface. 
     That is, it is possible to suppress the growth of the thin film on the wafer  200  on which the film is not desired to be formed by supplying the adsorption control agent to the surface of the wafer  200  before supplying the deposition gas thereto. In other words, it is possible to inhibit the surface adsorption of the precursor molecules contained in the precursor gas by adsorbing the adsorption control agent on the surface of the wafer  200 . 
     B-2: [Second Step] 
     Residual Gas Removal 
     After the Ti-containing layer is formed, the valve  324  is closed to stop the supply of the TiCl 4  gas. 
     Then, the unreacted TiCl 4  gas, the TiCl 4  gas contributed to the formation of the Ti-containing layer, or the reaction byproduct, which remains within the process chamber  201 , is removed from the interior of the process chamber  201 . 
     B-3: [Third Step] 
     NH 3  Gas Supply 
     After removing the residual gas within the process chamber  201 , the valve  334  is opened to allow a NH 3  gas as the reaction gas to flow through the gas supply pipe  330 . The flow rate of the NH 3  gas is regulated by the MFC  332 . The NH 3  gas is supplied from the gas supply hole  430   a  of the nozzle  430  into the process chamber  201  and is exhausted from the exhaust pipe  231 . At this time, the NH 3  gas is supplied to the wafer  200 . In parallel with this, the valve  534  is opened to allow a N 2  gas to flow through the gas supply pipe  530 . The flow rate of the N 2  gas flowing through the gas supply pipe  530  is regulated by the MFC  532 . The N 2  gas is supplied into the process chamber  201  together with the NH 3  gas and is exhausted from the exhaust pipe  231 . At this time, the valves  514  and  524  are opened to allow a N 2  gas to flow through the gas supply pipes  510  and  520 , thereby preventing the NH 3  gas from entering the nozzles  410  and  420 . The N 2  gas is supplied into the process chamber  201  via the gas supply pipes  310  and  320  and the nozzles  410  and  420  and is exhausted from the exhaust pipe  231 . 
     At this time, the internal pressure of the process chamber  201  may be set at a pressure which falls within a range of, for example, 10 to 2,000 Pa, for example, 100 Pa, by regulating the APC valve  243 . The supply flow rate of the NH 3  gas controlled by the MFC  322  may be set at a flow rate which falls within a range of, for example, 0.1 to 2 slm. The supply flow rates of the N 2  gas controlled by the MFCs  512 ,  522  and  532  may be set at a flow rate which falls within a range of, for example, 0.2 to 3 slm. The time, during which the NH 3  gas is supplied to the wafer  200 , may be set at a time which falls within a range of, for example, 1 to 120 seconds. The temperature of the heater  207  at this time may be set at the same temperature as that used at the TiCl 4  gas supply step. 
     The gases flowing through the process chamber  201  at this time are only the NH 3  gas and the N 2  gas. The NH 3  gas is substitution-reacted with at least a portion of the Ti-containing layer formed on the SiN layer of the wafer  200  at the first step described above. During the substitution reaction, Ti contained in the Ti-containing layer and N contained in the NH 3  gas are bonded to form a TiN film containing Ti and N on the SiN layer on the wafer  200 . That is, no TiN film is formed on the Si layer and the SiO 2  layer on the wafer  200 . 
     B-4: [Fourth Step] 
     Residual Gas Removal 
     After the TiN film is formed, the valve  334  is closed to stop the supply of the NH 3  gas. 
     Then, the unreacted NH 3  gas, the NH 3  gas contributed to the formation of the TiN film, or the reaction byproduct, which remains within the process chamber  201 , is removed from the interior of the process chamber  201  according to the same processing procedures as those of the first step described above. 
     A state in which the TiN film is formed on the SiN layer is illustrated in  FIGS. 6A to 6C and 7A .  FIG. 6A  is a model diagram illustrating a state of the surface of the wafer immediately after a TiCl 4  gas is supplied,  FIG. 6B  is a model diagram illustrating a state of the surface of the wafer after exposure to the TiCl 4  gas, and  FIG. 6C  is a model diagram illustrating a state of the surface of the wafer immediately after a NH 3  gas is supplied.  FIG. 7A  is a model diagram illustrating a state of the surface of the wafer after exposure to the NH 3  gas. 
     Referring to  FIG. 7A , it can be seen that the surfaces of the Si layer and the SiO 2  layer on the wafer  200  are terminated with the organic ligand (organically terminated) on the surface of the wafer  200 . Further, it can be seen that the TiN film containing Ti and N is formed on the surface of the SiN layer on the wafer  200 . That is, it can be seen that the surfaces of the Si layer and the SiO 2  layer are organically terminated such that no TiN film is formed on the surfaces. 
     Performing a Predetermined Number of Times 
     Then, a cycle which sequentially performs the first step to the fourth step described above by alternately supplying the TiCl 4  gas as the precursor gas and the NH 3  gas as the reaction gas such that they are not mixed with each other is performed once or more (a predetermined number of times (n times)), whereby a TiN film having a predetermined thickness (for example, several nanometers) may be formed on the SiN layer of the wafer  200 , as illustrated in  FIG. 7B . The aforementioned cycle may be performed multiple times. 
     Further, in the pre-processing described above, there has been described a configuration in which a pulse supply is performed by alternately performing the adsorption control agent supply step (HMDSN gas supply) and the purge step (residual gas removal) a plurality of times, but the adsorption control agent supply step (HMDSN gas supply) and the purge step (residual gas removal) may be sequentially and consecutively performed once in the process chamber  201  and then the film-forming process described above may be performed in the process chamber  201 . 
     After-Purge and Atmospheric Pressure Return 
     The N 2  gas is supplied from each of the gas supply pipes  510 ,  520  and  530  into the process chamber  201  and is exhausted from the exhaust pipe  231 . The N 2  gas acts as a purge gas. Thus, the interior of the process chamber  201  is purged with an inert gas and the gas or the byproduct, which remains within the process chamber  201 , is removed from the interior of the process chamber  201  (after-purge). Thereafter, the internal atmosphere of the process chamber  201  is substituted by the inert gas (inert gas substitution). The internal pressure of the process chamber  201  is returned to an atmospheric pressure (atmospheric pressure return). 
     Wafer Unloading 
     Next, the seal cap  219  is moved down by the boat elevator  115  to open the lower end of the outer tube  203 . Then, the processed wafers  200  supported on the boat  217  are unloaded from the lower end of the outer tube  203  to the outside of the outer tube  203  (boat unloading). Thereafter, the processed wafers  200  are discharged from the boat  217  (wafer discharging). 
     (3) Effects According to Embodiments of the Present Disclosure 
     In the present embodiment, the surface of the wafer  200  is first exposed to the HMDSN gas to organically terminate the surfaces of the Si layer and the SiO 2  layer. Thus, the precursor molecules are adsorbed only on the SiN layer which is not organically terminated. That is, the precursor molecules may not be easily adsorbed on the Si layer and the SiO 2  layer on which the organic ligand contained in the HMDSN gas is adsorbed, such that the TiN film may not be formed. Further, the precursor molecules are adsorbed on the SiN layer on which the organic ligand contained in the HMDSN gas is not adsorbed, thereby selectively growing the TiN film. 
     That is, the kind of the surface of the wafer  200  on which the organic ligand contained in the adsorption control agent is adsorbed may be set different by controlling the temperature of the wafer  200  when the wafer  200  is exposed to the adsorption control agent such that film formation may be performed according to the kind of the surface of the wafer. In other words, the kind of the surface of the wafer  200  on which the film is to be selectively grown may be controlled. 
     As a result, according to the present embodiment, it is possible to provide a technique capable of forming a semiconductor device in which the film is selectively formed on the wafer  200 . 
     (4) Other Embodiments 
     Next, other embodiments in which films are formed according to a kind of the surface of the wafer by controlling the temperature of the wafer  200  when the wafer  200  is exposed to the adsorption control agent will be described. Hereinafter, an example in which a TiN film is selectively grown on a SiO 2  layer and a SiN layer on a wafer  200  including a Si layer as a first region and the SiO 2  layer and the SiN layer as a second region, as base films, on a surface of the wafer  200  will be described. 
     The substrate processing (the process of manufacturing a semiconductor device) according to the embodiments includes: a step of organically terminating a surface of a Si layer by supplying a HMDSN gas as an adsorption control agent containing an organic ligand to a wafer  200  while regulating a temperature of the wafer  200  including the Si layer, a SiN layer, and a SiO 2  layer on a surface of the wafer  200  depending on a composition of the Si layer; and a step of selectively growing a TiN film on the SiO 2  layer and the SiN layer by supplying a TiCl 4  gas as a precursor gas and a NH 3  gas as a reaction gas, as deposition gases, to the wafer  200 . 
     A state in which the surface of the Si layer is organically terminated is illustrated in  FIGS. 8A to 8C .  FIG. 8A  is a model diagram illustrating a state immediately after the surface of the wafer  200  on which the Si layer, the SiN layer, and the SiO 2  layer are formed is exposed to the HMDSN gas,  FIG. 8B  is a model diagram illustrating a state of the surface of the wafer  200  after exposure to the HMDSN gas, and  FIG. 8C  is a model diagram illustrating a state after the state of the surface of the wafer  200  after the exposure to the HMDSN gas in  FIG. 8B . 
     Referring to  FIGS. 8A and 8B , on the surface of the wafer  200  after exposure to the HMDSN gas, H molecules on the Si layer and the SiO 2  layer adsorbed on the surface with the HMDSN gas are bonded to N molecules of the HMDSN gas to generate NH 3  to be desorbed. Further, Si(Me) 3  containing a methyl group as an organic ligand is adsorbed on a place from which the H molecules are desorbed, to organically terminate the surfaces of the Si layer and the SiO 2  layer. However, at a temperature which falls within a range of 300 to 500 degree C., Si(Me) 3  adsorbed on the SiO 2  layer may be separated and desorbed from a surface of the SiO 2  layer, as illustrated in  FIG. 8C . Alternatively, the organic ligand contained in the HMDSN gas is not adsorbed on the SiN layer and the SiO 2  layer from the beginning. Thus, the precursor molecules are adsorbed only on the SiO 2  layer and the SiN layer which are not organically terminated. That is, the precursor molecules may not be easily adsorbed on the Si layer on which the organic ligand contained in the HMDSN gas is adsorbed, such that the TiN film may not be formed. Further, the precursor molecules may be adsorbed on the SiO 2  layer and the SiN layer on which the organic ligand contained in the HMDSN gas is not adsorbed, thereby selectively growing the TiN film. 
     That is, the temperature of the wafer  200  when the wafer  200  is exposed to the HMDSN gas in the embodiments may be a temperature which falls within a range of, for example, 300 to 500 degrees C., specifically 300 to 400 degrees C. in some embodiments, or specifically 330 to 350 degrees C. in some embodiments, as a temperature at which the organic ligand contained in the HMDSN gas is adsorbed only on the Si layer but not adsorbed on the SiO 2  layer and the SiN layer such that only the surface of the Si layer is organically terminated. At a temperature lower than 300 degrees C., the organic ligand (the methyl group or the like) contained in the HMDSN gas may remain adsorbed even on the SiO 2  layer, making it difficult to adsorb the precursor molecules to the SiO 2  layer. At a temperature higher than 500 degrees C., the organic ligand contained in the HMDSN gas may not be adsorbed not only on the SiO 2  layer but also on the Si layer, or may be separated and desorbed from the surfaces of the layers even when the organic ligand is adsorbed on the layers. 
     That is, a substrate selectivity of the adsorption control agent for adsorption may be changed by changing the temperature of the wafer when the wafer is exposed to the adsorption control agent, thereby changing a film formation selectivity. For example, by using the HMDSN gas as the adsorption control agent, a film can be formed only on the SiN layer among the Si layer, the SiO 2  layer and the SiN layer at a lower wafer temperature (100 to 250 degrees C.) at which the methyl group contained in the HMDSN gas is adsorbed on the Si layer and the SiO 2  layer but not adsorbed on the SiN layer, and the film can be formed on the SiO 2  layer and the SiN layer among the Si layer, the SiO 2  layer and the SiN layer at a higher wafer temperature (300 to 500 degrees C.) at which the methyl group contained in the HMDSN gas is adsorbed only on Si layer but not adsorbed on the SiO 2  layer and the SiN layer. 
     That is, a specific kind of the surface of the wafer  200  is organically terminated by exposing the surface of the wafer  200  to the adsorption control agent as the pre-processing. Thus, the precursor molecules are adsorbed only on a specific kind of the surface of the wafer  200  which is not organically terminated. The precursor molecules may not be easily adsorbed on a specific kind of the surface of the wafer  200  on which the adsorption control agent is adsorbed, such that a film may not be formed on the specific kind of the surface of the wafer  200  on which the adsorption control agent is adsorbed. Further, the precursor molecules may be adsorbed on a specific kind of the surface of the wafer  200  on which the adsorption control agent is not adsorbed, enabling the selective growth on the specific kind of the surface of the wafer  200  on which the adsorption control agent is not adsorbed. 
     Further, in the aforementioned embodiments, there have been described cases where the methyl group contained in the HMDSN gas is used as the adsorption control agent, but the present disclosure is not limited to the aforementioned embodiments. A gas containing alkylamine in the ligand may be used as the adsorption control agent, a methyl group containing a ligand smaller than that of other ethyl groups or the like is more effective when it is desired to densely spread the alkylamine, and ethyl groups or the like having a large ligand is less volatile and thus more effective when high heat resistance is desired. In addition, as the adsorption control agent, a gas containing molecules having characteristics that the probability of adsorption on the surface of the wafer  200  depends on the kind of the wafer such as the Si layer, the SiO 2  layer, and the SiN layer may be used. 
     That is, the substrate selectivity of the adsorption control agent for adsorption may be changed by changing the ligand having the substrate selectivity of the adsorption control agent, thereby changing the selectivity of film formation. For example, the adsorption control agent can be selectively adsorbed on the SiO 2  layer and the Si layer by using dialkylamine as the ligand having the substrate selectivity of the adsorption control agent, such that a film may not be formed on the SiO 2  layer and the Si layer. 
     Similarly, in the aforementioned embodiments, there have been described the cases where the TiN film is selectively grown with the deposition gas, but the present disclosure is not limited to the aforementioned embodiments. The present disclosure may also be applied to a case where a kind of film to be formed at a low temperature, for example, an ultra-low temperature SiO film, is selectively grown. 
     In addition, in the aforementioned embodiments, there have been described the cases where the pre-processing as the organic termination step and the film-forming process as the selective growth step are performed in one process chamber  201 , but the present disclosure is not limited to the aforementioned embodiments. For example, the present disclosure may be similarly applied to a case where each step is performed in a different process chamber by using a cluster-type apparatus including a plurality of process chambers. In this case, a transfer system and a control part may be shared. Further, the present disclosure may be similarly applied to a case where each step is performed by a different substrate processing apparatus by using a substrate processing system including a plurality of substrate processing apparatuses. 
     Further, in the aforementioned embodiments, there have been described the cases where films are formed by using a batch-type process furnace capable of processing a plurality of wafers at a time, but the present disclosure is not limited to the aforementioned embodiments. For example, the present disclosure may be similarly applied to, for example, a case where films are formed by using a single-wafer-type process furnace capable of processing a single wafer or several wafers at a time. Further, the present disclosure may be similarly applied to, for example, a case where all the process chambers included in each of the cluster-type apparatus and the substrate processing system described above may be batch-type process furnaces, single-wafer-type process furnaces, or a combination thereof. 
     Although various exemplary embodiments of the present disclosure have been described above, the present disclosure is not limited to the embodiments but may be used in combination as appropriate. 
     (5) Examples 
     Next, a difference in film thickness of a TiN film formed depending on a temperature of a wafer when the TiN film is formed on the wafer on which a Si layer, a SiO 2  layer, and a SiN layer are formed as base films by using the substrate processing apparatus  10  described above and the substrate processing described with reference to  FIG. 4  will be described with reference to  FIGS. 9A, 9B, 10A and 10B .  FIGS. 9A and 9B  show results of selective film formation of a TiN film at a wafer temperature of 200 degrees C., and  FIGS. 10A and 10B  show results of selective film formation of the TiN film at a wafer temperature of 350 degrees C. 
     As shown in  FIG. 9A , it was confirmed that the TiN film is formed on the SiN layer according to the number of cycles immediately after the start of the film-forming process described above at the wafer temperature of 200 degrees C. On the other hand, it was confirmed that the TiN film as shown in  FIG. 9B  is not formed on the SiO 2  layer and the Si layer unless the film-forming process described above is performed 100 cycles or more. This is considered to be because, at the wafer temperature of 200 degrees C., the surface of the SiO 2  layer and the surface of the Si layer are organically terminated and the surface of the SiN layer is not organically terminated up to less than 100 cycles. That is, the TiN film can be selectively formed on the SiN layer when the film-forming process is stopped before the film formation begins on the surface of the SiO 2  layer and the surface of the Si layer (before the desorption or decomposition of the adsorption control agent on the surface of the SiO 2  layer and the surface of the Si layer occurs). 
     Furthermore, as shown in  FIG. 10A , it was confirmed that a TiN film is formed on the SiN layer and the SiO 2  layer according to the number of cycles immediately after the start of the film-forming process described above at the wafer temperature of 350 degrees C. On the other hand, it was confirmed that the TiN film as shown in  FIG. 10B  is not formed on the Si layer unless the film-forming process described above is performed more than 100 cycles. This is considered to be because, at the wafer temperature of 350 degrees C., the surface of the Si layer is organically terminated up to about 100 cycles. That is, the TiN film can be selectively formed on the SiN layer and on the SiO 2  layer when the film-forming process is stopped before the film formation begins on the surface of the Si layer (before the desorption or decomposition of the adsorption control agent on the surface of the Si layer occurs). 
     From the aforementioned results, it can be seen that the selectivity may be changed depending on the film-forming temperature by supplying the adsorption control agent before supplying the deposition gas to perform the organic termination on the surface of the base film. 
     According to the present disclosure in some embodiments, it is possible to selectively form a film on a substrate. 
     While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosures. Indeed, the embodiments described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the disclosures. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosures.