Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and program

Abstract

The invention provides a technology capable of improving uniformity of film thickness and embedding characteristics in film formation. The present invention performs a cycle for a predetermined number of times on a substrate, the cycle performing the following steps in this order: (a) a step for supplying a first modifying gas, which is an inorganic halogen element-containing gas; (b) a step for supplying a starting material gas; (c) a step for supplying a second modifying gas, which is an inorganic halogen element-containing gas; and (d) a step for supplying a reaction gas.

Description

Technical Field

[0001] The present disclosure relates to a substrate processing method, a method for manufacturing a semiconductor device, a substrate processing apparatus, and a program. Background Art

[0002] As device shapes have become increasingly miniaturized and complex in recent LSI manufacturing processes, higher step coverage and higher embedding characteristics have been required in film formation (see, for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-69407 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present disclosure provides a technology that can improve the uniformity of film thickness and embedding characteristics during film formation.

[0008] Other objects and novel features will become apparent from the description of this specification and the accompanying drawings.

[0009] Technical means of solving problems

[0010] According to one embodiment of the present invention, a technology is provided, which cycles a substrate a predetermined number of times, wherein the cycles sequentially (in this order) perform the following steps: (a) a step of supplying a first modifying gas which is an inorganic halogen-containing gas; (b) a step of supplying a raw material gas; (c) a step of supplying a second modifying gas which is an inorganic halogen-containing gas; and (d) a step of supplying a reaction gas.

[0011] Effects of the Invention

[0012] According to the present disclosure, in film formation, uniformity of film thickness and embedding characteristics can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG. 1 is a longitudinal sectional view showing a schematic structure of a vertical processing furnace of a substrate processing apparatus according to an embodiment of the present disclosure.

[0014] FIG. 2 is a schematic structural diagram of a controller of a substrate processing apparatus according to an embodiment of the present disclosure, and is a diagram showing a control system of the controller in the form of a block diagram.

[0015] FIG. 3 is a diagram illustrating a substrate processing method according to an embodiment of the present disclosure.

[0016] FIG. 4 is a diagram showing the supply amount of each gas in a film forming sequence according to an embodiment of the present disclosure.

[0017] FIG. 5 is a diagram illustrating execution of the substrate processing method of FIG. 3 .

[0018] FIG. 6 is a graph showing partial pressures of various gases in a film forming sequence according to an embodiment of the present disclosure.

[0019] FIG. 7 is a diagram showing a film formation sequence according to the first modification example.

[0020] FIG. 8 is a diagram showing a film formation sequence according to the second modification example.

[0021] FIG. 9 is a diagram showing a film formation sequence according to a third modification example.

[0022] FIG. 10 is a diagram showing a film formation sequence according to a fourth modification.

[0023] FIG. 11 is a diagram showing a film formation sequence according to the fifth modification example. DETAILED DESCRIPTION

[0024] The following description is provided using the accompanying drawings. However, in the following description, the same structural elements are sometimes given the same figure marks and their repeated description is omitted. In addition, in order to make the description clearer, the accompanying drawings are sometimes only schematically represented compared to the actual method, but they are only examples and do not limit the interpretation of the present invention. In addition, the accompanying drawings used in the following description are all schematic, and the dimensional relationship of each element shown in the accompanying drawings, the ratio of each element, etc. may not always be consistent with the actual ones. In addition, the dimensional relationship of each element, the ratio of each element, etc. may not always be consistent between multiple drawings.

[0025] Hereinafter, a preferred embodiment of the present invention will be described using the accompanying drawings. The substrate processing device 10 is configured as an example of a device, which is used in a process of manufacturing a semiconductor device (component), namely, a substrate processing process. First, the substrate processing device used in the embodiment will be described. Specifically, the substrate processing device is a manufacturing device for a semiconductor device, and is used in a process of manufacturing a semiconductor device. In the following description, a substrate processing device that performs film forming processing on multiple substrates (wafers) at a time is used as an example of a substrate processing device, and the structure is described.

[0026] (1) Structure of substrate processing apparatus

[0027] FIG. 1 is a schematic structural diagram of a vertical type processing furnace of a substrate processing device of the present invention, and is a longitudinal sectional view of a portion of the processing furnace. As shown in FIG. 1 , the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 is cylindrical and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas with heat.

[0028] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is configured to engage with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the tube of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0029] In the processing chamber 201, nozzles 249a to 249e as the first to fifth supply parts are respectively arranged to penetrate the side walls of the manifold 209. In FIG. 1, three nozzles, nozzles 249a to 249c, are depicted. Since two nozzles, nozzles 249d to 249e, would complicate the drawing, their illustration is omitted. Nozzles 249a to 249e are also referred to as the first to fifth nozzles. Nozzles 249a to 249e are made of, for example, heat-resistant materials such as quartz or SiC. Gas supply pipes 232a to 232e are respectively connected to nozzles 249a to 249e. Nozzles 249a to 249e are different nozzles.

[0030] In the gas supply pipes 232a~232e, mass flow controllers (MFC) 241a~241e as flow controllers (flow control units) and valves 243a~243e as opening and closing valves are respectively provided in order from the upstream side of the airflow. Gas supply pipes 232f~232j are respectively connected to the downstream side of the gas supply pipes 232a~232e than the valves 243a~243e. In the gas supply pipes 232f~232j, MFCs 241f~241j and valves 243f~243j are respectively provided in order from the upstream side of the airflow. The gas supply pipes 232a~232j are made of metal materials such as SUS, for example.

[0031] The nozzles 249a to 249e are respectively arranged in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a top view, and stand upward along the inner wall of the reaction tube 203 from the bottom to the top, with the arrangement direction of the wafer 200 facing upward. That is, the nozzles 249a to 249e are respectively arranged along the wafer arrangement area in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged. Gas supply holes 250a to 250d for supplying gas are respectively provided on the side of the nozzles 249a to 249e. The gas supply holes 250a to 250d are respectively opened in a manner opposite to (face to face with) the exhaust port 231a in a top view, and are capable of supplying gas to the wafer 200. A plurality of gas supply holes 250a to 250d are provided from the bottom to the top of the reaction tube 203.

[0032] From the gas supply pipe 232a, the raw material gas is supplied into the processing chamber 201 via the MFC241a, the valve 243a, and the nozzle 249a as a processing gas. The raw material gas is, for example, a halogen-containing gas (halogen gas) containing a halogen element, and for example, a gas containing a metal element (metal-containing gas) can be used. Here, the halogen element is, for example, fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). The halogen-containing gas can use, for example, a chloride gas containing Cl. When the term "raw material" is used in this specification, it sometimes refers to "liquid raw material in a liquid state", sometimes refers to "raw material gas in a gaseous state", or sometimes refers to both.

[0033] From the gas supply pipe 232b, the first modifying gas (also referred to as the first film formation inhibiting gas or the first inhibitor) of the inorganic halogen-containing gas is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b. The first modifying gas is, for example, a halogen-containing gas, such as a hydrogen halide gas.

[0034] From the gas supply pipe 232c, a reaction gas is supplied as a processing gas into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c. For example, a nitrogen (N)-containing gas (nitriding gas, nitriding agent) can be used as the reaction gas.

[0035] From the gas supply pipe 232d, a second modified gas (also referred to as a second film formation inhibiting gas or a second inhibitor) as an inorganic halogen-containing gas is supplied into the processing chamber 201 via the MFC 241d, the valve 243d, and the nozzle 249d. The second modified gas is, for example, a halogen-containing gas, such as a hydrogen halide gas.

[0036] The etching gas is supplied from the gas supply pipe 232 e into the processing chamber 201 via the MFC 241 e , the valve 243 e , and the nozzle 249 e .

[0037] From the gas supply pipes 232f to 232j, inert gas such as nitrogen (N2) is supplied into the processing chamber 201 via the MFCs 241f to 241j, valves 243f to 243j, and nozzles 249a to 249e. The N2 gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0038] The raw material gas supply system is mainly composed of a gas supply pipe 232a, MFC241a, and a valve 243a. The first modified gas supply system is mainly composed of a gas supply pipe 232b, MFC241b, and a valve 243b. The reaction gas supply system is mainly composed of a gas supply pipe 232c, MFC241c, and a valve 243c. The second modified gas supply system is mainly composed of a gas supply pipe 232d, MFC241d, and a valve 243d. The etching gas supply system is mainly composed of a gas supply pipe 232e, MFC241e, and a valve 243e. The inert gas supply system is mainly composed of gas supply pipes 232f~232j, MFC241f~241j, and valves 243f~243j.

[0039] In addition, the first modified gas and the second modified gas may be set to the same modified gas. In this case, the nozzle 249d of the second modified gas supply system may be set to be unused, and only the nozzle 249b of the first modified gas supply system may be used to supply the first modified gas and the second modified gas into the processing chamber 201. When this structure is adopted, the second modified gas supply system (gas supply pipe 232d, MFC241d, valve 243d) and the inert gas supply system composed of the gas supply pipe 232i, MFC241i, and valve 243i can be deleted from the substrate processing apparatus shown in FIG. 1, thereby simplifying the structure of the substrate processing apparatus.

[0040] Among the various supply systems described above, any one or all of the supply systems may also be configured as an integrated supply system 248 in which valves 243a to 243j, MFCs 241a to 241j, etc. are integrated. The integrated supply system 248 is configured to be connected to the gas supply pipes 232a to 232j, respectively, and to control the supply of various gases into the gas supply pipes 232a to 232j, i.e., the opening and closing of the valves 243a to 243j or the flow rate adjustment performed by the MFCs 241a to 241j, etc., through the controller 121 described later.

[0041] An exhaust port 231a for exhausting the ambient gas in the processing chamber 201 is provided below the side wall of the reaction tube 203. The exhaust port 231a is provided at a position opposite (face to face) to the nozzles 249a~249e (gas supply holes 250a~250e) across the wafer 200. The exhaust port 231a can also be provided along the side wall of the reaction tube 203 from the bottom to the top, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust and vacuum exhaust stop in the processing chamber 201. Furthermore, while the vacuum pump 246 is in operation, the valve opening is adjusted based on pressure information detected by the pressure sensor 245, thereby enabling the pressure in the processing chamber 201 to be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable that the vacuum pump 246 is included in the exhaust system.

[0042] Below the manifold 209, a sealing cover 219 is provided as a furnace port cover body that can hermetically seal the lower end opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS, and is formed into a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b is provided as a sealing member that abuts against the lower end of the manifold 209. Below the sealing cover 219, a rotating mechanism 267 is provided to rotate the wafer boat 217 described later. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217.

[0043] The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The wafer boat elevator 115 is configured as a conveying device (conveyance mechanism) for moving the wafer 200 into and out of the processing chamber 201 by lifting and lowering the sealing cover 219. Under the manifold 209, a gate 219s as a furnace cover body is provided, which can airtightly close the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The gate 219s is formed of a metal material such as SUS, for example, and is formed in a disc shape. On the upper surface of the gate 219s, an O-ring 220c as a sealing member abutting against the lower end of the manifold 209 is provided. The opening and closing action (lifting action or rotation action, etc.) of the gate 219s is controlled by the gate opening and closing mechanism 115s.

[0044] The wafer boat 217 as a substrate support is configured to support multiple wafers 200, for example, 25 to 200 wafers, in a horizontal posture and in a state where the centers are aligned with each other in a vertical direction and in multiple stages, that is, to arrange them in a spaced manner. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the lower part of the wafer boat 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple stages. In addition, in this specification, regarding the range of numerical values, for example, when it is recorded as 25 to 200 pieces, it means 25 pieces (inclusive) or more and 200 pieces (inclusive) or less. That is, 25 pieces and 200 pieces are included in the range of numerical values. This applies not only to the number of objects, but also to all numerical values ​​recorded in this specification such as pressure, flow rate, time, and temperature.

[0045] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The power supply state of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0046] As shown in FIG2 , the controller 121 as a control unit (control unit) is configured as a computer, and is provided with a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 configured as a touch panel, etc.

[0047] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), etc. In the storage device 121c, a control program for controlling the action of the substrate processing device, and a process recipe that records the program or conditions for the substrate processing described later, etc. can be readable and stored. The process recipe is combined in a manner that enables the controller 121 to execute each program in the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, process recipes, control programs, etc. are simply collectively referred to as programs. In addition, process recipes are also referred to as recipes. When the word "program" is used in this specification, there are cases where only the recipe alone is included, only the control program alone is included, or both are included. RAM121b is configured as a memory area (work area) that temporarily stores programs or data read by CPU121a.

[0048] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241j, valves 243a to 243j, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, gate opening and closing mechanism 115s, etc.

[0049] The CPU 121a is configured to read out and execute a control program from the storage device 121c, and to read out a recipe from the storage device 121c based on input of an operation command from the input / output device 122. The CPU 121a is configured to control the following actions according to the contents of the read recipe: flow rate adjustment actions of various gases performed by the MFCs 241a to 241j, opening and closing actions of the valves 243a to 243j, opening and closing actions of the APC valve 244 and pressure adjustment actions performed by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment actions of the heater 207 based on the temperature sensor 263, rotation of the wafer boat 217 and rotation speed adjustment actions performed by the rotating mechanism 267, lifting and lowering actions of the wafer boat 217 performed by the wafer boat elevator 115, opening and closing actions of the gate 219s performed by the gate opening and closing mechanism 115s, and the like.

[0050] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, etc. The storage device 121c or the external storage device 123 is configured as a computer-readable recording medium. Hereinafter, they are also simply collectively referred to as recording media. When the term "recording medium" is used in this specification, there is a case where only the storage device 121c monomer is included, a case where only the external storage device 123 monomer is included, or a case where both are included. In addition, providing the program to the computer can also be performed without using the external storage device 123, but using a communication unit such as the Internet or a dedicated line.

[0051] (2) Substrate processing steps

[0052] Fig. 3 is a diagram for explaining a substrate processing method according to an embodiment of the present disclosure. Fig. 4 and Fig. 6 are diagrams for showing a film forming sequence according to an embodiment of the present disclosure. Fig. 5 is a diagram for explaining execution of the substrate processing method.

[0053] As a tool of a semiconductor device (module) manufacturing method (substrate processing method), an example of a process of forming a film on a substrate (wafer) having grooves (grooves, recesses, or barrel-shaped recesses) formed on the surface is described using FIGS. 3 to 6. The process of forming a film is performed in a processing chamber 201 of a substrate processing apparatus in FIG. 1. In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by a controller 121 in FIG. 2.

[0054] The preferred film formation sequence (also referred to as a sequence) of this embodiment performs a predetermined number of cycles on the wafer 200, and the cycle sequentially performs the following steps:

[0055] (a) a step of supplying a first reforming gas which is an inorganic halogen-containing gas;

[0056] (b) a step of supplying raw material gas;

[0057] (c) a step of supplying a second reforming gas which is an inorganic halogen-containing gas;

[0058] (d) A step of supplying a reaction gas.

[0059] The sequence refers to the order described as (a)->(b)->(c)->(d).

[0060] In this embodiment, the following gases are used, for example. The first reforming gas and the second reforming gas are inorganic halogen-containing gases, for example, hydrogen halide gases. The raw material gas is a gas containing a metal element as the first element. The reaction gas is, for example, a N-containing gas.

[0061] Specifically, as shown in Figure 4, the film formation sequence is to divide the time so that the first modified gas, the raw gas containing the first element, the second modified gas, and the reaction gas flow are circulated a specified number of times (n times), thereby forming a film containing the first element (also simply referred to as a film).

[0062] Here, as shown in FIG5 , there are portions that are easily accessible to gas for thin film formation and portions that are difficult to reach on the surface of the substrate (wafer) 200. The portion that is easily accessible to gas is, for example, the upper portion 301 of a concave portion (or a barrel-shaped concave portion, a groove) 300 with a high aspect ratio. The portion that is difficult for gas to reach is, for example, the bottom (deep portion) 302 of the concave portion 300 with a high aspect ratio.

[0063] As shown in FIG. 3 , the substrate processing method includes the following steps (a), (b), (P1), (c), (d), and (P2) as a film formation sequence.

[0064] (a) First reforming gas supplying step (first reaction inhibiting gas supplying step)

[0065] (b) Raw material gas supply step (halogen-based raw material gas supply step)

[0066] (P1) First residual gas removal step

[0067] (c) Second reforming gas supplying step (second reaction inhibiting gas supplying step)

[0068] (d) Reaction gas supply step (including N gas supply step)

[0069] (P2) Residual Gas Removal Step

[0070] The loop of (a), (b), (P1), (c), (d), and (P2) is executed in the order described a predetermined number of times. The predetermined number of times is, for example, n times (n is an integer greater than or equal to 1).

[0071] As shown in FIG3 , thereafter, as an etching sequence, an etching step (e) for etching the formed film may be performed, and then the film formation sequence and the etching sequence may be cycled a predetermined number of times again to form a film. At this time, the predetermined number of times is L, where L is an integer greater than 0. Here, the case where L=0 means that the etching step (e) is not performed. That is, in the substrate processing method shown in FIG3 , (e) may not be performed, and the cycle of (a), (b), (P1), (c), (d), and (P2) may be performed a predetermined number of times in the order of the description.

[0072] Fig. 5 is a diagram illustrating the execution of the substrate processing method. Here, an example is described in which a film 400 is buried inside a barrel-shaped recess 300 formed on the surface of a substrate (wafer) 200. An upper portion 301 of the recess 300 can be regarded as a portion that is easily accessible to gas, and a bottom portion 302 of the recess 300 can be regarded as a portion that is difficult for gas to reach.

[0073] In the initial film formation cycle, the film formation sequence is performed n times, thereby thinly forming the film 400 on the inner wall of the barrel-shaped recess 300. Then, the etching sequence is performed to remove the film 400 in the upper portion 301 of the recess 300 by etching. Thus, the opening of the upper portion 301 of the recess 300 is widened so that the gas can easily reach the inside of the recess 300.

[0074] If the film forming sequence and the etching sequence are cycled multiple times, the interior of the recess 300 is gradually filled with the film 400 as shown in state A in FIG5 . Finally, as shown in state B, the interior of the recess 300 is completely filled with the film 400 .

[0075] In this specification, "performing a process (or process, cycle, step, etc.) a predetermined number of times" means that the process, etc. is performed once or more times. That is, it means performing the process more than once. FIG. 5 shows an example in which each process of the film formation sequence is repeated for n cycles, and each process of the film formation sequence and the etching sequence is repeated for L cycles. The value of n and the value of L are appropriately selected according to the film thickness required in the film finally formed. That is, the number of times each of the above processes is performed is determined according to the film thickness set as the target.

[0076] In this specification, "time division" means to divide in time. For example, in this specification, performing each process in time division means performing each process asynchronously, that is, not synchronously. In other words, it means performing each process intermittently (in pulses). That is, it means that the process gas supplied in each process is supplied in a manner that does not mix with each other. When each process is performed multiple times in time division, the process gas supplied in each process is supplied alternately in a manner that does not mix with each other.

[0077] In this specification, when the word "wafer" is used, it sometimes refers to "the wafer itself", or sometimes refers to "a laminate (assembly) of a wafer and a predetermined layer or film formed on its surface" (that is, the case where the predetermined layer or film formed on the surface is included and is referred to as a wafer). In addition, in this specification, when the word "the surface of the wafer" is used, it sometimes refers to "the surface (exposed surface) of the wafer itself", or refers to "the surface of a predetermined layer or film formed on the wafer, that is, the outermost surface of the wafer as a laminate". In this specification, the use of the word "substrate" is the same as the use of the word "wafer".

[0078] Therefore, in this specification, when it is stated that “a prescribed gas is supplied to the wafer”, it may mean “a prescribed gas is directly supplied to the surface (exposed surface) of the wafer itself”, or it may mean “a prescribed gas is supplied to the layer or film formed on the wafer, that is, to the outermost surface of the wafer as a laminated body”. In addition, in this specification, when it is stated that “a prescribed layer (or film) is formed on the wafer”, it may mean “a prescribed layer (or film) is directly formed on the surface (exposed surface) of the wafer itself”, or it may mean “a prescribed layer (or film) is formed on the layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminated body”.

[0079] In this specification, the processing temperature refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the time during which the processing is continued. This also applies to the following description.

[0080] Hereinafter, the substrate processing method of FIG. 3 will be described in detail.

[0081] (Substrate loading process)

[0082] In the substrate carrying step, (wafer loading and wafer boat loading) and (pressure adjustment and temperature adjustment) are performed.

[0083] (Wafer loading and wafer boat loading)

[0084] When a plurality of wafers 200 are loaded (wafer loading) into the wafer boat 217, the gate 219s is moved by the gate opening and closing mechanism 115s, and the lower end opening of the manifold 209 is opened (gate opening). Then, as shown in FIG. 1 , the wafer boat 217 supporting the plurality of wafers 200 is lifted by the wafer boat elevator 115 and moved into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b.

[0085] (Pressure adjustment and temperature adjustment)

[0086] The vacuum pump 246 performs vacuum exhaust (decompression exhaust) so that the space in the processing chamber 201, that is, the space where the wafer 200 is located, becomes the desired pressure (vacuum degree). 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. In addition, the heater 207 performs heating so that the wafer 200 in the processing chamber 201 becomes the desired processing temperature. At this time, the power-on status of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes the desired temperature distribution. In addition, the rotation mechanism 267 starts to rotate the wafer 200. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0087] (Film Formation Step)

[0088] Next, the film forming step is performed. The film forming step includes the following (a) first modified gas supply step (first reaction inhibiting gas supply step), (b) raw material gas supply step (halogen-based raw material gas supply step), (P1) first residual gas removal step, (c) second modified gas supply step (second reaction inhibiting gas supply step), (d) reaction gas supply step (N-containing gas supply step), (P2) residual gas removal step. Here, steps (a) to (P2) are performed a specified number of times. In addition, in this example, after steps (a) to (P2) are performed a specified number of times, the etching step (e) is performed.

[0089] (a) First reforming gas supplying step (first reaction inhibiting gas supplying step)

[0090] First, open valve 243b, and flow the first modified gas (first inorganic halogen-containing gas, first reaction-inhibiting gas) into gas supply pipe 232b. The first modified gas flowing in gas supply pipe 232b is flow-adjusted by MFC241b. The first modified gas after flow adjustment is supplied from nozzle 249b to processing chamber 201, and is discharged from exhaust pipe 231. At this time, the first modified gas is supplied to wafer 200. That is, the surface of wafer 200 is exposed to the first modified gas. At this time, valve 243g is opened at the same time, and N2 gas flows into gas supply pipe 232g. The N2 gas flowing in gas supply pipe 232g is flow-adjusted by MFC241g. The N2 gas after flow adjustment is supplied to processing chamber 201 together with the first modified gas, and is discharged from exhaust pipe 231.

[0091] At this time, as shown in Fig. 6, the partial pressure of the first modifying gas in the processing chamber 201 in (a) (hereinafter referred to as the partial pressure of the first modifying gas) may be greater than the partial pressure of the second modifying gas in the processing chamber 201 in (c) described later (hereinafter referred to as the partial pressure of the second modifying gas). Hereinafter, the case where the partial pressure of the first modifying gas is greater than the partial pressure of the second modifying gas is described as an example.

[0092] Here, the partial pressure of the first modified gas and the partial pressure of the second modified gas can be increased or decreased by, for example, the ratio of the amount (e.g., mass, volume, amount of substance, etc.) of the first modified gas and the second modified gas to the amount of all gases present in the processing chamber 201 (hereinafter referred to as the concentration of the first modified gas, the concentration of the second modified gas), and at least one of the pressures in the processing chamber 201 in (a) and (c) (hereinafter referred to as the total pressure in (a) and the total pressure in (c)). Therefore, in the case where the partial pressure of the first modified gas is greater than the partial pressure of the second modified gas, it is preferred to set the conditions for performing (a) and (c) in a manner that satisfies at least one of the conditions that the concentration of the first modified gas is higher than the concentration of the second modified gas and the conditions that the total pressure in (c) is higher than the total pressure in (a). It is more preferred to set the conditions for performing (a) and (c) in a manner that satisfies both conditions.

[0093] The concentration of the first modified gas can be changed, for example, by controlling the ratio of the flow rate of the first modified gas supplied to the processing chamber 201 per unit time to the flow rate of the inert gas in (a). In addition, the total pressure in (a) can be changed, for example, by controlling the ratio of the flow rate of the gas supplied to the processing chamber 201 per unit time to the flow rate of the gas discharged from the processing chamber 201 per unit time in (a).

[0094] Similarly, the concentration of the second modified gas can be changed by, for example, controlling the ratio of the flow rate of the second modified gas supplied to the processing chamber 201 per unit time to the flow rate of the inert gas in (c). In addition, the total pressure in (c) can be changed by, for example, controlling the ratio of the flow rate of the gas supplied to the processing chamber 201 per unit time to the flow rate of the gas discharged from the processing chamber 201 per unit time in (c).

[0095] At this time, the vacuum pump 246 and the APC valve 244 are appropriately adjusted to set the pressure in the processing chamber 201 to a (prescribed) pressure within the range of 1 to 13300 Pa, preferably within the range of 1 to 1330 Pa, and more preferably within the range of 1 to 133 Pa. When the pressure in the processing chamber 201 is higher than 13300 Pa, the first modified gas will react (or adsorb) excessively with the wafer 200, and there is a situation where a predetermined amount or more of the raw material gas described later is prevented from being adsorbed onto the surface (including the grooves) of the wafer 200. When the pressure in the processing chamber 201 is lower than 1 Pa, the adsorption barrier effect of the first modified gas on the raw material gas may not be fully obtained.

[0096] The supply flow rate of the first modified gas controlled by MFC241b is a flow rate less than the amount required to cover the entire surface of the wafer 200, for example, a (prescribed) flow rate within the range of 1 to 3000 sccm, preferably a (prescribed) flow rate within the range of 10 to 1000 sccm, and more preferably a (prescribed) flow rate within the range of 10 to 500 sccm. When the supply flow rate of the first modified gas is more than 3000 sccm, the first modified gas significantly enters the lower part of the groove, which may affect the film formation in the lower part of the groove. When the supply flow rate of the first modified gas is less than 1 sccm, it may be difficult to obtain the adsorption barrier effect of the first modified gas on the raw material gas.

[0097] The supply flow rate of the inert gas controlled by MFC241g is set to a (prescribed) flow rate within the range of 1 to 20,000 sccm, preferably a (prescribed) flow rate within the range of 10 to 15,000 sccm, and more preferably a (prescribed) flow rate within the range of 100 to 10,000 sccm. When the supply flow rate of the inert gas is more than 20,000 sccm, it may be difficult to obtain the adsorption barrier effect of the first modified gas on the raw material gas. When the supply flow rate of the inert gas is less than 1 sccm, the residual gas removal described later may not be fully performed.

[0098] The time for supplying the first modified gas to the wafer 200, i.e., the gas supply time (irradiation time), is set to a (prescribed) time in the range of 0.01 to 120 seconds, preferably a (prescribed) time in the range of 0.1 to 60 seconds, and more preferably a (prescribed) time in the range of 1 to 10 seconds. When the gas supply time is longer than 120 seconds, the first modified gas will react (adsorb) excessively with the wafer 200, and sometimes will hinder the reaction of the raw material gas above the prescribed amount with the surface of the wafer 200. When the gas supply time is shorter than 1 second, it may not be possible to fully obtain the adsorption barrier effect of the first modified gas on the raw material gas.

[0099] The temperature of the heater 207 is set so that the temperature of the wafer 200 becomes, for example, a (prescribed) temperature in the range of 200 to 600° C., preferably a (prescribed) temperature in the range of 200 to 550° C., and more preferably a (prescribed) temperature in the range of 300 to 500° C. This temperature is preferably set to the same temperature as that in the subsequent (b) raw material gas supply step.

[0100] (b) Raw material gas supply step (halogen-based raw material gas supply)

[0101] Then, the valve 243b is closed to stop the supply of the first reformed gas, and the valve 243c is closed to stop the supply of the inert gas.

[0102] Next, valve 243a is opened, and a raw material gas containing the first element (for example, a gas containing a halogen element) flows into the gas supply pipe 232a. The raw material gas flowing in the gas supply pipe 232a is flow-adjusted by MFC241a. The raw material gas after flow adjustment is supplied from nozzle 249a to the processing chamber 201 and is discharged from exhaust pipe 231. At this time, the raw material gas is supplied to the wafer 200. That is, the surface (including the groove) of the wafer 200 is exposed to the raw material gas. At this time, valve 243f is opened at the same time, and an inert gas such as N2 gas flows into the gas supply pipe 232f. The N2 gas flowing in the gas supply pipe 232f is flow-adjusted by MFC241f. The N2 gas after flow adjustment is supplied to the processing chamber 201 together with the raw material gas and is discharged from exhaust port 231a.

[0103] In (b), the adsorption of the raw material gas to the portion where the first modified gas is adsorbed in (a) is blocked, and the raw material gas is adsorbed to the portion where the first modified gas is not adsorbed. That is, in (b), the raw material gas is supplied to the wafer 200, and the raw material gas is preferentially adsorbed to the region that is not modified by the first modified gas.

[0104] At this time, the vacuum pump 246 and the APC valve 244 are appropriately adjusted to set the pressure in the processing chamber 201 to a (prescribed) pressure within the range of 1 to 70,000 Pa, preferably to a (prescribed) pressure within the range of 1 to 1333 Pa, and more preferably to a (prescribed) pressure within the range of 20 to 50 Pa. When the pressure in the processing chamber 201 is higher than 70,000 Pa, the residual gas removal described later may not be sufficiently performed. When the pressure in the processing chamber 201 is lower than 0.01 Pa, the reaction rate between the raw material gas and the surface of the wafer 200 may not be sufficiently obtained.

[0105] The supply flow rate of the raw gas controlled by MFC241a is sufficient to cover the entire surface of the wafer 200 (including the inner surface of the groove), for example, it is set to a (prescribed) flow rate within the range of 1 to 10,000 sccm, preferably set to a (prescribed) flow rate within the range of 10 to 5,000 sccm, and more preferably set to a (prescribed) flow rate within the range of 100 to 3,000 sccm. When the supply flow rate of the raw gas is more than 10,000 sccm, it is possible that impurities such as halogen elements enter the film in large quantities, and sometimes it is impossible to fully remove the residual gas described later. When the supply flow rate of the raw gas is less than 1 sccm, it is possible that the reaction rate between the raw gas and the surface of the wafer 200 cannot be fully obtained.

[0106] The supply flow rate of the N2 gas controlled by the MFC241f is set to a (prescribed) flow rate within the range of 1 to 20,000 sccm, preferably a (prescribed) flow rate within the range of 500 to 15,000 sccm, and more preferably a (prescribed) flow rate within the range of 600 to 800 sccm. When the supply flow rate of the N2 gas is more than 20,000 sccm, it may not be possible to fully obtain the reaction rate between the raw material gas and the surface of the wafer 200. When the supply flow rate of the N2 gas is less than 1 sccm, sometimes the residual gas removal described later cannot be fully performed.

[0107] The time for supplying the raw gas to the wafer 200, i.e., the raw gas supply time (irradiation time), is set to a (prescribed) time within the range of 0.1 to 500 seconds, preferably within the range of 1 to 300 seconds, and more preferably within the range of 3 to 200 seconds. When the raw gas supply time is longer than 500 seconds, the uniformity of the film thickness may be reduced due to the large amount of adsorption of the raw gas. When the raw gas supply time is less than 0.1 seconds, it is possible that the raw gas and the surface of the wafer 200 cannot fully react.

[0108] The temperature of the heater 207 is set so that the temperature of the wafer 200 becomes, for example, a (prescribed) temperature in the range of 200 to 600° C., preferably a (prescribed) temperature in the range of 200 to 550° C., and more preferably a (prescribed) temperature in the range of 300 to 500° C. When the temperature of the heater 207 is higher than 600° C., the thermal decomposition of the raw material gas is promoted, so that the uniformity of the film thickness is sometimes reduced, or a large amount of impurities enter, causing the resistivity to increase. On the other hand, when the temperature of the heater 207 is lower than 200° C., the reactivity with the surface of the wafer 200 becomes low, which may make film formation difficult.

[0109] The gases flowing in the processing chamber 201 are only the source gas and the N 2 gas. The first element-containing layer is formed on the wafer 200 (underlayer film on the surface) by supplying the source gas.

[0110] The first element containing layer may be a first element layer composed of the first element, or may be a first element layer containing elements other than the first element such as halogen elements, or may be an adsorption layer of raw material gas molecules (hereinafter also referred to as the adsorption layer of raw material molecules), or may include all of these. The first element layer containing elements other than the first element is a general term that includes, in addition to the continuous layer composed of the first element containing elements other than the first element, discontinuous layers and first element containing films formed by overlapping these layers containing elements other than the first element. There is also a case where a continuous layer composed of the first element containing elements other than the first element is referred to as a first element containing film containing elements other than the first element. The first element layer contains elements other than the first element, and the first element constituting the first element layer includes a structure in which the bond with elements other than the first element is not completely severed, and also includes a structure in which the bond with elements other than the first element is completely severed.

[0111] The adsorption layer of the raw material molecules includes a discontinuous adsorption layer in addition to the continuous adsorption layer composed of the raw material gas molecules. That is, the adsorption layer of the raw material molecules includes an adsorption layer of one molecule layer or a thickness less than one molecule layer composed of the raw material gas molecules. The raw material gas molecules constituting the adsorption layer of the raw material molecules also include a structure in which a part of the bond between the first element and an element other than the first element is cut. That is, the adsorption layer of the raw material molecules may be a physical adsorption layer of the raw material gas molecules, may be a chemical adsorption layer of the raw material gas molecules, or may include both.

[0112] Here, a layer with a thickness of less than 1 atomic layer refers to an atomic layer formed discontinuously, and a layer with a thickness of 1 atomic layer refers to an atomic layer formed continuously. A layer with a thickness of less than 1 molecular layer refers to a molecular layer formed discontinuously, and a layer with a thickness of 1 molecular layer refers to a molecular layer formed continuously. The first element-containing layer containing an element other than the first element may include both the first element layer containing an element other than the first element and an adsorption layer of the raw material gas. However, as described above, the first element-containing layer containing an element other than the first element will be represented by expressions such as "1 atomic layer" or "several atomic layers".

[0113] Under the condition that the raw material gas self-decomposes (thermally decomposes), the first element layer is formed by depositing the first element on the wafer 200. Under the condition that the raw material gas does not self-decompose (thermally decomposes), the adsorption layer of the raw material molecules is formed by adsorbing the molecules of the raw material gas on the wafer 200. Compared with forming the adsorption layer of the raw material molecules on the wafer 200, forming the first element layer on the wafer 200 can improve the film formation rate, which is preferred in this respect.

[0114] When the thickness of the first element-containing layer (hereinafter also referred to as the first layer) formed in the first (b) raw material gas supply step exceeds several atomic layers, the modification effect in the (d) reaction gas supply step (N-containing gas supply step) described later cannot reach the entire first layer. In addition, the minimum value of the thickness of the first layer is less than 1 atomic layer. Therefore, it is preferred to set the thickness of the first layer to be less than 1 atomic layer to about several atomic layers. By setting the thickness of the first layer to less than 1 atomic layer, that is, to 1 atomic layer or less than 1 atomic layer, the reaction efficiency in the (d) reaction gas supply step described later can be relatively improved, thereby shortening the time required for the reaction in the (d) reaction gas supply step. The time required to form the first layer in the (b) raw material gas supply step can also be shortened. As a result, the processing time per cycle can be shortened, and the total processing time can also be shortened. That is, the film formation rate can also be improved. In addition, by setting the thickness of the first layer to less than 1 atomic layer, the controllability of the film thickness uniformity can also be improved.

[0115] (P1) First residual gas removal step

[0116] Then, the valve 243a is closed to stop the supply of the raw material gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246, so that the first modified gas that has not reacted or has played a role as a reaction-inhibiting gas and the reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201. At this time, the gas remaining in the processing chamber 201 may not be completely removed, which is the same as the (b) raw material gas supply step.

[0117] (c) Second reforming gas supplying step (second reaction inhibiting gas supplying step)

[0118] Next, valve 243d is opened, and the second modified gas flows into the gas supply pipe 232d. The second modified gas flowing in the gas supply pipe 232d is flow-adjusted by MFC241d. The second modified gas after flow adjustment is supplied from nozzle 249d to the processing chamber 201, and is discharged from exhaust pipe 231. At this time, the second modified gas is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to the second modified gas. At this time, valve 243i is opened at the same time, and N2 gas flows into the gas supply pipe 232i. The N2 gas flowing in the gas supply pipe 232i is flow-adjusted by MFC241i. The N2 gas after flow adjustment is supplied to the processing chamber 201 together with the second modified gas, and is discharged from exhaust pipe 231.

[0119] The vacuum pump 246 and the APC valve 244 are appropriately adjusted so that the pressure in the processing chamber 201 is set to a (prescribed) pressure within the range of 1 to 13300 Pa, preferably within the range of 1 to 1330 Pa, and more preferably within the range of 1 to 133 Pa. When the pressure in the processing chamber 201 is higher than 13300 Pa, the second modified gas will react (or be adsorbed) excessively with the wafer 200, sometimes hindering the reaction of the first element containing layer described later with the reaction gas in an amount greater than a prescribed amount. When the pressure in the processing chamber 201 is lower than 1 Pa, the reaction rate of the second modified gas with the first element containing layer may not be sufficiently obtained.

[0120] The supply flow rate of the second modified gas controlled by MFC241d is a flow rate below the amount required to cover the entire surface of the wafer 200, for example, a (prescribed) flow rate within the range of 1 to 3000 sccm, preferably a (prescribed) flow rate within the range of 10 to 1000 sccm, and more preferably a (prescribed) flow rate within the range of 10 to 500 sccm. When the supply flow rate of the second modified gas is more than 3000 sccm, the second modified gas significantly enters the lower part of the groove, which may affect the film formation in the lower part of the groove. When the supply flow rate of the second modified gas is less than 1 sccm, it may not be possible to fully obtain the reaction-blocking effect of the second modified gas on the first element-containing layer and the reaction gas.

[0121] The supply flow rate of N2 gas controlled by MFC241g is set to a (prescribed) flow rate within the range of 1 to 20,000 sccm, preferably a (prescribed) flow rate within the range of 10 to 15,000 sccm, and more preferably a (prescribed) flow rate within the range of 100 to 10,000 sccm. When the supply flow rate of N2 gas is more than 20,000 sccm, the reaction rate of the second modified gas and the first element containing layer may not be fully obtained. When the supply flow rate of N2 gas is less than 1 sccm, the residual gas removal described later may not be fully performed.

[0122] The time for supplying the second modified gas to the wafer 200, i.e., the gas supply time (irradiation time), is set to, for example, a (prescribed) time in the range of 0.01 to 120 seconds, preferably a (prescribed) time in the range of 0.1 to 60 seconds, and more preferably a (prescribed) time in the range of 1 to 10 seconds. When the gas supply time is longer than 120 seconds, the second modified gas will react (adsorb) excessively with the wafer 200, and sometimes will hinder the reaction of the first element containing layer with a predetermined amount or more and the reaction gas. When the gas supply time is shorter than 1 second, the reaction hindering effect of the first element containing layer and the reaction gas may not be fully obtained.

[0123] The temperature of the heater 207 is set so that the temperature of the wafer 200 becomes, for example, a (prescribed) temperature in the range of 200 to 600° C., preferably a (prescribed) temperature in the range of 200 to 550° C., and more preferably a (prescribed) temperature in the range of 300 to 500° C. This temperature is preferably set to the same temperature as that in the subsequent (b) raw material gas supply step.

[0124] (d) Reaction Gas Supply Step

[0125] Next, valve 243c is opened, and a reaction gas flows into the gas supply pipe 232c. The reaction gas is, for example, a N-containing gas or a reducing gas. The reaction gas flowing in the gas supply pipe 232c is flow-regulated by MFC241c. The reaction gas after flow regulation is supplied from nozzle 249c to the processing chamber 201 and is discharged from exhaust pipe 231. At this time, valve 243h is opened at the same time, and N2 gas flows into the gas supply pipe 232h. The N2 gas flowing in the gas supply pipe 232h is flow-regulated by MFC241h. N2 gas is supplied to the processing chamber 201 together with the reaction gas and is discharged from exhaust pipe 231.

[0126] When the reaction gas is flowed, the pressure regulator 244 is appropriately adjusted so that the pressure in the processing chamber 201 is set to a (prescribed) pressure in the range of, for example, 0.01 to 13300 Pa, preferably a (prescribed) pressure in the range of 1 to 1330 Pa, and more preferably a (prescribed) pressure in the range of 10 to 133 Pa. When the pressure in the processing chamber 201 is higher than 13300 Pa, the residual gas removal described later may not be sufficiently performed. When the pressure in the processing chamber 201 is lower than 0.01 Pa, a sufficient film formation rate may not be obtained.

[0127] The supply flow rate of the reaction gas controlled by MFC241c is sufficient to cover the entire surface of the wafer 200, for example, it is set to a (prescribed) flow rate in the range of 10 to 50,000 sccm, preferably set to a (prescribed) flow rate in the range of 300 to 10,000 sccm, and more preferably set to a (prescribed) flow rate in the range of 1,000 to 8,000 sccm. The greater the supply flow rate of the reaction gas, the less impurities can be introduced into the film due to the raw material gas, so it is preferred. When it is more than 50,000 sccm, it is possible that the residual gas cannot be fully removed in the residual gas removal step described later. When the supply flow rate of the reaction gas is less than 10 sccm, it may not be able to fully react with the first element containing layer.

[0128] The supply flow rate of N2 gas controlled by MFC241h is set to a (prescribed) flow rate within the range of 10 to 20,000 sccm, preferably within the range of 400 to 15,000 sccm, and more preferably within the range of 400 to 7,500 sccm. When the supply flow rate of N2 gas is more than 20,000 sccm, the film formation rate may become too low. When the supply flow rate of N2 gas is less than 10 sccm, the reactive gas may not be fully supplied to the wafer 200.

[0129] The time for supplying the reaction gas to the wafer 200, i.e., the gas supply time (irradiation time), is set to a (prescribed) time within the range of 0.001 to 300 seconds, preferably within the range of 0.1 to 200 seconds, and more preferably within the range of 5 to 60 seconds. The longer the gas supply time, the less impurities can be introduced into the film due to the raw gas, so it is preferred. However, when it is longer than 300 seconds, the processing volume may be deteriorated. When the gas supply time is shorter than 0.001 seconds, the reaction speed with the first element containing layer may not be fully obtained.

[0130] The temperature of the heater 207 is set to the same temperature as that in the raw material gas supply step.

[0131] At this time, the gases flowing in the processing chamber 201 are only the reaction gas and the N2 gas. The reaction gas undergoes a substitution reaction with at least a portion of the first element containing layer formed on the wafer 200 in the raw material gas supply step and which has not reacted with the second modified gas in the second modified gas supply step. Through the substitution reaction, a layer containing the first element and the elements contained in the reaction gas is formed on the wafer 200. The first element and the elements contained in the reaction gas may contain other elements, which are derived from the first element containing layer that has not undergone the substitution reaction and the raw materials contained in the first element containing layer.

[0132] (P2) Residual Gas Removal Step

[0133] After forming the layer containing the first element and the elements contained in the reaction gas, the valve 243c is closed to stop the supply of the reaction gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246, so that the unreacted reaction gas, reaction by-products, and reaction gas that helped form the layer containing the first element and the elements contained in the reaction gas, which remain in the processing chamber 201, are removed from the processing chamber 201.

[0134] (Specified number of implementations)

[0135] The above film formation sequence ((a) first modified gas supply step, (b) raw gas supply step, (P1) first residual gas removal step, (c) second modified gas supply step, (d) reaction gas supply step, (P2) residual gas removal step) is regarded as one cycle, and only n cycles (n is an integer greater than 1) are performed on these processes. Thus, a film of a predetermined thickness (e.g., 0.1 to 10 nm) is formed on the wafer 200. The above cycle is preferably repeated multiple times.

[0136] When multiple cycles are performed, at least in each step after the second cycle, the part recorded as “supplying gas to wafer 200” means “supplying specified gas to the layer formed on wafer 200, that is, to the outermost surface of wafer 200 as a laminated body”, and the part recorded as “forming a specified layer on wafer 200” means “forming a specified layer on the layer formed on wafer 200, that is, on the outermost surface of wafer 200 as a laminated body”.

[0137] (e) Etching step (etching process)

[0138] Then, valve 243e is opened, and etching gas flows into gas supply pipe 232e. The etching gas flowing in gas supply pipe 232e is flow-regulated by MFC241e. The etching gas after flow regulation is supplied from nozzle 249e to processing chamber 201, and is discharged from exhaust pipe 231. At this time, etching gas is supplied to wafer 200. As a result, a part of the film formed on the surface of wafer 200 is etched. When the etching step is finished, valve 243e is closed to stop the supply of etching gas.

[0139] The vacuum pump 246 and the APC valve 244 are appropriately adjusted to set the pressure in the processing chamber 201 to a (prescribed) pressure within the range of 1 to 13300 Pa, preferably to a (prescribed) pressure within the range of 1 to 1330 Pa, and more preferably to a (prescribed) pressure within the range of 1 to 133 Pa.

[0140] The supply flow rate of the etching gas controlled by MFC241e is a flow rate less than the amount required to cover the entire surface of the wafer 200, for example, it is set to a (prescribed) flow rate in the range of 1~3000sccm, preferably it is set to a (prescribed) flow rate in the range of 10~1000sccm, and more preferably it is set to a (prescribed) flow rate in the range of 10~500sccm.

[0141] The supply flow rate of N2 gas controlled by MFC241h is set to a (prescribed) flow rate within the range of 1 to 40,000 sccm, for example, preferably a (prescribed) flow rate within the range of 10 to 3,000 sccm, and more preferably a (prescribed) flow rate within the range of 100 to 20,000 sccm.

[0142] The time for supplying etching gas to the wafer 200, i.e., the gas supply time (irradiation time), is set to a (prescribed) time within the range of 0.1 to 300 seconds, preferably within the range of 1 to 200 seconds, and more preferably within the range of 5 to 100 seconds.

[0143] In addition, after the above-mentioned (e) etching step, the APC valve 244 of the exhaust pipe 231 may be kept open, and the processing chamber 201 may be vacuum-exhausted by the vacuum pump 246. In addition, the above-mentioned (e) etching step and the vacuum exhaust of the processing chamber 201 after the above-mentioned (e) etching step may be performed in sequence for a predetermined number of times (one or more), and this may be regarded as the (e) etching step (etching process).

[0144] (Specified number of implementations)

[0145] The above-mentioned "n times of film formation sequence and etching sequence ((e) etching step)" process is regarded as one cycle, and these processes are performed only for L cycles (L is an integer greater than 0). Thus, a film of a predetermined thickness (for example, 0.1 to 10 nm) is formed on the wafer 200. In addition, this cycle is preferably repeated a plurality of times.

[0146] 5 , as shown in state A, the interior of the recess 300 is gradually filled with the film 400 . Finally, as shown in state B, the interior of the recess 300 is completely filled with the film 400 .

[0147] (Substrate removal process)

[0148] (Post-Purge Step and Atmospheric Pressure Restoration Step)

[0149] The valves 243f-243j are opened, and N2 gas is supplied from the gas supply pipes 232f-232j to the processing chamber 201, respectively, and discharged from the exhaust pipe 231. The N2 gas acts as a purge gas, thereby purging the processing chamber 201 with an inert gas, and the gas or by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Then, the ambient gas in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0150] Then, the sealing cover 219 is lowered by the wafer boat elevator 115 to open the lower end of the outer tube 203. Next, the processed wafer 200 is carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 while being supported by the wafer boat 217 (wafer unloading). Then, the processed wafer 200 is taken out of the wafer boat 217 (wafer unloading).

[0151] According to this embodiment, one or more of the following effects can be obtained.

[0152] As shown in FIG3 , the cycle is performed a predetermined number of times in the order of (a) -> (b) -> (c) -> (d). In (a) and (c), the first modified gas and the second modified gas preferentially modify the parts that are easy for the gas to reach (the upper part 301 of the recess 300, etc.), and the parts that are difficult for the gas to reach (the bottom 302 of the recess 300, etc.) are difficult to modify. Therefore, in (b), the adsorption of the raw material gas to the parts that are easy for the gas to reach is hindered, while the adsorption of the raw material gas to the parts that are difficult for the gas to reach is not easily hindered. In addition, in (d), the reaction of the reaction gas and the raw material gas in the parts that are easy for the gas to reach is hindered, and the reaction of the reaction gas and the raw material gas in the parts that are difficult for the gas to reach is not easily hindered. Therefore, a film of uniform thickness can be formed from the parts that are easy for the gas to reach to the parts that are difficult for the gas to reach (the bottom 302 of the recess 300, etc.). Since the halogen element is difficult to remain in the film as an impurity, the degradation of the electrical characteristics can be suppressed.

[0153] It is also possible to configure the area where the second modified gas is adsorbed on the substrate 200 in (c) to be smaller than the area where the first modified gas is adsorbed on the above-mentioned substrate in (a). For example, it is also possible to configure the area where the second modified gas in (c) modifies the bottom 302 of the recess 300 to be smaller than the area where the first modified gas in (a) modifies the bottom 302 of the recess 300. Thus, in (d), the area where the reaction between the raw gas and the reactive gas in the part where the gas is not easy to reach is not hindered becomes larger. Therefore, the raw gas that does not react in the part where the gas is not easy to reach is reduced, so that the degradation of the electrical characteristics of the film can be suppressed. Therefore, the increase (film increase) of the film thickness in the part where the gas is easy to reach is suppressed, so that the step coverage can be improved or the generation of holes can be suppressed. In addition, since the consumption of the reactive gas in the part where the gas is easy to reach is reduced, it becomes easy to reach the bottom. Therefore, the raw gas that does not react in the part where the gas is easy to reach is reduced.

[0154] It is also possible to configure such that the amount of the second modified gas adsorbed in the gas-inaccessible portion (e.g., the bottom 302 of the recess 300) in (c) is set to be less than the amount of the first modified gas adsorbed in the gas-inaccessible portion in (a). Thus, in (d), the reaction between the raw gas and the reactive gas in the gas-inaccessible portion becomes less obstructed. Thus, the reaction between the raw gas and the reactive gas in the gas-inaccessible portion becomes less obstructed, thereby improving step coverage or suppressing the generation of voids. In addition, since the unreacted raw gas in the gas-inaccessible portion is reduced, the impurities in the film are reduced, thereby improving the electrical properties of the film.

[0155] It is also possible to configure the second modified gas in (c) to be adsorbed in a portion that is easily accessible to the gas (e.g., 301 above the recess 300) in a larger amount than the amount adsorbed in a portion that is easily accessible to the gas in (a). Thus, in (d), the reaction between the raw gas and the reactive gas in the portion that is easily accessible to the gas becomes easily hindered. Thus, the increase in the film in the portion that is easily accessible to the gas can be suppressed, thereby improving the step coverage or suppressing the generation of holes. In addition, since the consumption of the reactive gas in the portion that is easily accessible to the gas is reduced, it is possible to make it easier for the gas to reach the portion that is difficult to reach. Therefore, since the unreacted raw gas in the portion that is difficult to reach to the gas is reduced, the impurities in the film are reduced, and the electrical properties of the film can be improved.

[0156] As shown in FIG6 , the treatment is performed in such a manner that the partial pressure of the second modified gas in the space (processing chamber 201) where the substrate 200 in (c) exists becomes lower than the partial pressure of the first modified gas in the space (processing chamber 201) in (a). When the partial pressure of the gas is reduced, the ease with which gas molecules collide is greatly reduced in the parts that are difficult for the gas to reach (e.g., the bottom 302 of the recess 300) than in the parts that are easy for the gas to reach (e.g., the top 301 of the recess 300). Therefore, in the parts that are difficult for the gas to reach, the adsorption amount of the second modified gas can be set to be less than that of the first modified gas. In addition, in the parts that are easy for the gas to reach, the adsorption amount of the second modified gas can be set to be more than that of the first modified gas. Thus, the reaction between the raw gas and the reaction gas can be less hindered in the parts that are difficult for the gas to reach.

[0157] In the etching sequence, the part that the etching gas easily reaches (e.g., the upper part 301 of the concave part 300) is easier to etch than the part that the gas does not easily reach (e.g., the bottom part 302 of the concave part 300). Therefore, the film thickness can be reduced in the part where the film is likely to increase, that is, in the part where the gas easily reaches. In this way, the step coverage can be improved or the generation of holes can be suppressed.

[0158] Alternatively, the raw material gas may be a gas containing the first element and a halogen element, and the reaction gas may be a reducing gas. By using a gas containing a halogen element that is unlikely to become an impurity and remain in the film as the raw material gas, an increase in the resistance of the metal film can be suppressed. In addition, by using a reducing gas as the reaction gas, oxidation of the metal film can be suppressed.

[0159] (Variation Example)

[0160] Next, several modified examples are described. In each modified example, in addition to the same effects as the above-mentioned embodiment, effects described below can also be obtained.

[0161] (First Modification)

[0162] Fig. 7 is a diagram showing the film formation timing of the first modification. As shown in Fig. 7, in the first modification, the flow rate of the second modified gas per unit time in (c) is less than the flow rate of the first modified gas per unit time in (a). By setting in this way, it is possible to set the condition where the partial pressure of the first modified gas in (a) is greater than the partial pressure of the second modified gas in (c).

[0163] (Second Modification)

[0164] FIG8 is a diagram showing the film formation timing of the second modification. As shown in FIG8, in the second modification, when the partial pressure of the second modified gas is lower than the partial pressure of the first modified gas, the supply time of the second modified gas in (c) is set to be longer than the supply time of the first modified gas in (a). Thus, the adsorption of the second modified gas to the bottom 302 of the recess 300 can be minimized, and the adsorption of the second modified gas to the upper part 301 of the recess 300 can be promoted. Therefore, at the bottom 302, the reaction gas becomes easy to reach, and the unreacted raw material gas is reduced. In addition, the step coverage of the formed film can be improved, and the generation of holes can be suppressed.

[0165] (Third Modification)

[0166] FIG. 9 is a diagram showing the film formation timing of the third variant. As shown in FIG. 9 , in the third variant, the supply time of the second modified gas in (c) can also be set to be shorter than the supply time of the first modified gas in (a). In this case, for the adsorption amount of the second modified gas, the part where the gas is easy to reach is greatly reduced compared with the part where the gas is difficult to reach. Therefore, the reaction gas becomes easy to reach the part where the gas is difficult to reach, and the unreacted raw material gas is reduced. In addition, the step coverage of the formed film can also be improved and the generation of holes can be suppressed. In addition, this situation is also established when the partial pressure of the first modified gas is less than the partial pressure of the second modified gas, and when the partial pressure of the first modified gas is greater than the partial pressure of the second modified gas. In addition, when the partial pressure of the first modified gas is greater than the partial pressure of the second modified gas, the supply time of the second modified gas is set to be shorter than the supply time of the first modified gas, thereby reducing the unreacted raw material gas and improving the step coverage.

[0167] (Fourth Modification)

[0168] FIG. 10 is a diagram showing the film formation timing of the fourth modification example. As shown in FIG. 10, in the fourth modification example, in the film formation cycles after the n1-th time (n1 is an integer of 2 or more and n or less, 2 ≤ n1 ≤ n), the partial pressure of the first modifying gas in the space (processing chamber 201) in (a) is set to be less than that in the film formation cycles before the n1-1-th time. In addition, instead of setting the partial pressure of the first modifying gas to be small, (a) may not be performed. As the cycle progresses, the concave portion 300 becomes shallower, reducing the adsorption amount of the first modifying gas or not performing adsorption, so that a hole-free film can still be formed. Therefore, by reducing the partial pressure of the first modifying gas or not performing (a), the adsorption inhibition of the source gas caused by the first modifying gas can be reduced, so that productivity can be improved.

[0169] Similarly, in the film formation cycles after the n2-th time (n2 is an integer of 2 or more and n or less, 2 ≤ n2 ≤ n), the partial pressure of the second modifying gas in the space (processing chamber 201) in (c) may be set to be less than that in the film formation cycles before the n2-1-th time, or (c) may not be performed.

[0170] In addition, in FIG. 10, the case where n2 is set to a value greater than n1 (n1 < n2) is taken as an example, but the fourth modification example is not limited thereto. For example, the fourth modification example may be performed by setting n1 to a value greater than n2 (n2 < n1). In addition, for example, the fourth modification example may be performed by setting n1 and n2 to equal values (n1 = n2). Here, when n2 is set to a value greater than n1 (n1 < n2), the reaction of the reaction gas based on the second modifying gas with the source gas is less likely to be inhibited than the adsorption of the source gas based on the first modifying gas, so that the unreacted source gas can be reduced, which is preferable.

[0171] (Fifth Modification Example)

[0172] FIG. 11 is a diagram showing the film formation timing of the fifth modification example. As shown in FIG. 11, in the fifth modification example, in the film formation cycles after the m1-th time (m1 is an integer of 2 or more and n or less, 2 ≤ m1 ≤ n), the supply time of the first modifying gas to the substrate 200 in (a) is set to be shorter than that in the film formation cycles before the m1-1-th time. In addition, instead of setting the supply time of the first modifying gas to be small, (a) may not be performed. As the cycle progresses, the concave portion 300 becomes shallower, reducing the adsorption amount of the first modifying gas or not performing adsorption, so that a hole-free film can still be formed. Therefore, since the adsorption inhibition of the source gas based on the first modifying gas in the concave portion 300 is reduced or eliminated, the step coverage can be improved or the generation of holes can be suppressed, and the productivity can be improved.

[0173] Similarly, it is also possible that in the film formation cycles after the m2-th time (m2 is an integer greater than or equal to 2 and less than or equal to n, 2 ≤ m2 ≤ n), the supply time of the second modification gas to the substrate 200 in (c) is set to be shorter than that in the film formation cycles before the (m2 - 1)-th time, or (c) is not performed.

[0174] In addition, in FIG. 11, the case where m2 is set to a value greater than m1 (m1 < m2) is taken as an example to show the film formation timing of the fifth modification example, but the present invention is not limited thereto. That is, it is also possible to perform the film formation timing of the fifth modification example by setting m1 to a value greater than m2 (m2 < m1). In addition, it is also possible to perform the film formation timing of the fifth modification example by setting m1 and m2 to equal values (m1 = m2). Here, when m2 is set to a value greater than m1 (m1 < m2), the reaction ratio of the reaction gas based on the second modification gas to the raw material gas is less likely to be inhibited by the adsorption of the raw material gas based on the first modification gas. Therefore, the unreacted raw material gas can be reduced, which is preferable.

[0175] In the above embodiment, as the raw material gas, for example, a gas containing a metal element can be used. The metal element can be, for example, tantalum (Ta), tungsten (W), titanium (Ti), cobalt (Co), yttrium (Y), ruthenium (Ru), aluminum (Al), hafnium (Hf), zirconium (Zr), molybdenum (Mo), niobium (Nb), manganese (Mn), nickel (Ni), silicon (Si), etc. It can also be appropriately applied to the case of forming any one of a nitride film, an oxide film, a carbide film, a boride film containing these elements, or a composite film thereof.

[0176] When forming a film containing the above metal element, as the raw material gas, a Ta-containing gas, a W-containing gas, a Ti-containing gas, a Co-containing gas, a Y-containing gas, a Ru-containing gas, an Al-containing gas, an Hf-containing gas, a Zr-containing gas, a Mo-containing gas, a Nb-containing gas, a Mn-containing gas, a Ni-containing gas, a Si-containing gas, etc. can be used.

[0177] When forming a film containing the above-mentioned metal elements, a gas containing a metal element and a halogen element can be used. As a gas containing a metal element and a halogen element, for example, tantalum pentachloride (TaCl5), tantalum pentafluoride (TaF5), tungsten hexachloride (WCl6), tungsten hexafluoride (WF6), titanium tetrachloride (TiCl4), titanium tetrafluoride (TiF4), cobalt dichloride (CoCl2), cobalt difluoride (CoF2), yttrium trichloride (YCl3), yttrium trifluoride (YF3), ruthenium trichloride (RuCl3), ruthenium trifluoride (RuF3), aluminum trichloride (AlCl3), aluminum trifluoride (AlF3), hafnium tetrachloride (HfCl4), hafnium tetrafluoride (HfF4), zirconium tetrachloride (Zirconium tetrachloride) ... (ZrCl4), zirconium tetrafluoride (ZrF4), molybdenum pentafluoride (MoF5), molybdenum pentachloride (MoCl5), niobium trifluoride (NbF3), niobium trichloride (NbCl3), manganese difluoride (MnF2), manganese dichloride (MnCl2), nickel difluoride (NiF2), nickel dichloride (NiCl2), tetrachlorosilane, also known as silicon chloride or silicon tetrachloride (SiCl4, abbreviated as: STC), dichlorosilane (SiH2Cl2, abbreviated as: DCS), monochlorosilane (SiH3Cl, abbreviated as: MCS), hexachlorodisilane, also known as disilicon hexachloride (Si2Cl6, abbreviated as: HCDS), etc.

[0178] When forming a film containing the above elements, as a reaction gas, for example, a reducing gas can be used. When a reducing gas is used as a reaction gas, oxidation of the substrate surface or the formed film is suppressed, so that the resistance increase of the film can be suppressed. As a reducing gas, for example, H2 gas, deutrium (D2) gas, borane (BH3) gas, diborane (B2H6) gas, carbon monoxide (CO) gas, ammonia (NH3), monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monogermane (GeH4) gas, digermane (Ge2H6), ethanol (C2H5OH), formic acid (HCOOH) can also be used. In addition, gases after plasma excitation of these gases can also be used.

[0179] In addition, when a film containing the above-mentioned elements is formed, a nitrogen (N)-containing gas, for example, can be used as a reaction gas. As the N-containing gas, for example, a gas containing NH bonds, such as nitrogen (N2) gas, nitrous oxide (N2O) gas, ammonia (NH3), diimide (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas, etc. can be used. In addition, as the gas containing NH bonds, in addition to the above-mentioned gases, an organic hydrazine-based gas can be used, such as methyl hydrazine-based gases such as monomethyl hydrazine ((CH3)HN2H2, abbreviated as: MMH) gas, dimethyl hydrazine ((CH3)2N2H2, abbreviated as: DMH) gas, trimethyl hydrazine ((CH3)2N2(CH3)H, abbreviated as: TMH) gas, and ethyl hydrazine-based gases such as ethyl hydrazine ((C2H5)HN2H2, abbreviated as: EH) gas. In addition, ethylamine gases such as triethylamine ((C2H5)3N, abbreviated as TEA) gas, diethylamine ((C2H5)2NH, abbreviated as DEA) gas, and monoethylamine (C2H5NH2, abbreviated as MEA) gas, methylamine gases such as trimethylamine ((CH3)3N, abbreviated as TMA) gas, dimethylamine ((CH3)2NH, abbreviated as DMA) gas, and monomethylamine (CH3NH2, abbreviated as MMA) gas, propylamine gases such as tripropylamine ((C3H7)3N, abbreviated as TPA) gas, dipropylamine ((C3H7)2NH, abbreviated as DPA) gas, and monopropylamine (C3H7NH2, abbreviated as MPA) gas, and triisopropylamine ([(CH3)2CH]3N, abbreviated as In some embodiments, the present invention may be used to prepare an isopropylamine gas such as tributylamine ((C4H9)3N, abbreviated as TBA) gas, dibutylamine ((C4H9)2NH, abbreviated as DBA) gas, monobutylamine ((C4H9NH2, abbreviated as MBA) gas, or isobutylamine gas such as triisobutylamine ([(CH3)2CHCH2]3N, abbreviated as TIBA) gas, diisobutylamine ([(CH3)2CHCH2]2NH, abbreviated as DIBA) gas, monoisobutylamine ((CH3)2CHCH2NH2, abbreviated as MIBA) gas. In addition, a gas obtained by subjecting such a gas to plasma excitation may be used. That is, as an amine gas, for example, (C2H5) X NH 3-X 、(CH3) X NH 3-X 、(C3H7) X NH 3-X 、[(CH3)2CH] X NH 3-X 、(C4H9) X NH 3-X、[(CH3)2CHCH2] X NH 3-X (In the chemical formula, X is an integer of 1 to 3) etc. When an organic hydrazine gas or an amine gas is used, the reactivity can be improved, and since carbon (C) can be incorporated into the membrane, the working function of the membrane can be adjusted by controlling the C concentration.

[0180] As the first modified gas and the second modified gas, for example, an inorganic halogen-containing gas (halogen gas) can be used. Since the inorganic halogen-containing gas does not contain C that easily enters the film, but is composed of halogen elements that easily detach from the film, the influence on the electrical characteristics can be suppressed. As the inorganic halogen-containing gas, for example, a hydrogen halide gas (hydrogen halide) can be used. Hydrogen halides, for example, hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), etc. can also be used. In addition, as the first modified gas or the second modified gas, an inorganic halogen-containing gas other than hydrogen halide gas, such as chlorine (Cl2), fluorine (F2), NF3 gas, tungsten hexafluoride (WF6) gas, etc. can also be used. In addition, different gases can also be used for the first modified gas and the second modified gas.

[0181] As the etching gas, for example, a gas containing a halogen element can be used. As the gas containing a halogen element, for example, a gas containing a halogen element such as chlorine (Cl2) gas, fluorine (F2) gas, NF3 gas, HF gas, or HCl gas can be used.

[0182] In the above embodiment, an example of using N2 gas as an inert gas has been described, but the present invention is not limited thereto, and rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas may also be used.

[0183] The above is specifically described according to the embodiments, but the present invention is not limited to the above-mentioned embodiments and embodiments, and various changes can be made. In addition, the above-mentioned method or modification can be used in combination as appropriate. The processing process and processing conditions at this time can be set to be the same as the processing process and processing conditions of the above-mentioned method or modification.

[0184] Description of Reference Numerals

[0185] 200: Wafer (substrate)

[0186] 201: Processing room

[0187] 248: Integrated supply system

[0188] 121: Controller (control unit).

Claims

1. A substrate processing method, characterized in that: The substrate is cycled a specified number of times, and the cycle sequentially performs the following steps: (a) a step of supplying a first reforming gas which is an inorganic halogen-containing gas; (b) a step of supplying raw material gas; (c) a step of supplying a second reforming gas which is an inorganic halogen-containing gas; (d) A step of supplying a reaction gas.

2. The substrate processing method according to claim 1, characterized in that: In (c), the region where the second modified gas is adsorbed on the substrate is set to be smaller than the region where the first modified gas is adsorbed on the substrate in (a).

3. The substrate processing method according to claim 1, characterized in that: The above-mentioned substrate has a recessed portion.

4. The substrate processing method according to claim 3, characterized in that: In (c), the amount of the second modified gas adsorbed on the bottom of the recessed portion is set to be smaller than the amount of the first modified gas adsorbed on the bottom of the recessed portion in (a).

5. The substrate processing method according to claim 3, characterized in that: The amount of the second modified gas adsorbed on the upper portion of the concave portion in (c) is set to be larger than the amount of the first modified gas adsorbed on the upper portion of the concave portion in (a).

6. The substrate processing method according to any one of claims 2, 4 and 5, characterized in that: The partial pressure of the second modified gas in the space where the substrate exists in (c) is lower than the partial pressure of the first modified gas in the space in (a).

7. The substrate processing method according to claim 6, characterized in that: In (c), the flow rate of the second modifying gas supplied to the substrate per unit time is smaller than the flow rate of the first modifying gas supplied to the substrate per unit time in (a).

8. The substrate processing method according to claim 6, characterized in that: The time for supplying the second modifying gas to the substrate in (c) is set to be longer than the time for supplying the first modifying gas to the substrate in (a).

9. The substrate processing method according to any one of claims 2, 4 and 5, characterized in that: The time for supplying the second modifying gas to the substrate in (c) is set to be shorter than the time for supplying the first modifying gas to the substrate in (a).

10. The substrate processing method according to claim 1, characterized in that: In the above-mentioned cycles after the n1th time, the partial pressure of the above-mentioned first modified gas in the space in (a) is set to be lower than that in the above-mentioned cycles before the n1-1th time, or (a) is not performed, wherein n1 is an integer greater than 2.

11. The substrate processing method according to claim 1, characterized in that: In the above-mentioned cycles after the n2th time, the partial pressure of the above-mentioned second modified gas in the space in (c) is set to be lower than that in the above-mentioned cycles before the n2-1th time, or (c) is not implemented, where n2 is an integer greater than 2.

12. The substrate processing method according to claim 1, characterized in that: In the above-mentioned cycles after the m1th time, the time for supplying the above-mentioned first reforming gas to the above-mentioned substrate in (a) is set to be shorter than that in the above-mentioned cycles before the m1-1th time, or (a) is not performed, wherein m1 is an integer greater than 2.

13. The substrate processing method according to claim 1, characterized in that: In the above-mentioned cycles after the m2th time, the time for supplying the above-mentioned second modified gas to the above-mentioned substrate in (c) is set to be shorter than the above-mentioned cycles before the m2-1th time, or (c) is not implemented, where m2 is an integer greater than 2.

14. The substrate processing method according to claim 1, characterized in that: At least one of the cycles further includes (e) supplying an etching gas to the substrate after performing (d).

15. The substrate processing method according to claim 14, characterized in that: The etching gas is a gas containing halogen elements.

16. The substrate processing method according to claim 1, characterized in that: The raw material gas is a gas containing metal elements and halogen elements, and the reaction gas is a reducing gas.

17. The substrate processing method according to claim 1, characterized in that: The first reformed gas and the second reformed gas are the same gas.

18. A method for manufacturing a semiconductor device, characterized in that: The substrate is cycled a specified number of times, and the cycle sequentially performs the following steps: (a) a step of supplying a first reforming gas which is an inorganic halogen-containing gas; (b) a step of supplying raw material gas; (c) a step of supplying a second reforming gas which is an inorganic halogen-containing gas; (d) A step of supplying a reaction gas.

19. A substrate processing device, characterized in that: have: a processing chamber that processes a substrate; a first modifying gas supply system for supplying a first modifying gas, which is an inorganic halogen-containing gas, to the substrate; a second modifying gas supply system for supplying a second modifying gas, which is an inorganic halogen-containing gas, to the substrate; a raw material gas supply system for supplying raw material gas to the substrate; a reaction gas supply system for supplying reaction gas to the substrate; A control unit is configured to control the first modifying gas supply system, the second modifying gas supply system, the raw material gas supply system, and the reaction gas supply system so as to perform a predetermined number of cycles on the substrate, wherein the cycles sequentially perform the following processes: (a) a process of supplying the first modifying gas; (b) a process of supplying the raw material gas; (c) a process of supplying the second modifying gas; and (d) a process of supplying the reaction gas.

20. A program, characterized in that The above program causes the substrate processing device to execute a cycle of a predetermined number of substrates through a computer, and the cycle sequentially executes the following processes: (a) a process of supplying a first reforming gas which is an inorganic halogen-containing gas; (b) a process of supplying raw material gas; (c) a process of supplying a second reforming gas which is an inorganic halogen-containing gas; (d) Process of supplying reaction gas.

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