JP2020074367A - Semiconductor device manufacturing method, substrate processing apparatus, and program - Google Patents

Abstract

A method for manufacturing a semiconductor device, a substrate processing apparatus, and a program for improving the characteristics of a barrier film formed on a substrate are provided. Kind Code: A1 In a processing furnace, a semiconductor device manufacturing method includes applying a first raw material gas containing a metal element and a second raw material gas containing an element different from the metal element to a substrate. a first step of supplying from gas supply pipes 232a and 232b so that at least part of the supply period of 2 steps are performed non-simultaneously a predetermined number of times to form a film containing a metal element and another element and further containing at least one of nitrogen and carbon on the substrate. [Selection drawing] Fig. 1

Description

  The present invention relates to a semiconductor device manufacturing method, a substrate processing apparatus, and a program.

As one of the steps of manufacturing a semiconductor device, a film forming process for forming a film (W film) containing, for example, tungsten (W) as a conductive metal film may be performed on a substrate. The W film can be formed, for example, by alternately supplying tungsten hexafluoride (WF ₆ ) gas to the substrate and supplying disilane (Si ₂ H ₆ ) gas to the substrate a predetermined number of times (for example, , Patent Document 1).

JP2012-62502A

When a metal film is formed using a gas containing fluorine (F) such as WF ₆ gas, F may remain in the formed metal film. The F remaining in the metal film diffuses toward a silicon oxide film (SiO film) or the like as a base previously formed on the substrate when a thermal diffusion process or the like is performed thereafter, thereby improving the performance of the semiconductor device. It may deteriorate. Therefore, before forming the metal film, there is a case where a titanium nitride film (TiN film) or the like is formed on the base as a diffusion suppressing film (barrier film) for suppressing the diffusion of F.

  An object of the present invention is to provide a technique for improving the characteristics of a barrier film formed on a substrate.

According to one aspect of the invention,
A first step of supplying a first source gas containing a metal element and a second source gas containing another element different from the metal element to the substrate so that at least a part of their respective supply periods overlap with each other. When,
A second step of supplying a reactive gas containing at least one of nitrogen and carbon to the substrate;
There is provided a technique including a step of forming a film containing the metal element and the other element and further containing at least one of nitrogen and carbon on the substrate by performing a cycle of performing the above-mentioned non-simultaneously a predetermined number of times. ..

  According to the present invention, the characteristics of the barrier film formed on the substrate can be improved.

FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in an embodiment of the present invention, showing a processing furnace portion in a vertical sectional view. FIG. 2 is a schematic configuration diagram of a vertical processing furnace of the substrate processing apparatus preferably used in one embodiment of the present invention, showing a processing furnace portion in a sectional view taken along the line AA of FIG. 1. It is a schematic block diagram of the controller of the substrate processing apparatus suitably used by one Embodiment of this invention, and is a figure which shows the control system of a controller with a block diagram. It is a figure which shows the timing of gas supply in one Embodiment of this invention. (A)-(c) is a figure which shows the modification of the timing of gas supply of one Embodiment of this invention, respectively. (A)-(c) is a figure which shows the modification of the timing of gas supply of one Embodiment of this invention, respectively. (A)-(c) is a figure which shows the modification of the timing of gas supply of one Embodiment of this invention, respectively. (A) And (b) is a figure which shows the modification of the timing of gas supply in one Embodiment of this invention, respectively. It is a schematic structure figure of a processing furnace of a substrate processing device used suitably by other embodiments of the present invention, and is a figure showing a processing furnace part by a longitudinal section. It is a schematic structure figure of a processing furnace of a substrate processing device used suitably by other embodiments of the present invention, and is a figure showing a processing furnace part by a longitudinal section. (A) And (b) is a figure which shows the timing of gas supply of a comparative example, respectively. (A) And (b) is a figure which shows the composition etc. of the film | membrane formed in the Example with a comparative example. It is a figure which shows the resistivity of the film | membrane formed in the Example with a comparative example.

<One Embodiment of the Present Invention>
An embodiment of the present invention will be described below with reference to FIGS. 1 to 3.

(1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjusting unit). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and has a cylindrical shape with an upper end closed and a lower end opened. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS) and has a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a seal member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is vertically installed like the heater 207. A processing container (reaction container) is mainly configured by the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to be able to accommodate a plurality of wafers 200 as substrates.

  Nozzles 249a to 249c are provided in the processing chamber 201 so as to penetrate the side wall of the manifold 209. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.

  The gas supply pipes 232a to 232c are provided with mass flow controllers (MFCs) 241a to 241c that are flow rate controllers (flow rate control units) and valves 243a to 243c that are opening / closing valves in order from the upstream side. Gas supply pipes 232d to 232f for supplying an inert gas are connected to the gas supply pipes 232a to 232c at downstream sides of the valves 243a to 243c, respectively. The gas supply pipes 232d to 232f are provided with MFCs 241d to 241f and valves 243d to 243f in this order from the upstream side.

  As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the upper part of the inner wall of the reaction tube 203 and the upper part of the wafer 200. It is provided so as to rise upward in the loading direction. That is, the nozzles 249a to 249c are provided along the wafer arranging region in a region horizontally surrounding the wafer arranging region on the side of the wafer arranging region where the wafers 200 are arranged. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c is opened so as to face the center of the reaction tube 203, and gas can be supplied toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

  As described above, in the present embodiment, the inner wall of the side wall of the reaction tube 203 and the end portions (peripheral edge portions) of the plurality of wafers 200 arranged in the reaction tube 203 have an annular shape in a plan view. The gas is transported via the nozzles 249a to 249c arranged in the vertically long space, that is, in the cylindrical space. Then, gas is jetted into the reaction tube 203 for the first time in the vicinity of the wafer 200 from the gas supply holes 250a to 250c opened in the nozzles 249a to 249c, respectively. The main gas flow in the reaction tube 203 is parallel to the surface of the wafer 200, that is, horizontal. With such a configuration, gas is uniformly supplied to each wafer 200. The gas flowing on the surface of the wafer 200 flows toward the exhaust port, that is, toward the exhaust pipe 231 described later. However, the direction of this gas flow is appropriately specified depending on the position of the exhaust port, and is not limited to the vertical direction.

From the gas supply pipe 232a, for example, a Ti-containing gas containing titanium (Ti) as a metal element is supplied as the first source gas into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a. Examples of the Ti-containing gas include a substance further containing at least one halogen element selected from the group consisting of chlorine (Cl), F, bromine (Br) and iodine (I), that is, a halide (titanium halide). A gas containing: can be used. As the gas containing titanium halide, for example, tetrachlorotitanium (TiCl ₄ ) gas containing Ti and Cl can be used. TiCl ₄ gas acts as a Ti source. In the present specification, when the term "raw material" is used, it means "a liquid raw material in a liquid state", "a raw material gas in a gaseous state", or both of them. There is a case.

From the gas supply pipe 232b, for example, a Si-containing gas containing silicon (Si) is passed through the MFC 241b, the valve 243b, and the nozzle 249b as the second raw material gas containing another element (dopant) different from the above metal element. And is supplied into the processing chamber 201. As the Si-containing gas, for example, a substance further containing hydrogen (H), that is, a gas containing silicon hydride can be used. As the gas containing silicon hydride, for example, monosilane (SiH ₄ ) gas can be used. SiH ₄ gas acts as a Si source.

As a reaction gas containing at least one of nitrogen (N) and carbon (C), for example, ammonia (NH ₃ ) gas that is an N-containing gas is supplied from the gas supply pipe 232c through the MFC 241c, the valve 243c, and the nozzle 249c. And is supplied into the processing chamber 201. NH ₃ gas acts as a nitriding agent, that is, an N source.

From the gas supply pipes 232d to 232f, for example, nitrogen (N ₂ ) gas is supplied as an inert gas through the MFCs 241d to 241f, the valves 243d to 243f, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c, respectively. It is supplied into 201.

  A first source gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. A second source gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. A reaction gas supply system is mainly configured by the gas supply pipe 232c, the MFC 241c, and the valve 243c. An inert gas supply system mainly includes the gas supply pipes 232d to 232f, the MFCs 241d to 241f, and the valves 243d to 243f.

  Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243f, MFCs 241a to 241f, and the like are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232f and supplies various gases into the gas supply pipes 232a to 232f, that is, the opening and closing operations of the valves 243a to 243f and the MFCs 241a to 241f. The flow rate adjusting operation and the like are configured to be controlled by the controller 121 described later. The integrated type supply system 248 is configured as an integrated type or a divided type integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232f in units of integrated units. It is configured so that maintenance, replacement, expansion, etc. can be performed in units of integrated units.

  The reaction pipe 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. In the exhaust pipe 231, a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator) are provided. A vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operated, and further, in a state where the vacuum pump 246 is operated, The pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

  Below the manifold 209, a seal cap 219 is provided as a furnace port lid that can hermetically close the lower end opening of the manifold 209. The seal cap 219 is made of a metal such as SUS and has a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 for rotating the boat 217 described later is installed. The rotating shaft 255 of the rotating mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 217 by rotating the boat 217. The seal cap 219 is configured to be vertically moved up and down by a boat elevator 115 as an elevating mechanism installed outside the reaction tube 203. The boat elevator 115 is configured so that the boat 217 can be carried in and out of the processing chamber 201 by moving the seal cap 219 up and down. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217, that is, the wafer 200, into and out of the processing chamber 201. Further, below the manifold 209, there is provided a shutter 219s as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209 while the seal cap 219 is being lowered by the boat elevator 115. The shutter 219s is made of a metal such as SUS and has a disk shape. On the upper surface of the shutter 219s, an O-ring 220c is provided as a seal member that contacts the lower end of the manifold 209. The opening / closing operation of the shutter 219s (elevating operation, rotating operation, etc.) is controlled by the shutter opening / closing mechanism 115s.

  The boat 217 as the substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200 in a horizontal posture and in a vertically aligned manner with the centers thereof aligned with each other in a multi-stage manner, that is, It is configured to be arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, a plurality of heat insulating plates 218 made of a heat resistant material such as quartz or SiC are supported in multiple stages.

  A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. The temperature inside the process chamber 201 has a desired temperature distribution by adjusting the degree of energization to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is L-shaped and is provided along the inner wall of the reaction tube 203.

  As shown in FIG. 3, a controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. Has been done. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via the internal bus 121e. An input / output device 122 configured as, for example, a touch panel or the like is connected to the controller 121.

  The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which a procedure and conditions of a film forming process, which will be described later, and the like are readablely stored. The process recipe is a combination that causes the controller 121 to execute each procedure in the film forming process described below and obtains a predetermined result, and functions as a program. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. The process recipe is also simply referred to as a recipe. When the term program is used in this specification, it may include only a recipe alone, only a control program alone, or both of them. The RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily stored.

  The I / O port 121d includes the MFCs 241a to 241f, the valves 243a to 243f, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the temperature sensor 263, the heater 207, the rotating mechanism 267, the boat elevator 115, the shutter opening / closing mechanism 115s, and the like. It is connected to the.

  The CPU 121a is configured to read and execute the control program from the storage device 121c, and also read the recipe from the storage device 121c in response to input of an operation command from the input / output device 122. The CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241f, opens and closes the valves 243a to 243f, opens and closes the APC valve 244, and adjusts the pressure by the APC valve 244 based on the pressure sensor 245 so as to follow the contents of the read recipe. Operation, start and stop of the vacuum pump 246, temperature adjustment operation of the heater 207 based on the temperature sensor 263, rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, raising / lowering operation of the boat 217 by the boat elevator 115, shutter opening / closing mechanism 115s. Is configured to control the opening / closing operation of the shutter 219s.

  The controller 121 installs the above program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory) 123 into a computer. It can be configured by. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, these are collectively referred to simply as a recording medium. When the term “recording medium” is used in this specification, it may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them. Note that the program may be provided to the computer by using communication means such as the Internet or a dedicated line without using the external storage device 123.

(2) Substrate Processing Step An example of a sequence for forming a film on a substrate will be described with reference to FIG. 4 as one step of manufacturing steps of a semiconductor device using the substrate processing apparatus described above. In the following description, the operation of each part of the substrate processing apparatus is controlled by the controller 121.

In the basic sequence shown in FIG.
Step 1 of supplying TiCl ₄ gas and SiH ₄ gas to the wafer 200 as a substrate so that at least some of the respective supply periods overlap with each other,
Step 2 of supplying NH ₃ gas to the wafer 200,
By performing a predetermined number of times (n times (n is an integer of 1 or more)) non-simultaneously, that is, without performing synchronization, a titanium nitride film (TiSiN) is formed on the wafer 200 as a film containing Ti, Si, and N. Film) is formed. The TiSiN film can also be referred to as a Si-doped TiN film.

  In the present specification, the above-described film forming sequence may be indicated as follows for convenience. The same notation is used in the description of the other embodiments.

(TiCl ₄ + SiH ₄ → NH ₃ ) × n ⇒ TiSiN

  When the word "wafer" is used in this specification, it means "a wafer itself" or "a laminated body (aggregate) of a wafer and a predetermined layer or film formed on the surface thereof". In some cases, it means a wafer including a predetermined layer or film formed on the surface. Further, in the present specification, when the term “wafer surface” is used, it means “the surface (exposed surface) of the wafer itself” or “the surface of a predetermined layer or film formed on the wafer”. That is, it may mean "the outermost surface of the wafer as a laminated body".

  Therefore, in the present specification, the phrase “supplying a predetermined gas to the wafer” means “supplying a predetermined gas directly to the surface of the wafer itself” or “on the wafer”. In some cases, it means that a predetermined gas is supplied to the layers and films formed in the above, that is, the outermost surface of the wafer as a laminated body. Further, in the present specification, the description of “forming a predetermined layer (or film) on the wafer” means “forming a predetermined layer (or film) directly on the surface of the wafer itself”. In some cases, it may mean that “a predetermined layer (or film) is formed on the layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminated body”.

  Further, the term “substrate” used in this specification is synonymous with the term “wafer”.

(Wafer charge and boat load)
When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter opening / closing mechanism 115s moves the shutter 219s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

(Pressure / temperature adjustment step)
The inside of the processing chamber 201, that is, the space in which the wafer 200 exists is evacuated by the vacuum pump 246 (decompressed exhaust) so as to have a desired pressure (degree of vacuum). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. The vacuum pump 246 maintains a state of being constantly operated at least until the processing on the wafer 200 is completed. Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to have a desired film forming temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. The heating of the inside of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed. Further, the rotation mechanism 267 starts rotating the boat 217 and the wafer 200. The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continuously performed at least until the processing on the wafer 200 is completed.

(Film forming step)
After that, the following steps 1 and 2 are sequentially executed.

[Step 1]
In this step, the TiCl ₄ gas and the SiH ₄ gas are supplied to the wafer 200 in the processing chamber 201 so that at least some of their supply periods overlap with each other. In the sequence shown in FIG. 4, the supply of these gases is started at the same time, and the supply of these gases is stopped at the same time.

Specifically, the valves 243a and 243b are opened, and TiCl ₄ gas and SiH ₄ gas are caused to flow into the gas supply pipes 232a and 232b, respectively. The flow rates of the TiCl ₄ gas and the SiH ₄ gas are adjusted by the MFCs 241a and 241b, respectively, supplied into the processing chamber 201 through the nozzles 249a and 249b, and exhausted from the exhaust pipe 231. At this time, the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied to the wafer 200. At this time, the valves 243d and 243e are simultaneously opened, and N ₂ gas is caused to flow into the gas supply pipes 232d and 232e, respectively. The flow rate of the N ₂ gas is adjusted by the MFCs 241d and 241e, the N ₂ gas is supplied into the processing chamber 201 together with the TiCl ₄ gas and the SiH ₄ gas, and is exhausted from the exhaust pipe 231. Further, in order to prevent the TiCl ₄ gas and SiH ₄ gas from entering the nozzle 249c, the valve 243f is opened and N ₂ gas is flown into the gas supply pipe 232f. The N ₂ gas is supplied into the processing chamber 201 via the gas supply pipe 232c and the nozzle 249c, and is exhausted from the exhaust pipe 231.

  At this time, the pressure in the processing chamber 201 (film forming pressure) is set to a predetermined pressure within the range of 1 to 3000 Pa, for example. The temperature of the wafer 200 (deposition temperature) is, for example, 300 to 600 ° C., preferably 320 to 550 ° C., and more preferably 350 to 500 ° C.

When the film forming temperature is lower than 300 ° C., the TiCl ₄ gas and the SiH ₄ gas supplied into the processing chamber 201 are insufficiently activated, and the first layer (a layer containing Ti and Si) to be described later on the wafer 200. ) May be difficult to form. This can be eliminated by setting the film forming temperature to 300 ° C. or higher. By setting the film forming temperature to 320 ° C. or higher, these gases supplied into the processing chamber 201 can be further activated and the first layer can be formed on the wafer 200 more efficiently. .. By setting the film forming temperature to 350 ° C. or higher, these effects can be obtained more reliably.

If the film formation temperature exceeds 600 ° C., the TiCl ₄ gas or SiH ₄ gas supplied into the processing chamber 201 may be excessively decomposed, and it may be difficult to form the first layer on the wafer 200. Further, the excessive reaction of these gases in the gas phase may increase the number of particles generated in the processing chamber 201, which may deteriorate the quality of the film forming process. By setting the film forming temperature to 600 ° C. or less, it is possible to properly suppress the decomposition of gas and form the first layer on the wafer 200. Further, it becomes possible to suppress the generation of particles in the processing chamber 201. By setting the film forming temperature to 550 ° C. or lower, it is possible to more appropriately suppress the decomposition of gas and more efficiently form the first layer on the wafer 200. Further, it becomes possible to more reliably suppress the generation of particles in the processing chamber 201. By setting the film forming temperature to 500 ° C. or lower, it becomes possible to more reliably obtain these effects.

Note that these conditions are in the vapor phase when the TiCl ₄ gas and the SiH ₄ gas are supplied to the wafer 200 in the processing chamber 201 so that at least some of the respective supply periods overlap. It can be said that the conditions are such that the decomposition and reaction of these gases can be appropriately suppressed.

The supply flow rate of the TiCl ₄ gas is, for example, a predetermined flow rate within the range of 0.01 to 2 slm, preferably 0.1 to 1.5 slm, and more preferably 0.2 to 1 slm. The supply flow rate of the SiH ₄ gas is, for example, a predetermined flow rate within the range of 0.001 to 2 slm, preferably 0.1 to 1.5 slm, and more preferably 0.1 to 1 slm. When the supply of TiCl ₄ gas and the supply of SiH ₄ gas overlap, the ratio of the flow rate of TiCl ₄ gas to the flow rate of SiH ₄ gas (TiCl ₄ / SiH ₄ flow rate ratio) is, for example, 0.01 to 100, preferably 0. The flow rates of the TiCl ₄ gas and the SiH ₄ gas are adjusted so that the values are in the range of 05 to 50, more preferably 0.1 to 10. The supply times of the TiCl ₄ gas and the SiH ₄ gas are, for example, predetermined times within a range of 0.1 to 20 seconds, respectively.

When the TiCl ₄ gas supply flow rate is less than 0.01 slm, the SiH ₄ gas supply flow rate exceeds 2 slm, or the TiCl ₄ / SiH ₄ flow rate ratio is less than 0.01, the TiSiN film deposition process is performed. It may be difficult to proceed. Further, the amount of Ti contained in the TiSiN film, that is, the ratio of the amount of Ti to the amount of Si (Ti / Si concentration ratio) becomes too small, and the conductivity that this film should have may be insufficient. By setting the supply flow rate of the TiCl ₄ gas to 0.01 slm or more, the supply flow rate of the SiH ₄ gas to 2 slm or less, or the TiCl ₄ / SiH ₄ flow rate ratio of 0.01 or more, the deposition rate of the TiSiN film is set. Can be increased to a practical level, and the composition of this film can be optimized so that sufficient conductivity can be imparted to this film. By forming the TiCl ₄ gas supply flow rate to 0.1 slm or more, the SiH ₄ gas supply flow rate to 1.5 slm or less, or the TiCl ₄ / SiH ₄ flow rate ratio of 0.05 or more, the formation of the TiSiN film is improved. The film rate can be further increased, and the conductivity of this film can be further improved. The TiCl ₄ gas supply flow rate is 0.2 slm or more, the SiH ₄ gas supply flow rate is 1 slm or less, or the TiCl ₄ / SiH ₄ flow rate ratio is 0.1 or more. Can be obtained.

If the supply flow rate of TiCl ₄ gas exceeds 2 slm, the supply flow rate of SiH ₄ gas becomes less than 0.001 slm, or the TiCl ₄ / SiH ₄ flow rate ratio exceeds 100, the amount of Si contained in the TiSiN film That is, the ratio of the amount of Si to the amount of Ti (Si / Ti concentration ratio) becomes too small, and the effect of suppressing diffusion of F (hereinafter also referred to as the F barrier effect) that should be exhibited by this film may be insufficient. The composition of this film is optimized by setting the supply flow rate of TiCl ₄ gas to 2 slm or less, the supply flow rate of SiH ₄ gas to 0.001 slm or more, and the TiCl ₄ / SiH ₄ flow rate ratio of 100 or less. It becomes possible for this film to exhibit a sufficient F barrier effect. The composition of this film is further improved by setting the TiCl ₄ gas supply flow rate to 1.5 slm or less, the SiH ₄ gas supply flow rate to 0.1 slm or more, and the TiCl ₄ / SiH ₄ flow rate ratio of 50 or less. By optimizing it, it becomes possible to further enhance the F barrier effect exhibited by this film. By setting the supply flow rate of the TiCl ₄ gas to 1 slm or less and setting the TiCl ₄ / SiH ₄ flow rate ratio to 10 or less, the above-described effect can be more reliably obtained.

The supply flow rate of the N ₂ gas supplied from each gas supply pipe is a predetermined flow rate in the range of, for example, 0 to 10 slm.

By simultaneously supplying TiCl ₄ gas and SiH ₄ gas to the wafer 200 under the above-described conditions, a layer containing Ti and Si is formed as the first layer (initial layer) on the outermost surface of the wafer 200. To be done. This layer is a layer containing Ti and Si in the state of Ti-Ti bond, Ti-Si bond, Si-Si bond, or the like. The composition of the first layer, that is, the ratio of the amount of Ti to the amount of Si contained in the layer (Ti / Si concentration ratio) can be adjusted to a wide range by adjusting the above TiCl ₄ / SiH ₄ flow rate ratio, for example. It is possible to control.

When the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied to the wafer 200 as in the present embodiment, the layer formed on the wafer 200 is more likely to be supplied than when the TiCl ₄ gas and the SiH ₄ gas are not simultaneously supplied. It is possible to reduce the amount of impurities such as Cl and H contained. This is because when the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied under the above-described conditions, these gases can react with each other on the surface of the wafer 200, and the Ti—Cl bond contained in these gases can be reacted. It is possible to break each of the Si and H bonds. As a result, the incorporation of Cl and H contained in these gases into the first layer, that is, the incorporation of impurities into the first layer can be suppressed. When Cl or H is taken in, the resistivity of the TiSiN film increases (that is, the conductivity decreases), but by suppressing the incorporation of Cl or H into the first layer, a lower resistivity can be obtained. It is possible to obtain a film having the above. Cl and H separated from Ti and Si react with each other to form gaseous by-products such as hydrochloric acid (HCl), chlorine (Cl ₂ ), and hydrogen (H ₂ ), most of which are It is detached from the surface of the wafer 200 without being taken into the first layer, and is removed from the inside of the processing chamber 201.

However, the above-mentioned effect of desorbing impurities is influenced by the TiCl ₄ / SiH ₄ flow rate ratio. For example, when the TiCl ₄ / SiH ₄ flow rate ratio is set to 1/1 and these gases can be reacted at a yield of 100% or more, the reaction of TiCl ₄ + SiH ₄ → Ti + Si + 4HCl theoretically leads to It is possible to make the amount of Cl and the like (the amount of Ti—Cl bond and Si—H bond) taken into the first layer zero. Even if the yield cannot be set to 100%, by setting the TiCl ₄ / SiH ₄ flow rate ratio to a small value (increasing the flow rate ratio of SiH ₄ gas), the Cl taken into the first layer is increased. It is possible to make the amount of zero. However, when the TiCl ₄ / SiH ₄ flow rate ratio is set excessively small by increasing the flow rate of SiH ₄ gas and the amount of Si contained in the TiSiN film is excessively increased, the conductivity of the TiSiN film decreases. There is. Under such circumstances, the magnitude of the TiCl ₄ / SiH ₄ flow rate ratio is limited to a certain extent, and as a result, Ti—Cl bond or Si—H bond is added in the first layer formed in step 1. May be taken in a trace amount. However, even in this case, by performing Step 2 described later, it is possible to break these bonds taken in the first layer and desorb Cl and the like from the first layer.

As in the present embodiment, by simultaneously supplying the TiCl ₄ gas and the SiH ₄ gas into the processing chamber 201, the effect of increasing the removal efficiency of HCl, which is a by-product, from the processing chamber 201 is further obtained. Will be available. This is because by supplying these gases at the same time, that is, by supplying not only TiCl ₄ gas but also SiH ₄ gas into the processing chamber 201 where HCl was generated, the reaction of HCl + SiH ₄ → SiCl ₄ + H ₂ This is because HCl is generated and HCl disappears. Thus, by increasing the efficiency of removing HCl from the inside of the processing chamber 201, it becomes possible to avoid the generation of further by-products such as ammonium chloride (NH ₄ Cl) in step 2 described later. As described later, by-products such as NH ₄ Cl may act as a steric hindrance that locally inhibits the adsorption of TiCl ₄ gas or SiH ₄ gas on the wafer 200. As in the present embodiment, the removal efficiency of HCl from the inside of the processing chamber 201 is increased and the generation of by-products such as NH ₄ Cl is suppressed, thereby inhibiting the local formation of the first layer within the surface of the wafer 200. Can be avoided. This makes it possible to improve the step coverage (coverage characteristic) and the in-plane film thickness uniformity of the TiSiN film formed on the wafer 200, respectively.

After the first layer is formed, the valves 243a and 243b are closed and the supply of TiCl ₄ gas and SiH ₄ gas is stopped. At this time, with the APC valve 244 kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and TiCl ₄ gas or SiH ₄ remaining in the processing chamber 201 after contributing to the formation of the unreacted or first layer. Gas and by-products are removed from the processing chamber 201. At this time, the valves 243d to 243f are kept open to maintain the supply of the N ₂ gas into the processing chamber 201. The N ₂ gas acts as a purge gas.

[Step 2]
After step 1 is completed, NH ₃ gas is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200.

Specifically, the valve 243c is opened with the valves 243a and 243b closed, and NH ₃ gas is caused to flow into the gas supply pipe 232c. Opening / closing control of the valves 243d to 243f is performed in the same manner as those in step 1. The flow rate of the NH ₃ gas is adjusted by the MFC 241c, is supplied into the processing chamber 201 through the nozzle 249c, and is exhausted from the exhaust pipe 231. At this time, NH ₃ gas is supplied to the wafer 200. The flow rate of the N ₂ gas is adjusted by the MFC 241f, the N ₂ gas is supplied into the process chamber 201 together with the NH ₃ gas, and the N ₂ gas is exhausted from the exhaust pipe 231.

At this time, the film forming pressure is set to a predetermined pressure within a range of 1 to 3000 Pa, for example. The supply flow rate of the NH ₃ gas is, for example, a predetermined flow rate within the range of 0.1 to 30 slm, preferably 0.2 to 20 slm, and more preferably 1 to 10 slm. The supply time of the NH ₃ gas is, for example, 0.01 to 30 seconds, preferably 0.1 to 20 seconds, and more preferably 1 to 15 seconds.

If the supply flow rate of the NH ₃ gas is less than 0.1 slm or the supply time of the NH ₃ gas is less than 0.01 seconds, the first layer cannot be modified (nitrided), and the first layer on the wafer 200 cannot be modified. In some cases, it may be difficult to form a TiSiN film. The first layer can be modified by setting the supply flow rate of the NH ₃ gas to 0.1 slm or more and the supply time of the NH ₃ gas to 0.01 seconds or more, and the TiSiN film is formed on the wafer 200. Can be formed. By setting the supply flow rate of the NH ₃ gas to 0.2 slm or more and the supply time of the NH ₃ gas to 0.1 seconds or more, the modification of the first layer is promoted and the TiSiN film formed on the wafer 200. It is possible to further optimize the composition of. Or not less than 1slm the supply flow rate of NH ₃ gas, the supply time of the NH ₃ gas by or with more than one second, so that these effects can be obtained more reliably.

Feed flow rate or exceeds the 30slm of the NH ₃ gas, the supply time of the NH ₃ gas or exceed 30 seconds, becomes a modification of the first layer (nitride) is excessive, properties of the TiSiN film formed on the wafer 200 May deteriorate. Further, if the supply of NH ₃ gas is continued under the condition that the amount of reforming of the first layer exceeds the saturation amount, the gas cost may increase and the productivity may decrease. NH ₃ or the supply flow rate of the gas and below 30 slm, that or the supply time of the NH ₃ gas and 30 seconds or less, the modification of the first layer can be properly restricted, formed on the wafer 200 TiSiN It is possible to avoid deterioration of the characteristics of the film. Further, it becomes possible to avoid an increase in gas cost and a decrease in productivity. NH ₃ or the supply flow rate than 20slm gas, the supply time of the NH ₃ gas by or with 20 seconds or less, is more appropriate the first layer modifying the characteristics of the TiSiN film formed on the wafer 200 It is possible to improve. By setting the supply flow rate of the NH ₃ gas to 10 slm or less and setting the supply time of the NH ₃ gas to 15 seconds or less, these effects can be more reliably obtained.

The supply flow rate of the N ₂ gas supplied from each gas supply pipe is a predetermined flow rate within the range of 0.1 to 50 slm, for example.

  The other processing conditions are the same as the processing conditions in step 1.

By supplying the NH ₃ gas into the processing chamber 201 under the above conditions, the nitriding process is performed on the first layer formed on the wafer 200 in step 1. That is, it is possible to incorporate N into the first layer by reacting Ti and Si contained in the first layer with N contained in the NH ₃ gas to bond them. As a result, the first layer is changed (modified) to the second layer (TiSiN layer) containing Ti, Si and N. The first layer is a layer containing N in a state of Ti-N bond, Ti-Si-N bond, Ti-N-Si bond, or the like.

As described above, even when Ti—Cl bonds or Si—H bonds are incorporated in the first layer formed in step 1, by performing this step, these bonds are broken. It becomes possible. Cl and H separated from Ti and Si react with each other to form by-products such as HCl, Cl ₂ and H ₂ . These by-products generated by performing this step are desorbed from the surface of the wafer 200 without being taken into the second layer, and are exhausted from the inside of the processing chamber 201. As a result, the second layer becomes a layer containing less impurities such as Cl than the first layer, that is, a high-quality layer having an extremely low impurity concentration.

After changing the first layer to the second layer, the valve 243c is closed and the supply of NH ₃ gas is stopped. Then, by the same processing procedure as in step 1, the unreacted NH ₃ gas remaining in the processing chamber 201 or the by-product after contributing to the above reaction is removed from the processing chamber 201.

[Performed a predetermined number of times]
By performing the above-described steps 1 and 2 non-simultaneously (alternately) a predetermined number of times (n times), a TiSiN film having a predetermined composition and a predetermined film thickness can be formed on the wafer 200. The above cycle is preferably repeated multiple times. That is, the thickness of the second layer formed when the above cycle is performed once is made smaller than the desired film thickness, and the TiSiN film formed by stacking the second layers has the desired film thickness. It is preferred to repeat the above cycle multiple times until the thickness is reached.

When the above-mentioned cycle is performed a plurality of times, HCl is produced as a by-product each time steps 1 and 2 are performed. This HCl may react with the NH ₃ gas supplied to the wafer 200 in step 2 to generate a further by-product such as NH ₄ Cl. As described above, NH ₄ Cl may act as a steric hindrance that locally inhibits the adsorption of gas on the wafer 200. For example, when HCl generated as a by-product reacts with Ti—NH _x (x is an integer of 1 or 2) that has been present on the surface of the first layer by performing step 2. , Ti—NH _y Cl (y is an integer of 1 to 3) is present on the surface of the second layer. This Ti—NH _y Cl, that is, ammonium chloride existing on the surface of the second layer, acts as a steric hindrance that locally inhibits the adsorption of TiCl ₄ gas or SiH ₄ gas on the surface of the wafer 200 in the next step 1. It works. However, this steric hindrance can be suppressed by improving the efficiency of removing HCl from the inside of the processing chamber 201 as in the present embodiment. That is, as in the present embodiment, by simultaneously supplying TiCl ₄ gas and SiH ₄ gas into the processing chamber 201 to improve the efficiency of removing HCl from the processing chamber 201, NH ₄ Cl that may cause steric hindrance. It is possible to suppress the generation of

Hereinafter, for reference, various reactions that occur when the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied into the processing chamber 201 will be described. As shown below, NH ₄ Cl as a by-product itself is used as a nitriding agent that promotes a TiN production from TiCl ₄ or a Si ₃ N ₄ production from SiH ₄ , that is, a nitriding reaction. Also works. That is, NH ₄ Cl as a by-product can also be regarded as a second reaction gas that assists the nitriding reaction by the NH ₃ gas. However, these reactions are unlikely to occur when the TiCl ₄ gas and the SiH ₄ gas are supplied into the processing chamber 201 non-simultaneously. In the present embodiment, since the TiCl ₄ gas and the SiH ₄ gas are supplied into the processing chamber 201 at the same time, the nitriding treatment can be performed more efficiently than in the case where these gases are not supplied at the same time, resulting in high production. It can be said that it exerts its sex.

2NH ₄ Cl + TiCl ₄ ⇒ TiN + 8HCl

4NH ₄ Cl + 4SiH ₄ ⇒ Si ₃ N ₄ + SiCl ₄ + 16H ₂
SiH ₄ + HCl ⇒ SiCl ₄ + 4H ₂
4NH ₄ Cl + 3SiCl ₄ ⇒ Si ₃ N ₄ + 16HCl

(Afterpurge / atmospheric pressure recovery step)
After the formation of the TiSiN film is completed, N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 232d to 232f and exhausted from the exhaust pipe 231. The N ₂ gas acts as a purge gas. As a result, the inside of the process chamber 201 is purged, and the gas and reaction by-products remaining in the process chamber 201 are removed from the process chamber 201 (afterpurge). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (replacement with an inert gas), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

(Boat unload and wafer discharge)
The boat elevator 115 lowers the seal cap 219 and opens the lower end of the manifold 209. Then, the processed wafer 200 is carried out of the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). The processed wafer 200 is taken out from the boat 217 (wafer discharge).

(3) Effects According to this embodiment, one or a plurality of effects described below can be obtained.

(A) Since the TiSiN film formed in the present embodiment contains Si in the film, it exhibits a higher F barrier effect than the TiN film containing no Si. Therefore, by forming the TiSiN film of the present embodiment between the SiO film and the W film, this film can be suitably used as a barrier film that suppresses diffusion of F from the W film to the SiO film. It will be possible. Further, the TiSiN film formed in this embodiment exhibits an F barrier effect equal to or higher than that even if the film thickness thereof is smaller than that of the SiN-free TiN film. It can be preferably used in an enhanced NAND flash memory or the like.

(B) In step 1, by simultaneously supplying TiCl ₄ gas and SiH ₄ gas to the wafer 200, these gases can be reacted with each other on the surface of the wafer 200. As a result, the first layer can be formed more efficiently and the TiSiN film deposition rate can be improved than in the case where these gases are not supplied simultaneously.

(C) In step 1, TiCl ₄ gas and SiH ₄ gas are simultaneously supplied to the wafer 200, and these gases react with each other on the surface of the wafer 200. Therefore, when these gases are not simultaneously supplied. Therefore, it is possible to reduce impurities such as Cl contained in the first layer. As a result, the TiSiN film can be a high-quality film having extremely low impurity concentration such as Cl and having high conductivity (having low resistivity).

(D) In step 1, since TiCl ₄ gas and SiH ₄ gas are simultaneously supplied to the wafer 200, HCl as a by-product is supplied to the processing chamber 201 more than when these gases are not supplied simultaneously. It is possible to efficiently remove it from the inside. This makes it possible to improve the film quality of the TiSiN film and avoid etching damage to members inside the processing chamber 201. Further, by efficiently removing HCl from the inside of the processing chamber 201, it is possible to suppress the generation of NH ₄ Cl that can act as a local steric hindrance, and to improve the step coverage of the TiSiN film and the in-plane film thickness uniformity. It is possible to improve the property.

(E) In Step 1, by simultaneously supplying the TiCl ₄ gas and the SiH ₄ gas to the wafer 200, the number of steps to be performed per cycle can be reduced from three to two. As a result, it is possible to shorten the time required for one cycle and simplify the cycle procedure. As a result, it is possible to improve the productivity of the film forming process.

(F) In step 1, in the film forming sequence of this embodiment in which the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied to the wafer 200, the Ti / Si concentration ratio in the first layer, that is, the composition of the TiSiN film Can be easily and widely controlled by adjusting the TiCl ₄ / SiH ₄ flow rate ratio. On the other hand, in the film forming sequence in which the TiCl ₄ gas and the SiH ₄ gas are not simultaneously supplied to the wafer 200, it is relatively difficult to control the composition of the TiSiN film over a wide range as in the present embodiment.

(G) The above effect is obtained when a Ti-containing gas other than TiCl ₄ gas is used as the first raw material gas, when a Si-containing gas other than SiH ₄ gas is used as the second raw material gas, and when NH ₃ gas is used as the reaction gas. The same can be obtained when using N-containing gases other than the above.

Examples of the Ti-containing gas include TiCl ₄ gas, chlorotitanium-based gas such as dichlorotitanium (TiCl ₂ ) gas and trichlorotitanium (TiCl ₃ ) gas, and fluoride titanium such as tetrafluoride titanium (TiF ₄ ). A system gas, that is, a titanium halide system gas can be used.

Further, for example, as the Si-containing gas, in addition to SiH ₄ gas, silicon hydride gas such as Si ₂ H ₆ gas and trisilane (Si ₃ H ₈ ) gas can be used. As the Si-containing gas, it is preferable to use a gas that does not react with the Ti-containing gas in the gas phase under the above processing conditions.

Further, for example, as the N-containing gas, in addition to NH ₃ gas, a hydrogen nitride-based gas such as diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas can be used.

Further, for example, as the inert gas, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to N ₂ gas.

(4) Modified Example The sequence of the film forming process in the present embodiment is not limited to the mode shown in FIG. 4 and can be modified as in the modified example described below.

(Modification 1)
As shown in FIG. 5A, in step 1, the supply of SiH ₄ gas and the supply of TiCl ₄ gas are simultaneously started, and the supply of SiH ₄ gas is stopped after the supply of TiCl ₄ gas is stopped. You can

  Also in this modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained.

Further, according to this modification, it is possible to increase the Si concentration of the TiSiN film formed on the wafer 200. This is because in step 1, when the supply of two kinds of gas is stopped at the same time, the adsorption sites of Si still exist (remain) on the surface of the wafer 200 or in the first layer at the time of stopping the gas supply. There are cases. In this case, as in this modification, by continuing the supply of the SiH ₄ gas even after the supply of the TiCl ₄ gas is stopped, Si can be added to the first layer, and the Si concentration of the first layer is further increased. It is possible to raise it. Further, even if the Si adsorption sites do not exist in the first layer at the time when the supply of the two kinds of gas is stopped at the same time, the SiH ₄ gas is stopped even after the supply of the TiCl ₄ gas is stopped as in this modification. By continuing the supply of the gas, Cl existing on the surface of the first layer can be replaced with Si, and the Si concentration of the first layer can be further increased. As a result of these, it is possible to further increase the Si concentration of the TiSiN film and further enhance the F barrier effect exhibited by this film. Incidentally, the inventors, etc., is stopped at Step 1 and the supply of the TiCl ₄ gas supply and SiH ₄ gases simultaneously, there is a case where the Si concentration of the first layer is for example a 3～5At%, of the TiCl ₄ gas It has been confirmed that it may be possible to increase the Si concentration of the first layer to, for example, 20 to 30 at% or more by continuing to supply the SiH ₄ gas even after the supply is stopped.

  Further, according to this modification, impurities such as Cl in the first layer can be further reduced, and the quality of the TiSiN film can be further improved. Further, it is possible to more reliably remove HCl and the like from the inside of the processing chamber 201, and it is possible to improve the quality of the film forming process.

(Modification 2)
As shown in FIG. 5 (b), step 1, starting the supply of the TiCl ₄ gas before the supply of the SiH ₄ gas, so as to stop the supply of feed and SiH ₄ gas TiCl ₄ gas simultaneously May be.

  Also in this modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained.

Further, according to this modification, it is possible to evenly secure the conductivity of the TiSiN film formed on the wafer 200 over the entire area of the surface of the wafer 200. This is because when the supply of TiCl ₄ gas is started before the supply of SiH ₄ gas as in this modification, the layer containing Ti is formed with a substantially uniform thickness over the entire area of the surface of the wafer 200. It becomes possible to form continuously (non-island shape and non-mesh shape). In this modification, by starting the supply of the SiH ₄ gas after setting the surface of the wafer 200 in such a state, Ti can be made to exist in every place on the wafer 200 to which the SiH ₄ gas is supplied. It is possible to form Ti—Si—N bonds or Ti—Si—Ti bonds at any position on the surface of the wafer 200. In this way, by continuously forming the chemical bond containing Ti, which is a conductive metal element, over the entire surface of the wafer 200, the conductivity of the TiSiN film is uniformly ensured over the entire surface of the wafer 200. It becomes possible.

On the other hand, in step 1, if the supply of the SiH ₄ gas is started before the supply of the TiCl ₄ gas, it becomes difficult to obtain the above effect. This is because, if the supply of SiH ₄ gas is started before the supply of TiCl ₄ gas in step 1, NH ₄ Cl as a by-product remaining on the surface of the wafer 200 formed in step 2 and the like, By reacting with SiH ₄ supplied in step 1, insulating Si ₃ N ₄ may be discontinuously formed (island-like or mesh-like) on the surface of the wafer 200. .. In this case, in the place where Si ₃ N ₄ is formed, N is in a state of being bonded to all Si bonds such as N—Si—N bond, and Ti—Si—N bond and Ti—Si bond are formed. It becomes difficult to newly form a —Ti bond, that is, a chemical bond containing Ti, which is a conductive metal element. As a result, the conductivity of the TiSiN film may locally decrease in the plane of the wafer 200.

Further, according to this modification, it is possible to properly suppress the amount of Si added to the TiSiN film. By appropriately reducing the Si concentration of the TiSiN film, it becomes possible to improve the step coverage of the TiSiN film. The inventors have found that when the Si concentration of the TiSiN film is set to 20%, the step coverage may be about 75.2%, while the Si concentration of the TiSiN film is set to 15%, the step coverage becomes 81.1%. It has been confirmed that it may be possible to increase the above. Note that this phenomenon is similarly obtained in other modified examples in which the SiH ₄ gas exposure amount of the wafer 200 is suppressed.

(Modification 3)
As shown in FIG. 5 (c), step 1, starting the supply of the TiCl ₄ gas before the supply of the SiH ₄ gas, so as to stop the supply of the TiCl ₄ gas before the supply of the SiH ₄ gas You can Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modifications 1 and 2 can be obtained.

(Modification 4)
As shown in FIG. 6A, in step 1, supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of TiCl ₄ gas before starting the supply of the SiH ₄ gas, may be less than the supply flow rate of the definitive TiCl ₄ gas after starting the supply of the SiH ₄ gas.

Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modification 3 can be obtained. Further, according to this modification, by setting the supply flow rate of the TiCl ₄ gas in step 1 as described above, the amount of Ti contained in the first layer is appropriately suppressed, that is, in the first layer. It is possible to properly secure the Si adsorption site in and to promote the addition of Si into the first layer. This makes it possible to increase the Si concentration of the TiSiN film and further enhance the F barrier effect exhibited by this film. Furthermore, by setting the TiCl ₄ gas supply flow rate in step 1 as described above, the amounts of Cl and H remaining in the first layer can be further reduced, and by-products such as HCl are generated. Can be reduced. Further, according to this modification, it is possible to sufficiently increase the Si concentration of the TiSiN film even if the period of time for which the SiH ₄ gas supply process is continuously performed after the supply of the TiCl ₄ gas is stopped is shortened. Therefore, it is possible to shorten the time required for one cycle and improve the productivity of the film forming process.

(Modification 5)
As shown in FIG. 6B, in step 1, the supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of TiCl ₄ gas may be controlled in the same manner as in Modification 4. Furthermore, the supply flow rate of definitive SiH ₄ gas after stopping the supply of the TiCl ₄ gas, may be less than the supply flow rate of the SiH ₄ gas before stopping the supply of the TiCl ₄ gas.

Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modifications 3 and 4 can be obtained. Further, by setting the supply flow rate of the SiH ₄ gas as described above, after the supply of the TiCl ₄ gas is stopped, Si is softly added to the first layer, and thus the first layer It is possible to add Si more uniformly over the entire area of.

(Modification 6)
As shown in FIG. 6C, in step 1, the supply start and supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of the SiH ₄ gas may be controlled as in the fifth modification. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modification 3 can be obtained. Further, similarly to the modified example 5, after the supply of the TiCl ₄ gas is stopped, Si is softly added to the first layer, and Si is more uniformly added over the entire area of the first layer. It becomes possible.

(Modification 7)
As shown in FIG. 7A, in step 1, supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of TiCl ₄ gas before starting the supply of the SiH ₄ gas, may be greater than the supply flow rate of the definitive TiCl ₄ gas after starting the supply of the SiH ₄ gas. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modification 3 can be obtained. Further, by setting the TiCl ₄ gas supply flow rate in Step 1 as described above, the effect described in Modification 2 can be more reliably obtained.

(Modification 8)
As shown in FIG. 7B, in step 1, supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of the TiCl ₄ gas may be controlled as in the modification 7. Furthermore, the supply flow rate of definitive SiH ₄ gas after stopping the supply of the TiCl ₄ gas, may be greater than the supply flow rate of the SiH ₄ gas before stopping the supply of the TiCl ₄ gas. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modification 7 can be obtained. Further, by setting the supply flow rate of the SiH ₄ gas in step 1 as described above, the effect described in the modification 1 can be obtained more reliably.

(Modification 9)
As shown in FIG. 7C, in step 1, the start and stop of supply of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of the TiCl ₄ gas may be controlled in the same manner as in Modification 7, and the supply flow rate of the SiH ₄ gas may be controlled in the same manner as in Modification 5. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modifications 5 and 7 can be obtained.

(Modification 10)
As shown in FIG. 8A, in step 1, supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of the SiH ₄ gas may be controlled as in the modification 8. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modification 3 can be obtained. Further, by setting the supply flow rate of the SiH ₄ gas in step 1 as described above, the effect described in the modification 1 can be obtained more reliably.

(Modification 11)
As shown in FIG. 8B, in step 1, supply start or supply stop of various gases may be controlled in the same manner as in the third modification. Then, the supply flow rate of the TiCl ₄ gas may be controlled in the same manner as in Modification ₄ , and the supply flow rate of the SiH ₄ gas may be controlled in the same manner as in Modification 8. Also in this modification, the same effects as those of the film forming sequence shown in FIG. 4 and modifications 3, 4, and 8 can be obtained.

(Processing conditions in modified example)
In each of the modified examples described above, the processing conditions when the SiH ₄ gas is supplied alone are as follows.

The pressure in the processing chamber 201 is a predetermined pressure within the range of 1 to 3000 Pa, for example. The supply flow rate of the SiH ₄ gas is, for example, a predetermined flow rate within the range of 0.001 to 2 slm, preferably 0.05 to 1.5 slm, and more preferably 0.1 to 1 slm. The supply time of the SiH ₄ gas is, for example, a predetermined time within the range of 0.01 to 30 seconds. Further, the supply flow rate of the N ₂ gas supplied from each gas supply pipe is, for example, a predetermined flow rate within the range of 0 to 10 slm.

Further, in each of the modified examples described above, the processing conditions when TiCl ₄ gas is supplied alone are as follows.

The pressure in the processing chamber 201 is a predetermined pressure within the range of 1 to 3000 Pa, for example. The supply flow rate of the TiCl ₄ gas is, for example, a predetermined flow rate within the range of 0.01 to 2 slm, preferably 0.1 to 1.5 slm, and more preferably 0.2 to 1 slm. The supply time of the TiCl ₄ gas is, for example, 0.1 to 30 seconds, preferably 0.5 to 20 seconds, and more preferably 1 to 10 seconds. The supply flow rate of the N ₂ gas supplied from each gas supply pipe is, for example, a predetermined flow rate within the range of 0.1 to 20 slm.

  Other processing conditions are the same as those of the film forming sequence shown in FIG. By setting the various processing conditions within the above range, the effects according to the respective modified examples can be properly obtained.

<Other Embodiments of the Present Invention>
The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention.

For example, as in the film formation sequence shown below, a hydrocarbon-based gas such as propylene (C ₃ H ₆ ) gas, that is, a C-containing gas is used as a reaction gas, and Ti, Si, and C are deposited on the wafer 200. A titanium carbide film (TiSiC film) may be formed as the included film. Even in this case, the same effect as that of the above-described embodiment can be obtained. Further, by doping C into the film, the work function of this film can be lowered.

(TiCl ₄ + SiH ₄ → C ₃ H ₆ ) × n ⇒ TiSiC

Further, for example, as in the film formation sequence shown below, an amine-based gas such as triethylamine ((C ₂ H ₅ ) ₃ N), abbreviated as TEA) or dimethylhydrazine ((CH ₃ ) ₂ N _{2 is used} as a reaction gas. A titanium carbonitride film (TiSiCN film) is used as a film containing Ti, Si, C, and N on the wafer 200 by using an organic hydrazine-based gas such as H ₂ , abbreviated: DMH), that is, a gas containing N and C. ) May be formed. Further, a plurality of types of reaction gases may be combined to form a TiSiCN film on the wafer 200. Even in these cases, the same effect as the above-described embodiment can be obtained. Further, by doping C into the film, the work function of this film can be lowered.

(TiCl ₄ + SiH ₄ → TEA) × n ⇒ TiSiCN

(TiCl ₄ + SiH ₄ → DMH) × n ⇒ TiSiCN

(TiCl ₄ + SiH ₄ → C ₃ H ₆ → NH ₃ ) × n ⇒ TiSiCN

  Further, for example, in the above-described embodiments and modifications, an example of forming a film containing Ti as a metal element on the substrate has been described, but the present invention is not limited to such an aspect. That is, in the present invention, in addition to Ti, zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), yttrium (Y), lanthanum (La), It can be preferably applied also when a film containing a metal element such as strontium (Sr), aluminum (Al), chromium (Cr), vanadium (V), gallium (Ga) is formed on a substrate. Further, although the present invention has been described with respect to an example of forming a film containing Si as another element, the present invention is not limited to such an aspect. That is, the present invention is suitable when a film containing germanium (Ge), boron (B), arsenic (As), phosphorus (P), Al, etc. as other elements in addition to Si is formed on the substrate. Can be applied to.

Further, according to the present invention, when a film containing a metalloid element such as Si, Ge, or B instead of a metal element is formed as in the film formation sequence described below, that is, an insulating film is formed instead of a conductive film. Even in such a case, it is possible to apply it suitably. In this case, a halosilane raw material gas such as tetrachlorosilane (SiCl ₄ ) gas can be used as the first raw material gas. As the reaction gas, an O-containing gas (oxidant) such as oxygen (O ₂ ) gas can be used in addition to the above-mentioned various reaction gases.

(SiCl ₄ + SiH ₄ → NH ₃ ) × n ⇒ SiN

(SiCl ₄ + SiH ₄ → C ₃ H ₆ ) × n ⇒ SiC

(SiCl ₄ + SiH ₄ → TEA) × n ⇒ SiCN

(SiCl ₄ + SiH ₄ → C ₃ H ₆ → NH ₃ → O ₂ ) × n ⇒ SiOCN

Further, for example, in step 1, with the APC valve 244 closed, the TiCl ₄ gas may be supplied to the depressurized processing chamber 201 all at once by flash flow. For example, a first tank (gas reservoir) configured as a pressurizing container is provided on the upstream side of the valve 243a in the gas supply pipe 232a, etc., and in step 1, the APC valve 244 is closed and the first tank The high-pressure TiCl ₄ gas filled in the chamber may be supplied into the processing chamber 201 at once by flash flow. By supplying the TiCl ₄ gas in this way, it is possible to shorten the period required for step 1 and improve the productivity of the film forming process.

Further, for example, in step 2, with the APC valve 244 closed, the NH ₃ gas may be supplied all at once by flash flow into the decompressed processing chamber 201. For example, in the gas supply pipe 232c, on the upstream side of the valve 243c or the like, a second tank (gas reservoir) configured as a pressurized container is provided, and in step 2, the APC valve 244 is closed and the second tank The high-pressure NH ₃ gas filled in may be supplied into the processing chamber 201 all at once by flash flow.

By supplying the NH ₃ gas in this way, it is possible to shorten the period required for step 2 and improve the productivity of the film forming process.

Further, by supplying the NH ₃ gas in this way, the by-products existing in the processing chamber 201 can be quickly discharged from the processing chamber 201. As a result, it is possible to suppress the incorporation of by-products into the TiSiN film and improve the film quality of this film. This is because HCl as a by-product is also generated by performing step 1 as described above, but when step 2 is performed, Cl adsorbed on the surface of the first layer becomes NH ₃ gas. It is also generated by substituting the contained N. HCl as a by-product may react with the NH ₃ gas supplied in step 2 to generate a new by-product such as NH ₄ Cl. On the other hand, by supplying the NH ₃ gas by the flash flow, it becomes possible to discharge HCl from the processing chamber 201 before a new by-product such as NH ₄ Cl is newly generated. As a result, the incorporation of NH ₄ Cl or the like into the TiSiN film can be suppressed.

  Further, in the present embodiment, the case has been described in which the first source gas, the second source gas, and the reaction gas are independently supplied into the processing chamber 201 using the three nozzles 249a to 249c. As described above, when various gases are independently supplied using different nozzles, the nozzle 249a for supplying the first raw material gas and the nozzle 249b for supplying the second raw material gas should be as close as possible to each other. Is good. With this configuration, the first source gas and the second source gas can be efficiently mixed. As a result, the composition and film quality of the film formed on the wafer 200 can be made uniform over the surface.

  Further, in the present embodiment, the case has been described in which the first source gas, the second source gas, and the reaction gas are independently supplied into the processing chamber 201 using the three nozzles 249a to 249c. However, the present invention is not limited to such an embodiment. For example, the nozzle 249a for supplying the first source gas and the nozzle 249b for supplying the second source gas may be shared, and two nozzles may be provided in the processing chamber 201. With this configuration, the first source gas and the second source gas can be efficiently mixed (premixed) in the nozzle. As a result, the composition and film quality of the film formed on the wafer 200 can be made uniform over the surface.

  It is preferable that the recipe used for the substrate processing is individually prepared according to the processing content and stored in the storage device 121c via the telecommunication line or the external storage device 123. Then, when starting the substrate processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from a plurality of recipes stored in the storage device 121c according to the processing content. As a result, it becomes possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility with one substrate processing apparatus. In addition, the burden on the operator can be reduced, and it becomes possible to quickly start the substrate processing while avoiding an operation error.

  The above-described recipe is not limited to the case of newly creating the recipe, but may be prepared by, for example, changing an existing recipe already installed in the substrate processing apparatus. When changing the recipe, the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium recording the recipe. Further, the input / output device 122 included in the existing substrate processing apparatus may be operated to directly change the existing recipe already installed in the substrate processing apparatus.

  In the above-described embodiment, an example in which a film is formed using a batch-type substrate processing apparatus that processes a plurality of substrates at once has been described. The present invention is not limited to the above-described embodiments, and can be suitably applied to, for example, the case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. Further, in the above-described embodiment, an example of forming a film by using the substrate processing apparatus having the hot wall type processing furnace has been described. The present invention is not limited to the above-described embodiment, and can be suitably applied to the case where a film is formed using a substrate processing apparatus having a cold wall type processing furnace.

  For example, the present invention can be suitably applied to the case where a film is formed using the substrate processing apparatus including the processing furnace 302 shown in FIG. The processing furnace 302 includes a processing container 303 that forms the processing chamber 301, a shower head 303s that supplies gas into the processing chamber 301 in a shower shape, and a support 317 that horizontally supports one or several wafers 200. A rotary shaft 355 that supports the support 317 from below, and a heater 307 provided on the support 317. Gas supply ports 332a to 332c are connected to the inlet of the shower head 303s. The gas supply ports 332a, 332b, 332c are connected to gas supply systems similar to the first source gas supply system, the second source gas supply system, and the reaction gas supply system of the above-described embodiment, respectively. A gas dispersion plate is provided at the outlet of the shower head 303s. An exhaust port 331 for exhausting the inside of the processing chamber 301 is provided in the processing container 303. An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 331.

  Further, for example, the present invention can be suitably applied to the case where a film is formed using the substrate processing apparatus including the processing furnace 402 shown in FIG. The processing furnace 402 includes a processing container 403 that forms the processing chamber 401, a support 417 that horizontally supports one or several wafers 200, a rotating shaft 455 that supports the support 417 from below, and a processing container. A lamp heater 407 that irradiates the wafer 200 in the light 403 with light and a quartz window 403w that transmits the light of the lamp heater 407 are provided. Gas supply ports 432a to 432c are connected to the processing container 403. The gas supply ports 432a, 432b, 432c are connected to gas supply systems similar to the first source gas supply system, the second source gas supply system, and the reaction gas supply system of the above-described embodiment, respectively. The gas supply ports 432a to 432c are provided at the sides of the end portion of the wafer 200 loaded into the processing chamber 401. The processing container 403 is provided with an exhaust port 431 for exhausting the inside of the processing chamber 401. An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 431.

  Even when these substrate processing apparatuses are used, the film forming process can be performed under the same processing procedure and processing conditions as those of the above-described embodiment and modification, and the same effects as those of the above-described embodiment and modification are obtained. Be done.

  Further, the above-described embodiments and modified examples can be appropriately combined and used. The processing procedure and processing condition at this time can be the same as the processing procedure and processing condition of the above-described embodiment, for example.

  Hereinafter, experimental results that support the effects obtained in the above-described embodiment and modification will be described.

(Example 1)
As Example 1, the substrate processing apparatus according to the above-described embodiment was used to form a TiSiN film on the wafer in the sequence shown in FIG. The processing condition of the film forming process was a predetermined condition within the processing condition range described in the above embodiment.

In addition, as Comparative Example 1a, the sequence shown in FIG. 11A, that is, the cycle in which the TiCl ₄ gas, the NH ₃ gas, and the SiH ₄ gas are sequentially and non-simultaneously supplied to the wafer is repeated, so that the TiSiN film is formed on the wafer. Formed.

Further, as Comparative Example 1b, the sequence shown in FIG. 11B, that is, the step of supplying TiCl ₄ gas to the wafer and the step of simultaneously supplying NH ₃ gas and SiH ₄ gas to the wafer are performed. A TiSiN film was formed on the wafer by an alternating repeating sequence.

  Then, the composition and the resistivity of each of the TiSiN films formed in Example 1 and Comparative Examples 1a and 1b were measured. The composition was measured by the X-ray photoelectron spectroscopy (XPS) method. FIG. 12A shows a list of compositions and resistivities of the films of Example 1 and Comparative Examples 1a and 1b. According to FIG. 12A, it can be seen that the TiSiN film of Example 1 has no great difference in the content rates of Ti, N, and Si as compared with the TiSiN films of Comparative Examples 1a and 1b. Further, it can be seen that the TiSiN film of Example 1 has significantly lower resistivity than the TiSiN films of Comparative Examples 1a and 1b, that is, has good conductivity. It is considered that this is because the TiSiN film of Example 1 has a lower Cl concentration than the TiSiN films of Comparative Examples 1a and 1b. That is, the film formed by the sequence shown in FIG. 4 is a high-quality film having a lower impurity concentration and excellent conductivity than the film formed by the sequence shown in FIGS. 11A and 11B. I understand. The film formed by the sequence shown in FIG. 4 contains Si to the same extent as the film formed by the sequence shown in FIGS. 11A and 11B, and therefore has the same F barrier function. I understand that

(Examples 2a to 2d)
As Example 2a, a TiSiN film was formed on a wafer by the film forming sequence shown in FIG. 4 using the substrate processing apparatus in the above-described embodiment. Further, as Examples 2b to 2d, using the substrate processing apparatus in the above-described embodiment, a TiSiN film was formed on the wafer according to the sequence shown in FIG. The processing conditions were common conditions within the processing condition range described in the above embodiments. In Examples 2b to 2d, the supply flow rate of the SiH ₄ gas continuously supplied after the supply of the TiCl ₄ gas was stopped was 0.225 slm, and the supply time was set to 6, 10 and 16 seconds, respectively.

Further, as Comparative Example 2, a TiN film was formed on the wafer by repeating the cycle of alternately supplying the TiCl ₄ gas and the NH ₃ gas to the wafer.

Then, the composition of each of the films formed in Examples 2a to 2d and Comparative Example 2 was measured by the XPS method. FIG. 12B shows a list of compositions in each film of Examples 2a to 2d and Comparative Example 2. From FIG. 12B, it can be seen that the TiSiN films of Examples 2a to 2d have a lower Cl concentration than the TiN film of Comparative Example 2. Further, it can be seen that the TiSiN films of Examples 2b to 2d have a lower Cl concentration than the TiSiN film of Example 2a. It can also be seen that the Cl concentration of the film decreases as the supply time of the SiH ₄ gas continuously supplied after the supply of the TiCl ₄ gas is stopped, that is, the exposure amount of the SiH ₄ gas to the wafer increases.

(Examples 3a and 3b)
As Examples 3a and 3b, the substrate processing apparatus according to the above-described embodiment was used, and the process of forming the TiSiN film on the wafer was performed plural times in the sequence shown in FIG. The processing conditions were common conditions within the processing condition range described in the above embodiments. The film thickness was changed within the range of 30Å to 100Å each time the film forming process was performed. The supply flow rate of the SiH ₄ gas continuously supplied after the supply of the TiCl ₄ gas was stopped was 0.9 slm, and the supply time was set to 6 seconds and 5 seconds in Examples 3a and 3b, respectively.

Further, as Comparative Example 3, a process of forming a TiN film on the wafer was performed a plurality of times by repeating the cycle of alternately supplying the TiCl ₄ gas and the NH ₃ gas to the wafer. The film thickness was changed within the range of 30Å to 100Å each time the film forming process was performed, as in the case of Examples 3a and 2b.

  Then, the resistivity of each film formed in Examples 3a and 3b and Comparative Example 3 was measured. The result is shown in FIG. In FIG. 13, the horizontal axis represents the film thickness (Å) and the vertical axis represents the resistivity (μΩcm). In the figure, the symbols ■, ●, and ◆ indicate Examples 3a and 3b and Comparative Example 3, respectively. According to FIG. 13, it can be seen that the films of Examples 3a and 3b have a resistivity equal to or lower than that of the film of Comparative Example 3 at a film thickness in the range of at least 30 to 40 Å.

200 wafers (substrates)
201 Processing room

Claims (9)

A first source gas containing a metal element and a halogen element and a second source gas containing another element different from the metal element and hydrogen are supplied to the substrate while exhausting the space in which the substrate exists. The first step of supplying so that at least some of the supply periods of
After the first step, a removing step of removing the first source gas, the second source gas, and the by-products generated in the first step from the space where the substrate exists,
A second step of supplying a reaction gas containing nitrogen to the substrate while exhausting the space where the substrate exists after the removing step;
A method of manufacturing a semiconductor device, comprising the step of forming a film containing the metal element, the other element, and nitrogen on the substrate by performing a cycle in which the above steps are performed non-simultaneously a predetermined number of times.   The method of manufacturing a semiconductor device according to claim 1, wherein in the first step, the supply of the first source gas and the supply of the second source gas are simultaneously started.   The method of manufacturing a semiconductor device according to claim 1, wherein in the first step, the supply of the first source gas is started before the supply of the second source gas.   The method of manufacturing a semiconductor device according to claim 1, wherein in the first step, the supply of the first source gas and the supply of the second source gas are stopped at the same time.   4. The method of manufacturing a semiconductor device according to claim 1, wherein in the first step, the supply of the first source gas is stopped before the supply of the second source gas. The first source gas is a Ti-containing gas containing Ti as the metal element,
The second raw material gas is a Si-containing gas containing Si as the other element,
The method of manufacturing a semiconductor device according to claim 1, wherein a TiSiN film is formed on the substrate.   The method for manufacturing a semiconductor device according to claim 6, wherein the Ti-containing gas further contains at least one selected from the group consisting of Cl, F, Br, and I. A processing chamber containing the substrate,
A gas for supplying a first source gas containing a metal element and a halogen element, a second source gas containing another element different from the metal element and hydrogen, and a reaction gas containing nitrogen to the substrate in the processing chamber. Supply system,
An exhaust system for exhausting the processing chamber,
A first process in which the first source gas and the second source gas are supplied to the substrate while exhausting the processing chamber so that at least a part of respective supply periods thereof overlaps; After that, a removal process of removing the first source gas, the second source gas, and a by-product generated in the first process from the process chamber, and exhausting the process chamber after the removal process. However, a film containing the metal element, the other element, and nitrogen is formed on the substrate by performing a cycle of performing the second process of supplying the reaction gas non-simultaneously on the substrate a predetermined number of times. A controller configured to control the gas supply system and the exhaust system to form
A substrate processing apparatus comprising. In the processing chamber of the substrate processing apparatus,
A first source gas containing a metal element and a halogen element and a second source gas containing another element different from the metal element and hydrogen with respect to the substrate accommodated in the processing chamber while exhausting the processing chamber. And a first procedure of supplying so that at least a part of each supply period overlaps,
After the first procedure, a removal procedure for removing the first source gas, the second source gas, and the by-products generated in the first procedure from the processing chamber,
A second step of supplying a reaction gas containing nitrogen to the substrate while exhausting the processing chamber after the removal step;
A program for causing the substrate processing apparatus to execute a procedure of forming a film containing the metal element, the other element, and nitrogen on the substrate by performing a cycle of performing the above-described non-simultaneously a predetermined number of times.