Abstract:
Provided are a semiconductor device manufacturing method and a substrate processing apparatus that are capable of increasing a work function of a film to be formed, in comparison with a related art. The method comprises: (a) supplying a metal-containing gas simultaneously with one selected from the group consisting of an oxygen-containing gas, a halogen-containing gas and combinations thereof into a processing chamber accommodating the substrate; and (b) supplying a nitrogen-containing gas with one of the oxygen-containing gas, the halogen-containing gas and the combinations thereof into the processing chamber.

Description:
CROSS-REFERENCE TO RELATED PATENT APPLICATION 
     This U.S. non-provisional patent application is a continuation of U.S. patent application Ser. No. 13/398,523 filed on Feb. 16, 2012 in USPTO, and claims priority under 35 U.S.C. §119 of Japanese Patent Application No. 2011-033243 filed on Feb. 18, 2011 and Japanese Patent Application No. 2012-017827 filed on Jan. 31, 2012, in the Japanese Patent Office, the entire contents of which are hereby incorporated by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a semiconductor device manufacturing method and a substrate processing apparatus. 
     2. Description of the Related Art 
     A process of forming a thin film on a substrate is one process in a semiconductor device manufacturing method, and processing of forming a thin film on a substrate is one example of processing by a substrate processing apparatus. One technique of forming a thin film on a substrate is a chemical vapor deposition (CVD) method. The CVD method is a method of forming a film, which is formed of an element included in a source molecule, on a substrate using a reaction of two or more kinds of source materials in a gas phase or on a substrate surface. In addition, as another technique of forming a thin film on a substrate, there is a technique in which two or more kinds of source materials used in film-forming are alternately supplied onto a substrate one by one and the film forming is controlled in the order of atomic layer using a surface reaction under certain film-forming conditions (a temperature, time, and so on). 
     As a metal film formed on a substrate, for example, a titanium nitride (TiN) film disclosed in Patent Document 1 may be exemplified. The TiN film may be formed by, for example, reacting titanium tetrachloride (TiCl 4 ) with ammonia (NH 3 ). 
     RELATED ART DOCUMENT 
     Patent Document 
     1. International Publication No. 2007/020874 
     SUMMARY OF THE INVENTION 
     However, according to a used material, a value of a work function of a film to be formed may be lower than a desired value. 
     It is an aspect of the present invention to provide a semiconductor device manufacturing method and a substrate processing apparatus capable of increasing a value of a work function of a film to be formed, in comparison with the related art. 
     In order to solve the problems, there is provided a semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method comprising: (a) supplying a metal-containing gas simultaneously with one selected from the group consisting of an oxygen-containing gas, a halogen-containing gas and combinations thereof into a processing chamber accommodating the substrate; and (b) supplying a nitrogen-containing gas with one of the oxygen-containing gas, the halogen-containing gas and the combinations thereof into the processing chamber. 
     The semiconductor device manufacturing method may further include removing the metal-containing gas remaining in the processing chamber after performing the step (a); removing the nitrogen-containing gas remaining in the processing chamber after performing the step (b); and removing the one of the oxygen-containing gas, the halogen-containing gas and the combination thereof remaining in the processing chamber after performing the step (c). 
     In addition, there is provided a semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method comprising: (a) simultaneously supplying a metal-containing gas and a nitrogen-containing gas into a processing chamber accommodating the substrate; and (b) supplying one selected from the group consisting of an oxygen-containing gas, a halogen-containing gas and combinations thereof into the processing chamber, wherein a time duration of supplying the metal-containing gas is shorter than that of the nitrogen-containing gas in the step (a), and the steps (a) and (b) are alternately performed as a temporally separated pulse. 
     Further, the present invention provides a semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method including repeating a cycle a plurality of times, wherein the cycle includes: (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated; (b) supplying a nitrogen-containing gas into the processing chamber; and (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber, wherein at least one of the steps (a) and (b) is performed while step (c) is performed. 
     Furthermore, in the semiconductor device manufacturing method, the steps (a) and (b) are alternately performed a plurality of times. 
     In addition, in the semiconductor device manufacturing method, the steps (a) and (b) are simultaneously performed. 
     Further, in the semiconductor device manufacturing method, an oxygen content or a halogen content of the metal-containing film formed on the substrate is controlled in at least one of the steps (a), (b) and (c) to be at a predetermined level. 
     Furthermore, there is provided a substrate processing apparatus comprising: a processing chamber configured to accommodate a substrate; a gas supply system configured to supply a metal-containing gas, a nitrogen-containing gas, and one selected from the group consisting of an oxygen-containing gas, a halogen-containing gas and combinations thereof into the processing chamber; and a controller configured to control the gas supply system to perform: (a) supplying the metal-containing gas simultaneously with the one selected from the group consisting of the oxygen-containing gas, the halogen-containing gas and the combinations thereof into the processing chamber; and (b) supplying the nitrogen-containing gas with the one selected from the group consisting of the oxygen-containing gas, the halogen-containing gas and the combinations thereof into the processing chamber. 
     In addition, the present invention provides a substrate processing method of forming a metal-containing film on the substrate, the method including: (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated; (b) supplying a nitrogen-containing gas into the processing chamber; and (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber, wherein the step (a) and the step (b) are alternately performed a plurality of times, and the step (c) is terminated only after the step (a) and the step (b) are alternately performed the plurality of times. 
     According to the present invention, it is possible to provide a semiconductor device manufacturing method and a substrate processing apparatus capable of increasing a value of a work function of a film to be formed, in comparison with the related art. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a perspective view showing a schematic configuration of a substrate processing apparatus in accordance with a first exemplary embodiment of the present invention; 
         FIG. 2  is a view showing a processing furnace included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 3  is a cross-sectional view of the processing furnace taken along line A-A of  FIG. 2 ; 
         FIG. 4  is a view schematically showing a first gas supply system, a second gas supply system and a third gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 5  is a block diagram showing a controller and members controlled by the controller, which are included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 6  is a flowchart showing an example of control in the first embodiment of the present invention; 
         FIG. 7  is a timing chart showing a sequence of a film-forming process in the first embodiment of the present invention; 
         FIG. 8  is a timing chart showing a first variant of the film-forming process in the first embodiment of the present invention; 
         FIG. 9  is a timing chart showing a second variant of the film-forming process in the first embodiment of the present invention; 
         FIG. 10  is a timing chart showing a third variant of the film-forming process in the first embodiment of the present invention; 
         FIG. 11  is a timing chart showing a fourth variant of the film-forming process in the first embodiment of the present invention; 
         FIG. 12  is a timing chart showing a fifth variant of the film-forming process in the first embodiment of the present invention; 
         FIG. 13  is a view schematically showing a first variant of the first gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 14  is a view schematically showing a second variant of the first gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 15  is a view schematically showing a third variant of the first gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 16  is a view schematically showing a fourth variant of the first gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 17  is a view schematically showing a fifth variant of the first gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 18  is a view schematically showing a variant of the third gas supply system included in the substrate processing apparatus shown in  FIG. 1 ; 
         FIG. 19  is a view schematically showing a first gas supply system and a second gas supply system included in a substrate processing apparatus in accordance with a second exemplary embodiment of the present invention; 
         FIG. 20  is a view schematically showing a first variant of the first gas supply system and the second gas supply system included in the substrate processing apparatus in accordance with the second exemplary embodiment of the present invention; and 
         FIG. 21  is a view schematically showing a second variant of the first gas supply system and the second gas supply system included in the substrate processing apparatus in accordance with the second exemplary embodiment of the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Hereinafter, an exemplary embodiment of the present invention will be described with reference to the accompanying drawings. A substrate processing apparatus in accordance with the embodiment is configured as one example of a semiconductor manufacturing apparatus used in manufacture of a semiconductor device (integrated circuits (IC)), and a semiconductor device manufacturing method is realized in the substrate processing apparatus in accordance with the embodiment. In the following description, as one example of the substrate processing apparatus, the case in which a vertical apparatus for performing film-forming processing of a substrate is used will be described. However, the present invention is not limited to the use of the vertical apparatus, but the present invention may use, for example, a sheet-feed type apparatus. 
       FIG. 1  shows a substrate processing apparatus  101  in accordance with a first embodiment of the present invention. As shown in  FIG. 1 , a cassette  110  in which a wafer  200 , which is an example of a substrate, is received is used in the substrate processing apparatus  101  and the wafer  200  is formed of a material such as silicon. The substrate processing apparatus  101  includes a housing  111 , in which a cassette stage  114  is installed. The cassette  110  is loaded onto the cassette stage  114  or unloaded from the cassette stage  114  by a conveyance apparatus (not shown) in process. 
     The cassette stage  114  is placed by a conveyance apparatus in process such that a wafer entrance of the cassette  110  is directed upward with the wafer  200  in the cassette  110  held in a vertical posture. The cassette stage  114  is operably configured to rotate the cassette  110  rightward 90° in a longitudinal direction thereof at a rear side of the housing  111  so that the wafer  200  in the cassette  110  is in a horizontal posture and the wafer entrance of the cassette  110  is directed to the rear side of the housing  111 . 
     A cassette shelf  105  is installed at substantially a center portion in the housing  111  in a forward/rearward direction thereof, and the cassette shelf  105  is configured to store a plurality of cassettes  110  in a multi-stage and a multi-column. A transfer shelf  123  in which the cassette  110  to be conveyed by a wafer transfer mechanism  125  is received is installed at the cassette shelf  105 . 
     A preliminary cassette shelf  107  is installed over the cassette stage  114  to preliminarily store the cassette  110 . 
     A cassette conveyance apparatus  118  is installed between the cassette stage  114  and the cassette shelf  105 . The cassette conveyance apparatus  118  includes a cassette elevator  118   a  that can be raised and lowered with holding the cassette  110 , and a cassette conveyance mechanism  118   b , which is a conveyance mechanism. The cassette conveyance apparatus  118  is configured to convey the cassette  110  between the cassette stage  114 , the cassette shelf  105  and the preliminary cassette shelf  107  by a continuous operation of the cassette elevator  118   a  and the cassette conveyance mechanism  118   b.    
     The wafer transfer mechanism  125  is installed in rear of the cassette shelf  105 . The wafer transfer mechanism  125  includes a wafer transfer apparatus  125   a  configured to rotate or move the wafer  200  straight in a horizontal direction, and a wafer transfer apparatus elevator  125   b  configured to raise and lower the wafer transfer apparatus  125   a . Tweezers  125   c  configured to pick up the wafer  200  are installed at the wafer transfer apparatus  125   a . The wafer transfer mechanism  125  is configured to charge the wafer  200  into a boat  217  or discharge the wafer  200  from the boat  217  using the tweezers  125   c  as a mounting part of the wafer  200  by a continuous operation of the wafer transfer apparatus  125   a  and the wafer transfer apparatus elevator  125   b.    
     A processing furnace  202  configured to anneal the wafer  200  is installed at a rear upper side of the housing  111 , and a lower end of the processing furnace  202  is configured to be opened/closed by a furnace port shutter  147 . 
     A boat elevator  115  configured to raise and lower the boat  217  with respect to the processing furnace  202  is installed under the processing furnace  202 . An arm  128  is connected to an elevation frame of the boat elevator  115 , and a seal cap  219  is horizontally installed at the arm  128 . The seal cap  219  is configured to close the lower end of the processing furnace  202  while vertically supporting the boat  217 . 
     The boat  217  includes a plurality of holding members, and is configured to horizontally hold a plurality of wafers  200  (for example, 50 to 150 wafers) concentrically aligned in a vertical direction. 
     A clean unit  134   a  configured to supply clean air, which is in a clean atmosphere, is installed over the cassette shelf  105 . The clean unit  134   a  includes a supply fan and an anti-vibration filter, and is configured to flow the clean air into the housing  111 . 
     A clean unit  134   b  configured to supply clean air is installed at a left end of the housing  111 . The clean unit  134   b  also includes a supply fan and an anti-vibration filter, and is configured to flow the clean air around the wafer transfer apparatus  125   a , the boat  217 , or the like. The clean air flows around the wafer transfer apparatus  125   a , the boat  217 , or the like, and then is exhausted to the outside of the housing  111 . 
     In the substrate processing apparatus  101  as configured above, when the cassette  110  is loaded onto the cassette stage  114  by the conveyance apparatus (not shown) in process, the cassette  110  is placed such that the wafer  200  is held on the cassette stage  114  in a vertical posture and the wafer entrance of the cassette  110  is directed upward. Next, the cassette  110  is rotated rightward 90° in a longitudinal direction thereof at the rear side of the housing  111  such that the wafer  200  in the cassette  110  is in a horizontal posture by the cassette stage  114  and the wafer entrance of the cassette  110  is directed to the rear side of the housing  111 . 
     Thereafter, the cassette  110  is automatically conveyed and delivered to a designated shelf position of the cassette shelf  105  or the preliminary cassette shelf  107  by the cassette conveyance apparatus  118  to be temporarily stored, and then transferred to the transfer shelf  123  from the cassette shelf  105  or preliminary cassette shelf  107  by the cassette conveyance apparatus  118  or directly conveyed to the transfer shelf  123 . 
     When the cassette  110  is transferred to the transfer shelf  123 , the wafer  200  is picked from the cassette  110  by the tweezers  125   c  of the wafer transfer apparatus  125   a  through the wafer entrance to be charged into the boat  217 . The wafer transfer apparatus  125   a  which delivered the wafer  200  to the boat  217  returns to the cassette  110  and charges the next wafer  200  to the boat  217 . 
     When a predetermined number of wafers  200  are charged into the boat  217 , the furnace port shutter  147  that closed the lower end of the processing furnace  202  is opened to open the lower end of the processing furnace  202 . Next, the boat  217  in which a group of wafers  200  are held is loaded into the processing furnace  202  by a raising operation of the boat elevator  115 , and the lower portion of the processing furnace  202  is closed by the seal cap  219 . 
     After the loading, the wafer  200  is arbitrarily processed in the processing furnace  202 . After the processing, in a reverse sequence of that mentioned above, the wafer  200  and the cassette  110  are unloaded to the outside of the housing  111 . 
     In addition, the substrate processing apparatus  101  includes a controller  900 . The controller  900  is an example of a control unit (control unit) configured to control the entire operation of the substrate processing apparatus  101 , and a CPU  932  (described later, see  FIG. 5 ), which is a portion of the controller  900 , is installed in, for example, the housing  111 . 
       FIGS. 2 and 3  show the processing furnace  202 . As shown in  FIGS. 2 and 3 , the processing furnace  202  configures a processing chamber  201 , which is an example of a processing chamber configured to accommodate the wafer  200 , and a heater  207 , which is a heating apparatus (heating unit) configured to heat the wafer  200 , is installed at the processing furnace  202 . The heater  207  includes an insulating member having a cylindrical shape with an upper side closed, and a plurality of heater wires, and has a unit in which the heater wires are installed at the insulating member. A reaction tube  203  formed of quartz and configured to process the wafer  200  is installed inside the heater  207 . 
     The seal cap  219 , which is a furnace port cover configured to hermetically close a lower end opening of the reaction tube  203 , is installed under the reaction tube  203 . The seal cap  219  is configured to contact the lower end of the reaction tube  203  from a lower side thereof in the vertical direction. The seal cap  219  is formed of a metal such as stainless steel and has a disc shape. An O-ring, which is a seal member in contact with the lower end of the reaction tube  203 , is installed on an upper surface of the seal cap  219 . A rotary mechanism  267  configured to rotate the boat is installed at the seal cap  219  opposite to the processing chamber  201 . A rotary shaft  255  of the rotary mechanism  267  passes through the seal cap to be connected to the boat  217  (described later), and is configured to rotate the wafer  200  by rotation of the boat  217 . The seal cap  219  is configured to be vertically raised and lowered by the boat elevator  115 , which is an elevation mechanism installed outside the reaction tube  203 , and thus, the boat  217  can be loaded into/unloaded from the inside of the processing chamber  201 . 
     A boat support frame  218  configured to support the boat  217  is installed at the seal cap  219 . The boat  217  includes a bottom plate  210  (see  FIG. 1 ) fixed to the boat support frame  218  and a top plate  211  disposed over the bottom plate  210 , and a plurality of columns  212  (see  FIG. 1 ) are installed between the bottom plate  210  and the top plate  211 . The plurality of wafers  200  are held on the boat  217 . The plurality of wafers  200  are supported by the columns  212  of the boat  217  at predetermined intervals in a horizontal posture. 
     In the processing furnace  202  as described above, in a state in which the plurality of wafers  200 , which are to be batch-processed, are stacked on the boat  217  in a multi-stage, the boat  217  is inserted into the processing chamber  201  with the boat  217  supported by the boat support frame  218 , and the heater  207  heats the wafer  200  inserted into the processing chamber  201  to a predetermined temperature. 
     A temperature sensor  263 , which is a temperature detector, is installed in the reaction tube  203 , and is configured such that a temperature in the processing chamber  201  arrives at a desired temperature distribution by adjusting a conduction state to the heater  207  based on temperature information detected by the temperature sensor  263 . The temperature sensor  263  has an L shape and is installed along an inner wall of the reaction tube  203 . 
     The boat  217  is installed at a center portion in the reaction tube  203 . The boat  217  is raised and lowered (goes in/come out) with respect to the reaction tube  203  by the boat elevator  115 . A boat rotary mechanism  267  configured to rotate the boat  217  to improve processing uniformity is installed at a lower end of the boat support frame  218  configured to support the boat  217 . As the boat rotary mechanism  267  is driven, the boat  217  supported by the boat support frame  218  can be rotated. 
     In addition, as shown in  FIGS. 2 and 3 , the substrate processing apparatus  101  includes a first gas supply system  300 , a second gas supply system  400  and a third gas supply system  500 . 
     The first gas supply system  300  is used as one example of a first gas supply system configured to supply a metal-containing gas into the processing chamber  201 , and includes a first gas supply pipe  310 . One end of the first gas supply pipe  310  is disposed inside the processing chamber  201 , and the other end is disposed outside the processing chamber  201 . In addition, the first gas supply system  300  includes a first nozzle  314 . 
     The first nozzle  314  is connected to the one end of the first gas supply pipe  310 , and extends in an arc-shaped space between the inner wall of the reaction tube  203  and the wafer  200 , which constitute the processing chamber  201 , in a vertical direction along the inner wall of the reaction tube  203  (in a stack direction of the wafers  200 ). Further, a plurality of gas supply holes  314   a  configured to supply a metal-containing gas are formed in a side surface of the first nozzle  314 . The gas supply holes  314   a  having the same opening size or gradually varied opening areas are formed in the first nozzle  314  from a lower portion to an upper portion thereof at predetermined opening pitches. 
     The second gas supply system  400  is used as a second gas supply system configured to supply a nitrogen-containing gas into the processing chamber  201 , and includes a second gas supply pipe  410 . One end of the second gas supply pipe  410  is disposed inside the processing chamber  201 , and the other end is disposed outside the processing chamber  201 . In addition, the second gas supply system  400  includes a second nozzle  414 . 
     The second nozzle  414  is connected to one end of the second gas supply pipe  410 , and extends in an arc-shaped space between the inner wall of the reaction tube  203  and the wafer  200 , which constitute the processing chamber  201 , in the vertical direction along the inner wall of the reaction tube  203  (in the stack direction of the wafers  200 ). In addition, a plurality of gas supply holes  414   a  configured to supply a nitrogen-containing gas are formed in a side surface of the second nozzle  414 . The gas supply holes  414   a  having the same opening size or gradually varied opening areas are formed in the second nozzle  414  from a lower portion to an upper portion thereof at predetermined opening pitches. 
     The third gas supply system  500  is used as a third gas supply system configured to supply one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber  201 , and includes a third gas supply pipe  510 . One end of the third gas supply pipe  510  is disposed inside the processing chamber  201 , and the other end is disposed outside the processing chamber  201 . In addition, the third gas supply system  500  includes a third nozzle  514 . 
     The third nozzle  514  is connected to the one end of the third gas supply pipe  510 , and extends in an arc-shaped space between the inner wall of the reaction tube  203  and the wafer  200 , which constitute the processing chamber  201 , in the vertical direction along the inner wall of the reaction tube  203  (in the stack direction of the wafers  200 ). In addition, a plurality of gas supply holes  514   a  configured to supply an oxygen-containing gas are formed in a side surface of the third nozzle  514 . The gas supply holes  514   a  having the same opening size or gradually varied opening areas are formed in the third nozzle  514  from a lower portion to an upper portion thereof at predetermined opening pitches. 
       FIG. 4  shows the first gas supply system  300 , the second gas supply system  400  and the third gas supply system  500 . 
     As shown in  FIG. 4 , the first gas supply system  300  includes the first gas supply pipe  310 , a bubbler  700  connected to the gas supply pipe  310 , and a valve  318  installed in the gas supply pipe  310  at an upstream side of the bubbler  700 . 
     The bubbler  700  includes an accommodating vessel  702  configured to accommodate a liquid source material, and is used as one example of an evaporator configured to generate a source gas by evaporating the liquid source material through bubbling. The accommodating vessel  702  is a sealed vessel, and TiCl 4  (titanium tetrachloride), which is an example of the liquid source material, is accommodated in the accommodating vessel  702 . 
     A carrier gas supply pipe  360  is connected to the accommodating vessel  702 . A carrier gas supply source (not shown) is connected to an upstream side of the carrier gas supply pipe  360 . In addition, a downstream side end of the carrier gas supply pipe is immersed in the liquid source material accommodated in the accommodating vessel  702 . Further, a mass flow controller  362  configured to control a supply flow rate of a carrier gas supplied from a carrier gas supply source and a valve  364  used to stop or initiate supply of the carrier gas are mounted on the carrier gas supply pipe  360 . 
     A gas that does not react with the liquid source material may be used as the carrier gas supplied using the carrier gas supply pipe  360 , for example, an inert gas such as N 2  gas or Ar gas may be used. 
     The valve  318  is used to stop or initiate supply of the source gas from the bubbler  700 . 
     In addition, the first gas supply system  300  includes a carrier gas supply pipe  330 , a mass flow controller  332  and a valve  334 . The carrier gas supply pipe  330  is used to supply a carrier gas, and is connected to the first gas supply pipe  310 . The mass flow controller  332  and the valve  334  are mounted on the carrier gas supply pipe  330  in a sequence of the mass flow controller  332  and the valve  334  from an upstream side. For example, N 2  gas is used as the carrier gas supplied through the carrier gas supply pipe  330 . 
     Further, the first gas supply system  300  includes a cleaning gas supply pipe  340 , a mass flow controller  342 , a valve  344  and a valve  346 . The cleaning gas supply pipe  340  is used to supply a cleaning gas, and connected to the first gas supply pipe  310  at a downstream side of a position to which the bubbler  700  is connected. The mass flow controller  342 , the valve  344  and the valve  346  are mounted on the cleaning gas supply pipe  340  in a sequence of the mass flow controller  342 , the valve  344  and the valve  346  from an upstream side. 
     Furthermore, the first gas supply system  300  includes a valve  350 . The valve  350  is mounted on the first gas supply pipe  310  at a downstream side of a position to which the carrier gas supply pipe  330  is connected and an upstream side of a position to which the cleaning gas supply pipe  340  is connected. 
     The first gas supply system  300  configured as above supplies TiCl 4  gas, which is an example of a metal-containing gas, into the processing chamber  201 . Instead of the configuration of the first gas supply system  300  to supply TiCl 4  gas into the processing chamber  201 , the first gas supply system  300  may be configured to supply tetrakisdimethylaminotitanium (TDMAT, Ti[N(CH 3 ) 2 ] 4 ) or tetrakisdiethylaminotitanium (TDEAT, Ti[N(CH 2 CH 3 ) 2 ] 4 ) into the processing chamber  201 . 
     The second gas supply system  400  includes the second gas supply pipe  410 , a mass flow controller  416  and a valve  418 . A supply source of NH 3  (ammonia) gas (not shown) is connected to an upstream side end of the second gas supply pipe  410 . The mass flow controller  416  and the valve  418  are mounted on the second gas supply pipe  410  in a sequence of the mass flow controller  416  and the valve  418  from an upstream side. The mass flow controller  416  is used as an example of a flow rate control apparatus (flow rate control unit), and the valve  418  is used as an example of an opening/closing valve. 
     In addition, the second gas supply system  400  includes a carrier gas supply pipe  430 , a mass flow controller  432  and a valve  434 . The carrier gas supply pipe  430  is used to supply a carrier gas and connected to the second gas supply pipe  410 . The mass flow controller  432  and the valve  434  are mounted on the carrier gas supply pipe  430  in a sequence of the mass flow controller  432  and the valve  434  from an upstream side. For example, N 2  gas is used as the carrier gas supplied through the carrier gas supply pipe  430 . 
     Further, the second gas supply system  400  includes a cleaning gas supply pipe  440 , a mass flow controller  442 , a valve  444  and a valve  446 . The cleaning gas supply pipe  440  is used to supply a cleaning gas and is connected to the second gas supply pipe  410 . The mass flow controller  442 , the valve  444  and the valve  446  are mounted on the cleaning gas supply pipe  440  in a sequence of the mass flow controller  442 , the valve  444  and the valve  446  from an upstream side. 
     In addition, the second gas supply system  400  includes a valve  450 . The valve  450  is mounted on the second gas supply pipe  410  at a downstream side of a position to which the carrier gas supply pipe  430  is connected and an upstream side of a position to which the cleaning gas supply pipe  440  is connected. 
     The second gas supply system  400  configured as above supplies NH 3  gas, which is an example of a nitrogen-containing gas, into the processing chamber  201 . Instead of the configuration of the second gas supply system  400  to supply the NH 3  gas into the processing chamber  201 , the second gas supply system  400  may be configured to supply N 2  (nitrogen) gas, N 2 O (nitrous oxide) gas, CH 6 N 2  (monomethylhydrazine) gas, etc., into the processing chamber  201 . 
     The third gas supply system  500  includes the third gas supply pipe  510 , a mass flow controller  516  and the valve  518 . A supply source of O 2  (oxygen) gas is connected to an upstream side end of the third gas supply pipe  510 . The mass flow controller  516  and the valve  518  are mounted on the third gas supply pipe  510  in a sequence of the mass flow controller  516  and the valve  518  from an upstream side. The mass flow controller  516  is used as one example of the flow rate control apparatus (flow rate control unit), and the valve  518  is used as an opening/closing valve. Instead of the configuration of the third gas supply system  500  to supply the O 2  gas into the processing chamber  201 , the third gas supply system  500  may be configured to supply the N 2 O (nitrous oxide) gas, etc., into the processing chamber  201 . 
     Further, the third gas supply system  500  includes a carrier gas supply pipe  530 , a mass flow controller  532  and a valve  534 . The carrier gas supply pipe  530  is used to supply a carrier gas and is connected to the third gas supply pipe  510 . The mass flow controller  532  and the valve  534  are mounted on the carrier gas supply pipe  530  in a sequence of the mass flow controller  532  and the valve  534  from an upstream side. For example, N 2  gas is used as the carrier gas supplied through the carrier gas supply pipe  530 . 
     Furthermore, the third gas supply system  500  includes a cleaning gas supply pipe  540 , a mass flow controller  542 , a valve  544  and a valve  546 . The cleaning gas supply pipe  540  is used to supply a cleaning gas and connected to the third gas supply pipe  510 . The mass flow controller  542 , the valve  544  and the valve  546  are mounted on the cleaning gas supply pipe  540  in a sequence of the mass flow controller  542 , the valve  544  and the valve  546  from an upstream side. 
     In addition, the third gas supply system  500  includes a valve  550 . The valve  550  is mounted on the third gas supply pipe  510  at a downstream side of a position to which the carrier gas supply pipe  530  is connected and an upstream side of a position to which the cleaning gas supply pipe  540  is connected. 
     A gas supply method in the embodiment is clearly distinguished from the conventional method of directly supplying a gas from one end of a lower side or an upper side of the reaction tube  203  into an arc-shaped elongated space defined by the inner wall of the reaction tube  203  and ends of the plurality of wafers  200  to flow the gas from the lower side to the upper side or from the upper side to the lower side so that each of the wafers  200  stacked in the reaction tube  203  reacts with the flowing gas. In this case, at an area adjacent to a gas supply part, the amount of gas is relatively increased (a concentration of the gas is relatively increased), and a film thickness of the thin film formed on the wafer  200  disposed at the area is increased. Meanwhile, at an area far away from the gas supply part, since the amount of gas that can arrive at the wafer  200  is reduced (the concentration of the gas is relatively increased), the film thickness of the thin film formed on the wafer  200  disposed at the area is reduced. Accordingly, since a difference in film thickness of the thin film generated between upper and lower sides of the wafers  200  stacked in the reaction tube  203  occurs, the conventional gas supply method is not preferable to a vertical batch-type apparatus. 
     Meanwhile, the gas supply method in the embodiment is characterized in that a gas is conveyed via the nozzles  314 ,  414  and  514  disposed in the arc-shaped space, the gas is initially ejected into the reaction tube  203  and around the wafer  200  through the gas supply hole  314   a ,  414   a  and  514   a  opened at the nozzle  314 ,  414  and  514 , and a main flow of the gas in the reaction tube  203  is parallel to a surface of the wafer  200 , i.e., a horizontal direction. As a result, the gas can be uniformly supplied to each of the wafers  200 , and the film thickness of the thin film formed on each of the wafers  200  can be uniformized. In addition, while the remaining gas after the reaction flows toward an exhaust port. i.e., in a direction of an exhaust pipe  231 , which will be described later, the flow direction of the remaining gas is not limited to the vertical direction but may be appropriately specified by a position of the exhaust port. 
     The exhaust pipe  231  configured to exhaust an atmosphere in the processing chamber  201  is installed at the reaction tube  203 . As shown in  FIG. 3 , when seen from a lateral cross-sectional view, the exhaust pipe  231  is installed at a side of the reaction tube  203  opposite to a side in which the gas supply hole  314   a  of the first nozzle  314 , the gas supply hole  414   a  of the second nozzle  414  and the gas supply hole  514   a  of the third nozzle  514  are formed, i.e., an opposite side of the gas supply holes  314   a ,  414   a  and  514   a  with the wafer  200  interposed therebetween. In addition, the exhaust pipe  231  is installed under positions in which the gas supply holes  314   a ,  414   a  and  515   a  are formed. According to the configuration, the gas supplied around the wafer  200  in the processing chamber  201  through the gas supply holes  314   a .  414   a  and  514   a  flows in a horizontal direction, i.e., in a direction parallel to the surface of the wafer  200 , flows downward, and then is exhausted through the exhaust pipe  231 . Similar to that described above, a main flow of the gas in the processing chamber  201  becomes a flow in a horizontal direction. A vacuum pump  246 , which is a vacuum exhaust apparatus, is connected to the exhaust pipe  231  via a pressure sensor  245 , which is a pressure detector (a pressure detecting part) configured to detect a pressure in the processing chamber  201 , and an automatic pressure controller (APC) valve  243 , which is a pressure regulator (a pressure regulating part), so that the pressure in the processing chamber  201  is vacuum-exhausted to a predetermined pressure (a degree of vacuum). In addition, the APC valve  243  is an opening/closing valve configured to open/close a valve to perform the vacuum-exhaust and stop the vacuum-exhaust in the processing chamber  201 , and adjust a valve opening angle to regulate the pressure. An exhaust system is mainly constituted by the exhaust pipe  231 , the APC valve  243 , the vacuum pump  246  and the pressure sensor  245 . 
       FIG. 5  shows the controller  900 . The controller  900  controls the first gas supply system  300 , the second gas supply system  400  and the third gas supply system  500  such that an oxygen content or a halogen content included in the metal-containing film formed on the wafer  200  is at a predetermined level. 
     In addition, the controller  900  includes a display  910  configured to display operation menus, and an operation input part  902  having a plurality of keys and into which various information and operation orders are input. Further, the controller  900  includes a CPU  932  configured to process the entire operation of the substrate processing apparatus  101 , a ROM  934  in which various programs including a control program are previously stored, a RAM  936  configured to temporarily store various data, an HDD  938  configured to store and hold various data, a display driver  912  configured to control display of various information to the display  910  and receive operation information from the display  910 , an operation input detection part  922  configured to detect an operation state of the operation input part  920 , and a communication interface (I/F) part  940 . 
     The communication I/F part  940  performs transmission and reception of various information to/from various members such as a temperature control unit  950  (described later), a pressure control unit  960  (described later), the vacuum pump  246 , the boat rotary mechanism  267 , the boat elevator  115 , the mass flow controllers  322 ,  342 ,  362 ,  416 ,  432 ,  442 ,  516 ,  532  and  542 , and a valve control unit  970  (described later). 
     The CPU  932 , the ROM  934 , the RAM  936 , the HDD  938 , the display driver  912 , the operation input detection part  922  and the communication I/F part  940  are connected to each other via a system bus  904 . For this reason, the CPU  932  can perform access to the ROM  934 , the RAM  936  and the HDD  938 , control of display of various information to the display  910  via the display driver  912  and recognition of operation information from the display  910 , and control of transmission and reception of various information to/from each member via the communication I/F part  940 . In addition, the CPU  932  can recognize an operation state of a use with respect to the operation input part  920  via the operation input detection part  922 . 
     The temperature control unit  950  includes the heater  207 , a heating power source  250  configured to supply power to the heater  207 , the temperature sensor  263 , a communication I/F part  952  configured to transmit and receive various information such as set temperature information to/from the controller  900 , and a heater control unit  292  configured to control power supply from the heating power source  250  to the heater  207  based on the received set temperature information and the temperature information from the temperature sensor  263 . The heater control unit  292  is realized by a computer. The communication I/F part  952  of the temperature control unit  950  is connected to the communication I/F part  940  of the controller  900  via a cable. 
     The pressure control unit  960  includes the APC valve  243 , the pressure sensor  245 , a communication I/F part  962  configured to transmit and receive various information such as set pressure information and opening/closing information of the APC valve  243  to/from the controller  900 , and an APC valve control unit  964  configured to control opening/closing or an opening angle of the APC valve  243  based on the set pressure information, opening/closing information of the APC valve  243 , and pressure information from the pressure sensor  245 . The APC valve control unit  964  is realized by the computer. The communication I/F part  962  of the pressure control unit  960  is connected to the communication I/F part  940  of the controller  900  via a cable. 
     The valve control unit  970  includes the valves  318 ,  334 ,  344 ,  346 ,  350 ,  364 ,  428 ,  444 ,  446 ,  450 ,  518 ,  534 ,  544 ,  546  and  550 , and an electromagnetic valve group  972  configured to control supply of air to the valves  318 ,  334 ,  344 ,  346 ,  350 ,  364 ,  428 ,  444 ,  446 ,  450 ,  518 ,  534 ,  544 ,  546  and  550 , which are air valves. The electromagnetic valve group  972  is connected to the communication I/F part  940  of the controller  900  via a cable. 
     As described above, the controller  900  is connected to each of the members such as the mass flow controllers  332 ,  342 ,  362 ,  416 ,  432  and  442 , the valves  318 ,  334 ,  344 ,  346 ,  350 ,  364 ,  418 ,  444 ,  446 ,  450 ,  518 ,  534 ,  544 ,  546  and  550 , the APC valve  243 , the heating power source  250 , the temperature sensor  263 , the pressure sensor  245 , the vacuum pump  246 , the boat rotary mechanism  267  and the boat elevator  115 . In addition, the controller  900  is configured to perform a flow rate control of the mass flow controllers  332 ,  342 ,  362 ,  416 ,  432  and  442 , an opening/closing operation control of the valves  318 ,  334 ,  344 ,  346 ,  350 ,  364 ,  418 ,  444 ,  446 ,  450 ,  518 ,  534 ,  544 ,  546  and  550 , a pressure control through an opening angle adjusting operation based on pressure information from the pressure sensor  245 , a temperature control through a power supply amount adjusting operation from the heating power source  250  to the heater  207  based on temperature information from the temperature sensor  263 , an initiation and stoppage control of the vacuum pump  246 , a rotational speed adjusting control of the boat rotary mechanism  267 , and an elevation operation control of the boat elevator  115 . 
     Hereinafter, an example of a method of forming a film on a substrate when a large scale integration (LSI) is manufactured, which is one process of manufacturing a semiconductor device, using the processing furnace  202  of the substrate processing apparatus will be described. In addition, in the following description, operations of the members constituting the substrate processing apparatus are controlled by the controller  900 . 
     In the embodiment, a method of forming a titanium oxynitride (TiON) film, in which oxygen is added (doped) to a titanium nitride film, which is a metal film, on a substrate using a method of alternately supplying a plurality of processing gases will be described. In the embodiment, for example, TiCl 4  is used as a titanium (Ti)-containing element and NH 3  is used as a nitriding gas. In the example, a titanium-containing gas supply system (a first element-containing gas supply system) is constituted by the first gas supply system  300 , a nitrogen-containing gas supply system (a second element-containing gas supply system) is constituted by the second gas supply system  400 , and an oxygen-containing gas supply system (a third element-containing gas supply system) is constituted by a third gas supply system  500 . 
       FIG. 6  shows an example of a control flow in the embodiment. The first gas supply system  300 , the second gas supply system  400  and the third gas supply system  500  are controlled by the control flow such that an oxygen content or a halogen content included in the metal-containing film formed on the wafer  200  is at a predetermined level. In addition, in the control flow, the controller  900  controls the substrate processing apparatus  101  as follows. That is, the heater  207  is controlled to maintain the inside of the processing chamber  201  at a temperature of, for example, 300° C. to 550° C., preferably, 450° C. or less, and more preferably, 450° C. 
     In addition, wafer charging is performed in step S 102 . That is, the plurality of wafers  200  are charged into the boat  217 . 
     In the following step S 104 , boat loading is performed. That is, the boat  217  on which the plurality of wafers  200  are supported is raised by the boat elevator  115  to be loaded into the processing chamber  201 . In this state, the seal cap  219  seals the lower end of the reaction tube  203  via an O-ring  220 . Next, the boat  217  is rotated by a boat driving mechanism  267  to rotate the wafer  200 . Next, as the vacuum pump  246  is operated, the APC valve  243  is opened to vacuum-exhaust the inside of the processing chamber  201 , and when a temperature of the wafer  200  arrives at 450° C. and is stably maintained (pressure and temperature adjustment, S 106 ), the next steps are sequentially performed in a state in which the temperature in the processing chamber  201  is maintained at 450° C. 
     In step (S 202 ), TiCl 4  is supplied. TiCl 4  is a liquid at a normal temperature. For this reason, in order to supply it into the processing chamber  201 , N 2  (nitrogen), which is an inert gas, used as one example of a carrier gas passes through the accommodating vessel  702  using the bubbler  700 , and is supplied into the processing chamber  201  with the carrier gas to an extent of evaporation. Instead of N 2 , He (helium), Ne (neon) and Ar (argon) may be used as the carrier gas. 
     More specifically, in step S 202 , the TiCl 4  flows through the first gas supply pipe  310  and the carrier gas (N 2 ) flows through the carrier gas supply pipe  330 . At this time, the valve  362 , the valve  318  of the first gas supply pipe  310 , the valve  334  of the carrier gas supply pipe  330  and the APC valve  243  of the exhaust pipe  231  are opened together. The carrier gas flows through the carrier gas supply pipe  330  to be flow rate-controlled by the mass flow controller  332 . The TiCl 4  flows through the first gas supply pipe  310  to be flow rate-adjusted through the mass flow controller  362  by adjusting a flow rate of the carrier gas supplied into the accommodating vessel  702 , mixed with the flow rate-adjusted carrier gas, supplied into the processing chamber  201  through the gas supply hole  314   a  of the first nozzle  314  to flow on the surface of the wafer  200  in a horizontal direction, and then exhausted through the exhaust pipe  231 . Here, a main flow of the gas in the processing chamber  201  becomes a flow in a horizontal direction, i.e., in a direction parallel to the surface of the wafer  200 . In addition, at this time, the APC valve  243  is appropriately adjusted to maintain the pressure in the processing chamber  201  within a range of 20 to 50 Pa, for example, 30 Pa. A supply amount of TiCl 4  controlled by the mass flow controller  362  is, for example, 1.0 to 2.0 g/min. A time of exposing the wafer  200  to the TiCl 4  is about 3 to 10 seconds. Here, the temperature of the heater  207  is set such that the temperature of the wafer is within a range of 300° C. to 550° C. for example, 450° C. 
     In step S 202 , the gas flowing into the processing chamber  201  contains TiCl 4  and N 2 , which is an inert gas, and there is no NH 3 . Accordingly. TiCl 4  does not cause a gas phase reaction but surface-reacts with a surface or a lower base film of the wafer  200 . 
     In step S 202 , when the valve  434  is opened and the inert gas flows through the carrier gas supply pipe  430  connected to the middle of the second gas supply pipe  410 , TiCl 4  can be prevented from entering the NH 3  side. In addition, when the valve  534  is opened and the inert gas flows through the carrier gas supply pipe  530  connected to the middle of the third gas supply pipe  510 , TiCl 4  can be prevented from entering the O 2  side. 
     In the next step S 204 , the remaining gas is removed. That is, in a state in which the valve  318  of the first gas supply pipe  310  is closed to stop supply of the TiCl 4  into the processing chamber  201  and the APC valve  243  of the exhaust pipe  231  is opened, the inside of the processing chamber  201  is exhausted by the vacuum pump  246  to 20 Pa or less, and the remaining TiCl 4  is eliminated from the inside of the processing chamber  201 . In addition, here, the gas remaining in the processing chamber  201  may not be completely eliminated, and the inside of the processing chamber  201  may not be completely purged. When an amount of the gas remaining in the processing chamber  201  is very small, there is no bad influence on step 2 performed thereafter. Here, there is no need to increase a flow rate of N 2  gas supplied into the processing chamber  201  to a large flow rate. For example, as substantially the same amount of gas as a volume of the reaction tube  203  (the processing chamber  201 ) is supplied, the purge can be performed to an extent in which there is no bad influence on step S 206 . As described above, as the inside of the processing chamber  201  is not completely purged, the purge time can be reduced and throughput can be improved. In addition, consumption of the N 2  gas can be suppressed to a minimum level. 
     In the next step S 206 , NH 3  is supplied. That is, the NH 3  flows through the second gas supply pipe  410  and the carrier gas (N 2 ) flows through the carrier gas supply pipe  430 . Here, the valve  418  of the second gas supply pipe  410 , the valves  434  and  450  of the carrier gas supply pipe  430  and the APC valve  243  of the exhaust pipe  231  are opened together. The carrier gas flows through the carrier gas supply pipe  430  to be flow rate-adjusted by the mass flow controller  432 . The NH 3  flows through the second gas supply pipe  410  to be flow rate-adjusted by the mass flow controller  416 , is mixed with the flow rate-adjusted carrier gas to be supplied into the processing chamber  201  through the gas supply hole  414   a  of the second nozzle  414 , flows on the wafer  200  in a horizontal direction, and then is exhausted through the exhaust pipe  231 . Here, a main flow of the gas in the processing chamber  201  becomes a flow in a horizontal direction. i.e., in a direction parallel to the surface of the wafer  200 . In addition, when the NH 3  flows, the APC valve  243  is appropriately adjusted to maintain the pressure in the processing chamber  201  within a range of 50 to 1000 Pa, for example, 60 Pa. A supply flow rate of the NH 3  controlled by the mass flow controller  416  is within a range of, for example, 1 to 10 slm. A time of exposing the wafer  200  to NH 3  is for example, 10 to 30 seconds. The temperature of the heater  207  at this time is a predetermined temperature within a range of 300° C. to 550° C., for example, 450° C. 
     In step S 206 , when the valve  334  is opened to flow an inert gas through the carrier gas supply pipe  330  connected to the middle of the first gas supply pipe  310 , the NH 3  can be prevented from entering the TiCl 4  side. In addition, when the valve  534  is opened to flow the inert gas through the carrier gas supply pipe  530  connected to the middle of the third gas supply pipe  510 , the NH 3  can be prevented from entering the O 2  side. 
     In step S 206 , as the NH 3  is supplied, the TiCl 4  and NH 3  are reacted with each other on the wafer  200  to form a titanium nitride (TiN) film on the wafer  200 . 
     In the next step S 208 , the remaining gas is removed. That is, the valve  418  of the second gas supply pipe  410  is closed to stop supply of the NH 3 . In addition, in a state in which the APC valve  243  of the exhaust pipe  231  is kept open, the processing chamber  201  is exhausted by the vacuum pump  246  to 20 Pa or less, and the remaining NH 3  is eliminated from the processing chamber  201 . In addition, here, the gas remaining in the processing chamber  201  may not be completely eliminated, and the inside of the processing chamber  201  may not be completely purged. When an amount of the gas remaining in the processing chamber  201  is very small, there is no bad influence on step S 210  performed thereafter. Here, there is no need to increase a flow rate of N 2  gas supplied into the processing chamber  201  to a large flow rate. For example, as substantially the same amount of gas as a volume of the reaction tube  203  (the processing chamber  201 ) is supplied, the purge can be performed to an extent in which there is no bad influence on step S 210 . As described above, as the inside of the processing chamber  201  is not completely purged, the purge time can be reduced and throughput can be improved. In addition, consumption of the N 2  gas can be suppressed to a minimum level. 
     In the next step S 210 , O 2  is supplied. That is, the O 2  flows through the third gas supply pipe  510 , and the carrier gas (N 2 ) flows through the carrier gas supply pipe  530 . At this time, the valves  518  and  550  of the third gas supply pipe  510 , the valves  534  and  550  of the carrier gas supply pipe  530  and the APC valve  243  of the exhaust pipe  231  are opened together. The carrier gas flows through the carrier gas supply pipe  530  to be flow rate-adjusted by the mass flow controller  532 . The O 2  flows through the third gas supply pipe  510  to be flow rate-adjusted by the mass flow controller  516 , is mixed with the flow rate-adjusted carrier gas to be supplied into the processing chamber  201  through the gas supply hole  514   a  of the third nozzle  514 , flows on the surface of the wafer  200  in a horizontal direction, and then is exhausted through the exhaust pipe  231 . Here, a main flow of the gas in the processing chamber  201  becomes a flow in a horizontal direction, i.e., in a direction parallel to the surface of the wafer  200 . When the O 2  flows, the APC valve  243  is appropriately adjusted to maintain the pressure in the processing chamber  201  within a range of 50 to 1,000 Pa, for example, 60 Pa. 
     In step S 210 , when the valve  334  is opened to flow the inert gas through the carrier gas supply pipe  330  connected to the middle of the first gas supply pipe  310 , the O 2  can be prevented from entering the TiCl 4  side. In addition, when the valve  434  is opened to flow the inert gas through the carrier gas supply pipe  430  connected to the middle of the second gas supply pipe  410 , the O 2  can be prevented from entering the NH 3  side. 
     In step S 210 , As the O 2  is supplied onto the titanium nitride (TiN) film, a titanium oxynitride (TiON) film is formed on the substrate. The TiON film has a higher work function than the TiN film. For this reason, for example, while Ru (ruthenium) has a much higher work function than Ti, the film having a relatively high work function can be formed, with no use of an expensive material. 
     In the next step S 212 , the remaining gas is removed. That is, the valve  518  of the third gas supply pipe  510  is closed to stop supply of the O 2 . In addition, in a state in which the APC valve  243  of the exhaust pipe  231  is kept open, the processing chamber  201  is exhausted by the vacuum pump  246  to 20 Pa or less to eliminate the remaining O 2  from the processing chamber  201 . In addition, here, the gas remaining in the processing chamber  201  may not be completely eliminated, and the inside of the processing chamber  201  may not be completely purged. When an amount of the gas remaining in the processing chamber  201  is very small, there is no bad influence on the next gas supply step. Here, there is no need to increase a flow rate of N 2  gas supplied into the processing chamber  201  to a large flow rate. For example, as substantially the same amount of gas as a volume of the reaction tube  203  (the processing chamber  201 ) is supplied, the purge can be performed to an extent in which there is no bad influence on the next gas supply step. As described above, as the inside of the processing chamber  201  is not completely purged, the purge time can be reduced and throughput can be improved. In addition, consumption of the N 2  gas can be suppressed to a minimum level. 
     In the next step S 220 , it is determined whether a series of steps from S 202  to S 212  have been performed a predetermined number of times. When it is determined that the steps have been performed the predetermined number of times, the next step S 402  is performed, and when it is determined that the steps have not been performed the predetermined number of times, the process returns to step S 202 . 
     In the film-forming process including steps S 202  to S 212  as described above, the TiON film is formed. 
     In the next step S 402 , the purge is performed (purging). In the next step S 404 , returning to an atmospheric pressure is performed. That is, the atmosphere in the processing chamber  201  is replaced with the inert gas, and the pressure in the processing chamber  201  returns to the normal pressure (returning to the atmospheric pressure). 
     In the next step S 406 , boat unloading is performed. That is, the seal cap  219  is lowered by the boat elevator  115  to open the lower end of the reaction tube  203 , and simultaneously, the processed wafer  200  supported on the boat  217  is unloaded from the lower end of the reaction tube  203  to the outside of the reaction tube  203  (boat unloading). 
     In the next step S 408 , wafer discharging is performed. That is, the processed wafer  200  is discharged from the boat  217  (wafer discharging). As described above, one film-forming processing (batch processing) is completed. In addition, after the completion of the film-forming processing, a cleaning gas may be appropriately supplied according to an amount of byproducts stuck to the inside of the reaction tube  203  to perform gas cleaning. 
       FIG. 7  is a timing chart showing a film-forming sequence of the TiON film in the film-forming process. The sequence corresponds to steps S 202  to S 220 . As shown in  FIG. 7 , in the film-forming process, a process of supplying TiCl 4  gas, which is a metal-containing gas, a process of supplying NH 3  gas, which is a nitrogen-containing gas, and a process of supplying O 2  gas, which is an oxygen-containing gas, are set as one cycle, and the cycle is repeated a predetermined number of times. Here, the number of cycles is determined according to a film thickness of a film to be formed, for example, when a film-forming rate is 1 Å/cycle, a film of 20 Å can be formed by performing 20 cycles. 
       FIG. 8  is a timing chart showing a first variant of the film-forming sequence in the film-forming process in accordance with the embodiment. In the film-forming sequence of the TiON film in the film-forming process in accordance with the embodiment, the process of supplying TiCl 4  gas, which is a metal-containing gas, the process of supplying NH 3  gas, which is a nitrogen-containing gas, and the process of supplying O 2  gas, which is an oxygen-containing gas, were set as one cycle, and the cycle was repeated a predetermined number of times. On the other hand, in the first variant, a process of supplying TiCl 4  gas, which is a metal-containing gas, and a process of supplying NH 3  gas, which is a nitrogen-containing gas, are set as one cycle, the cycle is repeated a plurality of times (3 times in the first variant), and then a process of supplying O 2  gas, which is an oxygen-containing gas, is performed. 
     In addition, in the first variant, the process of supplying TiCl 4  gas, which is a metal-containing gas, and the process of supplying NH 3  gas, which is a nitrogen-containing gas, are set as one cycle, the cycle is performed a plurality of times (3 times in the first variant) and then the process of supplying O 2  gas, which is an oxygen-containing gas, is performed, the series of processes are set as one cycle, and the cycle including the series of processes is repeated a plurality of times. 
     The first variant of the film-forming sequence in the film-forming process is realized by controlling the respective members of the substrate processing apparatus  101  using the controller  900 . 
       FIG. 9  is a timing chart showing a second variant of the film-forming sequence in the film-forming process in accordance with the embodiment. In the film-forming sequence of the TiON film in the film-forming process in accordance with the embodiment, the process of supplying TiCl 4  gas, which is a metal-containing gas, the process of supplying NH 3  gas, which is a nitrogen-containing gas, and the process of supplying O 2  gas, which is an oxygen-containing gas, were set as one cycle, and the cycle was repeated a predetermined number of times. On the other hand, in the second variant, a process of supplying TiCl 4  gas, which is a metal-containing gas, and a process of supplying NH 3  gas, which is a nitrogen-containing gas, are set as one cycle, the cycle is repeated a plurality of times (20 times in the first variant), and then a process of supplying O 2  gas, which is an oxygen-containing gas, is performed, completing a series of film-forming processes. 
     The second variant of the film-forming sequence in the film-forming process is realized by controlling the respective members of the substrate processing apparatus  101  using the controller  900 . 
       FIG. 10  is a timing chart showing a third variant of the film-forming sequence in the film-forming process in accordance with the embodiment. In the film-forming sequence of the TiON film in the film-forming process in accordance with the embodiment, the process of supplying TiCl 4  gas, which is a metal-containing gas, the process of supplying NH 3  gas, which is a nitrogen-containing gas, and the process of supplying O 2  gas, which is an oxygen-containing gas, were set as one cycle, and the cycle was repeated a predetermined number of times. On the other hand, in the third variant, a process of supplying TiCl 4  gas, which is a metal-containing gas, and a process of supplying NH 3  gas, which is a nitrogen-containing gas, are performed while a process of supplying O 2  gas, which is an oxygen-containing gas, is performed. 
     In addition, in the third variant, the process of supplying TiCl 4  gas, which is a metal-containing gas, and the process of supplying NH 3  gas, which is a nitrogen-containing gas, are set as one cycle, and the cycle is performed a plurality of times (20 times in the third variant). 
     The third variant of the film-forming sequence in the film-forming process is realized by controlling the respective members of the substrate processing apparatus  101  using the controller  900 . 
       FIG. 11  is a timing chart showing a fourth variant of the film-forming sequence in the film-forming process in accordance with the embodiment. As shown in  FIG. 11 , in the fourth variant, a process of supplying TiCl 4  gas, which is a metal-containing gas, and a process of supplying NH 3  gas, which is a nitrogen-containing gas, are performed while a process of supplying O 2  gas, which is an oxygen-containing gas, is performed. In addition, in the fourth variant, the process of supplying TiCl 4  gas, which is a metal-containing gas, and the process of supplying NH 3  gas, which is a nitrogen-containing gas, are simultaneously performed. Here, supply periods of the TiCl 4  gas. NH 3  gas and O 2  gas supplied into the processing chamber  201  may overlap each other, and timings of supply initiation and supply stoppage may not be equal to each other. 
     For example, in  FIG. 11 , the process of supplying TiCl 4  gas, which is a metal-containing gas, the process of supplying NH 3  gas, which is a nitrogen-containing gas, and the process of supplying O 2  gas, which is an oxygen-containing gas, are performed at substantially the same time. After the process of supplying TiCl 4  gas, which is a metal-containing gas, is terminated, the process of supplying NH 3  gas, which is a nitrogen-containing gas, is terminated, and after the process of supplying NH 3  gas, which is a nitrogen-containing gas, is terminated, the process of supplying O 2  gas, which is an oxygen-containing gas, is terminated. 
       FIG. 12  is a timing chart showing a fifth variant of the film-forming sequence of the TiON film in the film-forming process. In the fifth variant, a process of supplying TiCl 4  gas, which is a metal-containing gas, a process of supplying NH 3  gas, which is a nitrogen-containing gas, and a process of supplying O 2  gas, which is an oxygen-containing gas, are set as one cycle, and the cycle is repeated a plurality of times. 
     In the fifth variant, the process of supplying TiCl 4  gas, which is a metal-containing gas, and the process of supplying NH 3  gas, which is a nitrogen-containing gas, are initiated at substantially the same time, and after the process of supplying TiCl 4  gas, which is a metal-containing gas, is terminated, the process of supplying NH 3  gas, which is a nitrogen-containing gas, is terminated. 
       FIG. 13  shows a first variant of the first gas supply system  300 . The first gas supply system  300  in accordance with the first embodiment as described above includes the first gas supply pipe  310 , the bubbler  700 , the valve  318  disposed at the gas supply pipe  310  at an upstream side of the bubbler  700 , the carrier gas supply pipe  360 , the mass flow controller  362  mounted on the carrier gas supply pipe  360 , and the valve  364  mounted on the carrier gas supply pipe  360 . On the other hand, the first gas supply system  300  in accordance with the first variant includes a mass flow controller  370  and a valve  372 , in addition to the respective elements included in the first gas supply system  300  of the first embodiment. 
     The mass flow controller  370  is mounted on the first gas supply pipe  310  at a downstream side of the valve  318 . In addition, the valve  372  is mounted on the first gas supply pipe  310  at a downstream side of the mass flow controller  370 . The mass flow controller  370  and the valve  372  are controlled by the controller  900 . Further, when a flow rate of the supplied TiCl 4  gas is controlled, the mass flow controller  370  is controlled prior to the mass flow controller  362 . 
     The first variant of the first gas supply system  300  has the same configuration as the first gas supply system  300  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
       FIG. 14  shows a second variant of the first gas supply system  300 . The first gas supply system  300  in accordance with the second variant includes a valve  372 , in addition to the respective members included in the first gas supply system  300  in accordance with the first embodiment, and includes a mass flow controller  370  instead of the mass flow controller  362 . 
     The mass flow controller  370  is mounted on the first gas supply pipe  310  at a downstream side of the valve  318 . In addition, the valve  372  is mounted on the first gas supply pipe  310  at a downstream side of the mass flow controller  370 . The mass flow controller  370  and the valve  372  are controlled by the controller  900 . Further, when a flow rate of the supplied TiCl 4  gas is controlled, the mass flow controller  370  is controlled. 
     The second variant of the first gas supply system  300  has the same configuration as the first gas supply system  300  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
       FIG. 15  shows a third variant of the first gas supply system  300 . The first gas supply system  300  in accordance with the third variant includes a mass flow controller  370 , a valve  372 , and a vent pipe  376 , in addition to the respective members included in the first gas supply system  300  in accordance with the first embodiment. 
     The mass flow controller  370  is mounted on the first gas supply pipe  310  at a downstream side of the valve  318 . In addition, the valve  372  is mounted on the first gas supply pipe  310  at a downstream side of the mass flow controller  370 . The mass flow controller  370  and the valve  372  are controlled by the controller  900 . When a flow rate of the supplied TiCl 4  gas is controlled, the mass flow controller  370  is controlled prior to the mass flow controller  362 . 
     The vent pipe  376  is branched from the first gas supply pipe  310  at a downstream side of the valve  318  and an upstream side of the mass flow controller  370 , and connected to the first gas supply pipe  310 . 
     The third variant of the first gas supply system  300  has the same configuration as the first gas supply system  300  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
       FIG. 16  shows a third variant of the first gas supply system  300 . The first gas supply system  300  in accordance with the fourth variant includes a mass flow controller  370 , a valve  372 , and a heating tank  380 , in addition to the respective members included in the first gas supply system  300  in accordance with the first embodiment. 
     The mass flow controller  370  is mounted on the first gas supply pipe  310  at a downstream side of the valve  318 . In addition, the valve  372  is mounted on the first gas supply pipe  310  at a downstream side of the mass flow controller  370 . The mass flow controller  370  and the valve  372  are controlled by the controller  900 . Further, when a flow rate of the supplied TiCl 4  gas is controlled, the mass flow controller  370  is controlled prior to the mass flow controller  362 . 
     The heating tank  380 , which is a constant-temperature tank in which a temperature is constantly maintained, is used as a heating apparatus for heating the bubbler  700 , and is configured to surround the bubbler  700 , and heat the accommodating vessel  702  to heat the liquid TiCl 4  accommodated in the accommodating vessel  702  to easily evaporate the liquid TiCl 4 . 
     The fourth variant of the first gas supply system  300  has the same configuration as the first gas supply system  300  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
       FIG. 17  shows a fifth variant of the first gas supply system  300 . The first gas supply system  300  in accordance with the first embodiment includes the accommodating vessel  702  configured to accommodate a liquid source material, and the bubbler  700  used as an example of an evaporator configured to evaporate the liquid source material through bubbling to generate a source gas. On the other hand, the fifth variant includes an evaporator  720  configured to evaporate a liquid source material or various metal source materials dissolved in a solvent. The evaporator  720  is used as an example of an evaporator configured to generate a source gas. 
     The accommodating vessel  726  is connected to the evaporator  720  via a valve  722  and a liquid mass flow controller  724 . The accommodating vessel  726  accommodates a liquid source material or various metal source materials dissolved in a solvent, and the liquid source material or various metal source materials dissolved in the solvent are supplied into the evaporator  720  from the accommodating vessel  726  via the valve  722  and the liquid mass flow controller. 
     A carrier gas supply pipe  730  is connected to the accommodating vessel  726 , and a mass flow controller  732  and a valve  734  are mounted on the carrier gas supply pipe  730 . 
     In the fifth variant, the evaporator  720 , the valve  722 , the liquid mass flow controller  724 , the mass flow controller  732  and the valve  734  are controlled by the controller  900 . 
     The fifth variant of the first gas supply system  300  has the same configuration as the first gas supply system  300  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
       FIG. 18  shows a variant of the third gas supply system  500 . In the first gas supply system  300  in accordance with the first embodiment, an O 2  (oxygen) gas supply source (not shown) is connected to an upstream side end of the third gas supply pipe  510 , and O 2  gas supplied from the O 2  gas supply source is used as an oxygen-containing gas supplied into the processing chamber  201 . In the variant, a bubbler  570  is mounted on an upstream side end of the third gas supply pipe  510 , and vapor supplied from the bubbler  570  is used as an oxygen-containing gas. 
     The bubbler  570  includes an accommodating vessel  572  configured to accommodate H 2 O (water), and evaporates water through bubbling to generate vapor. The accommodating vessel  572  is a sealed vessel, and H 2 O is accommodated in the accommodating vessel  572 . A carrier gas supply pipe  576  is connected to the accommodating vessel  572 , and a mass flow controller  578  and a valve  580  are mounted on the carrier gas supply pipe  576 . 
     In the variant, a mass flow controller  592  is mounted on the third gas supply pipe  510  at an upstream side of the valve  518 , and a valve  594  is mounted on the third gas supply pipe  510  at an upstream side of the mass flow controller  592 . The mass flow controller  578 , the valve  580 , the mass flow controller  592  and the valve  594  are controlled by the controller  900 . 
     The variant of the third gas supply system  500  has the same configuration as the third gas supply system  500  in the first embodiment, except for the above description, and description of the same configuration will not be repeated. 
     The respective variants as described above may be combined and used. That is, one of the first to third variants of the sequence of the first film-forming process, the variant of the sequence of the second film-forming process, one of the first to fifth variants of the first gas supply system, and the variant of the third gas supply system may be combined to be used. 
       FIG. 19  schematically shows the first gas supply system and the second gas supply system included in the substrate processing apparatus  101  in accordance with the second embodiment of the present invention. 
     The substrate processing apparatus  101  in accordance with the first embodiment includes the first gas supply system  300 , the second gas supply system  400  and the third gas supply system  500 . The first gas supply system  300  is used as an example of the first gas supply system configured to supply a metal-containing gas into the processing chamber  201 , the second gas supply system  300  is used as an example of the second gas supply system configured to supply a nitrogen-containing gas into the processing chamber  201 , and the third gas supply system  500  is used as an example of the third gas supply system configured to supply a nitrogen-containing gas or a halogen-containing gas into the processing chamber  201 . On the other hand, in the second embodiment, the first gas supply system  300  is used as an example of the first gas supply system configured to supply a metal-containing gas into the processing chamber  201 , and simultaneously, also used as the third gas supply system configured to supply a nitrogen-containing gas or a halogen-containing gas into the processing chamber  201 . In addition, in the second embodiment, the second gas supply system  400  is used as an example of the second gas supply system configured to supply a nitrogen-containing gas into the processing chamber  201 , and simultaneously, also used as the third gas supply system configured to supply a nitrogen-containing gas or a halogen-containing gas into the processing chamber  201 . 
     In the second embodiment, the first gas supply system  300  includes an oxygen supply pipe  390 , a mass flow controller  392  and a valve  394 , in addition to the members included in the first gas supply system  300  of the first embodiment. A downstream side end of the oxygen supply pipe  390  is connected to the first gas supply pipe  310  via the carrier gas supply pipe  330 . In addition, an O 2  (oxygen) gas supply source (not shown) is connected to an upstream side end of the oxygen supply pipe  390 . 
     The mass flow controller  392  is used to adjust a flow rate of the supplied O 2  (oxygen) gas, and mounted on the oxygen supply pipe  390 . The valve  394  is used to stop and initiate supply of the O 2  (oxygen) gas, and mounted on the oxygen supply pipe  390  at a downstream side of the mass flow controller  392 . 
     In addition, in the second embodiment, the second gas supply system  400  includes an oxygen supply pipe  490 , a mass flow controller  492  and a valve  494 , in addition to the members included in the second gas supply system  400  of the first embodiment. A downstream side end of the oxygen supply pipe  490  is connected to the fourth gas supply pipe  410  via the carrier gas supply pipe  430 . In addition, an O 2  (oxygen) gas supply source (not shown) is connected to an upstream side end of the oxygen supply pipe  490 . 
     The mass flow controller  492  is used to adjust a flow rate of the supplied O 2  (oxygen) gas, and mounted on the oxygen supply pipe  490 . The valve  494  is used to stop and initiate supply of the O 2  (oxygen) gas, and mounted on the oxygen supply pipe  490  at a downstream side of the mass flow controller  492 . The mass flow controller  392 , the valve  394 , the mass flow controller  492  and the valve  494  are controlled by the controller  900 . 
     In addition, in the substrate processing apparatus  101  in accordance with the second embodiment of the present invention, one of the first to fifth variants of the first gas supply system  300  in the first embodiment may be used as the first gas supply system  300 . 
     The substrate processing apparatus  101  in accordance with the second embodiment is the same as the substrate processing apparatus  101  in accordance with the first embodiment, except the configuration as described above, and description of the same configuration will not be repeated. 
       FIG. 20  schematically shows a first variant of the first gas supply system  300  and the second gas supply system  400  included in the substrate processing apparatus  101  in accordance with the second embodiment of the present invention. In the first variant, in addition to the configurations included in the first gas supply system and the second gas supply system in the second embodiment of the present invention, a large diameter part  331  having an inner diameter larger than the other parts is formed in the carrier gas supply pipe  330 . The large diameter part  331  is formed at the carrier gas supply pipe  330  at a downstream side of a position to which the oxygen supply pipe  390  is connected, and O 2  gas is uniformly diffused to a carrier gas as the carrier gas and O 2  gas pass through the large diameter part  331 . 
     In addition, in the first variant, in addition to the configurations included in the first gas supply system and the second gas supply system in the second embodiment of the present invention, a large diameter part  431  having an inner diameter larger than the other parts is formed in the carrier gas supply pipe  430 . The large diameter part  431  is formed at the carrier gas supply pipe  430  at a downstream side of a position to which the oxygen supply pipe  490  is connected, and O 2  gas is uniformly diffused to a carrier gas as the carrier gas and O 2  gas pass through the large diameter part  431 . The first variant of the first gas supply system  300  and the second gas supply system  400  is the same as the second embodiment, except for the configuration as described above, and description of the same configuration will not be repeated. 
       FIG. 21  schematically shows a second variant of the first gas supply system  300  and the second gas supply system  400  included in the substrate processing apparatus  101  in accordance with the second embodiment of the present invention. In the first gas supply system  300  and the second gas supply system  400  in accordance with the second embodiment of the present invention. O 2  (oxygen) gas supply sources (not shown) are connected to upstream side ends of the oxygen supply pipe  390  and the oxygen supply pipe  490 , respectively, and O 2  gas supplied from the O 2  gas supply sources is used as an oxygen-containing gas supplied into the processing chamber  201 . On the other hand, in the second variant, one bubbler  660  is mounted on the upstream side ends of the oxygen supply pipe  390  and the oxygen supply pipe  490 , and vapor supplied from the bubbler  600  is used as an oxygen-containing gas. 
     The bubbler  600  includes an accommodating vessel  602  configured to accommodate H 2 O (water), and evaporate the water through bubbling to generate vapor. The accommodating vessel  602  is a sealed vessel, and H 2 O is accommodated in the accommodating vessel  602 . A carrier gas supply pipe  620  is connected to the accommodating vessel  602 , and a mass flow controller  622  and a valve  624  are mounted on the carrier gas supply pipe  620 . 
     In addition, in the second variant, the oxygen supply pipe  390  and the oxygen supply pipe  490  are connected to each other at an upstream side, a mass flow controller  606  is mounted on the connected portion, and the connected portion is connected to the bubbler  600 . The mass flow controller  606 , the valve  624  and the mass flow controller  622  are controlled by the controller  900 . The second variant of the first gas supply system  300  and the second gas supply system  400  is the same as the second embodiment, except for the configuration as described above, and description of the same configuration will not be repeated. 
     In the first embodiment, the second embodiment and the variants thereof, while the vapor is exemplarily used as O 2  gas, which is an oxygen-containing gas, instead of O 2  gas and vapor, or in combination of O 2  gas and vapor, for example, NO, N 2 O, O 3 , etc. may be used as the oxygen-containing gas. 
     In addition, in the first embodiment, the second embodiment and the variants thereof, while the oxygen-containing gas is supplied into the processing chamber  201 , in addition to supply of the oxygen-containing gas into the processing chamber  201 , a halogen-containing gas may be supplied into the processing chamber  201 . For example, a gas containing fluorine or chlorine may be used as the halogen-containing gas supplied into the processing chamber  201 . 
     As the halogen-containing gas instead of the oxygen-containing gas is supplied into the processing chamber  201 , an increase in electric resistance of a conductive thin film can be suppressed, electro-negativity of the conductive thin film can be increased, and as a result, a work function of the conductive thin film can be increased. 
     In addition, as an addition method, a supply time and a concentration of the oxygen-containing gas or the halogen-containing gas are varied, a ratio of oxygen included in the formed film can be controlled to a desired value. 
     EXEMPLARY EMBODIMENTS OF THE INVENTION 
     Hereinafter, exemplary embodiments of the present invention will be additionally stated. 
     [Supplementary Note 1] 
     A semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method including: 
     (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated: 
     (b) supplying a nitrogen-containing gas into the processing chamber; and 
     (c) supplying the metal-containing gas and the nitrogen-containing gas into the processing chamber, and supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber. 
     [Supplementary Note 2] 
     The semiconductor device manufacturing method according to Supplementary Note 1, wherein steps (a), (b) and (c) are set as one cycle, and the cycle is repeated a plurality of times. 
     [Supplementary Note 3] 
     The semiconductor device manufacturing method according to Supplementary Note 2, further including (d) removing the gas remaining in the processing chamber from the processing chamber, 
     wherein step (d) is performed at least one of between step (a) and step (b), between step (b) and step (c), and after step (c), and before step (a). 
     [Supplementary Note 4] 
     The semiconductor device manufacturing method according to Supplementary Note 1, wherein step (a) and step (b) are set as one cycle, the cycle is performed a plurality of times, and then step (c) is performed. 
     [Supplementary Note 5] 
     The semiconductor device manufacturing method according to Supplementary Note 4, further including (d) removing the gas remaining in the processing chamber from the processing chamber, 
     wherein step (d) is performed at least one of between step (a) and step (b), between step (b) and step (c), and after step (c), and before step (a). 
     [Supplementary Note 6] 
     A semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method including: 
     (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated; 
     (b) supplying a nitrogen-containing gas into the processing chamber; and 
     (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber, 
     wherein at least one of step (a) and step (b) is performed while step (c) is performed. 
     [Supplementary Note 7] 
     The semiconductor device manufacturing method according to Supplementary Note 6, wherein while step (c) is performed, step (a) and step (b) are alternately performed a plurality of times. 
     [Supplementary Note 8] 
     The semiconductor device manufacturing method according to Supplementary Note 6, wherein step (a) and step (b) are simultaneously performed. 
     [Supplementary Note 9] 
     The semiconductor device manufacturing method according to one of Supplementary Notes 1 to 8, wherein an oxygen content or a halogen content of the metal-containing film formed on the substrate is controlled in at least one of the steps (a), (b) and (c) to be at a predetermined level. 
     [Supplementary Note 10] 
     The semiconductor device manufacturing method according to Supplementary Note 9, wherein, in step (c), a supply amount of the oxygen-containing gas or the halogen-containing gas is controlled such that the oxygen content or the halogen content of the metal-containing film formed on the substrate is at the predetermined level. 
     [Supplementary Note 11] 
     A substrate processing apparatus including: 
     a processing chamber configured to accommodate a substrate; 
     a first gas supply system configured to supply a metal-containing gas into the processing chamber; 
     a second gas supply system configured to supply a nitrogen-containing gas into the processing chamber; 
     a third gas supply system configured to supply one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber; and 
     a control unit configured to control the first gas supply system, the second gas supply system and the third gas supply system, 
     wherein the control unit controls the first gas supply system, the second gas supply system and the third gas supply system such that an oxygen content or a halogen content of a metal-containing film formed on the substrate is at a predetermined level. 
     [Supplementary Note 12] 
     The substrate processing apparatus according to Supplementary Note 11, wherein the control unit controls the first gas supply system, the second gas supply system and the third gas supply system such that supply of the metal-containing gas into the processing chamber, supply of the nitrogen-containing gas into the processing chamber, and supply of one of the oxygen-containing gas, the halogen-containing gas and a combination thereof are set as one cycle and the cycle is repeated a plurality of times, and controls a supply amount of the oxygen-containing gas or the halogen-containing gas into the processing chamber by the third gas supply system such that the oxygen content or the halogen content of the metal-containing film formed on the substrate is at the predetermined level. 
     [Supplementary Note 13] 
     The substrate processing apparatus according to Supplementary Note 12, wherein the third gas supply system further includes: 
     a flow rate control mechanism configured to control a flow rate of the oxygen-containing gas or the halogen-containing gas; and 
     an opening/closing valve installed between the flow rate control mechanism and the processing chamber. 
     [Supplementary Note 14] 
     A method of forming a thin film, including: 
     a metal material supply process of supplying a metal material into a processing chamber, in which a substrate is accommodated, to form the thin film on the substrate; 
     a first supply process of supplying a first source material into the processing chamber to process at least one of reduction and nitridation of the metal material; and 
     a second supply process of supplying a second source material into the processing chamber to process at least one of oxidation and halogenation of the metal material, 
     wherein, in the second supply process, a flow rate of the second source material is controlled such that an introduction amount of oxygen or a halogen introduced into the thin film formed on the substrate becomes a predetermined value. 
     [Supplementary Note 15] 
     The method of forming a thin film according to Supplementary Note 14, wherein the second supply process includes: 
     a process of enabling supply of the second source material into the processing chamber using a valve; and 
     a process of stopping supply of the second source material into the processing chamber using the valve. 
     [Supplementary Note 16] 
     The method of forming a thin film according to Supplementary Note 14 or 15, wherein, in the second supply process, a flow rate of the second source material is independently controlled from a flow rate of another material supplied into the second supply system. 
     [Supplementary Note 17] 
     The method of forming a thin film according to one of Supplementary Notes 14 to 16, wherein, in the first supply process, the first source material is mixed with an inert gas and supplied, and in the second supply process, the second source material is mixed with the inert gas and supplied. 
     [Supplementary Note 18] 
     The method of forming a thin film according to Supplementary Note 17, further including: 
     a process of uniformly mixing the first source material and the inert gas; and 
     a process of uniformly mixing the second source material and the inert gas. 
     [Supplementary Note 19] 
     The method of forming a thin film according to one of Supplementary Notes 14 to 18, wherein the second supply process further includes at least one of a bubble generating process of generating bubbles in water accommodated in a water accommodating part; and an evaporating process of evaporating the water accommodated in the water accommodating part. 
     [Supplementary Note 20] 
     The method of forming a thin film according to one of Supplementary Notes 14 to 19, wherein the metal material supply process includes at least one of a process of mixing the metal material formed of a liquid material accommodated in a metal material accommodating part with a carrier gas; a process of heating the metal material formed of a liquid material accommodated in the metal material accommodating part; and a process of evaporating the metal material formed of a liquid material accommodated in the metal material accommodating part. 
     [Supplementary Note 21] 
     A thin film forming apparatus including: 
     a processing chamber configured to accommodate a substrate; 
     a metal material supply system configured to supply a metal material into the processing chamber to form a thin film on the substrate; 
     a first supply system configured to supply a first source material into the processing chamber to process at least one of reduction and nitridation of the metal material; and 
     a second supply system configured to supply a second source material to process at least one of oxidation and halogenation of the metal material, 
     wherein the second supply system includes a flow rate control mechanism configured to control a flow rate of the second source material, and 
     the flow rate control mechanism controls a flow rate of the second source material such that an introduction amount of oxygen or a halogen introduced into the thin film formed on the substrate becomes a predetermined value. 
     [Supplementary Note 22] 
     The thin film forming apparatus according to Supplementary Note 21, wherein the second supply system further includes a valve configured to enable supply of the second source material into the processing chamber and stop supply of the second source material into the processing chamber. 
     [Supplementary Note 23] 
     The thin film forming apparatus according to Supplementary Note 21 or 22, wherein the flow rate control mechanism independently controls a flow rate of the second source material from a flow rate of another material supplied into the second supply system. 
     [Supplementary Note 24] 
     A thin film forming apparatus including: 
     a processing chamber configured to accommodate a substrate; 
     a metal material supply system configured to supply a metal material into the processing chamber to form a thin film on the substrate; and 
     a first supply system configured to supply a first source material into the processing chamber to process at least one of reduction and nitridation of the metal material, 
     wherein the metal material supply system includes a first inert gas supply pipe configured to supply an inert gas into the metal gas supply system, 
     the first supply system includes a second inert gas supply pipe configured to supply the inert gas into the first supply system, 
     further including a second supply system configured to supply a second source material to process at least one of oxidation and halogenation of the metal material into one of the first inert gas supply pipe and the second inert gas supply pipe, 
     wherein the second supply system includes a flow rate control mechanism configured to control a flow rate of the second source material, and 
     the flow rate control mechanism controls a flow rate of the second source material such that an introduction amount of oxygen or a halogen introduced into the thin film formed on the substrate becomes a predetermined value. 
     [Supplementary Note 25] 
     The thin film forming apparatus according to Supplementary Note 24, wherein the first inert gas supply pipe includes a first large diameter part having a larger inner diameter than that of other parts, and 
     the second inert gas supply pipe includes a second large diameter part having a larger inner diameter than that of the other parts. 
     [Supplementary Note 26] 
     The thin film forming apparatus according to one of Supplementary Notes 21 to 25, wherein the second supply system further includes: 
     a water accommodating part configured to accommodate water; and 
     at least one of a bubble generating apparatus configured to generate bubbles from the water accommodated in the water accommodating part and an evaporating apparatus configured to evaporate the water accommodated in the water accommodating part. 
     [Supplementary Note 27] 
     The thin film forming apparatus according to one of Supplementary Notes 21 to 26, wherein the metal material supply system includes: 
     a metal material accommodating part configured to accommodate the metal material formed of a liquid material; and 
     at least one of a mixing apparatus configured to mix the metal material accommodated in the metal material accommodating part with a carrier gas, a heating apparatus configured to heat the metal material accommodated in the metal material accommodating part, and an evaporating apparatus configured to evaporate the metal material accommodated in the metal material accommodating part. 
     [Supplementary Note 28] 
     A semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method including repeating a cycle a plurality of times, wherein the cycle includes: 
     (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated; 
     (b) supplying a nitrogen-containing gas into the processing chamber; and 
     (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber. 
     [Supplementary Note 29] 
     A semiconductor device manufacturing method, including: 
     (a) forming a metal nitride film on a substrate by performing a cycle including supplying a metal-containing gas into a processing chamber in which the substrate is accommodated and supplying a nitrogen-containing gas into the processing chamber a plurality of times; and 
     (b) after step (a), performing a process of supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber to add oxygen into the metal nitride film. 
     [Supplementary Note 30] 
     A semiconductor device manufacturing method of forming a metal-containing film on a substrate, the method comprising repeating a cycle a plurality of times, 
     wherein the cycle includes: 
     (a) supplying a metal-containing gas into a processing chamber in which the substrate is accommodated; 
     (b) supplying a nitrogen-containing gas into the processing chamber; and 
     (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber, 
     wherein at least one of step (a) and step (b) is performed while step (c) is performed. 
     [Supplementary Note 31] 
     A substrate processing apparatus including: 
     a processing chamber configured to accommodate a substrate; 
     a first gas supply system configured to supply a metal-containing gas into the processing chamber; 
     a second gas supply system configured to supply a nitrogen-containing gas into the processing chamber; 
     a third gas supply system configured to supply one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber; and 
     a control unit configured to control the first gas supply system, the second gas supply system and the third gas supply system, 
     wherein the control unit controls the first gas supply system, the second gas supply system and the third gas supply system such that an oxygen content or a halogen content of a metal-containing film formed on the substrate is at a predetermined level. 
     [Supplementary Note 32] 
     A substrate processing method of forming a metal-containing film on a substrate, the method including repeating a cycle a plurality of times, 
     wherein the cycle includes: 
     (a) supplying a metal-containing gas into a processing chamber where the substrate is accommodated; 
     (b) supplying a nitrogen-containing gas into the processing chamber; and 
     (c) supplying one of an oxygen-containing gas, a halogen-containing gas and a combination thereof into the processing chamber. 
     [Supplementary Note 33] 
     A program causing a computer to function as a control unit configured to control a first gas supply system to supply a metal-containing gas of a predetermined amount into a processing chamber in which a substrate is accommodated, 
     control a second gas supply system to supply a nitrogen-containing gas of a predetermined amount into the processing chamber, 
     control a third gas supply system to supply one of an oxygen-containing gas, a halogen-containing gas and a combination thereof of a predetermined amount into the processing chamber; and 
     control an exhaust system configured to exhaust the processing chamber such that the processing chamber is exhausted in a predetermined exhaust amount. 
     [Supplementary Note 34] 
     A computer-readable recording medium in which the program according to Supplementary Note 33 is recorded.