Processing method, semiconductor device manufacturing method, program, and processing device

Abstract

The present invention includes: a) a step of supplying a first gas containing a first element and a first halogen to a member having an oxide film, thereby removing at least a portion of the oxide film; (b) a step of supplying an oxygen-containing gas to the member; (c) a step of supplying a second gas containing a second halogen to the member, in an atmosphere not containing oxygen; and (d) a step of sequentially performing (a), (b), and (c).

Description

Processing method, method for manufacturing a semiconductor device, program, and processing apparatus.

[0001] This disclosure relates to a processing method, a method for manufacturing a semiconductor device, a program, and an processing apparatus.

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

[0003] Patent Document 1: Japanese Unexamined Patent Publication No. 2023-46964

[0004] In the process of forming a film, the desired film characteristics may not be obtained.

[0005] This disclosure provides a technology capable of improving film properties.

[0006] According to one aspect of the present disclosure, a technology is provided that includes the steps of: a) supplying a first gas containing a first element and a first halogen to a member having an oxide film to remove at least a portion of the oxide film; b) supplying an oxygen-containing gas to the member; c) supplying a second gas containing a second halogen to the member in an oxygen-free atmosphere; and d) performing steps a), b), and c) in order.

[0007] According to this disclosure, it is possible to improve film properties.

[0008] This is a schematic diagram of the vertical processing furnace of an apparatus according to one embodiment of the present disclosure, showing the processing furnace 202 portion in a vertical cross-sectional view. This is a schematic diagram of a part of the vertical processing furnace of an apparatus according to one embodiment of the present disclosure, showing the processing furnace 202 portion in a cross-sectional view along line A-A in Figure 1. This is a schematic diagram of the control unit of an apparatus according to one embodiment of the present disclosure, showing the control system in a block diagram. This is a diagram showing an example of a flowchart for substrate processing according to one embodiment of the present disclosure. This is a diagram showing an example of a flowchart for a processing step according to one embodiment of the present disclosure. This is a model diagram of a member surface according to one embodiment of the present disclosure, where Figure 6(A) is a model of the member surface before processing, Figure 6(B) is a model diagram of the member surface after the first processing, Figure 6(C) is a model diagram of the member surface after the second processing, Figure 6(D) is a model diagram of the member surface after the third processing, and Figure 6(E) is a model diagram of the member surface after the fourth processing.

[0009] The following explanation will be given with reference to Figures 1 to 6. Please note that the drawings used in the following explanation are all schematic, and the dimensional relationships and ratios of each element shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of each element do not necessarily correspond between multiple drawings.

[0010] (1) As shown in the configuration diagram 1 of the processing apparatus, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism that activates the gas with heat.

[0011] 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 or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 (hereinafter referred to as MF209) is arranged concentrically with the reaction tube 203. The MF209 is made of a metal material such as stainless steel, and is formed in a cylindrical shape with open upper and lower ends. The upper end of the MF209 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 MF209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The processing vessel (reaction vessel) is mainly composed of the reaction tube 203 and the MF209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is carried out within this processing chamber 201.

[0012] Within the processing chamber 201, nozzles 249a to 249e, which serve as the first to fifth supply units, are provided so as to penetrate the side walls of the MF 209. Gas supply pipes 232a to 232e are connected to nozzles 249a to 249e, respectively. Nozzles 249a to 249e are all different nozzles, and nozzles 249b and 249d are each provided adjacent to nozzle 249c. Nozzles 249a and 249e are each provided adjacent to nozzles 249b and 249d on the opposite side from the side adjacent to 249c.

[0013] Gas supply pipes 232a to 232e are equipped with, in order from the upstream side of the gas flow, mass flow controllers (MFCs) 241a to 241e and valves 243a to 243e, which are flow control devices (flow control units). Downstream of valves 243a to 243e in gas supply pipes 232a to 232e, gas supply pipes 232f to 232j are connected, respectively. Gas supply pipes 232f to 232j are equipped with, in order from the upstream side of the gas flow, MFCs 241f to 241j and valves 243f to 243j, respectively. Gas supply pipes 232a to 232e are made of a metal material such as SUS.

[0014] Nozzles 249a to 249e are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, extending from the lower to the upper part of the inner wall of the reaction tube 203, rising upward in the direction of wafer 200 arrangement. That is, nozzles 249a to 249e 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, and are provided along the wafer arrangement region. In plan view, nozzle 249c is positioned to face the exhaust port 231a, described later, in a straight line with respect to the center of the wafer 200 being transported into the processing chamber 201. Nozzles 249b and 249d are positioned to sandwich a straight line L passing through the center of nozzle 249c and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (outer periphery of the wafer 200). Furthermore, nozzles 249a and 249e are positioned so as to sandwich a straight line L from both sides along the inner wall of the reaction tube 203, on the opposite side from the side adjacent to nozzle 249c of nozzles 249b and 249d. The straight line L is also the straight line passing through nozzle 249c and the center of the wafer 200. In other words, nozzle 249d can be said to be located on the opposite side of nozzle 249b with respect to the straight line L. Similarly, nozzle 249e can be said to be located on the opposite side of nozzle 249a with respect to the straight line L. Nozzles 249b and 249d are arranged symmetrically with respect to the straight line L as the axis of symmetry. Also, nozzles 249a and 249e are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250e for supplying gas are provided on the sides of nozzles 249a to 249e, respectively. Each of the gas supply holes 250a to 250e is opened so as to face (oppose) the exhaust port 231a in a plan view, and it is possible to supply gas toward the wafer 200. Multiple gas supply holes 250a to 250e are provided extending from the bottom to the top of the reaction tube 203.

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

[0016] From the gas supply pipe 232b, a reactant and an oxygen-containing gas are supplied to the processing chamber 201 as a second processing gas via the MFC 241b, valve 243b, and nozzle 249b.

[0017] From the gas supply pipe 232c, a hydrogen-containing gas is supplied to the processing chamber 201 as the third processing gas via the MFC 241c, valve 243c, and nozzle 249c.

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

[0019] From the gas supply pipe 232e, the raw material is supplied to the processing chamber 201 as the fifth processing gas via the MFC 241e, valve 243e, and nozzle 249e.

[0020] Inert gas is supplied from gas supply pipes 232f to 232j into the processing chamber 201 via MFCs 241f to 241j, valves 243f to 243j, gas supply pipes 232a to 232e, and nozzles 249a to 249e, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0021] The processing gas supply system is mainly composed of gas supply pipes 232a, 232b, 232c, 232d, 232e, MFCs 241a, 241b, 241c, 241d, 241e, and valves 243a, 243b, 243c, 243d, 243e. The inert gas supply system is mainly composed of gas supply pipes 232f to 232j, MFCs 241f to 241j, and valves 243f to 243j. In this disclosure, the gas supply system including gas supply pipe 232a, MFC 241a, and valve 243a is also referred to as the first supply system. Gas supply pipe 232f, MFC 241f, and valve 243f may also be considered as part of the first supply system. Furthermore, the gas supply system including gas supply pipe 232b, MFC 241b, and valve 243b is also referred to as the second supply system. Gas supply pipe 232g, MFC 241g, and valve 243g may also be considered as part of the second supply system. Furthermore, the gas supply system including gas supply pipe 232c, MFC 241c, and valve 243c is also referred to as the third supply system. Gas supply pipe 232h, MFC 241h, and valve 243h may also be considered as part of the third supply system. Furthermore, the gas supply system including gas supply pipe 232d, MFC 241d, and valve 243d is also referred to as the fourth supply system. Gas supply pipe 232i, MFC 241i, and valve 243i may also be considered as part of the fourth supply system. Furthermore, the gas supply system including the gas supply pipe 232e, MFC 241e, and valve 243e is also referred to as the fifth supply system. The gas supply pipe 232j, MFC 241j, and valve 243j may also be considered as part of the fifth supply system.

[0022] As shown in Figure 1, an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, in a plan view, the exhaust port 231a is located opposite (facing) the nozzles 249a to 249e (gas supply holes 250a to 250e) with the wafer 200 in between. The exhaust port 231a may also be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. As shown in Figure 1, a vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation from the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure inside the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0023] Below the MF209, a seal cap 219 (hereinafter SC219) is provided as a furnace opening cover capable of airtightly closing the lower end opening of the MF209. The SC219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the SC219 as a sealing member that contacts the lower end of the MF209. Below the SC219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the SC219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The SC219 is configured to be raised and lowered vertically by a boat elevator 115 (hereinafter BE115), which is a lifting mechanism installed outside the reaction tube 203. BE115 is configured as a transport device (transport mechanism) that moves the SC219 up and down to transport the wafer 200 into and out of the processing chamber 201. Below the MF209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the MF209 when the SC219 has been lowered and the boat 217 has been transported out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the MF209. The opening and closing operation of the shutter 219s is controlled by the shutter opening and closing mechanism 115s.

[0024] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in a multi-stage arrangement, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, a multi-stage insulation plate 218, also made of a heat-resistant material such as quartz or SiC, is supported.

[0025] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0026] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121.

[0027] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing apparatus, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe is a combination of steps in the substrate processing described later that cause the controller 121 to execute and obtain predetermined results, and functions as a program. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be simply referred to as "recipes." In this disclosure, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area where programs and data read by the CPU 121a are temporarily held.

[0028] The I / O port 121d is connected to the MFCs 241a to 241j, valves 243a to 243j, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, BE 115, shutter opening / closing mechanism 115s, etc.

[0029] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 241a to 241j, the opening and closing operation of valves 243a to 243j, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the BE 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0030] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, USB memory, and semiconductor memory such as SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this disclosure, the term recording media may include only the storage device 121c, only the external storage device 123, or both. The program (program product) may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] (2) Processing steps Using the processing apparatus described above, an example of a processing sequence for forming an oxide film on the surface of a component as one step in the manufacturing process of a semiconductor device will be explained mainly with reference to Figure 4, and an example of a processing sequence for removing the oxide film present on the surface of a component will be explained mainly with reference to Figures 5 and 6. In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0032] In the processing steps according to this embodiment (manufacturing steps for semiconductor devices), a) a step of supplying a first gas containing a first element and a first halogen to a member having an oxide film on its surface to remove at least a portion of the oxide film (first processing step); b) a step of supplying an oxygen-containing gas to the member (second processing step); c) a step of supplying a second gas containing a second halogen to the member in an oxygen-free atmosphere (third processing step); and d) a) b) c) in order to remove at least a portion of the oxide film present on the surface of the member.

[0033] In this disclosure, the term "component" may refer to a wafer as a substrate, a processing container, or a part provided inside the processing container. Parts provided inside the processing container may refer to, for example, a boat 217 as a substrate holder for holding the substrate, an insulating plate 218, a dummy wafer, a monitor wafer, nozzles 249a to 249e, etc.

[0034] In this disclosure, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this disclosure, the term "surface of a wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this disclosure, the phrase "form a predetermined layer on a wafer" may refer to directly forming a predetermined layer on the surface of the wafer itself or to forming a predetermined layer on top of a layer formed on the wafer. In this disclosure, the term "substrate" has the same meaning as the term "wafer."

[0035] As used herein, the term "agent" includes at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, an oxidizing agent may contain gaseous substances, may contain liquid substances such as mist-like substances, or may contain both.

[0036] (Wafer loading and boat loading) Once multiple wafers 200 are loaded into the boat 217, the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the MF 209. Then, as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the BE 115 and loaded into the processing chamber 201. In this state, the SC 219 seals the lower end of the MF 209 via the O-ring 220b.

[0037] (Pressure and Temperature Adjustment) The processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by a vacuum pump 246 so that it reaches the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and the APC valve 244 is controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by a heater 207 so that it reaches the desired film deposition temperature. At this time, the amount of power supplied to the heater 207 is controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all carried out continuously at least until the processing of the wafer 200 is completed.

[0038] (Film Formation Process) In the film formation process, a film is formed on the wafer 200. Here, an example of forming an oxide film on the wafer 200 is shown. Specifically, in the film formation process, raw materials and reactants are supplied to the wafer 200 to form an oxide film.

[0039] (Raw Material Supply Process) In the raw material supply process, valve 243e is opened and the raw material is flowed into the gas supply pipe 232e as the fifth processing gas. The flow rate of the raw material is adjusted by MFC 241e and supplied into the processing chamber 201 from the gas supply hole 250e of nozzle 249e and exhausted from exhaust pipe 231. At this time, the raw material is supplied to the wafer 200. At the same time, valve 243j may be opened and inert gas may be flowed into the gas supply pipe 232j. The flow rate of the inert gas flowing through gas supply pipe 232j is adjusted by MFC 241j. The inert gas is supplied into the processing chamber 201 together with the raw material and exhausted from exhaust pipe 231. This inert gas can be used as a diluent gas or carrier gas for the raw material. In addition, in order to prevent the raw material from entering nozzles other than nozzle 249e, the inert gas may be supplied from nozzles other than nozzle 249e.

[0040] Examples of processing conditions in raw material supply include: Raw material supply flow rate (excluding dilution gas): 0.1 to 10 g / min, more preferably 0.5 to 5 g / min Dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm Raw material supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm Processing temperature: 200 to 500°C, more preferably 200°C to 350°C Processing pressure: 100 to 10,000 Pa, more preferably 100 Pa to 1,000 Pa.

[0041] Here, numerical ranges such as "0.1 to 10 g / min" in this disclosure mean that the lower and upper limits are included within that range. For example, "0.1 to 10 g / min" means "0.1 g / min or more and 10 g / min or less". The same applies to other numerical ranges. Processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure refers to the pressure inside the processing chamber 201. Also, gas supply flow rate: 0 sccm means the case in which the gas is not supplied. These also apply in the following explanations.

[0042] As the raw material, a gas containing a molecule having a predetermined element and a ligand bonded to the predetermined element can be used. Examples of the predetermined element include metal elements, specifically transition metal elements, such as Group 4 elements like zirconium (Zr), hafnium (Hf), titanium (Ti), etc. Further examples of the metal element include, in addition to the above-mentioned Group 4 elements, tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W), etc.

[0043] Examples of the predetermined element include semi-metal elements, such as silicon (Si). The semi-metal elements in the present disclosure refer to, in addition to Si, boron (B), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te).

[0044] Examples of the ligand bonded to the predetermined element include organic ligands. Examples of the ligand bonded to the predetermined element include at least one of a hydrocarbon group and an amino group. Further examples of the hydrocarbon group bonded to the predetermined element include any one selected from the group consisting of an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentadienyl group, a cyclohexadienyl group, and a cycloheptatrienyl group, or a substituent thereof.

[0045] Examples of the raw material containing Zr as the predetermined element include, for example, tetrakisethylmethylaminozirconium (Zr[N(CH ３ )C ２ H ５ ] ４ ), tetrakisdiethylaminozirconium (Zr[N(C ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminozirconium (Zr[N(CH ３ ) ２ ] ４ ), Zr(MMP) ４ ), Zr(O-tBu) ４ ), tris-dimethylaminocyclopentadienyl zirconium ((C ５ H ５ )Zr[N(CH ３ ) ２ ]３ Gases such as ) can be used. One or more of these can be used as raw materials.

[0046] Furthermore, a raw material containing Hf as a specified element is, for example, tetrakisethylmethylaminohafnium (Hf[N(CH ３ ) C ２ H ５ ] ４ ), tetrakisdiethylaminohafnium (Hf[N(C) ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminohafnium (Hf[N(CH ３ ) ２ ] ４ ), Hf(O-tBu) ４ , Hf (MMP) ４ , Trisdimethylaminocyclopentadienylhafnium ((C ５ H ５ ) Hf[N(CH ３ ) ２ ] ３ Gases such as ) can be used. One or more of these can be used as raw materials.

[0047] Furthermore, a raw material containing Ti as a specified element is, for example, tetrakisethylmethylaminotitanium (Ti[N(CH ３ ) C ２ H ５ ] ４ ), tetrakisdiethylaminotitanium (Ti[N(C ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminotitanium (Ti[N(CH ３ ) ２ ] ４ ), Ti(O-tBu) ４ Ti (MMP) ４ Trisdimethylaminocyclopentadienyltitanium ((C ５ H ５ )Ti[N(CH ３ ) ２ ] ３Gases such as ) can be used. One or more of these can be used as raw materials.

[0048] Furthermore, as a raw material containing Al as a specified element, for example, organic gases or inorganic gases can be used. As an example of an organic gas, triethylaluminum ((C)) ２ H ５ ) ３ Al), trimethylaluminum ((CH ３ ) ３ Al), dimethylaluminum hydride ((CH ３ ) ２ AlH), dimethylethylamine allane (AlH ３ N(CH ３ ) ２ C ２ H ５ ) is an example of an inorganic gas, aluminum chloride (AlCl ３ ) are available. One or more of these can be used as raw materials.

[0049] Furthermore, organic gases and inorganic gases can be used as raw materials containing Si as a specified element. As organic gases, for example, aminosilane gases, i.e., gases containing Si and amino groups, can be used. As aminosilane gases, for example, (dimethylamino)trimethylsilane ((CH4) ３ ) ２ NSi(CH ３ ) ３ ), diethylaminotrimethylsilane ((C ２ H ５ ) ２ NSi(CH ３ ) ３ ), diethylaminotriethylsilane ((C ２ H ５ ) ２ NSi(C ２ H ５ ) ３ ), dimethylaminotriethylsilane ((CH ３ ) ２ NSi(C ２ H ５ ) ３), (dialkylamino)trialkylsilanes such as, (diisobutylamino)silane ((C ４ H ９ )), ２ NSiH ３ ), (diisopropylamino)silane ((C ３ H ７ )), ２ NSiH ３ ), etc. mono(dialkylamino)silanes, (ethylmethylamino)silane (SiH ３ (N(CH ３ )(C ２ H ５ )]]), (dimethylamino)silane (SiH ３ (N(CH ３ ) ２ ), etc. monoaminosilanes, trimethoxydimethylaminosilane ((CH ３ ) ２ NSi(OCH ３ ) ３ ), etc. trimethoxydialkylaminosilanes, bis(dimethylamino)dimethylsilane ([(CH ３ ) ２ N] ２ Si(CH ３ ) ２ ), etc. bis(dialkylamino)dialkylsilanes, tris(dimethylamino)methylsilane ([(CH ３ ) ２ N] ３ SiCH ３ ), etc. tris(dialkylamino)alkylsilanes, bis(diethylamino)silane ([(C ２ H ５ ) ２ N] ２ SiH ２ ), etc. bis(dialkylamino)silanes, bis(tert-butylamino)silane ([(C ４ H ９ NH] ２ SiH ２ ), etc. bis(monoalkylamino)silanes, tris(dimethylamino)silane ([(CH ３ ) ２ N] ３Tris(dialkylamino)silanes such as SiH) and tetrakis(dimethylamino)silane ([(CH ３ ) ２ N] ４ Gases such as tetrakis(dialkylamino)silanes (e.g., Si) can be used.

[0050] As for inorganic gases, tetrachlorosilane (SiCl ４ ) gas, monochlorosilane (SiH ３ Cl) gas, dichlorosilane (SiH ２ Cl ２ ) gas, trichlorosilane (SiHCl ３ ) gases, such as chlorosilane gases, can be used, which do not contain silicon-silicon bonds (i.e., bonds between specific elements) in a single molecule. In addition to chlorosilane gases, inorganic gases such as tetrafluorosilane (SiF) can also be used. ４ ) gas, difluorosilane (SiH ２ F ２ Fluorosilane gases such as ) gas, and tetrabromosilane (SiBr ４ ) gas, dibromosilane (SiH ２ Br ２ Bromosilane-based gases such as ) gas, and tetraiodosilane (SiI ４ ) gas, diiodosilane (SiH ２ I ２ It is also possible to use iodosilane-based gases such as ) gas, which do not contain silicon-silicon bonds (i.e., bonds between specific elements) in a single molecule. ２ Cl ６ ) gas, or octachlorotrisilane (Si ３ Cl ８ ) gas, monochlorodisilane (Si ２ H ５ Cl) gas, dichlorodisilane (Si ２ H ４ Cl ２ ) gas, trichlorodisilane (Si ２ H ３ Cl ３ ) gas, tetrachlorodisilane (Si ２ H ２ Cl ４) gas, monochlorotrisilane (Si ３ H ５ Cl) gas, dichlorotricilane (Si ３ H ４ Cl ２ A chlorosilane-based gas, such as ) gas, that contains a Si-Si bond (i.e., a bond between a predetermined element) in one molecule can be used. One or more of these can be used as raw materials.

[0051] (Reactant supply process) In the reactant supply process, valve 243b is opened and the reactant is flowed into the gas supply pipe 232b as the second processing gas. The reactant's flow rate is adjusted by MFC 241b and supplied into the processing chamber 201 from the gas supply hole 250b of nozzle 249b and exhausted from exhaust pipe 231. At this time, the reactant is supplied to the wafer 200. At the same time, valve 243g may be opened and an inert gas supplied into the gas supply pipe 232g. The inert gas flowing through the gas supply pipe 232g is adjusted by MFC 241g. The inert gas is supplied into the processing chamber 201 together with the reactant and exhausted from exhaust pipe 231. This inert gas can be used as a diluent gas or carrier gas for the reactant. In addition, in order to prevent the reactant from entering nozzles other than nozzle 249b, the inert gas may be supplied from nozzles other than nozzle 249b.

[0052] By supplying raw materials and reactants to a wafer 200, a film can be formed on the wafer 200 by the reaction of the raw materials and reactants on the wafer 200. The supply of raw materials and reactants may be performed simultaneously. Alternatively, the supply of raw materials and reactants may be performed separately and sequentially. Furthermore, the supply of raw materials and reactants may be performed separately and sequentially a predetermined number of times. The predetermined number of times is preferably one or an integer of two or more.

[0053] Examples of processing conditions in the reaction supply include: Reactant supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Reactant supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm Other conditions can be the same as those in the raw material supply.

[0054] An oxidizing agent can be used as the reactant. Specifically, oxygen (O) can be used as the oxidizing agent. ２ ) gas, ozone (O ３ ) Gas, water (H ２ O) Gas, hydrogen peroxide (H ２ O ２ ), hydrogen (H ２ ) Gas + O ２ A gas that has been activated, H ２ O gas + O ２ A gas that has been activated, H ２ O gas + O ３ At least one gas can be used.

[0055] In this manner, by supplying the raw materials and reactants to the wafer 200, an oxide film is formed on the wafer 200. In addition to the oxide film forming on the wafer 200, an oxide film is also formed on the components within the processing container. As the number of processing cycles (number of times the film formation process is performed) of the wafer 200 increases, the thickness of the oxide film formed on the components within the processing container also increases. When the thickness of the oxide film formed on these components reaches a predetermined thickness, cracks occur in the oxide film due to stress on the film, leading to particle generation. Therefore, a process to remove the oxide film formed on the components within the processing container becomes necessary. This process of removing the oxide film formed on the components within the processing container is also called a cleaning (CLN) process. Here, the components within the processing container refer to, for example, the parts that constitute the processing container (reaction tube 203) (including the processing container itself) or the parts provided inside the processing container (reaction tube 203), specifically, at least one of the following: reaction tube 203, boat 217, heat insulating plate 218, dummy wafer, monitor wafer, and nozzles 249a to 249e.

[0056] (Purge, wafer removal, count determination) After the film deposition process, the wafer 200 that has undergone the film deposition process is removed. First, the reaction tube 203 is purged to remove any remaining raw materials and reaction gases, and the inside of the reaction tube 203 is made into an inert gas atmosphere. After the inside of the reaction tube 203 is made into an inert gas atmosphere, the boat 217 is lowered to remove the processed wafer 200. After that, the count determination process is performed. In the count determination process, it is determined whether the film deposition process has been performed on the wafer 200 a predetermined number of times in the reaction tube 203. If it has been performed a predetermined number of times, it is determined to be Y, and the process moves to the next step. If it has not been performed a predetermined number of times, it is determined to be N, and the process moves to the next wafer. Note that if the film deposition process has been performed a predetermined number of times, it means that the CLN process is required for the component 200a.

[0057] The CLN process for component 200a will be explained below with reference to Figures 5 and 6. Here, component 200a, which has an oxide film on its surface, is exemplified by the inner wall of a processing container that houses a substrate. As shown in Figure 6(A), an oxide film 200b is formed on the surface of component 200a. In addition to the inner wall of the processing container, i.e., the inner wall of the reaction tube 203, component 200a may also be the surface of the boat 217, a dummy substrate, a monitor substrate, etc.

[0058] (Boat loading process) When the inner wall of the reaction tube 203, which serves as the processing container, is to be CLN'd along with the surface of the boat 217, the boat 217 may be loaded into the reaction tube 203, which serves as the processing container. At this time, no product substrates are placed on the boat 217. When CLNing dummy substrates or monitor substrates, the dummy substrates or monitor substrates may be placed on the boat 217.

[0059] (Pressure and Temperature Adjustment 1) Next, the reaction tube 203 is evacuated using the pump 246 so that the pressure inside the reaction tube 203 reaches a predetermined level. At this time, the pressure inside the reaction tube 203 is measured by the pressure sensor 245, and based on this measured pressure information, the APC valve 231a is feedback controlled to adjust the pressure inside the reaction tube 203. The reaction tube 203 is also heated by the heater 207 so that the inside reaches a predetermined first temperature. At this time, the power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 to adjust the temperature inside the reaction tube 203 so that the temperature inside the reaction tube 203 reaches a predetermined level. The operation of the pump 246 and the heating of the reaction tube 203 by the heater 207 are continued at least until the CLN process is completed.

[0060] A CLN process according to one aspect of the present disclosure comprises at least the first, second, and third processes shown in Figure 5.

[0061] (First Processing Step) In the first processing step, a first gas containing a first element and a first halogen is supplied as a first processing gas into the reaction tube 203, which serves as a processing vessel. Specifically, valve 243a is opened and the first gas flows into the gas supply pipe 232a. The flow rate of the first gas flowing through the gas supply pipe 232a is adjusted by MFC 241a and supplied into the processing chamber 201 from the gas supply hole 250a of nozzle 249a, and exhausted from exhaust pipe 231. At this time, the first gas is supplied into the reaction tube 203. It is preferable that the first processing step is carried out in an oxygen-free atmosphere into the reaction tube 203, which serves as a processing vessel. It is also preferable that the first processing step be carried out in a non-plasma state. The first gas, which serves as the first processing gas, reacts with the oxide film formed in the reaction tube 203 (preferably reacting in an oxygen-free atmosphere), thereby removing at least a portion of the oxide film.

[0062] Examples of processing conditions for the first treatment include: First gas flow rate: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm First gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm First temperature (first treatment temperature): 200°C to 800°C, more preferably 400°C to 550°C.

[0063] The first gas contains a first element and a first halogen. The first element is, for example, a group 1, group 13, group 14, or group 16 element. Specifically, these include hydrogen (H), silicon (Si), boron (B), aluminum (Al), gallium (Ga), indium (In), oxygen (O), and sulfur (S). The first halogen is, for example, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). Cl is preferred as the first halogen. Specific examples of the first gas include HCl and SiCl. ２ SiCl ４ , BCl ３ AlCl ３ GaCl ３ InCl ３ , SOCl ２ SO２ Cl, S ２ Cl ２ There is a gas containing a Group 13 element, preferably a gas containing a Group 13 element. For example, BCl ３ Gas can be used.

[0064] When at least a portion of the oxide film 200b formed on member 200a, as shown in Figure 6(A), is removed, four surfaces may be formed, as shown in Figure 6(B). Specifically, these four surfaces are: surface B1 where member 200a is exposed (indicated as "(B1)" in the figure), surface B2 where by-product 200d is formed on member 200a (indicated as "(B2)" in the figure), surface B3 where an oxide film 200c with reduced thickness is formed on member 200a (indicated as "(B3)" in the figure), and surface B4 where a by-product 200e is formed on the oxide film 200c with reduced thickness (indicated as "(B4)" in the figure). Here, the oxide film 200c with reduced thickness refers to an oxide film with reduced thickness after at least a portion of the oxide film 200b formed on member 200a has been removed. In this way, by performing the first treatment, at least a portion of member 200a (surface B1) is exposed. Furthermore, the oxide film 200b is preferably a metal oxide film, and more preferably a transition metal oxide film. In addition, in the first gas containing the first element and the first halogen, the first element is, for example, a group 13 element, and the first halogen is, for example, chlorine. When such film types and gases are used, oxides containing the first element (first oxide), i.e., a first substance containing the first element and oxygen, are formed as by-products 200d and 200e. The first substance (first oxide) is a substance in which the first element and the element oxygen do not have a stoichiometric composition, and if the first element is represented by the chemical formula M and oxygen O, then M ｘ O ｙ This can be shown as follows. When the first element is a group 13 element, an oxide containing the group 13 element is formed as the first substance (first oxide). When the first element is B, the first substance can be a substance in which x ≤ 2 and y < 3. Also, as the first substance, M ｘ O ｙ Cl ｚSubstances like the one shown may also be produced. Furthermore, by-products 200d and 200e may include substances containing the first element, the first halogen, and oxygen, as well as substances produced by the partial decomposition of the first gas. Such by-products 200d and 200e present a problem in that they are incorporated into the film formed on the product substrate during the subsequent film deposition process. Therefore, it is necessary to reduce the amount of by-products 200d and 200e. However, because the material composition of these by-products 200d and 200e is not stoichiometric, it is difficult to identify effective reactants for removal or effective treatment conditions for removal. The second and third treatment steps are performed as steps to remove these by-products 200d and 200e.

[0065] (Second Processing Step) In the second processing step, an oxygen-containing gas is supplied as the second processing gas into the reaction tube 203, which serves as the processing vessel. This oxidizes the by-products 200d and 200e. By oxidizing the by-products 200d and 200e, the oxide containing the first element (first oxide) contained in the by-products 200d and 200e is brought closer to the stoichiometric ratio. This oxide containing the first element, which is brought closer to the stoichiometric ratio (second oxide), is called the second substance. In the second processing step, valve 243b is opened, and the oxygen-containing gas is flowed into the gas supply pipe 232b as the second processing gas. The oxygen-containing gas supplied into the gas supply pipe 232b has its flow rate adjusted by MFC 241b. The flow-adjusted oxygen-containing gas is supplied into the processing chamber 201 from the gas supply hole 250a of nozzle 249b and exhausted from the exhaust pipe 231. At this time, the oxygen-containing gas is supplied into the reaction tube 203. Furthermore, the second processing step is preferably performed without plasma.

[0066] The by-products 200d and 200e may adhere to the member 200a, and it is preferable to allow them to settle on the member 200a while undergoing oxidation.

[0067] As a method for oxidizing the by-products 200d and 200e and fixing them on the member 200a, a method using an oxygen-containing gas and another reaction gas (also called an additive gas) is preferred. An example of the other reaction gas is a hydrogen-containing gas. In other words, in the second processing step, it is preferable to supply an oxygen-containing gas as a second processing gas and a hydrogen-containing gas as a third processing gas into the reaction tube 203, which serves as the processing vessel. Here, it is preferable to supply the oxygen-containing gas and the hydrogen-containing gas into the processing vessel and activate them within the vessel, particularly by heating. The supply of the oxygen-containing gas is as described above.

[0068] The supply of hydrogen-containing gas will now be explained. Valve 243c is opened, and hydrogen-containing gas is supplied into the gas supply pipe 232c as the third processing gas. The hydrogen-containing gas flowing into the gas supply pipe 232c is flow-controlled by the MFC 241c. The flow-controlled hydrogen-containing gas flows from the gas supply pipe 232c to the nozzle 249c, is supplied into the reaction pipe 203 from the gas supply hole 249a, and is exhausted from the exhaust pipe 231. At this time, hydrogen-containing gas is supplied into the reaction pipe 203.

[0069] By supplying oxygen-containing gas and hydrogen-containing gas to member 200a under the following processing conditions, the by-products 200d and 200e can be modified into a second substance with a composition close to that of a stoichiometric material.

[0070] Examples of processing conditions in the second process include: Oxygen-containing gas supply amount: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Hydrogen-containing gas supply amount: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Dilution gas (inert gas) supply flow rate: 0 to 100,000 sccm, more preferably 1,000 to 50,000 sccm Oxygen-containing gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Hydrogen-containing gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds First temperature (first processing temperature): 400 to 800°C Processing pressure: 100 to 26,600 Pa, more preferably 1,330 to 26,600 Pa The processing temperature may be the same as the processing temperature in the first process. By setting the processing temperature in the first process and the processing temperature in the second process to the same temperature, the time required to adjust the temperature from the processing temperature in the first process to the processing temperature in the second process can be shortened, thereby shortening the overall processing time. In other words, the time required for maintenance of the processing equipment can be shortened, and the downtime of the processing equipment (the time when substrates cannot be processed) can be shortened. Furthermore, when using both oxygen-containing gas and hydrogen-containing gas, the first temperature is preferably a temperature at which thermal activation is possible. Preferably, the processing pressure is lower than that of other processing steps, specifically, for example, the third processing step described later.

[0071] Examples of oxygen-containing gases include oxygen (O ２ ) gas, ozone gas (O ３ ) Gas, water (H ２ O) Gas, hydrogen peroxide (H ２ O ２ ) gas, hydrogen (H ２ ) + O ２ At least one gas, such as a gas, can be used. Furthermore, a gas obtained by activating at least one gas can also be used.

[0072] Furthermore, in this specification, "H ２ Gas + O ２ The joint listing of two gases, such as "gas", is H ２ Gas and O ２This refers to a mixed gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe before being supplied into the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and then mixed (postmixed) within the processing chamber 201.

[0073] Examples of hydrogen-containing gases include H ２ Gas, deuterium (D ２ ) Gas, H ２ O gas, H ２ O ２ At least one gas can be used, such as a gas. Preferably, the gas is elemental hydrogen. ２ Gas, D ２ There is gas.

[0074] By performing this process, the surface of member 200a changes from the state shown in Figure 6(B) to the state shown in Figure 6(C). Surface B1 of member 200a becomes surface C1 (indicated as "(C1)" in the figure) where the surface of member 200a is exposed. Surface B2, where the by-product 200d is exposed, becomes surface C2 (indicated as "(C2)" in the figure) where the by-product 200d is modified and the second substance 200f is formed. Surface B3, where the oxide film 200c with reduced thickness is exposed, becomes surface C3 (indicated as "(C3)" in the figure) where the oxide film 200c is modified and the oxide film 200g approaching the stoichiometric ratio is formed. Also, surface B4, where the by-product 200e is exposed, becomes surface C4 (indicated as "(C4)" in the figure) where the by-product 200e is modified and the second substance 200h is formed. The oxide film 200c present beneath the by-product 200e is thought to consist of areas where the oxide film 200c remains in its original state, and areas where, due to modification, an oxide film 200g approaching a stoichiometric ratio is formed. In this way, the second treatment is performed to cause oxide to form on the surface of the component 200a.

[0075] Next, the third treatment is performed. The third treatment is a process to remove the second substance. Before performing the third treatment to remove the second substance, pressure and temperature adjustments are carried out.

[0076] (Pressure and Temperature Adjustment 2) In pressure and temperature adjustment 2, the temperature is adjusted to a second temperature at which the second substance is removed in the third treatment. The second temperature is preferably lower than the first temperature.

[0077] (Third Processing Step) In the third processing step, a second gas containing a second halogen is supplied as the fourth processing gas into the reaction tube 203, which serves as the processing vessel, in an oxygen-free atmosphere. In this way, the second substances 200f and 200h are removed. Specifically, valve 243d is opened and the second gas is supplied as the fourth processing gas into the gas supply pipe 232d. The flow rate of the second gas is adjusted by MFC 241d and supplied into the processing chamber 201 from the gas supply hole 250d of nozzle 249d and exhausted from the exhaust pipe 231. At this time, the second gas is supplied into the reaction tube 203. At this time, valve 243i may be opened and an inert gas may be flowed into the gas supply pipe 232i. The flow rate of the inert gas that has flowed through the gas supply pipe 232i is adjusted by MFC 241i. The inert gas is supplied into the processing chamber 201 together with the second gas and exhausted from the exhaust pipe 231. This inert gas can be used as a diluent gas or carrier gas for the second gas. In order to prevent the second gas from entering nozzles other than nozzle 249d, the inert gas may be supplied from nozzles other than nozzle 249d. The third processing step is preferably performed without plasma.

[0078] The second substance can be removed by supplying the second gas as the fourth processing gas under the following processing conditions.

[0079] Examples of processing conditions in the second process include: Second gas supply amount: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Dilution gas (inert gas) supply flow rate: 0 to 100,000 sccm, more preferably 1,000 to 50,000 sccm Second gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Second temperature (second processing temperature): 200 to 650°C, more preferably 200 to 400°C Processing pressure: 100 to 26,600 Pa, more preferably 1,330 to 26,600 Pa.

[0080] The second gas contains a second halogen. The second halogen is preferably a different element from the first halogen. For example, the second halogen is fluorine (F). Specifically, the second gas containing such a second halogen is fluorine (F). ２ ) gas, hydrogen fluoride (HF) gas, nitrogen trifluoride (NF ３ ) gas, fluorine trichloride (ClF ３ At least one gas can be used, such as ) gas. In the following example, NF ３ This section describes an example using gas.

[0081] By performing this process, the surface of member 200a changes from the state shown in Figure 6(C) to the state shown in Figure 6(D). Surface C1 of member 200a becomes surface D1 (indicated as "(D1)" in the figure) where the surface of member 200a is exposed. Surface C2 becomes surface D2 (indicated as "(D2)" in the figure) where the second substance 200f is removed and the surface of member 200a is exposed. Surface C3 becomes surface D3 (indicated as "(D3)" in the figure) where an oxide film 200i is formed, with at least a portion of the oxide film 200g removed. Surface C4 becomes surface D4 (indicated as "(D4)" in the figure) where an oxide film 200i is formed, with the second substance 200h removed and at least a portion of the oxide film 200c removed. Furthermore, by processing at the second temperature, the second gas can be preferentially reacted with the second substance (second oxide) 200f, 200h rather than with the surface (surface D1) of member 200a. In other words, the etching amount of the second substance 200f, 200h can be made greater than the etching amount of the surface of member 200a.

[0082] (Counting Determination) Next, it is determined whether the first, second, and third processes have been performed a predetermined number of times. The predetermined number is an integer of 1 or more. If the first, second, and third processes have been performed a predetermined number of times, it is determined as Y, and the process moves to the next process. If they have not been performed a predetermined number of times, it is determined as N, and the process returns to the first process.

[0083] (Fourth Treatment) Next, the fourth treatment will be described. In the fourth treatment, raw materials and reactants are supplied to coat the components inside the treatment container. The same treatment and conditions as those used for the film formation treatment described above can be used for this fourth treatment.

[0084] By performing the fourth treatment, the surface of member 200a changes from the state shown in Figure 6(D) to the state shown in Figure 6(E). Surfaces D1 and D2 of member 200a have surfaces E1 and E2 (indicated as "(E1)" and "(E2)" in the figure) where an oxide film 200j is formed on the exposed surface of member 200a. Surfaces D3 and D4 have surfaces E3 and E4 (indicated as "(E3)" and "(E4)" in the figure) where an oxide film 200j is formed on top of an oxide film 200i.

[0085] The processing steps are carried out in this manner.

[0086] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained: (a) to (r).

[0087] (a) By supplying a first gas containing a first element and a first halogen to a member having an oxide film on its surface, at least a portion of the oxide film on the surface of the member can be removed. (b) By supplying the first gas in an oxygen-free atmosphere, oxygen-containing gas is not supplied to the atmosphere of the space in which the member is exposed, thereby suppressing film formation on the member due to the reaction between the first gas and the oxygen-containing gas. (c) By supplying an oxygen-containing gas to a member from which at least a portion of the oxide film has been removed, an oxide film can be formed on the surface of the member with a by-product composition close to stoichiometric ratio. (d) By supplying a second gas containing a second halogen in an oxygen-free atmosphere to a member that has formed an oxide film close to stoichiometric ratio, the oxide film close to stoichiometric ratio can be removed. Furthermore, by not including oxygen, the reaction between oxygen and the second halogen in the second gas can be suppressed, and the number of molecules of the second gas that come into contact with the oxide film close to stoichiometric ratio can be increased. In addition, re-oxidation of the oxide film close to stoichiometric ratio can be suppressed during the removal process by the second gas. (e) By using chlorine as the first halogen, at least a portion of the oxide film formed on the surface of the member can be etched. (f) The oxide film formed on the surface of the member is preferably a metal oxide film. More preferably, it is a transition metal oxide film. Even more preferably, it is a Group 4 oxide film. By supplying a gas containing chlorine as the first gas to such an oxide film, the efficiency of removing the oxide film formed on the surface of the member can be improved. (g) By supplying the first gas in an oxygen-free atmosphere, the formation of oxides of the first element can be suppressed. This can also be called supplying the first gas without supplying an oxygen-containing gas. (h) By supplying the first gas in a non-plasma atmosphere, plasma decomposition of the first gas in the gas phase can be suppressed. If plasma decomposition occurs in the gas phase, the effect of removing the film formed on the surface of the member is reduced. Also, decomposition may lead to the deposition of a film with the first element as the main element. For example, the first gas may be a halide containing boron, specifically BCl ３ This section explains the case using BCl.３ If plasma is generated during supply, BCl ３ → B + Cl ｘ An unintended reaction occurs (without considering the valency), making it difficult to remove the oxide film from the material. Also, B ｘ O ｙ The problem arises that it is not possible to generate the second gas. (i) By supplying the second gas in a non-plasma atmosphere, damage to the material can be reduced. The decomposition of the second gas causes the decomposition products of the second gas to etch the material, which is a problem. Furthermore, etching of the material can cause problems such as particle generation. (j) By supplying the second gas in a non-plasma atmosphere, plasma decomposition of the second gas in the gas phase can be suppressed. The problem of not being able to obtain the desired reaction due to the decomposition of the second gas can be suppressed. The first element is boron, the second substance is boron oxide, and the second gas is NF ３ In the case of gas, NF ３ +B ２ O ３ →BF ｘ +NO ｘ(k) The second substance can be removed by the desired reaction (valence not considered), but if the second gas decomposes, it becomes difficult to generate this reaction. (k) When supplying the oxygen-containing gas, supplying a hydrogen-containing gas and thermally activating it can generate OH radicals and atomic oxygen, thereby improving the efficiency of generating the oxide film of the first element. Although activation may be performed using plasma, it is preferable to use radicals and atomic oxygen rather than ionic components to modify the first substance into the second substance to every corner of the material. (l) By performing the process at a temperature of 400°C or lower, etching of the material itself by the second gas can be suppressed. (m) By making the pressure in the space where the material is located when the first gas is supplied higher than the pressure when the oxygen-containing gas is supplied, the removal rate of the oxide film on the material can be improved. (n) By making the pressure in the space where the material is located when the second gas is supplied higher than the pressure when the oxygen-containing gas is supplied, the amount of fluorination of the second substance can be increased, and the removal rate of the second substance can be improved. (o) By lowering the pressure when supplying the oxygen-containing gas compared to the pressure when supplying other gases, the oxygen-containing gas can be more easily activated. This makes it possible to modify the first substance into a second substance with a composition close to its stoichiometric composition. (p) By performing the steps of supplying the first gas to remove at least a portion of the oxide film on the member, supplying the oxygen-containing gas, and supplying the second gas containing the second halogen in an oxygen-free atmosphere on the member a predetermined number of times (1 or an integer of 2 or more), the amount of oxide film removed from the member can be increased. (q) By using chlorine as the first halogen in the first gas, the amount of volatilization of the oxide film formed on the member can be increased. Furthermore, even if the oxide film formed on the member is a metal oxide film, for example, a High-K film, its volatilization can be increased. (r) By using fluorine as the second halogen in the second gas, the amount of volatilization of oxides containing the first element generated by the supply of the first gas can be increased.

[0088] In the embodiments described above, the case where the first element is boron was explained, but the invention is not limited to this. The technology of this disclosure may also be applicable when the first element is an element other than those of Group 13. Furthermore, the technology may also be applicable when the first element is a metalloid (B, Si, Ge, As, etc.). Even in this case, at least one of the effects described in this disclosure can be obtained. In addition, the invention was explained in terms of removing a metal oxide film, preferably a transition metal, and more preferably an oxide film of a Group 4 element, but the invention is not limited to this. The technology of this disclosure may also be applicable to removing an oxide film of a Group 13 metal element.

[0089] It is preferable to prepare (or have multiple) process recipes (programs describing processing procedures and conditions, etc.) used in these processes individually, according to the content of the substrate processing (type of film to be formed, composition ratio, film quality, film thickness, processing procedure, processing conditions, etc.). When starting the process, it is preferable to appropriately select an appropriate process recipe from among the multiple process recipes according to the content of the process. Specifically, it is preferable to pre-store (install) the multiple process recipes prepared individually according to the content of the process into the storage device 121c of the substrate processing apparatus via a telecommunications line or a recording medium (external storage device 123) that records the process recipes. When starting the process, it is preferable for the CPU 121a of the substrate processing apparatus to appropriately select an appropriate process recipe from among the multiple process recipes stored in the storage device 121c according to the content of the process. With this configuration, a single substrate processing apparatus can form thin films of various types, composition ratios, film quality, and film thickness in a general-purpose and reproducible manner. In addition, the burden on the operator (the burden of inputting processing procedures and processing conditions, etc.) can be reduced, and the process can be started quickly while avoiding operational errors.

[0090] Furthermore, this disclosure can also be implemented, for example, by changing the process recipe of an existing substrate processing apparatus. When changing the process recipe, it is possible to install the process recipe relating to this disclosure into the existing substrate processing apparatus via a telecommunications line or a recording medium on which the process recipe is stored, or to change the process recipe itself to the process recipe relating to this disclosure by operating the input / output device of the existing substrate processing apparatus.

[0091] Furthermore, this disclosure can be used, for example, in the manufacturing process of NAND flash memory, DRAM, LOGIC, etc., which have a three-dimensional structure.

[0092] The above-described embodiments illustrate an example of processing using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above-described embodiments and can be suitably applied, for example, to processing using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of processing using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can be suitably applied to processing using a substrate processing apparatus having a cold-wall type processing furnace.

[0093] Even when using these substrate processing devices, each process can be performed using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0094] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications.

[0095] [Explanation of symbols] 200a Component 200b Oxide film

[0096] The disclosure of Japanese Patent Application No. 2025-015058, filed on 31 January 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually described as being incorporated by reference.

Claims

1. A processing method comprising: a) supplying a first gas containing a first element and a first halogen to a member having an oxide film on its surface to remove at least a portion of the oxide film; b) supplying an oxygen-containing gas to the member; c) supplying a second gas containing a second halogen to the member in an oxygen-free atmosphere; and d) performing a) b) c) in order.

2. a) The processing method according to claim 1, wherein the first gas is supplied in an oxygen-free atmosphere.

3. The processing method according to claim 1, wherein a), b), and c) are each performed in a non-plasma state.

4. b) The processing method according to claim 1, wherein a hydrogen-containing gas is supplied to the member.

5. b) The treatment method according to claim 4, wherein the oxygen-containing gas and the hydrogen-containing gas are activated.

6. b) The processing method according to claim 4, wherein the oxygen-containing gas and the hydrogen-containing gas are heated and activated.

7. The processing method according to claim 1, wherein a first oxide containing the first element is formed on the surface of the member.

8. b) The treatment method according to claim 7, wherein the first element is a group 13 element, and the first oxide is an oxide containing the group 13 element.

9. The processing method according to claim 1, wherein step d) is performed a predetermined number of times.

10. The processing method according to claim 1, wherein the first halogen and the second halogen are different elements.

11. The treatment method according to claim 1, wherein the first halogen is chlorine and the second halogen is fluorine.

12. The processing method according to claim 1, wherein a) and b) are performed at a first temperature, and c) is performed at a second temperature.

13. The processing method according to claim 12, wherein the second temperature is lower than the first temperature.

14. The processing method according to claim 1, wherein the member is a processing container for housing a substrate.

15. The processing method according to claim 1, wherein a portion of the oxide film is removed to expose at least a portion of the member.

16. The processing method according to claim 12 or 13, wherein in b) a second oxide containing the first element is formed on the surface of the member, and c) is carried out at a second temperature in which the second gas reacts preferentially with the second oxide than with the member.

17. The processing method according to claim 1, wherein b) is performed at a pressure lower than the pressure in c).

18. A method for manufacturing a semiconductor device, comprising: a) a step of supplying a first gas containing a first element and a first halogen to a member on which an oxide film has been formed by processing a substrate, thereby removing at least a portion of the oxide film; b) a step of supplying an oxygen-containing gas to the member; c) a step of supplying a second gas containing a second halogen to the member in an oxygen-free atmosphere; and d) a) a) b) c) in order.

19. A program that causes a computer to cause a processing device to execute the following steps: a) a first gas containing a first element and a first halogen to be supplied to a member having an oxide film to remove at least a portion of the oxide film; b) an oxygen-containing gas to be supplied to the member; c) a second gas containing a second halogen to be supplied to the member in an oxygen-free atmosphere; and d) a) a) b) c) in order.

20. A processing apparatus comprising: a first supply system for supplying a first gas containing a first element and a first halogen to a member; a second supply system for supplying an oxygen-containing gas to the member; a third supply system for supplying a second gas containing a second halogen to the member; and a control unit configured to control the first supply system, the second supply system, and the third supply system so as to perform: a) a process of supplying the first gas to the member on which an oxide film has been formed by processing a substrate, in order to remove at least a portion of the oxide film; b) a process of supplying the oxygen-containing gas to the member; c) a process of supplying the second gas to the member in an oxygen-free atmosphere; and d) a process of performing a) b) c) in order.

Images