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

Abstract

The present invention relates to a processing method, a semiconductor device manufacturing method, a processing apparatus, and a program product. The object is to simplify a manufacturing process of a semiconductor device. A semiconductor device manufacturing method has the following steps: (a) a step of modifying a surface of a substrate of one of a first substrate and a second substrate in a manner of F-termination by supplying a fluorine-containing radical generated from a fluorine-containing gas to the substrate in which the first substrate and the second substrate are exposed on the surface; and (b) a step of forming a film on a surface of the other substrate different from the one substrate among the first substrate and the second substrate by supplying a film formation gas to the substrate in which the surface of the one substrate is modified.

Description

[0001] This application is a divisional application of Chinese invention patent application No. 202010015642.4, filed on January 7, 2020, entitled "Method for manufacturing a semiconductor device, substrate processing apparatus and recording medium". Technical Field

[0002] This invention relates to processing methods, methods for manufacturing semiconductor devices, processing apparatus, and process products. Background Technology

[0003] As a step in the manufacturing process of semiconductor devices, there is a situation where a film is selectively grown and formed on the surface of a specific substrate among a variety of substrates exposed on the substrate surface (hereinafter, this process will also be referred to as selective growth or selective film formation) (see, for example, Patent Document 1).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2013-243193 Summary of the Invention

[0005] The problem that the invention aims to solve The purpose of this invention is to provide a technology that simplifies the manufacturing process of semiconductor devices.

[0006] Methods for solving problems According to one aspect of the present invention, a technique for performing the following steps is provided: (a) A process of modifying the surface of one of the first and second substrates by supplying fluorine-containing free radicals generated from a fluorine-containing gas to a substrate on which the first and second substrates are exposed, thereby modifying the surface of the substrate in an F-terminal manner; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

[0007] This application relates to the following: Item 1. A method for manufacturing a semiconductor device, comprising the following steps: (a) A process of modifying the surface of one of the first and second substrates by supplying fluorine-containing free radicals generated from a fluorine-containing gas to a substrate on which the first and second substrates are exposed, thereby modifying the surface of the substrate in an F-terminal manner; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

[0008] Item 2, the method of manufacturing a semiconductor device according to Item 1, wherein, in (a), the surface of the substrate of the device is modified by SiF end capping.

[0009] Item 3, the method of manufacturing a semiconductor device according to Item 1, wherein, in (a), the surface of the substrate of the device is modified in a non-etching manner.

[0010] Item 4. A method for manufacturing a semiconductor device according to Item 1, wherein, in (a), the surface of the substrate of one substrate is modified while suppressing the modification of the surface of the other substrate.

[0011] Item 5. A method for manufacturing a semiconductor device according to Item 1, wherein, in (b), the film is formed on the surface of the other substrate instead of on the surface of one of the substrates.

[0012] Item 6. A method for manufacturing a semiconductor device according to Item 1, wherein, in (a), the fluorine-containing gas is supplied in an atmosphere in the presence of a dummy catalyst, thereby generating the fluorine-containing free radical.

[0013] Item 7. The method of manufacturing a semiconductor device according to Item 6, wherein the dummy catalyst comprises silicon whose outermost surface is not covered by a native oxide film.

[0014] Item 8. The method for manufacturing a semiconductor device according to Item 6, wherein the dummy catalyst contains silicon material with silicon exposed on the outermost surface.

[0015] Item 9. The method of manufacturing a semiconductor device according to Item 6, wherein the dummy catalyst comprises silicon in which the natural oxide film formed on the outermost surface has been removed.

[0016] Item 10. A method for manufacturing a semiconductor device according to Item 6, wherein the dummy catalyst comprises a reactive gas that promotes the decomposition of the fluorine-containing gas.

[0017] Item 11. The method for manufacturing a semiconductor device according to Item 6, wherein the dummy catalyst comprises at least one of oxygen, nitrous oxide gas, nitrogen dioxide gas, nitric oxide gas, hydrogen fluoride gas, ammonia gas, and hydrogen gas.

[0018] Item 12. A method for manufacturing a semiconductor device according to Item 1, wherein the first substrate comprises an oxygen-containing film and the second substrate comprises an oxygen-free film.

[0019] Item 13. A method for manufacturing a semiconductor device according to Item 1, wherein the first substrate comprises an oxide film and the second substrate comprises a nitride film.

[0020] Item 14. A method for manufacturing a semiconductor device according to Item 1, wherein the first substrate comprises a film containing silicon and oxygen, and the second substrate comprises a film containing silicon and nitrogen.

[0021] Item 15. A method for manufacturing a semiconductor device according to Item 1, wherein the substrate of one of the substrates is the first substrate and the other substrate is the second substrate.

[0022] Item 16. A method for manufacturing a semiconductor device according to Item 1, wherein (a) and (b) are carried out in a non-plasma atmosphere.

[0023] Item 17. A method for manufacturing a semiconductor device according to Item 1, wherein, in (a), the fluorine-containing gas is activated by plasma, heating or light irradiation to generate fluorine-containing free radicals.

[0024] Item 18. The method for manufacturing a semiconductor device according to Item 1 further comprises the following steps: (c) A process of eliminating the F-end formed on the surface of one of the substrates by contacting the substance that reacts with fluorine with the surface of the substrate after a film has been formed on the surface of the other substrate.

[0025] Item 19, a substrate processing apparatus, comprising: Processing chamber, for substrates to be processed; A fluorine-containing gas supply system that supplies fluorine-containing gas to the substrate inside the processing chamber; A film-forming gas supply system that supplies film-forming gas to the substrate within the processing chamber; A heater that heats the substrate within the processing chamber; and The control unit is configured to control the fluorine-containing gas supply system, the film-forming gas supply system, and the heater in such a manner as the following process is performed in the processing chamber: (a) A treatment that modifies the surface of one of the first and second substrates by supplying fluorine-containing radicals generated from the fluorine-containing gas to a substrate exposing the first and second substrates on its surface in an F-terminal manner; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying the film-forming gas to the substrate after surface modification of the substrate of the first substrate.

[0026] Item 20. A computer-readable recording medium having a program that causes a substrate processing apparatus to perform the following steps within the processing chamber of the substrate processing apparatus by means of a computer, the steps being: (a) The step of modifying the surface of one of the first and second substrates by supplying fluorine-containing radicals generated from a fluorine-containing gas to a substrate exposing the first and second substrates on its surface in an F-terminated manner; and (b) The step of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

[0027] Invention Effects According to the present invention, the manufacturing process of semiconductor devices can be simplified. Attached Figure Description

[0028] Figure 1 This is a schematic configuration diagram of a longitudinal processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention, showing a portion of the processing furnace 202 in a longitudinal sectional view.

[0029] Figure 2 This is a schematic diagram of the longitudinal processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention. Figure 1 The AA-line sectional view shows part of the processing furnace 202.

[0030] Figure 3 This is a schematic configuration diagram of the controller 121 of a substrate processing apparatus preferably used in one aspect of the present invention, and is a block diagram showing the control system of the controller 121.

[0031] Figure 4 This is a diagram illustrating the processing timing during selective growth according to one aspect of the present invention.

[0032] Figure 5 (a) is a partially enlarged cross-sectional view of the surface of the wafer 200 exposed on the surface of the substrate 200a containing a silicon oxide film and the substrate 200b containing a silicon nitride film, respectively. Figure 5 (b) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the surface of the substrate 200a has been selectively modified using fluorine-containing free radicals generated from fluorine-containing gas; Figure 5 (c) is a partially enlarged cross-sectional view of the surface of the wafer 200 after a silicon nitride film has been selectively formed on the surface of the substrate 200b. Figure 5 (d) is to Figure 5 (c) is a partial enlarged cross-sectional view of the surface of wafer 200 after it has been exposed to the atmosphere.

[0033] Figure 6 This is a partially enlarged cross-sectional view of the surface of the substrate 200a in the wafer 200 before modification treatment.

[0034] Figure 7 (a) ~ Figure 7 (d) are magnified cross-sectional views of the surface of the substrate 200a in the modified wafer 200.

[0035] Figure 8 These are graphs showing the measurement results of the thickness of the silicon nitride film formed on the wafer.

[0036] Explanation of reference numerals in the attached figures 200 wafers (substrates) 200a substrate (substrate 1) 200b substrate (second substrate) Detailed Implementation

[0037] <One aspect of the present invention> The following is mainly based on Figures 1-4 This invention is described in one aspect.

[0038] (1) Composition of substrate processing device like Figure 1 As shown, the processing furnace 202 has a heater 207 as a heating mechanism (temperature control unit). The heater 207 is cylindrical and is vertically mounted by being supported on a retaining plate. The heater 207 also functions as an activation mechanism (activation unit) that uses heat to activate (excite) the gas.

[0039] 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 that is closed at the top and open at the bottom. 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 that is open at both the top and bottom. The upper end of the manifold 209 engages with 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 processing container. The processing chamber 201 is configured to accommodate a wafer 200, which serves as a substrate. Processing of the wafer 200 is performed within this processing chamber 201.

[0040] Inside the processing chamber 201, nozzles 249a to 249c, serving as the first to third supply sections, are respectively provided through the side wall of the manifold 209. These nozzles are also referred to as the first to the third nozzles. The nozzles 249a to 249c are made of heat-resistant materials such as quartz or SiC. The nozzles 249a to 249c are connected to gas supply pipes 232a to 232c. The nozzles 249a to 249c are distinct nozzles, and each nozzle is adjacent to a nozzle 249b.

[0041] Mass flow controllers (MFCs) 241a-241c, serving as flow controllers (flow control units), and valves 243a-243c, serving as on / off valves, are sequentially installed on gas supply pipes 232a-232c, starting from the upstream side of the airflow. Gas supply pipes 232d-232f are connected downstream of gas supply pipes 232a-232c, respectively, compared to valves 243a-243c. MFCs 241d-241f and valves 243d-243f are sequentially installed on gas supply pipes 232d-232f, starting from the upstream side of the airflow. Gas supply pipes 232a-232f are, for example, made of a metal material such as SUS.

[0042] like Figure 2 As shown, nozzles 249a to 249c are arranged in a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, and are respectively positioned upwards along the inner wall of the reaction tube 203 towards the arrangement direction of the wafer 200. That is, nozzles 249a to 249c are arranged along the wafer arrangement area, in a region that horizontally surrounds the wafer arrangement area to the side of the wafer arrangement area where the wafer 200 is arranged. When viewed from above, nozzle 249b is arranged so that it is aligned with the exhaust port 231a (described later) in a straight line, clamping the center of the wafer 200 being moved into the processing chamber 201. Nozzles 249a and 249c are arranged so that a straight line L (which passes through the center of nozzle 249b and exhaust port 231a) is clamped from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). Straight line L also passes through the center of nozzle 249b and wafer 200. That is, nozzle 249c can also be positioned on the opposite side of nozzle 249a, sandwiching a straight line L. Nozzles 249a and 249c are arranged linearly symmetrically about the straight line L. Gas supply holes 250a to 250c for supplying gas are provided on the sides of nozzles 249a to 249c. Gas supply holes 250a to 250c open in a manner that faces exhaust port 231a when viewed from above, and can supply gas toward wafer 200. Multiple gas supply holes 250a to 250c are provided from the bottom to the top of reaction tube 203.

[0043] A gas containing halogens and silicon (Si), the main element constituting the film formed on the wafer 200, is supplied into the processing chamber 201 through gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a. This gas is a halosilane gas. The halosilane gas functions as the film-forming gas, i.e., the Si source (raw material gas). Halogens include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). For example, a chlorosilane gas containing Si and Cl, such as silicon tetrachloride (SiCl4), can be used as the halosilane gas.

[0044] Fluorine (F) gas is supplied into the processing chamber 201 from the gas supply pipe 232b via MFC 241b, valve 243b, and nozzle 249b. For example, chlorine trifluoride (ClF3) gas can be used as the F-containing gas.

[0045] Hydrogen nitride gas, which is a nitrogen-containing gas, is supplied into the processing chamber 201 through gas supply pipe 232c via MFC 241c, valve 243c, and nozzle 249c. The hydrogen nitride gas functions as a film-forming gas, i.e., a nitrogen source (nitriding gas, nitriding agent). For example, ammonia (NH3) gas can be used as a hydrogen nitride gas.

[0046] As an inactive gas, nitrogen (N2) gas is supplied to the processing chamber 201 from gas supply pipes 232d to 232f via MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The N2 gas functions as a purge gas, carrier gas, dilution gas, etc.

[0047] The film-forming gas supply system (raw material gas supply system and reaction gas supply system) mainly consists of gas supply pipes 232a and 232c, MFC 241a and 241c, and valves 243a and 243c. The fluorine-containing gas supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The inactive gas supply system mainly consists of gas supply pipes 232d to 232f, MFC 241d to 241f, and valves 243d to 243f.

[0048] Any or all of the aforementioned supply systems can also be configured as an integrated supply system 248, which integrates valves 243a-243f, MFCs 241a-241f, etc. The integrated supply system 248 is configured to connect to gas supply pipes 232a-232f respectively, and controls the supply of various gases into the gas supply pipes 232a-232f, i.e., the opening and closing of valves 243a-243f, and the flow regulation by MFCs 241a-241f, etc., through the controller 121 described later. The integrated supply system 248 can be configured as a single-piece or separate integrated unit, and can be disassembled and assembled relative to the gas supply pipes 232a-232f, etc., at the integrated unit level, allowing for maintenance, replacement, and addition of the integrated supply system 248 at the integrated unit level.

[0049] Below the side wall of the reaction tube 203, there is an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201. Figure 2 As shown, the exhaust port 231a, when viewed from above, is positioned opposite (facing) the nozzles 249a-249c (gas supply holes 250a-250c) while the wafer 200 is clamped. The exhaust port 231a may also be positioned along the side wall of the reaction tube 203 from bottom to top, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, serving as a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245 (pressure detector, pressure detection unit) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 (pressure regulator, pressure regulating unit). The APC valve 244 is configured to open and close when the vacuum pump 246 is activated, thereby enabling vacuum exhaust and stopping of vacuum exhaust within the processing chamber 201. Furthermore, by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is activated, the pressure within the processing chamber 201 can be regulated. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also possible to include the vacuum pump 246 within the exhaust system.

[0050] Below the manifold 209, a sealing cover 219, serving as a furnace opening cover, is provided to hermetically seal the lower opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209. Below the sealing cover 219, a rotation mechanism 267 is provided to rotate the crystal boat 217 (described later). The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. The sealing cover 219 is configured to move vertically upwards and downwards via a crystal boat lift 115, which is a lifting mechanism located outside the reaction tube 203. The crystal boat lift 115 is configured as a conveying device (conveyor mechanism), which moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219. Below the manifold 209 is a gate 219s serving as a furnace opening cover, which, when the sealing cover 219 is lowered and the crystal boat 217 is removed from the processing chamber 201, can hermetically seal the lower opening of the manifold 209. The gate 219s is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the gate 219s, an O-ring 220c, serving as a sealing member, abuts against the lower end of the manifold 209. The opening and closing actions (lifting, rotating, etc.) of the gate 219s are controlled by the gate opening and closing mechanism 115s.

[0051] The crystal boat 217, serving as a substrate support, is configured such that multiple wafers 200, for example 25 to 200 wafers, are arranged horizontally and with their centers aligned in a vertical direction, supported by multiple layers, i.e., arranged with open intervals. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the crystal boat 217, a heat-insulating plate 218, also made of a heat-resistant material such as quartz or SiC, is supported by multiple layers.

[0052] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. Based on the temperature information detected by the temperature sensor 263, the energizing status of the heater 207 is adjusted, thereby achieving the desired temperature distribution within the processing chamber 201. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203.

[0053] like Figure 3As shown, the controller 121, serving as the control unit (control unit), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an 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. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel.

[0054] The storage device 121c is configured such as flash memory or HDD (Hard Disk Drive). The storage device 121c stores, in a readable manner, a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions, as described later. The process flow is a combination of methods that enable the controller 121 to execute each step of the substrate processing described later and obtain a predetermined result, and functions as a program. Hereinafter, the process flow, control program, etc., will be simply referred to as a program. Furthermore, the process flow will be abbreviated as process. When the term "program" is used in this specification, it may include only the process flow, only the control program, or both. RAM 121b is configured as a storage area (working area) for temporarily storing programs, data, etc., read by the CPU 121a.

[0055] I / O port 121d is connected to the aforementioned MFC241a~241f, valves 243a~243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, crystal boat elevator 115, gate opening and closing mechanism 115s, etc.

[0056] CPU 121a is configured to read and execute a control program from storage device 121c, and to read a process from storage device 121c in response to inputs of operation commands from input / output device 122. CPU 121a is configured to control, according to the read process content, various gas flow regulation operations performed using MFCs 241a to 241f, opening and closing operations of valves 243a to 243g, opening and closing operations of APC valve 244, pressure regulation operations performed using APC valve 244 based on pressure sensor 245, starting and stopping vacuum pump 246, temperature regulation operations of heater 207 based on temperature sensor 263, rotation and rotation speed regulation operations of crystal boat 217 performed using rotation mechanism 267, lifting and lowering operations of crystal boat 217 performed using crystal boat elevator 115, and opening and closing operations of gate 219s performed using gate opening and closing mechanism 115s.

[0057] The controller 121 is configured to install the aforementioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, a CD-ROM such as an MO disk, or a semiconductor memory such as a USB flash drive. The storage device 121c and the external storage device 123 constitute a recording medium that can be read by a computer. Hereinafter, they will be collectively referred to as recording media. When the term "recording medium" is used in this specification, there may be cases where only the storage device 121c is included, cases where only the external storage device 123 is included, or cases where both are included. It should be noted that the program can also be provided to the computer without using the external storage device 123, but using communication means such as the Internet or a dedicated line.

[0058] (2) Substrate processing process Main use Figure 4 , Figure 5 (a) ~ Figure 5 (d) illustrates the following example of selective growth (selective film formation) processing sequence, namely, using the substrate processing apparatus described above as a step in the manufacturing process of a semiconductor device, a film is selectively grown on the surface of a specific substrate among various substrates exposed on the surface of the wafer 200, which serves as the substrate, to form a film. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0059] exist Figure 4 In the film formation sequence shown, the following steps are performed: Step A involves supplying F-containing free radicals generated from ClF3 (a fluorine-containing gas) to a wafer 200 on which a first substrate (substrate 200a) containing a silicon oxide film (SiO film) and a second substrate (substrate 200b) containing a silicon nitride film (SiN film) are exposed, thereby modifying the surface of one of the substrates 200a and 200b (in this case, substrate 200a) by F-termining; and Step B involves supplying SiCl4 gas and NH3 gas as film-forming gases to the wafer 200 after surface modification of substrate 200a, thereby forming a SiN film on the surface of another substrate (substrate 200b) that is different from the aforementioned substrate 200a and substrate 200b.

[0060] It should be noted that, Figure 4 The diagram illustrates a scenario in which the following steps are performed non-simultaneously a specified number of times (n times, where n is an integer greater than or equal to 1): step B1, which supplies SiCl4 gas to wafer 200, and step B2, which supplies NH3 gas to wafer 200.

[0061] For convenience, this instruction manual also contains... Figure 4 The film formation timing shown is as follows. The same description is used in the following descriptions of variations, etc.

[0062] ClF3→(SiCl4→NH3)×n SiN When the term "wafer" is used in this specification, it may refer to the wafer itself or to a laminate of the wafer and a specified layer or film formed on its surface. When the term "surface of the wafer" is used in this specification, it may refer to the surface of the wafer itself or to the surface of a specified layer, etc., formed on the wafer. When the phrase "forming a specified layer on the wafer" is used in this specification, it may refer to forming the specified layer directly on the surface of the wafer itself or forming the specified layer on top of a layer, etc., formed on the wafer. The term "substrate" used in this specification has the same meaning as when the term "wafer" is used.

[0063] (Wafer filling and crystal boat loading) After multiple wafers 200 are loaded into the crystal boat 217 (wafer filling), the gate 219s is moved by the gate opening and closing mechanism 115s, opening the lower end opening of the manifold 209 (gate opening). Then, as... Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat elevator 115 and moved into the processing chamber 201 (crystal boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 by means of an O-ring 220b.

[0064] like Figure 5 As shown in (a), the wafer 200 is in a state where multiple substrates (here, as an example, substrate 200a containing a SiO film (as an oxygen (O) film, i.e., an oxide film) and substrate 200b containing a SiN film (as a nitride film, i.e., a non-O film, i.e., a non-oxide film) are pre-exposed on the surface of the wafer 200. Substrate 200a has […] over the entire area (the entire surface). Figure 6 The surface shown is hydroxyl (OH)-terminated. For substrate 200b, it has many areas of surface that are not OH-terminated, that is, it has some areas of surface that are OH-terminated.

[0065] (Pressure and temperature regulation) Vacuum pump 246 performs vacuum venting (pressure reduction venting) to bring the processing chamber 201, where the wafer 200 is located, to the desired pressure (vacuum level). The pressure within the processing chamber 201 is measured by pressure sensor 245, and the APC valve 244 is controlled based on this measured pressure information. Additionally, heater 207 heats the wafer 200 within the processing chamber 201 to the desired processing temperature. The energization of heater 207 is controlled based on temperature information detected by temperature sensor 263 to achieve the desired temperature distribution within the processing chamber 201. Furthermore, rotation of the wafer 200 using rotation mechanism 267 is initiated. Venting of the processing chamber 201, heating of the wafer 200, and rotation all continue at least until the processing of the wafer 200 is completed.

[0066] (Selective growth) Then, perform steps A through B in sequence.

[0067] [Step A] In this step, ClF3 gas is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 with substrates 200a and 200b exposed on its surface.

[0068] Specifically, valve 243b is opened, allowing ClF3 gas to flow into gas supply pipe 232b. The ClF3 gas flow rate is regulated by MFC 241b, supplied to processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, ClF3 gas is supplied to wafer 200 (ClF3 gas supply). Then, valves 243d and 243f are opened, supplying N2 gas to processing chamber 201 via nozzles 249a and 249c, respectively. Alternatively, N2 gas supply may not be implemented.

[0069] As a processing condition in this step, an example can be given: ClF3 gas supply flow rate: 1–2000 sccm, preferably 1–500 sccm ClF3 gas supply time: 1 second to 60 minutes N2 gas supply flow rate (each gas supply pipe): 0~10000sccm Processing temperature: room temperature (25℃) to 300℃, preferably room temperature to 200℃ Processing pressure: 1-2000 Pa, preferably 1-1000 Pa.

[0070] The conditions described herein are not conditions for etching the surface of substrate 200a, but rather conditions that allow the surface of substrate 200a to be modified in an F-terminal manner, as described later.

[0071] It should be noted that the numerical range "1~2000Pa" in this specification refers to including both the lower and upper limits within the range. Therefore, for example, "1~2000Pa" means "above 1 Pa and below 2000 Pa". The same applies to other numerical ranges.

[0072] When the processing temperature in this step is below room temperature (25°C), the surface modification of substrate 200a may be insufficient. By setting the processing temperature above room temperature, the surface modification of substrate 200a can be sufficiently performed. If the processing temperature exceeds 300°C, at least one of the substrate films 200a and 200b, especially substrate 200b, may be etched and suffer etch damage. By setting the processing temperature below 300°C, etching of at least one of the substrate films 200a and 200b, especially substrate 200b, can be suppressed, and etch damage to the surface of substrate 200b can be prevented. This effect can be reliably obtained by setting the processing temperature below 200°C.

[0073] By supplying ClF3 gas to wafer 200 under the above conditions, F-containing free radicals can be generated from the ClF3 gas, causing the surface of substrate 200a to react with the F-containing free radicals. Examples of F-containing free radicals include F, ClF2, and ClF. In this step, through the action of the F-containing free radicals generated from the ClF3 gas, the surface of substrate 200a can be modified by F-termining without etching. The modified substrate 200a has an F-terminated surface. Specifically, the OH groups on the surface of substrate 200a, such as... Figure 7 As illustrated in (a), the surface of substrate 200a is replaced by an F-containing substance such as F, and is thus F-terminated. Because the surface of substrate 200a is F-terminated, a film-forming reaction is less likely to occur on the surface of substrate 200a in step B described later. More precisely, this prolongs the incubation time until the film-forming reaction occurs. It should be noted that the F-terminated surface of substrate 200a becomes a substantially organic-free surface.

[0074] like Figure 5As shown in (b), in this step, the surface of substrate 200a can be selectively (preferably) modified while suppressing the surface modification of substrate 200b. At this time, there are also cases where a portion of the surface of substrate 200b is modified, but the amount of modification is small compared to the amount of modification of the surface of substrate 200a. This selective (preferential) modification is possible because many regions of the surface of substrate 200b before the start of step A are not OH-terminated, while the entire surface of substrate 200a is OH-terminated. Since OH-termination sites are not formed in many regions of the surface of substrate 200b, F-termination sites are not formed in many of these regions. However, as described above, there are also cases where OH-termination sites are formed in a portion of the surface of substrate 200b, and in these cases, F-termination sites are formed in that portion of the surface by the action of F-containing free radicals. In contrast, on the surface of substrate 200a, since OH-termination sites are formed throughout the entire surface region, very stable F-termination sites are formed throughout the entire surface region under the action of F-containing free radicals.

[0075] It should be noted that a portion of the surface of substrate 200b is also etched due to the action of F-containing free radicals. However, even when a portion of the surface of substrate 200b is etched, the amount of etching is very small, and the surface of substrate 200b can be kept largely undamaged by adjusting the processing conditions. Whether a portion of the surface of substrate 200b is modified or etched, adsorption sites will still be maintained in many areas of the surface of substrate 200b.

[0076] After selectively modifying the surface of substrate 200a in substrates 200a and 200b, valve 243b is closed to stop the supply of ClF3 gas to the processing chamber 201. Then, the gas and other gases remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps as the purging in step A.

[0077] As an F-containing gas, in addition to ClF3 gas, fluorine (F2) gas, chlorine fluoride gas (ClF) gas, F2 + nitric oxide (NO) gas, ClF3 + NO gas, ClF + NO gas, nitrogen trifluoride (NF3) gas, nitrosyl fluoride (FNO) gas, tungsten hexafluoride (WF6) gas, or a mixture of the above gases can be used.

[0078] [Step B] In this step, steps B1 and B2 are executed sequentially.

[0079] [Step B1] In this step, SiCl4 gas is supplied to the wafer 200 in the processing chamber 201, i.e., the wafer 200a in the substrates 200a and 200b, after selective modification of the surface of the wafer 200a.

[0080] Specifically, valve 243a is opened, allowing SiCl4 gas to flow into gas supply pipe 232a. The SiCl4 gas flow rate is regulated by MFC 241a, supplied to processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, SiCl4 gas is supplied to wafer 200 (SiCl4 gas supply). Alternatively, valves 243e and 243f can be opened to supply N2 gas to processing chamber 201 via nozzles 249b and 249c, respectively.

[0081] As a processing condition in this step, an example can be given: SiCl4 gas supply flow rate: 1–2000 sccm, preferably 10–1000 sccm SiCl4 gas supply time: 1–180 seconds, preferably 1–120 seconds Processing temperature: 350–600℃, preferably 400–550℃ Processing pressure: 1~2000Pa, preferably 10~1333Pa.

[0082] Other processing conditions are the same as those in step A.

[0083] By supplying SiCl4 gas to the wafer 200 under the above conditions, a Si-containing layer containing Cl is formed on the surface of substrate 200b, which includes unmodified regions, within substrates 200a and 200b. That is, the Si-containing layer containing Cl is formed starting from the unmodified regions in substrate 200b, i.e., the regions that maintain adsorption sites. The Si-containing layer containing Cl is formed by the chemical adsorption, physical adsorption, and partial decomposition of SiCl4 on the surface of substrate 200b, resulting in a substance (SiCl4)... x The Si-containing layer, consisting of Cl, is formed through chemical adsorption and Si accumulation resulting from the thermal decomposition of SiCl4. The Si-containing layer can be SiCl4, SiCl4, or other similar materials. x The adsorption layer (physical adsorption layer, chemisorption layer) can also be a Si stack containing Cl. In this specification, the Si layer containing Cl will be referred to simply as the Si layer.

[0084] In this step, a Si-containing layer can be selectively formed on the surface of substrate 200b while simultaneously suppressing the formation of a Si-containing layer on the surface of substrate 200a. It should be noted that, in cases where the surface modification of substrate 200a is insufficient for some reason, a very small amount of Si-containing layer may form on the surface of substrate 200a. However, even in this case, the thickness of the Si-containing layer formed on the surface of substrate 200a is much thinner than the thickness of the Si-containing layer formed on the surface of substrate 200b. This selective formation of the Si-containing layer is achieved because the F-terminals present on the surface of substrate 200a act as the main obstacle to the formation of the Si-containing layer (Si adsorption) on the surface of substrate 200a, functioning as an inhibitor. It should be noted that the F-terminals present on the surface of substrate 200a do not disappear during this step but are stably maintained.

[0085] After forming a Si-containing layer on the surface of substrate 200b, valve 243a is closed to stop the supply of SiCl4 gas to the processing chamber 201. Then, the gas and other gases remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps as in step A (purging).

[0086] In addition to SiCl4, other gaseous gases that can be used as raw material gases (film-forming gases) include monochlorosilane (SiH3Cl, abbreviated as MCS), dichlorosilane (SiH2Cl2, abbreviated as DCS), trichlorosilane (SiHCl3, abbreviated as TCS), hexachlorosilane (Si2Cl6, abbreviated as HCDS), octachlorotrisilane (Si3Cl8, abbreviated as OCTS), bromosilane (SiBr4), and iodosilane (SiI4).

[0087] [Step B2] In this step, NH3 gas is supplied to the wafer 200, i.e., the Si-containing layer formed on the substrate 200b, within the processing chamber 201.

[0088] Specifically, valve 243c is opened, allowing NH3 gas to flow into gas supply pipe 232c. The flow rate of NH3 gas is regulated by MFC 241c, supplied into processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this time, NH3 gas is supplied to wafer 200 (NH3 gas supply). Alternatively, valves 243d and 243e can be opened to supply N2 gas into processing chamber 201 via nozzles 249a and 249b, respectively.

[0089] As a processing condition in this step, an example can be given: NH3 gas supply flow rate: 10~10000sccm NH3 gas supply time: 1–60 seconds, preferably 5–50 seconds Processing pressure: 1~4000Pa, preferably 1~1333Pa.

[0090] Other processing conditions are the same as those in step A.

[0091] By supplying NH3 gas to the wafer 200 under the above conditions, at least a portion of the Si-containing layer formed on the surface of the substrate 200b is nitrided (modified). Through the modification of the Si-containing layer, a silicon nitride layer (SiN layer) containing Si and N is formed on the surface of the substrate 200b. During the formation of the SiN layer, impurities such as Cl contained in the Si-containing layer are converted into a gaseous substance containing at least Cl during the modification reaction of the Si-containing layer with NH3 gas, and are discharged from the processing chamber 201. Thus, the SiN layer becomes a layer with fewer impurities such as Cl compared to the Si-containing layer formed in step B1. It should be noted that the surface of the substrate 200a is also not modified during this step and is maintained. That is, the surface of the substrate 200a is not modified (NH-terminated) and is stably maintained in an F-terminated state.

[0092] After forming a SiN layer on the surface of substrate 200b, valve 243c is closed to stop the supply of NH3 gas to the processing chamber 201. Then, the gas and other gases remaining in the processing chamber 201 are removed from the processing chamber 201 through the same processing steps as in step A (purging).

[0093] In addition to NH3, other hydrogen nitride gases such as diazoxide (N2H2), hydrazine (N2H4), and N3H8 can be used as reactant gases (film-forming gases).

[0094] [Number of times specified for implementation] By performing steps B1 and B2 asynchronously a specified number of times (n times, where n is an integer greater than or equal to 1), thus achieving the desired result. Figure 5 As shown in (c), a SiN film can be selectively formed on the surface of substrate 200b, one of the substrates 200a and 200b exposed on the surface of wafer 200. Preferably, the above cycle is repeated multiple times. That is, it is preferable that the thickness of the SiN layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated multiple times until the film thickness formed by stacking SiN layers reaches the desired film thickness.

[0095] It should be noted that during steps B1 and B2, the F-terminals present on the surface of substrate 200a are maintained and do not disappear, therefore no SiN film is formed on the surface of substrate 200a. However, in cases where the modification of the surface of substrate 200a is insufficient for some reason, a very small amount of SiN film may be formed on the surface of substrate 200a. Even in this case, the thickness of the SiN film formed on the surface of substrate 200a is much thinner than the thickness of the SiN film formed on the surface of substrate 200b. In this specification, the term "selectively forming a SiN film on the surface of substrate 200b" in substrates 200a and 200b includes not only the case where no SiN film is formed on the surface of substrate 200a, but also, as described above, the case where a very thin SiN film is formed on the surface of substrate 200a.

[0096] (Post-purge and atmospheric pressure recovery) After the selective formation of the SiN film on the substrate 200b is completed, N2 gas is supplied as a purge gas into the processing chamber 201 through nozzles 249a to 249c, and exhaust is performed through exhaust port 231a. This purges the processing chamber 201, removing residual gases and reaction byproducts (post-purge). Subsequently, the atmosphere in the processing chamber 201 is replaced with an inactive gas (inactive gas replacement), and the pressure in the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0097] (Crystal boat unloading and wafer removal) The sealing cap 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the crystal boat 217, is then removed from the lower end of the manifold 209 (crystal boat unloading) and moved to the outside of the reaction tube 203. After unloading, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s using an O-ring 220c (gate closing). The processed wafer 200 is then removed from the crystal boat 217 after being moved to the outside of the reaction tube 203 (wafer removal).

[0098] It should be noted that, as Figure 5 As shown in (d), the F-terminals present on the surface of substrate 200a disappear upon exposure of the processed wafer 200 to the atmosphere, reacting with a specified reactant, specifically with atmospheric moisture (H2O). That is, the F-terminals present on the surface of substrate 200a can be removed by exposing the processed wafer 200 to the atmosphere. By removing the F-terminals from the surface of substrate 200a, the surface state of substrate 200a is reset, enabling film deposition processes on the surface of substrate 200a in subsequent steps.

[0099] (3) Effects of this method According to this method, one or more of the effects shown below can be obtained.

[0100] (a) By performing steps A and B, a SiN film can be selectively formed on the surface of substrate 200b, one of the substrates 200a and 200b exposed on the surface of wafer 200. This simplifies the manufacturing process, for example, by omitting patterning processes such as photolithography during semiconductor device fabrication. As a result, semiconductor device productivity can be improved and manufacturing costs reduced.

[0101] (b) After step B, by exposing the processed wafer 200 to the atmosphere, the F-terminals present on the surface of the substrate 200a as inhibitors can be removed. In this way, since the F-terminals can be easily removed, there is no need to set up a separate inhibitor removal process, which simplifies the semiconductor device manufacturing process, improves the semiconductor device productivity, and reduces manufacturing costs.

[0102] (c) Since at least one of steps A and B, preferably each of steps A and B, is performed in a non-plasma atmosphere, plasma damage to the wafer 200 can be avoided, and the method can be applied to processes where plasma damage is a concern.

[0103] (d) For example, if a groove or other recess is formed on the surface of the wafer 200, a film identical to the target film is formed on the bottom surface of the recess, and a film different from the target film is formed on the side surface, and film formation is performed by CVD, alternating feed material method, or the like by filling the recess, then pores and seams may occur in the formed film depending on the shape of the recess. According to the method of this approach, bottom-up growth of the film from the bottom surface of the recess upwards can be achieved, and pore-free and seam-free filling can be performed.

[0104] (e) Additionally, for example, when using a SiN film as a mask, if the SiN film is etched, the shape of the mask may become deformed. In this case, by using the method of this approach, the shape of the mask can be repaired, and etching can be performed in the desired shape until the desired etching process is completed.

[0105] (f) Additionally, for example, in the case of SADP (Self-Aligned Double Patterning), repeated exposure and etching can lead to a deterioration in micro-precision. In this case, the patterning accuracy can be improved by selectively growing the film thickness using the method described herein.

[0106] (g) The above-mentioned effects can be obtained in the case of using F-containing gases other than ClF3, raw material gases other than SiCl4, reaction gases other than NH3, and inactive gases other than N2.

[0107] <Other aspects of the invention> The present invention has been specifically described above. However, the present invention is not limited to the above-described manner and various modifications can be made without departing from its spirit.

[0108] For example, in step A, the generation of F-containing radicals can also be promoted by supplying F-containing gas in an atmosphere in which a dummy catalyst is present. That is, in step A, the generation of F-containing radicals can also be promoted by supplying F-containing gas into the processing chamber 201 containing the dummy catalyst, and by supplying the radicals generated in this way to the surface of the wafer 200, the surface of substrate 200a in the substrates 200a and 200b can be selectively (preferably) modified. Here, the so-called dummy catalyst is a substance that promotes the decomposition of F-containing gas to promote the generation of F-containing radicals from the F-containing gas. By utilizing the effect of the dummy catalyst generated by contacting the F-containing gas with the dummy catalyst, the generation of F-containing radicals from the F-containing gas can be promoted to generate F-containing radicals efficiently.

[0109] As a dummy catalyst, for example, solid Si whose outermost surface is not covered by a native oxide film (SiO film) can be used, i.e., a Si component with the Si material exposed on its outermost surface. Such a component can be, for example, a Si wafer obtained by removing the native oxide film formed on its outermost surface through cleaning with an aqueous hydrogen fluoride (HF) solution, such as a bare Si wafer (hereinafter referred to as "bare wafer"). It should be noted that a bare wafer stored in the atmosphere has a native oxide film formed on its outermost surface, and the Si material is not exposed on its outermost surface; in this state, the bare wafer cannot be used as a dummy catalyst. In order for the bare wafer to function as a dummy catalyst, the native oxide film formed on the outermost surface of the bare wafer needs to be removed to create a state where the Si material is exposed on its outermost surface.

[0110] When using a bare wafer with its natural oxide film removed as a dummy catalyst, the bare wafer with the natural oxide film removed and the wafer 200 to be processed are held together at a predetermined position in a crystal boat 217. By moving the crystal boat 217 into the processing chamber 201 in this state, the bare wafer serving as the dummy catalyst can be contained within the processing chamber 201. It should be noted that, in this case, it is preferable to alternately load the bare wafer serving as the dummy catalyst and the wafer 200 to be processed onto the crystal boat 217, spaced apart by one wafer, with the upper surface of the wafer 200 to be processed facing (opposite) to the surface of the bare wafer serving as the dummy catalyst, and to position the bare wafer directly above the substrate 200a. In this case, in step A, F-containing free radicals can be efficiently generated by contacting the F-containing gas with the bare wafer serving as the dummy catalyst, and the F-containing free radicals generated in this way can be efficiently supplied to the substrate 200a.

[0111] Regarding the processing steps and conditions in the growth process at this time, except for setting the bare wafer after removing the natural oxide film that serves as a dummy catalyst onto the wafer boat 217, the processing steps and conditions can be set to be the same as those described above. In this case, in step A, in an atmosphere where the bare wafer, which serves as a dummy catalyst, i.e., Si, is present, ClF3 gas, which contains F, is supplied as an F-containing gas, thereby carrying out the following exemplified reaction on the surface of the wafer 200. In the various reaction formulas exemplified below, (s) indicates that the substance is a solid (solid phase), and (g) indicates that the substance is a gas (gas phase). In the atmosphere where Si is present, various F-containing substances generated from the ClF3 gas, such as F, ClF2, ClF, SiF2, and SiF3, are equivalent to F-containing free radicals.

[0112] Si(s)+ClF3(g)→SiF(s)+ClF2(g) SiF(s)+ClF2(g)→SiF2(s)+ClF(g) SiF2(s)+ClF(g)→SiF3(s)+Cl(g) ClF3(g)→ClF2(g)+F(g) In this case, the same effect as described above can be obtained. Furthermore, in step A, by supplying F-containing gas in an atmosphere where a dummy catalyst is present, the generation of F-containing free radicals within the processing chamber 201 is promoted, increasing the amount of F-containing free radicals generated, compared to supplying F-containing gas in an atmosphere without a dummy catalyst. As a result, in step A, surface modification of the substrate 200a can be facilitated, and the selective formation of the SiN film on the surface of the substrate 200b can be performed more reliably. Additionally, by using a dummy catalyst, the processing temperature in step A can be lowered, effectively suppressing surface etching of the substrate 200b in step A and effectively suppressing etching damage to the surface of the substrate 200b.

[0113] It should be noted that, as a dummy catalyst, Si-based plates (Si plates), Si-based chips (Si chips), Si-based wafers (Si wafers), and Si-based blocks (Si blocks) can also be used instead of bare wafers. When using the above components as dummy catalysts, in the same way as when using bare wafers as dummy catalysts, it is necessary to remove the natural oxide film formed on the outermost surface of these components, so that the Si material is exposed on the outermost surface.

[0114] Alternatively, a Si film can be pre-formed (pre-coated) on the surface of components within the processing chamber 201 (the inner wall of the reaction tube 203, the surface of the crystal boat 217, etc.) before selective growth, and this Si film (pre-coated film) can be used as a dummy catalyst. The Si film used as the pre-coated film can be formed using silane-based gases such as silane (SiH4) gas, and via CVD. The Si film can be in an amorphous (non-crystalline) state, a polycrystalline (polycrystalline) state, or a mixed-crystal state of amorphous and polycrystalline Si film.

[0115] Examples of processing conditions for forming Si films include: SiH4 gas supply flow rate: 10~2000sccm N2 gas supply flow rate (each gas supply pipe): 0~10000sccm Gas supply time: 10–400 minutes Processing temperature: 450~550℃, preferably 450~530℃ Processing pressure: 1~900Pa.

[0116] In this case, in step A, by contacting the F-containing gas with the Si film (pre-coated film) which serves as a dummy catalyst, F-containing radicals can be generated efficiently, and the F-containing radicals generated in this way can be efficiently supplied to the substrate 200a.

[0117] It should be noted that, in addition to Si films, SiN films, silicon carbide films (SiC films), silicon carbonitride films (SiCN films), silicon-rich SiN films (SiRN films), silicon-rich SiC films (SiRC films), and silicon-rich SiCN films (SiRCN films) can also be used as pre-coated films. That is, in addition to Si, Si-containing films containing C and N can also be used as pre-coated films. For example, SiN films, SiC films, SiCN films, SiRN films, SiRC films, and SiRCN films as pre-coated films can be formed by using aminosilane-based gases such as ethylmethylaminosilane (SiH3[N(CH3)(C2H5)]), dimethylaminosilane (SiH3[N(CH3)2]), diisopropylaminosilane (SiH3[N(C3H7)2]), and disec-butylaminosilane (SiH3[H(C4H9)2]) and formed by CVD. The processing conditions at this time can be set to the same conditions as those used when forming the Si film, which is described above as a pre-coated film. It should be noted that the aminosilane gas is a gas containing Si and an amino group, or more specifically, a gas containing at least Si, N, and C as constituent elements.

[0118] Under the above circumstances, F-containing gas can also be brought into contact with SiN film, SiC film, SiCN film, SiRN film, SiRC film, or SiRCN film (pre-coated film) as a pseudo-catalyst in step A, thereby efficiently generating F-containing free radicals, and such efficiently generated F-containing free radicals can be efficiently supplied to substrate 200a.

[0119] Regarding the processing steps and conditions in the selective growth process when using the pre-coated film as a dummy catalyst, except for pre-coating the film onto the surface of the component within the processing chamber 201, the processing steps and conditions can be set to be the same as described above. In this case of using the pre-coated film as a dummy catalyst, the same effect as when using a bare wafer as a dummy catalyst can be obtained. It should be noted that the pre-coated film in this case can also be referred to as a dummy catalyst film or a dummy catalyst pre-coated film.

[0120] Alternatively, after the wafer 200 to be processed is housed in the processing chamber 201 and before selective growth is performed, a Si film can be formed on the surface of the wafer 200, i.e., the surface of the substrates 200a and 200b, and this Si film can be used as a dummy catalyst, i.e., a dummy catalyst film. Besides Si films, SiN films, SiC films, SiCN films, SiRN films, SiRC films, SiRCN films, etc., can also be used as dummy catalyst films. That is, besides Si, Si-containing films containing C and N can also be used as dummy catalyst films. The gases and processing conditions used when forming the Si film, SiN film, SiC film, SiCN film, SiRN film, SiRC film, and SiRCN film used as dummy catalyst films can be set to be the same as those used when forming the aforementioned pre-coated film.

[0121] In the above scenario, in step A, by contacting the F-containing gas with the dummy catalyst film, F-containing free radicals can be generated efficiently, and these efficiently generated F-containing free radicals can be supplied to the substrate 200a. That is, the surface of the substrate 200a can be modified by F-termining. It should be noted that at this time, the dummy catalyst film formed on the surface of the substrate 200b is etched, exposing adsorption sites on the surface of the substrate 200b. At this time, there is also a possibility that the surface of the substrate 200b is slightly etched, but even in this case, the amount of etching is small, and the adsorption sites on its surface are maintained. It should be noted that since the substrate 200a is composed of a SiO film with strong Si-O bonds, its surface is not etched, but rather appropriately F-terminated and modified.

[0122] Regarding the processing steps and conditions for selective growth when using the aforementioned dummy catalyst film, except for forming the dummy catalyst film on the surface of wafer 200, they can be set to be the same as those described above. Even when using Si films, SiN films, SiC films, SiCN films, SiRN films, SiRC films, SiRCN films, etc., as dummy catalysts, the same effect as when using a bare wafer as a dummy catalyst can be obtained.

[0123] Furthermore, for example, not only solid dummy catalysts such as bare wafers, Si plates, Si chips, Si wafers, Si blocks, Si-containing pre-coated films, and Si-containing dummy catalyst films can be used, but gaseous dummy catalysts can also be used. As a gaseous dummy catalyst, i.e., a dummy catalyst gas, a gas that promotes the decomposition of F-containing gas by contacting it and generating F-containing free radicals from the F-containing gas can be used. Specifically, as a dummy catalyst gas, at least one of oxygen (O2), nitrous oxide (N2O), nitrogen dioxide (NO2), NO, HF, NH3, and hydrogen (H2) can be used. The supply of these gases can be, for example, simultaneously with the supply of F-containing gas into the processing chamber 201 using nozzles 249a, 249c, etc.

[0124] In this case, in step A, by simultaneously supplying the F-containing gas and the dummy catalyst gas into the processing chamber 201, the F-containing gas is supplied in an atmosphere where the dummy catalyst gas is present. At this time, the F-containing gas and the dummy catalyst gas can be brought into contact, thereby efficiently generating F-containing free radicals, which can then be efficiently supplied to the substrate 200a. It should be noted that, as long as the F-containing gas and the dummy catalyst gas are mixed within the processing chamber 201, the F-containing gas and the dummy catalyst gas can be supplied to the processing chamber 201 alternately or intermittently.

[0125] Regarding the processing steps and conditions during the growth process, except for supplying F-containing gas and dummy catalyst gas into the processing chamber 201, they can be set to be the same as those described above. When supplying F-containing gas and dummy catalyst gas in this way, the same effect as when using a bare wafer as a dummy catalyst can be obtained. Furthermore, when using a gaseous dummy catalyst, similarly to using a solid dummy catalyst, the processing temperature in step A can be lowered, effectively suppressing etching of the substrate 200b surface and etching damage to the substrate 200b surface in step A.

[0126] It should be noted that the term "catalyst" refers to a substance that, while remaining unchanged before and after a chemical reaction, alters the reaction rate. The substances mentioned above, as examples of pseudo-catalysts, all exhibit catalytic activity in promoting the production of fluorine-containing free radicals. However, some of these substances do change before and after the chemical reaction. For example, NO gas has catalytic properties, but when it reacts with fluorine-containing gas, a portion of its molecular structure decomposes, resulting in a change in its overall composition before and after the reaction. In this specification, substances that, despite their own changes before and after the chemical reaction, still alter the reaction rate are referred to as "pseudo-catalysts."

[0127] Alternatively, for example, in step A, the generation of F-containing radicals from the F-containing gas can be promoted by activating (exciting) the F-containing gas using plasma, heating, light irradiation, etc. In these cases, the same effect as described above can be obtained. Furthermore, by activating the F-containing gas in step A through plasma, heating, light irradiation, etc., the generation of F-containing radicals within the processing chamber 201 can be promoted, increasing the amount of F-containing radicals generated, compared to the case where the F-containing gas is not activated by these methods. As a result, surface modification of the substrate 200a can be promoted in step A, and the selective formation of the SiN film on the surface of the substrate 200b can be performed more reliably. Additionally, by using a dummy catalyst, the processing temperature in step A can be lowered. It should be noted that, when using plasma, in order to suppress plasma damage to the components within the wafer 200 and processing chamber 201, it is preferable to use a remote plasma method, where the F-containing gas is activated using plasma in a remote plasma unit located outside the processing chamber 201 and then supplied to the processing chamber 201.

[0128] Alternatively, for example, on the surface of wafer 200, not only the substrate 200a containing the SiO film and the substrate 200b containing the SiN film may be exposed, but also substrates containing conductive metal-based thin films such as tungsten (W) films, tungsten nitride (WN) films, and titanium nitride (TiN) films may be exposed. Alternatively, the substrate 200b containing the SiN film may be replaced, exposing the substrate containing the aforementioned metal-based thin films. In these cases, the same effect as described above can be obtained. That is, while avoiding film formation on the SiO film, films can be selectively formed on the surface of the SiN film and the aforementioned metal-based thin films.

[0129] Alternatively, for example, in step B, before starting the cycle of steps B1 and B2 which are not performed simultaneously, a step of supplying NH3 gas to the wafer 200 in the processing chamber 201 for a predetermined time (NH3 pre-flow) can be performed, i.e., to the wafer 200 after selectively modifying the surface of substrate 200a in substrates 200a and 200b. In this case, the F-terminals present on the surface of substrate 200a will not disappear but will be stably maintained, thus achieving the same effect as described above. In addition, the adsorption sites on the surface of substrate 200b can be optimized, improving the quality of the SiN film formed on substrate 200b.

[0130] Additionally, for example, in step B, besides SiCl4 gas, the aforementioned chlorosilane gases, titanium tetrachloride (TiCl4) gas, and other halometallic gases can also be used as the raw material gas. Furthermore, for example, besides N-containing gases such as NH3 gas, gases containing O such as O2 gas, gases containing both N and C such as triethylamine ((C2H5)3N, abbreviated as TEA) gas, gases containing C such as propylene (C3H6) gas, and gases containing boron (B) such as boron trichloride (BCl3) gas can also be used as the reaction gas. Furthermore, by employing the gas supply sequence shown below, films such as silicon oxynitride (SiON), silicon carbonitride (SiCN), silicon oxycarbonitride (SiOCN), silicon oxycarbonitride (SiOC), silicon boron nitride (SiBN), silicon boron carbonitride (SiBCN), titanium nitride (TiN), and titanium oxynitride (TiON) can be formed on the surface of the unmodified substrate 200b in substrates 200a and 200b. The F-terminals formed on the surface of substrate 200a are very stable; therefore, in the above case, i.e., when gases containing OH groups such as water vapor (H2O) or hydrogen peroxide (H2O2) are not used as the film-forming gas, the same effect as described above can be obtained.

[0131] ClF3→(SiCl4→NH3→O2)×n SiON ClF3→(HCDS→C3H6→NH3)×n SiCN ClF3→(HCDS→C3H6→NH3→O2)×n SiOCN ClF3→(HCDS→TEA→O2)×n SiOC(N) ClF3→(DCS→BCl3→NH3)×n SiBN ClF3→(DCS→C3H6→BCl3→NH3)×n SiBCN ClF3→(TiCl4→NH3)×n TiN ClF3→(TiCl4→NH3→O2)×n TiON Preferably, the process used for each process is prepared separately for the processing content and stored in the storage device 121c in advance via an electrical communication line and an external storage device 123. Furthermore, preferably, at the start of each process, the CPU 121a appropriately selects the appropriate process from the multiple processes stored in the storage device 121c according to the processing content. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses within a single substrate processing apparatus. Additionally, it reduces the operator's workload, avoids operational errors, and enables rapid initiation of each process.

[0132] The aforementioned process is not limited to newly created cases; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the corresponding process. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be operated to directly modify an existing process already installed in the substrate processing apparatus.

[0133] In the above-described method, an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time has been explained. The present invention is not limited to the above-described method; for example, it can also be appropriately applied when forming a film using a monolithic substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described method, an example of forming a film using a substrate processing apparatus equipped with a hot-wall type processing furnace has been explained. The present invention is not limited to the above-described method; it can also be appropriately applied when forming a film using a substrate processing apparatus equipped with a cold-wall type processing furnace.

[0134] When using the above-described substrate processing apparatus, each process can be performed under the same processing steps and conditions as described above, and the same effect as described above can be obtained.

[0135] The above methods can be used in appropriate combinations. For example, the processing steps and conditions can be set to be the same as those in the methods described above.

[0136]

Example

[0137] When preparing samples 1 and 2, step A is not performed before step B. When preparing samples 3 and 4, step A is performed before step B. When preparing samples 5 and 6, step A is performed in a state where the bare wafers, which serve as dummy catalysts and whose natural oxide film has been removed, are contained in the processing chamber before step B. It should be noted that samples 1 and 2 are prepared simultaneously under the same atmosphere (in the same processing chamber), samples 3 and 4 are prepared simultaneously under the same atmosphere, and samples 5 and 6 are prepared simultaneously under the same atmosphere. In the preparation of each sample, ClF3 gas is used as the F-containing gas in step A. Other processing conditions are the specified conditions within the range of processing conditions described above, and are common conditions for each sample.

[0138] After preparing samples 1–6, the thickness of the SiN film formed on the surface of the substrate of each wafer was measured. The results are shown in… Figure 8 In the middle. For example Figure 8 As shown, in samples 1 and 2, the thicknesses of the SiN films formed on the surface of the wafer substrate were 71.2 Å and 65.0 Å, respectively, confirming that sufficient selectivity could not be obtained without performing step A. In contrast, in samples 3 and 4, the thicknesses of the SiN films formed on the surface of the wafer substrate were 56.6 Å and 36.0 Å, respectively, confirming that high selectivity could be obtained by performing step A. Furthermore, in samples 5 and 6, the thicknesses of the SiN films formed on the surface of the wafer substrate were 42.4 Å and 5.3 Å, respectively, confirming that very high selectivity was obtained by supplying F-containing gas in the presence of a dummy catalyst in step A.

Claims

1. A processing method comprising the following steps: (a) (a1) A step of forming a dummy catalyst film on the surface of a substrate having a first substrate and a second substrate on its surface by supplying a silane-based gas to the substrate having the dummy catalyst film on its surface, and (a2) a step of supplying a fluorine-containing gas to the substrate having the dummy catalyst film on its surface, causing the fluorine-containing gas to contact the dummy catalyst film to generate fluorine-containing free radicals, thereby modifying the surface of one of the first substrates and the second substrate by F-termination; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

2. The processing method according to claim 1, wherein, In (a1), the dummy catalyst film is formed on the surfaces of the first substrate and the second substrate. In (a2), the dummy catalyst film formed on the surface of another substrate, which is different from the substrate of the first substrate and the second substrate, is etched.

3. The processing method according to claim 1 or 2, wherein, In (a2), the dummy catalyst film formed on the surface of the other substrate is etched to expose the adsorption sites on the surface of the other substrate.

4. The processing method according to any one of claims 1 to 3, wherein, The dummy catalyst membrane includes a Si-containing membrane.

5. The processing method according to any one of claims 1 to 4, wherein, The dummy catalyst membrane contains a Si membrane.

6. The processing method according to any one of claims 1 to 5, wherein, In (a2), the surface of the substrate of the one is modified by SiF end capping.

7. The processing method according to any one of claims 1 to 6, wherein, In (a2), the surface of the substrate of the one is modified in a non-etching manner.

8. The processing method according to any one of claims 1 to 7, wherein, In (a2), the surface of the substrate of one is modified while suppressing the modification of the surface of the other substrate.

9. The processing method according to any one of claims 1 to 8, wherein, In (b), the film is formed on the surface of the other substrate if the film is not formed on the surface of the substrate of the one substrate.

10. The processing method according to any one of claims 1 to 9, wherein, The first substrate includes an oxygen-containing membrane, and the second substrate includes a membrane different from the oxygen-containing membrane.

11. The processing method according to any one of claims 1 to 10, wherein, The first substrate contains an oxygen-containing membrane, and the second substrate contains a non-oxygen-containing membrane.

12. The processing method according to any one of claims 1 to 11, wherein, The first substrate comprises an oxide film, and the second substrate comprises a nitride film.

13. The processing method according to any one of claims 1 to 12, wherein, The first substrate comprises a membrane containing silicon and oxygen, and the second substrate comprises a membrane containing silicon and nitrogen.

14. The processing method according to any one of claims 1 to 13, wherein, The first substrate comprises a silicon oxide film, and the second substrate comprises a silicon nitride film.

15. The processing method according to any one of claims 1 to 14, wherein, The substrate of one of them is the first substrate, and the other substrate is the second substrate.

16. The processing method according to any one of claims 1 to 15, wherein, (a) and (b) were carried out in a non-plasma atmosphere.

17. The processing method according to any one of claims 1 to 16, wherein, It also includes: (c) a step of contacting the substrate after the substance that reacts with fluorine has formed a film on the surface of the other substrate with the surface of the substrate, thereby causing the F-end formed on the surface of the substrate to disappear.

18. A method for manufacturing a semiconductor device, comprising the following steps: (a) (a1) A step of forming a dummy catalyst film on the surface of a substrate having a first substrate and a second substrate on its surface by supplying a silane-based gas to the substrate having the dummy catalyst film on its surface, and (a2) a step of supplying a fluorine-containing gas to the substrate having the dummy catalyst film on its surface, causing the fluorine-containing gas to contact the dummy catalyst film to generate fluorine-containing free radicals, thereby modifying the surface of one of the first substrates and the second substrate by F-termination; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

19. A processing apparatus, comprising: A silane-based gas supply system that supplies silane-based gas to a substrate; A fluorine-containing gas supply system that supplies fluorine-containing gas to a substrate; A film-forming gas supply system that supplies film-forming gas to a substrate; and The control unit is configured to control the operation of the processing device to perform the following processing: (a) (a1) A process of forming a dummy catalyst film on the surface of a substrate by supplying the silane-based gas to a substrate having a first substrate and a second substrate on its surface, and (a2) a process of supplying the fluorine-containing gas to the substrate on which the dummy catalyst film is formed, causing the fluorine-containing gas to contact the dummy catalyst film to generate fluorine-containing free radicals, thereby modifying the surface of one of the first substrates and the second substrate by F-termining; and (b) A process of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

20. A program product which causes a processing device to perform the following steps via a computer: (a) (a1) The step of forming a dummy catalyst film on the surface of a substrate having a first substrate and a second substrate on its surface by supplying a silane-based gas to the substrate having the dummy catalyst film on its surface, and (a2) The step of supplying a fluorine-containing gas to the substrate having the dummy catalyst film on its surface, causing the fluorine-containing gas to contact the dummy catalyst film to generate fluorine-containing free radicals, thereby modifying the surface of one of the first substrates and the second substrate in an F-terminal manner; and (b) The step of forming a film on the surface of one of the first and second substrates, which is different from the substrate of the first substrate, by supplying a film-forming gas to the substrate after surface modification of the substrate of the first substrate.

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