Semiconductor device manufacturing methods, substrate processing methods, substrate processing apparatus and recording media

Abstract

The present application relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a recording medium. By appropriately suppressing the generation of particles due to a film formed in a processing container, the cleaning cycle is extended and the productivity of the film forming process is improved. A group of the following steps is repeated multiple times: (a) a step of moving a substrate into a processing container; (b) a step of supplying a film forming gas to a substrate supported by a support in the processing container to form a nitride film on the substrate; (c) a step of moving the processed substrate out of the processing container; (d) a step of supplying an oxidizing gas to the processing container after the processed substrate is moved out, oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and maintaining the other portion of the nitride film in a nitride film state without oxidation.

Description

Technical Field

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

[0002] As one of the manufacturing processes of semiconductor devices, there is a case where a film forming process such as a nitride film is formed on a substrate in a processing container (see, for example, Patent Document 1). When the film forming process is performed, since a film is also formed in the processing container and the film forming process is repeated, the film accumulates and piles up in the processing container. When the accumulated film formed in the processing container exceeds the critical film thickness, cracks and film peeling occurs, which causes particle and foreign matter contamination. Therefore, there is a case where the processing container is regularly cleaned and the accumulated film is removed, but the film forming process cannot be performed during the cleaning process. When the cleaning frequency is high, that is, when the cleaning cycle is short, the productivity of the film forming process is reduced.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2010-219308 Summary of the invention

[0006] Problems to be solved by the invention

[0007] An object of the present invention is to provide a method for appropriately suppressing the generation of particles due to a film formed in a processing container, thereby extending a cleaning cycle and improving the productivity of a film forming process.

[0008] Means for solving problems

[0009] According to one aspect of the present invention, there is provided a technique for repeating a group of the following steps a plurality of times:

[0010] (a) a step of loading a substrate into a processing container;

[0011] (b) supplying a film forming gas to the substrate supported by a support member in the processing container to form a nitride film on the substrate;

[0012] (c) a step of carrying out the processed substrate from the processing container;

[0013] (d) A process of supplying an oxidizing gas into the processing container after the processed substrate is moved out, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and maintaining the state of the nitride film without oxidizing other portions of the nitride film different from the portion.

[0014] Effects of the Invention

[0015] According to the present invention, it is possible to appropriately suppress the generation of particles due to a film formed in a processing container, thereby extending a cleaning cycle and improving the productivity of a film forming process. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 1 is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and shows a processing furnace 202 portion in a vertical cross-sectional view.

[0017] Figure 2 This is a schematic diagram of a vertical processing furnace of a substrate processing device preferably used in one embodiment of the present invention. Figure 1 A cross-sectional view taken along line AA shows a portion of the processing furnace 202 .

[0018] Figure 3 1 is a schematic diagram of the configuration of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0019] Figure 4 This is a diagram showing a comparison between a processing sequence in one embodiment of the present invention (processing sequence A) and a processing sequence in a comparative example (processing sequence B).

[0020] Figure 5 It is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a processing furnace 202 portion in a state where a support member is carried out in a vertical cross-sectional view.

[0021] Figure 6 It is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in Modification 1 of the present invention, and shows a processing furnace 202 portion in a vertical cross-sectional view. DETAILED DESCRIPTION

[0022] <One embodiment of the present invention>

[0023] The following mainly refers to Figure 1 to Figure 4 One embodiment of the present invention will be described.

[0024] (1) Configuration of substrate processing apparatus

[0025] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas using heat.

[0026] On the inner side of 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 upper end and a lower end open. The upper end of the manifold 209 is configured to engage with the lower end of the reaction tube 203 and 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 reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). A processing chamber 201 is formed in the hollow portion of the cylinder 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. The wafer 200 includes a product wafer as a product substrate and a dummy wafer as a dummy substrate. The dummy wafer includes a side dummy wafer arranged at the end of the area where the product wafers are arranged, and a filling dummy wafer arranged in a portion not filled with the product wafer.

[0027] Nozzles 249a to 249c as first to third supply parts are provided in the processing chamber 201 in a manner penetrating the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.

[0028] On the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as opening and closing valves are provided in order from the upstream side of the gas flow. Gas supply pipes 232d and 232g are connected to the downstream side of the gas supply pipe 232a compared with the valve 243a. Gas supply pipes 232e and 232h are connected to the downstream side of the gas supply pipe 232b compared with the valve 243b. Gas supply pipes 232f and 232i are connected to the downstream side of the gas supply pipe 232c compared with the valve 243c. On the gas supply pipes 232d to 232i, MFCs 241d to 241i and valves 243d to 243i are provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232i are made of metal materials such as SUS, for example.

[0029] like Figure 2As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, the nozzles 249a to 249c are respectively arranged from the lower part to the upper part of the inner wall of the reaction tube 203 in a manner of standing upward in the arrangement direction of the wafer 200. That is, the nozzles 249a to 249c are respectively arranged along the wafer arrangement area in the area which is on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounds the wafer arrangement area.

[0030] The nozzle 249a is arranged on the side farther from the exhaust port 231a described later than the nozzles 249b and 249c. That is, the nozzles 249b and 249c are arranged on the side closer to the exhaust port 231a than the nozzle 249a. In addition, the nozzles 249b and 249c are symmetrical with respect to the straight line passing through the center of the wafer 200 in the state where the wafer 200 is carried into the processing chamber 201, that is, the center of the reaction tube 203 and the center of the exhaust port 231a as the symmetry axis when viewed from above. In addition, the nozzles 249a and 249b are arranged so as to face each other on a straight line with the center of the reaction tube 203 sandwiched therebetween.

[0031] Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are opened toward the center of the reaction tube 203, respectively, and can supply gas to the wafer 200. The gas supply holes 250a and 250b are opened so as to face (oppose) the center of the reaction tube 203 on a straight line with the center of the wafer 200 sandwiched therebetween. A plurality of gas supply holes 250a to 250c are provided in the range from the bottom to the top of the reaction tube 203.

[0032] As a raw material (raw material gas), for example, a silane gas containing silicon (Si) as a main element constituting a film formed on the wafer 200 is supplied from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. As the silane gas, for example, a gas containing Si and a halogen, i.e., a halogenated silane gas can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halogenated silane gas, for example, a chlorosilane gas containing Si and Cl can be used.

[0033] As the nitriding gas (nitriding agent), for example, a gas containing nitrogen (N) and hydrogen (H), that is, a hydrogen nitride-based gas, is supplied from gas supply pipes 232b and 232c via MFCs 241b and 241c, valves 243b and 243c, and nozzles 249b and 249c into the processing chamber 201. The gas containing N and H is both a N-containing gas and a H-containing gas.

[0034] As the cleaning gas, for example, a fluorine (F)-containing gas is supplied from the gas supply pipe 232 d into the processing chamber 201 via the MFC 241 d , the valve 243 d , the gas supply pipe 232 a , and the nozzle 249 a .

[0035] As an oxidizing gas (oxidant), for example, a gas containing oxygen (O) is supplied from the gas supply pipe 232f into the processing chamber 201 via the MFC 241f, the valve 243f, the gas supply pipe 232c, and the nozzle 249c.

[0036] As a reducing gas (reducing agent), for example, a hydrogen (H)-containing gas is supplied from the gas supply pipe 232e via the MFC 241e, the valve 243e, the gas supply pipe 232b, and the nozzle 249b into the processing chamber 201. The H-containing gas alone cannot obtain an oxidizing effect, but it reacts with the O-containing gas under specific conditions to generate oxidizing species such as atomic oxygen (atomic oxygen, O), thereby playing a role in improving the oxidation treatment efficiency.

[0037] Inert gas is supplied from gas supply pipes 232g to 232i via MFCs 241g to 241i, valves 243g to 243i, gas supply pipes 232a to 232c, and nozzles 249a to 249c into the processing chamber 201. The inert 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 the gas supply pipe 232a, MFC241a, and valve 243a. The nitriding gas supply system (including N and H gas supply system) is mainly composed of the gas supply pipes 232b, 232c, MFC241b, 241c, valves 243b, 243c. The oxidizing gas supply system (including O gas supply system) is mainly composed of the gas supply pipe 232f, MFC241f, and valve 243f. The reducing gas supply system (including H gas supply system) is mainly composed of the gas supply pipe 232e, MFC241e, and valve 243e. The cleaning gas supply system (including F gas supply system) is mainly composed of the gas supply pipe 232d, MFC241d, and valve 243d. The inactive gas supply system is mainly composed of the gas supply pipes 232g~232i, MFC241g~241i, and valves 243g~243i.

[0039] It should be noted that the raw material gas, N- and H-containing gases, or both thereof are also referred to as film-forming gases, and the raw material gas supply system, N- and H-containing gas supply system, or both thereof are also referred to as film-forming gas supply systems. In addition, there are also cases where O-containing gas and H-containing gas, or both thereof are referred to as oxidizing gases, and there are also cases where O-containing gas supply systems and H-containing gas supply systems, or both thereof are referred to as oxidizing gas supply systems.

[0040] Any or all of the various gas supply systems described above may also be configured as an integrated gas supply system 248 formed by integrating valves 243a to 243i, MFCs 241a to 241i, etc. The integrated gas supply system 248 is connected to the gas supply pipes 232a to 232i, respectively, and is configured such that the supply action of various gases into the gas supply pipes 232a to 232i, that is, the opening and closing action of the valves 243a to 243i, the flow rate adjustment action performed by the MFCs 241a to 241i, etc., is controlled by the controller 121 described later. The integrated gas supply system 248 is configured as an integrated unit of an integral type or a split type, and is configured to be detachable relative to the gas supply pipes 232a to 232i, etc., as an integrated unit unit, and the integrated gas supply system 248 can be maintained, replaced, and added as an integrated unit unit.

[0041] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side wall of the reaction tube 203. The exhaust port 231a may be provided from the lower part to the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. 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 (AutoPressure Controller: automatic pressure controller) valve 244 as a pressure regulator (pressure regulating unit). The APC valve 244 is configured to open and close the valve in a state where the vacuum pump 246 is operated, thereby performing vacuum exhaust and stopping vacuum exhaust in the processing chamber 201. In addition, the valve opening is adjusted based on the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is operated, thereby adjusting the pressure in the processing chamber 201. 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 a vacuum pump 246 is included in the exhaust system.

[0042] A sealing cover 219 as a furnace port cover body capable of sealing the lower end opening of the manifold 209 in an airtight manner is provided below the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the wafer boat 217 described later is provided below the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 is connected to the wafer boat 217 in a manner that passes through the sealing cover 219. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. 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 boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cap 219 .

[0043] A shutter plate 219 s serving as a furnace port cover is provided below the manifold 209 . The shutter plate 219 s can hermetically seal the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer boat 217 is unloaded from the processing chamber 201 . Figure 5 The figure shows a state where the lower end opening of the manifold 209 is blocked by the gate 219s when the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The gate 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the gate 219s. The opening and closing action (lifting action, rotation action, etc.) of the gate 219s is controlled by the gate opening and closing mechanism 115s.

[0044] The wafer boat 217, which is a support member for supporting the substrate, is configured to support a plurality of wafers 200, for example, 25 to 200, in a horizontal posture and in a state where the centers are aligned with each other in a vertical direction and arranged in multiple stages, that is, arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. A heat shield 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages at the lower part of the wafer boat 217.

[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] like Figure 3As shown, the controller 121 as a control unit (control mechanism) is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. 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. An input / output device 122 such as a touch panel is connected to the controller 121.

[0047] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. A control program for controlling the operation of the substrate processing device, a processing procedure recording the steps and conditions of the processing described later, etc., are stored in a readable manner in the storage device 121c. The processing procedure is a combination of the controller 121 to perform each step in the processing described later and obtain a specified result, and functions as a program. Hereinafter, the processing procedure, the control program, etc. are also referred to as programs. In addition, the processing procedure is also referred to as a procedure. In this specification, the term "program" is used in situations where only the procedure is included, only the control program is included, or both the process unit and the control program are included. RAM121b is configured as a memory area (working area) for temporarily holding programs, data, etc. read by CPU121a.

[0048] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241i, valves 243a to 243i, 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 a control program from the storage device 121c and execute it, and to read a recipe from the storage device 121c in response to input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read recipe, flow rate adjustment operations of various gases by the MFCs 241a to 241h, opening and closing operations of the valves 243a to 243h, opening and closing operations of the APC valve 244 and pressure adjustment operations by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 based on the temperature sensor 263, rotation of the wafer boat 217 and rotation speed adjustment operations by the rotation mechanism 267, lifting and lowering operations of the wafer boat 217 by the wafer boat elevator 115, opening and closing operations of the shutter 219s by the shutter 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 on 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, an SSD, etc. The storage device 121c and the external storage device 123 are configured in the form of a computer-readable recording medium. Hereinafter, they are also referred to as recording media. In this specification, the term recording medium is used in situations where only the storage device 121c is included, only the external storage device 123 is included, or both the storage device 121c and the external storage device 123 are included. It should be noted that the provision of the program to the computer can also be carried out without using the external storage device 123 and using a communication mechanism such as the Internet or a dedicated line.

[0051] (2) Processing

[0052] Main Use Figure 4 An example of a processing sequence is described in which a group of the following steps is repeated multiple times: as one of the steps in the manufacturing process of a semiconductor device, a step of forming a nitride film on a wafer 200 as a substrate in a processing container using the above-mentioned substrate processing apparatus; a step of oxidizing and converting a part of the nitride film formed in the processing container after the processing into an oxide film, and maintaining the other part of the nitride film formed in the processing container after the processing in a nitride film state without being oxidized. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0053] In the processing sequence of this method, the group including the following steps is repeated multiple times:

[0054] (a) A step of loading the wafer 200 into a processing container;

[0055] (b) supplying a film forming gas to the wafer 200 supported by the wafer boat 217 as a support member in the processing container, thereby performing a process of forming a nitride film on the wafer 200;

[0056] (c) a step of removing the processed wafer 200 from the processing container;

[0057] (d) A process of supplying an oxidizing gas into a processing container after the processed chip 200 is moved out, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and maintaining other portions of the nitride film different from the portion in a nitride film state without being oxidized.

[0058] In addition, in the processing sequence of this embodiment, the group of (a), (b), (c), and (d) is repeated multiple times. That is, in the processing sequence of this embodiment, each time (a), (b), and (c) are performed, (d) is performed each time. In other words, in the processing sequence of this embodiment, each time a process of forming a nitride film on the wafer 200 is performed by (a), (b), and (c), (d) is performed.

[0059] Here, in addition to silicon nitride film (SiN film), nitride film containing carbon (C), oxygen (O), boron (B), etc. is also included in the nitride film. That is, the nitride film includes silicon nitride film (SiN film), silicon carbon nitride film (SiCN film), silicon oxynitride film (SiON film), silicon oxycarbon nitride film (SiOCN film), silicon boron carbon nitride film (SiBCN film), silicon boron nitride film (SiBN film), silicon boron oxycarbon nitride film (SiBOCN film), silicon boron oxynitride film (SiBON film), etc. In the following method, an example of forming a SiN film as a nitride film is described.

[0060] In the following manner, an example of forming a SiN film on a wafer 200 by performing a cycle including the following steps for a predetermined number of times (n times, n being an integer greater than 1) is described: a step of supplying a chlorosilane-based gas to the wafer 200 in (b); and a step of supplying a gas containing N and H to the wafer 200. In this specification, for convenience, there is also a case where such a gas supply sequence is shown as follows. The same expression is also used in the following description of other embodiments, modified examples, etc.

[0061]

[0062] In addition, the following example is described in the following manner: in (d), as oxidizing gases, O-containing gas and H-containing gas are simultaneously supplied into a processing container under reduced pressure after the processed chip 200 is moved out, so that a portion of the SiN film formed in the processing container in (b) is oxidized and converted into a SiO film, and other portions of the SiN film different from the portion maintain the state of the SiN film without being oxidized.

[0063] In this specification, the term "wafer" may be used to refer to the wafer itself or to refer to a stack of a wafer and a predetermined layer or film formed on the surface thereof. In this specification, the term "surface of the wafer" may be used to refer to the surface of the wafer itself or to refer to the surface of a predetermined layer, etc., formed on the wafer. In this specification, "a predetermined layer is formed on the wafer" may be used to refer to the formation of a predetermined layer directly on the surface of the wafer itself or to refer to the formation of a predetermined layer on a layer, etc., formed on the wafer. In this specification, the term "substrate" may be used to refer to the same meaning as the term "wafer".

[0064] (Wafer Filling)

[0065] A plurality of wafers 200 are filled in the wafer boat 217 (wafer filling). Afterwards, the shutter 219s is moved by the shutter opening and closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter opening). As described above, the wafers 200 include product wafers and dummy wafers. That is, as the wafers 200, the wafer boat 217 is filled with product wafers and dummy wafers.

[0066] (Crystal boat loading)

[0067] Afterwards, if Figure 1 As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0068] (Pressure regulation and temperature regulation)

[0069] After the wafer boat is loaded, vacuum exhaust (decompression exhaust) is performed by the vacuum pump 246 so that the space in the processing chamber 201, that is, the space where the wafer 200 is located, reaches a 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 (pressure regulated) based on the measured pressure information. In addition, the heater 207 heats the wafer 200 in the processing chamber 201 so that it reaches a 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 processing chamber 201 reaches a desired temperature distribution (temperature regulation). In addition, the rotation of the wafer 200 by the rotation mechanism 267 is started. 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.

[0070] (Film forming treatment)

[0071] After that, follow the steps 1 and 2 below.

[0072] [Step 1]

[0073] In step 1 , a chlorosilane-based gas is supplied to a wafer 200 in a processing chamber 201 .

[0074] Specifically, valve 243a is opened to allow chlorosilane gas to flow into gas supply pipe 232a. Chlorosilane gas is flow-regulated by MFC 241a, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, chlorosilane gas is supplied to wafer 200 (chlorosilane gas supply). At this time, valves 243g to 243i may be opened to supply inactive gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0075] The treatment conditions in this step may be exemplified as follows:

[0076] Chlorosilane gas supply flow rate: 0.01 to 2 slm, preferably 0.1 to 1 slm

[0077] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0078] Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0079] Processing temperature (temperature of the wafer 200 ): 400 to 700° C., preferably 500 to 650° C. Processing pressure (pressure in the processing chamber 201 ): 1 to 2666 Pa, preferably 67 to 1333 Pa.

[0080] It should be noted that the expression of a numerical range such as "1 to 2666 Pa" in this specification means that the lower limit and the upper limit are included in the range. Thus, for example, "1 to 2666 Pa" means "1 Pa or more and 2666 Pa or less". The same applies to other numerical ranges.

[0081] By supplying chlorosilane gas to the wafer 200 under the above conditions, a Si-containing layer containing Cl is formed on the outermost surface of the wafer 200 serving as a substrate. The Si-containing layer containing Cl is formed by physical adsorption, chemical adsorption, chemical adsorption of molecules of a substance obtained by partial decomposition of the chlorosilane gas, and accumulation of Si caused by thermal decomposition of the chlorosilane gas, etc. of molecules of the chlorosilane gas to the outermost surface of the wafer 200. The Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer, chemical adsorption layer) of molecules of the chlorosilane gas or molecules of a substance obtained by partial decomposition of the chlorosilane gas, or may be an accumulation layer of Si containing Cl. In this specification, the Si-containing layer containing Cl is also referred to as the Si-containing layer.

[0082] After the Si-containing layer is formed, the valve 243a is closed to stop the supply of the chlorosilane-based gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove (purge) the gas remaining in the processing chamber 201. At this time, the valves 243g to 243i may be opened to supply an inert gas into the processing chamber 201. The inert gas functions as a purge gas.

[0083] As chlorosilane-based gases, for example, monochlorosilane (SiH3Cl, abbreviated as MCS) gas, dichlorosilane (SiH2Cl2, abbreviated as DCS) gas, trichlorosilane (SiHCl3, abbreviated as TCS) gas, tetrachlorosilane (SiCl4, abbreviated as STC) gas, hexachlorodisilane gas (Si2Cl6, abbreviated as HCDS) gas, octachlorotrisilane (Si3Cl8, abbreviated as OCTS) gas, etc. can be used. It should be noted that, fluorosilane-based gases such as silicon tetrafluoride (SiF4) gas, bromosilane-based gases such as silicon tetrabromide (SiBr4) gas, and iodosilane-based gases such as silicon tetraiodide (SiI4) gas can be used instead of chlorosilane-based gases.

[0084] As the inert gas, a rare gas such as nitrogen (N 2 ) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. This also applies to each step described later.

[0085] [Step 2]

[0086] After step 1 is completed, a gas containing N and H is supplied to the wafer 200 in the processing chamber 201 , that is, the Si-containing layer formed on the wafer 200 .

[0087] Specifically, valves 243b and 243c are opened to allow N- and H-containing gases to flow into gas supply pipes 232b and 232c, respectively. The N- and H-containing gases are flow-regulated by MFCs 241b and 241c, respectively, and are supplied into the processing chamber 201 through nozzles 249b and 249c, respectively, and exhausted from exhaust port 231a. At this time, N- and H-containing gases are supplied to the wafer 200 (N- and H-containing gas supply). At this time, valves 243g to 243i may be opened to supply inactive gases into the processing chamber 201 through nozzles 249a to 249c, respectively. It should be noted that, at this time, N- and H-containing gases may be supplied from nozzle 249b instead of nozzle 249c, or N- and H-containing gases may be supplied from nozzle 249c instead of nozzle 249b. That is, N- and H-containing gases may be supplied from at least one of nozzles 249b and 249c.

[0088] The treatment conditions in this step may be exemplified as follows:

[0089] N and H containing gas supply flow rate: 0.1~10slm

[0090] N and H containing gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0091] Processing pressure (pressure in the processing chamber 201): 1 to 4000 Pa, preferably 1 to 3000 Pa.

[0092] The other processing conditions were set to be the same as those in step 1.

[0093] By supplying N and H containing gas to the wafer 200 under the above conditions, at least a portion of the Si containing layer formed on the wafer 200 is nitrided (modified). As a result, a silicon nitride layer (SiN layer) is formed as a layer containing Si and N on the outermost surface of the wafer 200 as a base. When the SiN layer is formed, impurities such as Cl contained in the Si containing layer constitute a gaseous substance containing at least Cl during the modification reaction of the Si containing layer by the N and H containing gas, and are exhausted from the processing chamber 201. As a result, the SiN layer becomes a layer with less impurities such as Cl than the Si containing layer formed in step 1.

[0094] After the SiN layer is formed, valves 243b and 243c are closed to stop the supply of N and H containing gas into the processing chamber 201. Then, the gas etc. remaining in the processing chamber 201 is exhausted (purged) from the processing chamber 201 by the same processing steps as the purging in step 1.

[0095] As the N and H-containing gas, for example, ammonia (NH 3 ) gas, diazenium (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, N 3 H 8 gas or other hydrogen nitride-based gas can be used.

[0096] [Perform a specified number of cycles]

[0097] By performing the above steps 1 and 2 non-simultaneously, i.e., non-synchronously, for a predetermined number of times (n times, n being an integer greater than 1), a SiN film of a predetermined thickness can be formed on the substrate with the surface of the wafer 200 as the substrate. Preferably, the above cycle is repeated multiple times. That is, it is preferred that the thickness of the SiN layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated multiple times until the thickness of the SiN film formed by stacking the SiN layers reaches the desired thickness.

[0098] It should be noted that during the film forming process, a deposit containing SiN film is also formed in the processing container, such as the inner wall of the processing container, that is, the inner wall of the reaction tube 203, the inner wall of the manifold 209, the surface of the nozzles 249a~249c, the surface of the wafer boat 217, etc.

[0099] (Post-purge and atmospheric pressure recovery)

[0100] After the process of forming a SiN film of a desired thickness on the wafer 200 is completed, an inactive gas is supplied from the nozzles 249a to 249c into the process chamber 201 as a purge gas, and the gas is exhausted from the exhaust port 231a. Thus, the process chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the process chamber 201 are removed from the process chamber 201 (post-purge). After that, the atmosphere in the process chamber 201 is replaced with an inactive gas (inactive gas replacement), and the pressure in the process chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0101] (Unloading of crystal boat)

[0102] After that, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). Figure 5 As shown, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s via the O-ring 220c (the gate is closed).

[0103] (Wafer Cooling)

[0104] After the wafer boat is unloaded, that is, after the shutter is closed, the processed wafers 200 are cooled to a predetermined temperature to be taken out while being supported by the wafer boat 217 (wafer cooling).

[0105] (Wafer removal)

[0106] After the wafer is cooled, the processed wafer 200 cooled to a predetermined temperature at which it can be taken out is taken out from the wafer boat 217 (wafer removal).

[0107] (Oxidation treatment of film deposited in furnace)

[0108] In parallel with the wafer cooling and wafer removal, an oxidation treatment is performed on the film attached to the furnace during the film forming process, that is, the deposit including the SiN film formed in the processing container during the film forming process. The oxidation treatment of the SiN film formed in the processing container is performed in a manner that the oxidation of the SiN film is unsaturated, that is, unsaturated oxidation.

[0109] That is, after the wafer boat is unloaded and the gate is closed, Figure 5 In the state of the wafer 200 being removed, in parallel with the wafer cooling and the wafer removal, an O-containing gas and a H-containing gas are simultaneously supplied as oxidizing gases into the processing container which is in a reduced pressure state (a state lower than the atmospheric pressure) after the processed wafer 200 is removed. Thus, during the film formation process, a portion of the SiN film formed in the processing container is oxidized and converted into a SiO film, and other portions of the SiN film, which are different from the portion, are kept in the state of the SiN film without being oxidized.

[0110] Specifically, after the gate is closed, valves 243f and 243e are opened to allow the O-containing gas and H-containing gas to flow into the gas supply pipes 232f and 232e, respectively. The O-containing gas and H-containing gas flowing in the gas supply pipes 232f and 232e are respectively adjusted in flow rate by MFC241f and 241e, and are supplied to the processing chamber 201 through nozzles 249c and 249b. The O-containing gas and the H-containing gas are mixed and reacted in the processing chamber 201, and then exhausted from the exhaust port 231a. At this time, the SiN film formed in the processing container is supplied with oxidizing species containing oxygen but not containing water (H2O), such as atomic oxygen generated by the reaction of the O-containing gas and the H-containing gas (O-containing gas + H-containing gas supply). At this time, valves 243g~243i can also be opened to supply inactive gas into the processing chamber 201 through nozzles 249a~249c.

[0111] The treatment conditions in this step may be exemplified as follows:

[0112] O-containing gas supply flow rate: 0.1~10slm

[0113] H-containing gas supply flow rate: 0.1~10slm

[0114] Inert gas supply flow rate (each gas supply pipe): 0~10slm

[0115] Each gas supply time: 15 to 60 minutes

[0116] Processing temperature (temperature in the processing chamber 201): 400 to 800°C, preferably 600 to 700°C

[0117] Processing pressure (pressure in the processing chamber 201): 1 to 2000 Pa, preferably 1 to 1000 Pa.

[0118] By supplying an O-containing gas and a H-containing gas to the SiN film formed in the processing container under the above conditions, it is possible to utilize the strong oxidizing power of oxidizing species such as atomic oxygen to oxidize a portion of the SiN film formed in the processing container and convert it into a SiO film, while maintaining the other portion of the SiN film different from the portion in the SiN film in the state of a SiN film without being oxidized. For example, it is possible to oxidize a portion of the surface side of the SiN film formed in the processing container and convert it into a SiO film, while maintaining the other portion of the SiN film different from the portion on the surface side (the portion on the opposite side to the surface side) in the SiN film in the state of a SiN film without being oxidized.

[0119] It should be noted that when a part of the SiN film formed in the processing container is converted into a SiO film by oxidation, it expands due to the intake of O. Therefore, the SiO film obtained by oxidizing a part of the SiN film formed in the processing container is thicker than the part of the SiN film formed in the processing container before oxidation (the oxidized part of the SiN film). There is a case where the thickness of the SiO film obtained by oxidizing a part of the SiN film formed in the processing container increases to a thickness of about 1.4 to 1.5 times the thickness of the part of the SiN film formed in the processing container before oxidation.

[0120] Based on the above situation, the total thickness of the stacked structure of the SiO film obtained by oxidizing a portion of the SiN film formed in the processing container and the unoxidized SiN film in the SiN film formed in the processing container, that is, the stacked film (hereinafter also referred to as SiO / SiN stacked film) is thicker than the thickness of the SiN film formed in the processing container before oxidation.

[0121] In addition, the stress (film stress, internal stress, residual stress) of the SiN film formed in the processing container is tensile stress, while the stress of the SiO film obtained by oxidizing a part of the SiN film formed in the processing container is compressive stress. When "+" represents tensile stress and "-" represents compressive stress, the stress of the SiN film formed in the processing container is, for example, about +1.0 to 1.5 GPa, and the stress of the SiO film obtained by oxidizing a part of the SiN film formed in the processing container is, for example, about -0.3 to 0.5 GPa.

[0122] Based on the above situation, the stress of the stacked film of the SiO film obtained by oxidizing a part of the SiN film formed in the processing container and the SiN film that is not oxidized and maintained in the SiN film formed in the processing container, that is, the overall stress of the SiO / SiN stacked film is less than the stress of the SiN film before oxidation formed in the processing container. This is because the tensile stress of the SiN film in the SiO / SiN stacked film and the compressive stress of the SiO film act in a mutually offset manner. By adjusting the thickness of the SiN film and the SiO film in the SiO / SiN stacked film, the stress balance of the tensile stress of the SiN film in the SiO / SiN stacked film and the compressive stress of the SiO film can be adjusted, and the respective stresses can be offset. That is, the overall stress of the SiO / SiN stacked film can be made close to zero by adjusting the stress balance, and in addition, the stress can be made zero. By reducing the stress of the film formed in the processing container in this way, it is possible to suppress the generation of particles due to the film formed in the processing container.

[0123] It should be noted that, from the perspective of suppressing the generation of particles due to the film formed in the processing container, it is preferred to make the stress of the SiO / SiN stacked film as a whole close to zero. However, in this case, the oxidation treatment of the SiN film formed in the processing container takes time. Figure 4 As shown in the processing sequence B, there is a case where the oxidation processing time, that is, the oxidation processing time of the deposited film in the furnace exceeds the total time of the wafer cooling time and the wafer removal time. Figure 4 In the process sequence B shown, there is a time when only the oxidation process of the deposited film in the furnace is performed, that is, a standby time when neither wafer cooling nor wafer removal is performed. In this case, there is a time when the film forming process cannot be performed, that is, the downtime of the substrate processing apparatus increases, which affects the productivity of the film forming process.

[0124] In addition, there is also a method of converting all of the SiN film formed in the processing container into a SiO film by completely oxidizing the SiN film formed in the processing container, that is, saturating the oxidation of the SiN film formed in the processing container. However, in this case, the oxidation treatment of the SiN film formed in the processing container is more time-consuming, and there is a case where the oxidation treatment time, that is, the oxidation treatment time of the film attached in the furnace, greatly exceeds the total time of the wafer cooling time and the wafer removal time. In this case, there is a time when the film forming process cannot be performed, that is, the downtime of the substrate processing device becomes longer, which greatly affects the productivity of the film forming process. It should be noted that when the SiN film formed in the processing container is completely converted into a SiO film by saturating the oxidation, the stress of the converted SiO film becomes a compressive stress.

[0125] In contrast, by not making the stress of the SiO / SiN stacked film as a whole zero or compressive stress, but making it tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, the oxidation processing time of the SiN film formed in the processing container can be shortened, such as Figure 4 As shown in the processing sequence A shown in , the oxidation treatment time of the SiN film formed in the processing container, that is, the oxidation treatment time of the film attached in the furnace can be made less than the total time of the wafer cooling time and the wafer removal time. In this case, the time when the film forming process cannot be performed does not change compared with the case where the oxidation treatment of the film attached in the furnace is not performed, and the productivity of the film forming process will not be affected. It should be noted that the inventors of the present application have found that even when the stress of the SiO / SiN stacked film as a whole is a tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container and is not zero, the particle generation suppression effect can be obtained. That is, by making the stress of the SiO / SiN stacked film as a whole a tensile stress smaller than the stress of the SiN film before oxidation formed in the processing container, the productivity of the film forming process can be maintained while exerting the particle generation suppression effect. It should be noted that if the oxidation treatment time of the film attached in the furnace is further shortened, the total time of the wafer cooling time and the wafer removal time is also shortened accordingly, and the productivity of the film forming process can also be improved.

[0126] It should be noted that the inventors of the present application have found that by making the ratio of the SiO film in the SiO / SiN stacked film 75% or less, preferably 70% or less, that is, making the ratio of the SiN film in the SiO / SiN stacked film 25% or more, preferably 30% or more, the stress of the SiO / SiN stacked film as a whole can be made into a tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, and the same effect as the above effect can be obtained. In addition, the inventors of the present application have found that when the ratio of the SiO film in the SiO / SiN stacked film formed in the oxidation treatment of the deposited film in the furnace exceeds 75%, the stress of the SiO / SiN stacked film as a whole becomes a compressive stress.

[0127] In addition, the inventors of the present application have discovered that by making the thickness of the oxidized portion of the SiN film formed in the processing container less than 65%, preferably less than 60%, of the thickness of the SiN film before oxidation formed in the processing container, that is, by making the thickness of the portion of the SiN film formed in the processing container that maintains the SiN film state and is not oxidized more than 35%, preferably more than 40%, of the thickness of the SiN film before oxidation formed in the processing container, the stress of the SiO / SiN stacked film as a whole can be made a tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, and the same effect as the above-mentioned effect can be obtained.

[0128] In addition, the inventors of the present application have discovered that by making the thickness of the oxidized portion of the SiN film formed in the processing container thinner than the thickness of the portion of the SiN film formed in the processing container that maintains the SiN film state and is not oxidized, it is easy to make the stress of the SiO / SiN stacked film as a whole have a tensile stress that is smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, and the same effect as the above-mentioned effect can be reliably obtained.

[0129] It should be noted that, when a part of the SiN film formed in the processing container is converted into a SiO film and another part of the SiN film, which is different from the part, is maintained in the state of a SiN film, pulse exhaust (intermittent exhaust) may be performed in the processing chamber 201 while continuously supplying an O-containing gas and a H-containing gas into the processing container, that is, the processing chamber 201. That is, the APC valve 244 as an exhaust valve may be repeatedly opened and closed multiple times while continuously supplying an O-containing gas and a H-containing gas into the processing chamber 201. In this case, the following steps are repeated multiple times: the step of supplying an O-containing gas and a H-containing gas into the processing chamber 201 while the APC valve 244 is opened, that is, after the processing chamber 201 is exhausted; and the step of supplying an O-containing gas and a H-containing gas into the processing chamber 201 while the APC valve 244 is closed, that is, the exhaust in the processing chamber 201 is stopped. It should be noted that when the APC valve 244 is opened, the exhaust pipe 231 is open, and when the APC valve 244 is closed, the exhaust pipe 231 is closed. When pulse exhaust is performed in the process chamber 201 while the O-containing gas and the H-containing gas are continuously supplied to the process chamber 201, it is also preferred to maintain the process chamber 201 in a reduced pressure state. It should be noted that the O-containing gas and the H-containing gas may be supplied to the process chamber 201 not only continuously but also intermittently. When the O-containing gas and the H-containing gas are intermittently supplied to the process chamber 201, it is preferred that at least a portion of the period during which the APC valve 244 is closed, that is, the period during which the exhaust in the process chamber 201 is stopped, overlaps with at least a portion of the period during which the O-containing gas and the H-containing gas are supplied to the process chamber 201.

[0130] like Figure 2As shown, nozzles 249c and 249b are both arranged near exhaust port 231a, and the O-containing gas and H-containing gas supplied from nozzles 249c and 249b, respectively, are exhausted from exhaust port 231a before being dispersed into the portion of the process chamber 201, for example, on the opposite side of exhaust port 231a. By repeatedly opening and closing APC valve 244 multiple times while continuously supplying O-containing gas and H-containing gas into process chamber 201, the timing of closing APC valve 244 can be increased, and O-containing gas and H-containing gas can be fully dispersed into the portion of the process chamber 201, for example, on the opposite side of exhaust port 231a. Thus, the SiN film formed in the process container, for example, on the opposite side of exhaust port 231a, can be fully oxidized. That is, the SiN film formed in the process container can be uniformly oxidized. It should be noted that the positional relationship between nozzles 249c, 249b and exhaust port 231a is not limited to. Figure 2 As shown, even with Figure 2 The same effect can be achieved with different positional relationships.

[0131] As the O-containing gas, one or more of oxygen (O2) gas, ozone (O3) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc. can be used.

[0132] As the H-containing gas, hydrogen (H2) gas, deuterium ( 2 H2) gas. 2 The H2 gas is referred to as D2 gas. In this step, the H-containing gas may not be supplied, and the O-containing gas may be supplied alone as the oxidizing gas.

[0133] In addition, in this step, at least one of the O-containing gas and the H-containing gas may be plasma-excited and supplied. For example, plasma-excited O2 gas and non-plasma-excited H2 gas may be supplied, or non-plasma-excited O2 gas and plasma-excited H2 gas may be supplied, or plasma-excited O2 gas and plasma-excited H2 gas may be supplied. In addition, plasma-excited O2 gas alone may be supplied without supplying the H-containing gas. By the above operation, the oxidation treatment time can be further shortened.

[0134] After the process of converting a part of the SiN film formed in the processing container into a SiO film and maintaining the other part of the SiN film in the state of the SiN film different from the part is completed, the valves 243f and 243e are closed to stop the supply of the O-containing gas and the H-containing gas into the processing chamber 201. Thereafter, as a purge gas, an inactive gas is supplied from the nozzles 249a to 249c into the processing chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (purging). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inactive gas (inactive gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0135] By the above series of treatments, when the above-mentioned groups (a), (b), (c), and (d) are repeated multiple times, the first group (first batch treatment), that is, Figure 4 The first operation (RUN) in the process is completed. Then, this group (batch processing) is performed multiple times, and in this process, the generation of particles due to the film formed in the processing container can be appropriately suppressed.

[0136] It should be noted that, as described above, the oxidation treatment of the film attached in the furnace is performed in a state where the shutter is closed. That is, the oxidation treatment of the film attached in the furnace is performed without moving (accommodating) the processed wafer boat 217 and the wafer 200 (product wafer, dummy wafer) into the processing container. Therefore, the above-mentioned oxidation treatment is not performed on the SiN film formed on the surface of the processed wafer boat 217 and the wafer 200 (product wafer, dummy wafer), and the SiN film formed on the surface of the wafer boat 217 and the wafer 200 (product wafer, dummy wafer) is not oxidized and remains in its original state, that is, the state of the SiN film is maintained.

[0137] Therefore, after the second group (the second batch of processing), that is, Figure 4 After the second operation in the process, the film forming process can be performed while the wafer 200 is supported by the wafer boat 217 having the SiN film formed on the surface, that is, the product wafer to be processed next and the dummy wafer having the SiN film formed on the surface are supported.

[0138] That is, after the second group (second batch processing), the wafer 200 contacts the wafer boat 217 via the SiN film formed on the surface of the wafer boat 217. Specifically, the wafer boat 217 contacts the product wafer to be processed next via the SiN film formed on the surface of the wafer boat 217. In addition, the wafer boat 217 contacts the dummy wafer via the SiN film formed on their respective surfaces. The SiN film formed on the surface of the wafer boat 217 and the surface (back side) of the product wafer are materials having thermal expansion coefficients close to each other. Therefore, even if they are heated and thermally expanded separately during the film forming process, since the degrees of their respective thermal expansion are close, the generation of particles from the above contact parts can be suppressed. In addition, the SiN film formed on the surface of the wafer boat 217 and the SiN film formed on the surface of the dummy wafer are made of the same material and have the same thermal expansion coefficient. Therefore, even if they are heated and thermally expanded separately during the film forming process, they thermally expand in the same way. Therefore, the generation of particles from the above contact parts can be suppressed.

[0139] (3) Effects of this method

[0140] According to this aspect, one or more of the following effects can be obtained.

[0141] In the oxidation treatment of the film attached in the furnace, a part of the SiN film formed in the processing container is oxidized and converted into a SiO film, and other parts of the SiN film different from the part are kept in the SiN film state without being oxidized, so that the stress balance of the film formed in the processing container can be adjusted, and the stress of the film formed in the processing container can be made smaller than the stress of the SiN film before oxidation formed in the processing container. Thus, by appropriately suppressing the generation of particles due to the film formed in the processing container, the cleaning cycle can be extended and the productivity of the film forming treatment can be improved.

[0142] In the oxidation treatment of the attached film in the furnace, a part of the SiN film formed in the processing container is oxidized and converted into a SiO film, and other parts of the SiN film different from this part are maintained in the SiN film state without being oxidized, thereby shortening the oxidation time and maintaining or improving productivity.

[0143] In the oxidation treatment of the film attached in the furnace, a part of the SiN film formed in the processing container is oxidized and converted into a SiO film, and the other part of the SiN film different from the part is maintained in the SiN film state without being oxidized. Therefore, compared with the case where the SiO film is deposited on the surface of the SiN film formed in the processing container, the cumulative film thickness in the processing container can be suppressed to be thinner, and the thickness of the SiN film itself formed in the processing container can be reduced. As a result, the risk of particle generation caused by the increase in the cumulative film thickness in the processing container and the thickness of the SiN film can be reduced. It should be noted that in the case where the SiO film is deposited on the surface of the SiN film formed in the processing container, the thickness of the SiN film itself formed in the processing container cannot be thinned, and its thickness remains unchanged.

[0144] In the oxidation treatment of the film attached in the furnace, a part of the SiN film formed in the processing container is oxidized and converted into a SiO film, and other parts of the SiN film different from the part are maintained in the SiN film state without being oxidized. Therefore, compared with the case where the SiO film is deposited on the surface of the SiN film formed in the processing container, the contamination at the interface between the SiO film and the SiN film can be reduced, the interface can be stabilized, and the film peeling at the interface can be suppressed. It should be noted that in the case where the SiO film is deposited on the surface of the SiN film formed in the processing container, it is believed that contamination occurs at the interface between the SiO film and the SiN film, and film peeling is likely to occur. In addition, it is also believed that there is a risk of particle generation due to the gas phase reaction when the SiO film is deposited.

[0145] By adjusting the thickness of the stacked film of the SiO film obtained by oxidizing a part of the SiN film formed in the processing container and the SiN film that is not oxidized and maintained in the SiN film formed in the processing container, that is, the SiN film and the SiO film in the SiO / SiN stacked film, the stress balance between the tensile stress of the SiN film and the compressive stress of the SiO film in the SiO / SiN stacked film can be adjusted. In this way, the respective stresses can be offset, and the stress of the SiO / SiN stacked film as a whole can be close to zero, and the stress can also be zero. In this way, the generation of particles due to the film formed in the processing container can be appropriately suppressed.

[0146] By making the overall stress of the SiO / SiN stacked film a tensile stress, that is, a tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, the oxidation treatment time can be shortened, and the productivity of the film forming process can be maintained or improved while achieving the effect of suppressing particle generation.

[0147] By making the ratio of SiO film in the SiO / SiN stacked film less than 75%, preferably less than 70%, the stress of the SiO / SiN stacked film as a whole can be made into a tensile stress smaller than the stress (tensile stress) of the SiN film before oxidation formed in the processing container, thereby achieving the effect of suppressing particle generation while maintaining or improving the productivity of the film forming process.

[0148] By performing the oxidation treatment of the film attached in the furnace without storing (carrying) the processed wafer boat 217 in the processing container, the SiN film formed on the surface of the wafer boat 217 can be maintained in the SiN film state without being oxidized. Therefore, after the second group (second batch processing), the film forming treatment can be performed in a state where the wafer 200 to be processed next is supported by the wafer boat 217 with the SiN film formed on the surface. That is, after the second group (second batch processing), the wafer 200 and the wafer boat 217 are in contact with each other through the SiN film formed on the surface of the wafer boat 217. Therefore, compared with the case where the SiN film formed on the surface of the wafer boat 217 is oxidized, the generation of particles from the contact portion between the wafer 200 and the wafer boat 217 can be suppressed.

[0149] It should be noted that when the processed wafer boat 217 is stored (carried) in the processing container and the attached film oxidation treatment is performed in the furnace, at least the surface of the SiN film formed on the surface of the wafer boat 217 is oxidized, and the outermost surface of the wafer boat becomes a SiO film. In this case, after the second group (second batch processing), the wafer 200 contacts the wafer boat 217 through the SiO film formed on the outermost surface of the wafer boat 217. In this case, the surface (back side) of the wafer 200 to be processed next and the SiO film formed on the outermost surface of the wafer boat 217 become materials with greatly different thermal expansion coefficients. Therefore, when they are heated and thermally expanded respectively during the film forming process, the friction of these contact parts becomes large due to the thermal expansion difference of each material, and there is a case where particles are generated from these contact parts.

[0150] By performing the oxidation treatment of the film attached in the furnace without accommodating (carrying) the processed wafer boat 217 and the wafer 200 (product wafer, dummy wafer) into the processing container, the SiN film formed on the surface of the wafer boat 217 and the wafer 200 (product wafer, dummy wafer) can be maintained in the SiN film state without being oxidized. Therefore, after the second group (second batch processing), the film forming treatment can be performed in a state where the product wafer to be processed next and the dummy wafer with the SiN film formed on the surface are supported by the wafer boat 217 with the SiN film formed on the surface. That is, after the second group (second batch processing), the wafer boat 217 and the product wafer to be processed next are in contact with each other through the SiN film formed on the surface of the wafer boat 217, and the wafer boat 217 and the dummy wafer are in contact with each other through the SiN film formed on their respective surfaces. Therefore, the generation of particles from the contact portion between the wafer 200 and the wafer boat 217 can be suppressed.

[0151] It should be noted that, when the processed wafer boat 217 is stored (carried) in the processing container and the oxidation treatment of the film attached in the furnace is performed, at least the surface of the SiN film formed on the surface of the wafer boat 217 is oxidized, and the outermost surface of the wafer boat becomes a SiO film. In this case, after the second group (second batch processing), the wafer 200 (the product wafer to be processed next, the dummy wafer with the SiN film formed on the surface) contacts the wafer boat 217 via the SiO film formed on the outermost surface of the wafer boat 217. In this case, the SiO film formed on the outermost surface of the wafer boat 217 and the surface (back surface) of the wafer 200 (the product wafer to be processed next, the dummy wafer with the SiN film formed on the surface) are materials with greatly different thermal expansion coefficients. Therefore, when they are heated and thermally expanded during the film forming process, the friction of these contact parts becomes large due to the difference in thermal expansion of each material, and particles may be generated from these contact parts.

[0152] In addition, by performing the in-furnace oxidation treatment of the attached film without accommodating (moving into) the processed wafer boat 217 into the processing container, the wafer boat loading time and wafer boat unloading time used for the in-furnace oxidation treatment of the attached film can be eliminated, and the time when the film forming treatment cannot be performed can be shortened accordingly, thereby improving the productivity of the film forming treatment.

[0153] By performing the oxidation treatment of the film deposited in the furnace in parallel with the cooling of the wafer, it is not necessary to set a time for performing the oxidation treatment of the film deposited in the furnace in addition to the cooling of the wafer, and the productivity of the film forming process can be maintained or improved. It should be noted that, depending on the conditions of the oxidation treatment of the film deposited in the furnace, the oxidation treatment of the film deposited in the furnace can also be performed in parallel with the cooling of the wafer and completed before the wafer is taken out.

[0154] By performing the oxidation treatment of the film deposited in the furnace in parallel with the cooling of the wafer and the removal of the wafer, it is not necessary to set a separate time for the oxidation treatment of the film deposited in the furnace in addition to the cooling of the wafer and the removal of the wafer, and the productivity of the film forming process can be maintained or improved. It should be noted that, depending on the conditions of the oxidation treatment of the film deposited in the furnace, the oxidation treatment of the film deposited in the furnace can also be performed in parallel with the cooling of the wafer and the removal of the wafer, and completed in the middle of the wafer removal.

[0155] When performing oxidation treatment of the film deposited in the furnace, while continuously supplying oxidation gas, i.e., O-containing gas and H-containing gas into the processing container, pulse exhaust is performed in the processing container, i.e., the exhaust valve is repeatedly opened and closed multiple times, so that the O-containing gas and H-containing gas can be sufficiently dispersed to the portion of the processing container, for example, on the opposite side of the exhaust port. Thus, the SiN film formed in the portion of the processing container, for example, on the opposite side of the exhaust port, can also be sufficiently oxidized. That is, the SiN film formed in the processing container can be uniformly oxidized.

[0156] Since the oxidation treatment of the film deposited in the furnace is performed for each batch (each operation), that is, each time a batch of processing is performed, compared with the case where the oxidation treatment of the film deposited in the furnace is performed each time when multiple batches are processed, a part of the SiN film can be oxidized while the SiN film formed in the processing container is thin. As a result, the oxidation treatment of the SiN film formed in the processing container can be performed in a region where the oxidation rate can be increased each time, and the oxidation treatment time can be shortened. On the other hand, when the oxidation treatment of the film deposited in the furnace is performed each time when multiple batches are processed, a part of the SiN film is oxidized while the SiN film formed in the processing container is thick. In this case, there is a case where the oxidation treatment needs to be performed in a region where the oxidation rate is reduced, and the oxidation treatment time is prolonged. It should be noted that, compared with the case where the oxidation treatment of the film deposited in the furnace is performed each time when multiple batches are processed, when the oxidation treatment of the film deposited in the furnace is performed each batch, the ratio of the SiO film in the accumulated film formed in the processing container can be increased, and the stress of the accumulated film can be further reduced. That is, by performing the oxidation treatment of the film deposited in the furnace for each batch, the particle generation suppression effect can be exerted, and the productivity of the film forming process can be maintained or improved while further improving this effect.

[0157] (4) Modification

[0158] The processing sequence of this method can be changed according to the following modified examples. These modified examples can be combined arbitrarily. Unless otherwise specified, the processing steps and processing conditions in each step of each modified example can be the same as the processing steps and processing conditions in each step of the above-mentioned processing sequence.

[0159] (Variant 1)

[0160] In step 2 of the film forming process, the N and H containing gas may be supplied to the wafer 200 in the process chamber 201 in a plasma-excited, i.e., activated, plasma state, i.e., the Si containing layer formed on the wafer 200. That is, in the film forming process, each gas may be supplied according to the gas supply sequence shown below to form a SiN film on the wafer 200.

[0161]

[0162] In this case, in step 2 of the film forming process, for example, Figure 6 As shown, the N- and H-containing gases supplied to the gas supply pipes 232b and 232c are respectively excited into plasma by remote plasma units 300b and 300c as plasma excitation units (plasma generation units), and are supplied into the processing chamber 201, wherein the remote plasma units 300b and 300c are respectively arranged on the downstream side of the gas supply pipes 232b and 232c compared with the valves 243b and 243c. It should be noted that in Figure 6 In, with Figure 1 The same parts are marked with the same figure marks, and the description of their structure is omitted.

[0163] The same effect as in the above-described method can also be obtained in this modification. In addition, according to this modification, the film forming process can be further cooled down compared to the case where the film forming process is performed in a non-plasma atmosphere according to the above-described method. Even in the case where the film forming process is performed at a lower temperature using plasma, the same effect as in the above-described method can be obtained.

[0164] (Variant 2)

[0165] When performing the oxidation treatment of the deposited film in the furnace, at least one of the O-containing gas and the H-containing gas may be plasma-excited, that is, activated into a plasma state and supplied into the processing chamber 201 .

[0166] In this case, in the oxidation treatment of the deposited film in the furnace, for example, Figure 6 As shown, remote plasma units 300b and 300c respectively disposed on the downstream side of the gas supply pipes 232b and 232c relative to the valves 243b and 243c may be used to excite at least one of the H-containing gas and the O-containing gas supplied to the gas supply pipes 232c and 232c into plasma from the gas supply pipes 232e and 232f and supply the plasma to the processing chamber 201. Figure 6 In, with Figure 1 The same parts are marked with the same figure marks, and the description of their structure is omitted.

[0167] It should be noted that, in the oxidation treatment of the deposited film in the furnace, it is also possible to excite the plasma of the gas containing O instead of the H-containing gas. In addition, it is also possible to excite the plasma of the gas containing H instead of the O-containing gas. In addition, it is also possible to excite the plasma of both the O-containing gas and the H-containing gas.

[0168] The same effects as those in the above-mentioned method can also be obtained in this variant. In addition, according to this variant, the temperature of the oxidation treatment of the film attached in the furnace can be further reduced compared to the case where the oxidation treatment of the film attached in the furnace is performed in a non-plasma atmosphere in the above-mentioned manner. In the case where the oxidation treatment of the film attached in the furnace is performed at a lower temperature using plasma as described above, the same effects as those in the above-mentioned method can be obtained. In addition, since the temperature of the oxidation treatment of the film attached in the furnace can be reduced, the processing temperature of the film forming process and the processing temperature of the oxidation treatment of the film attached in the furnace can be the same temperature, and the temperature change time in the processing container can be eliminated. As a result, the productivity of the film forming process can be further improved. In addition, especially when the H-containing gas plasma is excited and supplied, the Cl contained in the SiN film attached in the processing container can be detached to be removed, and the stress of the film attached in the processing container can be further reduced.

[0169] (Variant 3)

[0170] The oxidation treatment of the film deposited in the furnace can be performed not only in parallel with the cooling of the wafer and the removal of the wafer, but also in parallel with the wafer filling for the wafer 200 to be processed next. That is, the oxidation treatment of the film deposited in the furnace can be performed in parallel with the cooling of the wafer, the removal of the wafer, and the wafer filling for the wafer 200 to be processed next.

[0171] In this variation, the same effects as those of the above-described method can be obtained. In addition, according to this variation, the oxidation amount of the deposits including the SiN film formed in the processing container can be increased, the stress of the film formed in the processing container can be further reduced, and the generation of particles caused by the film formed in the processing container can be further suppressed.

[0172] (Variant 4)

[0173] In the film forming process, as a nitride film, in addition to the SiN film, a SiN film containing at least any one of C, O, and B may be formed. That is, in the film forming process, as a nitride film, a SiN film, a SiCN film, a SiON film, a SiOCN film, a SiBN film, a SiBCN film, a SiBOCN film, a SiBON film, etc. may be formed. When forming these films, in the film forming process, at least any one of a C-containing gas, an O-containing gas, and a B-containing gas may be further supplied from the film forming gas supply system.

[0174] Furthermore, in the film forming process, as a nitride film, in addition to a silicon-based nitride film (a silicon-containing nitride film, a silicon nitride film), a germanium-based nitride film (a germanium-containing nitride film, a germanium nitride film) may be formed. As a germanium nitride film (GeN film), for example, in addition to a GeN film, a GeN film containing at least any one of C, O, and B may be formed. When forming these films, in the film forming process, a Ge-containing gas is used instead of a Si-containing gas, and at least any one of a C-containing gas, an O-containing gas, and a B-containing gas may be supplied from a film forming gas supply system.

[0175] In addition, in the film forming process, as a nitride film, in addition to a silicon-based nitride film (containing a silicon nitride film, a silicon nitride film), a metal-based nitride film (containing a metal nitride film, a metal nitride film) may also be formed. As a metal nitride film, for example, an aluminum nitride film (AlN film), a titanium nitride film (TiN film), a zirconium nitride film (ZrN film), a hafnium nitride film (HfN film), a tantalum nitride film (TaN film), a tungsten nitride film (WN film), a molybdenum nitride film (MoN film), etc. may also be formed. In the case of forming these films, in the film forming process, instead of the Si-containing gas, at least any one of the Al-containing gas, the Ti-containing gas, the Zr-containing gas, the Hf-containing gas, the Ta-containing gas, the W-containing gas, and the Mo-containing gas may be supplied from the film forming gas supply system.

[0176] As described above, in the film formation process, a film containing at least one of a semiconductor element and a metal element and nitrogen may be formed as a nitride film.

[0177] In these cases, you can also use Figure 1 The substrate processing apparatus shown performs film forming processing in a non-plasma atmosphere, or uses Figure 6 The substrate processing apparatus shown is performed using plasma.

[0178] The same effects as those of the above-described embodiment can also be obtained in this modification.

[0179] <Other aspects of the present invention>

[0180] The embodiments of the present invention have been specifically described above, but the present invention is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present invention.

[0181] For example, after repeating the above-mentioned combination of (a), (b), (c), and (d) a plurality of times, the inside of the processing container may be cleaned.

[0182] That is, the above-mentioned combination of (a), (b), (c), and (d) is repeated multiple times, so that the SiO / SiN stacked film is accumulated in the processing container. In this case, the processing container can also be cleaned before the SiO / SiN stacked film accumulated in the processing container exceeds the critical film thickness and cracks or film peeling occurs.

[0183] When the cleaning process is performed in the processing container, in a state where no wafer 200 is contained in the processing container, F-containing gas is supplied from the cleaning gas supply system (F-containing gas supply system) into the processing container as a cleaning gas, and the gas is exhausted from the exhaust pipe 231. At this time, the F-containing gas may be supplied into the processing container in a state where a wafer boat 217 having a SiN film formed on the surface is contained in the processing container. In addition, at this time, the F-containing gas may be supplied into the processing container in a state where a dummy wafer having a SiN film formed on the surface is contained in the processing container.

[0184] The following are examples of treatment conditions in the cleaning treatment:

[0185] Processing temperature (temperature in processing chamber 201): 200~500℃

[0186] Processing pressure (pressure in processing chamber 201): 1330~26600Pa

[0187] F2 gas supply flow rate: 0.5~5slm

[0188] N2 gas supply flow rate: 1~20slm.

[0189] By cleaning, the film can be reset to its attached state in the processing container before the effect of the above method disappears, and then the effect of the above method can be obtained again. It should be noted that according to the above method, the accumulated thickness of the film in the processing container can be greatly increased until it exceeds the critical film thickness and becomes a state where cracking and film peeling occur, the cycle of the cleaning process described here can be greatly extended, and the productivity of the overall film forming process can be greatly improved.

[0190] It is preferred that the process used in each treatment is prepared separately according to the treatment content, and is stored in advance in the storage device 121c via the electrical communication line and the external storage device 123. In addition, it is preferred that when each treatment starts, the CPU 121a appropriately selects an appropriate process from the multiple processes stored in the storage device 121c according to the treatment content. In this way, it is possible to form a plurality of film types, composition ratios, film qualities, and film thicknesses using one substrate processing device with good reproducibility. In addition, it is possible to appropriately perform furnace-attached film oxidation treatment on films of various film types, composition ratios, film qualities, and film thicknesses formed in the processing container through these treatments. In addition, it is possible to start each treatment quickly while reducing the burden on the operator and avoiding operational errors.

[0191] The above process is not limited to the case of new preparation, for example, it can also be prepared by changing the existing process installed in the substrate processing device. In the case of changing the process, the changed process can also be installed in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, the input and output device 122 of the existing substrate processing device can be operated to directly change the existing process installed in the substrate processing device.

[0192] In the above-mentioned method, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and for example, it can also be preferably applied to the case of forming a film using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and it can also be preferably applied to the case of forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0193] When using the above substrate processing apparatus, each process can be performed with the same processing steps and processing conditions as those in the above-mentioned method and the above-mentioned modified example, and the same effect as that in the above-mentioned method and the above-mentioned modified example can be obtained.

[0194] The above-mentioned aspects and modifications can be used in combination as appropriate. The processing steps and processing conditions in this case may be the same as those in the above-mentioned aspects and modifications, for example.

Claims

1. A method for manufacturing a semiconductor device, comprising the step of repeating a group of the following steps a plurality of times: (a) a step of loading a substrate into a processing container; (b) supplying a film forming gas to the substrate supported by a support member in the processing container to form a nitride film on the substrate; (c) a step of carrying out the processed substrate from the processing container; and (d) supplying an oxidizing gas into the processing container after the processed substrate is unloaded, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and allowing other portions of the nitride film different from the portion to maintain the state of the nitride film without being oxidized, In (d), the ratio of the oxide film formed by oxidizing the portion of the nitride film formed in the processing container to the oxide film in the stacked film of the nitride film formed in the processing container while maintaining the state of the nitride film without being oxidized is less than 75%.

2. The method for manufacturing a semiconductor device according to claim 1, wherein: (d) is performed whenever (a), (b) and (c) are performed.

3. The method for manufacturing a semiconductor device according to claim 1, wherein: In (d), the stress of the stacked film of the oxide film formed by oxidizing the portion of the nitride film formed in the processing container and the nitride film formed in the processing container while maintaining the state of the nitride film without being oxidized is tensile stress as a whole.

4. The method for manufacturing a semiconductor device according to claim 1, wherein: (d) is performed without accommodating the support member in the processing container.

5. The method for manufacturing a semiconductor device according to claim 4, wherein: In (d), the nitride film formed on the surface of the support member in (b) is maintained in the state of the nitride film without being oxidized.

6. The method for manufacturing a semiconductor device according to claim 5, wherein: The second group and subsequent steps (b) are performed in the processing container in a state where the substrate to be processed next is supported by the support member having the nitride film formed on the surface thereof.

7. The method for manufacturing a semiconductor device according to claim 1, wherein: The substrate comprises a product substrate and a dummy substrate, (d) is performed when the support member, the product substrate, and the dummy substrate are not accommodated in the processing container.

8. The method for manufacturing a semiconductor device according to claim 7, wherein: In (d), the nitride film formed on the surfaces of the support member, the product substrate, and the dummy substrate in (b) is maintained in the state of the nitride film without being oxidized.

9. The method for manufacturing a semiconductor device according to claim 8, wherein: The second group and subsequent steps (b) are performed in the processing container in a state where the dummy substrate having the nitride film formed on the surface and the product substrate to be processed next are supported by the support having the nitride film formed on the surface.

10. The method for manufacturing a semiconductor device according to claim 1, wherein: The method further comprises the step of (e) cooling the processed substrate taken out of the processing container. (d) is performed in parallel with (e).

11. The method for manufacturing a semiconductor device according to claim 1, wherein: In (c), the processed substrate is carried out from the processing container in a state supported by the support member. The manufacturing method further comprises the following steps: (e) cooling the processed substrate after being removed from the processing container; and (f) a step of removing the processed substrate after the cooling from the support member, (d) is performed in parallel with (e) and (f).

12. The method for manufacturing a semiconductor device according to claim 11, wherein: The method further comprises the step of (g) filling the support with a substrate to be processed next, (d) is performed in parallel with (e), (f) and (g).

13. The method for manufacturing a semiconductor device according to claim 1, wherein: In (d), while the oxidizing gas is continuously or intermittently supplied into the processing container, an exhaust valve provided in an exhaust pipe for exhausting the processing container is repeatedly opened and closed. The exhaust pipe exhausts the processing container.

14. The method for manufacturing a semiconductor device according to claim 1, wherein: In (d), the processing container is pulse-exhausted while the oxidizing gas is continuously or intermittently supplied into the processing container.

15. The method for manufacturing a semiconductor device according to claim 1, wherein: In (d), the following steps are performed alternately a predetermined number of times: a step of supplying the oxidizing gas into the processing container while exhausting the processing container; and and supplying the oxidizing gas into the processing container while stopping exhaust in the processing container.

16. The method for manufacturing a semiconductor device according to claim 1, wherein: The oxidizing gas includes an oxygen-containing gas and a hydrogen-containing gas.

17. The method for manufacturing a semiconductor device according to claim 1, wherein: The nitride film is a film containing at least one of a semiconductor element and a metal element and nitrogen.

18. A substrate processing method, comprising the step of repeating a group of the following steps a plurality of times: (a) a step of loading a substrate into a processing container; (b) supplying a film forming gas to the substrate supported by a support member in the processing container to form a nitride film on the substrate; (c) a step of carrying out the processed substrate from the processing container; (d) supplying an oxidizing gas into the processing container after the processed substrate is unloaded, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and allowing other portions of the nitride film different from the portion to maintain the state of the nitride film without being oxidized, In (d), the ratio of the oxide film formed by oxidizing the portion of the nitride film formed in the processing container to the oxide film in the stacked film of the nitride film formed in the processing container while maintaining the state of the nitride film without being oxidized is less than 75%.

19. A substrate processing apparatus comprising: a processing container in which the substrate is processed; a support member that supports a substrate within the processing container; a film-forming gas supply system for supplying a film-forming gas to the substrate in the processing container; an oxidizing gas supply system for supplying oxidizing gas into the processing container; A transfer device that transfers the substrate into and out of the processing container; as well as A control unit configured to control the film forming gas supply system, the oxidizing gas supply system, and the transport device to perform a process that includes repeating a plurality of times a group of the following processes: (a) a process of carrying a substrate into the process container; (b) a process of supplying the film forming gas to the substrate supported by the support in the process container to form a nitride film on the substrate; and (c) a process of carrying the processed substrate out of the process container. (d) supplying the oxidizing gas into the processing container after the processed substrate is moved out, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and allowing other portions of the nitride film different from the portion to maintain the state of the nitride film without being oxidized, wherein in (d), the ratio of the oxide film in the stacked film of the oxide film formed by oxidizing the portion of the nitride film formed in the processing container and the nitride film formed in the processing container that maintains the state of the nitride film without being oxidized is less than 75%.

20. A computer-readable recording medium having a program recorded thereon, the program causing a substrate processing apparatus to execute, through a computer, a step of repeating a group of the following steps a plurality of times: (a) a step of loading a substrate into a processing container of the substrate processing apparatus; (b) supplying a film forming gas to the substrate supported by a support member in the processing container, thereby performing a process of forming a nitride film on the substrate; (c) a step of moving the processed substrate out of the processing container; (d) supplying an oxidizing gas into the processing container after the processed substrate is unloaded, thereby oxidizing a portion of the nitride film formed in the processing container in (b) and converting it into an oxide film, and allowing other portions of the nitride film different from the portion to maintain the state of the nitride film without being oxidized; and In (d), the step of making the ratio of the oxide film formed by oxidizing the part of the nitride film formed in the processing container and the oxide film in the stacked film of the nitride film formed in the processing container while maintaining the state of the nitride film without oxidation be less than 75%.

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