Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus, and program product

Abstract

The invention provides a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a program product, namely a technology for improving selectivity of selective growth. Provided is a method for producing a substrate having a first base and a second base exposed on the surface thereof, the method comprising: (a) a step for modifying the surface of the first base by supplying a first modifying agent containing one or more atoms to which a first functional group and a second functional group are directly bonded, and a second modifying agent containing one or more atoms to which a second functional group is directly bonded, to a substrate having the first base and the second base exposed on the surface thereof; a second modifier including atoms to which the first functional groups and the second functional groups are directly bonded, the number of the first functional groups contained in one molecule being less than the number of the first functional groups contained in one molecule of the first modifier; and (b) a step for forming a film on the surface of the second substrate by supplying a film-forming gas to the substrate after the surface of the first substrate has been modified.

Description

[0001] This invention is a divisional application of the invention application with application number 202111101866.8, invention name "Semiconductor device manufacturing method, substrate processing method, substrate processing device and storage medium", and application date September 18, 2021. Technical Field

[0002] The present disclosure relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing device, and a program product. Background Art

[0003] As semiconductor devices scale, the miniaturization of processing dimensions and the complication of processes have been promoted. In order to carry out fine and complex processing, it is necessary to repeat the high-precision pattern forming process many times, which increases the cost of manufacturing semiconductor devices. In recent years, selective growth has attracted attention as a method that can achieve high precision and low cost. Selective growth refers to the following technology: a film is selectively grown on the surface of a desired substrate among two or more substrates exposed on the surface of a substrate to form a film (for example, refer to Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-243193 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] However, if the selective growth continues, there is a possibility that a film may be locally formed on the surface of a substrate other than the desired substrate among the two or more substrates, thereby causing a decrease in selectivity.

[0009] An object of the present disclosure is to provide a technology for improving the selectivity of selective growth.

[0010] Solutions to Problems

[0011] According to one embodiment of the present disclosure, a technique for performing the following steps is provided:

[0012] (a) supplying a first modifying agent and a second modifying agent to a substrate having a first base and a second base exposed on a surface thereof, thereby modifying the surface of the first base, wherein the first modifying agent includes one or more atoms to which a first functional group and a second functional group are directly bonded, and the second modifying agent includes atoms to which the first functional group and the second functional group are directly bonded, and the number of the first functional groups contained in one molecule of the second modifying agent is less than the number of the first functional groups contained in one molecule of the first modifying agent; and

[0013] (b) A step of supplying a film-forming gas to the substrate after the surface of the first base has been modified, thereby forming a film on the surface of the second base.

[0014] Effects of the Invention

[0015] According to the present disclosure, the selectivity of selective growth can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 (a) is a schematic diagram showing an example of a hydroxyl (OH) terminal structure on the surface of a silicon oxide film (SiO film). Figure 1 (b) means in Figure 1 (a) is a schematic diagram of a region x which is formed after (dialkylamino)trialkylsilane is supplied to the surface of the SiO film and which is not completely covered with three alkyl groups derived from (dialkylamino)trialkylsilane. Figure 1 (c) means Figure 1 (b) shows a schematic diagram of a state in which a film-forming raw material is physically adsorbed in a region x on the surface of the SiO film.

[0017] Figure 2 (a) is a schematic diagram showing an example of the OH terminal structure on the surface of the SiO film. Figure 2 (b) means in Figure 2 (a) is a schematic diagram showing a state in which (dialkylamino)trialkylsilane is supplied to the surface of the SiO film and (dialkylamino)trialkylsilane is chemically adsorbed only on one of the two adjacent OH terminals, leaving some OH terminals remaining. Figure 2 (c) means Figure 2 (b) shows a schematic diagram of a state where the film-forming raw material is chemically adsorbed on the remaining OH terminals on the SiO film surface.

[0018] Figure 3 1 is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus preferably applied in one embodiment of the present disclosure, and shows a processing furnace 202 portion in a vertical cross-sectional view.

[0019] Figure 4 This is a schematic structural diagram of a vertical processing furnace of a substrate processing device preferably applicable in one embodiment of the present disclosure, and Figure 3 The processing furnace 202 is shown in the sectional view taken along line AA.

[0020] Figure 5 1 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably applied in one embodiment of the present disclosure, and shows a control system of the controller 121 in a block diagram.

[0021] Figure 6This is a diagram showing an example of a selective growth processing sequence according to one embodiment of the present disclosure.

[0022] Figure 7 (a) is a schematic diagram showing the chemical structure of the surface of the SiO film on the wafer 200 . Figure 7 (b) means that Figure 7 (a) is a schematic diagram of the chemical structure formed by supplying bis(dialkylamino)dialkylsilane to the surface of the SiO film. Figure 7 (c) means that Figure 7 (b) shows a schematic diagram of the chemical structure formed by supplying a substance containing O and H to the surface of the SiO film. Figure 7 (d) means that Figure 7 (c) is a schematic diagram of the chemical structure formed by supplying (dialkylamino)trialkylsilane to the surface of the SiO film.

[0023] Figure 8 (a)~ Figure 8 (d) is an enlarged cross-sectional view of the surface of the wafer 200 in each step of the selective growth according to one embodiment of the present disclosure. Figure 8 (a) is an enlarged cross-sectional view of the surface of the wafer 200 with the first substrate and the second substrate exposed on the surface. Figure 8 (b) is an enlarged cross-sectional view of the surface of the wafer 200 after the third modified layer is formed on the surface of the first substrate by performing step A. Figure 8 (c) is an enlarged cross-sectional view of the surface of the wafer 200 after a film is formed on the second substrate surface by performing step B. Figure 8 (d) is an enlarged cross-sectional view of the surface of the wafer 200 after the third modified layer is removed by performing step C.

[0024] Figure 9 It is a graph showing the evaluation results of Examples. DETAILED DESCRIPTION

[0025] The following is based on the research results obtained by the inventor of this case and refers to Table 1, Figures 1-2 to illustrate the failure of selection and the resulting reduction in selectivity of selective growth.

[0026] In addition, the drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements shown in the drawings are not necessarily consistent with the actual ones. In addition, the dimensional relationships and ratios of the elements among the multiple drawings are not necessarily consistent.

[0027] There is a method using an "inhibitor (also called a film formation inhibitor)" that preferentially chemically adsorbs to adsorption sites on the surface of a specific substrate (substrate A) exposed on the substrate surface during selective growth. This method inhibits film formation on the surface of substrate A by exposing the inhibitor to the substrate, allowing film growth on the surface of a substrate other than substrate A (substrate B), thereby achieving selective growth.

[0028] When the inhibitor is chemically adsorbed on the surface of substrate A, the reaction between the inhibitor and the film-forming raw material can be inhibited by the chemical stability of the structure of the chemically adsorbed inhibitor. In addition, the steric hindrance of the structure of the chemically adsorbed inhibitor can also be used to inhibit the film-forming raw material from reaching the surface of substrate A. As a result, the film formation on the surface of substrate A where the inhibitor is chemically adsorbed can be inhibited. The treatment of modifying a specific substrate surface to a state that can inhibit film formation using an inhibitor is called "modification". In this specification, the compound supplied to the substrate for the purpose of modification is called an inhibitor, but sometimes the remaining group of the compound after chemical adsorption on the substrate surface of the film-forming obstruction object through modification (equivalent to the above-mentioned "structure of the chemically adsorbed inhibitor") is called an inhibitor. That is, the term "inhibitor" used in this specification includes: the case of indicating "the compound supplied to the substrate for the purpose of modification"; the case of indicating "the remaining group of the compound after chemical adsorption on the substrate surface of the film-forming obstruction object through modification"; or both cases.

[0029] However, conventional methods using inhibitors have the following problem: as film formation continues, localized film formation may occur even on the surface of the modified substrate A. In this specification, localized film formation on the surface of substrate A (i.e., the modified substrate A) to which the inhibitor has chemically adsorbed is referred to as "selective failure." When selective failure occurs, the difference between the amount of film formed on the surface of the modified substrate A and the amount of film formed on the surface of substrate B decreases, resulting in a decrease in the selectivity of selective growth.

[0030] Selection failure occurs when the film-forming raw material adsorbs onto the modified substrate surface. This example illustrates this: the substrate being modified to hinder film formation is a SiO film, and the inhibitor is a (dialkylamino)trialkylsilane (hereinafter referred to as DAATAS), which has a structure with one amino group (dialkylamino group) and three alkyl groups bonded to the central Si atom.

[0031] It is known that there are adsorption sites, namely OH terminals, on the surface of the SiO film. The OH terminals have the three structures shown in Table 1 below.

[0032] Table 1

[0033]

[0034] DAATAS is chemically adsorbed on the surface of the SiO film by reacting the amino groups contained in DAATAS with the OH terminals present on the surface of the SiO film. When DAATAS is chemically adsorbed on the surface of the SiO film, the central atom of DAATAS, i.e., Si, remains bonded to three alkyl groups. Furthermore, the bond between the central atom of DAATAS, i.e., Si, and the amino groups is severed when the amino groups react with the OH terminals. In other words, the surface of the SiO film is bonded with a trialkylsilyl group, which is a residual group derived from DAATAS. The alkyl groups in the trialkylsilyl group are chemically stable and have the property of not easily reacting with film-forming raw materials. In addition, the steric hindrance of the three alkyl groups prevents the film-forming raw materials from reaching the surface of the SiO film. By utilizing these effects, DAATAS and the trialkylsilyl group can function as "inhibitors" and can selectively hinder film formation only on the surface of the SiO film.

[0035] Although modification with DAATAS as described above can inhibit film formation on the surface of the SiO film, the following two mechanisms are mentioned as mechanisms by which the film forming material is adsorbed on the SiO film surface, that is, mechanisms by which selection failure occurs.

[0036] 1. The film-forming raw material is physically adsorbed on the surface of the SiO film that is not completely covered by the steric hindrance of the three alkyl groups of DAATAS.

[0037] 2. The OH terminals remaining on the SiO film surface without chemical adsorption of DAATAS are chemically adsorbed as film-forming raw materials.

[0038] First refer to Figure 1 (a)~ Figure 1 (c) of the above 1. is explained. Here, Figure 1 (a)~ Figure 1 In (c), "R" represents an alkyl group. In addition, "PG" represents a film-forming raw material (raw material gas).

[0039] Regarding the physical adsorption of the film-forming raw material on the surface of the SiO film in 1. above, it tends to occur in the region where the OH terminals are "isolated" as shown in Table 1. Figure 1 As shown in (a), in the "isolated" OH termini, the adjacent OH termini are far away from each other, so Figure 1As shown in (b), even after DAATAS is chemically adsorbed on the OH terminal, a region x is formed where the SiO film surface is not completely covered by the three alkyl groups from DAATAS. In this case, when the film is formed, that is, when the film forming raw material is supplied to the modified substrate, as shown in FIG. Figure 1 As shown in (c), the film-forming raw material PG is physically adsorbed in region x on the SiO film surface, resulting in a selection failure. To suppress the physical adsorption of the film-forming raw material PG in region x on the SiO film surface, for example, it is conceivable to increase the molecular size of the alkyl group of the inhibitor, thereby expanding the film-forming inhibition region due to steric hindrance of the three alkyl groups.

[0040] Next, refer to Figure 2 (a)~ Figure 2 (c) of the above 2. is explained. Here, Figure 2 (a)~ Figure 2 In (c), "R" represents an alkyl group. In addition, "PG" represents a film-forming raw material (raw material gas).

[0041] Regarding the chemical adsorption between the remaining OH terminals on the surface of the SiO film and the film-forming raw materials in 2. above, it is easy to occur in the structure where the OH terminals such as "vicinal" and "germinal" listed in Table 1 are close to the surface of the SiO film. This is because: Figure 2 As shown in (a), when there are two OH terminals close to the SiO film surface, DAATAS can only be chemically adsorbed on one of them, and as shown in Figure 2 As shown in (b), OH terminals remain on the SiO film surface. More specifically, when DAATAS is chemically adsorbed on one of the two OH terminals close to each other on the SiO film surface, the three alkyl groups from DAATAS become steric hindrances, preventing DAATAS from being chemically adsorbed on the other OH terminal, and as shown in Figure 2 As shown in (b), the OH terminal is left on the surface of the SiO film. In this case, when the film is formed, that is, when the film forming raw material is supplied to the modified substrate, as shown in Figure 2 As shown in (c), the film-forming raw material PG chemically adsorbs to the remaining OH terminals on the SiO film surface, resulting in selection failure. To suppress the chemical adsorption of the remaining OH terminals on the SiO film surface and the film-forming raw material PG, for example, it is possible to reduce the molecular size of the alkyl group of the inhibitor so that the inhibitor is chemically adsorbed to each of the two adjacent OH terminals, thereby reducing the number of remaining OH terminals.

[0042] Based on these findings, the inventors of this application, through intensive research, have developed a technique for suppressing selection failure and improving the selectivity of selective growth by using two inhibitors with specific structures (specifically, a first modifier and a second modifier, described below) during modification. An example of this technique for suppressing selection failure and improving the selectivity of selective growth is described below as one embodiment of the present disclosure.

[0043] <One aspect of the present disclosure>

[0044] The following mainly refers to Figures 3-6 、 Figure 7 (a)~ Figure 7 (d) Figure 8 (a)~ Figure 8 (d) is used to illustrate one embodiment of the present disclosure.

[0045] (1) Structure of substrate processing apparatus

[0046] like Figure 3 As shown, the processing furnace 202 has a heater 207 as a temperature controller (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that uses thermal energy to activate (excite) the gas.

[0047] Inside heater 207, reaction tube 203 is arranged concentrically with heater 207. Reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and has a cylindrical shape with a closed top and an open bottom. Below reaction tube 203, a manifold 209 is arranged concentrically with reaction tube 203. Manifold 209 is made of a metal material such as stainless steel (SUS) and has a cylindrical shape with open top and bottom ends. The upper end of manifold 209 engages with the lower end of reaction tube 203 and is configured to support reaction tube 203. An O-ring 220a is provided between manifold 209 and reaction tube 203 as a sealing member. Reaction tube 203 is mounted vertically, similar to heater 207. The reaction tube 203 and manifold 209 primarily constitute a processing vessel (reaction container). The processing chamber 201 is formed within the hollow 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 performed in the processing chamber 201 .

[0048] Nozzles 249a to 249c, serving as the first to third supply units, are installed within the processing chamber 201, extending through the sidewalls of the manifold 209. These nozzles 249a to 249c are also referred to as the first to third nozzles, respectively. These nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to these nozzles, respectively. These nozzles 249a to 249c are distinct nozzles, and nozzles 249a and 249c are each located adjacent to nozzle 249b.

[0049] Gas supply pipes 232a to 232c are provided, in order from the upstream side of the gas flow, with flow controllers (flow control units) such as mass flow controllers (MFCs) 241a to 241c and on-off valves such as valves 243a to 243c. Gas supply pipes 232d, 232e, and 232h are connected downstream of valve 243a to gas supply pipe 232a. Gas supply pipes 232f and 232g are connected downstream of valves 243b and 243c to gas supply pipes 232b and 232c, respectively. MFCs 241d to 241h and valves 243d to 243h are provided, in order from the upstream side of the gas flow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0050] like Figure 4As shown, the nozzles 249a to 249c are arranged in a space in the form of a circular ring in plan view between the inner wall of the reaction tube 203 and the wafer 200, in a manner rising toward the upper side in the arrangement direction of the wafer 200 from the lower portion to the upper portion of the inner wall of the reaction tube 203. That is, the nozzles 249a to 249c are arranged in a region horizontally surrounding the wafer arrangement region of the wafer 200 on the side of the wafer arrangement region in a manner along the wafer arrangement region. In plan view, the nozzle 249b is arranged so as to oppose the exhaust port 231a in line with the center of the wafer 200 carried into the processing chamber 201. The nozzles 249a and 249c are arranged so as to sandwich the straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer peripheral portion of the wafer 200). The straight line L is also a straight line passing through the center of the nozzle 249b and the wafer 200. That is, it can also be said that the nozzle 249c is arranged on the opposite side from the nozzle 249a so as to sandwich the straight line L. The nozzles 249a and 249c are arranged in line symmetry with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided in the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are each opened in a manner opposing (facing) the exhaust port 231a in plan view, and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower portion to the upper portion of the reaction tube 203.

[0051] A first modifier as a surface modifier is supplied from the gas supply pipe 232a to the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0052] A second modifier as a surface modifier is supplied from the gas supply pipe 232h to the processing chamber 201 via the MFC 241h, the valve 243h, the gas supply pipe 232a, and the nozzle 249a.

[0053] A raw material gas as a film formation raw material is supplied from the gas supply pipe 232b to the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0054] A reaction gas, a substance containing oxygen (O) and hydrogen (H), is supplied from the gas supply pipe 232c to the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0055] A catalyst gas is supplied from the gas supply pipe 232d to the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a.

[0056] Inert gas is supplied from gas supply pipes 232e to 232g through MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c into the processing chamber 201. The inert gas functions as a purge gas, carrier gas, dilution gas, and the like.

[0057] The first modifier supply system (first surface modifier supply system) is primarily composed of gas supply pipe 232a, MFC 241a, and valve 243a. The second modifier supply system (second surface modifier supply system) is primarily composed of gas supply pipe 232h, MFC 241h, and valve 243h. The first modifier supply system and the second modifier supply system are also referred to as the modifier supply system (surface modifier supply system). The raw gas supply system is primarily composed of gas supply pipe 232b, MFC 241b, and valve 243b. The reaction gas supply system and the supply system for substances containing O and H are primarily composed of gas supply pipe 232c, MFC 241c, and valve 243c. The catalyst gas supply system is primarily composed of gas supply pipe 232d, MFC 241d, and valve 243d. The inert gas supply system is mainly composed of gas supply pipes 232e~232g, MFCs 241e~241g, and valves 243e~243g.

[0058] The first modifier and the second modifier function as inhibitors, so the modifier supply system (first modifier supply system, second modifier supply system) can also be referred to as the inhibitor supply system (first inhibitor supply system, second inhibitor supply system). Substances containing O and H also function as oxidants (oxidizing gases), so the supply system for substances containing O and H can also be referred to as an oxidant (oxidizing gas) supply system. When an oxidant (oxidizing gas) is used as the reaction gas, the reaction gas supply system can also be referred to as an oxidant (oxidizing gas) supply system. The raw material gas, reaction gas, and catalyst gas function as film-forming gases, so the raw material gas supply system, reaction gas supply system, and catalyst gas supply system can also be referred to as a film-forming gas supply system.

[0059] Any or all of the various supply systems described above can be configured as an integrated supply system 248, which integrates valves 243a-243h, MFCs 241a-241h, and the like. Integrated supply system 248 is connected to each of gas supply pipes 232a-232h and is configured to control the supply of various gases into gas supply pipes 232a-232h, including the opening and closing of valves 243a-243h and the flow rate adjustment of MFCs 241a-241h, via controller 121 (described later). Integrated supply system 248 is configured as a single or split integrated unit, and can be attached to and detached from gas supply pipes 232a-232h, etc., as a unit. Maintenance, replacement, and expansion of integrated supply system 248 can also be performed on a unit basis.

[0060] An exhaust port 231a is provided below the side wall of the reaction tube 203 for exhausting the ambient gas in the processing chamber 201. Figure 4 As shown, the exhaust port 231a is provided at a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 sandwiched therebetween in a top view. The exhaust port 231a can be provided along the side wall from the lower portion to the upper portion of the reaction tube 203, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is made of a metal material such as SUS. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller: automatic pressure controller) valve 244 serving as a pressure regulator (pressure regulating unit). The APC valve 244 is configured to enable and disable vacuum evacuation within the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation. Furthermore, the valve opening can be adjusted based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, thereby regulating the pressure within the processing chamber 201. The exhaust system is primarily comprised of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be considered to be included in the exhaust system.

[0061] Below the manifold 209, a sealing cover 219 is provided as a furnace port cover that can airtightly seal the lower end 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 is provided as a sealing component that abuts the lower end of the manifold 209. Below the sealing cover 219, a rotating mechanism 267 is provided for rotating the wafer boat 217 described later. The rotating shaft 255 of the rotating mechanism 267 is made of a metal material such as SUS and passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be able to be raised and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The wafer boat elevator 115 is configured as a conveying device (conveyance mechanism) that moves wafers 200 into and out of the processing chamber 201 (transportation) by raising and lowering the sealing cover 219. A gate 219s, serving as a furnace cover, is provided below the manifold 209. This gate 219s can airtightly seal the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer boat 217 is removed from the processing chamber 201. The gate 219s is made of a metal material such as SUS and is disc-shaped. An O-ring 220c, serving as a sealing member that abuts the lower end of the manifold 209, is provided on the upper surface of the gate 219s. The opening and closing movements (lifting and rotating movements, etc.) of the gate 219s are controlled by the gate opening and closing mechanism 115s.

[0062] The wafer boat 217, serving as a substrate support, is designed to support multiple wafers 200, for example, 25 to 200, in a horizontal position, aligned vertically in multiple layers, with their centers aligned. The wafer boat 217 is made of a heat-resistant material, such as quartz or SiC. Heat shields 218, also made of a heat-resistant material, such as quartz or SiC, are supported in multiple layers at the bottom of the wafer boat 217.

[0063] A temperature sensor 263 is provided within the reaction tube 203 as a temperature detector. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution within the processing chamber 201. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0064] like Figure 5As shown, the control unit (control unit), or controller 121, is configured as a computer and includes a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to controller 121.

[0065] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the storage device 121c, the following are stored in a readable manner: a control program for controlling the operation of the substrate processing device, a process recipe that records the steps or conditions of the substrate processing described later, etc. The process recipe is composed of a method in which the controller 121 enables the substrate processing device to execute the various steps in the substrate processing described later and to obtain a predetermined result, and functions as a program. In the following, process recipes or control programs, etc. are collectively referred to as programs. In addition, process recipes are also referred to as recipes for short. When the term "program" is used in this specification, sometimes it refers to only the recipe unit, sometimes it refers to only the control program unit, or sometimes it refers to both. RAM121b is configured as a memory area (work area) that temporarily holds the program or data read out by CPU121a.

[0066] The I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, gate opening and closing mechanism 115s, and the like.

[0067] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of an operation command from the input / output device 122. In accordance with the contents of the read recipe, the CPU 121a is configured to control the following: flow rate adjustment of various gases by the MFCs 241a to 241h; opening and closing of the valves 243a to 243h; opening and closing of the APC valve 244 and pressure adjustment by the APC valve 244 using the pressure sensor 245; starting and stopping of the vacuum pump 246; temperature adjustment of the heater 207 using the temperature sensor 263; rotation and rotation speed adjustment of the wafer boat 217 by the rotation mechanism 267; raising and lowering of the wafer boat 217 by the boat elevator 115; and opening and closing of the gate 219s by the gate opening and closing mechanism 115s.

[0068] The controller 121 can be constructed by installing the above-mentioned program stored in the external storage device 123 on a computer. The external storage device 123 includes, for example: a magnetic disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, an SSD, etc. The storage device 121c and the external storage device 123 constitute a computer-readable storage medium. Hereinafter, these will be collectively referred to as storage media. When the term "storage medium" is used in this specification, sometimes it refers to only the storage device 121c alone, sometimes it refers to only the external storage device 123 alone, or sometimes it refers to both. In addition, the provision of the program to the computer can also be carried out without using the external storage device 123, but by using communication means such as the Internet or a dedicated line.

[0069] (2) Substrate processing

[0070] Main Use Figure 6 、 Figure 7 (a)~ Figure 7 (d) Figure 8 (a)~ Figure 8 (d) of FIG. 1 illustrates an example of a processing sequence (gas supply sequence) for selectively forming a film on the surface of the second substrate, of the first and second substrates exposed on the surface of wafer 200, as a step in the semiconductor device manufacturing process using the aforementioned substrate processing apparatus. In the following description, the operations of the various components of the substrate processing apparatus are controlled by controller 121.

[0071] exist Figure 6 In the processing sequence shown, the following is performed:

[0072] (a) Step A of supplying a first modifying agent and a second modifying agent to a wafer 200 having a first substrate and a second substrate exposed on a surface thereof, thereby modifying the surface of the first substrate;

[0073] (b) Step B of supplying a film-forming gas to the wafer 200 after the surface of the first substrate has been modified, thereby selectively forming a film on the surface of the second substrate.

[0074] Here, the first modifier contains one or more atoms directly bonded to the first functional group and the second functional group. Furthermore, the second modifier contains atoms directly bonded to the first functional group and the second functional group, and the number of first functional groups contained in one molecule of the second modifier is less than the number of first functional groups contained in one molecule of the first modifier. Furthermore, the film-forming gas includes a raw material gas, a reaction gas, and a catalyst gas.

[0075] In addition, Figure 6 In the illustrated processing sequence, in step A, step A1, which supplies a first modifying agent to wafer 200, and step A2, which supplies a second modifying agent to wafer 200, are performed non-simultaneously and in the order of step A1 and step A2. Furthermore, step A includes step A3, which supplies a substance containing O and H to wafer 200. In step A, steps A1, A3, and A2 are performed sequentially.

[0076] In addition, Figure 6 In the processing sequence shown, the following cycle is performed a predetermined number of times (n times, n is an integer greater than or equal to 1) in step B, in which step B1 of supplying the raw material gas and the catalyst gas to the wafer 200 and step B2 of supplying the reaction gas and the catalyst gas to the wafer 200 are performed non-simultaneously. Figure 6 , for example, an example in which a substance containing O and H is used as a reaction gas is shown.

[0077] In addition, Figure 6 In the processing sequence shown, step C of heating the wafer 200 after the film is selectively formed on the surface of the second substrate is performed as post-processing for the selectively grown wafer 200. Step C is not necessarily performed and may be omitted.

[0078] In this specification, the above-mentioned processing sequence is also expressed as follows for the sake of convenience. The same expression is also used in the following description of other embodiments and modified examples.

[0079] First modifier → substance containing O and H → second modifier → (raw material gas + catalyst gas → reaction gas + catalyst gas) × n → post-treatment

[0080] In addition, Figure 6 In the example of using a substance containing O and H as a reaction gas, Figure 6 The processing sequence shown is expressed as follows.

[0081] First modifier → substance containing O and H → second modifier → (raw material gas + catalyst gas → substance containing O and H + catalyst gas) × n → post-treatment

[0082] When the term "wafer" is used in this specification, it sometimes refers to the wafer itself, and sometimes refers to the wafer and the stack of predetermined layers or films formed on its surface. When the term "surface of the wafer" is used in this specification, it sometimes refers to the surface of the wafer itself, and sometimes refers to the surface of a predetermined layer, etc. formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on the wafer", it sometimes refers to forming the predetermined layer directly on the surface of the wafer itself, and sometimes refers to forming the predetermined layer on top of a layer, etc. formed on the wafer. When only the term "substrate" is used in this specification, the meaning is the same as when the term "wafer" is used.

[0083] (Wafer loading and wafer boat introduction)

[0084] After a plurality of wafers 200 are loaded into the wafer boat 217 (wafer loading), the gate 219s is moved by the gate opening and closing mechanism 115s to open the lower end opening of the manifold 209 (gate opening). Figure 3 As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115 and loaded (boat introduction) into the processing chamber 201. In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0085] In addition, if Figure 8 As shown in (a), the first substrate and the second substrate are exposed on the surface of the wafer 200 filled in the wafer boat 217. The surface of the first substrate of the wafer 200 has OH terminals as adsorption points over the entire area (the entire surface). In other words, the surface of the first substrate of the wafer 200 has a surface with OH groups as terminals over the entire area (the entire surface). On the other hand, most of the surface of the second substrate of the wafer 200 has a surface that does not have OH groups as terminals.

[0086] (Pressure regulation and temperature regulation)

[0087] Afterwards, in order to make the space in the processing chamber 201 where the wafer 200 is located reach the required pressure (vacuum degree), vacuum exhaust (decompression exhaust) is performed using the vacuum pump 246. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, in order to make the wafer 200 in the processing chamber 201 reach the required processing temperature, it is heated by the heater 207. At this time, in order to achieve the required temperature distribution in the processing chamber 201, the power-on state of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263. In addition, the rotation of the wafer 200 is started using the rotation mechanism 267. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0088] (Step A)

[0089] Afterwards, the above-mentioned steps A1, A3, and A2 are performed in sequence.

[0090] Each step is described below.

[0091] (Step A1)

[0092] In step A1 , a first modifying agent is supplied to the wafer 200 in the processing chamber 201 , that is, the wafer 200 with the first base and the second base exposed on the surface.

[0093] Specifically, valve 243a is opened to allow the first modifier to flow into gas supply pipe 232a. The first modifier's flow rate is regulated by MFC 241a, supplied into processing chamber 201 via nozzle 249a, and exhausted through exhaust port 231a. At this point, the first modifier is supplied to wafer 200. Alternatively, valves 243e-243g may be opened to allow inert gas to be supplied into processing chamber 201 via nozzles 249a-249c, respectively.

[0094] By supplying the first modifier to the wafer 200 under the processing conditions described later, the surface of the first substrate can be selectively (preferentially) modified. That is, in step A1, the first modifier is selectively (preferentially) chemically adsorbed on the surface of the first substrate of the wafer 200 by utilizing the chemical reaction between the OH terminal on the surface of the first substrate and the first modifier, thereby enabling the surface of the first substrate to be modified. At this time, one or more of the two or more first functional groups possessed by the first modifier are detached due to the chemical reaction with the OH terminal, and the remaining groups from the first modifier containing the second functional group are present on the surface of the first substrate. In addition, a part of the remaining groups from the first modifier present on the surface of the first substrate is contained in the first functional group that was not used in the chemical reaction with the OH terminal. Therefore, on the surface of the first substrate modified with the first modifier, a first modified layer (specifically, for example, the one described later) is formed by the remaining groups from the first modifier in a state containing the first functional group and the second functional group. Figure 7 Here, the second functional group contained in the first modified layer is a functional group with high chemical stability.

[0095] After the surface of the first substrate is modified with the first modifying agent, valve 243a is closed to stop the supply of the first modifying agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any remaining first modifying agent and the like. At this point, valves 243e to 243g are opened, and an inert gas is supplied into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied through nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201.

[0096] The treatment conditions for supplying the first modifier in step A1 are preferably conditions that do not cause thermal decomposition (gas phase decomposition) of the first modifier itself. Specific examples include the following:

[0097] Treatment temperature: room temperature (25°C) to 500°C, preferably 50 to 300°C;

[0098] Processing pressure: 1-13300 Pa, preferably 50-1330 Pa;

[0099] First modifier supply flow rate: 1-3000 sccm, preferably 50-1000 sccm;

[0100] First modifier supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes;

[0101] Inert gas supply flow rate (each gas supply pipe): 0 to 20,000 sccm.

[0102] The following are examples of the processing conditions when purging is performed in step A1:

[0103] Treatment temperature: room temperature (25°C) to 500°C, preferably 50 to 300°C;

[0104] Processing pressure: 1~400Pa;

[0105] Inert gas supply flow rate (each gas supply pipe): 50-20000 sccm;

[0106] Inert gas supply time: 10 to 120 seconds.

[0107] Here, the description of the numerical range of "1 to 13,300 Pa" in this specification means that the range includes a lower limit and an upper limit. Therefore, for example, "1 to 13,300 Pa" means "above 1 Pa and below 13,300 Pa." The same applies to other numerical ranges. In addition, the processing temperature refers to the temperature of the wafer 200, and the processing pressure refers to the pressure within the processing chamber 201. In addition, "gas supply flow rate: 0 sccm" means that the gas is not supplied. These meanings also apply to the following description.

[0108] Furthermore, in step A1, the first modifier is also chemically adsorbed on a portion of the surface of the second substrate. However, the amount of the first modifier chemically adsorbed relative to the surface of the second substrate is minimal, while the amount of the first modifier chemically adsorbed on the surface of the first substrate is overwhelmingly greater. Thus, the significant difference in the amount of the first modifier chemically adsorbed on the surface of the second substrate and the surface of the first substrate is due to the fact that, as described above, the surface of the first substrate on wafer 200 has OH termini throughout its entirety, while the surface of the second substrate has no OH termini in most areas. Furthermore, this is also due to the fact that the processing conditions in step A1 are such that the first modifier will not undergo thermal decomposition (gas-phase decomposition) within processing chamber 201.

[0109] (Step A3)

[0110] After step A1 is completed, step A3 is performed. In step A3, a substance containing O and H is supplied to the wafer 200 in the processing chamber 201 after step A1 is completed, that is, the wafer 200 on which the first modified layer is formed on the surface of the first substrate. In addition, when supplying the substance containing O and H to the wafer 200, it is preferable to Figure 6 The catalyst gas is supplied together as shown. This promotes the chemical reaction described later and shortens the processing time of step A3. However, depending on the processing conditions, the supply of catalyst gas is not necessary and can be omitted. The following describes an example of the combined use of catalyst gas.

[0111] Specifically, valves 243c and 243d are opened, and a substance containing O and H is flowed into gas supply pipe 232c, while a catalyst gas is flowed into gas supply pipe 232d. The O and H-containing substance and catalyst gas are flow-regulated by MFCs 241c and 241d, respectively, and supplied into processing chamber 201 through nozzles 249c and 249a. After being supplied into processing chamber 201, they are mixed and exhausted through exhaust port 231a. At this point, the O and H-containing substance and catalyst gas are supplied to wafer 200. Alternatively, valves 243e to 243g may be opened, and inert gas may be supplied into processing chamber 201 through nozzles 249a to 249c, respectively.

[0112] By supplying a substance containing O and H and a catalyst gas to the wafer 200 under the processing conditions described later, an OH terminal can be formed in the first modified layer formed by step A1. That is, in step A3, the first functional group of the remaining group from the first modifier contained in the first modified layer formed on the surface of the first substrate is chemically reacted with the substance containing O and H, so that the first functional group contained in the first modified layer is replaced by an OH group. At this time, the second functional group contained in the first modified layer does not contribute to the above-mentioned chemical reaction and remains in the current state. Therefore, after supplying the substance containing O and H and the catalyst gas, an OH terminal is formed in the first modified layer, and the first modified layer is changed into a second modified layer having an OH terminal (specifically, for example, the second functional group described later). Figure 7 The second modified layer 20 shown in (c) still contains the second functional group among the remaining groups from the first modifier.

[0113] In step A3, it is sufficient that the reaction of replacing the first functional groups contained in the first modified layer with OH groups occurs. This reaction can be carried out in a non-plasma atmosphere and at a relatively low temperature, as described below. By carrying out step A3 in a non-plasma atmosphere and at a relatively low temperature, as described below, it is possible to suppress the first modified layer (residual groups from the first modifier) ​​from being detached and removed from the surface of the first substrate during the process of converting the first modified layer into the second modified layer.

[0114] After the first modified layer formed on the surface of the first substrate is transformed into the second modified layer, valves 243 c and 243 d are closed to stop the supply of the substance containing O and H and the catalyst gas into the processing chamber 201. Then, the remaining gas in the processing chamber 201 is removed (purged) from the processing chamber 201 using the same processing steps and processing conditions as those in the purge in step A1 described above.

[0115] The following are examples of treatment conditions when the substance containing O and H is supplied in step A3:

[0116] Treatment temperature: room temperature (25°C) to 500°C, preferably room temperature to 300°C;

[0117] Processing pressure: 1~101325Pa;

[0118] Supply flow rate of substances containing O and H: 10-10000 sccm;

[0119] Supply time of substances containing O and H: 1 second to 24 hours;

[0120] Catalyst gas supply flow rate: 0~10000sccm

[0121] Inert gas supply flow rate (each gas supply pipe): 0 to 20,000 sccm.

[0122] (Step A2)

[0123] After step A3 is completed, step A2 is performed. In step A2, the second modifying agent is supplied to the wafer 200 in the processing chamber 201 after step A3 is completed, that is, the wafer 200 having the second modified layer formed on the first base surface.

[0124] Specifically, valve 243h is opened to allow the second modifier to flow into gas supply pipe 232h. The second modifier's flow rate is regulated by MFC 241h and supplied into processing chamber 201 via gas supply pipe 232a and nozzle 249a. The second modifier is then exhausted through exhaust port 231a. At this point, the second modifier is supplied to wafer 200. Alternatively, valves 243e-243g may be opened to allow inert gas to be supplied into processing chamber 201 via nozzles 249a-249c, respectively.

[0125] By supplying the second modifier to the wafer 200 under the processing conditions described later, the second modifier can be chemically adsorbed on the OH terminal of the second modified layer formed on the surface of the first substrate. That is, in step A2, the second modifier is selectively (preferentially) chemically adsorbed on the surface of the first substrate of the wafer 200, specifically, on the surface of the second modified layer, by utilizing the chemical reaction between the OH terminal of the second modified layer and the second modifier, so that the surface of the first substrate can be further modified. At this time, the first functional group contained in the second modifier will be detached due to the chemical reaction with the OH terminal contained in the second modified layer, and the remaining group from the second modifier containing the second functional group is present on the surface of the first substrate, specifically, on the surface of the second modified layer, that is, the outermost surface of the first substrate. Compared with the first modifier, the second modifier contains fewer first functional groups in one molecule, so almost all of the first functional groups contained in the second modifier are used for chemical reaction with the OH terminal contained in the second modified layer. Therefore, a third modified layer (specifically, for example, the one described later) is formed on the outermost surface of the first substrate further modified by the second modifying agent.Figure 7 The third modified layer 30 shown in (d) contains: the remaining groups from the first modifying agent in a state containing the second functional group, and the remaining groups from the second modifying agent in a state containing the second functional group. As can be seen from the above, the first functional group will not remain in the third modified layer or the remaining amount of the first functional group will be very small. Here, Figure 8 (b) shows a state where the third modified layer is formed on the surface of the first base exposed on the surface of the wafer 200 .

[0126] After the surface of the first substrate is further modified by the second modifying agent, the valve 243h is closed to stop the supply of the second modifying agent into the processing chamber 201. Then, the remaining gas and the like in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing steps and processing conditions as those in the purge in step A1 described above.

[0127] The treatment conditions for supplying the second modifier in step A2 are preferably conditions that do not cause thermal decomposition (gas phase decomposition) of the second modifier itself. Specific examples include the following:

[0128] Treatment temperature: room temperature (25°C) to 500°C, preferably 50 to 300°C;

[0129] Processing pressure: 1-13300 Pa, preferably 50-1330 Pa;

[0130] Second modifier supply flow rate: 1-3000 sccm, preferably 50-1000 sccm;

[0131] Second modifier supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes;

[0132] Inert gas supply flow rate (each gas supply pipe): 0 to 20,000 sccm.

[0133] -First modifier and second modifier-

[0134] Here, the first modifier used in step A1 and the second modifier used in step A2 are described. The first modifier and the second modifier each contain one or more atoms to which the first functional group and the second functional group are directly bonded.

[0135] First modifier

[0136] The first functional group in the first modifier is preferably a functional group that enables chemical adsorption of the first modifier to an adsorption site (e.g., an OH terminus) on the surface of the first substrate. The first functional group preferably comprises an amino group, and more preferably comprises a substituted amino group. When the first modifier comprises an amino group (preferably a substituted amino group), the amount of chemical adsorption of the first modifier to the surface of the first substrate can be increased. In particular, from the perspective of adsorption to the first substrate, it is preferred that all first functional groups possessed by the first modifier are substituted amino groups.

[0137] The substituent of the substituted amino group is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group of the substituted amino group may be linear or branched. Specific examples of the alkyl group of the substituted amino group include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0138] The number of substituents possessed by the substituted amino group is 1 or 2, preferably 2. When the number of substituents possessed by the substituted amino group is 2, the two substituents may be the same or different.

[0139] The number of first functional groups in the first modifier can be greater than the number of first functional groups contained in one molecule of the second modifier, described later. Specifically, the number of first functional groups in the first modifier is an integer greater than 2, and an integer less than or equal to the valence of the atoms directly bonded to the first and second functional groups - 1. From the perspective of ease of obtaining the first modifier, the number of first functional groups in the first modifier is preferably 2. Furthermore, the multiple first functional groups in the first modifier may be the same or different.

[0140] The second functional group in the first modifier is preferably a functional group capable of modifying the surface of the first substrate into a film-forming-hindering region. The second functional group is preferably a chemically stable functional group, more preferably a hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or an aromatic hydrocarbon group. Alkyl groups are preferred as the hydrocarbon group. In particular, from the perspectives of high chemical stability and ease of availability, it is preferred that all second functional groups in the first modifier be alkyl groups.

[0141] The alkyl group as the second functional group is more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group contained in the substituted amino group may be linear or branched. Specific examples of the alkyl group contained in the substituted amino group include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0142] The number of second functional groups in the first modifier is an integer greater than or equal to 1, and may be an integer less than or equal to (the valence of the atoms directly bonded to the first and second functional groups) - (the number of first functional groups in the first modifier). If the number of first functional groups in the first modifier is 2, the number of second functional groups in the first modifier is preferably 2. The multiple second functional groups in the first modifier may be the same or different.

[0143] In the first modifier, as atoms directly bonded to the first functional group and the second functional group, there can be mentioned: carbon (C) atoms, silicon (Si) atoms, germanium (Ge) atoms, tetravalent metal atoms, etc. Here, as tetravalent metal atoms, there can be mentioned: titanium (Ti) atoms, zirconium (Zr) atoms, hafnium (Hf) atoms, molybdenum (Mo) atoms, tungsten (W) atoms, etc. In addition, as atoms directly bonded to the first functional group and the second functional group, in addition to tetravalent metal atoms, they can also be metal atoms that can be bonded to four or more ligands. In this case, the number of the second functional group can be increased, and a stronger effect can be exerted as an inhibitor.

[0144] Among them, as the atom directly bonded with the first functional group and the second functional group, C atom, Si atom, Ge atom are also preferred. This is because, when any of C atom, Si atom, and Ge atom is used as the atom directly bonded with the first functional group and the second functional group, any of the following characteristics can be obtained, namely: higher adsorption of the first modifier on the surface of the first substrate, and higher chemical stability of the first modifier after adsorption to the first substrate surface, i.e., the remaining group from the first modifier. Among them, as the atom directly bonded with the first functional group and the second functional group, Si atom is also more preferred. This is because, when Si atom is used as the atom directly bonded with the first functional group and the second functional group, a balance between the following two characteristics can be better achieved, namely: higher adsorption of the first modifier on the surface of the first substrate, and higher chemical stability of the first modifier after adsorption to the first substrate surface, i.e., the remaining group from the first modifier. In the atom to which the first functional group and the second functional group are directly bonded, the first functional group and the second functional group are directly bonded as described above, but in addition thereto, a hydrogen (H) atom or a third functional group may be bonded.

[0145] The third functional group bonded to the atom directly bonded to the first and second functional groups may be any functional group other than the functional groups mentioned above as the first and second functional groups. Examples of the third functional group include a functional group formed by appropriately combining two or more of a C atom, a Si atom, a Ge atom, a tetravalent metal atom, a metal atom capable of bonding to four or more ligands, an oxygen atom, a nitrogen (N) atom, and a H atom.

[0146] The first modifier includes one or more atoms directly bonded to the first functional group and the second functional group, but may also include two or more atoms directly bonded to the first functional group and the second functional group. For convenience, the atoms directly bonded to the first functional group and the second functional group are referred to as atoms Y. The two or more atoms Y may be directly bonded or bonded via a linking group. In addition, the number of atoms Y in the first modifier may be an integer greater than 1, for example, 1, 2, or 3 or more. Among them, the number of atoms Y in the first modifier is also preferably 1 or 2, more preferably 1.

[0147] When the number of atoms Y in the molecule of the first modifier is 2, examples of the linking group that bonds two atoms Y include -C n H 2n -, -O-, and -NR"-. Here, -C n H 2n n in - represents an integer greater than 1. In addition, as R in -NR"-, a H atom or an alkyl group can be mentioned. Among them, as a linking group that bonds two atoms Y, -C n H 2n -. -C n H 2n The n in - is preferably 1 to 5, more preferably 1 or 2.

[0148] The first modifier preferably has a structure comprising one or more tetravalent atoms directly bonded to the first and second functional groups. Preferably, the first modifier has a structure comprising one or more Si atoms directly bonded to the first and second functional groups. More preferably, the first modifier has a structure comprising one or more Si atoms directly bonded to the first and second functional groups. Further preferably, the first modifier has a structure comprising one or two Si atoms directly bonded to the first and second functional groups. In the case where the first modifier has a structure comprising two Si atoms directly bonded to the first and second functional groups, the two Si atoms may be directly bonded or bonded via the aforementioned linking group. Additionally, in the case where the first modifier has a structure comprising two Si atoms directly bonded to the first and second functional groups, the first functional group, the second functional group, and the aforementioned linking group are preferably only directly bonded to the two Si atoms. Furthermore, it is particularly preferred that the first modifier has a structure comprising one Si electrode directly bonded to the first and second functional groups. That is, the first modifier particularly preferably has a structure in which only the first functional group and the second functional group are directly bonded to Si as a central atom.

[0149] The first modifier preferably has a structure containing two amino groups in one molecule. Among them, the first modifier more preferably has a structure containing two amino groups and at least one alkyl group in one molecule. Among them, the first modifier further preferably has a structure containing two amino groups and two alkyl groups in one molecule.

[0150] In addition, the first modifier preferably has a structure in which two amino groups are bonded to the central atom, i.e., Si. More preferably, the first modifier has a structure in which two amino groups and at least one alkyl group are bonded to the central atom, i.e., Si. Further preferably, the first modifier has a structure in which two amino groups and two alkyl groups are bonded to the central atom, i.e., Si.

[0151] Furthermore, the amino group is preferably a substituted amino group as described above. The substituents possessed by the substituted amino group are as described above.

[0152] As the first modifier, for example, a compound represented by the following Formula 1 is preferably used.

[0153] Formula 1: R 1 ]n 1 -(X)-[R 2 ]m 1

[0154] In formula 1, R 1 represents the first functional group directly bonded to X, R 2 represents a second functional group or an H atom directly bonded to X, X represents a tetravalent atom selected from the group consisting of a C atom, a Si atom, a Ge atom, and a tetravalent metal atom, and n 1 Indicates 2 or 3, m 1 Indicates 1 or 2.

[0155] By R 1 The first functional group represented by has the same meaning as the first functional group described above, and the preferred examples are also the same. 1 In the case of 2 or 3, two or three R 1 , that is, the two or three first functional groups can be the same or different. 2 The second functional group represented by has the same meaning as the second functional group described above, and the preferred examples are also the same. 1 When the value is 2, the two R 2 One of them can be a H atom and the other can be a second functional group, or both can be second functional groups. 2 When both are second functional groups, the two second functional groups may be the same or different.

[0156] As the tetravalent atom represented by X, a Si atom is preferable.

[0157] As n1 , preferably 2.

[0158] As m 1 , preferably 2.

[0159] Examples of the first modifier include bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2, abbreviated as BDMADMS), bis(diethylamino)diethylsilane ([(C2H5)2N]2Si(C2H5)2, abbreviated as BDEADES), bis(dimethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2, abbreviated as BDMADES), bis(diethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2, abbreviated as BDMADES), Bis(dimethylamino)silane ([(C2H5)2N]2Si(CH3)2, abbreviated as BDEADMS), bis(dimethylamino)silane ([(CH3)2N]2SiH2, abbreviated as BDMAS), bis(dimethylaminodimethylsilyl)ethane ([(CH3)2N(CH3)2Si]2C2H6, abbreviated as BDMADMSE), bis(dipropylamino)silane ([(C3H7)2N]2SiH2, abbreviated as Bis(dipropylamino)dimethylsilane ([(C3H7)2N]2Si(CH3)2, abbreviated as BDPADMS), Bis(dipropylamino)diethylsilane ((C3H7)2N]2Si(C2H5)2, abbreviated as BDPADES), (dimethylsilyl)diamine ((CH3)2Si(NH2)2, abbreviated as DMSDA), (diethylsilyl)diamine ((C2H5)2S As the first modifier, one or more of these can be used.

[0160] Second modifier

[0161] The first functional group in the second modifier has the same meaning as the first functional group in the first modifier, and the same applies to the preferred examples. The number of the first functional groups in the second modifier is less than the number of the first functional groups contained in one molecule of the first modifier. That is, if the number of the first functional groups contained in one molecule of the first modifier is 2, the number of the first functional groups in the second modifier is 1, and if the number of the first functional groups contained in one molecule of the first modifier is 3, the number of the first functional groups in the second modifier is 1 or 2. From the viewpoint of the ease of obtaining the second modifier, it is preferred that the number of the first functional groups in the second modifier is 1. In addition, when the second modifier has multiple first functional groups, the multiple first functional groups may be the same or different.

[0162] The second functional group in the second modifier has the same meaning as the second functional group in the first modifier, and the same applies to the preferred examples. The number of second functional groups in the second modifier is an integer greater than 1, and can be an integer less than (the valence of the atoms directly bonded to the first functional group and the second functional group) - (the number of first functional groups in the second modifier). When the number of first functional groups in the first modifier is 1, the number of second functional groups in the second modifier is preferably 3. When the second modifier has multiple second functional groups, the multiple second functional groups may be the same or different.

[0163] The atoms directly bonded to the first and second functional groups in the second modifier have the same meaning as the atoms directly bonded to the first and second functional groups in the first modifier, and the same applies to preferred examples. In the second modifier, the atoms directly bonded to the first and second functional groups may also have a hydrogen atom or a third functional group bonded to them in addition to the first and second functional groups. The third functional group has the same meaning as the third functional group in the first modifier, and the same applies to preferred examples.

[0164] The second modifier preferably has a structure comprising a tetravalent atom directly bonded to the first and second functional groups. More preferably, the second modifier has a structure comprising only tetravalent atoms directly bonded to the first and second functional groups. The second modifier particularly preferably has a structure comprising one Si atom directly bonded to only the first and second functional groups. That is, the second modifier particularly preferably has a structure wherein only the first and second functional groups are directly bonded to the Si atom serving as the central atom.

[0165] The second modifier preferably has a structure containing one amino group in one molecule. It is also more preferred that the second modifier has a structure containing one amino group and at least one alkyl group in one molecule. It is further preferred that the second modifier has a structure containing one amino group and three alkyl groups in one molecule.

[0166] The second modifier preferably has a structure in which one amino group is bonded to the central Si atom. More preferably, the second modifier has a structure in which one amino group and at least one alkyl group are bonded to the central Si atom. Even more preferably, the second modifier has a structure in which one amino group and three alkyl groups are bonded to the central Si atom.

[0167] Furthermore, the amino group is preferably a substituted amino group as described above. The substituents possessed by the substituted amino group are as described above.

[0168] As the second modifier, for example, a compound represented by the following formula 2 is preferably used.

[0169] Formula 2: R 1 ]n 2 -(X)-[R 2 ]m 2

[0170] In formula 2, R 1 represents the first functional group directly bonded to X, R 2 represents a second functional group or an H atom directly bonded to X, X represents a tetravalent atom selected from the group consisting of a C atom, a Si atom, a Ge atom, and a tetravalent metal atom, and n 2 Indicates 1 or 2, m 2 Indicates 2 or 3.

[0171] By R 1 The first functional group represented by has the same meaning as the first functional group described above, and the preferred examples are also the same. 2 When the value is 2, the two R 1 The first functional groups may be the same or different. 2 The second functional group represented by has the same meaning as the second functional group described above, and the preferred examples are also the same. 2 2 or 3, two or three R 2 In the case of two or three R 2 When all the second functional groups are second functional groups, all the second functional groups may be the same or different.

[0172] As the tetravalent atom represented by X, a Si atom is preferable.

[0173] As n 2 , preferably 1.

[0174] As m 2 , preferably 3.

[0175] Examples of the second modifier include dimethylaminotrimethylsilane ((CH3)2NSi(CH3)3, abbreviated as DMATMS), diethylaminotriethylsilane ((C2H5)2NSi(C2H5)3, abbreviated as DEATES), dimethylaminotriethylsilane ((CH3)2NSi(C2H5)3, abbreviated as DMATES), diethylaminotrimethylsilane ((C2H5)2NSi(CH3)3, abbreviated as DEATMS), (trimethylsilyl)amine ((CH3)3SiNH2, abbreviated as TMSA), (triethylsilyl)amine ((C2H5)3SiNH2, abbreviated as TESA), (dimethylamino)silane ((CH3)2NSiH3, abbreviated as DMAS), and (diethylamino)silane ((C2H5)2NSiH3, abbreviated as DEAS). One or more of these modifiers may be used as the second modifier.

[0176] The first and second modifiers are supplied as gases to the wafer 200 via the aforementioned first and second modifier supply systems, respectively. However, at least a portion of these gases need not be in a gaseous state. In other words, as long as the formation of the first modified layer in step A1 and the formation of the third modified layer in step A2 can be achieved and the gases can be supplied to the wafer 200 via the aforementioned first and second modifier supply systems, at least a portion of the first and second modifiers need not be in a gaseous state.

[0177] - Inert gas -

[0178] In addition to nitrogen (N2), the inert gas used in steps A1 to A3 may include rare gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe). One or more of these gases may be used as the inert gas. This also applies to the steps using an inert gas described below.

[0179] - Substances containing O and H -

[0180] As the substance containing O and H used in step A3, oxygen-containing gases containing O-H bonds, such as water vapor (H2O gas) and hydrogen peroxide (H2O2) gas, can be used. In addition, as the substance containing O and H, oxygen-containing gases not containing O-H bonds, such as hydrogen (H2) + oxygen (O2) gas and H2 gas + ozone (O3) gas, can also be used. In this specification, the parallel description of the two gases "H2 gas + O2 gas" refers to a mixed gas of H2 gas and O2 gas. In the case of supplying a mixed gas, the two gases can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 separately through different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0181] Typically, the substance containing O and H is supplied to wafer 200 as a gas via the aforementioned O and H-containing substance supply system, and at least a portion of the substance does not need to be in a gaseous state. Specifically, if the second modified layer can be formed in step A3 and the substance can be supplied to wafer 200 via the aforementioned O and H-containing substance supply system, at least a portion of the substance containing O and H does not need to be in a gaseous state. For example, a portion of the substance may be in a liquid state, such as in a mist state. These aspects also apply to step B2, described later, using the substance containing O and H.

[0182] - Catalyst gas -

[0183] As the catalyst gas used in step A3, for example, an amine gas containing C, N, and H can be used. As the amine gas, for example, pyridine gas (C5H 5N py) gas, aminopyridine (C5H6N2) gas, methylpyridine (C6H7N) gas, lutidine (C7H9N) gas, piperazine (C4H 10 N2) gas, piperidine (C5H 11 Cyclic amine gases such as (C₂H₅)₃N (Cyclic amine gas), triethylamine ((C₂H₅)₃N, abbreviated: TEA) gas, and chain amine gases such as diethylamine ((C₂H₅)₂NH, abbreviated: DEA) gas can be used as the catalyst gas. These considerations also apply to Steps B1 and B2, which will be described later and use a catalyst gas.

[0184] <More specific embodiment of step A>

[0185] Here, refer to Figure 7 (a)~ Figure 7 (d) A more specific embodiment of the modification in step A is described. Figure 7 (a)~ Figure 7(d) is a diagram focusing on the reaction occurring on the first base surface of the wafer 200 , and is a diagram in which only the first base portion of the wafer 200 is extracted.

[0186] Here, the following example is described, that is, for a wafer 200 with an SiO film exposed on the surface as a first base, bis(dialkylamino)dialkylsilane (abbreviated as BDAADAS) is used as the first modifier, and (dialkylamino)trialkylsilane (abbreviated as DAATAS) is used as the second modifier. Figure 7 (a)~ Figure 7 In (d), both "R" and "R'" represent an alkyl group.

[0187] like Figure 7 As shown in (a), the surface of the SiO film exposed on the surface of the wafer 200 has a chemical structure having a large number of OH terminals. In step A1, when BDAADAS is supplied as a first modifier to the wafer 200, BDAADAS is chemically adsorbed on the surface of the SiO film.

[0188] More specifically, if Figure 7 As shown in (b), at the portion where the two OH ends are close to each other on the surface of the SiO film (e.g., the portion having the "adjacent" or "geminal" structure in Table 1), these two OH groups react with the two dialkylamino groups contained in one BDAADAS molecule, and one Si atom contained in one BDAADAS molecule bonds to two O atoms in the two OH groups to form a cross-linked structure (cross-linked structure) and chemical adsorption is performed. Due to this chemical adsorption, the two dialkylamino groups (equivalent to the first functional group) are separated from the BDAADAS molecule, and a residual group having two alkyl groups remains on the surface of the SiO film ( Figure 7 This is a way for BDAADAS to be chemically adsorbed on the surface of SiO film.

[0189] In addition, if Figure 7 As shown in (b), in the portion on the SiO film surface where the two OH terminals are far apart (e.g., the portion having the "isolated" structure in Table 1), one of the two OH groups reacts with a dialkylamino group contained in a BDAADAS molecule, and a Si atom contained in a BDAADAS molecule bonds with an O atom in the OH group to cause chemical adsorption. Due to this chemical adsorption, a dialkylamino group (equivalent to the first functional group) is separated from the BDAADAS molecule, and a remaining group having two alkyl groups and one dialkylamino group remains on the SiO film surface ( Figure 7This is another way for BDAADAS to chemically adsorb on the SiO film surface.

[0190] In this way, BDAADAS can be chemically adsorbed regardless of the structure of the OH terminal on the SiO film surface. As a result, a first modified layer 10 containing residual groups derived from BDAADAS, namely ">SiR2 groups" and "-SiR2 (NR'2) groups" is formed on the SiO film surface.

[0191] Next, in step A3 , a gas containing O and H, which is a substance containing O and H, is supplied to the wafer 200 , thereby forming OH terminals on the first modified layer 10 formed on the surface of the SiO film in step A1 .

[0192] More specifically, in step A3, the dialkylamino group contained in the first modified layer 10 formed in step A1 reacts with the gas containing O and H (specifically, a hydrolysis reaction), such as Figure 7 As shown in (c), the dialkylamino groups contained in the first modified layer 10 are replaced with OH groups. As a result, the first modified layer 10 formed on the SiO film surface is transformed into a second modified layer 20 having OH terminals. According to step A3, the dialkylamino groups are removed from the first modified layer 10 through the above reaction, so that the resulting second modified layer 20 contains almost no dialkylamino groups.

[0193] Next, in step A2 , DAATAS is supplied to the wafer 200 as a second modifying agent, and DAATAS is chemically adsorbed on the OH terminals of the second modified layer 20 formed in step A3 .

[0194] More specifically, the OH group at the OH terminal of the second modified layer 20 formed in step A3 reacts with the dialkylamino group contained in the DAATAS molecule, and the Si atom contained in the DAATAS molecule bonds with the O atom in the OH group to undergo chemical adsorption. Due to this chemical adsorption, one dialkylamino group (equivalent to the first functional group) is detached from the DAATAS, leaving a remaining group having three alkyl groups ( Figure 7 (d) “—SiR 3 group (trialkylsilyl group)”). This is one way of chemically adsorbing DAATAS on the second modified layer 20 .

[0195] Thus, a third modified layer 30 is formed on the surface of the SiO film. This third modified layer 30 contains residual groups derived from BDAADAS and residual groups derived from DAATAS. As described above, DAATAS, the second modifier, is a compound having a dialkylamino group corresponding to the first functional group. Therefore, the dialkylamino group is removed by the above reaction. As a result, the dialkylamino group is not easily incorporated into the resulting third modified layer 30, and is almost absent.

[0196] The outermost surface of the third modified layer 30, that is, the outermost surface of the SiO film, is covered with the remaining groups derived from BDAADAS and the remaining groups derived from DAATAS. In other words, the outermost surface of the SiO film is covered with the alkyl groups (equivalent to the second functional group) contained in the remaining groups derived from BDAADAS and the alkyl groups (equivalent to the second functional group) contained in the remaining groups derived from DAATAS. As a result, the outermost surface of the SiO film is capped with the alkyl groups (equivalent to the second functional group) contained in the remaining groups derived from BDAADAS and the alkyl groups (equivalent to the second functional group) contained in the remaining groups derived from DAATAS.

[0197] After the steps A1, A3, and A2 are sequentially performed, a third modified layer 30 is formed on the surface of the SiO film. The third modified layer 30 includes the remaining groups derived from BDAADAS and the remaining groups derived from DAATAS. Figure 6 As shown in (d), it has a relatively large number of chemically stable alkyl groups, a high density of chemically stable alkyl groups, and a trialkylsilyl group with significant steric hindrance as the residual group derived from DAATAS. Therefore, when film formation is performed on a wafer 200 having a SiO film with such a third modified layer 30 formed on its surface, physical and chemical adsorption of the film-forming raw materials on the SiO film surface can be effectively suppressed. That is, by using a wafer 200 modified by sequentially performing steps A1, A3, and A2, selective failure can be suppressed during subsequent film formation, improving the selectivity of selective growth.

[0198] (repeat)

[0199] In step A, steps A1 and A3 can be repeated multiple times. By repeating these steps, the first modifier can be more fully chemically adsorbed onto more OH ends on the surface of the first substrate, thereby more fully replacing the first functional groups contained in the first modified layer with OH groups. Therefore, by repeating these steps and then performing step A2, the modification density of the first substrate surface, that is, the termination rate of the second functional groups on the first substrate surface, can be increased.

[0200] Alternatively, steps A1, A3, and A2 may be repeated multiple times in step A. By repeating these steps, the modification density of the first substrate surface, that is, the termination rate of the second functional groups on the first substrate surface, can be increased. Furthermore, the above steps may be repeated as many times as necessary to achieve a desired modification density on the first substrate surface.

[0201] (Step B)

[0202] In step B, film-forming gases (raw material gases, reaction gases, catalyst gases) are supplied to wafer 200 after the first substrate surface has been modified in step A, i.e., after the third modified layer has been formed on the first substrate surface, to selectively form a film on the second substrate surface. Furthermore, in step B, the output of heater 207 is adjusted to maintain the temperature of wafer 200 below, and preferably below, the temperature of wafer 200 in step A.

[0203] In step B, a source gas and a reaction gas are alternately supplied to wafer 200 as film-forming gases, or a source gas and a reaction gas are alternately supplied to wafer 200 as film-forming gases. Preferably, a catalyst gas is supplied along with at least one of the source gas and the reaction gas. However, depending on the processing conditions, the supply of the catalyst gas is not essential and may be omitted. For example, any of the following process sequences may be performed in step B. The following process sequence only illustrates step B.

[0204] (raw material gas → reaction gas) × n

[0205] (raw material gas → reaction gas + catalyst gas) × n

[0206] (raw material gas + catalyst gas → reaction gas) × n

[0207] (raw material gas + catalyst gas → reaction gas + catalyst gas) × n

[0208] The following describes an example of using a catalyst gas in combination. Specifically, in step B, a raw material gas and a reaction gas are alternately supplied as film-forming gases, and the raw material gas and the reaction gas are supplied together with the catalyst gas. Specifically, in step B, the following steps B1 and B2 are sequentially performed. In addition, as described above, Figure 8 , for example, an example of using a substance containing O and H as the reaction gas is shown.

[0209] (Step B1)

[0210] In step B1 , a source gas and a catalyst gas are supplied to the wafer 200 in the processing chamber 201 , that is, the wafer 200 after the third modified layer is formed on the first substrate surface.

[0211] Specifically, valves 243b and 243d are opened, and the source gas flows into gas supply pipe 232b, while the catalyst gas flows into gas supply pipe 232d. The source gas and catalyst gas are flow-regulated by MFCs 241b and 241d, respectively, and supplied into processing chamber 201 through nozzles 249b and 249a. After being supplied into processing chamber 201, they are mixed and exhausted through exhaust port 231a. At this point, the source gas and catalyst gas are supplied to wafer 200. Alternatively, valves 243e to 243g may be opened, and inert gas may be supplied into processing chamber 201 through nozzles 249a to 249c, respectively.

[0212] By supplying the source gas and catalyst gas to the wafer 200 under the processing conditions described below, adsorption of the source gas on the third modified layer, i.e., the first base surface, can be suppressed, and the source gas can be selectively (preferentially) adsorbed on the second base surface. Thus, the source gas is adsorbed on the second base surface, forming a first layer having a thickness ranging from less than one atomic layer (one molecular layer) to several atomic layers (several molecular layers), for example.

[0213] In step B1, by supplying a catalyst gas along with the raw material gas, the reaction can be carried out in a non-plasma atmosphere and at relatively low temperatures, as described below. By forming the first layer in a non-plasma atmosphere and at relatively low temperatures, as described below, it is possible to suppress the third modified layer formed on the first base surface from being removed (detached) from the first base surface.

[0214] In addition, when the first layer is formed in step B1, the raw material gas will also be adsorbed on a part of the first substrate surface, but the adsorption amount is extremely small, and is a very small amount compared to the adsorption amount of the raw material gas on the second substrate surface. The reason why this selective (preferential) adsorption can be achieved is that a third modified layer that acts as a film-forming barrier layer is formed on the entire surface of the first substrate, and a third modified layer that acts as a film-forming barrier layer is not formed on most areas or the entire surface of the second substrate. And this is because the processing conditions in step B1 are set to conditions that prevent the raw material gas from undergoing gas-phase decomposition (self-decomposition) in the processing chamber 201. By setting the conditions that prevent the raw material gas from undergoing gas-phase decomposition, decomposition products such as intermediates produced by the gas-phase decomposition of the raw material gas will not accumulate on the first substrate surface and the second substrate surface, and the raw material gas can be selectively adsorbed on the second substrate surface.

[0215] After the first layer is selectively formed on the surface of the second substrate, valves 243b and 243d are closed to stop the supply of the source gas and catalyst gas into the processing chamber 201. Then, the remaining gas in the processing chamber 201 is removed (purged) from the processing chamber 201 using the same processing steps and processing conditions as those in the purge in step A1 described above.

[0216] The treatment conditions in this step are exemplified below:

[0217] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 120°C;

[0218] Processing pressure: 133~1333Pa;

[0219] Raw material gas supply flow rate: 1~2000sccm;

[0220] Raw gas supply time: 1 to 60 seconds;

[0221] Catalyst gas supply flow rate: 1-2000 sccm;

[0222] Inert gas supply flow rate (each gas supply pipe): 0 to 20,000 sccm.

[0223] - Raw material gas -

[0224] As a raw material gas, for example, a gas containing Si and halogen can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. The gas containing Si and halogen preferably contains halogen in the form of a chemical bond between Si and halogen. The gas containing Si and halogen may also contain C, and in this case, it is preferably contained in the form of a Si-C bond. As a gas containing Si and halogen, for example, a silane gas containing Si, Cl and an alkylene group and having a Si-C bond, that is, an alkylene chlorosilane gas can be used. Here, the alkylene group includes: methylene, ethylene, propylene, butylene, etc. The alkylene chlorosilane gas preferably contains Cl in the form of a Si-Cl bond and contains C in the form of a Si-C bond. In this way, as a raw material gas, for example, a gas containing Si and halogen, a gas containing Si, C and halogen, etc. can be used.

[0225] As raw material gases, for example, alkylene chlorosilane gases such as bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as BTCSM) gas and 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as BTCSE) gas can be used; alkyl chlorosilane gases such as 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated as TCDMDS) gas and 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated as DCTMDS) gas can be used; and gases containing a ring structure composed of Si and C and halogens such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C2H4Cl4Si2, abbreviated as TCDSCB) gas can be used. Inorganic chlorosilane gases such as tetrachlorosilane (SiCl₄, abbreviated as STC) gas, hexachlorodisilane (Si₂Cl₆, abbreviated as HCDS) gas, and octachlorotrisilane (Si₃Cl₈, abbreviated as OCTS) gas can be used as the raw material gas. One or more of these gases can be used as the raw material gas.

[0226] - Catalyst gas -

[0227] As the catalyst gas, for example, the same catalyst gas as the various catalyst gases exemplified in the above-mentioned step A3 can be used.

[0228] (Step B2)

[0229] In step B2, a reaction gas and a catalyst gas are supplied to the first layer selectively formed on the surface of the second substrate, i.e., wafer 200, in processing chamber 201 after the first layer is formed in step B1. An example using a substance containing O and H as the reaction gas will be described below.

[0230] Specifically, valves 243c and 243d are opened to allow a substance containing O and H to flow as a reaction gas into gas supply pipe 232c, while a catalyst gas is flowed into gas supply pipe 232d. The substance containing O and H and the catalyst gas are regulated in their respective flow rates by MFCs 241c and 241d, and supplied into processing chamber 201 via nozzles 249c and 249a. After being supplied into processing chamber 201, they are mixed and exhausted through exhaust port 231a. At this point, the substance containing O and H and the catalyst gas are supplied to wafer 200. Alternatively, valves 243e to 243g may be opened to allow an inert gas to be supplied into processing chamber 201 via nozzles 249a to 249c, respectively.

[0231] By supplying a substance containing O and H and a catalyst gas to wafer 200 under the processing conditions described below, at least a portion of the first layer formed on the second substrate surface in step B1 can be oxidized. Thus, a second layer formed on the second substrate surface by oxidizing the first layer is formed. Furthermore, during the formation of the second layer, impurities such as Cl contained in the first layer undergo an oxidation reaction with the substance containing O and H in the first layer, forming a gaseous substance containing impurities such as Cl, which is removed from the first layer and exhausted from processing chamber 201. As a result, the second layer contains less impurities such as Cl than the first layer.

[0232] In step B2, by supplying a catalyst gas together with a substance containing O and H, the above-mentioned reaction can be carried out in a non-plasma atmosphere and at relatively low temperature conditions, which will be described later. By thus forming the second layer in a non-plasma atmosphere and at relatively low temperature conditions, which will be described later, it is possible to suppress the third modified layer formed on the surface of the first substrate from being removed (detached) from the surface of the first substrate.

[0233] After the first layer formed on the surface of the second substrate is oxidized to form the second layer, valves 243c and 243d are closed to stop the supply of the substance containing O and H as the reaction gas and the catalyst gas into the processing chamber 201. Then, the remaining gas in the processing chamber 201 is removed (purged) from the processing chamber 201 using the same processing steps and processing conditions as those used in the purge in step A1.

[0234] The treatment conditions in this step are exemplified below:

[0235] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 120°C;

[0236] Processing pressure: 133~1333Pa;

[0237] Reaction gas supply flow rate: 1~2000sccm;

[0238] Reaction gas supply time: 1 to 60 seconds;

[0239] Catalyst gas supply flow rate: 1-2000 sccm;

[0240] Inert gas supply flow rate (each gas supply pipe): 0 to 20,000 sccm.

[0241] -Reaction gas-

[0242] When forming an oxide film, a substance containing O and H can be used as a reaction gas. As the substance containing O and H, for example, the same O and H-containing substances as the various O and H-containing substances exemplified in step A3 above can be used. In addition, as a reaction gas, oxygen (O2), ozone (O3) gas, nitrous oxide (N2O) gas, nitrous oxide (NO) gas, nitrous dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, and other oxygen (O)-containing gases can be used. Most of the substances containing O and H are oxygen-containing gases, so for convenience, the substances containing O and H are also referred to as oxygen-containing gases below. As a reaction gas, one or more of these can be used.

[0243] In addition, when forming a nitride film, a nitriding agent (nitriding gas) can be used as a reaction gas. As a nitriding agent, a gas containing N and H can be used. As a gas containing N and H, for example, ammonia (NH3), hydrazine (N2H4) gas, hydrazine (N2H2) gas, N3H8 gas, and other hydrogen nitride gases containing N-H bonds can be used. In addition, when forming a nitride film, it is sufficient to replace the above-mentioned substances containing O and H, oxidation, and oxidation reaction with nitriding agents, nitridation, and nitridation reactions, respectively. As a reaction gas, one or more of these can be used.

[0244] - Catalyst gas -

[0245] As the catalyst gas, for example, the same catalyst gas as the various catalyst gases exemplified in the above-mentioned step A3 can be used.

[0246] (Scheduled number of implementations)

[0247] By making the above-mentioned step B1 and step B2 be performed non-simultaneously, i.e., asynchronously, a predetermined number of times (n times, where n is an integer greater than 1), it is possible to Figure 8 As shown in (c), a film having a desired thickness is selectively formed on the surface of the second substrate of the first and second substrates exposed on the surface of the wafer 200. The above cycle is preferably repeated multiple times. In other words, the thickness of the second layer formed in each cycle is preferably made thinner than the desired film thickness, and the second layer is stacked, so that the above cycle is repeated multiple times until the selectively grown film reaches the desired film thickness.

[0248] Furthermore, during steps B1 and B2, a very small amount of film may be formed on the surface of the first substrate. However, in this case, the thickness of the film formed on the first substrate surface is also very thin compared to the thickness of the film formed on the second substrate surface. In this specification, "high selectivity of selective growth" not only refers to forming a film only on the second substrate surface, rather than forming a film entirely on the first substrate surface, but also includes the case where, as described above, a very thin film is formed on the first substrate surface, but a much thicker film is formed on the second substrate surface.

[0249] In the selective growth in step B, the resulting film varies depending on the type of raw material gas or reaction gas. For example, in step B, by using a gas containing Si, C, and halogen as the raw material gas and an oxygen-containing gas as the reaction gas, a silicon oxycarbide film (SiOC film) can be formed as a film. Alternatively, in step B, by using a gas containing Si, C, and halogen as the raw material gas and a gas containing N and H as the reaction gas, a silicon carbonitride film (SiCN film) can be formed as a film. Alternatively, in step B, by using a gas containing Si, C, and halogen as the raw material gas and an oxygen-containing gas and a gas containing N and H as the reaction gas, a silicon oxycarbonitride film (SiOCN film) can be formed as a film. Alternatively, in step B, by using a gas containing Si and halogen as the raw material gas and an oxygen-containing gas as the reaction gas, a silicon oxide film (SiO film) can be formed as a film. Furthermore, for example, by using a gas containing Si and halogen as a raw material gas and a gas containing N and H as a reaction gas in step B, a silicon nitride film (SiN film) can be formed as a film. As described above, various films such as silicon-based oxide films and silicon-based nitride films can be formed in step B. Furthermore, as described above, a catalyst gas is not necessarily required depending on the processing conditions. When no catalyst gas is used, the processing temperature in step B can be set to a predetermined temperature within the range of, for example, 200 to 500°C.

[0250] Furthermore, in the selective growth in step B, by using a raw material gas containing a metal element such as Al, Ti, Hf, Zr, Ta, Mo, or W as a raw material gas, and using an oxygen-containing gas or a gas containing N and H as a reaction gas, metal oxide films such as aluminum oxide films (AlO films), titanium oxide films (TiO films), hafnium oxide films (HfO films), zirconium oxide films (ZrO films), tantalum oxide films (TaO films), molybdenum oxide films (MoO), and tungsten oxide films (WO), and metal nitride films such as aluminum nitride films (AlN films), titanium nitride films (TiN films), hafnium nitride films (HfN films), zirconium nitride films (ZrN films), tantalum nitride films (TaN films), molybdenum nitride films (MoN), and tungsten nitride films (WN) can be formed as films. Furthermore, as described above, depending on the processing conditions, a catalyst gas is not necessarily required. Without using a catalyst gas, the processing temperature in step B can be set to a predetermined temperature within the range of, for example, 200 to 500°C.

[0251] (Step C)

[0252] In step C, the wafer 200 after selective growth is completed by performing steps A and B is subjected to annealing.

[0253] Specifically, after the selective growth is completed, the output of the heater 207 is adjusted in such a manner that the temperature in the processing chamber 201, that is, the temperature of the wafer 200 after the film is selectively formed on the surface of the second substrate, is higher than the temperature of the wafer 200 being selectively grown, preferably higher than the temperature of the wafer 200 being selectively grown, and the wafer 200 after selective growth is heated and annealed.

[0254] Thus, the function of the third modified layer on the surface of the first substrate as an inhibitor can be invalidated. Specifically, by annealing the selectively grown wafer 200, the second functional group contained in the third modified layer can be detached from the surface of the first substrate and removed, or the function of the second functional group as an inhibitor can be invalidated. In addition, the invalidation of the function of the second functional group as an inhibitor means that the molecular structure, atomic arrangement structure, etc. of the second functional group are changed, so that the adsorption of the film-forming gas (raw material gas, reaction gas, etc.) on the surface of the first substrate and the reaction between the surface of the first substrate and the film-forming gas (raw material gas, reaction gas, etc.) can be carried out.

[0255] In step C, the function of the third modified layer as an inhibitor is disabled, resetting the film formation-inhibiting state on the first substrate surface. This allows subsequent steps such as film formation on the first substrate surface to be performed. Furthermore, by annealing the selectively grown wafer 200, the second functional groups contained in the third modified layer are detached and removed from the first substrate surface, and the third modified layer itself is also detached and removed. Figure 9 (d) shows a state where the third modified layer itself is removed from the first base surface exposed on the surface of the wafer 200 .

[0256] Step C can be performed while N2 gas or other N-containing gas, H2 gas or other H-containing gas, O2 gas or other oxygen-containing gas, or a gas (assisting gas) that promotes the removal (desorption) of the second functional group (e.g., an alkyl group such as a methyl group) contained in the third modified layer is supplied into the processing chamber 201. Alternatively, the step C can be performed while the supply of the assisting gas into the processing chamber 201 is stopped. In addition to the aforementioned reactive gases, the assisting gas can also be used.

[0257] The treatment conditions in step C are exemplified below:

[0258] Processing temperature: 200-1000°C, preferably 400-700°C;

[0259] Processing pressure: 1~120000Pa;

[0260] Auxiliary gas supply flow rate: 0~50000sccm;

[0261] Auxiliary gas supply time: 1 to 18,000 seconds.

[0262] (Post-purge and atmospheric pressure recovery)

[0263] After the selective growth of the film on the second substrate surface is completed and the film formation-impeding state on the first substrate surface is reset, an inert gas serving as a purge gas is supplied into the processing chamber 201 from nozzles 249a to 249c and exhausted through exhaust port 231a. This purges the processing chamber 201, removing any remaining gas, reaction byproducts, and the like (post-purge). Subsequently, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (return to atmospheric pressure).

[0264] (Wafer boat export and wafer unloading)

[0265] The sealing cap 219 is then lowered by the boat elevator 115, opening the lower end of the manifold 209. The processed wafers 200, supported by the boat 217, are then unloaded from the lower end of the manifold 209 to the exterior of the reaction tube 203 (boat unloading). After the boat is unloaded, the gate 219s is moved, sealing the lower end opening of the manifold 209 with the gate 219s and the O-ring 220c (gate closing). After being unloaded to the exterior of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer unloading).

[0266] (3) Effects of this method

[0267] According to this aspect, one or more of the following effects can be obtained.

[0268] In step A, the selectivity in the selective growth can be improved by using the first modifier and the second modifier.

[0269] That is, the first modifier contains one or more atoms directly bonded with the first functional group and the second functional group, so that the first functional group of the first modifier can be chemically adsorbed at the adsorption site on the surface of the first substrate (for example, the OH end) in one molecule, which is more than the number of first functional groups contained in one molecule of the second modifier, for example, two or more. By making the first modifier have such a structure, the first modifier can be chemically adsorbed on the surface of the first substrate (at the adsorption site) regardless of the structure of the adsorption site on the surface of the first substrate (for example, the three structures of adjacent, geminal, and isolated OH ends), and more effectively. That is, the first modifier can be chemically adsorbed at the adsorption sites that exist throughout the entire surface of the first substrate. In addition, a second functional group with higher chemical stability exists on the surface of the first substrate after the first modifier is chemically adsorbed.

[0270] In addition, the second modifier includes atoms directly bonded to the first functional group and the second functional group, and the number of first functional groups contained in one molecule is less than the number of first functional groups contained in one molecule of the first modifier. The second modifier has such a structure, and the first modifier also has the above-mentioned structure, so that the second modifier can be chemically adsorbed on the first modifier. After the second modifier is chemically adsorbed on the first modifier, the surface of the first substrate has a high density of second functional groups with high chemical stability. In this state, the surface of the first substrate is capped with the second functional groups contained in the remaining groups from the first modifier and the second functional groups contained in the remaining groups from the second modifier.

[0271] For example, when a first modifier and a second modifier are sequentially applied, after the first modifier is chemically adsorbed on the surface of the first substrate, not only the second functional groups with higher chemical stability but also a portion of the first functional groups remain on the surface of the first substrate. By converting the remaining first functional groups on the surface of the first substrate into adsorption sites such as OH groups, the chemical reaction between the OH groups and the first functional groups of the second modifier can be utilized to chemically adsorb the second modifier on the OH groups. The second modifier contains more second functional groups with higher chemical stability in its molecules than the first modifier. Therefore, the surface of the first substrate after chemical adsorption of the second modifier has more second functional groups with higher chemical stability than before chemical adsorption of the second modifier. In addition, the density of the second functional groups with higher chemical stability is higher and the second functional groups with higher chemical stability are included, which constitute greater steric hindrance. In other words, on the surface of the first substrate after modification by the first and second modifiers, the second functional groups with higher chemical stability are present in greater numbers and at a higher density, and there is a significant steric hindrance caused by the second functional groups with higher chemical stability. In other words, in this state, the surface of the first substrate is densely capped with the chemically highly stable second functional groups contained in the residual groups from the first modifier and the chemically highly stable second functional groups contained in the residual groups from the second modifier. This effectively inhibits the adsorption of the raw material gas onto the surface of the first substrate during film formation. As a result, selective failure can be suppressed and the selectivity of selective growth can be improved.

[0272] In step A, by performing steps A1 and A2 non-simultaneously in that order, the chemical reaction can be appropriately staged (in multiple stages). As a result, the surface of the first substrate contains a large number of highly chemically stable second functional groups at a high density, and these highly chemically stable second functional groups provide significant steric hindrance. This effectively hinders the adsorption of the raw material gas onto the surface of the first substrate during film formation, thereby suppressing selection failure and further improving the selectivity of selective growth.

[0273] By sequentially performing Step A1, Step A3, and Step A2 in Step A, the chemical reaction described above can be more appropriately staged (in multiple stages). As a result, the surface of the first substrate contains a high density of chemically stable second functional groups, and these chemically stable second functional groups provide significant steric hindrance. This effectively hinders the adsorption of the raw material gas onto the surface of the first substrate during film formation, thereby suppressing selection failure and further improving the selectivity of selective growth.

[0274] In this case, a portion of the first modifying agent can be adsorbed on the surface of the first base in a state including at least one first functional group in step A1, so that the above-mentioned chemical reaction can occur more appropriately.

[0275] In addition, in this case, the first modifier can be adsorbed on the surface of the first substrate in a state containing the second functional group in step A1, and the second modifier can be adsorbed on the OH group (i.e., the adsorption site) in a state containing the second functional group in step A2, so that the above-mentioned chemical reaction occurs more appropriately.

[0276] Furthermore, in this case, in step A1, a portion of the first modifier can be adsorbed onto the first substrate surface by reacting two adjacent OH groups (i.e., adsorption sites) present on the first substrate surface with one molecule of the first modifier. Specifically, two adjacent OH groups present on the first substrate surface can react with two or more first functional groups in one molecule of the first modifier. This can hinder the adsorption of two OH groups in one molecule of the first modifier, allowing the aforementioned chemical reaction to occur more appropriately and efficiently.

[0277] In step A, by repeating steps A1 and A3 multiple times, and also by repeating steps A1, A3, and A2 multiple times, the surface modification density of the first substrate can be increased. In other words, by repeating these steps multiple times, the third modified layer can be more fully formed over the entire surface of the first substrate. By more fully forming the third modified layer over the entire surface of the first substrate, selection failure can be more effectively suppressed, further improving the selectivity of selective growth.

[0278] In step A3 , by supplying a gas containing O and H as a substance containing O and H to the wafer 200 , the first functional groups on the surface of the first substrate can be more efficiently converted to OH groups, and the above-mentioned chemical reaction can occur more appropriately.

[0279] The above-mentioned chemical reaction can be caused to occur more appropriately by using a first modifier having a first functional group number of 2 per molecule and a second modifier having a first functional group number of 1 per molecule. Furthermore, the above-mentioned chemical reaction can be caused to occur more appropriately by using a first modifier having a first functional group number of 2 per molecule and a second functional group number of 2 per molecule and a second modifier having a first functional group number of 1 per molecule and a second functional group number of 3 per molecule.

[0280] By using a first modifying agent having a structure including a tetravalent atom directly bonded to the first and second functional groups, and a second modifying agent having a structure including a tetravalent atom directly bonded to the first and second functional groups, the above-mentioned chemical reaction can be more appropriately caused.

[0281] The chemical reaction can be more appropriately caused by using a first modifier and a second modifier whose first functional group is an amino group. The chemical reaction can be more appropriately caused by using a first modifier and a second modifier whose first functional group is a substituted amino group.

[0282] The above chemical reaction can be more appropriately caused by using a first modifier and a second modifier whose second functional group is a hydrocarbon group. The above chemical reaction can be more appropriately caused by using a first modifier and a second modifier whose second functional group is an alkyl group.

[0283] By performing each step on a wafer 200 in which the first substrate is an oxide film and the second substrate is a film other than an oxide film, the above-described chemical reaction can occur more appropriately. By performing each step on a wafer 200 in which the first substrate is an oxygen-containing film (e.g., a SiO film) and the second substrate is a non-oxygen-containing film (e.g., a SiN film or a Si film), the above-described chemical reaction can occur more appropriately.

[0284] By performing steps A and B in a non-plasma atmosphere, the surface modification of the first substrate and the selective growth on the surface of the second substrate can be appropriately performed. In addition, by performing steps A and B in a non-plasma atmosphere, plasma damage to the wafer 200 can also be avoided.

[0285] (4) Modification

[0286] The processing sequence of this mode can be changed as shown in the following modification examples. These modification examples can be combined arbitrarily. In the case of no special instructions, the processing steps and processing conditions of each step of each modification example can be the same as the processing steps and processing conditions of each step of the above-mentioned processing sequence.

[0287] (Variation 1)

[0288] Before modification in step A, step A4 may be performed in which the surface of the wafer 200 is exposed to a hydrogen fluoride (HF) aqueous solution. By performing a cleaning treatment using the HF aqueous solution (also referred to as DHF cleaning) in step A4, a natural oxide film formed on at least one surface of the first substrate and the second substrate can be removed.

[0289] This variation also achieves the same effects as the above-described method. Furthermore, this variation allows the surface of the first substrate to be more effectively capped with OH groups. Consequently, in the subsequent modification step A, the third modified layer can be more fully formed on the entire surface of the first substrate. This further enhances the selectivity of selective growth.

[0290] (Variation 2)

[0291] Instead of supplying a substance containing O and H (e.g., a gas containing O and H) to the wafer 200 in step A3, the wafer 200 may be exposed to the atmosphere. That is, by exposing the wafer 200 to the atmosphere, the atmosphere (the water contained therein (H2O)) may be supplied to the wafer 200 as a substance containing O and H. In this modification, the same effect as that of the above-described method can be obtained. In this case, the water as the substance containing O and H may be a gas or a liquid, for example, in the form of mist.

[0292] <Other aspects of the present disclosure>

[0293] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the spirit and scope of the present disclosure.

[0294] For example, it is also possible not to perform post-treatment (step C) after selective growth in step B. In this case, the same effects as those of the above embodiment can be achieved, in addition to the effects of post-treatment. Sometimes, it is not necessary to reset the film formation-inhibiting state on the surface of the first substrate by a step performed after selective growth, and in this case, post-treatment is not necessary.

[0295] In addition, for example, the wafer 200 may also have a variety of films as the first substrate, and may also have a variety of films as the second substrate. As the films constituting the first substrate and the second substrate, in addition to the above-mentioned SiO film and SiN film, they may also be: SiOCN film, SiON film, SiOC film, SiC film, SiCN film, SiBN film, SiBCN film, Ge film, SiGe film and other films containing semiconductor elements, TiN film, W film and other films containing metal elements, amorphous carbon film (a-C film), etc. As long as it is a film with a surface that can be modified by the first modifier and the second modifier (that is, a surface with adsorption sites), it can be used as the first substrate. On the other hand, as long as it is a film with a surface that is not easily modified by the first modifier and the second modifier (that is, a surface with no adsorption sites or a surface with fewer adsorption sites), it can be used as the second substrate. In this case, the same effect as the above method can be obtained.

[0296] Recipes used in each process are preferably prepared separately according to the process content and stored in the storage device 121c via electronic communication lines and external storage device 123. Furthermore, when each process is started, the CPU 121a preferably selects an appropriate recipe from the multiple recipes stored in the storage device 121c based on the process content. This allows for the reproducible formation of films of various film types, composition ratios, film qualities, and film thicknesses in a single substrate processing apparatus. Furthermore, this reduces the burden on operators, prevents operational errors, and allows for the prompt initiation of each process.

[0297] The above-mentioned recipes are not limited to newly generated ones; for example, they can also be prepared by modifying an existing recipe already installed in a substrate processing device. When modifying a recipe, the modified recipe can be installed in the substrate processing device via an electronic communication line or a storage medium containing the recipe. Alternatively, the existing recipe installed in the substrate processing device can be modified directly by operating the input / output device 122 of the existing substrate processing device.

[0298] The above-described method describes an example of film formation using a batch-type substrate processing apparatus that processes multiple substrates at a time. The present disclosure is not limited to the above-described method and can also be advantageously applied to film formation using, for example, a single-wafer-type substrate processing apparatus that processes one or more substrates at a time. Furthermore, the above-described method describes an example of film formation using a substrate processing apparatus with a hot-wall processing furnace. The present disclosure is not limited to the above-described method and can also be advantageously applied to film formation using a substrate processing apparatus with a cold-wall processing furnace.

[0299] Even when these substrate processing apparatuses are applied, each process can be performed using the same processing steps and processing conditions as those of the above-described embodiment or modified example, and the same effects as those of the above-described embodiment or modified example can be obtained.

[0300] The above-mentioned embodiments or modifications can be used in combination as appropriate. The processing steps and processing conditions in this case may be the same as those in the above-mentioned embodiments or modifications.

[0301] Example

[0302] (Example 1)

[0303] As Example 1, a wafer with a SiO film as a first substrate and a SiN film as a second substrate exposed on its surface was used to produce a first evaluation sample by selectively growing a SiOC film according to the process sequence described above. In producing the first evaluation sample, BDAADAS was used as the first modifier, DAATAS was used as the second modifier, a gas containing H and O was used as the substance containing H and O, and a gas containing Si, C, and a halogen, a gas containing O and H, and an amine gas were used as the raw material gas, reaction gas, and catalyst gas, respectively. Furthermore, before the process sequence described above, the wafer with the SiO film and SiN film exposed on its surface was immersed in an aqueous HF solution (hereinafter referred to as DHF) diluted to 1% HF with H2O for 30 seconds. The process conditions for each step in producing the first evaluation sample were predetermined conditions within the range of process conditions for each step in the process sequence described above.

[0304] (Comparative Example 1)

[0305] As Comparative Example 1, a second evaluation sample was prepared using the same wafer as in Example 1, which had been immersed in DHF for 30 seconds. The selective growth of a SiOC film was performed using the same process sequence as described above, except that Steps A1 and A3 were omitted. The second modifier, source gas, reaction gas, catalyst gas, and process conditions for each step in preparing the second evaluation sample were the same as those used in preparing the first evaluation sample.

[0306] (Comparative Example 2)

[0307] As Comparative Example 2, a third evaluation sample was produced using the same wafer as in Example 1, which had been immersed in DHF for 30 seconds. The selective growth of a SiOC film was performed using the same process sequence as described above, except that Steps A3 and A2 were omitted. The first modifier, source gas, reaction gas, catalyst gas, and processing conditions in each step used to produce the third evaluation sample were the same as those used to produce the first evaluation sample.

[0308] After producing the first to third evaluation samples, the thickness of the SiOC film formed on the SiO film and the thickness of the SiOC film formed on the SiN film for each evaluation sample were measured. Next, the film thickness difference between the thickness of the SiOC film formed on the SiN film and the thickness of the SiOC film formed on the SiO film (hereinafter referred to as the film thickness difference) was calculated for each evaluation sample.

[0309] The result is Figure 9 Shown in. Figure 9 The horizontal axis shows Comparative Example 1 (second evaluation sample), Comparative Example 2 (third evaluation sample), and Example 1 (first evaluation sample) from the left, and the vertical axis shows the film thickness of the SiOC film. In the bar graph, the left column represents the film thickness of the SiOC film formed on the SiO film, and the right column represents the film thickness of the SiOC film formed on the SiN film. The line graph represents the film thickness difference. Figure 9 For convenience, the film thickness difference is referred to as selectivity. It is also shown that the larger the film thickness difference, the better the selectivity, and the smaller the film thickness difference, the worse the selectivity.

[0310] Depend on ​ It can be seen that the film thickness difference of Example 1 (first evaluation sample) is much greater than the film thickness differences of Comparative Example 1 (second evaluation sample) and Comparative Example 2 (third evaluation sample). Thus, it can be confirmed that the selectivity of selective growth can be greatly improved according to Example 1.

[0311] In addition, in other film formation evaluations conducted by the inventors of this case, it was confirmed that SiOC films can be selectively formed on the second substrates not only when the second substrate is a SiN film, but also when the second substrate is a single crystal Si, a-C film, a-Si film, AlO film, SiCN film, or TiN film.

Claims

1. A substrate processing method, characterized in that: have: (a) a step of modifying the first surface by sequentially performing the following steps: (a1) supplying a first modifying agent represented by the following formula 1 to a substrate having a first surface and a second surface; (a2) supplying a substance containing oxygen and hydrogen to the substrate; and (a3) ​​supplying a second modifying agent represented by the following formula 2 to the substrate; as well as (b) supplying a film-forming gas to the substrate after the first surface has been modified, thereby forming a film on the second surface; Formula 1: R 1 ]n 1 -(X)-[R 2 ]m 1 In formula 1, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 1 Indicates 2 or 3, m 1 Indicates 1 or 2, Formula 2: R 1 ]n 2 -(X)-[R 2 ]m 2 In formula 2, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 2 Indicates 1 or 2, m 2 Indicates 2 or 3.

2. The substrate processing method according to claim 1, wherein: In (a1), the first modifier is adsorbed on the first surface, In (a2), the first functional groups of a portion of the first modifier adsorbed on the first surface are replaced with hydroxyl groups, In (a3), the second modifier is adsorbed on the hydroxyl group.

3. The substrate processing method according to claim 2, wherein: In (a1), a portion of the first modifier is adsorbed on the first surface in a state including at least one first functional group.

4. The substrate processing method according to claim 2 or 3, characterized in that: In (a1), the first modifier is adsorbed on the first surface in a state including the second functional group. In (a3), the second modifier is adsorbed on the hydroxyl group in a state including the second functional group.

5. The substrate processing method according to any one of claims 2 to 4, characterized in that: In (a1), a portion of the first modifier is adsorbed on the first surface by the reaction between two adjacent hydroxyl groups present on the first surface and one molecule of the first modifier.

6. The substrate processing method according to any one of claims 1 to 5, characterized in that: In (a), (a1) and (a2) are performed multiple times, or (a1), (a2), and (a3) ​​are performed multiple times.

7. The substrate processing method according to any one of claims 1 to 6, characterized in that: In (a2), at least one of H 2 O gas, H 2 O 2 gas, H 2 gas+O 2 gas, and H 2 gas+O 3 gas is supplied to the substrate as the substance containing oxygen and hydrogen.

8. The substrate processing method according to any one of claims 1 to 7, characterized in that: In (a2), the substance containing oxygen and hydrogen and the catalyst are supplied to the substrate.

9. The substrate processing method according to any one of claims 1 to 8, wherein: In the formula 1, n 1 is 2, n in formula 2 2 is 1.

10. The substrate processing method according to any one of claims 1 to 9, characterized in that: The second functional group comprises a hydrocarbon group.

11. The substrate processing method according to any one of claims 1 to 10, characterized in that: (a) before carrying out (a1), also has: (a4) A step of exposing the surface of the substrate to an aqueous hydrogen fluoride solution.

12. The substrate processing method according to any one of claims 1 to 11, characterized in that: The first surface includes an oxide film, and the second surface includes a film other than the oxide film.

13. The substrate processing method according to any one of claims 1 to 12, characterized in that: The film-forming gas includes a raw material gas and a reaction gas.

14. The substrate processing method according to claim 13, wherein: In (b), the source gas and the reaction gas are alternately supplied to the substrate.

15. The substrate processing method according to any one of claims 1 to 13, characterized in that: The film-forming gas includes a raw material gas, a reaction gas, and a catalyst gas.

16. The substrate processing method according to claim 15, wherein: In (b), the source gas and the reaction gas are alternately supplied to the substrate, and the catalyst gas is supplied together with at least one of the source gas and the reaction gas.

17. A method for manufacturing a semiconductor device, characterized in that: have: (a) a step of modifying the first surface by sequentially performing the following steps: (a1) supplying a first modifying agent represented by the following formula 1 to a substrate having a first surface and a second surface; (a2) supplying a substance containing oxygen and hydrogen to the substrate; and (a3) ​​supplying a second modifying agent represented by the following formula 2 to the substrate; as well as (b) supplying a film-forming gas to the substrate after the first surface has been modified, thereby forming a film on the second surface; Formula 1: R 1 ]n 1 -(X)-[R 2 ]m 1 In formula 1, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 1 Indicates 2 or 3, m 1 Indicates 1 or 2, Formula 2: R 1 ]n 2 -(X)-[R 2 ]m 2 In formula 2, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 2 Indicates 1 or 2, m 2 Indicates 2 or 3.

18. A substrate processing device, characterized in that: have: A first modifying agent supply system that supplies a first modifying agent represented by the following formula 1 to the substrate; a substance supply system containing oxygen and hydrogen, which supplies the substance containing oxygen and hydrogen to the substrate; A second modifying agent supply system that supplies a second modifying agent represented by the following formula 2 to the substrate; a film-forming gas supply system for supplying a film-forming gas to the substrate; and a control unit configured to control the first modifier supply system, the second modifier supply system, the oxygen-and-hydrogen-containing substance supply system, and the film-forming gas supply system so as to perform: (a) a process of modifying the first surface by sequentially performing (a1) a process of supplying the first modifier to a substrate having a first surface and a second surface, (a2) a process of supplying the oxygen-and-hydrogen-containing substance to the substrate, and (a3) ​​a process of supplying the second modifier to the substrate; and (b) supplying the film-forming gas to the substrate after the first surface has been modified, thereby forming a film on the second surface. Formula 1: R 1 ]n 1 -(X)-[R 2 ]m 1 In formula 1, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 1 Indicates 2 or 3, m 1 Indicates 1 or 2, Formula 2: R 1 ]n 2 -(X)-[R 2 ]m 2 In formula 2, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 2 Indicates 1 or 2, m 2 Indicates 2 or 3.

19. A program product, characterized in that The computer enables the substrate processing apparatus to perform the following steps: (a) a step of modifying the first surface by sequentially performing (a1) a step of supplying a first modifying agent represented by the following formula 1 to a substrate having a first surface and a second surface, (a2) a step of supplying a substance containing oxygen and hydrogen to the substrate, and (a3) ​​a step of supplying a second modifying agent represented by the following formula 2 to the substrate; as well as (b) supplying a film-forming gas to the substrate after the first surface has been modified, thereby forming a film on the second surface, Formula 1: R 1 ]n 1 -(X)-[R 2 ]m 1 In formula 1, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or a hydrogen atom directly bonded to X, the second functional group includes a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 1 Indicates 2 or 3, m 1 Indicates 1 or 2, Formula 2: R 1 ]n 2 -(X)-[R 2 ]m 2 In formula 2, R 1 represents the first functional group directly bonded to X, the first functional group includes an amino group or a substituted amino group, R 2 represents a second functional group or an H atom directly bonded to X, the second functional group comprises a hydrocarbon group, X represents a tetravalent atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tetravalent metal atom, n 2 Indicates 1 or 2, m 2 Indicates 2 or 3.

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