Substrate processing apparatus, gas nozzle, semiconductor device manufacturing method, and program

Abstract

To provide a technique capable of inhibiting adhesion of deposits on a surface of a member in a processing container.SOLUTION: A substrate processing device includes: a processing container where substrates are accommodated; a first nozzle provided with a first discharge hole on a side thereof, the first discharge hole opening to face a substrate arrangement area where the substrates in the processing container are arranged; a second nozzle provided with a second discharge hole on a side thereof, the second discharge hole opening to face at least one of a face in a range different from the installation range of the discharge hole of sides of the first nozzle, and a space between a face in a range different from the installation range of the first discharge hole and the internal wall face of the processing container; a raw material gas supply system to supply raw material gas into the processing container through the first nozzle; and an inert gas supply system to supply inert gas into the processing chamber through the second nozzle.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] As one step in the manufacturing process of a semiconductor device, a step of processing a substrate in a processing vessel, for example, a step of supplying a gas to a substrate accommodated in the processing vessel to form a film on the substrate, may be performed (see, for example, Patent Document 1, etc.). During this process, if deposits adhere to the surface of a component in the processing vessel, for example, the outer surface of a nozzle that supplies raw materials, etc., the deposits may cause the generation of foreign matter (particles). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-225655 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique capable of suppressing adhesion of deposits to surfaces of components inside a processing vessel. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, a processing vessel in which a substrate is accommodated; a first nozzle having a first discharge hole formed on a side surface thereof, the first discharge hole opening toward a substrate arrangement area in the processing vessel where substrates are arranged; a second nozzle having a second discharge hole formed on a side surface thereof, the second discharge hole opening toward at least one of a surface of the side surface of the first nozzle in a range different from an installation range of the first discharge hole and a space between the surface in a range different from an installation range of the first discharge hole and an inner wall surface of the processing vessel; a source gas supply system configured to supply a source gas into the processing chamber through the first nozzle; an inert gas supply system configured to supply an inert gas into the processing chamber through the second nozzle. [Effects of the Invention]

[0006] According to the present disclosure, it is possible to suppress adhesion of deposits to the surfaces of components inside a processing vessel. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Figure 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a cross-sectional view of the processing furnace 202 taken along line AA in FIG. [Figure 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 4 is a diagram showing a processing sequence according to one embodiment of the present disclosure. [Figure 5] FIG. 5 is a diagram showing a cleaning sequence according to one embodiment of the present disclosure. [Figure 6] FIG. 6 is a diagram showing a modified cross-sectional configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure. [Figure 7] FIG. 7 is a diagram showing another modified example of the cross-sectional configuration of the vertical processing furnace of the substrate processing apparatus suitably used in one embodiment of the present disclosure. [Figure 8] FIG. 8 is a diagram showing yet another modified example of the cross-sectional configuration of the vertical processing furnace of the substrate processing apparatus suitably used in one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0010] A reaction tube 203 constituting a processing vessel is disposed inside the heater 207 and 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. A manifold 209 is disposed concentrically below the reaction tube 203. A processing chamber 201 is formed in the hollow cylindrical portion of the reaction tube 203. The processing chamber 201 is configured to accommodate (store) a plurality of wafers 200 as substrates, arranged at predetermined intervals in a direction perpendicular to the surfaces of the wafers 200. The wafers 200 are processed in this processing chamber 201. The ceiling (upper end) of the reaction tube 203 is formed in a dome shape.

[0011] Nozzles 249a, 249b, and 249c serving as first to third supply units are respectively provided in the processing chamber 201 so as to penetrate the bottom of the reaction tube 203. The nozzle 249b is detachably provided with respect to the reaction tube 203. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles.

[0012] It is also possible to provide a metal manifold below the reaction tube 203 to support the reaction tube 203, and to provide each nozzle so as to penetrate the sidewall of the metal manifold. In this case, the metal manifold may be further provided with an exhaust pipe 231, which will be described later. Even in this case, the exhaust pipe 231 may be provided below the reaction tube 203, instead of being provided on the metal manifold. In this way, the furnace opening of the process furnace 202 may be made of metal, and the nozzles and the like may be attached to the metal furnace opening.

[0013] Gas supply pipes 232a-232c are respectively provided, from the upstream side of the gas flow, with mass flow controllers (MFCs) 241a-241c, which are flow rate controllers (flow rate control parts), and valves 243a-243c, which are on-off valves. Gas supply pipe 232d is connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipe 232f is connected to gas supply pipe 232a downstream of its connection with gas supply pipe 232d. Gas supply pipe 232e is connected to gas supply pipe 232b downstream of valve 243b. Gas supply pipe 232g is connected to gas supply pipe 232c downstream of valve 243c. Gas supply pipes 232d-232g are respectively provided, from the upstream side of the gas flow, with MFCs 241d-241g and valves 243d-243g. The gas supply pipes 232a to 232g are made of a metal material such as SUS.

[0014] 2, the nozzles 249a to 249c are provided in a circular space in a plan view between the inner wall of the reaction tube 203 and the wafers 200, along the inner wall of the reaction tube 203 from the bottom to the top, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in areas horizontally surrounding the wafer arrangement area on the sides of the wafer arrangement area where the wafers 200 are arranged, along the wafer arrangement direction of the wafer arrangement area.

[0015] A first discharge hole (first supply port) for discharging (supplying) gas is provided on the side surface of the nozzle 249a along the wafer arrangement direction of the wafer arrangement area. The first discharge hole has a shape including a plurality of gas discharge holes 250a. The gas discharge holes 250a are provided from one end to the other end in the wafer arrangement direction. The gas discharge holes 250a are open to face the center of the reaction tube 203, i.e., to face the wafer arrangement area, and are capable of supplying gas toward the wafers 200. Each of the plurality of gas discharge holes 250a is formed, for example, by a circular or elliptical hole. The shapes of the gas discharge holes are the same for the second to eighth discharge holes and upper discharge holes described later.

[0016] The nozzle 249b has second discharge holes (second supply ports) for discharging gas provided on its side surface along the wafer arrangement direction of the wafer arrangement area. The second discharge holes include a plurality of gas discharge holes 250b1. The gas discharge holes 250b1 are provided from one end to the other end in the wafer arrangement direction. As shown in FIG. 2, the gas discharge holes 250b1 are open to at least one of (i) a surface of the side surface of the nozzle 249a that is different from the area where the gas discharge holes 250a are provided (i.e., a surface of the outer surface of the nozzle 249a exposed to the inside of the process chamber 201 that is different from the surface where the gas discharge holes 250a are provided in the circumferential direction of the nozzle 249a; hereinafter, this surface may be simply referred to as the "gas discharge hole non-installation surface"); and (ii) a space (gap) between the gas discharge hole non-installation surface of the nozzle 249a and the inner wall surface of the reaction tube 203. For example, gas discharge hole 250b1 is open toward a side surface of nozzle 249a that is opposite the installation range of gas discharge hole 250a in the radial direction of nozzle 249a (hereinafter also referred to as the back surface of nozzle 249a), and gas can be discharged toward the back surface of nozzle 249a. Note that gas discharge hole 250b1 is not provided at a position facing the wafer arrangement area. In other words, nozzle 249b does not have a gas discharge hole that opens toward the wafer arrangement area, and is configured not to supply gas toward the wafer arrangement area.

[0017] The nozzle 249b has a tip (upper end) provided with a gas discharge hole 250b2 as an upper discharge hole (upper supply port). As described above, the ceiling of the reaction tube 203 is dome-shaped. When multiple wafers 200 are arranged vertically inside the reaction tube 203, a space (hereinafter also referred to as an upper dome space) is formed inside the reaction tube 203 between the inner wall of the ceiling of the reaction tube 203 and the wafer 200 arranged at the upper end of the multiple wafers 200. The gas discharge hole 250b2 opens toward the space above the wafer arrangement region, i.e., the upper dome space, allowing gas to be efficiently discharged toward the upper dome space. The opening area of ​​the gas discharge hole 250b2 is larger than the opening area of ​​each of the gas discharge holes 250b1.

[0018] A third discharge hole (third supply port) for discharging gas is provided on the side surface of the nozzle 249c along the wafer arrangement direction. The third discharge hole has a shape including a plurality of gas discharge holes 250c. The plurality of gas discharge holes 250c are provided from one end side to the other end side in the wafer arrangement direction of the wafer arrangement area. As shown in FIG. 2, the gas discharge holes 250c open toward the center of the buffer chamber 237, which will be described later.

[0019] 2, the nozzles 249a and 249b are provided at positions adjacent to each other along the circumferential direction of the wafers 200 arranged in the wafer arrangement area. Specifically, the nozzles 249a and 249b are arranged at positions such that, in a plan view, a central angle θ formed by a line (first line) connecting the center of the wafer 200 and the center of the nozzle 249a and a line (second line) connecting the center of the wafer 200 and the center of the nozzle 249b (the central angle θ with respect to an arc having both ends at the centers of the nozzles 249a and 249b) is an acute angle, for example, within a range of 10 to 30°, preferably 10 to 20°.

[0020] The nozzle 249c is provided in a buffer chamber 237, which is a gas dispersion space. The buffer chamber 237 is provided in an annular space between the inner wall of the reaction tube 203 and the wafers 200, and in a portion extending from the lower part to the upper part of the inner wall of the reaction tube 203 along the arrangement direction of the wafers 200. That is, the buffer chamber 237 is provided in a region that horizontally surrounds the wafer arrangement area on the side of the wafer arrangement area and extends along the wafer arrangement area. Gas discharge holes 238 that discharge gas are provided at the end of the wall of the buffer chamber 237 adjacent to the wafers 200. The gas discharge holes 238 are open toward the wafer arrangement area and can discharge gas toward the wafers 200. A plurality of gas discharge holes 238 are provided from one end to the other end of the wafer arrangement area in the wafer arrangement direction.

[0021] From the gas supply pipe 232a, a raw material is supplied through the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. The raw material is used as one of the film forming agents.

[0022] A reactant is supplied from the gas supply pipe 232c through the MFC 241c, the valve 243c, and the nozzle 249c into the processing chamber 201. The reactant is used as one of the film forming agents.

[0023] A first cleaning gas is supplied from the gas supply pipe 232d through the MFC 241d, the valve 243d, and the nozzle 249a into the processing chamber 201. The first cleaning gas is used as one of the cleaning agents.

[0024] An additive gas that reacts with the cleaning gas is supplied from the gas supply pipe 232e into the processing chamber 201 via the MFC 241e, the valve 243e, and the nozzle 249b. The additive gas does not have a cleaning effect by itself, but reacts with the first cleaning gas to generate predetermined activated species, which act to improve the cleaning effect of the first cleaning gas. The additive gas is used as one of the cleaning agents.

[0025] Inert gas is supplied from the gas supply pipes 232b, 232f, and 232g through the MFCs 241b, 241f, and 241g, the valves 243b, 243f, and 243g, and the nozzles 249a to 249c into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0026] The raw material supply system (raw material gas supply system) mainly comprises the gas supply pipe 232a, the MFC 241a, and the valve 243a. The reactant supply system (reactant gas supply system) mainly comprises the gas supply pipe 232c and the valve 243c. The first cleaning gas supply system mainly comprises the gas supply pipe 232d and the valve 243d. The additive gas supply system mainly comprises the gas supply pipe 232e and the valve 243e. The inert gas supply system mainly comprises the gas supply pipes 232b, 232f, and 232g and the valves 243b, 243f, and 243g. Either or all of the raw material supply system and the reactant supply system are also referred to as a film-forming agent supply system. Either or all of the first cleaning gas supply system and the additive gas supply system are also referred to as a cleaning agent supply system.

[0027] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a-243g, MFCs 241a-241g, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a-232g, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a-232g, i.e., the opening and closing operation of the valves 243a-243g and the flow rate adjustment operation by the MFCs 241a-241g, etc., are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232g, etc., so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0028] As shown in FIG. 2 , two elongated rod-shaped electrodes 269 and 270 made of a conductor are provided in the buffer chamber 237, extending from the bottom to the top of the inner wall of the reaction tube 203 and rising upward in the arrangement direction of the wafers 200. The rod-shaped electrodes 269 and 270 are provided parallel to the nozzle 249c. The rod-shaped electrodes 269 and 270 are protected by being covered from top to bottom by an electrode protection tube 275. One of the rod-shaped electrodes 269 and 270 is connected to a high-frequency power supply 273 via a matcher 272, and the other is connected to earth, which is a reference potential. Here, the rod-shaped electrode 269 is connected to the high-frequency power supply 273 via the matcher 272, and the rod-shaped electrode 270 is connected to earth, which is a reference potential. By applying radio frequency (RF) power from a high frequency power supply 273 to between the rod-shaped electrodes 269 and 270 via a matching box 272 , plasma is generated in a plasma generation region 224 between the rod-shaped electrodes 269 and 270 .

[0029] The electrode protection tube 275 is configured so that each of the rod-shaped electrodes 269, 270 can be inserted into the buffer chamber 237 while being isolated from the atmosphere inside the buffer chamber 237. If the oxygen (O2) concentration inside the electrode protection tube 275 is similar to the O2 concentration in the outside air (atmosphere), the rod-shaped electrodes 269, 270 inserted into the electrode protection tube 275 will be oxidized by the heat from the heater 207. For this reason, the O2 concentration inside the electrode protection tube 275 can be reduced and the oxidation of the rod-shaped electrodes 269, 270 can be prevented by filling the inside of the electrode protection tube 275 with an inert gas or purging the inside of the electrode protection tube 275 with an inert gas using an inert gas purge mechanism.

[0030] A plasma excitation unit (activation mechanism) that excites (activates) the gas into a plasma state is mainly composed of the rod-shaped electrodes 269 and 270 and the electrode protection tube 275. The matching box 272 and the high-frequency power supply 273 may also be considered to be included in the plasma excitation unit. The buffer chamber 237 may also be considered to be included in the excitation unit.

[0031] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the bottom of the sidewall of the reaction tube 203. The exhaust port 231a may be provided along the sidewall of the reaction tube 203 from the bottom to the top, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure adjustment unit). The APC valve 244 can evacuate and stop the evacuation inside the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. A vacuum pump 246 may be included in the exhaust system.

[0032] A seal cap 219 serving as a furnace port cover capable of airtightly closing the lower end opening of the reaction tube 203 is provided below the reaction tube 203. The seal cap 219 is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220 serving as a sealing member that abuts against the lower end of the reaction tube 203 is provided on the upper surface of the seal cap 219. A rotation mechanism 267 for rotating a boat 217 (described later) is provided below the seal cap 219. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the boat 217, thereby rotating the wafers 200. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 serving as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0033] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals, in multiple stages. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages.

[0034] A temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 can be adjusted to a desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0035] 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. An external storage device 123 can also be connected to the controller 121.

[0036] The storage device 121c is configured with, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. Control programs for controlling the operation of the substrate processing apparatus, process recipes describing procedures and conditions for substrate processing (described later), etc., are readably recorded and stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (described later) that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipes, control programs, etc. are collectively referred to simply as programs. The process recipes are also simply referred to as recipes. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0037] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, and the like.

[0038] 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 an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241g, the opening and closing operation of the valves 243a to 243g, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, and the like.

[0039] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0040] (2) Substrate processing process An example of a method for processing a substrate as one step in the manufacturing process of a semiconductor device using the above-described substrate processing apparatus, i.e., a processing sequence for forming a film on a wafer 200 as a substrate, will be described mainly with reference to Fig. 4. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0041] In the processing sequence of this embodiment shown in FIG. (a) a step of supplying raw materials to the wafer 200 in the processing chamber (raw material supply step); (b) supplying a reactant to the wafer 200 in the processing chamber (reactant supply step); a predetermined number of times (n times, n is an integer of 1 or more) to form a film on the wafer 200; In (a), an inert gas is supplied from a nozzle 249b different from the nozzle 249a that supplies the raw material toward at least one of (i) a surface of the side of the nozzle 249a in a range different from the installation range of the gas discharge hole 250a, and (ii) a space between a surface in a range different from the installation range of the gas discharge hole 250a and the inner wall surface of the reaction tube 203.

[0042] In the processing sequence shown in FIG. 4, (a) shows an example in which raw material is supplied from nozzle 249a to wafer 200 in the processing vessel, and inert gas is supplied from nozzle 249b, which is different from nozzle 249a, toward at least one of (i) a surface on the side of nozzle 249a that is in a range different from the installation range of gas discharge hole 250a, and (ii) the space between a surface of nozzle 249a in a range different from the installation range of gas discharge hole 250a and the inner wall surface of reaction tube 203.

[0043] For convenience, the nozzles 249a to 249c are represented as R1 to R3 in Fig. 4. The nozzles are represented in the same manner in Fig. 5, which shows the cleaning sequence to be described later.

[0044] In this specification, for convenience, such a processing sequence (gas supply sequence) may be expressed as follows: Similar notations will be used in the following descriptions of other aspects and modifications.

[0045] (R1: raw material → R3: plasma-excited reactant) × n

[0046] The processing sequence shown in FIG. 4 illustrates an example in which a cycle of performing (a) and (b) in this order is performed a predetermined number of times (n times). In this case, n is an integer greater than or equal to 1. FIG. 4 also illustrates an example in which, after performing (a) and before performing (b), the space in which the wafer 200 exists (inside the processing vessel) is purged with an inert gas. Furthermore, when performing the cycle multiple times, the processing vessel may be purged with an inert gas after performing (b) and before performing (a). At least one of these methods can prevent the mixing of gases in the processing vessel, resulting in unintended reactions and particle generation.

[0047] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0048] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, a film-forming agent (raw material, reactant) may contain a gaseous substance, a liquid substance such as a mist substance, or both.

[0049] As used herein, the term "layer" includes at least one of a continuous layer and a discontinuous layer. The layer formed in each step described below may include a continuous layer, a discontinuous layer, or both.

[0050] (Wafer charge and boat load) 1, when a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the reaction tube via the O-ring 220. In this manner, the wafers 200 are prepared in the processing chamber 201.

[0051] (pressure and temperature regulation) After the boat loading is completed, the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the interior of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. The wafers 200 inside the processing chamber 201 are heated by the heater 207 so that the desired processing temperature is reached. At this time, the power supply to the heater 207 is feedback-controlled (temperature adjustment) based on temperature information detected by the temperature sensor 263 so that the interior of the processing chamber 201 has a desired temperature distribution. The rotation mechanism 267 also starts to rotate the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0052] (film formation step) Thereafter, the next raw material supply step and reactant supply step are carried out in sequence.

[0053] [Raw material supply step] In this step, a raw material (raw material gas) is supplied to the wafer 200 as a film forming agent.

[0054] Specifically, the valve 243a is opened to allow the raw material to flow into the gas supply pipe 232a (Step A). ​​The raw material is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 through each of the multiple gas discharge holes 250a provided on the side surface of the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the raw material is supplied to the wafer 200 from the side of the wafer 200 (raw material supply).

[0055] Furthermore, while the raw material is being supplied into the processing chamber 201 (during step A), the valve 243b is opened to allow an inert gas to flow into the gas supply pipe 232b at a first flow rate (step A'). The inert gas has a flow rate adjusted by the MFC 241b, is supplied into the processing chamber 201 via each of the multiple gas discharge holes 250b1 provided on the side surface of the nozzle 249b and the gas discharge hole 250b2 provided at the tip of the nozzle 249b, and is exhausted from the exhaust port 231a.

[0056] During step A, the valves 243f and 243g may be opened to supply an inert gas into the processing chamber 201 through the gas discharge holes 250a and 250c provided on the side surfaces of the nozzles 249a and 249c, respectively.

[0057] The processing conditions when supplying the raw material in the raw material supply step are as follows: Treatment temperature: 0 to 700°C, preferably room temperature (25°C) to 550°C, more preferably 40 to 500°C Treatment pressure: 1 to 2666 Pa, preferably 665 to 1333 Pa Raw material supply flow rate: 1 to 6000 sccm, preferably 2000 to 3000 sccm Inert gas supply flow rate (gas supply pipe 232b, first flow rate): 300 to 8000 sccm Inert gas supply flow rate (per gas supply pipe 232a, 232c): 0 to 10,000 sccm Each gas supply time: 1 to 10 seconds, preferably 1 to 3 seconds is exemplified.

[0058] In this specification, when a numerical range such as "0 to 700°C" is expressed, it means that the lower limit and the upper limit are included in the range. Therefore, for example, "0 to 700°C" means "0°C or higher and 700°C or lower." The same applies to other numerical ranges. In this specification, the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure means the pressure inside the processing chamber 201. The processing time means the time the processing continues. In addition, when the supply flow rate includes 0 sccm, 0 sccm means that the substance (gas) is not supplied. These also apply to the following explanations.

[0059] By supplying, for example, a chlorosilane-based gas as a raw material to the wafer 200 under the above-described processing conditions, a Si-containing layer containing Cl is formed on the top surface of the wafer 200 as a base. The Si-containing layer containing Cl is formed on the top surface of the wafer 200 by physical adsorption or chemical adsorption of chlorosilane-based gas molecules, physical adsorption or chemical adsorption of molecules of a substance formed by partial decomposition of the chlorosilane-based gas, or deposition of Si due to thermal decomposition of the chlorosilane-based gas. The Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of chlorosilane-based gas molecules or molecules of a substance formed by partial decomposition of the chlorosilane-based gas, or may be a deposition layer of Si containing Cl. In this specification, the Si-containing layer containing Cl will also be simply referred to as a Si-containing layer. Under the above-described processing conditions, physisorption or chemisorption of chlorosilane-based gas molecules or molecules of substances formed by decomposition of the chlorosilane-based gas onto the outermost surface of the wafer 200 occurs predominantly (preferentially), and little or no Si is deposited due to thermal decomposition of the chlorosilane-based gas. That is, under the above-described processing conditions, the Si-containing layer contains an overwhelming number of adsorption layers (physisorption layers or chemisorption layers) of chlorosilane-based gas molecules or molecules of substances formed by decomposition of the chlorosilane-based gas, and contains little or almost no deposition layer of Si containing Cl.

[0060] In the raw material supply step, while the raw material is being supplied from the nozzle 249a into the processing chamber 201, an inert gas is discharged into the processing chamber 201 using the nozzle 249b having the gas discharge holes 250b1 that open toward at least one of (i) a side surface of the nozzle 249a that is different from the area where the gas discharge holes 250a are installed, and (ii) a space between the side surface of the nozzle 249a that is different from the area where the gas discharge holes 250a are installed and the inner wall surface of the reaction tube 203. That is, step A' is performed in parallel with step A. This allows the side surface of the nozzle 249a (e.g., a side surface of the nozzle 249a other than the area where the gas discharge holes 250a are installed) to be purged with the inert gas during the execution of step A. As a result, it is possible to prevent the raw material, decomposed substances of the raw material, and the like (hereinafter, collectively referred to as "raw material-derived substances") from adhering to the side surface (outer surface) of the nozzle 249a. Furthermore, by suppressing adhesion of substances such as raw materials to the side surface of the nozzle 249a, it is possible to suppress the reaction between the raw material-derived substances adhered to the side surface of the nozzle 249a and the reactants in the reactant supply step described below. This makes it possible to suppress the adhesion of substances resulting from the reaction between the raw material-derived substances and the reactants to the side surface of the nozzle 249a. In other words, it is possible to suppress the adhesion of raw material-derived substances and substances resulting from the reaction between the raw material-derived substances and the reactants to the side surface of the nozzle 249a and the formation of deposits thereon. As a result, it is possible to suppress the generation of particles due to deposits, and it is possible to suppress the deterioration of the quality of the film ultimately formed on the wafer 200.

[0061] Furthermore, the nozzles 249a and 249b are provided at positions adjacent to each other along the circumferential direction of the wafer 200. This allows the inert gas discharged from the nozzle 249b (gas discharge holes 250b1 provided in the nozzle 249b) to reliably purge the side surface of the nozzle 249a. This also applies to the reactant supply step described later.

[0062] In step A', an inert gas is discharged into the processing chamber 201 using a nozzle 249b having a plurality of gas discharge holes 250b1 provided from one end to the other end in the wafer arrangement direction. This allows the side of the nozzle 249a to be purged from one end to the other end in the wafer arrangement direction. This also applies to the reactant supply step described later.

[0063] Furthermore, in step A', an inert gas is discharged into the processing chamber 201 using a nozzle 249b having gas discharge holes 250b1 that open toward the back surface of the nozzle 249a. As a result, during the execution of step A, the back surface of the nozzle 249a and the space between the back surface of the nozzle 249a and the inner wall surface of the reaction tube 203 (hereinafter, these will be collectively referred to as the "back surface side of the nozzle 249a"), where raw materials tend to accumulate, can be purged with the inert gas, making it possible to prevent raw materials from accumulating on the back surface side of the nozzle 249a. As a result, it is possible to reliably prevent raw material-derived substances from adhering to the side surface of the nozzle 249a. This also applies to the reactant supply step described later.

[0064] Furthermore, in step A', an inert gas is discharged into the processing chamber 201 using a nozzle 249b that does not have a gas discharge hole that opens toward the wafer arrangement area. This prevents the inert gas from being supplied toward the wafer arrangement area from the nozzle 249b. As a result, even when steps A and A' are performed in parallel, it is possible to prevent the source material supplied from the nozzle 249a from being dilution-depleted in the processing chamber 201. By preventing such dilution of the source material, it is possible to prevent the inert gas supplied from the nozzle 249b in the source supply step from affecting the formation rate of the layer formed on the wafer 200, the thickness and quality of the film finally formed on the wafer 200, and the like. This also applies to the reactant supply step described below.

[0065] In step A', the nozzle 249b having the gas discharge holes 250b2 is used to discharge the inert gas into the processing chamber 201. This allows the space above the wafer arrangement region (upper dome space) in the processing chamber 201, where the raw materials tend to accumulate, to be efficiently purged with the inert gas during the execution of step A. As a result, it is possible to prevent the adhesion of raw material-derived substances to the inner wall surface of the reaction tube 203, particularly to the inner wall surface of the ceiling portion of the reaction tube 203.

[0066] Furthermore, in step A', the inert gas is discharged into the process chamber 201 using the nozzle 249b equipped with the gas discharge holes 250b2 having an opening area larger than the opening area of ​​each of the gas discharge holes 250b1. This allows the upper dome space in the process chamber 201 to be purged more efficiently with the inert gas. As a result, it is possible to reliably prevent the deposition of raw material-derived substances on the inner wall surface of the reaction tube 203, particularly on the inner wall surface of the ceiling portion of the reaction tube 203. This also applies to the reactant supply step described later.

[0067] In this case, the diameter of the gas discharge holes 250b2 is set to, for example, 1.5 mm or more and 3.2 mm or less. This allows the upper dome space in the processing chamber 201 to be purged more efficiently with the inert gas. If the diameter of the gas discharge holes 250b2 is less than 1.5 mm, it may be difficult to efficiently purge the upper dome space in the processing chamber 201 with the inert gas. If the diameter of the gas discharge holes 250b2 exceeds 3.2 mm, the inert gas discharged from the gas discharge holes 250b2 may locally dilute the raw material in the processing chamber 201, particularly at the upper part in the wafer arrangement direction, and the uniformity between the wafer surfaces (such as film thickness uniformity and film quality uniformity) may be reduced.

[0068] After the Si-containing layer is formed, the valve 243a is closed to stop the supply of raw materials into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201. At this time, the valves 243b, 243f, and 243g are opened to supply an inert gas into the processing chamber 201. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201 (purging).

[0069] The flow rate (second flow rate) of the inert gas flowed into the gas supply pipe 232b during purging is set to be larger than the flow rate (first flow rate) of the inert gas flowed into the gas supply pipe 232b during step A'. That is, the flow rate (second flow rate) of the inert gas supplied from the nozzle 249b during purging is set to be larger than the flow rate (first flow rate) of the inert gas supplied from the nozzle 249b during step A'.

[0070] By setting the flow rate of the inert gas supplied from the nozzle 249b in this manner, the upper dome space within the processing chamber 201 can be efficiently purged with the inert gas, particularly the inert gas discharged from the gas discharge holes 250b2. This makes it possible to suppress the influence of the raw materials remaining in the processing chamber 201, particularly the upper dome space, on film formation. For example, it is possible to suppress mixing of the raw materials remaining in the upper dome space with the reactants supplied into the processing chamber 201 in the reactant supply step described below, as well as the resulting unintended reactions (e.g., gas-phase reactions or plasma gas-phase reactions) and particle generation. As a result, it is possible to suppress deterioration of uniformity between wafer surfaces. This also applies to purging in the reactant supply step described below.

[0071] The processing conditions for purging are as follows: Processing pressure: 1 to 20 Pa Inert gas supply flow rate (nozzle 249b, second flow rate): 1 to 10 slm Inert gas supply flow rate (per nozzle 249a, 249c): 1 to 10 slm Inert gas supply time: 1 to 200 seconds, preferably 1 to 40 seconds The processing temperature when purging in this step is preferably the same as the processing temperature when supplying the raw material.

[0072] As a raw material, for example, a silane-based gas containing silicon (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 halogen and Si, i.e., a halosilane-based gas can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halosilane-based gas, for example, the above-mentioned chlorosilane-based gas containing Cl and Si can be used.

[0073] As the raw material, for example, chlorosilane-based gases such as monochlorosilane (SiH3Cl) gas, dichlorosilane (SiH2Cl2) gas, trichlorosilane (SiHCl3) gas, tetrachlorosilane (SiCl4) gas, hexachlorodisilane gas (Si2Cl6) gas, octachlorotrisilane (Si3Cl8) gas, etc. One or more of these can be used as the raw material.

[0074] As the raw material, in addition to chlorosilane-based gases, for example, fluorosilane-based gases such as tetrafluorosilane (SiF4) gas and difluorosilane (SiH2F2) gas, bromosilane-based gases such as tetrabromosilane (SiBr4) gas and dibromosilane (SiH2Br2) gas, and iodosilane-based gases such as tetraiodosilane (SiI4) gas and diiodosilane (SiH2I2) gas can be used. One or more of these can be used as the raw material.

[0075] In addition to these, a gas containing an amino group and Si, i.e., an aminosilane-based gas, can also be used as a raw material. An amino group is a monovalent functional group formed by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and can be represented as -NH2, -NHR, or -NR2. R represents an alkyl group, and the two Rs in -NR2 may be the same or different.

[0076] As a raw material, 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(tertiarybutylamino)silane (SiH2[NH(C4H9)]2) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2]) gas can be used. One or more of these can be used as a raw material.

[0077] As the inert gas, nitrogen (N2) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. One or more of these can be used as the inert gas. This also applies to each step described below.

[0078] [Reactant Supply Step] After the raw material supply step is completed, a reactant (reaction gas) is supplied as a film-forming agent to the wafer 200, i.e., the Si-containing layer formed on the wafer 200. Here, an example will be described in which a nitrogen-containing nitriding agent (nitriding gas) is used as the reactant (reaction gas).

[0079] Specifically, the valve 243c is opened, and the nitriding agent is flowed into the gas supply pipe 232c (step B). The flow rate of the nitriding agent is adjusted by the MFC 241c, and the nitriding agent is supplied into the buffer chamber 237 through each of the plurality of gas discharge holes 250c provided on the side surface of the nozzle 249c. At this time, by applying RF power between the rod-shaped electrodes 269 and 270, the nitriding agent supplied into the buffer chamber 237 can be plasma-excited. The activated species Y generated by the plasma excitation of the nitriding agent are supplied into the processing chamber 201 through the gas discharge holes 238 and exhausted from the exhaust port 231a. At this time, the nitriding agent containing the activated species Y is supplied to the wafer 200 from the side of the wafer 200 (reactant supply).

[0080] Furthermore, while the reactants are being supplied into the processing chamber 201 (during step B), the valve 243b may be opened to allow the inert gas to flow into the gas supply pipe 232b at a third flow rate (step B'). At this time, in step B where the raw material is not supplied from the nozzle 249a, it is preferable that the third flow rate be set to a flow rate smaller than the first flow rate. The inert gas has a flow rate adjusted by the MFC 241b, is supplied into the processing chamber 201 through each of the multiple gas discharge holes 250b1 provided on the side surface of the nozzle 249b and the gas discharge hole 250b2 provided at the tip of the nozzle 249b, and is exhausted from the exhaust port 231a.

[0081] During step B, the valves 243f and 243g may be opened to supply an inert gas into the processing chamber 201 through the gas discharge holes 250a and 250c provided on the side surfaces of the nozzles 249a and 249c, respectively.

[0082] The processing conditions when supplying the nitriding agent in the reactant supply step are as follows: Treatment temperature: 0 to 700°C, preferably room temperature (25°C) to 550°C, more preferably 40 to 500°C Processing pressure: 1 to 500 Pa Nitriding agent supply flow rate: 100 to 10,000 sccm, preferably 1,000 to 2,000 sccm Inert gas supply flow rate (gas supply pipe 232b, third flow rate): 300 to 8000 sccm Inert gas supply flow rate (per gas supply pipe 232a, 232c): 0 to 10,000 sccm Each gas supply time: 1 to 180 seconds, preferably 1 to 60 seconds RF power: 100~1000W RF frequency: 13.56MHz or 27MHz is exemplified.

[0083] By supplying the nitriding agent to the wafer 200 in a plasma-excited state under the above-described processing conditions, at least a portion of the Si-containing layer formed on the wafer 200 is nitrided (modified). As a result, a silicon nitride layer (SiN layer) containing Si and N is formed on the top surface of the wafer 200 as a base. When the SiN layer is formed, impurities such as Cl contained in the Si-containing layer form a gaseous substance containing at least Cl during the process of the modification reaction of the Si-containing layer by the plasma-excited nitriding agent, and are exhausted from the processing chamber 201. As a result, the SiN layer contains fewer impurities such as Cl than the Si-containing layer formed in the raw material supply step.

[0084] In the reactant supply step, while the reactants are being supplied into the processing chamber 201 through the nozzle 249c, an inert gas is discharged into the processing chamber 201 using the nozzle 249b having the gas discharge holes 250b1 and 250b2. That is, step B' is performed in parallel with step B. This allows the back side of the nozzle 249a (e.g., the surface of the nozzle 249a other than the area where the gas discharge holes 250a are installed) and the upper dome space in the processing chamber 201 to be purged with the inert gas during the performance of step B. As a result, even if a raw material-derived substance adheres to at least one of the side surface of the nozzle 249a and the inner wall surface of the ceiling of the reaction tube 203 in the raw material supply step, it is possible to prevent the raw material-derived substance adhered to at least one of the side surface of the nozzle 249a and the inner wall surface of the ceiling of the reaction tube 203 from reacting with the reactants in the reactant supply step. By suppressing such a reaction, it is possible to reliably prevent the substances generated by the reaction between the raw material-derived substances and the reactants from adhering to at least one of the side surface of the nozzle 249a and the inner wall surface of the ceiling of the reaction tube 203, thereby reliably suppressing the generation of particles, etc.

[0085] After the SiN layer is formed, the valve 243c is closed to stop the supply of the nitriding agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedures and conditions as those for the purging in the raw material supply step described above. At this time, similar to the purging in the raw material supply step, it is preferable that the flow rate (second flow rate) of the inert gas flowed into the gas supply pipe 232b in the purging is set to be higher than the flow rate (third flow rate) of the inert gas flowed into the gas supply pipe 232b in step B'.

[0086] The reactant, i.e., the nitriding agent, may be, for example, a nitrogen (N) and H-containing gas. The N and H-containing gas may also be an N-containing gas or an H-containing gas. The nitriding agent preferably has an N-H bond.

[0087] As the nitriding agent, for example, a hydrogen nitride gas such as ammonia (NH3) gas, diazene (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas, etc. As the nitriding agent, one or more of these can be used.

[0088] In addition to these, a nitrogen (N), carbon (C) and H-containing gas can also be used as the nitriding agent. The N, C and H-containing gas can be, for example, an amine-based gas or an organic hydrazine-based gas. The N, C and H-containing gas can be an N-containing gas, a C-containing gas, an H-containing gas, or an N- and C-containing gas.

[0089] Examples of nitriding agents that can be used include ethylamine-based gases such as monoethylamine (C2H5NH2) gas, diethylamine ((C2H5)2NH) gas, and triethylamine ((C2H5)3N) gas; methylamine-based gases such as monomethylamine (CH3NH2) gas, dimethylamine ((CH3)2NH) gas, and trimethylamine ((CH3)3N) gas; and organic hydrazine-based gases such as monomethylhydrazine ((CH3)HN2H2) gas, dimethylhydrazine ((CH3)2N2H2) gas, and trimethylhydrazine ((CH3)2N2(CH3)H) gas. One or more of these can be used as the nitriding agent.

[0090] [Perform the specified number of times] By performing the above-described raw material supply step and reactant supply step asynchronously, i.e., alternately, a predetermined number of times (n times, where n is an integer greater than or equal to 1), a film, such as a silicon nitride film (SiN film), of a predetermined thickness can be formed on the wafer 200. The above-described cycle is preferably repeated multiple times. That is, it is preferable to make the thickness of the SiN layer formed per cycle thinner than the desired film thickness, and to repeat the above-described cycle multiple times until the thickness of the SiN film formed by stacking the SiN layers reaches the desired thickness. When a gas containing N, C, and H is used as the nitriding agent, a silicon carbonitride layer (SiCN layer), for example, can be formed in the reactant supply step. By performing the above-described cycle a predetermined number of times, a film, such as a silicon carbonitride film (SiCN film), can also be formed on the surface of the wafer 200.

[0091] (After purging and atmospheric pressure recovery) After forming a SiN film of a desired thickness on the wafer 200, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0092] (Boat unloading and wafer discharge) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafers 200, supported by the boat 217, are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After being unloaded to the outside of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer discharging).

[0093] (3) Cleaning process When the above-described substrate processing, i.e., processing of wafers 200, is performed, deposits including raw material-derived substances and substances resulting from the reaction between the raw material-derived substances and reactants (e.g., silicon nitrides such as SiN films) adhere to the surfaces of components within the processing chamber, such as the inner wall surface of the reaction tube 203, the side surfaces (outer surfaces) of the nozzles 249a-249c, and the surface of the boat 217. Therefore, as one step in the manufacturing process of a semiconductor device, after performing the above-described processing on wafers 200 a predetermined number of times (one or more times) using the above-described substrate processing apparatus, a cleaning process is performed to remove the above-described deposits (hereinafter, sometimes simply referred to as "deposits") adhering to the inside of the processing chamber. An example of a sequence for cleaning the inside of the processing chamber after processing wafers 200 will be described below, mainly with reference to FIG. 5. In the following description, the operation of each component constituting the substrate processing apparatus is controlled by the controller 121.

[0094] In the cleaning sequence of this embodiment shown in FIG. After the above-mentioned substrate processing has been performed, a step (cleaning step) of removing deposits adhering to the inside of the processing vessel is performed by supplying a first cleaning gas from one of nozzles 249a and 249b into the processing vessel and supplying an additive gas that reacts with the first cleaning gas from the other nozzle different from the one of nozzles 249a and 249b.

[0095] In the cleaning sequence shown in FIG. 5, an example is shown in which a first cleaning gas is supplied into the processing chamber 201 using the nozzle 249a as one nozzle, and an additive gas is supplied into the processing chamber 201 using the nozzle 249b as the other nozzle.

[0096] In this specification, for convenience, the above-described cleaning sequence may be expressed as follows: Similar notations will be used in the following descriptions of other aspects and modifications.

[0097] (R1: First cleaning gas + R2: Additional gas)

[0098] In addition, as in the cleaning sequence shown below, the nozzle 249b may be used as one nozzle to supply a first cleaning gas into the processing chamber 201, and the nozzle 249a may be used as the other nozzle to supply an additive gas into the processing chamber 201.

[0099] (R1: additive gas + R2: first cleaning gas)

[0100] (boat load) The empty boat 217 with deposits on its surface, i.e., the boat 217 not holding any wafers 200, is lifted by the boat elevator 115 and carried into the processing vessel with deposits on its surface, i.e., the processing chamber 201. In this state, the seal cap 219 seals the lower end of the reaction tube 203 via the O-ring 220.

[0101] (pressure and temperature regulation) After the boat loading is completed, the vacuum pump 246 evacuates (depressurizes) the processing chamber 201 to a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information (pressure adjustment). The processing chamber 201 is also heated by the heater 207 to a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 to achieve a desired temperature distribution inside the processing chamber 201 (temperature adjustment). The rotation mechanism 267 also starts rotating the boat 217. The evacuation of the processing chamber 201, the heating of the processing chamber 201, and the rotation of the boat 217 are all continued at least until the cleaning process is completed. The boat 217 does not necessarily have to be rotated.

[0102] (Cleaning step) After that, the next cleaning step is performed.

[0103] In this step, the first cleaning gas and the additive gas are supplied into the processing vessel while exhaust from the processing vessel is stopped, that is, while the exhaust system is closed.

[0104] Specifically, with the APC valve 244 fully closed and exhaust of the processing chamber 201 by the exhaust system stopped, valves 243d and 243e are opened to allow a first cleaning gas to flow into the gas supply pipe 232d and an additive gas to flow into the gas supply pipe 232e. The flow rate of the first cleaning gas is adjusted by the MFC 241d and supplied into the processing chamber 201 via the gas supply pipe 232a and the plurality of gas discharge holes 250a provided on the side surface of the nozzle 249a (first cleaning gas supply). The flow rate of the additive gas is adjusted by the MFC 241e and supplied into the processing chamber 201 via the gas supply pipe 232b, the plurality of gas discharge holes 250b1 provided on the side surface of the nozzle 249b, and the gas discharge hole 250b2 provided at the tip of the nozzle 249b (additive gas supply). At this time, the valves 243b, 243f, and 243g may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

[0105] The processing conditions for supplying the first cleaning gas and the additive gas in the cleaning step are as follows: First cleaning gas supply flow rate: 0.5 to 10 slm Additive gas supply flow rate: 0.5 to 5 slm First cleaning gas / additive gas flow rate ratio: 0.5 to 2 Inert gas supply flow rate (per gas supply pipe): 0.01 to 0.5 slm, preferably 0.01 to 0.1 slm Each gas supply time: 1 to 100 seconds, preferably 5 to 60 seconds Treatment temperature: less than 400°C, preferably 200 to 350°C is exemplified.

[0106] With the exhaust system closed, the first cleaning gas, the additive gas, and the like are supplied into the processing chamber 201, and the pressure inside the processing chamber 201 begins to rise. The pressure inside the processing chamber 201 that is ultimately reached by continuing to supply gas (ultimate pressure) is set to, for example, a pressure in the range of 1330 to 53320 Pa, and preferably 9000 to 15000 Pa.

[0107] When the pressure inside the processing chamber 201 reaches a predetermined pressure, the supply of the first cleaning gas and the additive gas into the processing chamber is stopped while exhaust from the processing chamber is stopped, thereby maintaining the first cleaning gas and the additive gas contained within the processing chamber. Specifically, with the APC valve 244 fully closed, the valves 243d and 243e are closed to stop the supply of the first cleaning gas and the additive gas into the processing chamber 201, respectively, and this state is maintained for a predetermined time. At the same time, the valves 243b, 243f, and 243g are opened to supply inert gas into the gas supply pipes 232b, 232f, and 232g. The inert gas is supplied into the processing chamber 201 via the nozzles 249a to 249c after its flow rate is adjusted by the MFCs 241b, 241f, and 241g. The inert gas is supplied to the processing chamber 201 via the nozzles 249a to 249c at the same flow rate, for example.

[0108] In the cleaning step, the processing conditions for confining the first cleaning gas and the additive gas are as follows: Inert gas supply flow rate (each gas supply pipe): 0.01 to 0.5 slm, preferably 0.01 to 0.1 slm Containment time: 10 to 200 seconds, preferably 50 to 120 seconds The other processing conditions are the same as those when the first cleaning gas and the additive gas are supplied, except that the pressure inside the processing chamber 201 continues to rise slightly due to the supply of the inert gas into the processing chamber 201.

[0109] Under the above-described processing procedures and processing conditions, for example, a fluorine-based gas is supplied as the first cleaning gas and for example, a nitrogen oxide-based gas is supplied as the additive gas, whereby the first cleaning gas and the additive gas can be mixed and reacted in the processing chamber 201. This reaction generates, for example, fluorine radicals (F * This allows generation of activated species such as fluorine-based gas (FNO), nitrosyl fluoride (FNO), etc. (hereinafter, these will be collectively referred to as FNO, etc.). As a result, a mixed gas containing fluorine-based gas and FNO, etc., is present in the processing chamber 201. The mixed gas containing fluorine-based gas and FNO, etc., comes into contact with components in the processing chamber 201, such as the inner wall of the reaction tube 203, the side surfaces of the nozzles 249a to 249c, and the surface of the boat 217. At this time, deposits adhering to the components in the processing chamber 201 can be removed by a thermochemical reaction (etching reaction). FNO, etc., promotes the etching reaction by the fluorine-based gas and increases the etching rate of the deposits, i.e., acts to assist etching.

[0110] In the cleaning step, an additive gas is supplied into the processing chamber 201 using a nozzle 249b having gas discharge holes 250b1 that open toward at least one of (i) a side surface of the nozzle 249a that is different from the installation area of ​​the gas discharge holes 250a, and (ii) a space between the side surface of the nozzle 249a that is different from the installation area of ​​the gas discharge holes 250a and the inner wall surface of the reaction tube 203. This allows FNO and the like to be preferentially generated near the nozzle 249a. As a result, the etching rate can be increased near the nozzle 249a (particularly on the back side), thereby improving etching efficiency. By increasing the etching rate near the nozzle 249a (particularly on the back side), deposits adhering to the side surface of the nozzle 249a can be efficiently removed.

[0111] Furthermore, the nozzles 249a and 249b are provided at positions adjacent to each other along the circumferential direction of the wafer 200. This allows FNO and the like to be generated preferentially and reliably near the nozzle 249a.

[0112] In the cleaning step, the nozzle 249b having a plurality of gas discharge holes 250b1 provided from one end to the other end in the wafer arrangement direction is used to supply the additive gas into the processing chamber 201. This allows FNO and the like to be preferentially generated in the vicinity of the nozzle 249a from one end to the other end in the wafer arrangement direction.

[0113] In the cleaning step, an additive gas is supplied into the processing chamber 201 using a nozzle 249b having gas discharge holes 250b1 that open toward the rear surface of the nozzle 249a. This allows FNO and the like to be preferentially generated on the rear surface side of the nozzle 249a. Therefore, it is possible to increase the etching rate on the rear surface side of the nozzle 249a, where raw materials and reactants tend to accumulate and deposits tend to adhere.

[0114] In addition, in the cleaning step, an additive gas is supplied into the processing chamber 201 using a nozzle 249b equipped with gas outlet holes 250b2. This allows FNO and the like to be preferentially generated in the upper dome space within the processing chamber 201. Therefore, the etching rate can be increased in the upper dome space where raw materials and reactants tend to stagnate and deposits tend to adhere, thereby improving the etching efficiency. As a result, deposits adhering to the inner wall surface of the ceiling of the reaction tube 203 can be efficiently removed.

[0115] The nozzle 249b for supplying the additive gas is more susceptible to etching damage than the nozzle 249a for supplying the first cleaning gas. For this reason, in the cleaning step, the additive gas is supplied into the processing chamber 201 using a nozzle 249b different from the nozzle 249a for supplying the raw material. The nozzle 249b for supplying the additive gas is detachably attached to the reaction tube 203. This reduces the possibility that etching damage to the nozzle 249b will affect the substrate processing using the nozzle 249a. For example, even if etching damage to the nozzle 249b occurs due to the intrusion or supply of the first cleaning gas into the nozzle 249b, the nozzle 249b can be easily replaced.

[0116] In the cleaning step, the nozzle 249a for supplying the raw material is used to supply the first cleaning gas into the processing chamber 201. This makes it possible to remove materials derived from the raw material adhering to the inside of the nozzle 249a and deposits formed on the inner wall surface of the nozzle 249a due to the intrusion of reactants into the nozzle 249a.

[0117] The first cleaning gas may be, for example, a gas containing halogen. The halogen-containing gas may be, for example, a fluorine-based gas. The fluorine-based gas may be, for example, fluorine (F2) gas, chlorine trifluoride (ClF3) gas, chlorine monofluoride (ClF) gas, or nitrogen trifluoride (NF3) gas. One or more of these may be used as the first cleaning gas.

[0118] As the additive gas, for example, a nitric oxide-based gas can be used. As the nitric oxide-based gas, for example, nitric oxide (NO) gas and nitrous oxide (NO) gas can be used. As the additive gas, one or more of these can be used.

[0119] As the additive gas, in addition to nitrogen oxide gas, for example, hydrogen (H2) gas, oxygen (O2) gas, isopropyl alcohol ((CH3)2CHOH) gas, methanol (CH3OH) gas, water vapor (H2O gas) can be used, and one or more of these can be used as the additive gas.

[0120] (After purging and atmospheric pressure recovery) After the cleaning of the inside of the processing vessel is completed, the APC valve 244 is opened, and an inert gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c, and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and by-products remaining in the processing chamber 201 after cleaning are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0121] (Boat unloading) Thereafter, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203. Then, the empty boat 217 is unloaded from the lower end of the reaction tube 203 to the outside of the reaction tube 203 (boat unloading). After this series of steps is completed, the substrate processing described above is resumed.

[0122] (4) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0123] (a) In the raw material supply step, while the raw material is being supplied from the nozzle 249a into the processing chamber 201 (during step A), an inert gas is discharged into the processing chamber 201 using the nozzle 249b having gas discharge holes 250b1 that open toward at least one of (i) a side surface of the nozzle 249a that is different from the area where the gas discharge holes 250a are installed, and (ii) a space between the side surface of the nozzle 249a that is different from the area where the gas discharge holes 250a are installed and the inner wall surface of the reaction tube 203. This allows the side surface of the nozzle 249a (e.g., a side surface of the nozzle 249a other than the area where the gas discharge holes 250a are installed) to be purged with the inert gas during raw material supply. As a result, it is possible to prevent raw material-derived substances from adhering to the side surface of the nozzle 249a. Furthermore, by preventing the adhesion of raw material-derived substances to the side surface of the nozzle 249a, it is possible to prevent the reactant from reacting with the raw material-derived substances attached to the side surface of the nozzle 249a in the reactant supply step. This makes it possible to prevent deposits containing raw material-derived substances and reaction products between the raw material-derived substances and the reactants from adhering to the side surface of the nozzle 249a, thereby making it possible to prevent particle generation and the like, and ultimately to prevent deterioration in the quality of the film formed on the wafer 200.

[0124] Furthermore, during the reactant supply step, while the reactant is being supplied into the processing chamber 201 through the nozzle 249c (during step B), an inert gas is discharged into the processing chamber 201 using the nozzle 249b having the gas discharge holes 250b1. This allows the side surface of the nozzle 249a to be purged with the inert gas during the reactant supply step. As a result, even if a source-derived substance adheres to the side surface of the nozzle 249a during the source-derived substance supply step, it is possible to prevent the reactant from reacting with the source-derived substance adhered to the side surface of the nozzle 249a during the reactant supply step. By preventing such a reaction, it is possible to reliably prevent the reactant between the source-derived substance and the reactant from adhering to the side surface of the nozzle 249a, thereby reliably preventing particle generation and the like.

[0125] Furthermore, in the cleaning step, an additive gas is supplied into the processing chamber 201 using the nozzle 249b having the gas discharge holes 250b1 described above. This allows FNO and the like to be preferentially generated near the nozzle 249a. Therefore, the etching rate near the nozzle 249a can be increased, and etching efficiency can be improved. As a result, deposits adhering to the side surface of the nozzle 249a can be efficiently removed.

[0126] (b) In the raw material supply step, during raw material supply, an inert gas is discharged into the processing chamber 201 using a nozzle 249b having gas discharge holes 250b1 that open toward the back surface of the nozzle 249a. This allows the back surface of the nozzle 249a, where the raw material is likely to accumulate, to be purged with the inert gas during raw material supply. As a result, it is possible to prevent the raw material from accumulating on the back surface of the nozzle 249a. By preventing the raw material from accumulating on the back surface of the nozzle 249a, it is possible to reliably prevent the raw material from adhering to the back surface of the nozzle 249a. As a result, it is possible to reliably prevent a substance containing the raw material and a reactant from adhering to the side surface of the nozzle 249a.

[0127] Furthermore, in the cleaning step, an additive gas is supplied into the processing chamber 201 using a nozzle 249b having gas discharge holes 250b1 that open toward the back surface of the nozzle 249a. This allows FNO and the like to be preferentially generated on the back surface side of the nozzle 249a. This makes it possible to increase the etching rate on the back surface side of the nozzle 249a, where raw materials and reactants tend to accumulate and deposits tend to adhere. As a result, it becomes possible to more efficiently remove deposits that have adhered to the side surface of the nozzle 249a.

[0128] (c) In the raw material supply step, the nozzle 249b having the gas discharge holes 250b2 is used to discharge the inert gas into the processing chamber 201. This allows the upper dome space in the processing chamber 201, where the raw material is likely to remain, to be efficiently purged with the inert gas during the raw material supply. As a result, it is possible to prevent the raw material from adhering to the inner wall surface of the ceiling of the reaction tube 203.

[0129] In the cleaning step, an additive gas is supplied into the processing chamber 201 using a nozzle 249b equipped with gas outlet holes 250b2. This allows FNO and the like to be preferentially generated in the upper dome space within the processing chamber 201. Therefore, the etching rate can be increased in the upper dome space where raw materials and reactants tend to stagnate and deposits tend to adhere, thereby improving the etching efficiency. As a result, deposits adhering to the inner wall surface of the ceiling of the reaction tube 203 can be efficiently removed.

[0130] (d) In the raw material supply step, the nozzle 249b, which does not have a gas discharge hole opening toward the wafer arrangement area, is used to discharge the inert gas into the processing chamber 201. This makes it possible to suppress dilution of the raw material supplied from the nozzle 249a in the processing chamber 201 during the raw material supply step. As a result, it is possible to suppress the inert gas supplied from the nozzle 249b from affecting the formation rate of the layer formed on the wafer 200 in the raw material supply step, the thickness and quality of the film finally formed on the wafer 200, and the like.

[0131] (e) In the raw material supply step, the flow rate (second flow rate) of the inert gas flowed into the gas supply pipe 232b during purging is set to be higher than the flow rate (first flow rate) of the inert gas flowed into the gas supply pipe 232b during raw material supply (during step A'). This makes it possible to efficiently purge the upper dome space in the processing chamber 201. As a result, it becomes possible to suppress the influence on film formation caused by raw materials remaining in the upper dome space in the processing chamber 201.

[0132] (f) The above-mentioned effects can be similarly obtained when a simultaneous supply method is used in the film-forming step, in which a source material and a reactant are simultaneously supplied to the wafer 200. The above-mentioned effects can also be similarly obtained when an alternating supply method is used in the cleaning step, in which a first cleaning gas and an additive gas are alternately supplied non-simultaneously.

[0133] (g) The above-mentioned effects can be similarly obtained when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the above-mentioned various raw materials, various reactants, various inert gases, various first cleaning gases, and various additive gases.

[0134] (5) Variations The substrate processing sequence in this embodiment can be modified as shown in the following variations. These variations can be combined as desired. Unless otherwise specified, the processing procedures and processing conditions for each step in each variation can be the same as the processing procedures and processing conditions for each step in the substrate processing sequence described above.

[0135] (Variation 1) As shown in the cleaning sequence below, in the cleaning step, a first cleaning gas may be supplied to one of nozzle 249a and nozzle 249b, and a second cleaning gas having a different composition (e.g., a different molecular structure) from the first cleaning gas may be supplied to the other nozzle of nozzle 249a and nozzle 249b.

[0136] (R1: First cleaning gas + R2: Second cleaning gas) (R1: Second cleaning gas + R2: First cleaning gas)

[0137] When the second cleaning gas is supplied from the nozzle 249a, the second cleaning gas supply system can be mainly configured by the gas supply pipe 232d, the MFC 241d, and the valve 243d.When the second cleaning gas is supplied from the nozzle 249b, the second cleaning gas supply system can be mainly configured by the gas supply pipe 232e, the MFC 241e, and the valve 243e.

[0138] The second cleaning gas may be, for example, a gas containing H and F (a fluorine-based gas containing H). The gas containing H and F may be, for example, hydrogen fluoride (HF) gas.

[0139] The processing procedures and conditions for supplying the first cleaning gas and the second cleaning gas may be the same as those for supplying the first cleaning gas in the above-described embodiment.

[0140] This modification also provides the same effects as the above-described embodiment. That is, by supplying the first cleaning gas or the second cleaning gas into the processing chamber 201 using the nozzle 249b, it is possible to efficiently remove deposits adhering to the side surface of the nozzle 249a. Furthermore, in this modification, multiple different types of cleaning gas (for example, two types) are used in the cleaning step. This makes it possible to more efficiently remove deposits adhering to the surfaces of components in the processing vessel.

[0141] (Variation 2) As shown in the cleaning sequence below, in the cleaning step, a first cleaning gas or a second cleaning gas may be supplied to nozzle 249b, which is one of nozzles 249a and 249b, and an inert gas may be supplied from nozzle 249a, which is the other nozzle different from nozzle 249b, into the processing chamber 201. The processing procedure and processing conditions for supplying the first cleaning gas or the second cleaning gas may be the same as those for supplying the first cleaning gas in the cleaning step of the above-mentioned aspect.

[0142] (R1: inert gas + R2: first cleaning gas) (R1: inert gas + R2: second cleaning gas)

[0143] This modification also provides the same effect as the above-described embodiment. That is, by supplying the first cleaning gas or the second cleaning gas into the processing chamber 201 using the nozzle 249b, it is possible to efficiently remove deposits attached to the side surface of the nozzle 249a.

[0144] (Variation 3) As shown in the cleaning sequence below, in the cleaning step, the first cleaning gas or the second cleaning gas may be supplied to one of the nozzles 249a to 249c, and the additive gas or the second cleaning gas may be supplied to another nozzle different from the one of the nozzles 249a to 249c. The process procedures and conditions for supplying the first cleaning gas or the second cleaning gas may be the same as those for supplying the first cleaning gas in the cleaning step of the above-mentioned embodiment. Furthermore, the process procedures and conditions for supplying the additive gas or the inert gas may be the same as those in the cleaning step of the above-mentioned embodiment.

[0145] (R1: inert gas + R2: first cleaning gas + R3: additive gas) (R1: inert gas + R2: second cleaning gas + R3: additive gas) (R1: inert gas + R2: additive gas + R3: first cleaning gas) (R1: inert gas + R2: additive gas + R3: second cleaning gas)

[0146] This modification also provides the same effects as those of the above-described embodiment. That is, by supplying any one of the first cleaning gas, the second cleaning gas, and the additive gas into the processing chamber 201 using the nozzle 249b, FNO and the like can be preferentially generated near the nozzle 249a. This makes it possible to efficiently remove deposits attached to the side surface of the nozzle 249a.

[0147] Furthermore, the cleaning sequence may be changed as follows.

[0148] (R1: First cleaning gas + R2: Inert gas + R3: Additive gas) (R1: Second cleaning gas + R2: Inert gas + R3: Additive gas)

[0149] (Variation 4) 6, in addition to the first to third supply units, nozzles 249d and 249e may be provided as fourth and fifth supply units, respectively, in the processing chamber 201. The nozzles 249d and 249e are also referred to as fourth and fifth nozzles, respectively.

[0150] A fourth discharge hole for discharging gas is provided on the side surface of nozzle 249d. The configuration of the fourth discharge hole can be the same as the configuration of gas discharge hole 250a provided on the side surface of nozzle 249a described above.

[0151] The nozzle 249e is detachably attached to the reaction tube 203. A fifth outlet hole for discharging gas is provided on a side surface of the nozzle 249e. The fifth outlet hole is open to at least one of (i) a surface of the side surface of the nozzle 249d in a range different from the installation range of the fourth outlet hole, and (ii) a space between a surface of the nozzle 249d in a range different from the installation range of the fourth outlet hole and the inner wall surface of the reaction tube 203. The other configurations can be the same as those of the nozzle 249b described above.

[0152] In this modification, the raw material supply system is configured to supply raw materials into the processing chamber 201 through the nozzles 249a and 249d, and the inert gas supply system is configured to supply an inert gas into the processing chamber 201 through the nozzles 249b and 249e. The first cleaning gas supply system is configured to supply a first cleaning gas into the processing chamber 201 through the nozzles 249a and 249d, and the additive gas supply system is configured to supply an additive gas into the processing chamber 201 through the nozzles 249b and 249e.

[0153] This modification also provides the same effects as those of the above-described embodiments and modifications. Specifically, by discharging an inert gas from the nozzles 249b and 249e during raw material supply or reactant supply, the side surfaces of the nozzles 249a and 249d (e.g., the surfaces of the side surfaces of the nozzles 249a and 249d other than the areas where the first discharge holes are provided and the areas where the fourth discharge holes are provided) can be purged with the inert gas. Furthermore, by supplying an additive gas into the processing chamber 201 from the nozzles 249b and 249e during cleaning, the etching rate near the nozzles 249a and 249d can be increased, thereby improving etching efficiency.

[0154] Alternatively, the nozzles 249b and 249e may be configured to supply the first cleaning gas or the second cleaning gas.

[0155] (Variation 5) 7, in addition to the first to third supply units, a nozzle 249f may be provided as a sixth supply unit in the processing chamber 201. The nozzle 249f is also referred to as a sixth nozzle. A sixth discharge hole for discharging gas is provided on a side surface of the nozzle 249f. The configuration of the sixth discharge hole may be the same as the configuration of the gas discharge hole 250a provided on the side surface of the nozzle 249a described above.

[0156] In this modification, in addition to the second outlet hole, a seventh outlet hole is further provided on the side surface of the nozzle 249b. The seventh outlet hole is open to face at least one of (i) a surface of the side surface of the nozzle 249f in a range different from the installation range of the sixth outlet hole, and (ii) a space between the surface of the nozzle 249f in a range different from the installation range of the sixth outlet hole and the inner wall surface of the reaction tube 203. The other configuration of the seventh outlet hole can be similar to the configuration of the second outlet hole (gas outlet hole 250b1) provided on the side surface of the nozzle 249b described above.

[0157] In this modification, the raw material supply system is configured to supply raw materials into the processing chamber 201 through the nozzles 249a and 249f. The first cleaning gas supply system is configured to supply a first cleaning gas into the processing chamber 201 through the nozzles 249a and 249f.

[0158] This modification also provides the same effects as the above-described embodiments and modifications. Specifically, by discharging an inert gas from the second and seventh outlets of nozzle 249b during raw material supply or reactant supply, the side surfaces of nozzles 249a and 249f (e.g., the surfaces of nozzles 249a and 249f other than the areas where the first and sixth outlets are provided) can be purged with the inert gas. Furthermore, by supplying the first cleaning gas, the second cleaning gas, or the additive gas from the second and seventh outlets of nozzle 249b during cleaning, the etching rate near nozzles 249a and 249f can be increased, thereby improving etching efficiency.

[0159] (Variation 6) For example, as shown in FIG. 8 , an eighth discharge hole may be further provided in addition to the second discharge hole on the side surface of the nozzle 249b. The eighth discharge hole is opened in a range of the side surface of the nozzle 249b that is different from the position facing the wafer arrangement area and different from the range of the second discharge hole. More preferably, the eighth discharge hole is opened so as not to face either a range of the side surface of the nozzle 249a that is different from the range of the first discharge hole or a space between the range of the side surface that is different from the range of the first discharge hole and the inner wall surface of the reaction tube 203. For example, as shown in FIG. 8 , the eighth discharge hole is provided on a side surface of the nozzle 249b that is approximately opposite to the gas discharge hole 250b1 in the circumferential direction and opens toward the inner wall surface of the reaction tube 203, thereby enabling gas to be discharged toward the inner wall surface of the reaction tube 203. The other configuration of the eighth discharge hole may be similar to the configuration of the second discharge hole provided on the side surface of the nozzle 249b described above.

[0160] This modification also provides the same effects as those of the above-described embodiment. Furthermore, this modification can suppress adhesion of raw material-derived substances to the inner wall surface of the reaction tube 203 during raw material supply, and can suppress adhesion of substances generated by the reaction between the raw material-derived substances and the reactants to the inner wall surface of the reaction tube 203. Furthermore, this modification can increase the etching rate near the inner wall surface of the reaction tube 203 during cleaning, and can efficiently remove deposits attached to the inner wall surface of the reaction tube 203.

[0161] <Other Aspects of the Present Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0162] For example, the present disclosure can be applied to the formation of a film containing, as a main element, a semiconductor element such as silicon (Si) or germanium (Ge), or a metal element such as zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), tungsten (W), or ruthenium (Ru) on a substrate. The processing procedures and processing conditions for supplying the film-forming agent can be the same as those in each step of the above-described embodiment. In these cases, the same effects as those of the above-described embodiment can be obtained.

[0163] Furthermore, for example, the present disclosure can also be applied to the case where a film containing elements such as oxygen (O), carbon (C), nitrogen (N), and boron (B) is formed on a substrate. For example, the present disclosure can also be applied to the case where a silicon oxide film (SiO film), a silicon oxycarbide film (SiOC film), a silicon oxycarbonitride film (SiOCN film), a silicon carbonitride film (SiCN film), a silicon boronitride film (SiBN film), a silicon boron carbonitride film (SiBCN film), or the like is formed on a substrate by the above-mentioned processing sequence using, as reactants, the above-mentioned nitrogen-containing gas, oxygen-containing gas such as HO gas, hydrogen peroxide (HO) gas, hydrogen (H) gas + oxygen (O) gas, or ozone (O) gas, carbon-containing gas such as ethylene (CH) gas, acetylene (CH) gas, or propylene (CH) gas, nitrogen- and carbon-containing gas such as triethylamine ((CH)N) gas or trimethylamine ((CH)N), or boron-containing gas such as diborane (BH) gas or trichloroborane (BCl) gas. The processing procedures and processing conditions for supplying the film-forming agent may be the same as those in the steps of the above-described embodiment, and in these cases, the same effects as those of the above-described embodiment can be obtained.

[0164] In this specification, the description of two gases together, such as "H gas + O gas," means a mixed gas of H gas and O gas. When a mixed gas is supplied, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be supplied separately from different supply pipes into the processing chamber 201 and mixed (postmixed) in the processing chamber 201.

[0165] It is preferable that the recipes used for each process are individually prepared according to the process content and recorded and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from the multiple recipes recorded and stored in the storage device 121c. This makes it possible to form films with various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing apparatus. It also reduces the burden on the operator, prevents operational errors, and enables each process to be started quickly.

[0166] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe already installed in the substrate processing apparatus, for example. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the modified recipe is recorded. Alternatively, an existing recipe already installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0167] In the above-described embodiment, an example has been described in which each of the first to eighth discharge holes is configured to include a plurality of discharge holes. The present disclosure is not limited to the above-described embodiment, and for example, at least one of the first to eighth discharge holes may be configured to include one or more slit-shaped holes provided on the side surface of the nozzle so as to extend in the extension direction of the nozzle (i.e., the arrangement direction of the substrate).

[0168] In the above-described embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied, for example, to a case where a film is formed using a single-wafer substrate processing apparatus that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied to a case where a film is formed using a substrate processing apparatus having a cold-wall processing furnace.

[0169] When using these substrate processing apparatuses, each process can be performed using the same processing procedures and conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0170] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example. [Explanation of symbols]

[0171] 200 wafers (substrates)

Claims

1. a processing vessel in which a substrate is accommodated; a first nozzle having a first discharge hole formed on a side surface thereof, the first discharge hole opening toward a substrate arrangement area in the processing vessel where substrates are arranged; a second nozzle having a second discharge hole provided in a side surface thereof, the second discharge hole opening toward at least one of a first surface, which is a surface in a range different from an installation range of the first discharge hole among the side surfaces of the first nozzle, and a space between a side surface of the first nozzle opposite to an installation range of the first discharge hole in a radial direction of the first nozzle among the side surfaces of the first nozzle, and an inner wall surface of the processing vessel; a source gas supply system configured to supply a source gas into the processing chamber through the first nozzle; an inert gas supply system configured to supply the inert gas into the processing vessel through the second nozzle so as to purge at least one of the first surface and the space with the inert gas. Substrate processing equipment.

2. In the substrate arrangement region, a plurality of the substrates are arranged at predetermined intervals in a direction perpendicular to the surfaces of the substrates, The first nozzles and the second nozzles are provided along an arrangement direction of the substrates and are provided adjacent to each other along a circumferential direction of the substrates. The substrate processing apparatus according to claim 1 .

3. 2. The substrate processing apparatus according to claim 1, wherein the second discharge hole is arranged to discharge the inert gas toward a side of the side of the first nozzle opposite to the installation range of the first discharge hole in the radial direction of the first nozzle.

4. The substrate processing apparatus according to claim 1 , wherein the second nozzle does not have a discharge hole at a position facing the substrate arrangement area.

5. The substrate processing apparatus according to claim 1 , wherein the second nozzle is detachable from the processing vessel.

6. 2. The substrate processing apparatus of claim 1, further comprising: a control unit configured to be able to control the source gas supply system and the inert gas supply system so that the inert gas is supplied into the processing vessel while the source gas is supplied into the processing vessel.

7. In the substrate arrangement region, a plurality of the substrates are arranged at predetermined intervals in a direction perpendicular to the surfaces of the substrates, The substrate processing apparatus according to claim 1 , wherein the second nozzle further comprises an upper discharge hole that opens toward a space above the substrate arrangement area.

8. The substrate processing apparatus according to claim 7 , wherein the upper discharge hole is provided at a tip of the second nozzle.

9. The substrate processing apparatus according to claim 7 , wherein an opening area of ​​the upper discharge hole is larger than an opening area of ​​the second discharge hole.

10. a third nozzle having a third discharge hole provided on a side surface thereof; a reactive gas supply system configured to supply a reactive gas into the processing chamber through the third nozzle; a control unit configured to be able to control the source gas supply system, the reactive gas supply system, and the inert gas supply system so as to perform a process of forming a film on the substrate accommodated in the processing vessel by performing a cycle including (a) a process of supplying the source gas into the processing vessel and (b) a process of supplying the reactive gas into the processing vessel a predetermined number of times, and to supply the inert gas from the second nozzle at a first flow rate in (a), and to supply the inert gas from the second nozzle at a second flow rate greater than the first flow rate between (a) and (b); The substrate processing apparatus according to claim 7 , further comprising:

11. The substrate processing apparatus of claim 1 , further comprising a first cleaning gas supply system configured to supply a first cleaning gas to one of the first nozzle and the second nozzle.

12. 12. The substrate processing apparatus according to claim 11, further comprising an additive gas supply system configured to supply an additive gas that reacts with the first cleaning gas to the other nozzle of the first nozzle and the second nozzle, which is different from the one nozzle.

13. 12. The substrate processing apparatus according to claim 11, further comprising a second cleaning gas supply system configured to supply a second cleaning gas having a composition different from that of the first cleaning gas to the other of the first nozzle and the second nozzle, the second cleaning gas having a composition different from that of the other of the first nozzle and the second nozzle.

14. a third nozzle having a third discharge hole provided on a side surface thereof; a reactive gas supply system configured to supply a reactive gas into the processing chamber through the third nozzle; a first cleaning gas supply system configured to supply a first cleaning gas to any one of the first nozzle, the second nozzle, and the third nozzle; an additive gas supply system configured to supply an additive gas that reacts with the first cleaning gas to another nozzle different from any one of the first nozzle, the second nozzle, and the third nozzle; The substrate processing apparatus of claim 1 , further comprising:

15. a fourth nozzle having a fourth discharge hole formed on a side surface thereof and opening toward the substrate arrangement area; a fifth nozzle having a fifth discharge hole provided on a side surface thereof, the fifth discharge hole opening toward at least one of a surface of the fourth nozzle in a range different from a range where the fourth discharge hole is installed and a space between the surface in a range different from the range where the fourth discharge hole is installed and the inner wall surface of the processing vessel, the source gas supply system is configured to supply the source gas into the processing vessel via the first nozzle and the fourth nozzle; The inert gas supply system is configured to supply the inert gas into the processing vessel through the second nozzle and the fifth nozzle. The substrate processing apparatus according to claim 1 .

16. a sixth nozzle having a sixth discharge hole formed on a side surface thereof and opening toward the substrate arrangement area; a seventh discharge hole is further provided on the side surface of the second nozzle, the seventh discharge hole opening toward at least one of a surface of the side surface of the sixth nozzle in a range different from the installation range of the sixth discharge hole and a space between the surface in a range different from the installation range of the sixth discharge hole and the inner wall surface of the processing vessel; The source gas supply system is configured to supply the source gas into the processing chamber through the first nozzle and the sixth nozzle. The substrate processing apparatus according to claim 1 .

17. 2. The substrate processing apparatus according to claim 1, wherein the side surface of the second nozzle further has an eighth discharge hole that opens into a surface in a range different from the range facing the substrate arrangement area and different from the installation range of the second discharge hole.

18. a first nozzle having a first discharge hole on a side surface thereof, the first discharge hole opening toward a substrate arrangement area in which substrates are arranged in a processing vessel; a first surface being a surface in a range different from the installation range of the first discharge hole; and a second discharge hole on a side surface thereof, the second discharge hole opening toward at least one of a first surface being a surface in a range different from the installation range of the first discharge hole, and a space between a side surface of the first nozzle opposite to the installation range of the first discharge hole in a radial direction of the first nozzle and an inner wall surface of the processing vessel; a gas nozzle connected to an inert gas supply system configured to supply an inert gas so as to purge at least one of the first surface and the space with the inert gas;

19. (a) supplying a source gas into a processing vessel through a first nozzle having a first outlet hole formed on a side surface thereof, the first outlet hole opening toward a substrate arrangement region in the processing vessel where substrates are arranged; (a') in (a), supplying the inert gas through a second nozzle different from the first nozzle, the second nozzle having a second discharge hole on its side surface that opens toward at least one of a first surface, which is a surface of the side surface of the first nozzle in a range different from an installation range of the first discharge hole, and a space between a side surface of the first nozzle opposite to the installation range of the first discharge hole in a radial direction of the first nozzle and an inner wall surface of the processing vessel, so as to purge at least one of the first surface and the space with the inert gas; A method for manufacturing a semiconductor device having the above structure.

20. (a) supplying a source gas into a processing vessel through a first nozzle having a first outlet hole formed on a side surface thereof, the first outlet hole opening toward a substrate arrangement region in which substrates are arranged within the processing vessel; (a') in (a), supplying the inert gas through a second nozzle different from the first nozzle, the second nozzle having a second discharge hole formed in the side surface thereof, the second discharge hole opening toward at least one of a first surface, which is a surface of the side surface of the first nozzle in a range different from an installation range of the first discharge hole, and a space between a side surface of the first nozzle opposite to an installation range of the first discharge hole in a radial direction of the first nozzle and an inner wall surface of the processing vessel, so as to purge at least one of the first surface and the space with the inert gas; A program that causes a computer to execute the above in a substrate processing apparatus.

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