Semiconductor device manufacturing method, nozzle cleaning method, substrate processing apparatus, and program

Abstract

To reduce film thickness fluctuations in the deposition process by effectively removing residual elements after cleaning.SOLUTION: The method comprises the steps of (a) supplying a cleaning gas to at least one nozzle of the plurality of nozzles after the substrate is processed and carried out in a reaction tube having a plurality of nozzles, (b) supplying a gas containing hydrogen and oxygen to at least one nozzle where the step (a) was performed, and (c) carrying out the next substrate in the reaction tube after the step (b).SELECTED DRAWING: Figure 1

Description

[Technical field]

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

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

[0003] [Patent Document 1] JP 2016-157871 A Summary of the Invention [Problem to be solved by the invention]

[0004] In the operation of semiconductor manufacturing equipment, as film formation processes are repeated, the accumulated film in the reaction chamber may peel off due to stress, causing problems such as particles. Therefore, when a certain amount of film accumulates, cleaning may be performed to remove the film. In recent years, gas cleaning, which uses reactive gas to remove the accumulated film, has been used as a cleaning method.

[0005] As the cleaning gas, there is a method of using a gas containing fluorine (F), such as F2 or NF3. In this method, elements such as fluorine contained in the cleaning gas remain after cleaning is completed, and may become a factor hindering the film formation process. In this case, problems such as film thickness fluctuations may occur in the film formation process before and after cleaning. To address this problem, measures such as removing the remaining elements by treatment using NH3 gas or coating a stack of accumulated films to contain the remaining elements may be taken.

[0006] The present disclosure provides a means for effectively removing residual elements after cleaning, thereby reducing film thickness variations in film formation processes. [Means for solving the problem]

[0007] According to one aspect of the present disclosure, After the substrate is processed in the reaction tube having a plurality of nozzles and removed, (a) supplying a cleaning gas to at least one of the plurality of nozzles; (b) supplying a gas comprising hydrogen and oxygen to the at least one nozzle where step (a) was performed; (c) after the step (b), loading a next substrate into the reaction tube; The present invention provides a technique having the following features: Effect of the Invention

[0008] According to the present disclosure, by effectively removing residual elements after cleaning, it is possible to reduce film thickness variations in a film formation process. [Brief description of the drawings]

[0009] [Figure 1] 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 portion in vertical cross section. [Diagram 2] 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, showing a processing furnace portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 2 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in one embodiment of the present disclosure, showing a control system of the controller in a block diagram. [Figure 4] 13 is a graph showing the results of film formation stability in the comparative examples. [Diagram 5] 1 is a graph showing the results of film formation stability in Examples. [Figure 6] FIG. 4 is a schematic diagram showing residual fluorine deactivation in a comparative example. [Figure 7] FIG. 2 is a schematic diagram showing residual fluorine deactivation in an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described with reference to the drawings as appropriate. Note that all of the drawings used in the following description are schematic, and the dimensional relationship between elements on the drawings, the ratio of each element, etc. do not necessarily match the actual ones. Furthermore, the dimensional relationship between elements, the ratio of each element, etc. do not necessarily match between multiple drawings.

[0011] In this specification, the term "wafer" may refer to the wafer itself or a laminate of the wafer and a predetermined layer or film formed on the surface thereof. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In this specification, the term "form a predetermined layer on the wafer" may refer to 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. In this specification, the term "substrate" is synonymous with the term "wafer". In addition, the wafer or substrate on which the above-mentioned predetermined layer or film is formed is referred to as a "semiconductor device".

[0012] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0013] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with an open upper end and a closed lower end. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a seal member. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in a cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be capable of accommodating a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0014] In the processing chamber 201, nozzles 249a, 249b, and 249c as a first supply unit, a second supply unit, and a third supply unit are provided so as to penetrate a side wall of the manifold 209, respectively. The nozzles 249a, 249b, and 249c are also referred to as a first nozzle, a second nozzle, and a third nozzle, respectively. The nozzles 249a, 249b, and 249c are each made of a heat-resistant material that is a nonmetallic material such as quartz or SiC. The nozzles 249a, 249b, and 249c are each configured as a shared nozzle used to supply multiple types of gases.

[0015] Gas supply pipes 232a, 232b, and 232c serving as first, second, and third pipes are connected to the nozzles 249a, 249b, and 249c, respectively. The gas supply pipes 232a, 232b, and 232c are configured as shared pipes used to supply a plurality of types of gas. Mass flow controllers (MFCs) 241a, 241b, and 241c serving as flow rate controllers (flow rate control parts) and valves 243a, 243b, and 243c serving as opening / closing valves are provided on the gas supply pipes 232a, 232b, and 232c, in this order from the upstream side of the gas flow.

[0016] Gas supply pipes 232d, 232e, 232f, 232g, and 232n are connected to the gas supply pipe 232a downstream of the valve 243a in this order. MFCs 241d, 241e, 241f, 241g, and 241n and valves 243d, 243e, 243f, 243g, and 243n are provided in the gas supply pipes 232d, 232e, 232f, 232g, and 232n in this order from the upstream side of the gas flow. A second heater 207a is attached to the gas supply pipes 232d and 232e downstream of the valves 243d and 243e.

[0017] Gas supply pipes 232h, 232i, 232j, and 232o are connected in this order to the gas supply pipe 232b downstream of the valve 243b. MFCs 241h, 241i, 241j, and 241o and valves 243h, 243i, 243j, and 243o are provided in the gas supply pipes 232h, 232i, 232j, and 232o in this order from the upstream side of the gas flow. A second heater 207b is attached to the gas supply pipes 232b and 232h downstream of the valves 243b and 243h.

[0018] Gas supply pipes 232k, 232l, 232m, and 232p are connected in this order to the gas supply pipe 232c downstream of the valve 243c. MFCs 241k, 241l, 241m, and 241p and valves 243k, 243l, 243m, and 243p are provided in the gas supply pipes 232k, 232l, 232m, and 232p in this order from the upstream side of the gas flow. A second heater 207c is attached to the gas supply pipes 232c and 232k downstream of the valves 243c and 243k.

[0019] The gas supply pipes 232a to 232p are made of a metal material. The material of the manifold 209 described above, and the material of the seal cap 219, the rotating shaft 255, and the exhaust pipe 231 described below may be the same as that of the gas supply pipes 232a to 232m.

[0020] As shown in FIG. 2, the nozzles 249a, 249b, and 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafer 200. That is, the nozzles 249a, 249b, and 249c are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged, so as to extend along the wafer arrangement region. Gas supply holes 250a, 250b, and 250c for supplying gas are provided on the side of the nozzles 249a, 249b, and 249c, respectively. The gas supply holes 250a, 250b, and 250c are each open toward the center of the wafer 200 in a plan view, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a, 250b, and 250c are provided from the lower part to the upper part of the reaction tube 203.

[0021] From the gas supply pipe 232a, a raw material gas is supplied via the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. The raw material gas refers to a raw material in a gaseous state, for example, a gas obtained by vaporizing a raw material in a liquid state at room temperature and normal pressure, or a raw material in a gaseous state at room temperature and normal pressure.

[0022] A first reactive gas is supplied from the gas supply pipes 232b, 232d, and 232k into the processing chamber 201 via the MFCs 241b, 241d, and 241k, the valves 243b, 243d, and 243k, and the nozzles 249b, 249a, and 249c, respectively.

[0023] From the gas supply pipes 232c, 232e, and 232h, the second reactive gas is supplied into the processing chamber 201 via the MFCs 241c, 241e, and 241h, the valves 243c, 243e, and 243h, and the nozzles 249c, 249a, and 249b, respectively. The second reactive gas may be a gas having a different molecular structure from the first reactive gas, or may be a gas having the same molecular structure as the first reactive gas. In the following description, an example in which the second reactive gas is a gas having a different molecular structure from the first reactive gas will be described.

[0024] Cleaning gas is supplied from the gas supply pipes 232f, 232i, and 232l into the processing chamber 201 via the MFCs 241f, 241i, and 241l, the valves 243f, 243i, and 243l, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c, respectively.

[0025] Additive gases are supplied from the gas supply pipes 232g, 232j, and 232m into the processing chamber 201 via the MFCs 241g, 241j, and 241m, the valve 243g, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c, respectively.

[0026] From the gas supply pipes 232n, 232o, and 232p, an inert gas such as nitrogen (N2) gas is supplied into the processing chamber 201 via the MFCs 241n, 241o, and 241p, the valves 243n, 243o, and 243p, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c. The N2 gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0027] A source gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, the valve 243a, and the nozzle 249a. A first reactive gas supply system is mainly composed of the gas supply pipes 232b, 232d, and 232k, the MFCs 241b, 241d, and 241k, the valves 243a, 243b, and 243c, and the nozzles 249a, 249b, and 249c. A second reactive gas supply system is mainly composed of the gas supply pipes 232c, 232e, and 232h, the MFCs 241c, 241e, and 241h, the valves 243c, 243e, and 243h, the gas supply pipes 232c, 232a, and 232b, and the nozzles 249c, 249a, and 249b. The first reactive gas supply system and the second reactive gas supply system may be collectively considered as a reactive gas supply system. A cleaning gas supply system is mainly composed of the gas supply pipes 232f, 232i, and 232l, the MFCs 241f, 241i, and 241l, and the valves 243f, 243i, and 243l. The gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c may also be included in the cleaning gas supply system. An additive gas supply system is mainly composed of the gas supply pipes 232g, 232j, and 232m, the MFCs 241g, 241j, and 241m, the valves 243g, 243j, and 243m, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c. An inert gas supply system is mainly configured by the gas supply pipes 232n, 232o, and 232p, the MFCs 241n, 241o, and 241p, the valves 243n, 243o, and 241p, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c.

[0028] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243p and the MFCs 241a-241p are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a-232p, respectively, and is configured such that the supply operation of various gases into the gas supply pipes 232a-232p, i.e., the opening and closing operation of the valves 243a-243p and the flow rate adjustment operation by the MFCs 241a-241p, are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or split type integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232p, etc., in units of integrated units, and is configured such that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of integrated units.

[0029] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, i.e., along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation, and further, to be able to adjust the pressure in the processing chamber 201 by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation. 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.

[0030] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS, and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217, which will be described later. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers (transports) the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219. A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is transported out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that contacts the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0031] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0032] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0033] 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.

[0034] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), and the like. A control program for controlling the operation of the substrate processing apparatus, a process recipe describing a procedure and conditions for film formation described later, and a cleaning recipe describing a procedure and conditions for cleaning described later are readably stored in the storage device 121c. The process recipe is a combination of procedures for film formation described later that are combined to obtain a predetermined result by making the controller 121 execute the procedures for film formation described later, and functions as a program. The cleaning recipe is a combination of procedures for cleaning described later that are combined to obtain a predetermined result by making the controller 121 execute the procedures for cleaning described later, and functions as a program. Hereinafter, the process recipe, cleaning recipe, control program, and the like are collectively referred to simply as a program. In addition, the process recipe and cleaning recipe are also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily stored.

[0035] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241p, valves 243a to 243p, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, second heaters 207a to 207c, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0036] 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 an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be capable of controlling the flow rate adjustment operation of various gases by the MFCs 241a to 241p, the opening and closing operations of the valves 243a to 243p, 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 temperature adjustment operation of the second heaters 207a to 207c, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc., in accordance with the contents of the read recipe.

[0037] The controller 121 as the control unit described above is configured to be capable of controlling the transport mechanism, the cleaning gas supply system which supplies the cleaning gas, and the reaction gas supply system which supplies the gas containing hydrogen and oxygen so as to perform the following processes: (a) a process of supplying a cleaning gas to the at least one nozzle after processing and removing a substrate (wafer 200) from the reaction tube 203; (b) a process of supplying a gas containing hydrogen and oxygen to the at least one nozzle in which the process (a) has been performed; and (c) a process of loading the next substrate (wafer 200) into the reaction tube 203 after the process (b).

[0038] The controller 121 executes the above-mentioned program stored in the external storage device 123, i.e., (a) a step of supplying a cleaning gas to at least one of a plurality of nozzles 249a, 249b, and 249c after a substrate (wafer 200) is processed in a reaction tube 203 having the plurality of nozzles 249a, 249b, and 249c and unloaded therefrom; (b) supplying a gas comprising hydrogen and oxygen to the at least one nozzle where step (a) has been performed; (c) after the step (b), loading a next substrate (wafer 200) into the reaction tube 203; A program for causing a substrate processing apparatus to execute the above by a computer. The program can be configured by installing the program in 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. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0039] (2) Manufacturing method of semiconductor device The method for manufacturing a semiconductor device according to the present disclosure using the above-mentioned substrate processing apparatus includes: After processing the substrate (wafer 200) in the reaction tube 203 having a plurality of nozzles 249a, 249b, and 249c and removing it, (a) supplying a cleaning gas to at least one of the plurality of nozzles 249a, 249b, and 249c; (b) supplying a gas comprising hydrogen and oxygen to the at least one nozzle where step (a) was performed; (c) after the step (b), loading a next substrate (wafer 200) into the reaction tube 203; has.

[0040] Here, the "plurality of nozzles" in the above manufacturing method refers to three nozzles in the above-mentioned substrate processing apparatus, but is not particularly limited as long as it is two or more nozzles.

[0041] (2-1) Processing of the substrate (wafer 200) In the above manufacturing method, the processing of the substrate (wafer 200) in the reaction tube 203 prior to the step (a) may be, for example, Step 1: supplying a source gas to the wafer 200 in the reaction tube 203 through a gas supply pipe 232a and a nozzle 249a; Step 2: after stopping the supply of the source gas into the reaction tube 203, the reaction tube 203 is evacuated to a vacuum while supplying a purge gas through the gas supply pipe 232n and the nozzle 249a to remove the source gas remaining in the processing chamber; Step 3 of supplying a first reaction gas to the wafer 200 in the reaction tube 203 through the gas supply pipe 232b and the nozzle 249b while supplying a second reaction gas to the wafer 200 in the reaction tube 203 through the gas supply pipe 232c and the nozzle 249c; Step 4: after stopping the supply of the first and second reaction gases into the reaction tube 203, evacuating the reaction tube 203 while supplying N2 gas as a purge gas through the gas supply pipes 232o, 232p and the nozzles 249b, 249c to remove the first and second reaction gases remaining in the process chamber; By performing the above non-simultaneous cycle a predetermined number of times (n times, n is an integer equal to or greater than 1), a film formation process can be performed in which a film containing a predetermined element is formed on the wafer 200. The exhaust process in steps 2 and 4 is performed through the exhaust pipe 231 from the exhaust port 231a.

[0042] As the source gas, for example, a halosilane-based gas containing Si as the main element (predetermined element) constituting the film and a halogen element is used. Halosilane is a silane having a halogen group. The halogen group includes a chloro group, a fluoro group, a bromo group, an iodine group, and the like. That is, the halogen group includes a halogen element such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). As the halosilane-based gas, for example, a source gas containing Si and Cl, that is, a chlorosilane-based gas, can be used. The chlorosilane-based gas acts as a Si source. As the chlorosilane-based gas, for example, hexachlorodisilane (Si2Cl6, abbreviated as HCDS) gas can be used. The HCDS gas is a gas containing an element (Si) that becomes solid by itself under the above-mentioned processing conditions, that is, a gas that can deposit a film by itself under the above-mentioned processing conditions.

[0043] The first reactive gas may be, for example, a hydrogen (H)-containing gas. The H-containing gas may be, for example, a hydrogen (H2) gas or a gas containing activated hydrogen.

[0044] The second reactive gas may be, for example, an oxygen (O)-containing gas. Examples of the O-containing gas include oxygen (O2) gas, water (H2O) gas, ozone (O3) gas, and gas containing activated oxygen.

[0045] The above-mentioned film formation process is expressed as follows. Note that "P / V" represents the purging process and the exhaust process in step 2 and step 4. (Source gas → P / V → First reactant gas + Second reactant gas → P / V) × n

[0046] (2-2) Cleaning process In the above manufacturing method, the cleaning process in the step (a) can be performed, for example, by supplying a cleaning gas into the reaction tube 203 from at least one of the nozzles 249a, 249b, and 249c. As the cleaning gas, for example, a fluorine (F)-containing gas can be used. As the fluorine-containing gas, for example, a fluorine (F2) gas or a nitrogen trifluoride (NF3) gas can be used. In the following, an example in which F2 gas is used as the cleaning gas will be described.

[0047] For example, when the raw material gas is supplied from the nozzle 249a, the cleaning gas can be supplied from the gas supply pipe 232f through the nozzle 249a. In this case, during the step (a), it is preferable not to supply the cleaning gas to the other nozzles 249b and 249c. In this way, when using a nozzle made of quartz, for example, etching by the fluorine-containing gas can be suppressed in the nozzle that does not flow the cleaning gas, and as a result, the life of the nozzle can be extended.

[0048] On the other hand, during the step (a), it is preferable to set the amount of gas supplied to the other nozzles 249b and 249c to which no cleaning gas is supplied to substantially zero. In this way, the cleaning gas supplied from the nozzle 249a flows into the other nozzles 249b and 249c, making it possible to perform a cleaning process for the nozzles to which no cleaning gas is supplied.

[0049] Moreover, the step (a) can be performed by supplying the cleaning gas into the reaction tube 203 from all of the nozzles 249a, 249b, and 249c. That is, by supplying the cleaning gas into the reaction tube 203 through the gas supply pipes 232f, 232i, and 232l and the nozzles 249a, 249b, and 249c, respectively, the uniformity of the cleaning process in the reaction tube 203 can be improved. In this case, the cleaning gas may be simultaneously supplied into the reaction tube 203 from all of the nozzles 249a, 249b, and 249c. In this way, by simultaneously supplying the cleaning gas from all of the nozzles 249a, 249b, and 249c, it is possible to prevent residual fluorine and reaction products (e.g., HF) generated in the step (b) described later from entering nozzles that do not supply the cleaning gas and causing fluorine to remain. At this time, if there is a period when cleaning gas is being supplied into the reaction tube 203 from all of the nozzles 249a, 249b, 249c, the timings at which the cleaning gas supply starts and ends at each nozzle do not have to be the same. However, from the viewpoint of preventing residual fluorine, HF, etc. from entering other nozzles, it is desirable to have the timings at which the cleaning gas supply ends at each nozzle be the same, and it is even more desirable to have the timings at which the cleaning gas starts be the same.

[0050] Among the multiple nozzles, it is desirable to supply additive gas to the nozzle in which the step (a) has been performed. For example, when cleaning gas is supplied from nozzle 249a, additive gas is supplied into reaction tube 203 via gas supply pipe 232g and nozzle 249a. When cleaning gas is supplied from nozzle 249b, additive gas is supplied into reaction tube 203 via gas supply pipe 232j and nozzle 249b. When cleaning gas is supplied from nozzle 249c, additive gas is supplied into reaction tube 203 via gas supply pipe 232m and nozzle 249c.

[0051] The additive gas used is a nitric oxide gas containing nitrogen (N) and oxygen (O). The nitric oxide gas does not have a cleaning effect by itself, but reacts with the cleaning gas to generate active species such as fluorine radicals and halogenated nitrosyl compounds, thereby improving the cleaning effect of the cleaning gas. Nitric oxide gas may be, for example, nitric oxide (NO) gas. By supplying the additive gas in this manner, for example, fluorine radicals (·F) can be generated by the cleaning gas and the additive gas, thereby improving the efficiency of the cleaning process.

[0052] In addition, when supplying the additive gas to the nozzle where the step (a) has been performed, it is preferable to supply the cleaning gas and the additive gas alternately, rather than simultaneously. This makes it possible to suppress, for example, a direct reaction between the cleaning gas and the additive gas, and by suppressing the amount of fluorine radicals (·F) that are generated, it becomes possible to suppress, for example, etching of a quartz nozzle.

[0053] The process of alternately supplying the cleaning gas and the additive gas in this way can be expressed as the following (Process A) and (Process B). Note that there are several patterns of the cleaning process, as described later. (Process A): (cleaning gas → P / V → additive gas → P / V) × n (Process B): (Additive gas → P / V → Cleaning gas → P / V) × n

[0054] <Cleaning process pattern 1> The system may be configured so that (Process A) or (Process B) is performed on one or more of the multiple nozzles. The system may be configured so that (Process A) or (Process B) is performed on each of the multiple nozzles. By performing (Process A) or (Process B) on one or more nozzles, a predetermined amount of cleaning gas and additive gas can be mixed in the nozzle, and the inside of the nozzle can be cleaned. Here, the predetermined amount means, for example, the amount of cleaning gas remaining in the nozzle by being adsorbed, etc., that reacts with the additive gas that is supplied later.

[0055] <Cleaning process pattern 2> Also, it may be configured so that (Process A) or (Process B) is performed simultaneously on all the nozzles. By performing the processes simultaneously on all the nozzles, it is possible to make the cleaning speed of all the nozzles and their surroundings uniform.

[0056] <Cleaning process pattern 3> Also, it may be configured to perform (Process A) for one nozzle and (Process B) for the other nozzle. Specifically, it is configured to perform (Process A) for nozzle 249b and (Process B) for nozzle 249c. With this configuration, cleaning gas and additive gas can be simultaneously supplied into reaction tube 203. By simultaneously supplying cleaning gas and additive gas, it is possible to improve the efficiency of the cleaning process in reaction tube 203. Furthermore, by sequentially changing the supply positions of cleaning gas and additive gas, it is possible to suppress uneven cleaning in multiple nozzles and reaction tube 203, and it is possible to uniformly clean the inside of the nozzles and reaction tube 203.

[0057] At this time, the nozzle 249a may be caused to perform (Process C) of continuously supplying the inert gas. By continuously supplying the inert gas from the nozzle 249a, it is possible to suppress a sudden reaction between the gas supplied from the nozzle 249b and the gas supplied from the nozzle 249c on the nozzle side in the reaction tube 203. In addition, the inert gas supplied from the nozzle 249a can act as a guide for the gas supplied from the nozzles 249b and 249c, and can contribute to uniform cleaning in the reaction tube 203. In addition, the nozzle 249a may be caused to perform (Process A) or (Process B). Also, it may be configured to perform (Process A) or (Process B) and (Process C) in order.

[0058] The cleaning process may be performed by combining a plurality of the above-mentioned processing patterns.

[0059] (2-3) Fluorine deactivation treatment In the above manufacturing method, the fluorine deactivation treatment in the step (b) can be performed, for example, by supplying a gas containing hydrogen and oxygen to the nozzle that supplied the cleaning gas into the reaction tube 203 in the step (a). Here, the "gas containing hydrogen and oxygen" is preferably a mixed gas obtained by supplying hydrogen (H2) gas and oxygen (O2) gas from separate gas supply pipes and mixing them at least at the nozzle, but may also be a gas containing hydrogen (H) atoms and oxygen (O) atoms in one molecule, such as water vapor (H2O) or hydrogen peroxide (H2O2). For example, the fluorine (F2) or fluorine ions (F) remaining in the reaction tube can be deactivated by a mixed gas of H2 gas and O2 gas. - The reaction equation representing the mechanism for removing NH3 is thought to be as follows:

[0060] 3H2+O2+F2→2HF+2H2O

[0061] 2H2+O2+2F - →2HF+2OH -

[0062] In addition, the following reaction is thought to occur due to the water (H2O) produced by the mixture of H2 gas and O2 gas.

[0063] H2O+F - →HF+OH -

[0064] Here, by supplying H2 gas as the first reactive gas and O2 gas as the second reactive gas from separate gas supply pipes and adjusting the flow rate with each MFC, it becomes possible to perform a fluorine removal process according to the chemical state of fluorine remaining in the nozzle or reaction tube. For example, the flow rate ratio of the first reactive gas and the second reactive gas is changed according to the state of fluorine remaining in the nozzle or reaction tube. In addition, the flow rate ratio may be adjusted to change according to the member for removing the residual fluorine. Here, the member is the nozzle or reaction tube. For example, the flow rate ratio may be configured to be different between the process of removing the residual fluorine in the nozzle and the process of removing the residual fluorine in the reaction tube. In addition, the flow rate for each process may be configured to be different.

[0065] For example, when a cleaning gas is supplied from the nozzle 249a, a first reactive gas is supplied from the gas supply pipe 232d and a second reactive gas is supplied from the gas supply pipe 232e, and the mixed gas is supplied from the nozzle 249a into the reaction tube 203. When a cleaning gas is supplied from the nozzle 249b, a first reactive gas is supplied from the gas supply pipe 232b and a second reactive gas is supplied from the gas supply pipe 232h, and the mixed gas is supplied from the nozzle 249a into the reaction tube 203. When a cleaning gas is supplied from the nozzle 249c, a first reactive gas is supplied from the gas supply pipe 232k and a second reactive gas is supplied from the gas supply pipe 232c, and the mixed gas is supplied from the nozzle 249a into the reaction tube 203.

[0066] Here, in the step (a), when the cleaning gas is supplied into the reaction tube 203 from all of the nozzles 249a, 249b, and 249c, a mixed gas of the first reaction gas and the second reaction gas is supplied into the reaction tube 203 from all of the nozzles 249a, 249b, and 249c, so that the fluorine removal process inside the reaction tube 203 can be more reliably performed. That is, when the gas is supplied to any one nozzle, there is a possibility that residual fluorine or reaction products may enter the other nozzles (backflow into the nozzles), but by supplying the gas from all of the nozzles, such backflow into the nozzles can be suppressed.

[0067] In this step (b), it is preferable to heat the nozzles 249a, 249b, and 249c by the heater 207 for heating the reaction tube 203 so that the gas containing hydrogen and oxygen is activated in the nozzles 249a, 249b, and 249c. In this way, by heating and reacting the H2 gas with the O2 gas, it is possible to generate a plurality of types of active species such as hydroxyl group active species (·OH), oxygen active species (·O), and hydrogen active species (·O) in addition to water (H2O). Therefore, even if the fluorine remaining in the reaction tube 203 exists in a plurality of chemical states, the fluorine remaining in the nozzles 249a, 249b, and 249c to which the fluorine-containing gas is supplied can be deactivated by the plurality of active species, and the fluorine can be removed.

[0068] In addition, when the plurality of nozzles 249a, 249b, 249c are heated by the heater 207 that heats the reaction tube 203 as described above, the plurality of nozzles 249a, 249b, 249c are heated so that the main regions of the plurality of nozzles 249a, 249b, 249c are heated to a substantially uniform temperature. Preferably, the plurality of nozzles 249a, 249b, 249c are heated so that the above-mentioned reaction occurs between the first reaction gas and the second reaction gas in the main regions of the plurality of nozzles 249a, 249b, 249c. Specifically, at least one of the plurality of nozzles 249a, 249b, 249c and the heater 207 is arranged so that the main region 249d of the plurality of nozzles 249a, 249b, 249c is arranged inside the end of the heater 207. Here, the main region 249d of the nozzles 249a, 249b, and 249c refers to a region where various gases are supplied to the substrate (wafer 200), preferably the product substrate, in other words, a region where the substrate (wafer 200) is subjected to various processes in the reaction tube 203. Note that the region where various gases are supplied to the substrate (wafer 200) desirably includes a portion where the gas supply holes 250a, 250b, and 250c from which gas is discharged in the nozzles 249a, 249b, and 249c are not provided. Furthermore, it is desirable that the region where the gas supply holes 250a, 250b, and 250c are provided faces at least the heater 207. Moreover, a substantially uniform temperature means that, for example, the temperature difference between the hottest point and the coldest point in the region is within 3°C. In this way, by heating the main regions of the nozzles 249a, 249b, and 249c to a substantially uniform temperature, the fluorine deactivation process can be performed uniformly in the main regions of the nozzles 249a, 249b, and 249c. In addition, it is possible to supply a plurality of types of activated species generated in the main region 249d of the nozzles 249a, 249b, and 249c to at least the processing region of the reaction tube 203 where the wafer 200 is placed. This allows the cleaning of the processing region of the reaction tube 203 to be performed uniformly.

[0069] Here, it is preferable that the heater 207 is divided into a plurality of zones along the gas flow direction in the plurality of nozzles 249a, 249b, and 249c, and that the temperature is changed so that the temperature control of the plurality of zones is different between the step (a) and the step (b). For example, it is preferable that the reaction tube 203 shown in FIG. 1 is divided into a plurality of zones in the vertical direction, and that the control unit (controller 121) can control the temperature of the heater 207 for each of the plurality of zones.

[0070] For example, in the cleaning process of the step (a), it is desirable to control the temperature so as to provide a temperature gradient such that the temperature of the zone located on the upper side is higher than that of the zone located on the lower side. By providing such a temperature gradient, even if the amount of cleaning gas reaching the upper side of the nozzle or the upper side of the reaction tube is reduced, the reactivity of the cleaning gas can be improved by increasing the temperature on the upper side, and uniform cleaning process can be achieved from the upper side to the lower side of the nozzle or reaction tube. Note that, when a step of supplying an additive gas is provided after the step (a), it is desirable to control the temperature so as to provide a similar temperature gradient.

[0071] In the fluorine deactivation treatment in step (b), it is possible to control all the zones to have substantially the same temperature. In this way, it is possible to perform the fluorine deactivation treatment in the nozzles 249a, 249b, and 249c corresponding to all the zones. Note that the substantially uniform temperature here means, for example, that the temperature difference between the hottest zone and the coldest zone is within 3°C.

[0072] On the other hand, when the gas flow direction in the nozzles 249a, 249b, and 249c is from bottom to top as shown in Fig. 1, it is desirable to control the temperature of the lower end zone to a higher temperature than the other zones in the fluorine deactivation treatment in the step (b). This allows the hydrogen-oxygen containing gas to be preheated in the lower end zone, in other words, in the upstream zone, and shortens the heating time to the suitable reaction temperature in the reaction tube 203.

[0073] The first and second reactive gases are preheated by the second heater 207a provided downstream of the valve 243d of the gas supply pipe 232d that supplies the first reactive gas and the valve 243e of the gas supply pipe 232e that supplies the second reactive gas, respectively, to remove residual fluorine in the gas supply pipe 232a up to the nozzle 249a. Similarly, the first and second reactive gases are preheated by the second heater 207b provided downstream of the valve 243b of the gas supply pipe 232b that supplies the first reactive gas and the valve 243h of the gas supply pipe 232h that supplies the second reactive gas, respectively, to remove residual fluorine in the gas supply pipe 232b up to the nozzle 249b. Furthermore, the first and second reactant gases are preheated by the second heater 207c provided downstream of the valve 243k of the gas supply pipe 232k that supplies the first reactant gas and the valve 243c of the gas supply pipe 232c that supplies the second reactant gas, respectively, thereby removing residual fluorine in the gas supply pipe 232c up to the nozzle 249c. Note that, although an example in which the first and second reactant gases are heated in separate gas supply pipes has been shown here, the first and second reactant gases may be heated after being mixed together.

[0074] In the method for cleaning a semiconductor device by the above-mentioned steps (a) and (b), the cleaning gas enables cleaning and fluorine deactivation in the reaction tube 203 and the nozzles 249a, 249b, and 249c.

[0075] (2-4) Re-processing the substrate (wafer 200) After the cleaning process and the fluorine deactivation process in the reaction tube 203 and the nozzles 249a, 249b, and 249c are completed by the steps (a) and (b), the next substrate (wafer 200) is loaded into the reaction tube 203 in the step (c). The loaded next substrate (wafer 200) is subjected to the process of the substrate (wafer 200) described in the above (2-1). EXAMPLES

[0076] An embodiment of the method for manufacturing a semiconductor device according to the present invention will now be described.

[0077] In the following description, the expression of a numerical range such as "75 to 200°C" means that the lower limit and the upper limit are included in the range. Thus, for example, "75 to 200°C" means "75°C or higher and 200°C or lower." The same applies to other numerical ranges.

[0078] <Experimental Overview> In the examples and comparative examples, the film-forming process for forming a film on the wafer was performed several times, and then the cleaning process and the process of supplying the additive gas in the above-mentioned step (a) were alternately repeated several times. Then, the fluorine deactivation process in the above-mentioned step (b) was performed, and the film-forming process was repeated again. The film thickness was measured for the wafer obtained by each film-forming process.

[0079] <Film formation process> The following film formation process mentioned in (2-1) above was carried out. Note that the procedures such as setting and initial cleaning prior to the film formation process are omitted.

[0080] (Source gas → P / V → First reactant gas + Second reactant gas → P / V) × n

[0081] First, the wafer 200 was loaded into the reaction tube 203, and then, in step 1, HCDS gas was supplied as a source gas into the reaction tube 203 from the gas supply pipe 232a (first pipe) and the nozzle 249a (first nozzle).

[0082] Next, in step 2, the reaction tube 203 was evacuated to a vacuum while N2 gas was supplied (or not supplied) as a purge gas from the gas supply pipe 232n through the first piping and the first nozzle, to remove the source gas remaining in the processing chamber.

[0083] Then, in step 3, H2 gas as a first reactive gas was supplied to the wafers 200 in the reaction tube 203 via the gas supply pipe 232b (second piping) and the nozzle 249b (second nozzle), while O2 gas as a second reactive gas was supplied via the gas supply pipe 232c (third piping) and the nozzle 249c (third nozzle).

[0084] Finally, in step 4, a purge gas was supplied from the gas supply pipe 232o through the second pipe and the second nozzle, and at the same time, a purge gas was supplied from the gas supply pipe 232p through the third pipe and the third nozzle, while evacuating the reaction tube 203 to remove the first reaction gas and the second reaction gas remaining in the processing chamber.

[0085] The above steps 1 to 4 were repeated a predetermined number of times. The treatment conditions in each step were as follows. Raw material gas supply flow rate: 0.01 to 2 slm, preferably 0.1 to 1 slm Purge gas supply flow rate: 0 to 10 slm First reactant gas supply flow rate: 0.1 to 10 slm Second reactant gas supply flow rate: 0.1 to 10 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Treatment temperature: 250 to 800°C, preferably 400 to 700°C Treatment pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa

[0086] <Cleaning process> After the wafer was unloaded after the film formation process, the cleaning process mentioned in (2-2) above was carried out using all of the first, second and third nozzles. Here, the following process was carried out for each nozzle. Each process was carried out in parallel. First nozzle (nozzle 249a): Process C Second nozzle (nozzle 249b): Treatment A Third nozzle (nozzle 249c): Process B

[0087] That is, N2 gas as an inert gas is continuously supplied from the gas supply pipe 232n through the first pipe and the first nozzle during the cleaning process. In addition, F2 gas as a cleaning gas and NO gas as an additive gas are sequentially supplied from the gas supply pipe 232i and the gas supply pipe 232j through the second pipe and the second nozzle so as to correspond to the order of process A. In addition, cleaning gas and additive gas are sequentially supplied from the gas supply pipe 232l and the gas supply pipe 232m through the third pipe and the third nozzle so as to correspond to the order of process B. Here, process A and process B are simultaneously performed by each nozzle.

[0088] The above-mentioned supply of the cleaning gas and the supply of the additive gas were repeated a predetermined number of times under the following processing conditions. Cleaning gas supply flow rate: 1 to 20 slm, preferably 5 to 15 slm Additive gas supply flow rate: 0.1 to 2 slm, preferably 0.5 to 1.5 slm Each gas supply time: 10 to 120 seconds, preferably 20 to 40 seconds Treatment temperature: 250 to 400°C, preferably 250 to 350°C Treatment pressure: 1 to 1000 Torr, preferably 10 to 500 Torr

[0089] <Fluorine deactivation treatment> After the above cleaning treatment, the fluorine deactivation treatment mentioned in (2-3) above was carried out using all of the first nozzle, the second nozzle, and the third nozzle.

[0090] First, H2 gas as a first reactive gas was supplied from the gas supply pipe 232d, and O2 gas as a second reactive gas was supplied from the gas supply pipe 232e, both through the first pipe and the first nozzle, into the reaction tube 203. At the same time, the first reactive gas was supplied from the gas supply pipe 232b, and the second reactive gas was supplied from the gas supply pipe 232h, both through the second pipe and the second nozzle, into the reaction tube 203. At the same time, the first reactive gas was supplied from the gas supply pipe 232k, and the second reactive gas was supplied from the gas supply pipe 232c, both through the first pipe and the first nozzle, into the reaction tube 203. The ratio of the supply flow rate of the first reactive gas to the second reactive gas was set to approximately 1:1. Other processing conditions were as follows. First reactant gas supply flow rate: 1 to 10 slm Second reactant gas supply flow rate: 1 to 10 slm Each gas supply time: 30 to 300 minutes, preferably 100 to 150 minutes Processing temperature: 600~800℃ Treatment pressure: 5 to 133 Pa, preferably 5 to 30 Pa

[0091] In the comparative example, neither the first nor the second reactive gas was supplied from the first piping and the first nozzle, only the first reactive gas was supplied from the gas supply pipe 232b from the second piping and the second nozzle, and only the second reactive gas was supplied from the gas supply pipe 232c from the third piping and the third nozzle.

[0092] <Result> The results of the film formation stability in the comparative example and the embodiment are shown in Figures 4 and 5, respectively. In Figures 4 and 5, the vertical axis of the graph represents the film thickness of the wafer 200 (the increase or decrease from the reference film thickness is expressed in units of angstroms), and the horizontal axis represents the number of film formation processes. The dashed lines in both figures represent the reference film thickness. Furthermore, in both figures, the arrows indicate the points in time when the cleaning process and the fluorine deactivation process were performed.

[0093] In the comparative example, when the cleaning process and the fluorine deactivation process were performed after the third film formation process, the film thickness immediately decreased by about 0.5 from the reference film thickness. In particular, the decrease in film thickness became more noticeable after the 41st treatment.

[0094] On the other hand, in the example, when the cleaning process and the fluorine deactivation process were performed after the sixth film formation process, the film thickness decreased immediately after the sixth film formation process, but the decrease was less than 0.1. Then, the film thickness stabilized after the 14th process.

[0095] In the comparative example, as shown in the schematic diagram of FIG. 6, only the first reactive gas was supplied from the nozzle 249b (second nozzle), and only the second reactive gas was supplied from the nozzle 249c (third nozzle), and neither the first reactive gas nor the second reactive gas was supplied from the nozzle 249a (first nozzle). As a result, in the region indicated by B in the figure, which includes the processing chamber 201 and the exhaust pipe 231 in the reaction tube 203, the first reactive gas and the second reactive gas were sufficiently mixed, so that the fluorine deactivation process was sufficiently performed. However, in the region indicated by A in the figure near the nozzles 249a, 249b, and 249c, the first reactive gas and the second reactive gas were not sufficiently mixed, so that it is presumed that the fluorine deactivation process was not sufficiently performed, which adversely affected the subsequent film formation process.

[0096] On the other hand, in the embodiment, both the first and second reactive gases were supplied from all of the nozzles 249a (first nozzle), 249b (second nozzle), and 249c (third nozzle) as shown in the schematic diagram of Fig. 7. As a result, it is presumed that the first and second reactive gases were sufficiently mixed not only in the region B in the figure but also in the region A, so that the fluorine deactivation process was sufficiently performed and the subsequent film formation process was performed satisfactorily.

[0097] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the embodiments of the present disclosure are not limited to the above embodiments and may be modified in various ways without departing from the spirit and scope of the present disclosure.

[0098] In the film formation process, a film may be formed on the wafer 200 by the following gas supply sequence. The above-mentioned cleaning process can also be suitably applied to the nozzles and reaction tubes in which the following materials are formed.

[0099] (Si-containing source gas → carbon-containing gas → nitriding gas → oxidizing gas (second reaction gas)) × n ⇒ SiOCN (Si-containing source gas → oxidizing gas (second reactant gas) → nitriding gas) × n ⇒ SiON (Si-containing source gas → nitriding gas → oxidizing gas (second reaction gas)) × n ⇒ SiON (Si-containing source gas → nitriding gas) × n ⇒ SiN Here, the carbon-containing gas is, for example, propylene gas (C3H6 gas), and the nitriding gas is, for example, ammonia gas (NH3 gas).

[0100] It is preferable that the recipes used for each process are prepared individually according to the process contents and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing device. It is also possible to reduce the burden on the operator and quickly start each process while avoiding operational errors.

[0101] The above-mentioned recipes may not only be created anew, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. In addition, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0102] In the above-mentioned embodiment, the cleaning gas is exemplified by F2 gas and NF3 gas as a fluorine-containing gas. The present disclosure is not limited to the above-mentioned embodiment, and examples thereof include hydrogen fluoride (HF) gas, carbon tetrafluoride (CF4), and chlorine trifluoride (ClF3). It is preferable that the cleaning gas contains at least one of F2, NF3, HF, CF4, and ClF3.

[0103] In the above embodiment, an example of cleaning using a gas containing fluorine as a cleaning gas has been described. The present disclosure is not limited to the above embodiment, and may be applicable to, for example, a case where a cleaning gas containing a halogen element is used. Here, the halogen element is chlorine (Cl), fluorine (F), bromine (Br), or iodine (I).

[0104] In the above-mentioned embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0105] When using these substrate processing apparatuses, each process can be performed under the same process procedures and conditions as in the above embodiment, and the same effects as in the above embodiment can be obtained.

[0106] The above-mentioned aspects may be used in combination as appropriate. The processing procedures and processing conditions in this case may be the same as those of the above-mentioned aspects.

[0107] <Preferred aspects of the present disclosure> Preferred aspects of the present disclosure will be described below.

[0108] (Appendix 1) According to one aspect of the present disclosure, After the substrate is processed in the reaction tube having a plurality of nozzles and removed, (a) supplying a cleaning gas to at least one of the plurality of nozzles; (b) supplying a gas comprising hydrogen and oxygen to the at least one nozzle where step (a) was performed; (c) after the step (b), loading a next substrate into the reaction tube; A method for manufacturing a semiconductor device having the above structure is provided.

[0109] (Appendix 2) The method according to claim 1, preferably comprising: In the step (a), the cleaning gas is not supplied to any of the plurality of nozzles other than the at least one nozzle.

[0110] (Appendix 3) The method according to claim 1 or 2, preferably comprising In the step (a), the amount of gas supplied to nozzles other than the at least one nozzle among the plurality of nozzles is set to substantially zero.

[0111] (Appendix 4) The method according to claim 1, preferably comprising: The step (a) is carried out for all of the plurality of nozzles.

[0112] (Appendix 5) The method according to claim 1 or 4, preferably comprising The step (a) is carried out for all of the plurality of nozzles at the same time.

[0113] (Appendix 6) The method according to any one of appendix 1 to 5, preferably comprising: (d) supplying a gas containing nitrogen and oxygen to the nozzles among the plurality of nozzles in which the step (a) has been performed.

[0114] (Appendix 7) The method according to claim 6, preferably comprising: (e) The steps (a) and (d) are alternately performed.

[0115] (Appendix 8) The method according to any one of appendices 1 to 7, preferably comprising: (f) heating the nozzles with a heater so that the gas containing hydrogen and oxygen in the step (b) is activated within the nozzles;

[0116] (Appendix 9) The method according to claim 8, preferably comprising: In step (f), a main region of the plurality of nozzles is heated to a substantially uniform temperature.

[0117] (Appendix 10) The method according to claim 8 or 9, preferably comprising: In the step (f), heating is performed by the heater disposed at a position corresponding to the region in the reaction tube where the substrate is located.

[0118] (Appendix 11) The method according to claim 10, preferably comprising: The substrate is a product substrate.

[0119] (Appendix 12) The method according to claim 8, preferably comprising: Either or both of the plurality of nozzles and the heater are disposed so that a region in which at least the holes of the plurality of nozzles are provided faces the heater.

[0120] (Appendix 13) The method according to any one of claims 8 to 12, preferably comprising: The heater is configured by being divided into a plurality of zones along a flow direction of the gas in the plurality of nozzles, (g) The temperatures are changed in the steps (a) and (b) so that the temperature controls of the plurality of zones are different.

[0121] (Appendix 14) The method according to claim 13, preferably comprising: In the step (b), the temperatures of at least the zones corresponding to the processing regions of the substrate are controlled to be substantially the same temperature.

[0122] (Appendix 15) The method according to claim 13, preferably comprising: In the step (b), the temperature of the lower end zone of the plurality of zones is controlled to be higher than the temperatures of the other zones.

[0123] (Appendix 16) The method according to any one of Supplementary Notes 1 to 15, preferably comprising: (h) heating the hydrogen and oxygen containing gas by a second heater outside the reaction tube.

[0124] (Appendix 17) According to yet another aspect of the present disclosure, After the substrate is processed in the reaction tube having a plurality of nozzles and removed, (a) supplying a cleaning gas to at least one of the plurality of nozzles; (b) supplying a gas comprising hydrogen and oxygen to the at least one nozzle where step (a) was performed; A method for cleaning a nozzle having a

[0125] (Appendix 18) According to yet another aspect of the present disclosure, a reaction tube in which the substrate is processed; a transport mechanism for transporting a substrate into and out of the reaction tube; A plurality of nozzles for supplying various gases to the reaction tube; a cleaning gas supply system for supplying a cleaning gas to at least one of the plurality of nozzles; a hydrogen-oxygen-containing gas supply system that supplies a gas containing hydrogen and oxygen to the at least one nozzle; A control unit configured to be able to control the transport mechanism, the cleaning gas supply system, and the hydrogen / oxygen-containing gas supply system so as to perform each treatment (each step) of Appendix 1; A substrate processing apparatus having a

[0126] (Appendix 19) According to yet another aspect of the present disclosure, There is provided a program for causing a substrate processing apparatus to execute each procedure (each step) of Supplementary Note 1 by a computer, or a computer-readable recording medium having the program recorded thereon. [Explanation of symbols]

[0127] 121 Control Unit 200 wafers (substrates) 201 Processing Room 203 Reaction tube 232a Gas supply pipe (first pipe) 232b Gas supply pipe (second piping) 232c Gas supply pipe (third pipe) 249a Nozzle (1st nozzle) 249b Nozzle (2nd Nozzle) 249c Nozzle (3rd Nozzle)

Claims

1. (a) (a1) supplying a gas containing silicon element to a substrate in a processing chamber via a first supply unit; (a2) supplying a reactive gas to the substrate via a second supply unit; a step of performing the above a predetermined number of times to form a film on the substrate; (b) after (a), (b1) supplying a gas containing fluorine into the processing chamber via a plurality of supply parts including the first supply part and the second supply part; (b2) supplying a gas containing nitrogen and oxygen into the processing chamber via the plurality of supply parts; A step of carrying out (c) after (b), supplying a gas containing hydrogen and oxygen into the processing chamber via the plurality of supply parts; The processing method according to claim 1,

2. The processing method of claim 1, wherein in (c), the gas containing hydrogen and oxygen is simultaneously supplied via the multiple supply parts.

3. In (a), (a3) supplying at least one of the silicon element-containing gas and the reaction gas to the substrate via a third supply unit as one of the plurality of supply units; The method according to claim 1 or 2, further comprising the steps of:

4. In (a2), hydrogen gas as one of the reactive gases is supplied to the substrate via the second supply unit; (a3) at least partially simultaneously with (a2), supplying oxygen gas as one of the reactive gases to the substrate via the third supply unit; (c) supplying a mixed gas of the hydrogen gas and the oxygen gas as the gas containing hydrogen and oxygen into the processing chamber via all of the supply units among the plurality of supply units; The method of claim 3.

5. The plurality of supply units supply at least one of the silicon element-containing gas and the reaction gas to the substrate in (a).

5. The method according to claim 1 .

6. The processing method according to claim 1 , wherein in (b1), the supply of the fluorine-containing gas via the multiple supply parts is performed simultaneously.

7. The fluorine-containing gas is F ２ Gas and NF ３ A gas containing at least one of the following gases:

7. The method according to any one of claims 1 to 6.

8. In (b), (b1) and (b2) are performed alternately.

8. The method according to claim 1 .

9. (c) heating the first supply unit with a heater so that the gas containing hydrogen and oxygen is activated in the first supply unit; 9. The method according to any one of claims 1 to 8.

10. (c) heating a main region of the first supply section to a substantially uniform temperature; The method of claim 9.

11. The heater is configured by being divided into a plurality of zones along a flow direction of the gas in the processing chamber, In step (c), the temperature of at least one of the zones corresponding to a processing region of the substrate is controlled to be substantially the same temperature. The method of claim 9.

12. The heater is configured by being divided into a plurality of zones along a flow direction of the gas in the processing chamber, In (c), the temperature of the lower end zone of the plurality of zones is controlled to be higher than the temperatures of the other zones. The method of claim 9.

13. The gas containing hydrogen and oxygen is a mixed gas obtained by mixing hydrogen gas and oxygen gas.

13. A method according to any one of claims 1 to 3 or claims 5 to 12.

14. In (c), the gas containing hydrogen and oxygen is heated and activated by a second heater outside the reaction tube containing the substrate.

14. A method according to any one of the preceding claims.

15. The processing method according to claim 1, wherein in (b2), a gas containing nitrogen and oxygen is supplied into the processing chamber via the multiple supply parts.

16. The processing method according to claim 1, wherein in (a2), a gas containing hydrogen and oxygen is supplied to the substrate as the reactive gas.

17. (a) (a1) supplying a gas containing silicon element to a substrate in a processing chamber via a first supply unit; (a2) supplying a reactive gas to the substrate via a second supply unit; a step of performing the above a predetermined number of times to form a film on the substrate; (b) after (a), (b1) supplying a gas containing fluorine into the processing chamber via a plurality of supply parts including the first supply part and the second supply part; (b2) supplying a gas containing nitrogen and oxygen into the processing chamber via the plurality of supply parts; A step of carrying out (c) after (b), supplying a gas containing hydrogen and oxygen into the processing chamber via the plurality of supply parts; and then forming a film on a next substrate in step (a). A method for manufacturing a semiconductor device having the above structure.

18. A plurality of supply units including at least a first supply unit and a second supply unit; a processing chamber into which gas is supplied via the plurality of supply units; a supply system configured to supply a gas containing silicon element to the first supply unit, a reactive gas to the second supply unit, a gas containing fluorine to all of the supply units, a gas containing nitrogen and oxygen to at least one of the supply units, and a gas containing hydrogen and oxygen to all of the supply units; (a) (a1) supplying the silicon element-containing gas to the substrate in the processing chamber via the first supply unit; (a2) supplying a reactive gas to the substrate via a second supply unit; a process of forming a film on the substrate by performing the process a predetermined number of times; (b) after (a), (b1) supplying the fluorine-containing gas into the processing chamber via a plurality of supply units including the first supply unit and the second supply unit; (b2) supplying a gas containing nitrogen and oxygen into the processing chamber via the plurality of supply units; A process of performing (c) after (b), supplying the gas containing hydrogen and oxygen into the processing chamber via the plurality of supply units; A control unit configured to be able to control the supply system to perform the above-mentioned A substrate processing apparatus comprising:

19. (a) (a1) supplying a gas containing silicon element to a substrate in a processing chamber via a first supply unit; (a2) supplying a reactive gas to the substrate via a second supply unit; a step of repeating the above a predetermined number of times to form a film on the substrate; (b) after (a), (b1) supplying a fluorine-containing gas into the processing chamber via a plurality of supply units including at least the first supply unit and the second supply unit; (b2) supplying a gas containing nitrogen and oxygen into the processing chamber via the plurality of supply parts; (c) after (b), supplying a gas containing hydrogen and oxygen into the processing chamber through the plurality of supply units; A program for causing a computer to execute the above in a substrate processing apparatus.

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