JP7166367B2 - Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus, and program - Google Patents

Description

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

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

JP 2012-62502 A

When forming a metal film using a gas containing fluorine (F) such as _WF6 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 formed in advance on the substrate when a thermal diffusion process or the like is performed thereafter, and deteriorates the performance of the semiconductor device. It may deteriorate. Therefore, before forming the metal film, a process of forming a titanium nitride film (TiN film) or the like as a diffusion suppression film (barrier film) for suppressing the diffusion of F may be performed on the underlayer.

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

According to one aspect of the invention,
A first step of supplying a first raw material gas containing a metal element and a second raw material gas containing another element different from the metal element to the substrate so that at least a part of the respective supply periods overlap. When,
a second step of supplying a reactive gas containing at least one of nitrogen and carbon to the substrate;
are performed a predetermined number of times non-simultaneously to form a film containing the metal element and the other element and further containing at least one of nitrogen and carbon on the substrate. .

According to the present invention, it is possible to improve the properties of the barrier film formed on the substrate.

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, and is a longitudinal sectional view showing a processing furnace portion; FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a cross-sectional view showing the processing furnace portion taken along the line AA of FIG. 1; 1 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a block diagram showing a control system of the controller; FIG. FIG. 4 is a diagram showing the timing of gas supply in one embodiment of the present invention; 4(a) to 4(c) are diagrams showing modified examples of gas supply timing according to an embodiment of the present invention. 4(a) to 4(c) are diagrams showing modified examples of gas supply timing according to an embodiment of the present invention. 4(a) to 4(c) are diagrams showing modified examples of gas supply timing according to an embodiment of the present invention. (a) and (b) are diagrams each showing a modification of gas supply timing in one embodiment of the present invention. FIG. 4 is a schematic configuration diagram of a processing furnace of a substrate processing apparatus preferably used in another embodiment of the present invention, and is a longitudinal sectional view showing a processing furnace portion; FIG. 4 is a schematic configuration diagram of a processing furnace of a substrate processing apparatus preferably used in another embodiment of the present invention, and is a longitudinal sectional view showing a processing furnace portion; (a) and (b) are diagrams each showing the timing of gas supply in a comparative example. (a) and (b) are diagrams showing the compositions of films formed in Examples and comparative examples. FIG. 4 is a diagram showing the resistivity of films formed in Examples and Comparative Examples.

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

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

A reaction tube 203 is arranged concentrically with the heater 207 inside 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 a closed upper end and an open lower end. A manifold 209 is arranged concentrically with the reaction tube 203 below the reaction tube 203 . The manifold 209 is made of metal such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages the lower end of the reaction tube 203 and is configured to support the reaction tube 203 . An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. Reactor tube 203 is mounted vertically like heater 207 . A processing vessel (reaction vessel) is mainly configured by the reaction tube 203 and the manifold 209 . A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured 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 (MFC) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as opening/closing valves in this order from the upstream side. Gas supply pipes 232d to 232f for supplying inert gas are connected to the gas supply pipes 232a to 232c downstream of the valves 243a to 243c, respectively. The gas supply pipes 232d-232f are provided with MFCs 241d-241f and valves 243d-243f, respectively, in this order from the upstream side.

As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part of the inner wall of the reaction tube 203, and the nozzles 249a to 249c. They are provided so as to rise upward in the stacking direction. In other words, the nozzles 249a to 249c are provided on the sides of the wafer arrangement area in which the wafers 200 are arranged, in a region horizontally surrounding the wafer arrangement area, along the wafer arrangement area. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250 a to 250 c are open to face the center of the reaction tube 203 and can supply gas toward the wafers 200 . A plurality of gas supply holes 250 a to 250 c are provided from the bottom to the top 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 portion (periphery portion) of the plurality of wafers 200 arranged in the reaction tube 203 form an annular shape in plan view. Gas is conveyed through nozzles 249a to 249c arranged in a vertically long space, ie, a cylindrical space. Then, the gas is jetted into the reaction tube 203 for the first time near 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, in the horizontal direction. With such a configuration, the gas is uniformly supplied to each wafer 200 . The gas that has flowed on the surface of the wafer 200 flows toward an exhaust port, that is, an exhaust pipe 231, which will be described later. However, the direction of gas flow is appropriately specified depending on the position of the exhaust port, and is not limited to the vertical direction.

A Ti-containing gas containing titanium (Ti) as a metal element, for example, is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a as the first raw material gas. As the Ti-containing gas, for example, 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) can be used. As the gas containing titanium halide, for example, tetrachlorotitanium (TiCl ₄ ) gas containing Ti and Cl can be used. _TiCl4 gas acts as a Ti source. In this specification, when the word "raw material" is used, it means "a liquid raw material in a liquid state", or means "a raw material gas in a gaseous state", or both of them. sometimes.

From the gas supply pipe 232b, a Si-containing gas containing silicon (Si), for example, as a second raw material gas containing another element (dopant) different from the metal elements described above is supplied through the MFC 241b, the valve 243b, and the nozzle 249b. and 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. _SiH4 gas acts as a Si source.

From the gas supply pipe 232c, a reaction gas containing at least one of nitrogen (N) and carbon (C), such as ammonia (NH ₃ ) gas, which is an N-containing gas, is supplied through the MFC 241c, the valve 243c, and the nozzle 249c. and supplied into the processing chamber 201 . _NH3 gas acts as a nitriding agent, ie N source.

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

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

Any or all of the 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 adjustment operation and the like are configured to be controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or divided integrated unit, and can be attached/detached to/from the gas supply pipes 232a to 232f or the like in units of integrated units. It is configured so that maintenance, replacement, expansion, etc. can be performed on an integrated unit basis.

The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 . The exhaust pipe 231 is supplied with a pressure sensor 245 as a pressure detector (pressure detector) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator). , a vacuum pump 246 as an evacuation device is connected. By opening and closing the APC valve 244 while the vacuum pump 246 is operating, the inside of the processing chamber 201 can be evacuated and stopped. By adjusting the valve opening based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted. An exhaust system is mainly composed of the exhaust pipe 231 , the APC valve 244 and the pressure sensor 245 . A vacuum pump 246 may be considered to be included in the exhaust system.

Below the manifold 209, a seal cap 219 is provided as a furnace mouth cover capable of hermetically closing the lower end opening of the manifold 209. As shown in FIG. The seal cap 219 is made of metal such as SUS, and is shaped like a disc. An O-ring 220 b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209 . Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. A rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217 . The rotating mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217 . The seal cap 219 is vertically moved up and down by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203 . The boat elevator 115 is configured to move the boat 217 into and out of the processing chamber 201 by raising and lowering the seal cap 219 . The boat elevator 115 is configured as a transport device (transport mechanism) that transports the boat 217 , that is, the wafers 200 into and out of the processing chamber 201 . Further, below the manifold 209, a shutter 219s is provided as a furnace port cover that can airtightly close the lower end opening of the manifold 209 while the seal cap 219 is lowered by the boat elevator 115. The shutter 219s is made of metal such as SUS, and is shaped like a disc. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. As shown in FIG. The opening/closing operation (elevating operation, rotating operation, etc.) of the shutter 219s is controlled by the shutter opening/closing mechanism 115s.

The boat 217 as a substrate support supports a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal posture, aligned vertically with their centers aligned with each other, and supported in multiple stages. It is configured to be spaced and arranged. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, 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 . By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is L-shaped and 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. It is The RAM 121b, storage device 121c, and I/O port 121d are configured to exchange data with the CPU 121a via an 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, a 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 describing the procedure, conditions, and the like of the film forming process described later are stored in a readable manner. The process recipe functions as a program in which the controller 121 is made to execute each procedure in the film forming process described later and a predetermined result can be obtained. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. A process recipe is also simply referred to as a recipe. When the term "program" is used in this specification, it may include only a single recipe, only a single control program, or both. The RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily held.

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

The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read recipes from the storage device 121c in response to input of operation commands from the input/output device 122 and the like. The CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241f, the opening and closing operations of the valves 243a to 243f, the opening and closing operations of the APC valve 244, and the pressure adjustment by the APC valve 244 based on the pressure sensor 245 so as to follow the content of the read recipe. operation, starting and stopping 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, elevation operation of the boat 217 by the boat elevator 115, shutter opening/closing mechanism 115s It is configured to control the opening/closing operation of the shutter 219s by means of.

The controller 121 installs the above-described 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, 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 computer-readable recording media. Hereinafter, these are also collectively referred to simply as recording media. 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. The program may be provided to the computer using communication means such as the Internet or a dedicated line without using the external storage device 123 .

(2) Substrate Processing Process A sequence example of forming a film on a substrate as one process of manufacturing a semiconductor device using the substrate processing apparatus described above will be described with reference to FIG. In the following description, the controller 121 controls the operation of each component of the substrate processing apparatus.

In the basic sequence shown in Figure 4,
a step 1 of supplying TiCl ₄ gas and SiH ₄ gas to a wafer 200 as a substrate so that at least a part of each supply period overlaps;
Step 2 of supplying NH ₃ gas to the wafer 200;
are performed a predetermined number of times (n times (n is an integer equal to or greater than 1)), so that a titanium nitride film (TiSiN membrane). The TiSiN film can also be referred to as a Si-doped TiN film.

In this specification, the film formation sequence described above may be indicated as follows for convenience. Note that the same notation is used in the description of other embodiments and the like.

(TiCl ₄ +SiH ₄ →NH ₃ )×n ⇒ TiSiN

In this specification, when the word "wafer" is used, it means "wafer itself" or "laminate (aggregate) of wafer and predetermined layers, films, etc. formed on its surface". In other words, the term "wafer" may be used to include predetermined layers, films, and the like formed on the surface. In addition, when the term "wafer surface" is used in this specification, it may mean "the surface (exposed surface) of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer. , that is, the outermost surface of the wafer as a laminate".

Therefore, in this specification, the expression "supplying a predetermined gas to the wafer" may mean "directly supplying a predetermined gas to the surface of the wafer" or "supplying the predetermined gas directly to the surface of the wafer". "supplying a predetermined gas to a layer, film, etc., formed on the wafer, that is, the outermost surface of the wafer as a laminate". Further, in the present specification, when it is stated that "a predetermined layer (or film) is formed on a wafer", it means "directly forming a predetermined layer (or film) on the surface of the wafer itself". In some cases, it means "to form a predetermined layer (or film) on a layer, film, etc. formed on a wafer, that is, on the outermost surface of the wafer as a laminate".

Further, the use of the term "substrate" in this specification has the same meaning as the use of the term "wafer".

(wafer charge and boat load)
When the boat 217 is loaded with a plurality of wafers 200 (wafer charge), the shutter 219s is moved by the shutter opening/closing mechanism 115s 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 load). 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 (reduced pressure) by the vacuum pump 246 so that it has a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. The vacuum pump 246 keeps operating at least until the processing of the wafer 200 is completed. Also, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired film formation temperature. At this time, the energization state of 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. Heating of the inside of the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed. Also, the rotation of the boat 217 and the wafers 200 by the rotation mechanism 267 is started. Rotation of the boat 217 and the wafers 200 by the rotation mechanism 267 continues at least until the processing of the wafers 200 is completed.

(Deposition 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 part of the respective supply periods overlap. The sequence shown in FIG. 4 shows a case where the supply of these gases is started simultaneously and the supply of these gases is stopped simultaneously.

Specifically, valves 243a and 243b are opened to flow TiCl ₄ gas and SiH ₄ gas into gas supply pipes 232a and 232b, respectively. TiCl ₄ gas and SiH ₄ gas are adjusted in flow rate by MFCs 241a and 241b, respectively, supplied into the processing chamber 201 through nozzles 249a and 249b, and exhausted through an exhaust pipe 231. FIG. At this time, TiCl ₄ gas and SiH ₄ gas are simultaneously supplied to the wafer 200 . At this time, the valves 243d and 243e are simultaneously opened to flow _N2 gas into the gas supply pipes 232d and 232e, respectively. The N ₂ gas is flow-controlled by the MFCs 241 d and 241 e , 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 . In order to prevent TiCl ₄ gas and SiH ₄ gas from entering the nozzle 249c, the valve 243f is opened to allow N ₂ gas to flow into the gas supply pipe 232f. N ₂ gas is supplied into the processing chamber 201 through the gas supply pipe 232 c and the nozzle 249 c and exhausted through the exhaust pipe 231 .

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

If the film formation temperature is less than 300° C., activation of the TiCl ₄ gas and SiH ₄ gas supplied into the processing chamber 201 becomes insufficient, and a first layer (a layer containing Ti and Si) described later on the wafer 200 is formed. ) may be difficult to form. By setting the film formation temperature to 300° C. or higher, it is possible to solve this problem. By setting the film formation temperature to 320° C. or higher, these gases supplied into the processing chamber 201 are further activated, and the first layer can be formed on the wafer 200 more efficiently. . By setting the film formation temperature to 350° C. or higher, it is possible to obtain these effects more reliably.

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

It should be noted that these conditions were obtained in the gas phase when the TiCl ₄ gas and the SiH ₄ gas were supplied to the wafer 200 in the processing chamber 201 so that at least part of the respective supply periods overlapped. It can be said that this is a condition that can appropriately suppress the decomposition and reaction of these gases.

Also, 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, more preferably 0.2 to 1 slm. The SiH ₄ gas is supplied at a predetermined flow rate, for example, in the range of 0.001 to 2 slm, preferably 0.1 to 1.5 slm, more preferably 0.1 to 1 slm. When TiCl ₄ gas and SiH ₄ gas are supplied at the same time, 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 0.01. The flow rates of TiCl ₄ gas and SiH ₄ gas are adjusted to a value within the range of 0.5-50, more preferably 0.1-10. The supply times of TiCl ₄ gas and SiH ₄ gas are each set to a predetermined time within a range of 0.1 to 20 seconds, for example.

If 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 formation process may be difficult to proceed. In addition, 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 the film should have may be insufficient. By setting the supply flow rate of TiCl ₄ gas to 0.01 slm or more, the supply flow rate of SiH ₄ gas to 2 slm or less, or the flow rate ratio of TiCl ₄ /SiH ₄ to 0.01 or more, the deposition rate of the TiSiN film is reduced. can be increased to a practical level, the composition of this film can be optimized, and sufficient conductivity can be imparted to this film. By setting the supply flow rate of TiCl ₄ gas to 0.1 slm or more, the supply flow rate of SiH ₄ gas to 1.5 slm or less, or the flow rate ratio of TiCl ₄ /SiH ₄ to 0.05 or more, the TiSiN film can be grown. The film rate can be further increased, and the conductivity of this film can be further improved. By setting the supply flow rate of TiCl ₄ gas to 0.2 slm or more, the supply flow rate of SiH ₄ gas to 1 slm or less, or the flow rate ratio of TiCl ₄ /SiH ₄ to 0.1 or more, the above effects are more reliable. obtained in

When the TiCl ₄ gas supply flow rate exceeds 2 slm, the SiH ₄ gas supply flow rate is 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 In other words, the ratio of the amount of Si to the amount of Ti (Si/Ti concentration ratio) becomes too small, and the F diffusion suppression effect (hereinafter also referred to as the F barrier effect) that the film should exhibit may be insufficient. The composition of this film is optimized by setting the TiCl ₄ gas supply flow rate to 2 slm or less, the SiH ₄ gas supply flow rate to 0.001 slm or more, or the TiCl ₄ /SiH ₄ flow rate ratio to 100 or less. , it becomes possible to exhibit a sufficient F barrier effect in this film. 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, or the TiCl ₄ /SiH ₄ flow rate ratio to 50 or less, the composition of this film is further improved. By optimizing the film, 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 effects can be obtained more reliably.

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

By simultaneously supplying TiCl ₄ gas and SiH ₄ gas to the wafer 200 under the above conditions, a layer containing Ti and Si is formed as a first layer (initial layer) on the outermost surface of the wafer 200. be done. This layer is a layer containing Ti and Si in the form of, for example, 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), for example, can be adjusted over a wide range by adjusting the above-mentioned TiCl ₄ /SiH ₄ flow rate ratio. It is possible to control

Note that when the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied to the wafer 200 as in the present embodiment, the layers formed on the wafer 200 are more affected than when these gases are supplied non-simultaneously. It becomes possible to reduce the amount of impurities such as Cl and H contained. This is because when TiCl ₄ gas and SiH ₄ gas are simultaneously supplied under the above conditions, these gases can be reacted with each other on the surface of the wafer 200, and the Ti—Cl bonds contained in these gases can be and Si—H bonds can be cut. As a result, it becomes possible to suppress the incorporation of Cl and H contained in these gases into the first layer, that is, the incorporation of impurities into the first layer. When Cl and H are taken in, the resistivity of the TiSiN film increases (that is, the conductivity decreases). It is possible to obtain a film having Note that 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 detaches from the surface of the wafer 200 without being incorporated into the first layer and is removed from the processing chamber 201 .

However, the impurity desorption effect described above is affected by the TiCl ₄ /SiH ₄ flow rate ratio. For example, if the flow ratio of TiCl ₄ /SiH ₄ is 1/1 and these gases can be reacted with a yield of 100% or more, the reaction of TiCl ₄ +SiH ₄ →Ti + Si + 4HCl theoretically yields: It is possible to reduce the amount of Cl and the like (the amount of Ti--Cl bonds and Si--H bonds) taken into the first layer to zero. In addition, even if the yield cannot be 100%, by setting the TiCl ₄ /SiH ₄ flow ratio small (increasing the SiH ₄ gas flow ratio), the Cl incorporated into the first layer can be set to zero. However, if the TiCl ₄ /SiH ₄ flow rate ratio is set too 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 these circumstances, the magnitude of the TiCl ₄ /SiH ₄ flow rate ratio is subject to certain restrictions, and as a result, Ti—Cl bonds and Si—H bonds are formed in the first layer formed in step 1. may be incorporated in small amounts. 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.

By simultaneously supplying the TiCl ₄ gas and the SiH ₄ gas into the processing chamber 201 as in the present embodiment, the effect of increasing the efficiency of removing HCl, which is a by-product, from the processing chamber 201 can be further obtained. will be available. This is because by simultaneously supplying these gases, that is, by supplying not only TiCl ₄ gas but also SiH ₄ gas into the processing chamber 201 where HCl is generated, the reaction of HCl+SiH ₄ →SiCl ₄ +H ₂ occurs. This is because HCl is generated and disappears. By increasing the removal efficiency of HCl from the processing chamber 201 in this way, it becomes possible to avoid the generation of further by-products such as ammonium chloride (NH ₄ Cl) in step 2 described later. As will be described later, by-products such as NH ₄ Cl may act as steric hindrance that locally inhibits adsorption of TiCl ₄ gas or SiH ₄ gas onto wafer 200 . As in the present embodiment, by increasing the efficiency of removing HCl from the processing chamber 201 and suppressing the generation of by-products such as NH ₄ Cl, local formation inhibition of the first layer within the plane of the wafer 200 can be prevented. can be avoided. As a result, the step coverage (coverage characteristic) and the in-plane film thickness uniformity of the TiSiN film formed on the wafer 200 can be improved.

After the first layer is formed, valves 243a and 243b are closed and the supply of TiCl ₄ gas and SiH ₄ gas is stopped respectively. 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 the remaining unreacted TiCl ₄ gas or SiH ₄ gas remaining in the processing chamber 201 after contributing to the formation of the first layer is removed. Gases and by-products are removed from the processing chamber 201 . At this time, the valves 243 d to 243 f are kept open to maintain the supply of N ₂ gas into the processing chamber 201 . _N2 gas acts as a purge gas.

[Step 2]
After step 1 is finished, 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 while the valves 243a and 243b are closed, and the NH ₃ gas is allowed to flow through the gas supply pipe 232c. The opening/closing control of the valves 243d to 243f is controlled in the same manner as in step 1. The NH ₃ gas has its flow rate adjusted by the MFC 241c, is supplied into the processing chamber 201 through the nozzle 249c, and is exhausted from the exhaust pipe 231. FIG. At this time, NH ₃ gas is supplied to the wafer 200 . The N ₂ gas is flow-controlled by the MFC 241 f, supplied into the processing chamber 201 together with the NH ₃ gas, and 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, more preferably 1 to 10 slm. The supply time of NH ₃ gas is, for example, a predetermined time within the range of 0.01 to 30 seconds, preferably 0.1 to 20 seconds, and more preferably 1 to 15 seconds.

If the NH ₃ gas supply flow rate is less than 0.1 slm or the NH ₃ gas supply time is less than 0.01 seconds, the first layer cannot be reformed (nitrided), and the wafer 200 is It may be difficult to form a TiSiN film on the substrate. 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, the first layer can be modified, and a TiSiN film can be 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 reformation of the first layer is accelerated and the TiSiN film formed on the wafer 200 is improved. It is possible to optimize the composition of By setting the supply flow rate of the NH ₃ gas to 1 slm or more and the supply time of the NH ₃ gas to 1 second or more, these effects can be obtained more reliably.

If the NH ₃ gas supply flow rate exceeds 30 slm or the NH ₃ gas supply time exceeds 30 seconds, the modification (nitridation) of the first layer becomes excessive, and the properties of the TiSiN film formed on the wafer 200 become 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 saturated amount, the gas cost may increase and the productivity may decrease. By setting the supply flow rate of the NH ₃ gas to 30 slm or less and the supply time of the NH ₃ gas to 30 seconds or less, the reformation of the first layer can be appropriately restricted, and the TiSiN formed on the wafer 200 can be reduced. It becomes possible to avoid deterioration of film characteristics. Also, it is possible to avoid an increase in gas cost and a decrease in productivity. By setting the supply flow rate of the NH ₃ gas to 20 slm or less and the supply time of the NH ₃ gas to 20 seconds or less, the modification of the first layer is further optimized, and the characteristics of the TiSiN film formed on the wafer 200 are improved. can be improved. By setting the supply flow rate of the NH ₃ gas to 10 slm or less and the supply time of the NH ₃ gas to 15 seconds or less, these effects can be obtained more reliably.

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

Other processing conditions are the same as the processing conditions in step 1. FIG.

By supplying NH ₃ gas into the processing chamber 201 under the above conditions, the first layer formed on the wafer 200 in step 1 is subjected to nitridation. That is, by reacting and bonding Ti or Si contained in the first layer with N contained in the NH ₃ gas, N can be incorporated into the first layer. As a result, the first layer is changed (modified) into a second layer (TiSiN layer) containing Ti, Si and N. The first layer is a layer containing N in a state such as a Ti--N bond, a Ti--Si--N bond, or a Ti--N--Si bond.

As described above, even if Ti—Cl bonds and Si—H bonds are taken into the first layer formed in step 1, these bonds are cut by performing this step. becomes possible. Cl and H separated from Ti and Si form by-products such as HCl, Cl ₂ and H ₂ by reacting with each other. These by-products generated by performing this step are desorbed from the surface of the wafer 200 without being incorporated into the second layer, and are exhausted from 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 with an extremely low impurity concentration.

After changing the first layer to the second layer, the valve 243c is closed and the supply of _NH3 gas is stopped. Then, the NH ₃ gas and by-products remaining in the processing chamber 201 that have not reacted or have contributed to the above reaction are removed from the processing chamber 201 by the same processing procedure as in step 1 .

[Predetermined number of times]
A TiSiN film having a predetermined composition and a predetermined film thickness can be formed on the wafer 200 by performing a predetermined number of cycles (n times) in which steps 1 and 2 are performed non-simultaneously (alternately). 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 thickness, and the thickness of the TiSiN film formed by laminating the second layer is the desired thickness. Preferably, the above cycle is repeated multiple times until a thickness is achieved.

Note that when the above cycle is performed multiple 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 produce further by-products such as NH ₄ Cl. NH ₄ Cl may act as a steric hindrance that locally inhibits adsorption of gas onto wafer 200 as described above. For example, when HCl produced as a by-product reacts with Ti—NH _x (where x is an integer of 1 or 2) present on the surface of the first layer by performing step 2 , Ti—NH _y Cl (y is an integer of 1 to 3) exists on the surface of the second layer. This Ti—NH _y Cl, that is, ammonium chloride present on the surface of the second layer acts as a steric hindrance that locally inhibits the adsorption of the TiCl ₄ gas or SiH ₄ gas to the surface of the wafer 200 in the next step 1. It works. However, this steric hindrance can be suppressed by improving the removal efficiency of HCl from 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, which can be a steric hindrance, is removed. It is possible to suppress the generation of

For reference, various reactions occurring when TiCl ₄ gas and SiH ₄ gas are simultaneously supplied into the processing chamber 201 are described below. As shown below, NH ₄ Cl as a by-product is itself a nitriding agent that promotes the formation of TiN from TiCl ₄ and the formation of Si ₃ N ₄ from SiH ₄ , that is, the 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 NH ₃ gas. However, these reactions are less likely to occur when TiCl ₄ gas and SiH ₄ gas are supplied into the processing chamber 201 non-simultaneously. In this embodiment, the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied into the processing chamber 201, so that the nitriding process can be performed more efficiently than when these gases are supplied non-simultaneously, resulting in high productivity. It can also be said that it exhibits sexuality.

_2NH4Cl + _TiCl4 ⇒ TiN+8HCl

_{4NH4Cl + 4SiH4} ⇒ _Si3N4 + _SiCl4 + _16H2
SiH ₄ +HCl ⇒ SiCl ₄ +4H _2
4NH4Cl + _3SiCl4 ⇒ _Si3N4 + _16HCl

(After-purge/atmospheric pressure return 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 232 d to 232 f and exhausted from the exhaust pipe 231 . _N2 gas acts as a purge gas. As a result, the inside of the processing chamber 201 is purged, and gas remaining in the processing chamber 201 and reaction by-products are removed from the inside of the processing chamber 201 (afterpurge). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).

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

(3) Effects According to this embodiment, one or more of the following effects can be obtained.

(a) Since the TiSiN film formed in this embodiment contains Si in the film, it exhibits a higher F barrier effect than a TiN film containing no Si. Therefore, by forming the TiSiN film of this embodiment between the SiO film and the W film, this film can be suitably used as a barrier film that suppresses the diffusion of F from the W film toward the SiO film. It becomes possible. In addition, even if the TiSiN film formed in this embodiment is thinner than the Si-free TiN film, it exhibits an F barrier effect equal to or greater than that of the Si-free TiN film. It can be suitably 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 than when these gases are supplied non-simultaneously, making it possible to improve the deposition rate of the TiSiN film.

(c) In step 1, the TiCl ₄ gas and the SiH ₄ gas are simultaneously supplied to the wafer 200, and these gases are reacted with each other on the surface of the wafer 200, so if these gases are supplied non-simultaneously 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 an extremely low concentration of impurities such as Cl and high conductivity (low resistivity).

(d) In step 1, since TiCl ₄ gas and SiH ₄ gas are simultaneously supplied to the wafer 200, more HCl as a by-product is can be effectively removed from within. As a result, it is possible to improve the film quality of the TiSiN film and avoid etching damage to the members inside the processing chamber 201 . In addition, by efficiently removing HCl from the inside of the processing chamber 201, it is possible to suppress the generation of NH ₄ Cl, which may act as a local steric hindrance, and improve the step coverage of the TiSiN film and the uniformity of the in-plane film thickness. It is possible to improve the performance.

(e) By simultaneously supplying TiCl ₄ gas and SiH ₄ gas to the wafer 200 in step 1, it is possible to reduce the number of steps performed per cycle from three to two. As a result, it is possible to shorten the time required for one cycle and simplify the cycle procedure. Thereby, it is also possible to improve the productivity of the film forming process.

(f) In step 1, in the film formation sequence of the present embodiment in which TiCl ₄ gas and 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 a film formation sequence in which TiCl ₄ gas and SiH ₄ gas are supplied non-simultaneously 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 effects are obtained when a Ti-containing gas other than _TiCl4 gas is used as the first source gas, when a Si-containing gas other than _SiH4 gas is used as the second source gas, and when _NH3 gas is used as the reaction gas. It can be obtained in the same manner even when other N-containing gases are used.

For example, the Ti-containing gas includes TiCl ₄ gas, chlorotitanium-based gas such as dichlorotitanium (TiCl ₂ ) gas and trichlorotitanium (TiCl ₃ ) gas, and titanium fluoride such as tetrafluoride titanium (TiF ₄ ). A titanium-based gas, ie, a titanium halide-based 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, hydrogen nitride gases such as diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, and N ₃ H ₈ gas can be used in addition to NH ₃ gas.

Further, for example, as the inert gas, in addition to _N2 gas, rare gases such as Ar gas, He gas, Ne gas, and Xe gas can be used.

(4) Modifications The sequence of the film forming process in this embodiment is not limited to the mode shown in FIG. 4, and can be modified as in the following modifications.

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

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

Moreover, 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 the two kinds of gases is stopped at the same time, adsorption sites of Si still exist (remain) in the surface of the wafer 200 and the first layer at the time of stopping the gas supply. Sometimes. In this case, Si can be added to the first layer by continuing to supply the _SiH4 gas even after stopping the supply of the _TiCl4 gas, as in this modification, and the Si concentration in the first layer can be further increased to can be increased. In addition, even if there are no Si adsorption sites in the first layer at the time when the supply of the two kinds of gases is stopped at the same time, SiH ₄ gas remains unchanged even after the supply of the TiCl ₄ gas is stopped, as in this modification. By continuing to supply the gas, Cl existing on the surface of the first layer can be replaced with Si, and the Si concentration in the first layer can be further increased. As a result of these, it becomes possible to further increase the Si concentration of the TiSiN film and further enhance the F barrier effect exhibited by this film. The inventors have found that if the supply of TiCl ₄ gas and the supply of SiH ₄ gas are stopped at the same time in step 1, the Si concentration of the first layer may become, for example, ₃ to 5 at %. It has been confirmed that the Si concentration of the first layer can be increased to, for example, 20 to 30 atomic % 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 film quality of the TiSiN film can be further improved. In addition, it is possible to more reliably remove HCl and the like from inside 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), in step 1, the supply of _TiCl4 gas is started before the supply of _SiH4 gas, and the supply of _TiCl4 gas and the supply of _SiH4 gas are stopped at the same time. may

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

Further, according to this modification, the conductivity of the TiSiN film formed on the wafer 200 can be evenly secured over the entire 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 to have a substantially uniform thickness over the entire surface of the wafer 200 . It can be formed continuously (non-island and non-mesh). In this modification, by starting the supply of the SiH ₄ gas after the surface of the wafer 200 is in such a state, Ti can always be present at all locations on the wafer 200 to which the SiH ₄ gas is supplied. It is possible to form a Ti--Si--N bond or a Ti--Si--Ti bond at any point within the surface of the wafer 200. FIG. In this way, by continuously forming chemical bonds containing Ti, which is a conductive metal element, over the entire surface of the wafer 200, the conductivity of the TiSiN film is evenly secured over the entire surface of the wafer 200. becomes possible.

On the other hand, if the supply of SiH ₄ gas is started before the supply of TiCl ₄ gas in step 1, it is 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 formed in step 2 and remaining on the surface of the wafer 200, etc. Insulating Si ₃ N ₄ may be formed discontinuously (island-like or mesh-like) on the surface of the wafer 200 by reacting with the SiH ₄ supplied in step 1. . In this case, in the portion where Si ₃ N ₄ is formed, N is bonded to all Si bonds like N—Si—N bonds, and Ti—Si—N bonds and Ti—Si - Ti bond, ie, it becomes difficult to form a new chemical bond containing Ti, which is a conductive metal element. As a result, the conductivity of the TiSiN film may be locally reduced within the plane of the wafer 200 .

Further, according to this modification, it is possible to appropriately suppress the amount of Si added to the TiSiN film. By keeping the Si concentration of the TiSiN film appropriately low, it is possible to improve the step coverage of the TiSiN film. The inventors found that when the Si concentration of the TiSiN film is 20%, the step coverage may be about 75.2%. It has already been confirmed that there are cases where it is possible to increase it further. Note that this phenomenon is similarly obtained in other modifications in which the SiH ₄ gas exposure amount of the wafer 200 is suppressed.

(Modification 3)
As shown in FIG. 5(c), in step 1, the supply of _TiCl4 gas is started before the supply of _SiH4 gas, and the supply of _TiCl4 gas is stopped before the supply of _SiH4 gas. can be Also in this modification, the same effects as those of the film formation sequence shown in FIG. 4 and modifications 1 and 2 can be obtained.

(Modification 4)
As shown in FIG. 6A, 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 before starting the supply of the SiH ₄ gas may be lower than the supply flow rate of the 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, It is possible to appropriately secure the adsorption site of Si in and 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 supply flow rate of the TiCl ₄ gas in step 1 as described above, the amount of Cl and H remaining in the first layer can be further reduced, and by-products such as HCl are generated. can be made smaller. Further, according to this modification, even if the execution period of the SiH ₄ gas supply process that is continuously performed after stopping the supply of the TiCl ₄ gas is shortened, it is possible to sufficiently increase the Si concentration of the TiSiN film. Therefore, the time required for one cycle can be shortened, and the productivity of the film forming process can be improved.

(Modification 5)
As shown in FIG. 6B, 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 the fourth modification. Furthermore, the supply flow rate of SiH ₄ gas after stopping the supply of TiCl ₄ gas may be lower than the supply flow rate of SiH ₄ gas before stopping the supply of TiCl ₄ gas.

Also in this modified example, the same effects as those of the film forming sequence shown in FIG. 4 and modified examples 3 and 4 can be obtained. In addition, by setting the supply flow rate of the SiH ₄ gas as described above, after stopping the supply of the TiCl ₄ gas, the addition of Si into the first layer is performed softly. Si can be added more uniformly over the entire area of .

(Modification 6)
As shown in FIG. 6C, 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 SiH ₄ gas may be controlled in the same manner 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. In addition, as in Modification 5, the addition of Si into the first layer is performed softly after stopping the supply of TiCl ₄ gas, and Si is added more uniformly over the entire first layer. becomes possible.

(Modification 7)
As shown in FIG. 7A, 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 before starting the supply of the SiH ₄ gas may be larger than the supply flow rate of the 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 supply flow rate of the TiCl ₄ gas in step 1 as described above, the effect described in modification 2 can be obtained more reliably.

(Modification 8)
As shown in FIG. 7B, 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 the seventh modification. Furthermore, the supply flow rate of SiH ₄ gas after stopping the supply of TiCl ₄ gas may be higher than the flow rate of SiH ₄ gas before stopping the supply of TiCl ₄ gas. Also in this modified example, the same effect as in the film forming sequence shown in FIG. 4 and in Modified Example 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 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 the seventh modification, and the supply flow rate of the SiH ₄ gas may be controlled in the same manner as in the fifth modification. 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, 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 SiH ₄ gas may be controlled in the same manner as in the eighth 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, by setting the supply flow rate of the SiH ₄ gas in step 1 as described above, the effect described in modification 1 can be obtained more reliably.

(Modification 11)
As shown in FIG. 8B, 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 the fourth modification, and the supply flow rate of the SiH ₄ gas may be controlled in the same manner as in the eighth modification. Also in this modification, effects similar to 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 modifications described above, the processing conditions when SiH ₄ gas is supplied alone are as follows.

The pressure inside the processing chamber 201 is set to a predetermined pressure within a range of 1 to 3000 Pa, for example. In addition, the SiH ₄ gas is supplied at a predetermined flow rate, for example, in the range of 0.001 to 2 slm, preferably 0.05 to 1.5 slm, 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. Also, the supply flow rate of the N ₂ gas supplied from each gas supply pipe is set to a predetermined flow rate within a range of 0 to 10 slm, for example.

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

The pressure inside the processing chamber 201 is set to a predetermined pressure within a 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, 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 set at a predetermined flow rate within the range of 0.1 to 20 slm, for example.

Other processing conditions are the same as those of the film formation sequence shown in FIG. By setting the various processing conditions within the ranges described above, it is possible to appropriately obtain effects corresponding to the respective modifications.

<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 embodiments, and various modifications can be made without departing from the spirit of the present invention.

For example, as in the film formation sequence described below, a hydrocarbon-based gas such as propylene (C ₃ H ₆ ) gas, that is, a C-containing gas, is used as the reaction gas, and Ti, Si, and C are deposited on the wafer 200. A titanium carbide film (TiSiC film) may be formed as the containing film. Even in this case, effects similar to those of the above-described embodiment can be obtained. In addition, by doping the film with C, it is possible to lower the work function of the film.

(TiCl ₄ +SiH ₄ →C ₃ H ₆ )×n ⇒ TiSiC

Further, for example, as in the film formation sequence described below, the reaction gas may be an amine-based gas such as triethylamine ((C ₂ H ₅ ) ₃ N), abbreviation: TEA), or dimethylhydrazine ((CH ₃ ) ₂ N ₂ H ₂ (abbreviation: DMH) or other organic hydrazine-based gas, that is, a gas containing N and C, is used to form a titanium carbonitride film (TiSiCN film) on the wafer 200 as a film containing Ti, Si, C, and N. ) may be formed. Alternatively, a TiSiCN film may be formed on the wafer 200 by combining a plurality of types of reaction gases. Even in these cases, effects similar to those of the above-described embodiments can be obtained. In addition, by doping the film with C, it is possible to lower the work function of the film.

(TiCl ₄ +SiH ₄ →TEA)×n ⇒ TiSiCN

( _TiCl4 + _SiH4 →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, examples of forming a film containing Ti as a metal element on a substrate have been described, but the present invention is not limited to such aspects. That is, in addition to Ti, the present invention provides zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), yttrium (Y), lanthanum (La), It can also be suitably applied when a film containing metal elements such as strontium (Sr), aluminum (Al), chromium (Cr), vanadium (V), and gallium (Ga) is formed on a substrate. Moreover, although the present invention has been described as 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 also suitable for forming on a substrate a film containing other elements such as germanium (Ge), boron (B), arsenic (As), phosphorus (P), and Al, in addition to Si. can be applied to

The present invention also applies to the case of forming a film containing a metalloid element such as Si, Ge, or B instead of a metal element, that is, forming an insulating film instead of a conductive film, as in the film formation sequence described below. Even in the case, it is possible to apply preferably. In this case, a halosilane source gas such as tetrachlorosilane (SiCl ₄ ) gas can be used as the first source gas. In addition to the various reaction gases described above, an O-containing gas (oxidizing agent) such as oxygen (O ₂ ) gas can be used as the reaction gas.

(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, the TiCl ₄ gas may be supplied all at once by flash flow into the depressurized processing chamber 201 while the APC valve 244 is closed. For example, a first tank (gas reservoir) configured as a pressurized container is provided on the upstream side of the valve 243a in the gas supply pipe 232a. The high-pressure TiCl ₄ gas filled in the chamber 201 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 time required for step 1 and improve the productivity of the film formation process.

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

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

Further, by supplying the NH ₃ gas in this manner, by-products present in the processing chamber 201 can be rapidly discharged from the processing chamber 201 . As a result, it is possible to suppress 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 performing step 2, Cl adsorbed on the surface of the first layer is converted to NH ₃ gas. It is also generated by substituting with the included N. HCl as a by-product may react with the NH ₃ gas supplied in step 2 to produce new by-products such as NH ₄ Cl. On the other hand, by supplying NH ₃ gas by flash flow, HCl can be discharged from the processing chamber 201 before by-products such as NH ₄ Cl are newly generated. As a result, it becomes possible to suppress the incorporation of NH ₄ Cl and the like into the TiSiN film.

Further, in this embodiment, the case where 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 has been described. In this way, when various gases are supplied independently using different nozzles, the nozzle 249a for supplying the first raw material gas and the nozzle 249b for supplying the second raw material gas are arranged as close as possible. is good. By configuring in this way, it is possible to efficiently mix the first source gas and the second source gas. As a result, the composition and quality of the film formed on the wafer 200 can be made uniform over the surface.

Further, in this embodiment, the case where 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 has been described. However, the invention is not limited to such embodiments. For example, the nozzle 249a that supplies the first source gas and the nozzle 249b that supplies the second source gas may be shared, and two nozzles may be provided in the processing chamber 201 . With this configuration, it is possible to efficiently mix (premix) the first source gas and the second source gas in the nozzle. As a result, the composition and quality of the film formed on the wafer 200 can be made uniform over the surface.

Recipes used for substrate processing are preferably prepared individually according to the processing contents and stored in the storage device 121c via an electric communication 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 among the plurality of recipes stored in the storage device 121c according to the processing content. As a result, a single substrate processing apparatus can form films having various film types, composition ratios, film qualities, and film thicknesses with good reproducibility. In addition, the burden on the operator can be reduced, and substrate processing can be started quickly while avoiding operational errors.

The recipe described above is not limited to the case of newly creating the recipe, but may be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus, for example. 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. Alternatively, an existing recipe already installed in the substrate processing apparatus may be directly changed by operating the input/output device 122 provided in the existing substrate processing apparatus.

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

For example, the present invention can be suitably applied to the case of forming a film using a substrate processing apparatus having a processing furnace 302 shown in FIG. The processing furnace 302 includes a processing chamber 303 forming a processing chamber 301, a shower head 303s supplying gas into the processing chamber 301 in a shower-like manner, and a support base 317 supporting one or several wafers 200 in a horizontal posture. , a rotating shaft 355 that supports the support table 317 from below, and a heater 307 provided on the support table 317 . Gas supply ports 332a to 332c are connected to the inlet of the shower head 303s. The gas supply ports 332a, 332b, and 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 embodiments, respectively. A gas distribution plate is provided at the outlet of the showerhead 303s. The processing container 303 is provided with an exhaust port 331 for exhausting the inside of the processing chamber 301 . The exhaust port 331 is connected to an exhaust system similar to the exhaust system of the above-described embodiment.

Also, for example, the present invention can be suitably applied to the case of forming a film using a substrate processing apparatus having a processing furnace 402 shown in FIG. The processing furnace 402 includes a processing chamber 403 forming a processing chamber 401, a support base 417 supporting one or several wafers 200 in a horizontal position, a rotary shaft 455 supporting the support base 417 from below, and a processing chamber 401. A lamp heater 407 for irradiating light toward the wafer 200 in 403 and a quartz window 403w for transmitting the light from the lamp heater 407 are provided. Gas supply ports 432 a to 432 c are connected to the processing container 403 . The gas supply ports 432a, 432b, and 432c are connected to gas supply systems similar to the first raw material gas supply system, the second raw material gas supply system, and the reaction gas supply system of the above embodiments, respectively. The gas supply ports 432a to 432c are provided on the sides of the wafers 200 loaded into the processing chamber 401, respectively. The processing container 403 is provided with an exhaust port 431 for exhausting the inside of the processing chamber 401 . The exhaust port 431 is connected to an exhaust system similar to the exhaust system of the above-described embodiment.

Even when these substrate processing apparatuses are used, the film formation process can be performed under the same processing procedures and processing conditions as those of the above-described embodiment and modifications, and the same effects as those of the above-described embodiments and modifications can be obtained. be done.

Also, the above-described embodiments, modifications, and the like can be used in combination as appropriate. The processing procedure and processing conditions at this time can be, for example, the same as the processing procedures and processing conditions of the above-described embodiment.

Experimental results that support the effects obtained in the above-described embodiments and modifications will be described below.

(Example 1)
As Example 1, a TiSiN film was formed on a wafer according to the sequence shown in FIG. 4 using the substrate processing apparatus of the above-described embodiment. The processing conditions for the film forming process were predetermined conditions within the range of the processing conditions described in the above-described embodiment.

Further, as Comparative Example 1a _, a _TiSiN film was formed _on the wafer by repeating the sequence shown in FIG. formed.

Further, as Comparative _{Example 1b ,} the sequence shown in FIG. An alternating sequence formed a TiSiN film on the wafer.

Then, the composition and resistivity of each TiSiN film formed in Example 1 and Comparative Examples 1a and 1b were measured. The composition was measured using an X-ray photoelectron spectroscopy (XPS) method. FIG. 12(a) shows a list of compositions and resistivities in the films of Example 1 and Comparative Examples 1a and 1b. As can be seen from FIG. 12(a), the TiSiN film of Example 1 does not have a large difference in the content of Ti, N and Si compared to the TiSiN films of Comparative Examples 1a and 1b. In addition, it can be seen that the TiSiN film of Example 1 has a remarkably low resistivity, that is, has good conductivity, as compared with the TiSiN films of Comparative Examples 1a and 1b. This is probably 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 has a lower impurity concentration than the film formed by the sequence shown in FIGS. I understand. In addition, since 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. I know it will be.

(Examples 2a-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 of the above-described embodiment. Further, as Examples 2b to 2d, a TiSiN film was formed on a wafer using the substrate processing apparatus of the above-described embodiment according to the sequence shown in FIG. 5(a). The processing conditions were common conditions within the range of the processing conditions described in the above embodiments. In Examples 2b to 2d, the supply flow rate of the SiH ₄ gas continuously supplied after stopping the supply of the TiCl ₄ gas was set to 0.225 slm, and the supply times were set to 6, 10, and 16 seconds, respectively.

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

Then, the composition of each film formed in Examples 2a to 2d and Comparative Example 2 was measured using the XPS method. FIG. 12(b) shows a list of compositions in each film of Examples 2a to 2d and Comparative Example 2. As shown in FIG. As can be seen from FIG. 12B, the TiSiN films of Examples 2a to 2d have lower Cl concentrations than the TiN film of Comparative Example 2. FIG. Also, it can be seen that the TiSiN films of Examples 2b to 2d have lower Cl concentrations than the TiSiN film of Example 2a. It is also found that the Cl concentration of the film decreases as the supply time of the SiH ₄ gas continuously supplied after stopping the supply of the TiCl ₄ gas, that is, the exposure amount of the SiH ₄ gas to the wafer is increased.

(Examples 3a and 3b)
As Examples 3a and 3b, the substrate processing apparatus of the above embodiment was used, and the process of forming a TiSiN film on the wafer was performed multiple times according to the sequence shown in FIG. 5(a). The processing conditions were common conditions within the range of the processing conditions described in the above embodiments. The film thickness was changed within the range of 30 Å to 100 Å each time film formation was performed. The supply flow rate of the SiH ₄ gas continuously supplied after stopping the supply of the TiCl ₄ gas was set to 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, the process of forming a TiN film on the wafer was performed multiple times by repeating the cycle of alternately supplying TiCl ₄ gas and NH ₃ gas to the wafer. As in Examples 3a and 2b, the film thickness was changed within the range of 30 Å to 100 Å each time film formation was performed.

Then, the resistivity of each film formed in Examples 3a and 3b and Comparative Example 3 was measured. The results are shown in FIG. In FIG. 13, the horizontal axis indicates film thickness (Å), and the vertical axis indicates resistivity (μΩcm). In the figure, ▪, ●, and ♦ marks indicate Examples 3a and 3b and Comparative Example 3, respectively. It can be seen from FIG. 13 that the films of Examples 3a and 3b exhibit similar or lower resistivities than the films of Comparative Example 3, at least at film thicknesses in the range of 30-40 Å.

200 wafer (substrate)
201 processing chamber

Claims (13)

While evacuating the space in which the substrate exists, 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 applied to the substrate. By starting the supply of the first raw material gas before the supply of the second raw material gas and supplying the first raw material gas and the second raw material gas so that at least a part of each supply period overlaps, the first raw material gas and the second raw material gas a first step of forming a layer containing the metal element by reacting the gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the space in which the substrate exists;
forming a film containing the metal element on the substrate by performing a predetermined number of cycles of non-simultaneously performing
In the first step,
producing a by-product containing a molecule composed of the halogen element and hydrogen;
The generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the space in which the substrate exists, and are further reacted with the second raw material gas to produce the halogen element and the other element. A method of manufacturing a semiconductor device that converts to by-products containing constituent molecules. While evacuating the space in which the substrate exists, 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 applied to the substrate, respectively. and by stopping the supply of the first raw material gas before the supply of the second raw material gas , the first raw material gas and the second raw material gas a first step of forming a layer containing the metal element by reacting the gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the space in which the substrate exists;
forming a film containing the metal element on the substrate by performing a predetermined number of cycles of non-simultaneously performing
In the first step,
producing a by-product containing a molecule composed of the halogen element and hydrogen;
The generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the space in which the substrate exists, and are further reacted with the second raw material gas to produce the halogen element and the other element. A method of manufacturing a semiconductor device that converts to by-products containing constituent molecules. 2. The method of manufacturing a semiconductor device according to claim 1, wherein said reactive gas is a gas containing nitrogen. The first raw material 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,
forming a TiSiN film on the substrate
4. The method of manufacturing a semiconductor device according to claim 3 . The Ti-containing gas is a chlorotitanium-based gas,
5. The method of manufacturing a semiconductor device according to claim 4 , wherein said Si-containing gas is a silicon hydride gas. The Ti-containing gas is tetrachlorotitanium gas,
5. The method of manufacturing a semiconductor device according to claim 4 , wherein said Si-containing gas is monosilane gas. 7. The method of manufacturing a semiconductor device according to claim 1 , wherein said first step is performed under conditions in which said first source gas and said second source gas do not react in a gas phase. . While evacuating the space in which the substrate exists, 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 applied to the substrate. By starting the supply of the first raw material gas before the supply of the second raw material gas and supplying the first raw material gas and the second raw material gas so that at least a part of each supply period overlaps, the first raw material gas and the second raw material gas a first step of forming a layer containing the metal element by reacting the gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the space in which the substrate exists;
forming a film containing the metal element on the substrate by performing a predetermined number of cycles of non-simultaneously performing
In the first step,
producing a by-product containing a molecule composed of the halogen element and hydrogen;
The generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the space in which the substrate exists, and are further reacted with the second raw material gas to produce the halogen element and the other element. A method of processing a substrate that converts it to a by-product containing constituent molecules. While evacuating the space in which the substrate exists, 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 applied to the substrate, respectively. and by stopping the supply of the first raw material gas before the supply of the second raw material gas, the first raw material gas and the second raw material gas a first step of forming a layer containing the metal element by reacting the gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the space in which the substrate exists;
forming a film containing the metal element on the substrate by performing a predetermined number of cycles of non-simultaneously performing
In the first step,
producing a by-product containing a molecule composed of the halogen element and hydrogen;
The generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the space in which the substrate exists, and are further reacted with the second raw material gas to produce the halogen element and the other element. A method of processing a substrate that converts it to a by-product containing constituent molecules. a processing chamber containing the substrate;
a gas supply system 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 to the substrate in the processing chamber; ,
an exhaust system for exhausting the inside of the processing chamber;
While evacuating the inside of the processing chamber, the first source gas and the second source gas are supplied to the substrate before the supply of the first source gas is started, and and supplying the first source gas and the second source gas so as to overlap at least part of the respective supply periods, thereby forming the layer containing the metal element by reacting the first source gas and the second source gas on the surface of the substrate. and a second process of supplying the reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while evacuating the inside of the processing chamber. and are performed non-simultaneously a predetermined number of times to control the gas supply system and the exhaust system so as to form a film containing the metal element on the substrate. a control unit;
with
In the first process, by-products containing molecules composed of the halogen element and hydrogen are generated, and the generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the processing chamber. and further reacting with the second source gas to convert to by-products containing molecules composed of the halogen element and the other element. a processing chamber containing the substrate;
a gas supply system 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 to the substrate in the processing chamber; ,
an exhaust system for exhausting the inside of the processing chamber;
While evacuating the inside of the processing chamber, the first source gas and the second source gas are supplied to the substrate so that at least a part of each supply period overlaps, and the supply of the first source gas is performed. By stopping the supply before the supply of the second source gas, the first source gas and the second source gas are reacted on the surface of the substrate to form the layer containing the metal element. a first process, and a second process of supplying the reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while evacuating the inside of the processing chamber. a control unit configured to be capable of controlling the gas supply system and the exhaust system so as to form a film containing the metal element on the substrate by performing non-simultaneous cycles a predetermined number of times;
with
In the first process, by-products containing molecules composed of the halogen element and hydrogen are generated, and the generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the processing chamber. and further reacting with the second source gas to convert to by-products containing molecules composed of the halogen element and the other element. In the processing chamber of the substrate processing apparatus,
While evacuating the inside of the processing chamber, a first raw material gas containing a metal element and a halogen element and a second raw material gas containing hydrogen and an element different from the metal element are applied to the substrate accommodated in the processing chamber. and starting the supply of the first source gas before the supply of the second source gas, and supplying the first source gas and the a first step of forming a layer containing the metal element by reacting the second source gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the inside of the processing chamber;
is performed a predetermined number of times, thereby forming a film containing the metal element on the substrate,
In the first step, by-products containing molecules composed of the halogen element and hydrogen are generated, and the generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the processing chamber. A program for causing the substrate processing apparatus to execute a procedure of reacting with the second raw material gas and converting the by-products containing molecules composed of the halogen element and the other element into a by-product containing the halogen element and the other element. In the processing chamber of the substrate processing apparatus,
While evacuating the inside of the processing chamber, a first raw material gas containing a metal element and a halogen element and a second raw material gas containing hydrogen and an element different from the metal element are applied to the substrate accommodated in the processing chamber. and are supplied so that at least a part of the respective supply periods overlap, and the supply of the first source gas is stopped before the supply of the second source gas, so that the first source gas and the a first step of forming a layer containing the metal element by reacting the second source gas on the surface of the substrate;
a second step of supplying a reaction gas that reacts with the layer containing the metal element to the substrate on which the layer containing the metal element is formed while exhausting the inside of the processing chamber;
is performed a predetermined number of times, thereby forming a film containing the metal element on the substrate,
In the first step, by-products containing molecules composed of the halogen element and hydrogen are generated, and the generated by-products containing molecules composed of the halogen element and hydrogen are exhausted from the processing chamber. A program for causing the substrate processing apparatus to execute a procedure of reacting with the second raw material gas and converting the by-products containing molecules composed of the halogen element and the other element into a by-product containing the halogen element and the other element.

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