Method for cleaning a nozzle, substrate processing method, method for manufacturing semiconductor device, substrate processing device, and recording medium

Abstract

This application relates to a nozzle cleaning method, a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium. This application reduces film thickness variations during film deposition by effectively removing residual elements after cleaning. This application provides a nozzle cleaning method comprising: (a) supplying a cleaning gas to at least one of the multiple nozzles after processing and removing a substrate from a reaction tube having multiple nozzles; and (b) supplying a gas containing hydrogen and oxygen to at least one nozzle after step (a).

Description

Technical Field

[0001] This disclosure relates to a method for cleaning nozzles, a method for processing substrates, a method for manufacturing semiconductor devices, a substrate processing apparatus, and a recording medium. Background Technology

[0002] As a step in the manufacturing process of a semiconductor device, a step of processing a substrate in a processing container is sometimes performed (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-157871 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] In semiconductor manufacturing equipment, due to repeated film deposition processes, the accumulated film in the reaction chamber can sometimes peel off due to stress, causing problems such as particle formation. Therefore, after a certain amount of film has accumulated, cleaning is required to remove the film. In recent years, gas cleaning using reactive gases to remove the accumulated film has been adopted as a cleaning method.

[0008] Methods using fluorine (F)-containing gases, such as F2 and NF3, as cleaning gases can sometimes leave residues after cleaning, hindering film formation. This can lead to issues such as changes in film thickness during the pre- and post-cleaning processes. Countermeasures to this problem sometimes include methods such as removing residual elements by treating with NH3 gas or similar methods, or overlapping and coating accumulated films to seal in residual elements.

[0009] This disclosure provides a method for reducing film thickness variation during film formation by effectively removing residual elements after cleaning.

[0010] Methods for solving problems

[0011] According to one aspect of this disclosure, a method for cleaning a nozzle is provided, which, after processing and removing a substrate in a reaction tube having a plurality of nozzles, comprises: (a) a step of supplying a cleaning gas to at least one of the plurality of nozzles and (b) a step of supplying a gas containing hydrogen and oxygen to the at least one nozzle after the step (a).

[0012] Invention Effects

[0013] According to this disclosure, by effectively removing residual elements after cleaning, it is possible to reduce film thickness variations during film formation. Attached Figure Description

[0014] Figure 1 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in one embodiment of the present disclosure, showing the furnace portion in a longitudinal cross-sectional view.

[0015] Figure 2 This is a schematic configuration diagram of a vertical processing furnace suitable for use in one embodiment of the present disclosure, which is based on... Figure 1 The AA-line cross-sectional view shows the furnace section.

[0016] Figure 3 This is a schematic configuration diagram of a controller for a substrate processing apparatus suitable for use in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller.

[0017] Figure 4 This is a graph showing the film-forming stability results in the comparative examples.

[0018] Figure 5 This is a graph showing the results of film formation stability in the embodiments.

[0019] Figure 6 This is a schematic diagram showing the deactivation of residual fluorine in the comparative example.

[0020] Figure 7 This is a schematic diagram showing the deactivation of residual fluorine in the embodiment.

[0021] Symbol Explanation

[0022] 121: Control unit; 200: Wafer (substrate); 201: Processing chamber; 203: Reaction tube; 232a: Gas supply pipe (first piping); 232b: Gas supply pipe (second piping); 232c: Gas supply pipe (third piping); 249a: Nozzle (first nozzle); 249b: Nozzle (second nozzle); 249c: Nozzle (third nozzle). Detailed Implementation

[0023] <One way of this disclosure>

[0024] The following description, with reference to the accompanying drawings, describes one aspect of this disclosure. It should be noted that the drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements shown in the drawings need not be consistent with reality. Furthermore, the dimensional relationships and ratios of the elements in multiple drawings need not be the same.

[0025] In this specification, the term "wafer" sometimes means "the wafer itself" and sometimes means "a laminate of a wafer and a predetermined layer or film formed on its surface." Similarly, the term "wafer surface" sometimes means "the surface of the wafer itself" and sometimes means "the surface of a predetermined layer formed on the wafer." When described as "forming a predetermined layer on the wafer," it sometimes means "forming a predetermined layer directly on the surface of the wafer itself" and sometimes means "forming a predetermined layer on a layer formed on the wafer." The term "substrate" is used in the same way as "wafer." Furthermore, the wafer or substrate on which the aforementioned predetermined layers or films are formed is referred to as a "semiconductor device."

[0026] (1) Composition of substrate processing device

[0027] like Figure 1 As shown, the processing furnace 202 has a heater 207 that functions as a temperature regulator (heating unit). The heater 207 is cylindrical in shape and is vertically mounted, supported by a retaining plate. The heater 207 also functions as an activation mechanism (activation unit) that uses heat to activate (excite) the gas.

[0028] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed into a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 is connected to the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, just like the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow part of the cylindrical part of the processing container. The processing chamber 201 is configured to accommodate the wafer 200, which serves as a substrate. The wafer 200 is processed within the processing chamber 201.

[0029] Inside the processing chamber 201, nozzles 249a, 249b, and 249c are respectively installed as a first supply section, a second supply section, and a third supply section, penetrating the side wall of the manifold 209. Nozzles 249a, 249b, and 249c can also be referred to as the first nozzle, the second nozzle, and the third nozzle, respectively. Nozzles 249a, 249b, and 249 are made of, for example, heat-resistant materials such as quartz or SiC (non-metallic materials). Nozzles 249a, 249b, and 249c are configured as shared nozzles for supplying multiple gases.

[0030] Nozzles 249a, 249b, and 249c are connected to gas supply pipes 232a, 232b, and 232c, which serve as the first, second, and third piping, respectively. Gas supply pipes 232a, 232b, and 232c are configured as shared piping for supplying multiple gases. In gas supply pipes 232a, 232b, and 232c, starting from the upstream side of the gas flow, mass flow controllers (MFCs) 241a, 241b, and 241c (flow controllers, flow control units) and valves 243a, 243b, and 243c (on / off valves) are sequentially installed.

[0031] Downstream of valve 243a in gas supply pipe 232a, it is sequentially connected to gas supply pipes 232d, 232e, 232f, 232g, and 232n. In gas supply pipes 232d, 232e, 232f, 232g, and 232n, starting from the upstream side of the gas flow, MFCs 241d, 241e, 241f, 241g, and 241n, and valves 243d, 243e, 243f, 243g, and 243n, are respectively installed. It should be noted that a second heater 207a is installed downstream of valves 243d and 243e in gas supply pipes 232d and 232e.

[0032] Downstream of valve 243b from gas supply pipe 232b, gas supply pipes 232h, 232i, 232j, and 232o are connected in sequence. Within gas supply pipes 232h, 232i, 232j, and 232o, MFCs 241h, 241i, 241j, and 241o, and valves 243h, 243i, 243j, and 243o, are sequentially installed starting from the upstream side of the gas flow. It should be noted that a second heater 207b is installed downstream of valves 243b and 243h on gas supply pipes 232b and 232h.

[0033] Downstream of valve 243c, gas supply pipe 232c is connected to gas supply pipes 232k, 232l, 232m, and 232p. Within gas supply pipes 232k, 232l, 232m, and 232p, starting from the upstream side of the gas flow, MFCs 241k, 241l, 241m, and 241p, and valves 243k, 243l, 243m, and 243p, are installed sequentially. It should be noted that a second heater 207c is installed downstream of valves 243c and 243k in gas supply pipes 232c and 232k.

[0034] Gas supply pipes 232a to 232p are made of metal. It should be noted that the materials of the aforementioned manifold 209, the sealing cap 219, the rotating shaft 255, and the exhaust pipe 231 can also be the same as those of the gas supply pipes 232a to 232m.

[0035] like Figure 2 As shown, nozzles 249a, 249b, and 249c are respectively arranged as follows: In a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 (viewed from top to bottom), they are vertically positioned upwards along the inner wall of the reaction tube 203, facing the direction of wafer 200 arrangement. That is, in the region horizontally surrounding the wafer arrangement region of the wafer 200, nozzles 249a, 249b, and 249c are respectively arranged along the wafer arrangement region. Gas supply holes 250a, 250b, and 250c are respectively provided on the sides of nozzles 249a, 249b, and 249c. Gas supply holes 250a, 250b, and 250c open towards the center of the wafer 200 (viewed from top to bottom), enabling gas supply to the wafer 200. Multiple gas supply ports 250a, 250b, and 250c are provided from the bottom to the top of the reaction tube 203.

[0036] The raw material gas is supplied to the processing chamber 201 from the gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a. The raw material gas is a gaseous raw material, such as a gas obtained by vaporizing a raw material that is liquid at room temperature and pressure, or a raw material that is gaseous at room temperature and pressure.

[0037] The first reaction gas is supplied to the processing chamber 201 from gas supply pipes 232b, 232d, 232k via MFCs 241b, 241d, 241k, valves 243b, 243d, 243k, and nozzles 249b, 249a, 249c.

[0038] The second reactant gas is supplied to the processing chamber 201 from gas supply pipes 232c, 232e, 232h via MFCs 241c, 241e, 241h, valves 243c, 243e, 243h, and nozzles 249c, 249a, 249b. It should be noted that the second reactant gas can be a gas with different molecular composition than the first reactant gas, or it can be a gas with the same molecular composition. The following description provides an example of using a gas with different molecular composition than the first reactant gas.

[0039] Clean gas is supplied to the treatment chamber 201 from gas supply pipes 232f, 232i, 232l via MFCs 241f, 241i, 241l, valves 243f, 243i, 243l, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c.

[0040] The added gas is supplied to the processing chamber 201 from gas supply pipes 232g, 232j, 232m via MFC 241g, 241j, 241m, valve 243g, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c.

[0041] As an inactive gas, nitrogen (N2) gas is supplied to the processing chamber 201 from gas supply pipes 232n, 232o, 232p via MFCs 241n, 241o, 241p, valves 243n, 243o, 243p, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c. N2 gas functions as a purge gas, carrier gas, dilution gas, etc.

[0042] The raw material gas supply system mainly consists of gas supply pipe 232a, MFC 241a, valve 243a, and nozzle 249a. The first reaction gas supply system mainly consists of gas supply pipes 232b, 232d, and 232k, MFCs 241b, 241d, and 241k, valves 243a, 243b, and 243c, and nozzles 249a, 249b, and 249c. The second reaction gas supply system mainly consists of gas supply pipes 232c, 232e, and 232h, MFCs 241c, 241e, and 241h, valves 243c, 243e, and 243h, gas supply pipes 232c, 232a, and 232b, and nozzles 249c, 249a, and 249b. Alternatively, the first and second reaction gas supply systems can be collectively referred to as the reaction gas supply system. The clean gas supply system mainly consists of gas supply pipes 232f, 232i, and 232l, MFCs 241f, 241i, and 241l, and valves 243f, 243i, and 243l. Alternatively, gas supply pipes 232a, 232b, and 232c, and nozzles 249a, 249b, and 249c can also be incorporated into the clean gas supply system. An additional gas supply system mainly consists of gas supply pipes 232g, 232j, and 232m, MFCs 241g, 241j, and 241m, valves 243g, 243j, and 243m, gas supply pipes 232a, 232b, and 232c, and nozzles 249a, 249b, and 249c. The inactive gas supply system mainly consists of gas supply pipes 232n, 232o, 232p, MFC 241n, 241o, 241p, valves 243n, 243o, 243p, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c.

[0043] Any or all of the aforementioned gas supply systems can also be configured as an integrated gas supply system 248, which integrates valves 243a-243p, MFCs 241a-241p, etc. The integrated gas supply system 248 is configured to be connected to gas supply pipes 232a-232p respectively, and the supply of various gases into the gas supply pipes 232a-232p is controlled by the controller 121 (described later), namely, the opening and closing of valves 243a-243p, and the flow adjustment by MFCs 241a-241p, etc. The integrated supply system 248 is configured as an integrated unit or a separate integrated unit, which can be installed and disassembled relative to the gas supply pipes 232a-232p, etc., and can be maintained, replaced, or added to the integrated supply system 248 in a manner that allows for maintenance, replacement, and addition of integrated units.

[0044] An exhaust port 231a for venting the atmosphere inside the processing chamber 201 is provided below the side wall of the reaction tube 203. The exhaust port 231a can be provided from the lower part to the upper part of the side wall of the reaction tube 203, that is, along the wafer alignment area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to the vacuum pump 246, which is a vacuum venting device, via a pressure sensor 245, which is a pressure detector (pressure detection unit), and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit), to detect the pressure inside the processing chamber 201. The APC valve 244 is configured such that by opening and closing the valve while the vacuum pump 246 is operating, vacuum venting can be performed and stopped inside the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening based on the pressure information detected by the pressure sensor 245. The exhaust system mainly consists of exhaust pipe 231, APC valve 244, and pressure sensor 245. Incorporating vacuum pump 246 into the exhaust system may also be considered.

[0045] Below the manifold 209, a sealing cap 219, serving as a furnace opening cover, is provided to airtightly seal the lower opening of the manifold 209. The sealing cap 219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the sealing cap 219, an O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209. Below the sealing cap 219, a rotation mechanism 267 is provided to rotate the wafer cassette 217 (described later). The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cap 219 and is connected to the wafer cassette 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer cassette 217. The sealing cap 219 is configured to move vertically via a wafer cassette lift 115, which serves as a lifting mechanism, located outside the reaction tube 203. The wafer cassette lift 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cap 219. A baffle 219s, serving as a furnace opening cover, is provided below the manifold 209. The baffle 219s can airtightly seal the lower opening of the manifold 209 when the sealing cap 219 is lowered and the wafer cassette 217 is removed from the processing chamber 201. The baffle 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c, serving as a sealing member abutting against the lower end of the manifold 209, is provided on the upper surface of the baffle 219s. The opening and closing actions (raising, lowering, rotating, etc.) of the baffle 219s are controlled by the baffle opening and closing mechanism 115s.

[0046] The wafer cassette 217, serving as a substrate support, is configured to support multiple wafers (e.g., 25 to 200) 200 in a horizontal orientation, aligned center-to-center, in a multi-segment arrangement in the vertical direction, i.e., arranged with intervals between them. The wafer cassette 217 is made of heat-resistant materials such as quartz or SiC. At the lower part of the wafer cassette 217, a heat-insulating plate 218, for example made of heat-resistant materials such as quartz or SiC, is supported in multiple segments.

[0047] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. The energizing of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving the desired temperature distribution within the processing chamber 201. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0048] like Figure 3 As shown, the controller 121, serving as the control unit (control unit), is configured as a computer having a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, storage device 121c, and I / O interface 121d are configured to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122, such as a touch panel.

[0049] The storage device 121c is configured such as flash memory or HDD (Hard Disk Drive). The storage device 121c stores and can read control programs that control the operation of the substrate processing apparatus, process recipes that describe the film formation process and conditions (described later), and cleaning recipes that describe the cleaning process and conditions (described later). The process recipe combines the various processes in the film formation process (described later) so that the controller 121 executes them and obtains a predetermined result, functioning as a program. The cleaning recipe combines the various processes in the cleaning process (described later) so that the controller 121 executes them and obtains a predetermined result, functioning as a program. Hereinafter, the process recipe, cleaning recipe, and control program will be simply referred to as a program. Furthermore, the process recipe and cleaning recipe will be simply referred to as recipes. When using the term "program" in this specification, sometimes only a single recipe is included, sometimes only a single control program is included, and sometimes both are included. RAM 121b is configured as a storage area (working area) for temporarily storing programs, data, etc., read by the CPU 121a.

[0050] I / O interface 121d is connected to the aforementioned MFC241a~241p, valves 243a~243p, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, second heaters 207a~207c, rotating mechanism 267, wafer box elevator 115, baffle switch mechanism 115s, etc.

[0051] CPU 121a is configured to read and execute control programs from storage device 121c, and simultaneously read recipes from storage device 121c according to input operation instructions from input / output device 122. CPU 121a is also configured to control, according to the read recipe, various gas flow adjustment actions performed by MFCs 241a-241p, opening and closing actions of valves 243a-243p, opening and closing actions of APC valve 244, pressure adjustment actions performed by APC valve 244 based on pressure sensor 245, starting and stopping vacuum pump 246, temperature adjustment actions of heater 207 based on temperature sensor 263, temperature adjustment actions of second heaters 207a-207c, rotation and rotation speed adjustment actions of wafer cassette 217 performed by rotation mechanism 267, lifting and lowering actions of wafer cassette 217 performed by wafer cassette elevator 115, and opening and closing actions of baffle 219s performed by baffle switch mechanism 115s.

[0052] The controller 121, which is the control unit mentioned above, is configured to control the transport mechanism, the clean gas supply system for supplying clean gas, and the reaction gas supply system for supplying gases containing hydrogen and oxygen. After processing the substrate (wafer 200) in the reaction tube 203 and removing it, it performs (a) the process of supplying clean gas to at least one nozzle, (b) the process of supplying gases containing hydrogen and oxygen to at least one nozzle after the process of (a), and (c) the process of moving the next batch of substrates (wafer 200) into the reaction tube 203 after the process of (b).

[0053] The controller 121 can be configured by installing the above-described program stored in the external storage device 123 into a computer, the program causing the substrate processing apparatus to perform the following processes via the computer: after processing and removing a substrate (wafer 200) in a reaction tube 203 having a plurality of nozzles 249a, 249b, 249c, (a) supplying a cleaning gas to at least one of the plurality of nozzles 249a, 249b, 249c, (b) supplying a gas containing hydrogen and oxygen to the at least one nozzle after the process (a), and (c) after the process (b), transferring the next batch of substrates (wafer 200) into the reaction tube 203.

[0054] External storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, optical discs such as MO disks, and semiconductor memories such as USB memories. Storage device 121c and external storage device 123 constitute a recording medium capable of being read by a computer. Hereinafter, they will be collectively referred to as recording media. When using the term "recording medium" in this specification, sometimes only storage device 121c is included, sometimes only external storage device 123 is included, or sometimes both are included. It should be noted that providing programs to a computer may also be done without using external storage device 123, but rather using communication methods such as the Internet or dedicated lines.

[0055] (2) Semiconductor device manufacturing method

[0056] The semiconductor device manufacturing method of this disclosure using the above-described substrate processing apparatus includes the following steps after processing and removing the substrate (wafer 200) in a reaction tube 203 having multiple nozzles 249a, 249b, 249c:

[0057] (a) The step of supplying cleaning gas to at least one of the plurality of nozzles 249a, 249b, 249c.

[0058] (b) The process of supplying a gas containing hydrogen and oxygen to at least one nozzle after the process described in (a) above, and

[0059] (c) The process of moving the next batch of substrates (wafers 200) into the reaction tube 203 after the process described in (b).

[0060] Here, the so-called "multiple nozzles" in the above manufacturing method refers to three nozzles in the above substrate processing apparatus, but there is no particular limitation as long as there are two or more nozzles.

[0061] (2-1) Processing of substrate (wafer 200)

[0062] In the above manufacturing method, regarding the processing of the substrate (wafer 200) in the reaction tube 203 prior to step (a), for example, a film formation process can be performed as follows: by performing steps 1 to 4 sequentially a predetermined number of times (n times, where n is an integer greater than or equal to 1) without simultaneous execution of steps 1 to 4, a film containing predetermined elements is formed on the wafer 200 as a film. Steps 1 to 4 are respectively:

[0063] Step 1 involves supplying raw material gas to the wafer 200 within the reaction tube 203 via the gas supply pipe 232a and the nozzle 249a.

[0064] After stopping the supply of raw material gas to the reaction tube 203, purge gas is supplied through the gas supply pipe 232n and nozzle 249a, while vacuum exhaust is performed inside the reaction tube 203 to remove the residual raw material gas from the processing chamber, step 2.

[0065] Step 3, in which a first reaction gas is supplied to the wafer 200 within the reaction tube 203 via gas supply pipe 232b and nozzle 249b, and a second reaction gas is supplied simultaneously via gas supply pipe 232c and nozzle 249c, and

[0066] Step 4 involves stopping the supply of the first and second reaction gases to the reaction tube 203, supplying N2 gas as purging gas through the gas supply pipes 232o, 232p and nozzles 249b, 249c, and simultaneously performing vacuum exhaust in the reaction tube 203 to remove the residual first and second reaction gases from the treatment chamber.

[0067] The exhaust treatment in steps 2 and 4 is carried out through exhaust pipe 231 from exhaust port 231a.

[0068] It should be noted that, as the feed gas, for example, a halosilane gas containing Si, the main element (predetermined element) constituting the membrane, and a halogen element can be used. A halosilane is a silane containing a halogen group. Halogen groups include chlorine, fluorine, bromine, and iodine groups. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). As a halosilane gas, for example, a feed gas containing Si and Cl can be used, i.e., a chlorosilane gas. Chlorosilane gases function as a Si source. As a chlorosilane gas, for example, hexachlorodisilane (Si₂Cl₆, abbreviated as HCDS) gas can be used. HCDS gas is a gas containing an element (Si) that, under the above processing conditions, becomes solid on its own; that is, it is a gas capable of independently depositing a membrane under the above processing conditions.

[0069] For example, a hydrogen (H) gas can be used as the first reactant gas. For example, hydrogen (H2) gas or a gas containing activated hydrogen can be used as the H-containing gas.

[0070] As the second reactant gas, for example, an oxygen-containing (O) gas can be used. Examples of O-containing gases include oxygen (O2), water (H2O), ozone (O3), and gases containing activated oxygen.

[0071] The above film-forming treatment is represented as follows. It should be noted that "P / V" represents the purging and degassing treatments in steps 2 and 4.

[0072] (raw material gas → P / V → first reactant gas + second reactant gas → P / V) × n

[0073] (2-2) Cleaning treatment

[0074] In the above manufacturing method, the cleaning process in step (a) can be performed, for example, by supplying a cleaning gas into the reaction tube 203 from at least one of nozzles 249a, 249b, and 249c. For example, a fluorine (F) gas can be used as the cleaning gas. For example, fluorine (F2) gas or nitrogen trifluoride (NF3) gas can be used as the fluorine-containing gas. Hereinafter, F2 gas will be used as an example of the cleaning gas.

[0075] For example, when supplying raw material gas from nozzle 249a, cleaning gas can be supplied from gas supply pipe 232f via nozzle 249a. In this case, it is desirable not to supply cleaning gas to other nozzles 249b, 249c during the above-described process (a). By doing so, for example when using quartz nozzles, etching caused by fluorine-containing gas can be suppressed for nozzles through which cleaning gas does not flow, and thus, as a result, the life of the nozzles can be extended.

[0076] On the other hand, during the above-described process (a), it is desirable that the gas supply to the other nozzles 249b and 249c, which are not supplied with cleaning gas, is substantially zero. By doing so, the cleaning gas supplied from nozzle 249a will flow into the other nozzles 249b and 249c, thereby enabling cleaning treatment of the nozzles that are not supplied with cleaning gas.

[0077] Furthermore, the aforementioned step (a) can be implemented by supplying cleaning gas into the reaction tube 203 from all nozzles 249a, 249b, and 249c. That is, by supplying cleaning gas into the reaction tube 203 via gas supply pipes 232f, 232i, and 232l and nozzles 249a, 249b, and 249c respectively, the uniformity of the cleaning process within the reaction tube 203 can be improved. Alternatively, in this case, cleaning gas can also be supplied into the reaction tube 203 from all nozzles 249a, 249b, and 249c simultaneously. In this way, by supplying cleaning gas from all nozzles 249a, 249b, and 249c simultaneously, residual fluorine and reaction products (e.g., HF) generated in step (b) described later can be suppressed from entering nozzles where cleaning gas is not supplied, thus preventing fluorine residue. At this time, if there is a time period for supplying clean gas into the reaction tube 203 from all nozzles 249a, 249b, and 249c, the start and end times of the supply of clean gas in each nozzle may not be the same. However, from the point of view of preventing residual fluorine, HF, etc. from entering other nozzles, it is desirable that the end time of the supply of clean gas in each nozzle is the same, and even more desirable that the start time is also the same.

[0078] It should be noted that it is desirable to supply additive gas to the nozzles in which the above-described process (a) has been performed among multiple nozzles. For example, when cleaning gas is supplied from nozzle 249a, additive gas is supplied into the reaction tube 203 via gas supply pipe 232g and nozzle 249a. Similarly, when cleaning gas is supplied from nozzle 249b, additive gas is supplied into the reaction tube 203 via gas supply pipe 232j and nozzle 249b. Furthermore, when cleaning gas is supplied from nozzle 249c, additive gas is supplied into the reaction tube 203 via gas supply pipe 232m and nozzle 249c.

[0079] It should be noted that, as the additive gas, a nitric oxide-based gas containing nitrogen (N) and oxygen (O) can be used. Nitric oxide-based gases do not act as cleaning gases on their own, but they enhance the cleaning effect of the cleaning gas by reacting with the cleaning gas to generate reactive species such as fluorine radicals and halonitrosyl compounds. For example, nitric oxide (NO) gas can be used as a nitric oxide-based gas. Therefore, by supplying it, since fluorine radicals (·F) can be generated from, for example, the cleaning gas and the additive gas, the efficiency of the cleaning process can be improved.

[0080] It should be noted that when supplying additive gas to a nozzle that has undergone the above-described process (a), it is desirable not to supply cleaning gas and additive gas simultaneously, but to do so alternately. This can suppress, for example, the direct reaction between cleaning gas and additive gas, suppress the amount of fluorine radicals (·F) generated, and thereby suppress etching of nozzles made of materials such as quartz.

[0081] This alternating supply of cleaning gas and additive gas can be represented as "Process A" and "Process B" as follows. It should be noted that the cleaning process has multiple modes, as described below.

[0082] "Treatment A": (Clean gas → P / V → Add gas → P / V) × n

[0083] "Process B": (Add gas → P / V → Clean gas → P / V) × n

[0084] <Cleaning Processing Mode 1>

[0085] It can be configured to perform "treatment A" or "treatment B" on one or more nozzles. It can also be configured to perform "treatment A" or "treatment B" on multiple nozzles separately. By performing "treatment A" or "treatment B" on one or more nozzles, cleaning gas and additive gas can be mixed in a predetermined amount within the nozzle, enabling cleaning within the nozzle. Here, the predetermined amount refers to the amount of cleaning gas remaining within the nozzle due to adsorption, for example, that reacts with subsequently supplied additive gas.

[0086] <Cleaning Processing Mode 2>

[0087] Alternatively, it can be configured to perform "treatment A" or "treatment B" on all nozzles simultaneously. By performing treatment on all nozzles simultaneously, the cleaning speed of all nozzles and their surroundings can be kept consistent.

[0088] <Cleaning Processing Mode 3>

[0089] Alternatively, it can be configured to perform "process A" on one nozzle and "process B" on the other nozzles. Specifically, "process A" can be performed in nozzle 249b while "process B" is performed simultaneously in nozzle 249c. With this configuration, both cleaning gas and additive gas can be supplied to the reaction tube 203 simultaneously. By simultaneously supplying cleaning gas and additive gas, the efficiency of cleaning treatment within the reaction tube 203 can be improved. Furthermore, by sequentially changing the supply positions of the cleaning gas and additive gas, uneven cleaning within the multiple nozzles and the reaction tube 203 can be suppressed, enabling uniform cleaning of the nozzles and the reaction tube 203.

[0090] It should be noted that at this time, an inert gas ("process C") can be continuously supplied to nozzle 249a. By continuously supplying an inert gas to nozzle 249a, the vigorous reaction between the gas supplied from nozzle 249b and the gas supplied from nozzle 249c on the nozzle side within the reaction tube 203 can be suppressed. Furthermore, the inert gas supplied from nozzle 249a can also guide the gas supplied from nozzles 249b and 249c, contributing to the cleaning and homogenization within the reaction tube 203. It should also be noted that "process A" or "process B" can also be performed in nozzle 249a. Alternatively, it can be configured to sequentially perform "process A" or "process B" and "process C".

[0091] It should be noted that cleaning can also be performed by combining multiple of the above-mentioned treatment methods.

[0092] (2-3) Fluorine deactivation treatment

[0093] In the above manufacturing method, the fluorine deactivation treatment in step (b) can be carried out, for example, by supplying a gas containing hydrogen and oxygen to a nozzle into which a cleaning gas was supplied to the reaction tube 203 in step (a). Here, "gas containing hydrogen and oxygen" preferably refers to a mixed gas obtained by supplying hydrogen (H2) gas and oxygen (O2) gas separately from different gas supply pipes and mixing them at least at the nozzle, but it can also be a gas containing both hydrogen (H) atoms and oxygen (O) atoms in one molecule, such as water vapor (H2O) or hydrogen peroxide (H2O2). For example, it means that the residual fluorine (F2) or fluoride ions (F2O3) in the reaction tube is deactivated by a mixed gas of H2 and O2 gas. -The reaction formula for the removal mechanism can be considered as follows.

[0094] 3H₂ + O₂ + F₂ → 2HF + 2H₂O

[0095] 2H₂ + O₂ + 2F⁻ → 2HF + 2OH⁻

[0096] Alternatively, it can be assumed that the following reaction occurs through water (H2O) produced by the mixture of H2 and O2 gases.

[0097] H₂O + F⁻ → HF + OH⁻

[0098] Here, by supplying H2 gas as the first reactant gas and O2 gas as the second reactant gas from different gas supply pipes and adjusting their flow rates by an MFC, fluoride removal can be performed according to the chemical state of the fluoride remaining in the nozzle and reaction tube. For example, the flow rate ratio of the first reactant gas and the second reactant gas can be changed according to the state of the fluoride remaining in the nozzle and reaction tube. Alternatively, the flow rate ratio can be changed according to the component from which residual fluoride is to be removed. Here, the component refers to the nozzle and the reaction tube. For example, the flow rate ratio in the process of removing residual fluoride in the nozzle can be different from the flow rate ratio in the process of removing residual fluoride in the reaction tube. Alternatively, the flow rate can be different for each process.

[0099] For example, when a cleaning gas is supplied from nozzle 249a, a first reactant gas is supplied from gas supply pipe 232d and a second reactant gas is supplied from gas supply pipe 232e, and the mixture is supplied from nozzle 249a into reaction tube 203. Alternatively, when a cleaning gas is supplied from nozzle 249b, a first reactant gas is supplied from gas supply pipe 232b and a second reactant gas is supplied from gas supply pipe 232h, and the mixture is supplied from nozzle 249a into reaction tube 203. Furthermore, when a cleaning gas is supplied from nozzle 249c, a first reactant gas is supplied from gas supply pipe 232k and a second reactant gas is supplied from gas supply pipe 232c, and the mixture is supplied from nozzle 249a into reaction tube 203.

[0100] Here, in step (a) above, when clean gas is supplied into the reaction tube 203 from all nozzles 249a, 249b, and 249c, supplying a mixture of the first and second reaction gases into the reaction tube 203 from all nozzles 249a, 249b, and 249c enables more reliable fluoride removal from the reaction tube 203. That is, while there is a possibility of residual fluoride or reaction products entering other nozzles when supplying to any one nozzle (backflow into the nozzle), supplying from all nozzles suppresses such backflow.

[0101] It should be noted that in this step (b), it is desirable to heat the multiple nozzles 249a, 249b, and 249c by the heater 207 of the heating reaction tube 203, so that the gas containing hydrogen and oxygen is activated within the nozzles 249a, 249b, and 249c. Thus, by heating and reacting H2 and O2 gases, multiple types of active species, such as hydroxyl (·OH), oxygen (·O), and hydrogen (·O), can be generated in addition to water (H2O). Therefore, even if the fluorine remaining in the reaction tube 203 exists in multiple chemical states, the fluorine remaining in the nozzles 249a, 249b, and 249c supplied with fluorine-containing gas can be deactivated by these multiple active species, thereby removing the fluorine.

[0102] It should be noted that when the plurality of nozzles 249a, 249b, 249c are heated by the heater 207 of the heating reaction tube 203 as described above, the heating is carried out in a manner that makes the main regions of the plurality of nozzles 249a, 249b, 249c reach a substantially uniform temperature. Preferably, the plurality of nozzles 249a, 249b, 249c are heated so that the first and second reactant gases undergo the aforementioned reactions 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 such that the main region 249d of the plurality of nozzles 249a, 249b, 249c is positioned further inward than the end of the heater 207. Here, the main region 249d of nozzles 249a, 249b, and 249c refers to the region where various gases are supplied to the substrate (wafer 200), preferably the product substrate; in other words, it refers to the region where the substrate (wafer 200) undergoes various processes within the reaction tube 203. It should be noted that this region where various gases are supplied to the substrate (wafer 200) preferably includes the portions of nozzles 249a, 249b, and 249c where gas supply holes 250a, 250b, and 250c are not provided. Furthermore, it is desirable that the region where these gas supply holes 250a, 250b, and 250c are provided is at least opposite to the heater 207. Additionally, substantially uniform temperature means, for example, that the temperature difference between the highest and lowest temperature locations within this region is within 3°C. Thus, by heating the main regions of nozzles 249a, 249b, and 249c to achieve a substantially uniform temperature, fluorine deactivation treatment can be uniformly performed within these main regions. Furthermore, multiple types of active species generated within the main regions 249d of nozzles 249a, 249b, and 249c can be supplied to at least the processing area of ​​the reaction tube 203 where the wafer 200 is mounted. This allows for uniform cleaning of the processing area of ​​the reaction tube 203.

[0103] Here, it is desirable that the heater 207 be configured such that it is divided into multiple zones along the flow direction of the gas within the plurality of nozzles 249a, 249b, 249c, so that the temperature is changed in a manner that the temperature control of the plurality of zones is different in steps (a) and (b). For example, Figure 1 In the reaction tube 203 shown, it is desirable to divide it into multiple sections in the vertical direction, and the control unit (controller 121) can control the temperature of the heater 207 for these multiple sections.

[0104] For example, in the cleaning process of step (a) above, it is desirable to control the temperature by setting a temperature tilt, whereby the temperature of the upper section is higher than the temperature of the lower section. By setting such a temperature tilt, even if the amount of cleaning gas reaching the upper side of the nozzle and 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, enabling uniform cleaning from the upper side of the nozzle and the upper side of the reaction tube to the lower side. It should be noted that if a step of supplying additive gas is set after step (a) above, it is also desirable to control the temperature by setting the same temperature tilt.

[0105] Furthermore, in the fluorine deactivation treatment of step (b) above, it is possible to control the process so that all zones reach substantially the same temperature. By doing so, fluorine deactivation treatment can be performed in nozzles 249a, 249b, and 249c corresponding to all zones. It should be noted that "substantially the same temperature" here means, for example, that the temperature difference between the zone with the highest temperature and the zone with the lowest temperature is within 3°C.

[0106] On the other hand, such as Figure 1 As shown, when the gas flow direction in nozzles 249a, 249b, and 249c is from bottom to top, in the fluorine deactivation treatment of step (b) above, it is desirable to control the temperature of the lower side section to be higher than the temperature of the other sections. This allows the gas containing hydrogen and oxygen to be preheated in the lower side section (in other words, the upstream section), thus shortening the heating time required to reach the appropriate reaction temperature in the reaction tube 203.

[0107] It should be noted that by preheating the first and second reactant gases respectively through valve 243d of the gas supply pipe 232d supplying the first reactant gas and valve 243e of the gas supply pipe 232e supplying the second reactant gas, residual fluorine in the gas supply pipe 232a up to nozzle 249a can be removed. Similarly, by preheating the first and second reactant gases respectively through valve 243b of the gas supply pipe 232b supplying the first reactant gas and valve 243h of the gas supply pipe 232h supplying the second reactant gas, residual fluorine in the gas supply pipe 232b up to nozzle 249b can be removed. Furthermore, by preheating the first and second reactant gases respectively by a second heater 207c located downstream of valve 243k in the gas supply pipe 232k supplying the first reactant gas and valve 243c in the gas supply pipe 232c supplying the second reactant gas, residual fluorine in the gas supply pipe 232c up to nozzle 249c can be removed. It should be noted that, here, an example is shown where the first and second reactant gases are heated in separate gas supply pipes, but it is also possible to configure the first and second reactant gases to be heated after mixing.

[0108] In the cleaning method for the semiconductor device through the above-described steps (a) and (b), cleaning and fluorine deactivation can be performed by cleaning gas in the reaction tube 203 and nozzles 249a, 249b, 249c.

[0109] (2-4) Further processing of the substrate (wafer 200)

[0110] After the cleaning and fluorine deactivation processes (a) and (b) described above are completed in the reaction tube 203 and nozzles 249a, 249b, and 249c, the next batch of substrates (wafers 200) is transferred into the reaction tube 203 as part of process (c). The next batch of substrates (wafers 200) then undergoes the substrate (wafer 200) processing described in (2-1) above.

[0111] Example

[0112] The following describes an embodiment of the semiconductor device manufacturing method of this application.

[0113] It should be noted that in the following descriptions, the numerical range "75~200℃" means that both the lower and upper limits are included within the range. Therefore, for example, "75~200℃" means "above 75℃ and below 200℃". The same applies to other numerical ranges.

[0114] <Experiment Summary>

[0115] In the examples and comparative examples, a film formation process was first performed multiple times on the wafer. Then, the cleaning process and the supply of additive gas in step (a) were repeated alternately multiple times. After the fluorine deactivation process in step (b) was performed, the film formation process was repeated again. The film thickness was measured for the wafers obtained in each film formation process.

[0116] <Film Formation Treatment>

[0117] Perform the film-forming treatment described in (2-1) above. It should be noted that the setup and initial cleaning procedures before the film-forming treatment are omitted.

[0118] (raw material gas → P / V → first reactant gas + second reactant gas → P / V) × n

[0119] First, a wafer 200 is moved into the reaction tube 203. Then, as step 1, HCDS gas, which is used as a raw material gas, is supplied into the reaction tube 203 from the gas supply pipe 232a (first piping) and the nozzle 249a (first nozzle).

[0120] Next, as step 2, N2 gas is supplied (or not supplied) from the gas supply pipe 232n via the first piping and the first nozzle as a purging gas, while the reaction tube 203 is evacuated to remove the raw material gas remaining in the processing chamber.

[0121] Then, as step 3, H2 gas, which is the first reaction gas, is supplied to the wafer 200 in the reaction tube 203 via the gas supply pipe 232b (second pipe) and the nozzle 249b (second nozzle), while O2 gas, which is the second reaction gas, is supplied via the gas supply pipe 232c (third pipe) and the nozzle 249c (third nozzle).

[0122] Finally, as step 4, purge gas is supplied from gas supply pipe 232o via the second piping and the second nozzle, and purge gas is supplied from gas supply pipe 232p via the third piping and the third nozzle to perform vacuum exhaust in reaction tube 203 and remove the first and second reaction gases remaining in the treatment chamber.

[0123] Repeat steps 1 through 4 a predetermined number of times. Furthermore, the processing conditions for each step are as follows.

[0124] Raw material gas supply flow rate: 0.01–2 slm, preferably 0.1–1 slm.

[0125] Purge gas supply flow rate: 0–10 slm

[0126] First reaction gas supply flow rate: 0.1–10 slm.

[0127] Second reaction gas supply flow rate: 0.1–10 slm.

[0128] Gas supply time: 1–120 seconds, preferably 1–60 seconds.

[0129] Processing temperature: 250–800℃, preferably 400–700℃.

[0130] Processing pressure: 1~2666Pa, preferably 67~1333Pa.

[0131] <Cleaning Treatment>

[0132] After the wafer has undergone film deposition, the cleaning process described in (2-2) above is performed using all of the first, second, and third nozzles. Each nozzle is treated as follows: The respective treatments are performed in parallel.

[0133] First nozzle (nozzle 249a): Processing C

[0134] Second nozzle (nozzle 249b): Process A

[0135] Third nozzle (nozzle 249c): Processing B

[0136] That is, in the cleaning process, N2 gas, which is an inactive gas, is continuously supplied from gas supply pipe 232n via a first piping and a first nozzle. Additionally, F2 gas, serving as a cleaning gas, and NO gas, serving as an additive gas, are sequentially supplied from gas supply pipes 232i and 232j via a second piping and a second nozzle, corresponding to process A. Furthermore, cleaning gas and additive gas are sequentially supplied from gas supply pipes 232l and 232m via a third piping and a third nozzle, corresponding to process B. Here, process A and process B are performed simultaneously in each nozzle.

[0137] The supply of clean gas and the supply of additive gas are repeated a predetermined number of times. Furthermore, the processing conditions are as follows.

[0138] Clean gas supply flow rate: 1–20 slm, preferably 5–15 slm.

[0139] Add gas supply flow rate: 0.1–2 slm, preferably 0.5–1.5 slm.

[0140] Gas supply time: 10–120 seconds, preferably 20–40 seconds.

[0141] Processing temperature: 250–400℃, preferably 250–350℃.

[0142] Processing pressure: 1 to 1000 Torr, preferably 10 to 500 Torr.

[0143] <Fluoride Deactivation Treatment>

[0144] After the above cleaning process, the fluorine deactivation process described in (2-3) is carried out using all of the first, second and third nozzles.

[0145] First, H2 gas, serving as the first reactant gas, and O2 gas, serving as the second reactant gas, are supplied to the reaction tube 203 via first piping and first nozzle, respectively, from gas supply pipes 232d and 232e. Simultaneously, the first and second reactant gases are supplied to the reaction tube 203 via second piping and second nozzle, respectively, from gas supply pipes 232b and 232h. Furthermore, the first and second reactant gases are simultaneously supplied to the reaction tube 203 via first piping and first nozzle, respectively, from gas supply pipes 232k and 232c. The ratio of the supply flow rates of the first and second reactant gases is approximately 1:1. Other processing conditions are described below.

[0146] First reaction gas supply flow rate: 1-10 slm.

[0147] Second reaction gas supply flow rate: 1-10 slm.

[0148] Gas supply time: 30–300 minutes, preferably 100–150 minutes.

[0149] Processing temperature: 600~800℃

[0150] Processing pressure: 5–133 Pa, preferably 5–30 Pa.

[0151] It should be noted that in the comparative example, neither the first reactant gas nor the second reactant gas is supplied from the first piping and the first nozzle. The first reactant gas from the gas supply pipe 232b is supplied only from the second piping and the second nozzle, and the second reactant gas from the gas supply pipe 232c is supplied only from the third piping and the third nozzle.

[0152] <Results>

[0153] The results of film formation stability in the comparative examples and the embodiments are shown below. Figure 4 and Figure 5 It should be noted that, Figure 4 and Figure 5In the graphs, the vertical axis represents the film thickness of wafer 200 (in angstroms, indicating the increase or decrease relative to the reference film thickness), and the horizontal axis represents the number of film deposition processes. Additionally, the dashed lines in both graphs represent the reference film thickness. Furthermore, in both graphs, arrows indicate the time points when cleaning and fluorine deactivation processes were performed.

[0154] In the comparative example, after cleaning and fluorine deactivation following the third film-forming process, the film thickness immediately decreased by approximately 0.5 compared to the baseline film thickness. In particular, the reduction in film thickness became more significant after the 41st treatment.

[0155] On the other hand, in the embodiment, after cleaning and fluorine deactivation treatment following the sixth film-forming process, the film thickness immediately decreased, but by less than 0.1 mm. Moreover, the film thickness stabilized after the 14th treatment.

[0156] In the comparative examples, such as Figure 6 As shown in the schematic diagram, the first reactant gas is supplied only from nozzle 249b (the second nozzle), and the second reactant gas is supplied only from nozzle 249c (the third nozzle), while neither the first nor the second reactant gas is supplied from nozzle 249a (the first nozzle). As a result, in the area shown by B in the figure (which includes the processing chamber 201 within the reaction tube 203 and the exhaust pipe 231), the first and second reactant gases are sufficiently mixed, thus enabling adequate fluorine deactivation. However, in the vicinity of nozzles 249a, 249b, and 249c shown by A in the figure, the mixing of the first and second reactant gases is insufficient, thus preventing adequate fluorine deactivation, which is presumably detrimental to subsequent film formation processes.

[0157] On the other hand, in the embodiments, such as Figure 7 As shown in the schematic diagram, both the first and second reactant gases are supplied from all nozzles 249a (first nozzle), 249b (second nozzle), and 249c (third nozzle). As a result, the first and second reactant gases are thoroughly mixed in both region B and region A of the diagram, thus enabling sufficient fluorine deactivation and suggesting that subsequent film formation can proceed well.

[0158] <Other methods of this disclosure>

[0159] The above details the manner of this disclosure. However, the manner of this disclosure is not limited to the above, and various modifications may be made without departing from its essence.

[0160] In the film formation process, a film can also be formed on wafer 200 via the gas supply process shown below. The above cleaning process is also suitable for nozzles and reaction tubes made of the materials shown below.

[0161]

[0162] Here, carbon-containing gases include, for example, propylene gas (C3H6 gas), and nitrided gases include, for example, ammonia gas (NH3 gas).

[0163] The formulations for each process are preferably prepared separately according to the processing requirements and stored in the storage device 121c via a communication circuit and an external storage device 123. Furthermore, it is preferable that, at the start of each process, the CPU 121a selects a suitable formulation from the multiple formulations stored in the storage device 121c based on the processing requirements. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses using a single substrate processing apparatus. In addition, it reduces operator workload, avoids operational errors, and enables rapid initiation of each process.

[0164] The above-mentioned formula is not limited to the case of making a new one. For example, it can also be prepared by changing an existing formula that is already installed in the substrate processing apparatus. When changing the formula, the changed formula can be installed in the substrate processing apparatus via a communication circuit and a recording medium that records the formula. In addition, the existing formula that is already installed in the substrate processing apparatus can be directly changed by operating the input / output device 122 of the existing substrate processing apparatus.

[0165] In the above description, F2 and NF3 gases were used as examples of cleaning gases and fluorine-containing gases. This disclosure is not limited to the above methods; for example, hydrogen fluoride (HF), carbon tetrafluoride (CF4), and chlorine trifluoride (ClF3) gases can be listed. It should be noted that the cleaning gas preferably contains at least one of F2, NF3, HF, CF4, and ClF3.

[0166] The above method uses fluorine-containing gas as an example for cleaning. This disclosure is not limited to the above method; for example, it can also be applied when using cleaning gases containing halogen elements. Here, halogen elements refer to chlorine (Cl), fluorine (F), bromine (Br), and iodine (I).

[0167] The above method is illustrated using a batch substrate processing apparatus that processes multiple substrates at a time to form a film. This disclosure is not limited to the above method; for example, it can also be suitably applied when forming a film using a single-piece substrate processing apparatus that processes one or more substrates at a time. Furthermore, the above method is illustrated using a substrate processing apparatus equipped with a hot-wall type furnace to form a film. This disclosure is not limited to the above method; it can also be suitably applied when forming a film using a substrate processing apparatus equipped with a cold-wall type furnace.

[0168] When using these substrate processing devices, each process can be performed using the same processing procedures and conditions as described above, and the same effect as described above can be obtained.

[0169] Furthermore, the above methods can be used in appropriate combinations. In this case, the processing procedures and conditions can be the same as those in the methods described above.

Claims

1. A method for cleaning a nozzle and a reaction tube, comprising: (a) A process of forming a film in a substrate and a reaction tube by performing (a1) and (a2) the following steps a predetermined number of times. (a1) The process of supplying raw material gas to the substrate in the reaction tube via the first nozzle, (a2) The process of supplying the reactant gas to the substrate via a second nozzle, (b) Following step (a), the step of supplying a fluorine-containing cleaning gas into the reaction tube via the first nozzle and the second nozzle, as in step (b1), is performed. (c) The step of supplying a mixture of H2 and O2 gas into the reaction tube via the first nozzle and the second nozzle after step (b). The temperature inside the reaction tube in step (c) is higher than the temperature inside the reaction tube in step (b).

2. The method according to claim 1, wherein, In step (b), the cleaning gas is supplied into the reaction tube via all nozzles, including the first nozzle and the second nozzle, arranged within the reaction tube. In step (c), the mixed gas is supplied into the reaction tube via all the nozzles.

3. The method according to claim 1, wherein, For the first nozzle and the second nozzle, step (a) is performed simultaneously.

4. The method according to claim 1, wherein, The step (b) further includes (b2): a step of supplying a gas containing nitrogen and oxygen into the reaction tube via the first nozzle and the second nozzle.

5. The method according to claim 4, wherein, In step (b), steps (b1) and (b2) are performed alternately.

6. The method according to claim 1, wherein, In step (c), the first nozzle and the second nozzle are heated by a heater, thereby activating the mixed gas within the first nozzle and the second nozzle.

7. The method according to claim 6, wherein, In step (c), heating is performed so that the main areas of the first nozzle and the second nozzle reach a substantially uniform temperature.

8. The method according to claim 6, wherein, In step (c), heating is performed by the heater, which is positioned in a location corresponding to the area of ​​the substrate within the reaction tube.

9. The method according to claim 8, wherein, The substrate is the product substrate.

10. The method of claim 6, wherein, The first nozzle and the second nozzle and the heater are configured such that the regions of the first nozzle and the second nozzle that are at least provided with holes are located opposite to the heater.

11. The method according to claim 6, wherein, In step (b), the first nozzle and the second nozzle are heated by the heater. The heater is constructed by dividing the gas flow direction within the first nozzle and the second nozzle into multiple sections. In steps (b) and (c), the temperature is changed so that the temperature control of the multiple zones is different.

12. The method according to claim 11, wherein, In step (c), the temperature of at least one of the plurality of partitions corresponding to the processing area of ​​the substrate is controlled to be substantially the same.

13. The method of claim 11, wherein, In step (c), the temperature of the lower partition among the plurality of partitions is controlled to be higher than the temperature of the other partitions.

14. The method according to claim 1, wherein, It further includes: (e) a step in which the mixed gas is heated by a second heater outside the reaction tube.

15. A substrate processing method, comprising: (a) A process of forming a film in a substrate and a reaction tube by performing (a1) and (a2) the following steps a predetermined number of times. (a1) The process of supplying raw material gas to the substrate in the reaction tube via the first nozzle, (a2) The process of supplying the reactant gas to the substrate via a second nozzle, (b) Following step (a), the step of supplying a fluorine-containing cleaning gas into the reaction tube via the first nozzle and the second nozzle, as in step (b1), is performed. (c) The step of supplying a mixture of H2 and O2 gas into the reaction tube via the first nozzle and the second nozzle after step (b), and (d) The process of transferring the next batch of substrates into the reaction tube after step (c). The temperature inside the reaction tube in step (c) is higher than the temperature inside the reaction tube in step (b).

16. A method for manufacturing a semiconductor device, comprising: (a) A process of forming a film in a substrate and a reaction tube by performing (a1) and (a2) the following steps a predetermined number of times. (a1) The process of supplying raw material gas to the substrate in the reaction tube via the first nozzle, (a2) The process of supplying the reactant gas to the substrate via a second nozzle, (b) Following step (a), the step of supplying a fluorine-containing cleaning gas into the reaction tube via the first nozzle and the second nozzle, as in step (b1), is performed. (c) The step of supplying a mixture of H2 and O2 gas into the reaction tube via the first nozzle and the second nozzle after step (b), and (d) The process of transferring the next batch of substrates into the reaction tube after step (c). The temperature inside the reaction tube in step (c) is higher than the temperature inside the reaction tube in step (b).

17. A substrate processing apparatus comprising: The reaction tubes inside process the substrate. Compared to the transport mechanism for moving the substrate into and out of the reaction tube, The first nozzle that supplies various gases to the reaction tube A second nozzle supplies various gases to the reaction tube. A raw material gas supply system that supplies raw material gas via the first nozzle. The reaction gas supply system supplies reaction gas via the second nozzle. A clean gas supply system that supplies fluorine-containing clean gas to the first nozzle and the second nozzle. A hydrogen-oxygen gas supply system that supplies a mixture of H2 and O2 gases to the first nozzle and the second nozzle. Heating the heating section inside the reaction tube, and The control unit is configured to control the conveying mechanism, the raw material gas supply system, the reaction gas supply system, the clean gas supply system, and the hydrogen-oxygen gas supply system in such a way that the temperature inside the reaction tube processed in (c) is higher than the temperature inside the reaction tube processed in (b) to perform the following processes: (a) A process of forming a film in a substrate and a reaction tube by performing (a1) and (a2) a predetermined number of times. (a1) The process of supplying the raw material gas to the substrate in the reaction tube via the first nozzle. (a2) The process of supplying the reactive gas to the substrate via the second nozzle, (b) Following the treatment in (a), the process of supplying the cleaning gas into the reaction tube via the first nozzle and the second nozzle (b1) is performed. (c) Following the treatment in (b), a process containing the mixed gas is supplied into the reaction tube via the first nozzle and the second nozzle, and (d) The process of transferring the next batch of substrates into the reaction tube after the process in (c).

18. A computer-readable recording medium containing a program that enables a board processing apparatus to perform the following processes via a computer: (a) A process of forming a film in a substrate and a reaction tube by performing (a1) and (a2) the following steps a predetermined number of times. (a1) The process of supplying raw material gas to the substrate in the reaction tube via the first nozzle. (a2) The process of supplying reactive gas to the substrate via a second nozzle, (b) Following process (a), the process of supplying a fluorine-containing cleaning gas into the reaction tube via the first nozzle and the second nozzle, as described in (b1), is performed. (c) The process of supplying a mixture of H2 and O2 gas into the reaction tube via the first nozzle and the second nozzle after process (b), and (d) The process of transferring the next batch of substrates into the reaction tube after process (c). The temperature inside the reaction tube in process (c) is higher than the temperature inside the reaction tube in process (b).

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