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

Abstract

To provide a technology that can suppress the rise in piping temperature due to the reaction between the inner surface and the gas when oxygen-containing gas is supplied through piping whose inner surface is composed of a metal-containing material.SOLUTION: A method has (a) a process of performing first processing on a substrate contained in a processing container by supplying a first process gas into the processing container via a first piping different from a second piping while the second piping, whose inner surface is composed of a metal-containing material and connected to the processing container, is heated to a first temperature or higher; and (b) a process of performing second processing on the substrate by supplying a second process gas containing oxygen into the processing container via the second piping while the temperature of the second piping is lowered to a temperature equal to or lower than a second temperature lower than the first temperature.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a process of forming a film on a substrate is sometimes performed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 090738 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can suppress an increase in pipe temperature caused by a reaction between an inner surface and an oxygen-containing gas when the gas is supplied through the pipe whose inner surface is made of a metal-containing material. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) performing a first process on a substrate accommodated in a processing vessel by supplying a first process gas into the processing vessel through a first pipe different from a second pipe, the second pipe being connected to the processing vessel and having an inner surface made of a metal-containing material, while heating the second pipe to a first temperature or higher; (b) performing a second process on the substrate by supplying a second process gas containing oxygen into the process vessel through the second pipe while the temperature of the second pipe is reduced to a second temperature lower than the first temperature; The present invention provides a technique having the following features: Effect of the Invention

[0006] According to the present disclosure, when an oxygen-containing gas is supplied through a pipe whose inner surface is made of a metal-containing material, it is possible to suppress an increase in the pipe temperature caused by a reaction between the inner surface and the gas. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 4 is a diagram showing a processing sequence according to an embodiment of the present disclosure. [Diagram 5] FIG. 5 is a flow chart showing a substrate processing process according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 5. Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0009] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a temperature control unit (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0010] A reaction tube 203 is disposed concentrically with the heater 207 inside 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 in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal-containing material such as stainless steel (SUS) and is formed in a cylindrical shape with an open upper end and a closed lower end. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a seal member. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in a cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be capable of accommodating a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0011] Nozzles 249a to 249c serving as first to third supply units are provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209, respectively. 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. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249b and 249c is provided adjacent to the nozzle 249a.

[0012] Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The gas supply pipes 232a to 232c are each configured as a shared pipe used to supply a plurality of types of gas. Mass flow controllers (MFCs) 241a to 241c, which are flow rate controllers (flow rate control parts), and valves 243a to 243c, which are on-off valves, are provided on the gas supply pipes 232a to 232c, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232d and 232e are connected to the downstream side of the valve 243a of the gas supply pipe 232a. MFCs 241d and 241e and valves 243d and 243e are provided on the gas supply pipes 232d and 232e, respectively, in order from the upstream side of the gas flow. A gas supply pipe 232f is connected to the downstream side of the valve 243b of the gas supply pipe 232b. Gas supply pipe 232f is provided with MFC 241f and valve 243f in this order from the upstream side of the gas flow. Gas supply pipe 232g is connected to gas supply pipe 232c downstream of valve 243c. Gas supply pipe 232g is provided with MFC 241g and valve 243g in this order from the upstream side of the gas flow. Gas supply pipes 232a to 232g are made of a metal-containing material such as SUS, and their inner surfaces are also made of a metal-containing material such as SUS. In this specification, gas supply pipes 232a, 232b, and 232d may be referred to as a first pipe, or may be referred to collectively as a first pipe, and gas supply pipe 232c may be referred to as a second pipe.

[0013] Pipe temperature sensors 234a, 234b, and 234d, which are temperature detectors, are attached to the upstream side of the MFCs 241a, 241b, and 241d of the gas supply pipes 232a, 232b, and 232d as the first pipes. Pipe temperature sensor 234c is attached to the upstream side of the MFC 241c of the gas supply pipe 232c as the second pipe. The pipe temperature sensor can be configured by a known temperature sensor such as a thermocouple. In this embodiment, pipe heaters 233a, 233b, and 233d as heating parts are attached to the outer periphery of the gas supply pipes 232a, 232b, and 232d as the first pipes. Pipe heater 233b is attached to the outer periphery of 232c as the second pipe.

[0014] As shown in FIG. 2, the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged, so as to extend along the wafer arrangement region. In a plan view, the nozzle 249a is arranged to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249b and 249c are arranged to sandwich a straight line L passing through the nozzle 249a and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249a and the center of the wafer 200. In other words, the nozzle 249c is provided on the opposite side of the nozzle 249b across the line L. The nozzles 249b and 249c are arranged in line symmetry with the line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are each opened to face (face) the exhaust port 231a in a plan view, and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0015] A source gas serving as a first process gas is supplied from the gas supply pipe 232a into the process chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0016] A second reactant gas serving as a first process gas is supplied from the gas supply pipe 232b into the process chamber 201 via the MFC 241b, a valve 243b, and a nozzle 249b.

[0017] A second process gas containing oxygen (O) is supplied from the gas supply pipe 232c into the process chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0018] A first reactive gas serving as a first process gas is supplied from the gas supply pipe 232d into the process chamber 201 via the MFC 241d, the valve 243d, and the nozzle 249a.

[0019] From the gas supply pipes 232e to 232g, an inert gas is supplied via the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0020] The source gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The second reactive gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The second process gas supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The first reactive gas supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The inert gas supply system is mainly composed of the gas supply pipes 232e to 232g, the MFCs 241e to 241g, and the valves 243e to 243g. In this embodiment, the source gas supply system, the first reactive gas supply system, and the second reactive gas supply system are collectively referred to as the first process gas supply system. Nozzles connected to the gas supply pipes constituting the various supply systems described above may be included in each of the supply systems.

[0021] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243g and the MFCs 241a-241g are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a-232g, and the supply operation of various substances (various gases) into the gas supply pipes 232a-232g, that is, the opening and closing operation of the valves 243a-243g and the flow rate adjustment operation by the MFCs 241a-241g, are controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated or split type integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232g, etc., and maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0022] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is made of a metal-containing material such as SUS. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 can evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, can adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal-containing material such as SUS, and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217, which will be described later. A rotation shaft 255 of the rotation mechanism 267 is made of a metal-containing material such as SUS, and is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0024] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. The shutter 219s is made of a metal-containing material such as SUS, and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that comes into contact with the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0025] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0026] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Fig. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. 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 configured as, for example, a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121.

[0028] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are recorded and stored in a readable manner. The process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.

[0029] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, piping temperature sensors 234a to 234d, heater 207, piping heaters 233a to 233d, rotation mechanism 267, boat elevator 115, shutter opening and closing mechanism 115s, etc.

[0030] The CPU 121a is configured to be able to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be able to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241g, the opening and closing operations of the valves 243a to 243g, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc., in accordance with the contents of the read recipe.

[0031] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Substrate processing A method of processing a substrate as one step in a manufacturing process of a semiconductor device using the above-mentioned substrate processing apparatus, i.e., an example of a series of processing sequences including a film formation sequence for forming a film on a wafer 200 as a substrate, will be described mainly with reference to Figures 4 and 5. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0033] In the processing sequence of this embodiment, (a) a step A of performing a first process on the wafer 200 accommodated in the processing vessel by supplying a first process gas into the processing vessel through a first pipe (gas supply pipes 232a, 232b, 232d) different from the second pipe while heating a second pipe (gas supply pipe 232c) connected to the processing vessel and having an inner surface made of a metal-containing material to a first temperature or higher; (b) a step B of performing a second process on the wafer 200 by supplying a second process gas containing oxygen into the process vessel through the second pipe while the temperature of the second pipe is lowered to a second temperature lower than the first temperature; has.

[0034] In the processing sequence of this embodiment, in step A, A step a1 of supplying a source gas as a first process gas to the wafer 200; Step a2 of supplying a first reaction gas as a first process gas to the wafer 200; Step a3 of supplying a second reaction gas as a first process gas to the wafer 200; The following example shows how a film is formed on a wafer 200 by performing a cycle including the steps a predetermined number of times (n times, where n is an integer of 1 or 2 or more). In this specification, the source gas, the first reactant gas, and the second reactant gas may each be referred to as a first process gas, or these may be collectively referred to as a first process gas.

[0035] In the processing sequence of this embodiment, in step B, An example will be shown in which a film formed on the wafer 200 is treated by supplying a second process gas containing oxygen (O) to the wafer 200.

[0036] In addition, the processing sequence in this embodiment further includes step C, during the period between step A and step B, of lowering the temperature of the second piping from a temperature equal to or higher than the first temperature to a second temperature that is lower than the first temperature.

[0037] In the following, an example in which a silicon oxynitride film (SiON film) is formed on the wafer 200 will be described.

[0038] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples and other aspects.

[0039] (Source gas → First reaction gas → Second reaction gas) × n → Second pipe temperature drop → Second process gas containing O

[0040] The term "wafer" used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on a wafer", it may mean that a predetermined layer is formed directly on the surface of the wafer itself or that a predetermined layer is formed on a layer or the like formed on the wafer. When the term "substrate" is used in this specification, it is synonymous with the term "wafer".

[0041] The term "layer" as used herein includes at least one of a continuous layer and a discontinuous layer. For example, the Si-containing layer described below may include a continuous layer, a discontinuous layer, or both.

[0042] In this specification, when the first process gas and the second process gas containing O are described as being adsorbed to or reacting with the surface of the wafer 200, this refers not only to the case where they are adsorbed to or reacted with the wafer surface without being decomposed, but also to the case where they are decomposed or an intermediate generated by the detachment of their ligands is adsorbed to or reacts with the surface of the wafer 200.

[0043] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this manner, the wafers 200 are prepared (provided) in the processing chamber 201.

[0044] (Pressure and temperature regulation) After the boat loading is completed, the inside of the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafers 200 in the processing chamber 201 are heated by the heater 207 so that the wafers 200 are at a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0045] (Temperature setting of second pipe) Thereafter, the second pipe (gas supply pipe 232c) is heated by the pipe heater 233c so that the temperature in the second pipe becomes equal to or higher than the first temperature. At this time, the state of electricity supply to the pipe heater 233c is feedback-controlled based on temperature information detected by the pipe temperature sensor 234c so that the second pipe has a desired temperature distribution. At this time, it is preferable that the first pipe (gas supply pipes 232a, 232b, 232d) is also heated by the pipe heaters 233a, 233b, and 233d so that the temperature in the first pipe becomes equal to or higher than the first temperature. In addition, the timing of performing the process of heating the second pipe to the first temperature is not limited to after the pressure adjustment and the temperature adjustment, and may be started at the same time as or before any of wafer charging and boat loading, pressure adjustment, and temperature adjustment.

[0046] (First process: Step A) Then, the following steps a1, a2, and a3 are executed in sequence.

[0047] [Step a1] In this step, a source gas is supplied to the wafer 200 in the processing chamber 201 .

[0048] Specifically, the valve 243a is opened to allow the source gas to flow into the gas supply pipe 232a (first pipe). The flow rate of the source gas is adjusted by the MFC 241a, and the source gas is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the source gas is supplied to the wafer 200 (source gas supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249c. The inert gas supplied through the nozzles 249b and 249c also acts as an intrusion suppression gas that suppresses the source gas in the processing chamber from intruding (backflowing) into the nozzles 249a and 249b.

[0049] The processing conditions for supplying the raw material gas in this step are as follows: Treatment temperature: 350 to 900°C, preferably 500 to 900°C, more preferably 600 to 800°C Treatment pressure: 1 to 10,000 Pa, preferably 10 to 1,333 Pa First pipe temperature: The first temperature or higher, for example, 160 to 250° C., preferably 180 to 250° C. Second pipe temperature: higher than or equal to the first temperature, for example, 160 to 250°C, preferably 180 to 250°C Raw material gas supply flow rate: 0.01 to 3 slm, preferably 0.1 to 1 slm Raw material gas supply time: 10 to 120 seconds, preferably 20 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm Examples include:

[0050] In this specification, the expression of a numerical range such as "350 to 900°C" means that the lower limit and the upper limit are included in the range. Therefore, for example, "350 to 900°C" means "350°C or more and 900°C or less". The same applies to other numerical ranges. In this specification, the process temperature means the temperature of the wafer 200 or the temperature in the process chamber 201, and the process pressure means the pressure in the process chamber 201, in other words, the pressure in the space in which the wafer 200 exists. In addition, the process time means the time the process continues. In addition, the pipe temperature means the temperature in the pipe. In addition, when the supply flow rate includes 0 slm, 0 slm means a case in which the substance (gas) is not supplied. These are the same in the following explanation.

[0051] Under the above-mentioned conditions, a silicon (Si)-containing layer containing chlorine (Cl) is formed on the top surface of the wafer 200 as a base by supplying, for example, a chlorosilane-based gas as a raw material gas to the wafer 200. The Si-containing layer containing Cl is formed on the top surface of the wafer 200 by physical adsorption or chemical adsorption of molecules of the chlorosilane-based gas, physical adsorption or chemical adsorption of molecules of a substance obtained by decomposing a part of the chlorosilane-based gas, deposition of Si by thermal decomposition of the chlorosilane-based gas, or the like. The Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of molecules of the chlorosilane-based gas or molecules of a substance obtained by decomposing a part of the chlorosilane-based gas, or may be a deposition layer of Si containing Cl. In this specification, the Si-containing layer containing Cl is also simply referred to as a Si-containing layer.

[0052] As the source gas, for example, a silane-based gas containing Si as the main element constituting the film formed on the wafer 200 can be used. As the silane-based gas, for example, a gas containing Si and a halogen, that is, a halosilane-based gas can be used. The halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halosilane-based gas, for example, the above-mentioned chlorosilane-based gas containing Si and Cl can be used.

[0053] As the source gas, for example, a chlorosilane-based gas such as monochlorosilane (SiH3Cl) gas, dichlorosilane (SiH2Cl2) gas, trichlorosilane (SiHCl3) gas, tetrachlorosilane (SiCl4) gas, hexachlorodisilane gas (Si2Cl6) gas, octachlorotrisilane (Si3Cl8) gas, etc. As the source gas, one or more of these can be used.

[0054] As the raw material gas, in addition to the chlorosilane-based gas, for example, a fluorosilane-based gas such as tetrafluorosilane (SiF4) gas or difluorosilane (SiH2F2) gas, a bromosilane-based gas such as tetrabromosilane (SiBr4) gas or dibromosilane (SiH2Br2) gas, or an iodosilane-based gas such as tetraiodosilane (SiI4) gas or diiodosilane (SiH2I2) gas can be used. One or more of these can be used as the raw material gas.

[0055] In addition to these, the source gas may be, for example, a gas containing Si and an amino group, i.e., an aminosilane-based gas. An amino group is a monovalent functional group obtained by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and can be represented as -NH2, -NHR, or -NR2. R represents an alkyl group, and the two Rs in -NR2 may be the same or different.

[0056] As the source gas, for example, aminosilane gas such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4) gas, tris(dimethylamino)silane (Si[N(CH3)2]3H) gas, bis(diethylamino)silane (Si[N(C2H5)2]2H2) gas, bis(tertiarybutylamino)silane (SiH2[NH(C4H9)]2) gas, (diisopropylamino)silane (SiH3[N(C3H7)2]) gas, etc. can be used. As the source gas, one or more of these can be used.

[0057] As the inert gas, for example, nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, or other rare gases can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0058] After the Si-containing layer is formed, the valve 243a is closed to stop the supply of the source gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove (purge) gas remaining in the processing chamber 201. At this time, the valves 243e to 243g are opened to supply an inert gas into the processing chamber 201. The inert gas acts as a purge gas.

[0059] [Step a2] After step a1 is completed, a first reaction gas is supplied to the wafer 200 in the processing chamber 201, that is, to the Si-containing layer formed on the wafer 200.

[0060] Specifically, the valve 243d is opened to allow a first reactive gas to flow into the gas supply pipe 232d (first piping). The flow rate of the first reactive gas is adjusted by the MFC 241d, and the first reactive gas is supplied into the processing chamber 201 via the nozzle 249a and exhausted from the exhaust port 231a. At this time, the first reactive gas is supplied to the wafer 200 (first reactive gas supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c.

[0061] The process conditions for supplying the first reactive gas in this step are as follows: First reactant gas supply flow rate: 0.01 to 4 slm, preferably 0.3 to 1 slm First reaction gas supply time: 1 to 60 seconds, preferably 5 to 20 seconds Other processing conditions may be the same as those in step a1.

[0062] Under the above-mentioned conditions, by supplying, for example, an O-containing gas as a first reactive gas to the wafer 200, at least a part of the Si-containing layer formed on the wafer 200 is oxidized (modified). As a result, a silicon oxide layer (SiO layer) is formed as a layer containing Si and O on the top surface of the wafer 200 as a base. In this embodiment, for example, an O-containing gas is used as the first reactive gas. Hereinafter, the first reactive gas may be referred to as a first O-containing gas.

[0063] The reactivity of the first O-containing gas used in this step with the metal-containing material constituting the inner surface of the gas supply pipe 232d (first pipe) is lower than the reactivity of the second O-containing process gas used in step B described below with the metal-containing material constituting the inner surface of the gas supply pipe 232c (second pipe). The reactivity here mainly includes the ease with which an oxidation reaction occurs (oxidizing power). As a result, even if the inner surface of the gas supply pipe 232d is made of a metal-containing material, it is possible to suppress an increase in the temperature of the gas supply pipe 232d due to the reaction between the first O-containing gas and the metal-containing material in this step.

[0064] The first reactive gas may be, for example, oxygen (O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc. One or more of these may be used as the first reactive gas.

[0065] In addition, as the first reactive gas, a gas containing O and H, such as water vapor (H2O), H2 gas + O2 gas, H2O gas + O2 gas, H2O gas + N2O gas, or H2O gas + NO gas, can also be used. In this case, deuterium ( 2 One or more of these gases can be used as the first reactive gas.

[0066] The first reactive gas is not limited to the above example, and may be appropriately selected from among O-containing gases that have a lower reactivity with the metal-containing material that constitutes the inner surface of the gas supply pipe 232d than the second process gas. In addition, as the first reactive gas that has a lower reactivity than the second process gas, a gas of the same type as the second process gas (i.e., a gas with the same molecular structure) and a lower concentration than the second process gas (for example, the second process gas diluted with a dilution gas, etc.) may be selected.

[0067] In addition, in this specification, the description of two gases together, such as "H2 gas + O2 gas", means a mixed gas of H2 gas and O2 gas. When a mixed gas is supplied, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be separately supplied into the processing chamber 201 from different supply pipes and mixed (postmixed) in the processing chamber 201. When the two gases are separately supplied into the processing chamber 201 from different supply pipes, it is preferable that the O-containing gas is supplied into the processing chamber 201 through the gas supply pipe 232d (first pipe) and the other gas (including the case where the other gas is also an O-containing gas) is supplied into the processing chamber 201 through another gas supply pipe.

[0068] After the SiO film is formed, the valve 243d is closed to stop the supply of the first reaction gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201 from the processing chamber 201. Then, the gases remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure as the purging in step a1.

[0069] [Step a3] After step a2 is completed, a second reaction gas is supplied to the wafer 200 in the processing chamber 201, that is, to the SiO layer formed on the wafer 200.

[0070] Specifically, the valve 243b is opened to allow the second reactive gas to flow into the gas supply pipe 232b (first piping). The flow rate of the second reactive gas is adjusted by the MFC 241b, and the second reactive gas is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust port 231a. At this time, the second reactive gas is supplied to the wafer 200 (second reactive gas supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249c.

[0071] The process conditions for supplying the second reaction gas in this step are as follows: Second reactant gas supply flow rate: 0.1 to 20 slm, preferably 1 to 10 slm Second reactant gas supply time: 1 to 120 seconds, preferably 3 to 15 seconds Other processing conditions may be the same as those in step a1.

[0072] Under the above-mentioned conditions, for example, a nitrogen (N) and H-containing gas is supplied as a second reactive gas to the wafer 200, whereby at least a portion of the SiO layer formed on the wafer 200 is nitrided (modified). As a result, a silicon oxynitride layer (SiON layer) is formed as a layer containing Si, O, and N on the top surface of the wafer 200 as a base.

[0073] The second reaction gas may be, for example, a nitriding gas. The nitriding gas may be, for example, the N- and H-containing gas described above. The N- and H-containing gas may be both an N-containing gas and an H-containing gas.

[0074] As the second reactive gas, for example, a hydrogen nitride gas such as ammonia (NH3) gas, diazane (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas, etc. As the second reactive gas, one or more of these can be used.

[0075] After the SiON film is formed, the valve 243b is closed to stop the supply of the second reaction gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201 from the processing chamber 201. Then, the gases remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure as the purging in step a1.

[0076] [Perform the specified number of times] By performing the above steps a1 to a3 in this order non-simultaneously, i.e., without synchronization, a cycle is performed n times (n is an integer of 1 or 2 or more) to form a film of a predetermined thickness, for example a SiON film of a predetermined thickness, on the surface of the wafer 200 as a base. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the SiON layer formed per cycle thinner than the desired film thickness, and to repeat the above cycle multiple times until the thickness of the SiON film formed by stacking the SiON layers reaches the desired thickness.

[0077] As described above, in step A, an inert gas as an intrusion suppression gas is supplied from the nozzle 249c into the processing chamber 201. However, by supplying the intrusion suppression gas alone, it may not be possible to prevent by-products generated in the processing chamber 201 from invading the nozzle 249c and the gas supply pipe 232c. Furthermore, in step A, if the second pipe temperature is lower than the first temperature, for example, lower than 160°C, when the by-products generated in the processing chamber 201 invade (flow back) from inside the processing chamber 201 into the second pipe, it may be difficult to prevent the invaded by-products from adhering (accumulating) inside the second pipe. To address this issue, by setting the second pipe temperature to the first temperature or higher, it is possible to prevent the by-products invading from inside the processing chamber 201 from adhering to the second pipe. By setting the second pipe temperature to a temperature higher than the first temperature, for example, a temperature higher than the first temperature by 20°C or more, it is possible to more effectively prevent the by-products invading from inside the processing chamber 201 from adhering (accumulating) inside the second pipe. The temperature equal to or higher than the first temperature can be said to be a temperature at which by-products can be prevented from adhering to the inside of the second pipe. However, if the second pipe temperature is excessively high, for example, 250° C. or higher, pipe accessories made of resin or the like, such as sealing members, may be burned. Therefore, it is preferable to set the second pipe temperature to, for example, 250° C. or lower. Note that the by-products adhering to the inside of the second pipe may include by-products that have entered from the processing chamber 201, as well as by-products that are generated by thermal decomposition or the like of the first processing gas that has entered the second pipe in the second pipe.

[0078] (2nd pipe temperature drop treatment: Step C) After the end of step A and before the start of step B described below, the set temperature of the second pipe, i.e., the control temperature of the pipe heater 233c, is changed from the first temperature to the third temperature. At this time, the state of electricity supply to the pipe heater 233c is feedback-controlled based on the temperature information detected by the pipe temperature sensor 234c so that the second pipe temperature has a desired temperature distribution. The third temperature is a temperature lower than the second temperature, which is lower than the first temperature. Wait until the second pipe temperature drops to the second temperature.

[0079] (Second process: Step B) When the second pipe temperature drops from the first temperature to the second temperature, step B is started at that timing. In this step, a second process gas containing O is supplied to the wafer 200 in the process chamber 201, i.e., the SiON film formed on the wafer 200. Hereinafter, the second process gas containing O may be simply referred to as the second process gas.

[0080] Specifically, the valve 243c is opened to allow the second process gas to flow into the gas supply pipe 232c (second piping). The flow rate of the second process gas is adjusted by the MFC 241c, and the second process gas is supplied into the process chamber 201 through the nozzle 249c and exhausted from the exhaust port 231a. At this time, the second process gas is supplied to the wafer 200 (second process gas supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the process chamber 201 through each of the nozzles 249a to 249c.

[0081] Here, when the second process gas, which is an O-containing gas, is supplied into the gas supply pipe 232c (second pipe) whose inner surface is made of a metal-containing material, an oxidation reaction may occur between the second process gas and the metal-containing material such as SUS that constitutes the inner surface. Heat generated by the oxidation reaction may increase the temperature of the second pipe, burn pipe accessories made of resin or the like, such as sealing members, and generate pollutants due to the burn.

[0082] More specifically, nickel (Ni) contained in, for example, SUS, etc., may act as a catalyst for the second process gas containing O, and may decompose the second process gas to generate O atoms (atomic oxygen). The O atoms thus generated are highly reactive, and therefore tend to cause an oxidation reaction with the metal-containing material and the associated heat generation. If the temperature rise of the second pipe progresses due to this heat generation, the above-mentioned catalytic reaction and the generation of O atoms are accelerated further, making it difficult to suppress the temperature rise of the second pipe.

[0083] In this step, as described below, the second process gas is supplied while the second piping temperature is kept below the second temperature, thereby maintaining a state in which no oxidation reaction substantially occurs and suppressing a temperature rise in the second piping.

[0084] In this step, the processing conditions for supplying the second processing gas are as follows: Second piping temperature: The second temperature or lower, for example, 0 to 155°C, preferably room temperature (25) to 150°C, more preferably 100 to 120°C. Second treatment gas supply concentration: 100 to 300 g / m 3 , preferably 200 to 300 g / m 3 Second treatment gas supply time: 30 to 180 minutes, preferably 45 to 120 minutes Other processing conditions may be the same as those in step a1.

[0085] By supplying the second processing gas to the wafer 200 under the above-mentioned conditions, the SiON film formed on the wafer 200 can be treated, for example, by removing impurities contained in the SiON film, repairing defects, and densifying and hardening the SiON film.

[0086] If the first pipe temperature is less than the first temperature, for example, less than 160°C, it may be difficult to prevent the by-products of the first processing gas that is supplied in step A and remains in the first pipe from adhering (accumulating) in the first pipe. By setting the first pipe temperature to the first temperature or higher in step B, it is possible to prevent the by-products of the first processing gas that remains in the first pipe from adhering to the first pipe. Furthermore, by setting the first pipe temperature to a temperature higher than the first temperature, for example, a temperature higher than the first temperature by 20°C or more in step B, it is possible to more effectively prevent the by-products of the first processing gas that remains in the first pipe from adhering to the first pipe. A temperature higher than the first temperature can be said to be a temperature that can prevent the by-products of the first processing gas from adhering to the first pipe. However, if the first pipe temperature is excessively high, for example, 250°C or higher, pipe accessories made of resin or the like, for example, sealing members, may be burned. Therefore, it is preferable to set the first pipe temperature to, for example, 250°C or lower.

[0087] In addition, if the first pipe temperature is lower than the first temperature, for example, lower than 160° C., when the by-products of the second process gas generated in the process chamber 201 in step B invade (flow back) from the process chamber 201 into the first pipe, it may be difficult to prevent the by-products from adhering to the inside of the first pipe. By setting the first pipe temperature to the first temperature or higher in step B, it is possible to prevent the by-products of the second process gas that has invaded the first pipe from adhering to the inside of the first pipe. Furthermore, by setting the first pipe temperature to a temperature higher than the first temperature, for example, a temperature higher than the first temperature by 20° C. or more in step B, it is possible to more effectively prevent the by-products of the second process gas that has invaded the first pipe from adhering to the inside of the first pipe. The temperature higher than the first temperature can be referred to as a temperature at which the by-products of the second process gas can be prevented from adhering to the inside of the first pipe.

[0088] In addition, when the second pipe temperature exceeds the second temperature, for example, when it exceeds 155°C, it may be difficult to avoid an oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. As a result, it becomes difficult to suppress the rise in the second pipe temperature, and it becomes difficult to avoid the burning of pipe accessories made of resin, such as sealing members, and the generation of pollutants. By setting the second pipe temperature at or below the second temperature, it becomes possible to suppress an oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. By setting the second pipe temperature at or below the second temperature, for example, at or below 150°C, it is possible to effectively suppress an oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. By setting the second pipe temperature at or below the second temperature, for example, at or below 120°C, it is possible to further effectively suppress an oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. The second temperature can be said to be a temperature at which no substantial reaction occurs between the metal-containing material and the second processing gas. The first temperature may refer to a temperature at which substantial reaction between the metal-containing material and the second process gas occurs.

[0089] However, if the second pipe temperature is excessively low, for example, below 0°C, when even a small amount of by-products generated by supplying the second processing gas into the processing chamber 201 enters (backflows) into the second pipe, it may be difficult to prevent the by-products from adhering to the second pipe. By setting the second pipe temperature to, for example, 0°C or higher, when the by-products generated in the processing chamber 201 enter the second pipe, it is possible to reduce the amount of by-products adhering to the second pipe. Furthermore, by setting the second pipe temperature to 25°C or higher, when the by-products generated in the processing chamber 201 enter the second pipe, it is possible to more significantly reduce the amount of by-products adhering to the second pipe. Furthermore, by setting the second pipe temperature to 100°C or higher, it is possible to more reliably reduce the amount of by-products adhering to the second pipe when the by-products generated in the processing chamber 201 enter the second pipe.

[0090] The second process gas supply time can be longer than the supply time per cycle of the first O-containing gas exemplified in step a2. The second process gas supply time can be longer than the supply time per cycle of the first process gas in step A (the total supply time of the source gas, the first reactant gas, and the second reactant gas).

[0091] The second process gas may be, for example, an O-containing gas obtained by plasma-exciting an O-containing gas using a plasma excitation unit (not shown). The plasma-excited O-containing gas may contain, for example, atomic oxygen (O) or hydroxyl radicals (OH radicals). The first O-containing gas exemplified in step a2 may be used as the O-containing gas to be plasma-excited.

[0092] The second processing gas may include at least one of hydrogen peroxide (H2O2) gas and ozone (O3) gas.

[0093] The second process gas is not limited to the above-mentioned examples, and can be appropriately selected from among O-containing gases that cause a substantial exothermic reaction with the metal-containing material that constitutes the inner surface of the gas supply pipe 232c (second pipe).

[0094] The second process gas may be an O-containing gas having a higher activity than the first O-containing gas. More specifically, the second reaction gas may be appropriately selected from O-containing gases having a higher reactivity with the metal-containing material constituting the inner surface of the gas supply pipe 232c than the first process gas. One or more of these may be used as the second process gas.

[0095] If the second pipe temperature becomes a fourth temperature (upper limit temperature / critical temperature) higher than the second temperature during the execution time of this step, the supply of the second process gas, etc. is stopped and execution of this step is stopped. Then, when the second pipe temperature drops to the second temperature, execution of this step is resumed.

[0096] When the execution time of this step reaches a predetermined time, the execution of this step ends.

[0097] (After purging and atmospheric pressure recovery) After step B is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0098] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0099] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0100] (a) In step B, when the second processing gas is supplied through the second pipe, the temperature of the second pipe is lowered to a second temperature lower than the first temperature, thereby suppressing a temperature rise in the second pipe. Specifically, in step B, when the second processing gas is supplied through the second pipe, the temperature of the second pipe is lowered to a second temperature at which an oxidation reaction does not occur between the metal-containing material constituting the inner surface of the second pipe and the second processing gas, thereby suppressing a temperature rise in the second pipe. By suppressing a temperature rise in the second pipe, for example, it is possible to prevent burnout of pipe accessories made of resin, such as sealing members, and also to prevent the generation of pollutants caused by an oxidation reaction between the metal-containing material and the second processing gas.

[0101] In step B, while the second process is being performed, the second piping temperature is continuously maintained at or below the second temperature, thereby making it possible to reliably prevent burning of sealing members and the like and generation of contaminants.

[0102] Furthermore, in step A, when the first processing gas is supplied through the first piping, the second piping is heated to a first temperature or higher, thereby preventing by-products from adhering to the inside of the second piping even if by-products generated by supplying the first processing gas into the processing chamber 201 enter the second piping from inside the processing chamber 201. In detail, in step A, when the first processing gas is supplied, the second piping temperature is set to a first temperature or higher, which is a temperature at which by-products of the first processing gas do not adhere to the inside of the second piping, thereby preventing the by-products from adhering to the inside of the second piping.

[0103] Furthermore, in step A, by continuously maintaining the second piping temperature at or above the first temperature while the first process is being performed, it is possible to reliably prevent by-products of the first process gas from adhering to the inside of the second piping.

[0104] (b) The rise in pipe temperature is a problem that becomes more pronounced when a gas that is highly reactive (highly active) with the metal-containing material that constitutes the inner surface of the pipe is used. In this embodiment, an O-containing gas that is more active than the first O-containing gas is used as the second process gas in step B, so that the effect of suppressing the rise in pipe temperature according to the present disclosure can be significantly obtained.

[0105] (c) Between step A and step B, the first process and the second process are performed in the same process chamber without removing the substrate from the process chamber 201. This makes it possible to prevent contamination of the substrate and adhesion of particles that may occur during the loading and unloading of the substrate. Also, by reducing the loading and unloading of the substrate, productivity (throughput) may be improved in some cases.

[0106] (d) In step A, the supply of the second process gas into the processing chamber 201 through the second pipe is not carried out, thereby suppressing the temperature rise of the second pipe. Specifically, in step A, where the temperature of the second pipe is equal to or higher than the first temperature at which an oxidation reaction occurs between the metal-containing material constituting the inner surface of the second pipe and the second process gas, the supply of the second process gas is not carried out, thereby preventing the reaction itself from occurring. This reliably suppresses the temperature rise of the second pipe. By suppressing the temperature rise of the second pipe, it is possible to prevent the burnout of pipe accessories made of, for example, resin, such as sealing members, and also to prevent the generation of pollutants caused by the oxidation reaction between the metal-containing material and the second process gas.

[0107] (e) In step B, the supply of the first process gas into the processing chamber 201 is not performed, thereby preventing the adhesion of by-products of the first process gas to the inside of the second pipe. Specifically, in step B, in which the second pipe temperature is maintained at or below the second temperature at which it is difficult to prevent the adhesion of by-products of the first process gas, the supply of the first process gas is not performed, thereby preventing the by-products from being generated. This reliably prevents the adhesion of by-products of the first process gas to the inside of the second pipe.

[0108] (f) In step B, the supply of other gases, excluding the second process gas and the inert gas, into the processing chamber 201 is not performed, thereby preventing the adhesion of by-products of the other gases to the inside of the second pipe. Specifically, in step B, in which the second pipe temperature is maintained at or below the second temperature at which adhesion of by-products of the other gases is difficult to prevent, the supply of the other gas is not performed, thereby preventing the by-products from being generated. This can reliably prevent the by-products of the other gases from adhering to the inside of the second pipe.

[0109] (g) In step B, by maintaining the temperature of the first piping, which has been heated to or above the first temperature in step A, at or above the first temperature, it is possible to suppress by-products of the first processing gas supplied in step A and remaining in the first piping from adhering to the inside of the first piping. In detail, also in step B, by maintaining the temperature of the first piping at or above the first temperature, which is a temperature at which by-products of the first processing gas do not adhere to the inside of the first piping, it is possible to suppress by-products of the first processing gas supplied in step A and remaining in the first piping from adhering to the inside of the first piping. Furthermore, in step B, by maintaining the temperature of the first piping heated to or above the first temperature in step A at or above the first temperature, even if by-products of the second process gas supplied in step B enter the first piping, the by-products can be prevented from adhering to the inside of the first piping. In detail, also in step B, by setting the temperature of the first piping to be equal to or above the first temperature at which the by-products of the second process gas do not adhere to the inside of the first piping, the by-products of the second process gas can be prevented from adhering to the inside of the first piping.

[0110] In step B, while the second process is being performed, the first piping temperature is continuously maintained at or above the first temperature, thereby making it possible to reliably obtain the above-mentioned effect.

[0111] (h) In step B, when the temperature of the second piping becomes a fourth temperature (upper limit temperature / critical temperature) higher than the second temperature during the second process, the second process is stopped, thereby preventing the temperature of the second piping from exceeding the upper limit temperature (fourth temperature).

[0112] (i) In the period between step A and step B, step C is executed in which the temperature of the second piping is lowered to the second temperature while the first process and the second process are not performed, thereby making it possible to suppress the temperature of the second piping from increasing due to the second process being performed.

[0113] (j) In step C, by starting step B at the timing when the second pipe temperature has dropped to the second temperature, the time required for dropping the second pipe temperature can be shortened and the throughput can be improved.

[0114] (k) In step C, by setting the second piping temperature to a third temperature lower than the second temperature, even if heat is generated in the second piping in step B due to, for example, an unintended oxidation reaction, the second piping temperature can be maintained at or below the second temperature, and a rapid temperature rise can be prevented.

[0115] (l) In steps A and B, the supply of nitrogen-containing gas into the processing chamber 201 through the second piping is not performed, and this makes it possible to prevent the generation of particles, nitric acid (HNO3), and the like, which may corrode the piping, etc., due to the mixing of the second processing gas containing O with the nitrogen-containing gas in the second piping.

[0116] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0117] For example, in the above-mentioned embodiment, the case where the temperature of the second pipe is decreased from the first temperature to the second temperature in step C after the supply of the first processing gas is stopped (after the execution of step A is completed) has been described as an example. However, the present disclosure is not limited to such an embodiment. For example, a process of decreasing the temperature of the second pipe from the first temperature to the second temperature may be started while continuing the supply of the first processing gas (i.e., while step A is being executed). In this case, too, the same effect as the above-mentioned embodiment can be obtained. Furthermore, since the decrease in the temperature of the second pipe is started while step A is being executed, the cycle time can be shortened and the throughput can be further improved.

[0118] For example, a fluoride layer of the metal-containing material may be formed by performing a fluoride treatment on the inner surface of the second pipe. By previously forming a fluoride layer on the inner surface of the second pipe made of a metal-containing material, the occurrence of an oxidation reaction between the second processing gas and the metal-containing material can be more reliably suppressed, and the effect of suppressing the temperature rise of the second pipe in the above-mentioned embodiment can be further enhanced. For example, a layer of the fluorinated metal-containing material (i.e., a fluoride layer) can be formed on the inner surface of the second pipe by previously exposing the inner surface of the second pipe to a fluorine (F)-containing gas such as F2 gas. In addition, a known fluoride treatment technique can also be used as a method for forming a fluoride layer on the inner surface of the second pipe.

[0119] In addition, the fluoride layer may be formed on the inner surface of the first pipe as well as the second pipe. Also, the fluoride layer may not be formed on the inner surface of the first pipe, but may be formed only on the inner surface of the second pipe.

[0120] For example, an oxide film such as a silicon oxide film (SiO film) may be formed by performing a film formation process on the inner surface of the second pipe. By forming an oxide film in advance on the inner surface of the second pipe made of a metal-containing material so as to cover the inner surface, it is possible to more reliably suppress the occurrence of an oxidation reaction between the second processing gas and the metal-containing material, and to further enhance the effect of suppressing the temperature rise of the second pipe in the above-mentioned embodiment. For example, a cycle including a step of supplying a raw material gas containing silicon (Si) and a step of supplying an O-containing gas as an oxidizing agent to the inner surface of the second pipe is performed a predetermined number of times, whereby a Si-containing oxide film can be formed (deposited) on the inner surface of the second pipe. In addition, a known film formation process technique can be used as a method of forming an oxide film on the inner surface of the second pipe.

[0121] In addition, an oxide film may be formed on the inner surface of the first pipe as well as the second pipe. Also, an oxide film may be formed only on the inner surface of the second pipe without forming an oxide film on the inner surface of the first pipe.

[0122] For example, in step C, after changing the control temperature of the pipe heater 233c from the first temperature to the third temperature, the power supply to the pipe heater 233c may be stopped at least until the second pipe temperature drops from the first temperature to the third temperature. Also, in step C, instead of changing the control temperature of the pipe heater 233c from the first temperature to the third temperature, the power supply to the pipe heater 233c may simply be stopped. Also, when lowering the second pipe temperature, a cooling device (not shown) may be used. In these cases, the same effect as the above-mentioned embodiment can be obtained. Furthermore, when a cooling device is used, the time required to lower the temperature of the second pipe can be shortened, and the throughput can be improved. The cooling device can be configured, for example, by an air cooling device, a water cooling device, a Peltier type cooling device, or the like.

[0123] For example, in the above-mentioned embodiment, SUS is used as an example of the metal-containing material constituting the inner surface of the first pipe and the second pipe. However, the present disclosure is not limited to such an embodiment. For example, the metal-containing material constituting the inner surface of the first pipe and the second pipe may be iron (Fe), copper (Cu), aluminum (Al), nickel (Ni), etc., or may be Hastelloy (registered trademark) in which Fe, molybdenum (Mo), chromium (Cr), etc. are added to Ni, or Inconel (registered trademark) in which Fe, Cr, niobium (Nb), Mo, etc. are added to Ni. In these cases, the same effects as those of the above-mentioned embodiment can be obtained.

[0124] For example, in the above-mentioned embodiment, the predetermined element contained in the raw material gas is Si. However, the present disclosure is not limited to such an embodiment. For example, the predetermined element may be a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), Nb, Al, Mo, tungsten (W), germanium (Ge), etc. In these cases, a metal oxide film such as a titanium oxynitride film (TiON film), a zirconium oxynitride film (ZrON film), a hafnium oxynitride film (HfON film), a tantalum oxynitride film (TaON film), a niobium oxynitride film (NbON film), an aluminum oxynitride film (AlON film), a molybdenum oxynitride film (MoON film), a tungsten oxynitride film (WON film), a germanium oxynitride film (GeON film), etc. is formed. In these cases, the same effect as the above-mentioned embodiment can be obtained.

[0125] It is preferable that the recipes used for each process are prepared individually according to the process contents, and are recorded and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes recorded and stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing device. It is also possible to reduce the burden on the operator, and to quickly start each process while avoiding operational errors.

[0126] The above-mentioned recipes may not only be newly created, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. Also, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0127] In the above-mentioned embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0128] When using these substrate processing apparatuses, each process can be performed according to the same process procedures and under the same process conditions as in the above-mentioned aspects and modifications, and the same effects as in the above-mentioned aspects and modifications can be obtained.

[0129] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in such a case may be the same as those of the above-mentioned aspects and modifications. [Explanation of symbols]

[0130] 200 wafers (substrates) 232a, 232b, 232d First pipe 232c Second Pipe

Claims

1. (a) performing a first process on a substrate accommodated in a processing vessel by supplying a first process gas into the processing vessel through a first pipe different from a second pipe, the second pipe being in a state in which the second pipe is heated to a first temperature or higher; (b) performing a second process on the substrate by supplying a second process gas containing oxygen into the process vessel through the second pipe while the temperature of the second pipe is reduced to a second temperature lower than the first temperature; and A substrate processing method comprising the steps of:

2. In step (a), the supply of the second process gas into the process vessel through the second pipe is not performed. The method of claim 1 .

3. (b) The supply of the first process gas into the process vessel is not performed. The method of claim 1 .

4. In (b), supply of gases other than the second process gas and the inert gas into the processing vessel is not performed. The substrate processing method according to claim 1 .

5. an inner surface of the first pipe is made of the metal-containing material; the first process gas comprises a first oxygen-containing gas; the first oxygen-containing gas has a lower reactivity with the metal-containing material than the second process gas has a reactivity with the metal-containing material; The method of claim 1 .

6. the second processing gas is a gas containing at least one of hydrogen peroxide gas, ozone gas, and plasma-excited oxygen-containing gas; The method of claim 1 .

7. In (b), the state in which the temperature of the first pipe is heated to or higher than the first temperature is maintained. The method of claim 1 .

8. the second temperature being a temperature at which no reaction occurs between the metal-containing material and the second process gas; The method of claim 1 .

9. the first temperature is a temperature at which a reaction between the metal-containing material and the second process gas occurs; The method of claim 1 .

10. In (a), a temperature of the second pipe is maintained at or above the first temperature while the first process is being performed. The method of claim 1 .

11. (b) maintaining a temperature of the second pipe at or below the second temperature while the second process is being performed; The method of claim 1 .

12. (b) maintaining a temperature of the first pipe at or above the first temperature while the second process is being performed; The method of processing a substrate according to any one of claims 1, 10 and 11.

13. In (b), when the temperature of the second pipe becomes a fourth temperature higher than the second temperature during the execution of the second process, the execution of the second process is stopped. The method of claim 1 .

14. In the period between (a) and (b): (c) decreasing the temperature of the second pipe to the second temperature while the first treatment and the second treatment are not being performed; The method of claim 1 .

15. In (c), (b) is started at a timing when the temperature of the second pipe drops to the second temperature. The method of claim 1 .

16. In (c), a control temperature of a heater provided to heat the second pipe is set to a third temperature lower than the second temperature. The method of claim 1 .

17. In (a) and (b), the supply of a nitrogen-containing gas into the processing vessel through the second pipe is not performed. The method of claim 1 .

18. (a) performing a first process on a substrate accommodated in a processing vessel by supplying a first process gas into the processing vessel through a first pipe different from a second pipe, the second pipe being in a state in which the second pipe is heated to a first temperature or higher; (b) performing a second process on the substrate by supplying a second process gas containing oxygen into the process vessel through the second pipe while the temperature of the second pipe is reduced to a second temperature lower than the first temperature; and A method for manufacturing a semiconductor device having the above structure.

19. (a) performing a first process on a substrate accommodated in a processing vessel by supplying a first process gas into the processing vessel through a first pipe different from a second pipe, the second pipe being in a state in which the second pipe is heated to a first temperature or higher; (b) performing a second process on the substrate by supplying a second process gas containing oxygen into the process vessel through the second piping while the temperature of the second piping is reduced to a second temperature lower than the first temperature; and A program for causing a computer to execute the above in a substrate processing apparatus.

20. a processing vessel for processing a substrate; a first process gas supply system configured to supply a first process gas into the process vessel via a first pipe connected to the process vessel; a second process gas supply system configured to supply a second process gas containing oxygen into the process vessel through a second pipe different from the first pipe, the second pipe having an inner surface made of a metal-containing material and connected to the process vessel; a heater for heating the second pipe; (a) performing a first process on the substrate by supplying the first process gas into the process vessel through the first piping while the second piping is heated to a first temperature or higher; (b) performing a second process on the substrate by supplying the second process gas into the process chamber through the second piping while lowering the temperature of the second piping to a second temperature lower than the first temperature; and a control unit configured to be able to control the first process gas supply system, the second process gas supply system, and the heater so as to perform the above-mentioned steps; The substrate processing apparatus includes:

Images