Substrate processing method, semiconductor device manufacturing method, 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 method of manufacturing a semiconductor device, a program, and a substrate processing apparatus. [Background Art]

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

[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 capable of suppressing an increase in pipe temperature caused by a reaction between the inner surface and oxygen-containing gas when the oxygen-containing gas is supplied through a pipe whose inner surface is formed of a metal-containing material. [Means for Solving the Problem]

[0005] According to one aspect of the present disclosure, (a) a step of performing a first process on a substrate accommodated in a processing container by supplying a first processing gas into the processing container through a first pipe different from a second pipe, in a state where the second pipe whose inner surface is formed of a metal-containing material and connected to the processing container is heated to a first temperature or higher; (b) a step of performing a second process on the substrate by supplying a second processing gas containing oxygen into the processing container through the second pipe, in a state where the temperature of the second pipe is lowered to a second temperature or lower that is lower than the first temperature; a technique including the above steps is provided. [Effect of the Invention]

[0006] According to this disclosure, when supplying an oxygen-containing gas through a pipe whose inner surface is made of a metal-containing material, it is possible to suppress the rise in pipe temperature due to the reaction between the inner surface and the gas. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion in a vertical cross-sectional view. [Figure 2] Figure 2 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion as a cross-sectional view along line AA in Figure 1. [Figure 3] Figure 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4] Figure 4 shows a processing sequence in one aspect of the present disclosure. [Figure 5] Figure 5 is a flowchart showing the flow of the substrate processing process in one aspect of this disclosure. [Modes for carrying out the invention]

[0008] <One aspect of this disclosure> The following description will explain one aspect of this disclosure, primarily with reference to Figures 1 to 5. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and proportions of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and proportions of the elements do not necessarily correspond between multiple drawings.

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

[0010] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in 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-containing material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages 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 sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The processing vessel (reaction vessel) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within this processing chamber 201.

[0011] Within the processing chamber 201, nozzles 249a to 249c, which serve as the first to third supply units, are provided so as to penetrate the side walls of the manifold 209. Nozzles 249a to 249c are also referred to as the first nozzle to the third nozzle, respectively. 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 nozzles 249a to 249c, respectively. Nozzles 249a to 249c are all different nozzles, and nozzles 249b and 249c are each provided adjacent to nozzle 249a.

[0012] Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c, respectively. Gas supply pipes 232a to 232c are configured as shared piping used for supplying multiple types of gas. In order from the upstream side of the gas flow, gas supply pipes 232a to 232c are equipped with mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, respectively. Downstream of valve 243a in gas supply pipe 232a, gas supply pipes 232d and 232e are connected, respectively. In gas supply pipes 232d and 232e, MFCs 241d and 241e and valves 243d and 243e are equipped, respectively, in order from the upstream side of the gas flow. Downstream of valve 243b in gas supply pipe 232b, gas supply pipe 232f is connected. Gas supply pipe 232f is equipped with MFC 241f and valve 243f in order from the upstream side of the gas flow. Gas supply pipe 232g is connected downstream of valve 243c on gas supply pipe 232c. Gas supply pipe 232g is equipped with MFC 241g and valve 243g in 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 the same metal-containing material such as SUS. In this specification, gas supply pipes 232a, 232b, and 232d may each be referred to as the first piping, or collectively as the first piping, and gas supply pipe 232c may be referred to as the second piping.

[0013] In the first gas supply pipes 232a, 232b, and 232d, pipe temperature sensors 234a, 234b, and 234d are installed upstream of the MFCs 241a, 241b, and 241d, respectively. In the second gas supply pipe 232c, pipe temperature sensor 234c is installed upstream of the MFC 241c. The pipe temperature sensors can be made up of known temperature sensors such as thermocouples. In this embodiment, pipe heaters 233a, 233b, and 233d are installed on the outer circumference of the first gas supply pipes 232a, 232b, and 232d, respectively. In the second pipe 232c, pipe heater 233b is installed on the outer circumference.

[0014] As shown in FIG. 2, the nozzles 249a to 249c are respectively provided in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, so as to rise upward along the upper portion from the lower portion of the inner wall of the reaction tube 203 toward the upper side in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are respectively provided along the wafer arrangement region in a region that horizontally surrounds the wafer arrangement region, on the side of the wafer arrangement region where the wafers 200 are arranged. In a plan view, the nozzle 249a is arranged so as to face in a straight line with an exhaust port 231a described later across the center of the wafer 200 carried into the processing chamber 201. The nozzles 249b and 249c are arranged so as 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 peripheral portion 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. That is, it can also be said that the nozzle 249c is provided on the opposite side to the nozzle 249b across the straight line L. The nozzles 249b and 249c are arranged axisymmetrically with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. Each of the gas supply holes 250a to 250c is opened so as to face (opposite to) the exhaust port 231a in a plan view, enabling gas supply toward the wafer 200. A plurality of the gas supply holes 250a to 250c are provided from the lower portion to the upper portion of the reaction tube 200.

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

[0016] From the gas supply pipe 232b, a second reaction gas as a first processing gas is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

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

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

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

[0020] A raw material gas supply system is mainly constituted by the gas supply pipe 232a, the MFC 241a, and the valve 243a. A second reactive gas supply system is mainly constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. A second processing gas supply system is mainly constituted by the gas supply pipe 232c, the MFC 241c, and the valve 243c. A first reactive gas supply system is mainly constituted by the gas supply pipe 232d, the MFC 241d, and the valve 243d. An inert gas supply system is mainly constituted by the gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g. In the present embodiment, the raw material gas supply system, the first reactive gas supply system, and the second reactive gas supply system are collectively referred to as a first processing gas supply system. Nozzles connected to the gas supply pipes constituting the various supply systems described above may each be included in the corresponding supply system.

[0021] Of the various supply systems described above, one or all of them may be configured as an integrated supply system 248, which is comprised of valves 243a to 243g and MFCs 241a to 241g, etc. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232g, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232g, i.e., the opening and closing operation of valves 243a to 243g and the flow rate adjustment operation by MFCs 241a to 241g, etc., is controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or segmented integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232g, etc., in units of the integrated unit, and is configured so that maintenance, replacement, and expansion of the integrated supply system 248 can be performed in units of the integrated unit.

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

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of hermetically 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 disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 is made of a metal-containing material such as SUS and is connected to the boat 217 by passing through the seal cap 219. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0024] Below the manifold 209, a shutter 219s is provided as a furnace opening 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 removed from the processing chamber 201. The shutter 219s is made of a metal-containing material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as lifting and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0025] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0026] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0028] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing device, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe functions as a program, combining the procedures in the substrate processing described later so that the controller 121 causes the substrate processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be referred to simply as "recipes." In this specification, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

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

[0030] The CPU 121a is configured 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 input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by MFCs 241a to 241g, the opening and closing operation of valves 243a to 243g, the opening and closing operation of APC valve 244 and the pressure adjustment operation of APC valve 244 based on pressure sensor 245, the starting and stopping of vacuum pump 246, the temperature adjustment operation of heater 207 based on temperature sensor 263, the rotation and rotation speed adjustment operation of boat 217 by rotation mechanism 267, the raising and lowering operation of boat 217 by boat elevator 115, and the opening and closing operation of shutter 219s by 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, onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, and semiconductor memory such as USB memory and SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Substrate processing process Using the substrate processing apparatus described above, a method for processing a substrate as one step in the manufacturing process of a semiconductor device, that is, a series of processing sequences including a film deposition sequence for forming a film on a wafer 200 as a substrate, will be explained mainly with reference to Figures 4 and 5. In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0033] In the processing sequence of this embodiment, (a) Step A, in which a first processing is performed on a wafer 200 housed in a processing container by heating a second pipe (gas supply pipe 232c), which is connected to the processing container and whose inner surface is made of a metal-containing material, to a first temperature or higher, and supplying a first processing gas into the processing container via a first pipe (gas supply pipes 232a, 232b, 232d) that is different from the second pipe, and (b) Step B, in which the wafer 200 is subjected to a second treatment by supplying a second treatment gas containing oxygen into the treatment container through the second pipe while the temperature of the second pipe is lowered to a second temperature or lower than the first temperature, It holds.

[0034] In this embodiment, in the processing sequence, in step A, Step a1 involves supplying a raw material gas as the first processing gas to the wafer 200, Step a2 involves supplying a first reaction gas as a first processing gas to the wafer 200, Step a3 involves supplying a second reaction gas as a first processing gas to the wafer 200, This example shows how to form a film on a wafer 200 by performing a predetermined number of cycles (n times, where n is an integer of 1 or more than 2) that include the above. In this specification, the raw material gas, the first reaction gas, the second reaction gas, or all of them together may be referred to as the first treatment gas.

[0035] In this embodiment, in the processing sequence, in step B, This example shows how to treat a film formed on a wafer 200 by supplying a second treatment gas containing oxygen (O) to the wafer 200.

[0036] Furthermore, in the processing sequence of this embodiment, an example is shown in which, during the period between step A and step B, the temperature of the second pipe is reduced from a temperature equal to or greater than the first temperature to a second temperature that is lower than the first temperature.

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

[0038] In this specification, the processing sequence described above may also be shown as follows for convenience. The same notation will be used in the following descriptions of modifications and other embodiments.

[0039] (Raw material gas → First reaction gas → Second reaction gas) × n → Second pipe temperature reduction → Second treatment gas containing O

[0040] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this specification, when it is stated that "a predetermined layer is formed on the wafer," it may mean that the predetermined layer is formed directly on the surface of the wafer itself or that the predetermined layer is formed on a layer already formed on the wafer. In this specification, the term "substrate" has the same meaning as when it is used with the term "wafer."

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

[0042] In this specification, when describing the adsorption or reaction of the first processing gas and the second processing gas containing O to the surface of the wafer 200, it may include not only the mode in which they adsorb or react to the wafer surface while remaining undecomposed, but also the mode in which they decompose or intermediates generated by the detachment of their ligands adsorb or react to the surface of the wafer 200.

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

[0044] (Pressure adjustment and temperature adjustment) After the boat loading is complete, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by a vacuum pump 246 to achieve the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by a heater 207 to reach the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on the temperature information detected by a temperature sensor 263 to ensure that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0045] (Temperature setting for the second pipe) Subsequently, the second piping (gas supply pipe 232c) is heated by the pipe heater 233c so that the temperature inside it reaches the first temperature or higher. At this time, the amount of power supplied to the pipe heater 233c is feedback-controlled based on the temperature information detected by the pipe temperature sensor 234c so that the temperature inside the second piping is the desired temperature distribution. At this time, it is preferable that the temperature inside the first piping (gas supply pipes 232a, 232b, 232d) is also heated by the pipe heaters 233a, 233b, and 233d so that it reaches the first temperature or higher. Furthermore, the timing of the process of heating the temperature inside the second piping to the first temperature is not limited to after pressure adjustment and temperature adjustment, but may be started simultaneously with or before 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 order.

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

[0048] Specifically, valve 243a is opened, and the raw material gas flows into the gas supply pipe 232a (first piping). The flow rate of the raw material gas is regulated by MFC 241a and supplied into the processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the raw material gas is supplied to the wafer 200 (raw material gas supply). At this time, valves 243e to 243g may also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively. The inert gas supplied via nozzles 249b and 249c also acts as an intrusion suppression gas, preventing raw material gas and other substances in the processing chamber from entering (backflowing) into nozzles 249a and 249b.

[0049] The processing conditions when supplying the raw material gas in this step are as follows: Processing temperature: 350-900°C, preferably 500-900°C, more preferably 600-800°C Processing pressure: 1 to 10,000 Pa, preferably 10 to 1,333 Pa First piping temperature: Above the first temperature, for example, 160-250°C, preferably 180-250°C. Second piping temperature: Above the first temperature, for example, 160-250°C, preferably 180-250°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): 0-10 slm Examples are given.

[0050] In this specification, numerical ranges such as "350~900°C" mean that the lower and upper limits are included within that range. For example, "350~900°C" means "350°C or more and 900°C or less." The same applies to other numerical ranges. In this specification, processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure means the pressure inside the processing chamber 201, in other words, the pressure in the space where the wafer 200 is located. Processing time means the time during which the processing is continued. Pipe temperature means the temperature inside the pipe. When 0 slm is included in the supply flow rate, 0 slm means the case in which the substance (gas) is not supplied. These also apply in the following explanations.

[0051] Under the conditions described above, by supplying a chlorosilane-based gas, for example, as a raw material gas to the wafer 200, a silicon (Si)-containing layer containing chlorine (Cl) is formed on the outermost surface of the wafer 200, which serves as the substrate. The Si-containing layer containing Cl is formed by physical or chemical adsorption of molecules of the chlorosilane-based gas onto the outermost surface of the wafer 200, physical or chemical adsorption of molecules of substances obtained by the decomposition of part of the chlorosilane-based gas, and deposition of Si by thermal decomposition of the chlorosilane-based gas. The Si-containing layer containing Cl may be an adsorption layer (physical or chemical adsorption layer) of molecules of chlorosilane-based gas or molecules of substances obtained by the decomposition of part of the chlorosilane-based gas, or it may be a deposited layer of Si containing Cl. In this specification, the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.

[0052] As the raw material 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 halogens, i.e., a halosilane-based gas, can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halosilane-based gas, for example, the chlorosilane-based gas mentioned above containing Si and Cl can be used.

[0053] As raw material gases, for example, chlorosilane gases such as monochlorosilane (SiH3Cl) gas, dichlorosilane (SiH2Cl2) gas, trichlorosilane (SiHCl3) gas, tetrachlorosilane (SiCl4) gas, hexachlorodisilane (Si2Cl6) gas, and octachlorotrisilane (Si3Cl8) gas can be used. One or more of these can be used as raw material gases.

[0054] As raw material gases, in addition to chlorosilane gases, other gases that can be used include fluorosilane gases such as tetrafluorosilane (SiF4) gas and difluorosilane (SiH2F2) gas, bromosilane gases such as tetrabromosilane (SiBr4) gas and dibromosilane (SiH2Br2) gas, and iodosilane gases such as tetraiodosilane (SiI4) gas and diiodosilane (SiH2I2) gas. One or more of these can be used as raw material gases.

[0055] In addition to the above, other gases containing Si and amino groups, i.e., aminosilane gases, can also be used as raw material gases. 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. Note that R represents an alkyl group, and the two R's in -NR2 may be the same or different.

[0056] For example, aminosilane gases 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(tert-butylamino)silane (SiH2[NH(C4H9)]2) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2]) gas can also be used as raw material gases. One or more of these can be used as raw material gases.

[0057] Examples of inert gases that can be used include nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe). One or more of these can be used as the inert gas. This also applies to each of the steps described later.

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

[0059] [Step a2] After step a1 is completed, the 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, valve 243d is opened, and the first reaction gas flows into the gas supply pipe 232d (first piping). The flow rate of the first reaction gas is adjusted by MFC 241d and supplied into the processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the first reaction gas is supplied to the wafer 200 (first reaction gas supply). At this time, valves 243e to 243g may also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0061] The processing conditions when supplying the first reaction gas in this step are as follows: First reaction 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 This is an example. Other processing conditions can be the same as the processing conditions in step a1.

[0062] Under the conditions described above, by supplying, for example, an oxygen-containing gas as the first reaction gas to the wafer 200, at least a portion of the Si-containing layer formed on the wafer 200 is oxidized (modified). As a result, a silicon oxide layer (SiO layer) containing Si and O is formed on the outermost surface of the wafer 200, which serves as the substrate. In this embodiment, for example, an oxygen-containing gas is used as the first reaction gas. Hereinafter, the first reaction gas may be referred to as the first oxygen-containing gas.

[0063] The reactivity of the first oxygen-containing gas used in this step with respect to the metal-containing material constituting the inner surface of the gas supply pipe 232d (first pipe) is smaller than the reactivity of the second oxygen-containing treatment gas used in step B, described later, with respect to the metal-containing material constituting the inner surface of the gas supply pipe 232c (second pipe). Here, reactivity mainly includes the ease with which oxidation reactions occur (oxidizing power). As a result, even if the inner surface of the gas supply pipe 232d is made of a metal-containing material, the rise in temperature of the gas supply pipe 232d due to the reaction between the first oxygen-containing gas and the metal-containing material in this step can be suppressed.

[0064] Examples of the first reaction gases that can be used include oxygen (O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, and carbon dioxide (CO2) gas. One or more of these can be used as the first reaction gas.

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

[0066] The first reaction gas is not limited to those exemplified, and can be appropriately selected from among oxygen-containing gases whose reactivity with the metal-containing material constituting the inner surface of the gas supply pipe 232d is lower than that of the second treatment gas. Furthermore, as the first reaction gas with lower reactivity than the second treatment gas, it is also possible to select a gas of the same type as the second treatment gas (i.e., a gas with the same molecular structure) but with a lower concentration (for example, a second treatment gas diluted with a diluent gas).

[0067] Furthermore, in this specification, the joint mention of two gases, such as "H2 gas + O2 gas," refers to a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe before being supplied to the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and mixed (postmixed) within the processing chamber 201. When the two gases are supplied separately to the processing chamber 201 from different supply pipes, it is preferable that the O-containing gas is supplied to the processing chamber 201 via the gas supply pipe 232d (first piping), and the other gas (including cases where the other gas is also an O-containing gas) is supplied to the processing chamber 201 via another gas supply pipe.

[0068] After the SiO film is formed, 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 any remaining gaseous substances from the processing chamber 201. Then, the remaining gases from the processing chamber 201 are removed from the processing chamber 201 using the same procedure as the purging in step a1 (purging).

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

[0071] The processing conditions when supplying the second reaction gas in this step are as follows: Second reaction gas supply flow rate: 0.1 to 20 slm, preferably 1 to 10 slm Second reaction gas supply time: 1 to 120 seconds, preferably 3 to 15 seconds This is an example. Other processing conditions can be the same as the processing conditions in step a1.

[0072] Under the conditions described above, by supplying a gas containing nitrogen (N) and hydrogen as a second reaction gas to the wafer 200, 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 on the outermost surface of the wafer 200, which serves as the substrate, as a layer containing Si, O, and N.

[0073] As the second reaction gas, for example, a nitriding gas can be used. As the nitriding gas, for example, the above-mentioned N and H-containing gas can be used. The N and H-containing gas is both an N-containing gas and an H-containing gas.

[0074] As the second reaction gas, for example, hydrogen nitride-based gases such as ammonia (NH3) gas, diazene (N2H2) gas, hydrazine (N2H4) gas, and N3H8 gas can be used. One or more of these can be used as the second reaction gas.

[0075] After the SiON film is formed, 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 any remaining gaseous substances from the processing chamber 201. Then, the remaining gases from the processing chamber 201 are removed from the processing chamber 201 using the same procedure as the purging in step a1 (purging).

[0076] [Perform the prescribed number of times] By performing steps a1 to a3 described above non-simultaneously, i.e., without synchronization, in this order, n times (where n is 1 or an integer of 2 or more), a predetermined thickness of film, for example, an SiON film of a predetermined thickness, can be formed on the surface of the wafer 200 as a substrate. 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 SiON layers reaches the desired thickness.

[0077] As mentioned above, in step A, an inert gas is supplied to the processing chamber 201 from the nozzle 249c as an intrusion-inhibiting gas. However, supplying only the intrusion-inhibiting gas may not be sufficient to prevent by-products generated in the processing chamber 201 from entering the nozzle 249c and the gas supply pipe 232c. Furthermore, in step A, if the temperature of the second pipe is below the first temperature, for example, below 160°C, it may be difficult to prevent by-products generated in the processing chamber 201 from adhering (accumulating) inside the second pipe when they enter (backflow) from the processing chamber 201 into the second pipe. To address these issues, raising the temperature of the second pipe to the first temperature or higher makes it possible to suppress the adhesion of by-products that have entered from the processing chamber 201 to the second pipe. By raising the temperature of the second pipe to a temperature higher than the first temperature, for example, 20°C or more higher than the first temperature, the adhesion (accumulation) of by-products that have entered from the processing chamber 201 to the second pipe can be suppressed more effectively. A temperature above the first temperature can be defined as a temperature at which the adhesion of by-products to the inside of the second pipe can be suppressed. However, if the temperature of the second pipe is excessively high, for example, if it is above 250°C, pipe accessory components made of resin, such as sealing members, may burn out. For this reason, it is preferable to set the temperature of the second pipe to, for example, 250°C or lower. The by-products that adhere to the inside of the second pipe may include not only by-products that have entered from the processing chamber 201, but also by-products generated when the first processing gas that has entered the second pipe undergoes thermal decomposition or the like inside the second pipe.

[0078] (Second pipe temperature reduction treatment: Step C) After step A is completed and before 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 amount of power supplied to the pipe heater 233c is feedback-controlled based on the temperature information detected by the pipe temperature sensor 234c so that the temperature of the second pipe reaches the desired temperature distribution. The third temperature is lower than the second temperature, which is lower than the first temperature. The system waits until the temperature of the second pipe drops to the second temperature.

[0079] (Second process: Step B) Step B is started when the temperature of the second piping drops from the first temperature to the second temperature. In this step, a second processing gas containing oxygen is supplied to the wafer 200 in the processing chamber 201, that is, to the SiON film formed on the wafer 200. Hereinafter, the second processing gas containing oxygen may simply be referred to as the second processing gas.

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

[0081] Here, when a second treatment gas containing oxygen 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 metal-containing material such as SUS that makes up the inner surface and the second treatment gas. The heat generated by the oxidation reaction raises the temperature of the second pipe, causing charring of pipe accessory components made of resin, such as sealing members, and may also generate contaminants due to the charring.

[0082] More specifically, nickel (Ni) contained in materials such as SUS can act as a catalyst on the second processing gas containing oxygen, decomposing the gas and generating oxygen atoms (atomic oxygen). Because the oxygen atoms generated in this way are highly reactive, they easily cause oxidation reactions with metal-containing materials and generate heat. If the temperature of the second piping rises due to this heat, the catalytic reaction and generation of oxygen atoms described above are further accelerated, making it difficult to suppress the temperature rise of the second piping.

[0083] In this step, as will be described later, the second treatment gas is supplied while the temperature of the second pipe is kept below the second temperature, thereby maintaining a state in which oxidation reactions do not substantially occur and suppressing the temperature rise of the second pipe.

[0084] The processing conditions when supplying the second processing gas in this step are as follows: Second piping temperature: Below the second temperature, for example, 0 to 155°C, preferably room temperature (25°C) to 150°C, more preferably 100 to 120°C. Second treatment gas supply concentration: 100-300 g / m³ 3 Preferably 200-300 g / m 3 Second processing gas supply time: 30 to 180 minutes, preferably 45 to 120 minutes This is an example. Other processing conditions can be the same as the processing conditions in step a1.

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

[0086] Furthermore, if the temperature of the first pipe falls below the first temperature, for example, below 160°C, it may become difficult to prevent the by-products of the first processing gas supplied in step A and remaining in the first pipe from adhering (accumulating) inside the first pipe. By raising the temperature of the first pipe to the first temperature or higher in step B, it becomes possible to prevent the by-products of the first processing gas remaining in the first pipe from adhering inside the first pipe. Moreover, by raising the temperature of the first pipe to a temperature higher than the first temperature in step B, for example, 20°C or more higher than the first temperature, the adhesion of by-products of the first processing gas remaining in the first pipe can be suppressed more effectively. A temperature of the first temperature or higher can be defined as a temperature at which the adhesion of by-products of the first processing gas inside the first pipe can be suppressed. However, if the temperature of the first pipe is excessively high, for example, 250°C or higher, pipe accessory members made of resin, such as sealing members, may burn out. Therefore, it is preferable to set the temperature of the first pipe to, for example, 250°C or lower.

[0087] Furthermore, if the temperature of the first pipe is below the first temperature, for example, below 160°C, it may be difficult to prevent the by-products of the second processing gas generated in the processing chamber 201 in step B from entering (backflowing) into the first pipe. By raising the temperature of the first pipe to the first temperature or higher in step B, it becomes possible to prevent the by-products of the second processing gas that have entered the first pipe from adhering to the first pipe. Moreover, by raising the temperature of the first pipe to a temperature higher than the first temperature in step B, for example, a temperature 20°C or more higher than the first temperature, it is possible to more effectively prevent the by-products of the second processing gas that have entered the first pipe from adhering to the first pipe. A temperature of the first temperature or higher can be defined as a temperature at which the by-products of the second processing gas can be prevented from adhering to the first pipe.

[0088] Furthermore, if the temperature of the second pipe exceeds the second temperature, for example, if it exceeds 155°C, it may become difficult to avoid the oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second treatment gas. This makes it difficult to suppress the rise in the temperature of the second pipe, and thus difficult to avoid the burning of pipe accessory components made of resin, such as sealing components, and the generation of contaminants. By keeping the temperature of the second pipe below the second temperature, it is possible to suppress the oxidation reaction between the metal-containing material, which is a component of the inner surface of the second pipe, and the second treatment gas. By keeping the temperature of the second pipe below the second temperature, for example, below 150°C, the oxidation reaction between the metal-containing material, which is a component of the inner surface of the second pipe, and the second treatment gas can be effectively suppressed. By keeping the temperature of the second pipe below the second temperature, for example, below 120°C, the oxidation reaction between the metal-containing material, which is a component of the inner surface of the second pipe, and the second treatment gas can be suppressed even more effectively. The second temperature can be defined as the temperature at which no substantial reaction occurs between the metal-containing material and the second treatment gas. The first temperature can be defined as the temperature at which a substantial reaction occurs between the metal-containing material and the second treatment gas.

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

[0090] Furthermore, the supply time for the second treatment gas can be longer than the supply time for each cycle of the first oxygen-containing gas exemplified in step a2. Also, the supply time for the second treatment gas can be longer than the supply time for each cycle of the first treatment gas in step A (total supply time of the raw material gas, first reaction gas, and second reaction gas).

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

[0092] Furthermore, the second treatment gas can be a gas containing at least one of hydrogen peroxide (H2O2) gas and ozone (O3) gas.

[0093] The second processing gas is not limited to those exemplified, and can be appropriately selected from among oxygen-containing gases that produce a substantial exothermic reaction with the metal-containing material constituting the inner surface of the gas supply pipe 232c (second piping).

[0094] Furthermore, as the second treatment gas, an oxygen-containing gas with higher reactivity than the first oxygen-containing gas can be used. More specifically, the second reaction gas can be appropriately selected from among oxygen-containing gases that have a higher reactivity with the metal-containing material constituting the inner surface of the gas supply pipe 232c than the first treatment gas. One or more of these can be used as the second treatment gas.

[0095] If, during the execution time of this step, the temperature of the second pipe reaches the fourth temperature (upper limit temperature / critical temperature), which is higher than the second temperature, the supply of the second processing gas, etc., will be stopped, and the execution of this step will be halted. Then, once the temperature of the second pipe drops back down to the second temperature, the execution of this step will be resumed.

[0096] When the execution time for this step reaches a predetermined time, the execution of this step is terminated.

[0097] (After-purge and return to atmospheric pressure) After step B is completed, inert gas is supplied as a purge gas into the processing chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purge). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0098] (Boat unloading and wafer discharge) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutters 219s are moved, and the lower end opening of the manifold 209 is sealed by the shutters 219s via the O-ring 220c (shutter closing). After the processed wafer 200 has been unloaded from the reaction tube 203, it is removed from the boat 217 (wafer discharge).

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

[0100] (a) In step B, when supplying the second processing gas through the second piping, the temperature of the second piping can be lowered to a second temperature or lower, which is lower than the first temperature, thereby suppressing the temperature rise of the second piping. Specifically, in step B, when supplying the second processing gas through the second piping, the temperature of the second piping can be lowered to a second temperature or lower, which is below the second temperature at which oxidation reaction between the metal-containing material constituting the inner surface of the second piping and the second processing gas does not occur, thereby suppressing the temperature rise of the second piping. By suppressing the temperature rise of the second piping, for example, burnout of piping accessory members made of resin, such as sealing members, can be prevented, and the generation of contaminants caused by oxidation reaction between the metal-containing material and the second processing gas can be prevented.

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

[0102] Furthermore, in step A, when supplying the first processing gas through the first piping, the second piping is heated to a temperature of 1 or higher. This suppresses the adhesion of by-products generated when the first processing gas is supplied into the processing chamber 201 to the second piping, even if these by-products enter the second piping from the processing chamber 201. Specifically, in step A, when supplying the first processing gas, the temperature of the second piping is set to a temperature of 1 or higher, which is the temperature at which by-products of the first processing gas do not adhere to the inside of the second piping. This suppresses the adhesion of these by-products to the inside of the second piping.

[0103] Furthermore, in step A, by continuously maintaining the temperature of the second pipe at or above the first temperature while the first process is being performed, the adhesion of by-products of the first process gas to the inside of the second pipe can be reliably suppressed.

[0104] (b) The rise in pipe temperature is a more pronounced issue when a gas with high reactivity (high activity) is used that reacts well with the metal-containing material constituting the inner surface of the pipe. In this embodiment, in step B, an oxygen-containing gas with higher activity than the first oxygen-containing gas is used as the second treatment gas, so the effect of suppressing pipe temperature rise according to this disclosure can be significantly obtained.

[0105] (c) Between step A and step B, the substrate is not removed from the processing chamber 201, and both the first and second processing are performed within the same processing chamber. This prevents contamination of the substrate and adhesion of particles that may occur during the loading and unloading of the substrate. In addition, reducing the loading and unloading of the substrate may improve productivity (throughput).

[0106] (d) In step A, the temperature rise of the second piping can be suppressed by not supplying the second treatment gas into the treatment chamber 201 via the second piping. Specifically, in step A, when the temperature of the second piping is above the first temperature, which is the temperature at which an oxidation reaction occurs between the metal-containing material constituting the inner surface of the second piping and the second treatment gas, the supply of the second treatment gas is not carried out to prevent the reaction itself from occurring. This ensures that the temperature rise of the second piping is suppressed. By suppressing the temperature rise of the second piping, for example, burnout of piping accessory members made of resin, such as sealing members, can be prevented, and the generation of contaminants caused by the oxidation reaction between the metal-containing material and the second treatment gas can be prevented.

[0107] (e) In step B, by not supplying the first processing gas into the processing chamber 201, the adhesion of by-products of the first processing gas to the inside of the second piping can be suppressed. Specifically, in step B, where the temperature of the second piping is maintained at or below the second temperature, which is a temperature at which it is difficult to suppress the adhesion of by-products of the first processing gas, the supply of the first processing gas is not carried out to prevent the generation of the by-products themselves. This ensures that the adhesion of by-products of the first processing gas to the inside of the second piping is reliably avoided.

[0108] (f) In step B, by not supplying any gases other than the second processing gas and inert gas into the processing chamber 201, the adhesion of by-products of the other gases to the inside of the second piping can be suppressed. Specifically, in step B, where the temperature of the second piping is maintained at or below the second temperature, which is a temperature at which the adhesion of by-products of the other gases is difficult to suppress, the supply of the other gases is not carried out to prevent the generation of such by-products. This ensures that the adhesion of by-products of the other gases to the inside of the second piping is reliably avoided.

[0109] (g) In step B, by maintaining the temperature of the first pipe, which was heated to a first temperature or higher in step A, at or above the first temperature, it is possible to suppress the adhesion of by-products of the first processing gas supplied in step A and remaining in the first pipe to the inside of the first pipe. More specifically, in step B as well, by maintaining the temperature of the first pipe 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 pipe, it is possible to suppress the adhesion of by-products of the first processing gas supplied in step A and remaining in the first pipe to the inside of the first pipe. Furthermore, in step B, by maintaining the temperature of the first pipe, which was heated to a temperature of 1 or higher in step A, at or above the 1st temperature, even if by-products of the second processing gas supplied in step B enter the first pipe, it is possible to suppress the adhesion of these by-products to the inside of the first pipe. Specifically, in step B as well, by setting the temperature of the first pipe to a temperature of 1 or higher, which is the temperature at which by-products of the second processing gas do not adhere to the inside of the first pipe, it is possible to suppress the adhesion of by-products of the second processing gas to the inside of the first pipe.

[0110] In step B, the above effect can be reliably obtained by continuously maintaining the temperature of the first pipe at or above the first temperature while the second process is being performed.

[0111] (h) In step B, if the temperature of the second pipe becomes higher than the second temperature (the fourth temperature, or critical temperature) during the execution of the second process, the second process is stopped, thereby preventing the temperature of the second pipe from exceeding the upper limit temperature (the fourth temperature).

[0112] (i) During the period between step A and step B, step C is performed to lower the temperature of the second pipe to the second temperature while the first and second treatments are not performed, thereby suppressing the temperature rise of the second pipe by performing the second treatment.

[0113] (j) In step C, by starting step B when the temperature of the second pipe has dropped to the second temperature, the time required to lower the temperature of the second pipe can be shortened, thereby improving throughput.

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

[0115] (l) In steps A and B, by not supplying nitrogen-containing gas into the treatment chamber 201 via the second piping, it is possible to prevent the generation of particles and nitric acid (HNO3), etc., which may corrode the piping, etc., due to the mixing of the O-containing second treatment gas and the nitrogen-containing gas in the second piping.

[0116] <Other aspects of this disclosure> The aspects of this disclosure have been specifically described above. However, this disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0117] For example, in the above-described embodiment, the case in step C was explained as one in which the temperature of the second pipe is lowered from the first temperature to the second temperature after the supply of the first processing gas has been stopped (after the execution of step A has been completed). However, this disclosure is not limited to this embodiment. For example, the process of lowering the temperature of the second pipe from the first temperature to the second temperature may be started while the supply of the first processing gas is being continued (i.e., while step A is being executed). In this case as well, the same effects as in the above-described embodiment can be obtained. Furthermore, since the temperature of the second pipe is lowered while step A is being executed, the cycle time can be shortened and throughput can be further improved.

[0118] For example, a fluorinated layer of the metal-containing material may be formed on the inner surface of the second pipe by applying a fluorination treatment. By pre-forming a fluorinated layer on the inner surface of the second pipe, which is made of a metal-containing material, the occurrence of oxidation reactions between the second treatment 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-described embodiment can be further enhanced. For example, a layer of fluorinated metal-containing material (i.e., a fluorinated layer) can be formed on the inner surface of the second pipe by pre-exposing the inner surface of the second pipe to a fluorine (F)-containing gas such as F2 gas. Alternatively, known fluorination treatment techniques can be used as a method for forming a fluorinated layer on the inner surface of the second pipe.

[0119] Furthermore, the fluorine layer may be formed on the inner surface of the first pipe as well as the second pipe. Alternatively, the fluorine layer may be formed only on the inner surface of the second pipe, without forming it on the inner surface of the first pipe.

[0120] For example, an oxide film such as a silicon oxide film (SiO film) may be formed on the inner surface of the second pipe by applying a film deposition treatment. By pre-forming an oxide film on the inner surface of the second pipe, which is made of a metal-containing material, so as to cover the inner surface, the occurrence of an oxidation reaction between the second treatment 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 embodiment can be further enhanced. For example, a Si-containing oxide film can be formed (deposited) on the inner surface of the second pipe by performing a predetermined number of cycles including the step of supplying a raw material gas containing silicon (Si) and the step of supplying an O-containing gas as an oxidizing agent to the inner surface of the second pipe. Alternatively, known film deposition techniques can be used as a method for forming an oxide film on the inner surface of the second pipe.

[0121] Furthermore, an oxide film may be formed on the inner surface of the first pipe as well as the second pipe. Alternatively, an oxide film may be formed only on the inner surface of the second pipe, without forming one 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 until at least the temperature of the second pipe drops from the first temperature to the third temperature. Alternatively, 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. Furthermore, a cooling device (not shown) may be used when lowering the temperature of the second pipe. In these cases as well, the same effects as in the above-described embodiment can be obtained. Moreover, when a cooling device is used, the time required to cool the second pipe can be shortened and throughput can be improved. The cooling device can be configured as, for example, an air cooler, a water cooler, a Peltier cooler, etc.

[0123] For example, in the embodiments described above, SUS was used as an example of the metal-containing material constituting the inner surfaces of the first and second pipes. However, this disclosure is not limited to such embodiments. For example, the metal-containing material constituting the inner surfaces of the first and second pipes may be iron (Fe), copper (Cu), aluminum (Al), or nickel (Ni), or Hastelloy®, which is Ni with Fe, molybdenum (Mo), chromium (Cr), etc. added, or Inconel®, which is Ni with Fe, Cr, niobium (Nb), Mo, etc. added. In these cases as well, the same effects as in the embodiments described above can be obtained.

[0124] For example, in the above-described embodiment, the case in which the predetermined element contained in the raw material gas is Si was used as an example. However, this disclosure is not limited to such embodiments. For example, the predetermined element may be a metallic element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), Nb, Al, Mo, tungsten (W), or germanium (Ge). In these cases, metallic oxide films such as titanium oxynitride film (TiON film), zirconium oxynitride film (ZrON film), hafnium oxynitride film (HfON film), tantalum oxynitride film (TaON film), niobium oxynitride film (NbON film), aluminum oxynitride film (AlON film), molybdenum oxynitride film (MoON film), tungsten oxynitride film (WON film), or germanium oxynitride film (GeON film) are formed. In these cases as well, the same effects as in the above-described embodiment can be obtained.

[0125] It is preferable that the recipes used for each process be prepared individually according to the processing content, recorded and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes recorded and stored in the storage device 121c according to the processing content. This makes it possible to form films of various film types, composition ratios, film quality, and film thickness with good reproducibility using a single substrate processing device. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0126] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed in the board processing device. When modifying a recipe, the modified recipe may be installed in the board processing device via a telecommunications line or a recording medium containing the recipe. Alternatively, existing recipes already installed in the board processing device may be directly modified by operating the input / output device 122 provided in the existing board processing device.

[0127] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0128] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0129] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications. [Explanation of Symbols]

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

Claims

1. (a) A step of performing a first treatment on a substrate contained in a processing container by heating a second pipe connected to a processing container to a first temperature or higher, with the inner surface of the second pipe being made of a metal-containing material, and supplying a first treatment gas into the processing container via a first pipe different from the second pipe, (b) A step of performing a second treatment on the substrate by supplying a second treatment gas containing oxygen into the treatment container via the second pipe while the temperature of the second pipe is lowered to a second temperature or lower than the first temperature, A substrate processing method having the following characteristics.

2. (a) In this case, the supply of the second processing gas into the processing container via the second piping is not performed. The substrate processing method according to claim 1.

3. (b) In this case, the supply of the first processing gas into the processing container is not performed. The substrate processing method according to claim 1.

4. (b) In this case, the supply of gases other than the second processing gas and the inert gas into the processing container is not carried out. A substrate processing method according to any one of claims 1 to 3.

5. The inner surface of the first pipe is made of the metal-containing material, The first processing gas includes a first oxygen-containing gas. The reactivity of the first oxygen-containing gas with respect to the metal-containing material is less than the reactivity of the second treatment gas with respect to the metal-containing material. The substrate processing method according to 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 substrate processing method according to claim 1.

7. (b) In this case, the temperature of the first pipe is maintained at or above the first temperature. The substrate processing method according to claim 1.

8. The second temperature is a temperature at which no reaction occurs between the metal-containing material and the second processing gas. The substrate processing method according to claim 1.

9. The first temperature is the temperature at which the reaction between the metal-containing material and the second processing gas occurs. The substrate processing method according to claim 1.

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

11. (b) In the second process, the temperature of the second pipe is kept below the second temperature while the second process is being performed. The substrate processing method according to claim 1.

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

13. (b) If the temperature of the second pipe becomes a fourth temperature higher than the second temperature while the second process is being executed, the execution of the second process is stopped. The substrate processing method according to claim 1.

14. During the period between (a) and (b), (c) The process further comprises the step of lowering the temperature of the second pipe to the second temperature while the first and second processes are not performed. The substrate processing method according to claim 1.

15. (c) In this case, (b) is started when the temperature of the second pipe drops to the second temperature. The substrate processing method according to claim 1.

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

17. In (a) and (b), the supply of nitrogen-containing gas to the processing container via the second piping is not carried out. The substrate processing method according to claim 1.

18. (a) A step of performing a first treatment on a substrate contained in a processing container by heating a second pipe connected to a processing container to a first temperature or higher, with the inner surface of the second pipe being made of a metal-containing material, and supplying a first treatment gas into the processing container via a first pipe different from the second pipe, (b) A step of performing a second treatment on the substrate by supplying a second treatment gas containing oxygen into the treatment container via the second pipe while the temperature of the second pipe is lowered to a second temperature or lower than the first temperature, A method for manufacturing a semiconductor device having

19. (a) A procedure for performing a first treatment on a substrate housed in a processing container, wherein the inner surface of the second pipe connected to the processing container is made of a metal-containing material, and the second pipe is heated to a first temperature or higher, and a first processing gas is supplied into the processing container via a first pipe different from the second pipe, and (b) A procedure for performing a second treatment on the substrate by supplying a second treatment gas containing oxygen into the treatment container via the second pipe while the temperature of the second pipe is lowered to a second temperature or lower than the first temperature, A program that causes a circuit board processing unit to execute commands via a computer.

20. A processing container for processing substrates, A first processing gas supply system supplies a first processing gas into the processing container via a first pipe connected to the processing container, A second processing gas supply system, whose inner surface is made of a metal-containing material and which supplies a second processing gas containing oxygen into the processing container via a second pipe different from the first pipe connected to the processing container, A heater for heating the aforementioned second pipe, (a) A process of performing a first process on the substrate by supplying the first processing gas into the processing container via the first piping while the second piping is heated to a first temperature or higher, (b) A process of performing a second process on the substrate by supplying the second processing gas into the processing container via the second piping while the temperature of the second piping is lowered to a second temperature or lower than the first temperature, A control unit is configured to control the first processing gas supply system, the second processing gas supply system, and the heater to perform the following: A substrate processing apparatus.

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