Substrate processing method, semiconductor device manufacturing method, recording medium, and substrate processing apparatus

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a recording medium, and a substrate processing apparatus. Provided is a technique whereby, when a gas containing oxygen is supplied through a pipe having an inner surface made of a metal-containing material, an increase in the temperature of the pipe due to a reaction between the inner surface and the gas can be suppressed. The method includes: (a) a step of performing a first process on a substrate accommodated in a processing container by supplying a first process gas into the processing container through a first pipe different from a second pipe while heating the second pipe to a first temperature or higher, the second pipe being connected to the processing container and having an inner surface made of a metal-containing material; and (b) a step of performing a second process on the substrate by supplying a second process gas containing oxygen into the process container through the second pipe in a state where the temperature of the second pipe is reduced to a second temperature or less that is lower than the first temperature.

Description

Technical Field

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

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

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2012 / 090738 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention provides a technology capable of suppressing a rise in the temperature of a pipe caused by a reaction between the inner surface and the gas when a gas containing oxygen is supplied through the pipe whose inner surface is made of a metal-containing material.

[0008] Means for solving problems

[0009] According to one embodiment of the present invention, a technology is provided, which has:

[0010] (a) supplying a first processing gas into the processing container via a first pipe different from the second pipe while heating a second pipe having an inner surface made of a metal-containing material and connected to the processing container to a first temperature or higher, thereby performing a first processing on a substrate accommodated in the processing container; and

[0011] (b) supplying a second processing gas containing oxygen into the processing container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature, thereby performing a second processing on the substrate.

[0012] Effects of the Invention

[0013] According to the present invention, when a gas containing oxygen is supplied through a pipe whose inner surface is made of a metal-containing material, a rise in the temperature of the pipe caused by a reaction between the inner surface and the gas can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] [ Figure 1 ] Figure 1 This is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and shows a processing furnace 202 portion in a vertical cross-sectional view.

[0015] [ Figure 2 ] Figure 2 FIG. 1 is a schematic diagram of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present invention. Figure 1 A cross-sectional view of a portion of the processing furnace 202 is shown along the line AA.

[0016] [ Figure 3 ] Figure 3 This is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0017] [ Figure 4 ] Figure 4 This is a diagram showing a processing sequence in one embodiment of the present invention.

[0018] [ Figure 5 ] Figure 5 This is a flowchart showing the flow of a substrate processing step in one embodiment of the present invention.

[0019] Description of Reference Numerals

[0020] 200 wafers (substrate)

[0021] 232a, 232b, 232d first piping

[0022] 232c 2nd piping DETAILED DESCRIPTION

[0023] <One embodiment of the present invention>

[0024] The following are the main references Figure 1 to Figure 5 One embodiment of the present invention is described. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings are not necessarily consistent with the actual ones. In addition, the dimensional relationship of each element, the ratio of each element, etc. are not necessarily consistent between multiple drawings.

[0025] (1) Configuration of substrate processing apparatus

[0026] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature adjustment unit (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported by a holding plate. The heater 207 functions as an activation mechanism (excitation unit) that activates (excites) the gas by heat.

[0027] A reaction tube 203 is disposed inside the heater 207 in a concentric circle with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO 2) or silicon carbide (SiC) and other heat-resistant materials, and are formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is composed of a metal-containing material such as stainless steel (SUS) and is formed into a cylindrical shape with an upper and lower end open. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a as a sealing component is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured in a manner that can accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201.

[0028] In the processing chamber 201, nozzles 249a to 249c as the first to third supply parts are respectively provided in a manner penetrating the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as the 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 respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and the nozzles 249b and 249c are respectively provided adjacent to the nozzle 249a.

[0029] Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The gas supply pipes 232a to 232c are respectively configured as common pipes for supplying a plurality of gases. Mass flow controllers (MFCs) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as opening and closing valves are respectively provided on the gas supply pipes 232a to 232c, in order from the upstream side of the gas flow. Gas supply pipes 232d and 232e are respectively connected to the downstream side of the gas supply pipe 232a compared to the valve 243a. MFCs 241d and 241e and valves 243d and 243e are respectively provided on the gas supply pipes 232d and 232e, in order from the upstream side of the gas flow. A gas supply pipe 232f is connected to the downstream side of the gas supply pipe 232b compared to the valve 243b. On the gas supply pipe 232f, MFC241f and valve 243f are provided in sequence from the upstream side of the gas flow. On the downstream side of the gas supply pipe 232c compared with the valve 243c, a gas supply pipe 232g is connected. On the gas supply pipe 232g, MFC241g and valve 243g are provided in sequence from the upstream side of the gas flow. The 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, the gas supply pipes 232a, 232b, and 232d are sometimes referred to as the first pipe individually or collectively, and the gas supply pipe 232c is referred to as the second pipe.

[0030] On the upstream side of MFC241a, 241b, 241d of the gas supply pipes 232a, 232b, 232d as the first pipe, pipe temperature sensors 234a, 234b, 234d as temperature detectors are installed respectively. On the upstream side of MFC241c of the gas supply pipe 232c as the second pipe, a pipe temperature sensor 234c is installed. The pipe temperature sensor is composed of a known temperature sensor such as a thermocouple. In addition, in this embodiment, pipe heaters 233a, 233b, 233d as heating units are installed on the outer periphery of the gas supply pipes 232a, 232b, 232d as the first pipe. A pipe heater 233b is installed on the outer periphery of 232c as the second pipe.

[0031] like Figure 2As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, nozzles 249a to 249c are respectively provided in a manner of standing upright from the lower part of the inner wall of the reaction tube 203 along the upper part and toward the upper side of the arrangement direction of the wafer 200. That is, the nozzles 249a to 249c are respectively provided in a manner of horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged, along the wafer arrangement area. In a plan view, the nozzle 249a is arranged in a manner of facing the exhaust port 231a described later on a straight line with the center of the wafer 200 carried into the processing chamber 201 sandwiched therebetween. The nozzles 249b and 249c are arranged in a manner of sandwiching a straight line L passing through the center of the nozzle 249a and 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 center of the nozzle 249a and the wafer 200. That is, the nozzle 249c can also be arranged on the side opposite to the nozzle 249b with the straight line L sandwiched therebetween. The nozzles 249b and 249c are arranged line-symmetrically 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. The gas supply holes 250a to 250c are respectively opened in a manner opposite to (facing) the exhaust port 231a when viewed from above, and can supply gas to the wafer 200. A plurality of gas supply holes 250a to 250c are provided in the range from the bottom to the top of the reaction tube 203.

[0032] A source gas as a first process gas is supplied into the process chamber 201 from the gas supply pipe 232 a via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0033] The second reaction gas as the first process gas is supplied into the process chamber 201 from the gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the nozzle 249 b .

[0034] A second process gas containing oxygen (O) is supplied into the process chamber 201 from the gas supply pipe 232 c via the MFC 241 c , the valve 243 c , and the nozzle 249 c .

[0035] A first reaction gas as a first process gas is supplied into the process chamber 201 from the gas supply pipe 232 d via the MFC 241 d , the valve 243 d , and the nozzle 249 a .

[0036] Inert gas is supplied from gas supply pipes 232e to 232g into the processing chamber 201 via MFCs 241e to 24g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0037] The raw gas supply system is mainly composed of a gas supply pipe 232a, MFC241a, and valve 243a. The second reaction gas supply system is mainly composed of a gas supply pipe 232b, MFC241b, and valve 243b. The second processing gas supply system is mainly composed of a gas supply pipe 232c, MFC241c, and valve 243c. The first reaction gas supply system is mainly composed of a gas supply pipe 232d, MFC241d, and valve 243d. The inactive gas supply system is mainly composed of gas supply pipes 232e to 232g, MFC241e to 241g, and valves 243e to 243g. In this embodiment, the raw gas supply system, the first reaction gas supply system, and the second reaction gas supply system are collectively referred to as the first processing gas supply system. The nozzles connected to the gas supply pipes constituting the above-mentioned various supply systems can also be included in the supply system respectively.

[0038] Any or all of the above-mentioned various supply systems can be configured as an integrated supply system 248 in which valves 243a to 243g, MFCs 241a to 241g, etc. are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a to 232g, respectively, and is configured so that the controller 121 described later controls the operation of supplying various substances (various gases) into the gas supply pipes 232a to 232g, that is, the opening and closing operation of the valves 243a to 243g, the flow rate adjustment operation performed by the MFCs 241a to 241g, etc. The integrated supply system 248 is configured in the form of an integrated unit of an integral type or a split type, and is configured so that the gas supply pipes 232a to 232g, etc. can be installed and removed as an integrated unit, and the integrated supply system 248 can be maintained, replaced, and added as an integrated unit.

[0039] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2As shown, the exhaust port 231a is arranged at a position opposite (facing) to the nozzles 249a to 249c (gas supply holes 250a to 250c) while sandwiching the chip 200 when viewed from above. The exhaust port 231a can also be arranged from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the chip 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 regulating unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust and vacuum exhaust stop in the processing chamber 201. In addition, the valve opening is adjusted based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, thereby enabling the pressure in the processing chamber 201 to be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable that the vacuum pump 246 is included in the exhaust system.

[0040] Below the manifold 209, a sealing cover 219 as a furnace port cover body capable of hermetically closing the lower end opening of the manifold 209 is provided. The sealing cover 219 is made of a metal-containing material such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b as a sealing member abutting against the lower end of the manifold 209 is provided. Below the sealing cover 219, a rotating mechanism 267 for rotating the wafer boat 217 described later is provided. The rotating shaft 255 of the rotating mechanism 267 is made of a metal-containing material such as SUS, penetrates the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured in such a way that the wafer 200 is rotated by rotating the wafer boat 217. The sealing cover 219 is configured in such a way that it is lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219 .

[0041] Below the manifold 209, a gate 219s is provided as a furnace cover, and the gate 219s can hermetically close the lower end opening of the reaction tube 203 in a state where the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The gate 219s is made of a metal-containing material such as SUS and is formed in a disc shape. On the upper surface of the gate 219s, an O-ring 220c is provided as a sealing member that abuts against the lower end of the manifold 209. The opening and closing action (lifting action, rotation action, etc.) of the gate 219s is controlled by the gate opening and closing mechanism 115s.

[0042] The wafer boat 217 as a substrate support is configured to support multiple wafers 200 (e.g., 25 to 200) in a horizontal posture and with their centers aligned with each other in a vertical direction in multiple layers, that is, arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the wafer boat 217, a heat insulation plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple layers.

[0043] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is set to a desired temperature distribution by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0044] like Figure 3 As shown, the controller 121 as a control unit (control means) is configured in the form of a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 such as a touch panel. In addition, the controller 121 can be connected to an external storage device 123.

[0045] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. A control program for controlling the operation of the substrate processing device, a process process recording the steps and conditions of the substrate processing described later, etc. are recorded and stored in a readable manner in the storage device 121c. The process process is a combination of a controller 121 that enables the substrate processing device to perform each step in the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, the process process, the control program, etc. are also simply referred to as a program. In addition, the process process is also referred to as a process. In this specification, the use of the term program includes a case where only the process is included, a case where only the control program is included, or a case where both are included. RAM121b is configured as a storage area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0046] The I / O port 121d is connected to the above-mentioned MFC241a~241g, valves 243a~243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, piping temperature sensor 234a~234d, heater 207, piping heater 233a~233d, rotating mechanism 267, wafer boat elevator 115, gate opening and closing mechanism 115s, etc.

[0047] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a process from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control the following actions according to the contents of the read process: flow rate adjustment actions of various substances (various gases) by the MFCs 241a to 241g, opening and closing actions of the valves 243a to 243g, opening and closing actions of the APC valve 244 and pressure adjustment actions by the APC valve 244 based on the pressure sensor 245, starting and stopping of the vacuum pump 246, temperature adjustment actions of the heater 207 based on the temperature sensor 263, rotation of the wafer boat 217 and rotation speed adjustment actions by the rotating mechanism 267, lifting and lowering actions of the wafer boat 217 by the wafer boat elevator 115, opening and closing actions of the gate 219s by the gate opening and closing mechanism 115s, etc.

[0048] The controller 121 can be constructed by installing the above-mentioned program recorded and stored in the external storage device 123 in the computer. The external storage device 123 includes, for example, magnetic disks such as HDD, optical disks such as CD, optical magnetic disks such as MO, USB memory, semiconductor memory such as SSD, etc. The storage device 121c and the external storage device 123 are constructed in the form of a computer-readable recording medium. Hereinafter, they are also simply referred to as recording media. In this specification, the use of the term recording medium includes the case where only the storage device 121c is included alone, the case where only the external storage device 123 is included alone, or the case where both are included. It should be noted that providing the program to the computer can also be carried out without using the external storage device 123 and using communication means such as the Internet and dedicated lines.

[0049] (2) Substrate processing step

[0050] A method for processing a substrate using the above-mentioned substrate processing apparatus as one of the steps in the manufacturing process of a semiconductor device, that is, an example of a series of processing sequences including a film forming sequence for forming a film on a wafer 200 as a substrate, mainly using Figure 4 , Figure 5 In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121 .

[0051] The processing sequence in this method includes:

[0052] (a) in a state where a second pipe (gas supply pipe 232c) connected to the processing container and having an inner surface made of a metal-containing material is heated to a first temperature or higher, a first processing gas is supplied into the processing container via a first pipe (gas supply pipes 232a, 232b, 232d) different from the second pipe, thereby performing a first process on a wafer 200 accommodated in the processing container; and

[0053] (b) Step B of performing a second process on the wafer 200 by supplying a second process gas containing oxygen into the process container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature.

[0054] It should be noted that the processing sequence in this method shows that in step A, the following steps are performed:

[0055] Step a1 of supplying a raw material 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, and step a3 of supplying a second reaction gas as a first process gas to the wafer 200

[0056] An example of forming a film on the wafer 200 by executing a cycle a predetermined number of times (n times, where n is an integer greater than or equal to 1 or 2).

[0057] In this specification, each of the source gas, the first reaction gas, and the second reaction gas, or all of them may be collectively referred to as a first process gas.

[0058] It should be noted that, in the processing sequence of this embodiment, an example is shown in which the film formed on the wafer 200 is maintained (treated) by supplying the second processing gas containing oxygen (O) to the wafer 200 in step B.

[0059] In addition, the processing sequence in this embodiment shows an example in which step C is further included between step A and step B to reduce the temperature of the second pipe from a temperature higher than the first temperature to a second temperature lower than the first temperature.

[0060] In addition, in the following, an example in which a silicon oxynitride film (SiON film) is formed as a film on the wafer 200 will be described.

[0061] In this specification, for convenience, the above-mentioned processing sequence may be shown as follows. The same notation is also used in the following description of modified examples, other aspects, etc.

[0062] (raw material gas → first reaction gas → second reaction gas) × n → second pipe temperature decreases → second process gas containing O

[0063] The term "wafer" used in this specification includes the case where it refers to the wafer itself, and the case where it refers to a stack of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification includes the case where it refers to the surface of the wafer itself, and the case where it refers to the surface of a predetermined layer, etc. formed on the wafer. In this specification, the case where "a predetermined layer is formed on the wafer" includes the case where a predetermined layer is directly formed on the surface of the wafer itself, and the case where a predetermined layer is formed on a layer, etc. formed on the wafer. In this specification, the case where the term "substrate" is used has the same meaning as the case where the term "wafer" is used.

[0064] The term "layer" used in this specification 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.

[0065] In this specification, the description of the first processing gas and the second processing gas containing O being adsorbed on the surface of the chip 200 and reacting respectively includes not only a method in which the above-mentioned gases are directly adsorbed on the surface of the chip in an undecomposed state and react, but sometimes also includes a method in which the above-mentioned gases are decomposed, their ligands are separated, and the intermediates generated are adsorbed on the surface of the chip 200 and react.

[0066] (Wafer filling and wafer boat loading)

[0067] When a plurality of wafers 200 are loaded (wafer filling) into the wafer boat 217, the gate opening and closing mechanism 115s is used to move the gate 219s to open the lower end opening of the manifold 209 (gate opening). Figure 1 As shown, the wafer boat 217 supporting a plurality of wafers 200 is lifted by the wafer boat elevator 115 and loaded into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared (provided) in the processing chamber 201.

[0068] (Pressure regulation and temperature regulation)

[0069] After the loading of the wafer boat is completed, the vacuum pump 246 is used to perform vacuum exhaust (decompression exhaust) in such a manner that the space in the processing chamber 201, that is, the space where the wafer 200 exists, becomes the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, the heater 207 is used to heat the wafer 200 in the processing chamber 201 so that it becomes the desired processing temperature. At this time, the power-on state of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes the desired temperature distribution. In addition, the rotation of the wafer 200 by the rotation mechanism 267 is started. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0070] (Temperature setting of the second pipe)

[0071] Then, the pipe heater 233c is used to heat the second pipe (gas supply pipe 232c) in such a manner that the temperature in the second pipe becomes the first temperature or a temperature higher than the first temperature. At this time, the power supply status of the pipe heater 233c is feedback-controlled based on the temperature information detected by the pipe temperature sensor 234c so that the temperature distribution in the second pipe becomes the desired temperature distribution. At this time, it is preferred to heat the first pipe (gas supply pipes 232a, 232b, 232d) by using the pipe heaters 233a, 233b, and 233d respectively in such a manner that the temperature in the first pipe (gas supply pipes 232a, 232b, and 232d) also becomes the first temperature or a temperature higher than the first temperature. In addition, the time point of the process of heating in such a manner that the temperature in the second pipe becomes the first temperature is not limited to after the pressure regulation and the temperature regulation, and can also be set to start at the same time as the wafer filling and the wafer boat loading, the pressure regulation, and the temperature regulation, or at a time point earlier than them.

[0072] (First process: step A)

[0073] Then, execute the following steps a1, a2, and a3 in sequence.

[0074] [Step a1]

[0075] In this step, a source gas is supplied to the wafer 200 in the processing chamber 201 .

[0076] Specifically, valve 243a is opened to allow raw material gas to flow into gas supply pipe 232a (first pipe). The raw material gas is flow-regulated by MFC 241a, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, raw material gas is supplied to wafer 200 (raw material gas supply). At this time, valves 243e to 243g may be opened to allow inactive gas to be supplied into processing chamber 201 via each of nozzles 249a to 249c. The inactive gas supplied via nozzles 249b and 249c also acts as an intrusion suppression gas to suppress the intrusion (backflow) of raw material gas etc. in the processing chamber into nozzles 249a and 249b.

[0077] As the processing conditions when supplying the raw material gas in this step, the following can be exemplified:

[0078] Treatment temperature: 350-900°C, preferably 500-900°C, more preferably 600-800°C Treatment pressure: 1-10000 Pa, preferably 10-1333 Pa

[0079] First piping temperature: above the first temperature, for example, 160 to 250°C, preferably 180 to 250°C

[0080] Second piping temperature: higher than the first temperature, for example, 160 to 250°C, preferably 180 to 250°C

[0081] Raw material gas supply flow rate: 0.01 to 3 slm, preferably 0.1 to 1 slm

[0082] Raw material gas supply time: 10 to 120 seconds, preferably 20 to 60 seconds

[0083] Inert gas supply flow rate (per gas supply pipe): 0~10slm

[0084] It should be noted that the expression of a numerical range such as "350-900°C" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, the so-called "350-900°C" means "above 350°C and below 900°C". The same applies to other numerical ranges. In addition, the so-called processing temperature in this specification means the temperature of the chip 200 or the temperature in the processing chamber 201, and the processing pressure means the pressure in the processing chamber 201, in other words, the pressure of the space where the chip 200 exists. In addition, the so-called processing time means the time for which the processing continues. In addition, the so-called piping temperature means the temperature in the piping. In addition, the supply flow rate includes the case of 0slm, and the so-called 0slm means the case where the substance (gas) is not supplied. These are also the same in the following descriptions.

[0085] By supplying, for example, chlorosilane-based gas as a raw material gas to the wafer 200 under the above conditions, a silicon (Si)-containing layer containing chlorine (Cl) is formed on the outermost surface of the wafer 200 serving as a substrate. The Si-containing layer containing Cl is formed by physical adsorption or chemical adsorption of molecules of the chlorosilane-based gas to the outermost surface of the wafer 200, physical adsorption or chemical adsorption of molecules of a substance formed by decomposition of a part of the chlorosilane-based gas to the outermost surface of the wafer 200, deposition of Si caused by thermal decomposition of the chlorosilane-based gas, and the like. The Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer, chemical adsorption layer) of molecules of the chlorosilane-based gas or molecules of a substance formed by decomposition of 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 referred to as the Si-containing layer for short.

[0086] 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 a halogen, that is, a halogenated silane-based gas can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halogenated silane-based gas, for example, the above-mentioned chlorosilane-based gas containing Si and Cl can be used.

[0087] As the raw material gas, for example, monochlorosilane (SiH 3 Cl) gas, dichlorosilane (SiH 2 Cl 2 ) gas, trichlorosilane (SiHCl 3 ) gas, tetrachlorosilane (SiCl 4 ) gas, hexachlorodisilane gas (Si 2 Cl 6 ) gas, octachlorotrisilane (Si 3 Cl 8 As the raw material gas, one or more of these can be used.

[0088] As the raw material gas, in addition to chlorosilane-based gases, for example, tetrafluorosilane (SiF 4 ) gas, difluorosilane (SiH 2 F 2 ) gas, such as fluorosilane gas, tetrabromosilane (SiBr 4 ) gas, dibromosilane (SiH 2 Br 2 ) gas, such as bromosilane gas, tetraiodosilane (SiI 4 ) gas, diiodosilane (SiH 2 I 2 As the raw material gas, one or more of these can be used.

[0089] As the raw material gas, in addition to the above, for example, a gas containing Si and an amino group, i.e., an aminosilane-based gas, can also be used. The amino group is a monovalent functional group obtained by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine. 2 , -NHR, -NR 2 It should be noted that R represents an alkyl group, -NR 2 The two R's in may be the same or different.

[0090] As the raw material gas, for example, tetrakis(dimethylamino)silane (Si[N(CH 3 ) 2 ] 4 ) gas, tris(dimethylamino)silane (Si[N(CH 3 ) 2 ] 3 H) gas, bis(diethylamino)silane (Si[N(C 2 H 5 ) 2 ] 2 H 2 ) gas, bis(tert-butylamino)silane (SiH 2 [NH(C 4 H 9 )] 2 ) gas, (diisopropylamino)silane (SiH 3 [N(C 3 H 7 ) 2 As the raw material gas, one or more of them can be used.

[0091] As the inert gas, nitrogen (N 2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas and other rare gases. As the inert gas, one or more of them can be used. This is also the same in each step described later.

[0092] After the Si-containing layer is formed, the valve 243a is closed to stop supplying the raw material gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to exhaust (purge) the residual gas 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 functions as a purge gas.

[0093] [Step a2]

[0094] After step a1 is completed, the first reaction gas is supplied to the wafer 200 in the processing chamber 201 , that is, the Si-containing layer formed on the wafer 200 .

[0095] Specifically, the valve 243d is opened, and the first reaction gas flows into the gas supply pipe 232d (first pipe). The first reaction gas is flow-regulated by the MFC 241d, supplied to the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the first reaction gas is supplied to the wafer 200 (first reaction gas supply). At this time, the valves 243e to 243g may be opened, and the inert gas may be supplied to the processing chamber 201 through each of the nozzles 249a to 249c.

[0096] As the processing conditions when the first reaction gas is supplied in this step, the following can be exemplified:

[0097] First reaction gas supply flow rate: 0.01 to 4 slm, preferably 0.3 to 1 slm

[0098] First reaction gas supply time: 1 to 60 seconds, preferably 5 to 20 seconds.

[0099] The other processing conditions can be the same as those in step a1.

[0100] By supplying, for example, an O-containing gas as the first reaction gas to the wafer 200 under the above conditions, 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) is formed as a layer containing Si and O on the outermost surface of the wafer 200 serving as a base. In this embodiment, as the first reaction gas, for example, an O-containing gas may be used. Hereinafter, the first reaction gas may be referred to as the first O-containing gas.

[0101] 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 processing gas used in step B described later with the metal-containing material constituting the inner surface of the gas supply pipe 232c (second pipe). The so-called reactivity here mainly includes the ease of occurrence of oxidation reaction (oxidizing power). Therefore, even if the inner surface of the gas supply pipe 232d is composed of a metal-containing material, the temperature rise of the gas supply pipe 232d caused by the reaction of the first O-containing gas with the metal-containing material in this step can be suppressed.

[0102] As the first reaction gas, for example, oxygen (O 2 ) gas, nitrous oxide (N 2 O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO 2 ) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, etc. As the first reaction gas, one or more of these can be used.

[0103] Alternatively, water vapor (H 2 O), H 2 Gas+O 2 Gas, H 2 O gas + O 2 Gas, H 2 O gas + N 2 O gas, H 2 O gas + NO gas or other gas containing O and H. In this case, deuterium ( 2 H 2 ) gas to replace H 2 As the first reaction gas, one or more of these can be used.

[0104] It should be noted that the first reaction gas is not limited to the gases exemplified, and can also be appropriately selected from O-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 process gas. In addition, as the first reaction gas whose reactivity is lower than that of 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 that of the second process gas (for example, the second process gas diluted with a diluent gas, etc.) can also be selected.

[0105] In addition, in this manual, “H 2 Gas+O 2 Gas" means H 2 Gas and O 2Mixed gas of gases. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe and then supplied to the processing chamber 201, or the two gases may be supplied to the processing chamber 201 through different supply pipes and mixed (postmixed) in the processing chamber 201. When the two gases are supplied to the processing chamber 201 through different supply pipes, it is preferred that the O-containing gas is supplied to 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 to the processing chamber 201 through other gas supply pipes.

[0106] After the SiO film is formed, the valve 243d is closed to stop supplying the first reaction gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to exhaust gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. Then, the gas and the like remaining in the processing chamber 201 are exhausted (purged) from the processing chamber 201 by the same processing steps as those in step a1.

[0107] [Step a3]

[0108] After step a2 is completed, the second reaction gas is supplied to the wafer 200 in the processing chamber 201 , that is, the SiO layer formed on the wafer 200 .

[0109] Specifically, the valve 243b is opened, and the second reaction gas flows into the gas supply pipe 232b (first pipe). The second reaction gas is flow-regulated by the MFC 241b, supplied to the processing chamber 201 through the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the second reaction gas is supplied to the wafer 200 (second reaction gas supply). At this time, the valves 243e to 243g may be opened, and the inert gas may be supplied to the processing chamber 201 through each of the nozzles 249a to 249c.

[0110] As the processing conditions when the second reaction gas is supplied in this step, the following can be exemplified:

[0111] Second reaction gas supply flow rate: 0.1 to 20 slm, preferably 1 to 10 slm

[0112] Second reaction gas supply time: 1 to 120 seconds, preferably 3 to 15 seconds.

[0113] The other processing conditions can be the same as those in step a1.

[0114] By supplying a gas containing nitrogen (N) and H, for example, as the second reaction gas to the wafer 200 under the above conditions, 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 outermost surface of the wafer 200 serving as a base.

[0115] As the second reaction gas, for example, a nitriding gas can be used. As the nitriding gas, for example, the above-mentioned gas containing N and H can be used. The gas containing N and H is both a gas containing N and a gas containing H.

[0116] As the second reaction gas, for example, ammonia (NH 3 ) gas, diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) Gas, N 3 H 8 As the second reaction gas, one or more of these can be used.

[0117] After the SiON film is formed, the valve 243b is closed to stop supplying the second reaction gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to exhaust gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. Then, the gas and the like remaining in the processing chamber 201 are exhausted (purged) from the processing chamber 201 by the same processing steps as the purging in step a1.

[0118] [Number of times the regulations are implemented]

[0119] By performing the above steps a1 to a3 in a non-simultaneous, i.e., asynchronous, sequential cycle n times (n is an integer greater than 1 or 2), it is possible to form, for example, a SiON film of a predetermined thickness on the substrate with the surface of the wafer 200 as a substrate as a film of a predetermined thickness. The above cycle is preferably repeated a plurality of times. That is, it is preferred that the thickness of the SiON layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated a plurality of times until the film thickness of the SiON film formed by stacking SiON layers reaches the desired film thickness.

[0120] As described above, in step A, an inert gas is supplied from the nozzle 249c to the processing chamber 201 as an intrusion suppression gas. However, the supply of the intrusion suppression gas alone may not be able to prevent the byproducts generated in the processing chamber 201 from intruding into the nozzle 249c and the gas supply pipe 232c. In addition, in step A, if the temperature of the second pipe is lower than the first temperature, for example, lower than 160°C, when the byproducts generated in the processing chamber 201 intrude (backflow) into the second pipe from the processing chamber 201, it is difficult to suppress the intruded byproducts from adhering (depositing) in the second pipe. In view of such a problem, by making the temperature of the second pipe higher than the first temperature, it is possible to suppress the byproducts intruding from the processing chamber 201 from adhering to the second pipe. By making the temperature of the second pipe 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 suppress the byproducts intruding from the processing chamber 201 from adhering (depositing) in the second pipe. The temperature above the first temperature can be said to be a temperature that can suppress the attachment of byproducts to the second pipe. However, if the temperature of the second pipe is excessively high, for example, above 250°C, pipe-attached parts made of resin or the like, such as sealing parts, may burn out. Therefore, it is preferred that the temperature of the second pipe be set to, for example, below 250°C. It should be noted that, in addition to the byproducts intruding from the processing chamber 201, the byproducts attached to the second pipe may also include byproducts generated by the first processing gas intruding into the second pipe being thermally decomposed in the second pipe.

[0121] (Second Pipe Temperature Lowering Process: Step C)

[0122] After step A is completed and before step B described later is started, the set temperature of the second pipe, that is, the control temperature of the pipe heater 233c is changed from the first temperature to the third temperature. At this time, the power supply status of 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 becomes the desired temperature distribution. The third temperature is a temperature lower than the second temperature which is lower than the first temperature. Waiting is performed until the second pipe temperature drops to the second temperature.

[0123] (Second Process: Step B)

[0124] After the second pipe temperature is lowered from the first temperature to the second temperature, step B is started at this point in time. In this step, the second process gas containing O is supplied to the wafer 200 in the process chamber 201, that is, 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.

[0125] Specifically, the valve 243c is opened, and the second process gas flows into the gas supply pipe 232c (second pipe). The second process gas is flow-regulated by the MFC 241c, supplied to 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, and the inactive gas may be supplied to the process chamber 201 through each of the nozzles 249a to 249c.

[0126] Here, by supplying the second process gas containing O 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 constituting the inner surface and the second process gas. The heat generated by the oxidation reaction may increase the temperature of the second pipe, and may burn the pipe-attached parts such as the sealing part made of resin or the like, and generate pollutants due to the burning.

[0127] More specifically, there is a case where, for example, nickel (Ni) contained in SUS or the like acts as a catalyst on the second process gas containing O, decomposing the second process gas to generate O atoms (atomic oxygen). The O atoms generated in this way are highly reactive, and thus are prone to an oxidation reaction with the metal-containing material and the accompanying heat generation. If the temperature of the second pipe is increased due to the heat generation, the above-mentioned catalytic reaction and the generation of O atoms are further accelerated, and it becomes difficult to suppress the temperature increase of the second pipe.

[0128] In this step, as described later, by supplying the second process gas with the second pipe temperature being set to the second temperature or lower, a state where substantially no oxidation reaction occurs is maintained, thereby suppressing a temperature rise in the second pipe.

[0129] As the processing conditions when the second processing gas is supplied in this step, the following can be exemplified:

[0130] Second pipe temperature: below the second temperature, for example, 0 to 155°C, preferably room temperature (25) to 150°C, more preferably 100 to 120°C

[0131] Second process gas supply concentration: 100-300 g / m 3 , preferably 200-300g / m 3

[0132] Second process gas supply time: 30 to 180 minutes, preferably 45 to 120 minutes.

[0133] The other processing conditions can be the same as those in step a1.

[0134] By supplying the second process gas to the wafer 200 under the above conditions, the SiON film formed on the wafer 200 can be maintained (for example, removal of impurities contained in the SiON film, repair of defects, densification and hardening of the SiON film).

[0135] It should be noted that if the temperature of the first pipe is lower than the first temperature, for example, lower than 160°C, it may become difficult to suppress the byproducts of the first process gas supplied in step A and remaining in the first pipe from being attached (deposited) in the first pipe. By setting the temperature of the first pipe to be higher than the first temperature in step B, the byproducts of the first process gas remaining in the first pipe can be suppressed from being attached to the first pipe. In addition, by setting the temperature of the first pipe to be a temperature higher than the first temperature (for example, a temperature higher than the first temperature by 20°C or more), the byproducts of the first process gas remaining in the first pipe can be more effectively suppressed from being attached to the first pipe. The temperature above the first temperature can be said to be a temperature that can suppress the byproducts of the first process gas from being attached to the first pipe. However, if the temperature of the first pipe is too high, for example, higher than 250°C, the pipe attachment parts such as the sealing parts made of resin or the like may be burned. Therefore, it is preferred to set the temperature of the first pipe to be, for example, lower than 250°C.

[0136] In addition, if the temperature of the first pipe is lower than the first temperature, for example, lower than 160° C., when the byproducts of the second process gas generated in the processing chamber 201 in step B intrude (backflow) into the first pipe from the processing chamber 201, it may be difficult to suppress the byproducts from adhering to the first pipe. By setting the temperature of the first pipe to be higher than the first temperature in step B, it is possible to suppress the byproducts of the second process gas that intrude into the first pipe from adhering to the first pipe. In addition, by setting the temperature of the first pipe to be 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 suppress the byproducts of the second process gas that intrude into the first pipe from adhering to the first pipe. The temperature higher than the first temperature can be said to be a temperature that can suppress the byproducts of the second process gas from adhering to the first pipe.

[0137] It should be noted that if the temperature of the second pipe exceeds the second temperature, for example, exceeds 155°C. It sometimes becomes difficult to avoid the 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 increase in the temperature of the second pipe, so it becomes difficult to suppress the occurrence of burning of the pipe accessories such as the sealing component composed of resin, etc., and the generation of pollutants. By making the temperature of the second pipe below the second temperature, it is possible to suppress the oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. By making the temperature of the second pipe below the second temperature, for example, below 150°C, it is possible to effectively suppress the oxidation reaction between the metal-containing material constituting the inner surface of the second pipe and the second processing gas. By making the temperature of the second pipe below the second temperature, for example, below 120°C. It is possible to further effectively suppress the 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 process gas, and the first temperature can be said to be a temperature at which a substantial reaction occurs between the metal-containing material and the second process gas.

[0138] However, if the temperature of the second pipe is too low, for example, below 0°C, even when only a small amount of byproducts generated by the second process gas supplied to the processing chamber 201 intrudes (backflows) into the second pipe, it sometimes becomes difficult to suppress the byproducts from adhering to the second pipe. By setting the temperature of the second pipe to, for example, above 0°C, the amount of byproducts adhering to the second pipe can be reduced when the byproducts generated in the processing chamber 201 intrude into the second pipe. In addition, by setting the temperature of the second pipe to above 25°C, the amount of byproducts adhering to the second pipe when the byproducts generated in the processing chamber 201 intrude into the second pipe can be more significantly reduced. In addition. By setting the temperature of the second pipe to above 100°C, the amount of byproducts adhering to the second pipe when the byproducts generated in the processing chamber 201 intrude into the second pipe can be more reliably reduced.

[0139] It should be noted that the second process gas supply time can be set to be longer than the supply time of each cycle of the first O-containing gas illustrated in step a2. In addition, the second process gas supply time can be set to be longer than the supply time of each cycle of the first process gas in step A (the total supply time of the raw material gas, the first reaction gas, and the second reaction gas).

[0140] As the second processing gas, for example, an O-containing gas obtained by plasma-exciting an O-containing gas using a plasma excitation unit (not shown) can be used. The plasma-excited O-containing gas may contain, for example, atomic oxygen (O), hydroxyl radicals (OH radicals), etc. As the plasma-excited O-containing gas, the first O-containing gas exemplified in step a2 can be used.

[0141] In addition, as the second processing gas, a gas containing hydrogen peroxide (H 2 O 2 ) gas, and ozone (O 3 ) gases.

[0142] The second processing gas is not limited to the exemplified gases, and can be appropriately selected from oxygen-containing gases that generate a substantial heat-generating reaction with the metal-containing material constituting the inner surface of the gas supply pipe 232c (second pipe).

[0143] In addition, as the second process gas, an O-containing gas having a higher activity than the first O-containing gas can be used. More specifically, the second reaction gas can 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. As the second process gas, one or more of these can be used.

[0144] It should be noted that, during the execution time of this step, when the second pipe temperature reaches a fourth temperature (upper limit temperature / critical temperature) higher than the second temperature, the supply of the second processing gas, etc. is stopped, and the execution of this step is stopped. After the second pipe temperature drops to the second temperature, the execution of this step is restarted.

[0145] When the execution time of this step reaches the specified time, the execution of this step ends.

[0146] (Post-purge and atmospheric pressure recovery)

[0147] After step B is completed, an inert gas is supplied from each of the nozzles 249a to 249c as a purge gas into the processing chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the residual gas, reaction by-products, etc. in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Then, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0148] (Wafer boat unloading and wafer removal)

[0149] Then, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After the wafer boat is unloaded, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s with the aid of the O-ring 220c (gate closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer boat 217 (wafer taking out).

[0150] (3) Effects of this method

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

[0152] (a) In step B, when the second process 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 the temperature rise of the second pipe. Specifically, in step B, when the second process gas is supplied through the second pipe, the temperature of the second pipe is lowered to a second temperature at which no oxidation reaction occurs between the metal-containing material constituting the inner surface of the second pipe and the second process gas, thereby suppressing the temperature rise of the second pipe. By suppressing the temperature rise of the second pipe, it is possible to prevent the burning of pipe-attached parts such as a sealing part made of resin, etc., and also to prevent the generation of pollutants caused by the oxidation reaction between the metal-containing material and the second process gas.

[0153] In step B, by continuously maintaining the second pipe temperature at or below the second temperature while the second process is being performed, it is possible to reliably prevent the occurrence of burning of the sealing member and the like and the generation of contaminants.

[0154] In addition, in step A, by heating the second pipe to a temperature higher than the first temperature when the first process gas is supplied through the first pipe, even if the byproducts generated by the first process gas being supplied into the process chamber 201 intrude into the second pipe from the process chamber 201, the byproducts can be prevented from being attached to the second pipe. Specifically, in step A, by setting the temperature of the second pipe to a temperature higher than the first temperature at which the byproducts of the first process gas do not attach to the second pipe when the first process gas is supplied, the byproducts can be prevented from being attached to the second pipe.

[0155] 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, it is possible to reliably suppress the byproducts of the first process gas from being attached to the second pipe.

[0156] (b) It should be noted that when using a gas that is highly reactive (highly active) with the metal-containing material constituting the inner surface of the pipe, the rise in the pipe temperature becomes a more significant issue. In this method, in step B, since an O-containing gas having a higher activity than the first O-containing gas is used as the second processing gas, the effect of suppressing the temperature rise of the pipe brought about by the present invention can be significantly obtained.

[0157] (c) During the period from step A to step B, the first process and the second process are performed in the same process chamber without moving the substrate out of the process chamber 201. This can prevent contamination of the substrate and adhesion of particles that may occur with the moving in and out of the substrate. In addition, by reducing the moving in and out of the substrate, productivity (throughput) can sometimes be improved.

[0158] (d) In step A, by not implementing the supply of the second processing gas into the processing chamber 201 via the second piping, the temperature rise of the second piping can be suppressed. Specifically, in step A where the temperature of the second piping is above the first temperature, which is the temperature at which the oxidation reaction between the metal-containing material constituting the inner surface of the second piping and the second processing gas occurs, by not implementing the supply of the second processing gas, the reaction itself can be prevented from occurring. Thus, the temperature rise of the second piping can be reliably suppressed. By suppressing the temperature rise of the second piping, it is possible to prevent the burning of piping accessories such as resin, such as sealing components, and also to prevent the generation of pollutants caused by the oxidation reaction between the metal-containing material and the second processing gas.

[0159] (e) In step B, by not supplying the first process gas into the process chamber 201, it is possible to suppress the byproducts of the first process gas from being attached to the second pipe. Specifically, in step B where the temperature of the second pipe is maintained at a second temperature or lower than a temperature at which it is difficult to suppress the attachment of the byproducts of the first process gas, by not supplying the first process gas, the byproducts themselves are not generated. Thus, it is possible to reliably prevent the byproducts of the first process gas from being attached to the second pipe.

[0160] (f) In step B, by not supplying other gases except the second process gas and the inert gas into the processing chamber 201, it is possible to suppress the byproducts of the other gases from being attached to the second pipe. Specifically, in step B where the temperature of the second pipe is maintained at a temperature below the second temperature at which it is difficult to suppress the attachment of the byproducts of the other gases, by not supplying the other gases, the byproducts are not generated. Thus, it is possible to reliably prevent the byproducts of the other gases from being attached to the second pipe.

[0161] (g) In step B, by maintaining the temperature of the first pipe heated to a temperature higher than the first temperature in step A at the first temperature or higher, it is possible to suppress the byproducts of the first process gas supplied in step A and remaining in the first pipe from being attached to the first pipe. Specifically, in step B, by maintaining the temperature of the first pipe at a temperature higher than the first temperature at which the byproducts of the first process gas do not adhere to the first pipe, it is possible to suppress the byproducts of the first process gas supplied in step A and remaining in the first pipe from being attached to the first pipe.

[0162] Furthermore, in step B, by maintaining the temperature of the first pipe heated to a temperature higher than the first temperature in step A at the first temperature or higher, even if the byproduct of the second process gas supplied in step B enters the first pipe, it is possible to suppress the byproduct from being attached to the first pipe. Specifically, in step B, by making the temperature of the first pipe higher than the first temperature at which the byproduct of the second process gas does not adhere to the first pipe, it is possible to suppress the byproduct of the second process gas from being attached to the first pipe.

[0163] In step B, the first pipe temperature is continuously maintained at or above the first temperature while the second process is being performed, so that the above-mentioned effect can be reliably obtained.

[0164] (h) In step B, when the temperature of the second pipe reaches a fourth temperature (upper limit temperature / critical temperature) higher than the second temperature during the second process, the second process is stopped to prevent the second pipe temperature from exceeding the upper limit temperature (fourth temperature).

[0165] (i) During the period between step A and step B, step C of lowering the temperature of the second pipe to the second temperature is performed without performing the first and second treatments, thereby suppressing the temperature increase of the second pipe due to the second treatment.

[0166] (j) In step C, by starting step B at the time when the second pipe temperature drops to the second temperature, the time for the second pipe temperature to drop can be shortened, thereby improving throughput.

[0167] (k) In step C, by setting the second pipe temperature to a third temperature lower than the second temperature, even if heat is generated in the second pipe due to, for example, an undesired oxidation reaction in step B, the second pipe temperature can be maintained below the second temperature, thereby preventing a sudden temperature rise.

[0168] (l) In step A and step B, by not supplying the nitrogen-containing gas into the processing chamber 201 through the second pipe, it is possible to prevent particles and nitric acid (HNO) that may corrode the pipe and the like from being generated in the second pipe due to mixing the second processing gas containing O and the nitrogen-containing gas. 3 )wait.

[0169] <Other aspects of the present invention>

[0170] As mentioned above, although the form of this invention was demonstrated concretely, this invention is not limited to the said form, Various changes are possible within the range which does not deviate from the summary.

[0171] For example, in the above method, the case where the temperature of the second pipe is lowered 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 terminated) is described as an example. However, the present invention is not limited to such a method. For example, it can also be set as a process in which the temperature of the second pipe is lowered from the first temperature to the second temperature while the first processing gas is continuously supplied (i.e., during the execution of step A). ​​In this case, the same effect as the above method can be obtained. In addition, since the temperature of the second pipe is lowered during the execution of step A, the cycle time can be shortened and the throughput can be further improved.

[0172] For example, the inner surface of the second pipe may be subjected to fluorination treatment to form a fluoride layer containing a metal material. By forming a fluoride layer on the inner surface of the second pipe composed of a metal material in advance, the oxidation reaction between the second processing gas and the metal material can be more reliably suppressed, and the effect of suppressing the temperature rise of the second pipe in the above-mentioned method can be further improved. For example, by exposing the inner surface of the second pipe to fluoride in advance, the fluoride layer can be formed. 2 The second pipe may be treated in a fluorine (F)-containing gas such as a gas, thereby forming a fluorinated metal-containing material layer (i.e., a fluorinated layer) on the inner surface of the second pipe. In addition, a known fluorination treatment technique may be used as a method for forming a fluorinated layer on the inner surface of the second pipe.

[0173] It should be noted that the fluoride layer may be formed similarly not only on the second pipe but also on the inner surface of the first pipe. In addition, the fluoride layer may not be formed on the inner surface of the first pipe but only on the inner surface of the second pipe.

[0174] For example, by subjecting the inner surface of the second pipe to a film forming treatment, an oxide film such as a silicon oxide film (SiO film) is formed. By forming an oxide film in advance on the inner surface of the second pipe composed of a metal-containing material in a manner that covers the inner surface, the oxidation reaction between the second processing gas and the metal-containing material can be more reliably suppressed, and the temperature rise suppression effect of the second pipe in the above-mentioned manner can be further improved. For example, by performing a cycle including a process of supplying a raw material gas containing silicon (Si) to the inner surface of the second pipe and a process of supplying an O-containing gas as an oxidant for a predetermined number of times, a Si-containing oxide film can be formed (deposited) on the inner surface of the second pipe. In addition, as a method of forming an oxide film on the inner surface of the second pipe, a known film forming treatment technique can also be used.

[0175] It should be noted that the oxide film may be formed on the inner surface of the first pipe as well as the second pipe. In addition, the oxide film may not be formed on the inner surface of the first pipe but only on the inner surface of the second pipe.

[0176] For example, in step C, after the control temperature of the pipe heater 233c is changed from the first temperature to the third temperature, the power supply to the pipe heater 233c may be stopped until at least the second pipe temperature is reduced from the first temperature to the third temperature. In addition, in step C, the control temperature of the pipe heater 233c may not be changed from the first temperature to the third temperature, but only the power supply to the pipe heater 233c may be stopped. In addition, when the temperature of the second pipe is reduced, a cooling device not shown in the figure may also be used. In the above case, the same effect as the above method can also be obtained. In addition, when a cooling device is used, the time required for cooling the second pipe can be shortened, and the throughput can be improved. The cooling device may be composed of, for example, an air cooling device, a water cooling device, a Peltier cooling device, etc.

[0177] For example, in the above-mentioned method, SUS is used as an example of a metal-containing material constituting the inner surface of the first pipe and the second pipe. However, the present invention is not limited to such a method. 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, INCONEL (registered trademark) in which Fe, Cr, niobium (Nb), Mo, etc. are added to Ni, etc. In the above-mentioned case, the same effect as the above-mentioned method can be obtained.

[0178] For example, in the above method, the case where the specified element contained in the raw material gas is Si can be used as an example for explanation. However, the present invention is not limited to such a method. For example, the specified element can also be a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), Nb, Al, Mo, tungsten (W), germanium (Ge), etc. In the above case, a titanium oxide nitride film (TiON film), a zirconium oxide nitride film (ZrON film), a hafnium oxide nitride film (HfON film), a tantalum oxide nitride film (TaON film), a niobium oxide nitride film (NbON film), an aluminum oxide nitride film (AlON film), a molybdenum oxide nitride film (MoON film), a tungsten oxide nitride film (WON film), a germanium oxide nitride film (GeON film), etc. can be formed. In the above case, the same effect as the above method can also be obtained.

[0179] The process used for each treatment is prepared separately according to the treatment content, and it is preferable that it is recorded and stored in the storage device 121c in advance via the electric communication line and the external storage device 123. In addition, when starting each treatment, it is preferable that the CPU 121a appropriately selects a suitable process from the multiple processes recorded and stored in the storage device 121c according to the treatment content. In this way, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility in one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each treatment can be started quickly.

[0180] The above process is not limited to the case of newly making, and for example, it can also be prepared by changing an existing process installed in a substrate processing device. When changing a process, it can also be set to install the changed process in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, it can also be set to operate the input / output device 122 of the existing substrate processing device to directly change the existing process installed in the substrate processing device.

[0181] In the above-mentioned method, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and can be appropriately applied, for example, when 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 method, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and can be appropriately applied when a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0182] When these substrate processing apparatuses are used, each process can be performed under the same process steps and process conditions as those of the above-mentioned embodiment and modified examples, and the same effects as those of the above-mentioned embodiment and modified examples can be obtained.

[0183] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing steps and processing conditions in this case may be the same as those of the above-mentioned aspects and modifications, for example.

Claims

1. A substrate processing method, comprising: (a) supplying a first processing gas into the processing container via a first pipe different from the second pipe while heating a second pipe having an inner surface made of a metal-containing material and connected to the processing container to a first temperature or higher, thereby performing a first processing on a substrate accommodated in the processing container; and (b) supplying a second processing gas containing oxygen into the processing container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature, thereby performing a second processing on the substrate.

2. The substrate processing method according to claim 1, wherein: In (a), the second process gas is not supplied into the process container through the second pipe.

3. The substrate processing method according to claim 1, wherein: In (b), the first process gas is not supplied into the process container.

4. The substrate processing method according to any one of claims 1 to 3, wherein: In (b), the supply of gases other than the second process gas and the inert gas into the process container is not performed.

5. The substrate processing method according to claim 1, wherein: 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 the metal-containing material is lower than the reactivity of the second process gas with the metal-containing material.

6. The substrate processing method according to claim 1, wherein: The second processing gas is a gas including at least any one of hydrogen peroxide gas, ozone gas, and plasma-excited oxygen-containing gas.

7. The substrate processing method according to claim 1, wherein: In (b), the temperature of the first pipe is maintained in a state where the temperature is heated to or higher than the first temperature.

8. The substrate processing method according to claim 1, wherein: The second temperature is a temperature at which a reaction between the metal-containing material and the second process gas does not occur.

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

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

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

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

13. The substrate processing method according to claim 1, wherein: In (b), when the temperature of the second pipe reaches a fourth temperature higher than the second temperature during execution of the second process, execution of the second process is stopped.

14. The substrate processing method according to claim 1, wherein: During the period between (a) and (b), there is also: (c) a step of lowering the temperature of the second pipe to the second temperature without performing the first treatment and the second treatment.

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

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

17. The substrate processing method according to claim 1, wherein: In (a) and (b), the nitrogen-containing gas is not supplied into the processing container through the second pipe.

18. A method for manufacturing a semiconductor device, comprising: (a) supplying a first processing gas into the processing container via a first pipe different from the second pipe while heating a second pipe having an inner surface made of a metal-containing material and connected to the processing container to a first temperature or higher, thereby performing a first processing on a substrate accommodated in the processing container; and (b) supplying a second processing gas containing oxygen into the processing container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature, thereby performing a second processing on the substrate.

19. A computer-readable recording medium having a program recorded thereon for causing a substrate processing apparatus to execute the following steps using a computer: (a) supplying a first processing gas into the processing container via a first pipe different from the second pipe while heating a second pipe having an inner surface made of a metal-containing material and connected to the processing container to a first temperature or higher, thereby performing a first processing on a substrate accommodated in the processing container; and (b) supplying a second process gas containing oxygen into the process container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature, thereby performing a second process on the substrate.

20. A substrate processing apparatus comprising: a processing vessel that processes the substrate; a first processing gas supply system for supplying a first processing gas into the processing container via a first pipe connected to the processing container; a second processing gas supply system for supplying a second processing gas containing oxygen into the processing container via a second pipe different from the first pipe and having an inner surface made of a metal-containing material and connected to the processing container; a heater that heats the second pipe; and A control unit configured to control the first process gas supply system, the second process gas supply system, and the heater to perform: (a) supplying the first process gas into the process container through the first pipe while the second pipe is heated to a first temperature or higher, thereby performing a first process on the substrate; and (b) supplying the second process gas into the process container through the second pipe while lowering the temperature of the second pipe to a second temperature lower than the first temperature, thereby performing a second process on the substrate.

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