Method of manufacturing semiconductor device, substrate processing method, substrate processing apparatus, and storage medium

Abstract

The present invention provides a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a storage medium, that is, a technique for improving the selectivity of selective growth. The method has the following steps: (a) a step of supplying a first modifier and a second modifier to a substrate on which a first substrate and a second substrate are exposed on the surface, so as to modify the surface of the first substrate, wherein the first modifier contains one or more atoms directly bonded with a first functional group and a second functional group, and the second modifier contains atoms directly bonded with the first functional group and the second functional group, and the number of the first functional groups contained in one molecule of the second modifier is less than the number of the first functional groups contained in one molecule of the first modifier; and (b) a step of supplying a film-forming gas to the substrate after the surface of the first substrate is modified, so as to form a film on the surface of the second substrate.

Description

Technical Field

[0001] The present disclosure relates to a method of manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a storage medium. Background Art

[0002] As semiconductor devices are scaled down, the miniaturization of processing dimensions and the complexity of processes have advanced. In order to perform fine and complex processing, it is necessary to repeat a high-precision patterning process multiple times, increasing the cost of manufacturing semiconductor devices. In recent years, selective growth has attracted attention as a method capable of achieving high precision and low cost. Selective growth is a technique in which a film is selectively grown on the surface of a desired one of two or more substrates exposed on the surface of a substrate for film formation (for example, see Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-243193 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] However, if selective growth continues, there is a possibility that local film formation may occur on the surfaces of substrates other than the desired substrate among two or more substrates, resulting in a decrease in selectivity.

[0008] An object of the present disclosure is to provide a technique for improving the selectivity of selective growth.

[0009] Means for Solving the Problems

[0010] According to one aspect of the present disclosure, there is provided a technique for performing the following steps:

[0011] (a) A step of supplying a first modifier and a second modifier to a substrate on which a first substrate and a second substrate are exposed on the surface, thereby modifying the surface of the first substrate, wherein the first modifier contains one or more atoms directly bonded to a first functional group and a second functional group, and the second modifier contains atoms directly bonded to the first functional group and the second functional group and the number of the first functional groups contained in one molecule is less than the number of the first functional groups contained in one molecule of the first modifier; and

[0012] (b) A step of supplying a film-forming gas to the substrate after modifying the surface of the first substrate, thereby forming a film on the surface of the second substrate.

[0013] Effects of the Invention

[0014] According to the present disclosure, the selectivity of selective growth can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 (a) of is a schematic diagram showing an example of the hydroxyl (OH) terminal structure on the surface of a silicon oxide film (SiO film). Figure 1 (b) of is a schematic diagram showing a region x that is not completely covered by three alkyl groups derived from (dialkylamino)trialkylsilane after supplying (dialkylamino)trialkylsilane to the surface of the SiO film shown in (a) of. Figure 1 (c) of is a schematic diagram showing the state in which a film-forming raw material is physically adsorbed on the region x on the surface of the SiO film shown in (b) of. Figure 1 (c) of is a schematic diagram showing the state in which a film-forming raw material is physically adsorbed on the region x on the surface of the SiO film shown in (b) of. Figure 1 (c) of is a schematic diagram showing the state in which a film-forming raw material is physically adsorbed on the region x on the surface of the SiO film shown in (b) of.

[0016] Figure 2 (a) of is a schematic diagram showing an example of the OH terminal structure on the surface of the SiO film. Figure 2 (b) of is a schematic diagram showing the state in which (dialkylamino)trialkylsilane is chemically adsorbed only on one of the two adjacent OH terminals and there are remaining OH terminals after supplying (dialkylamino)trialkylsilane to the surface of the SiO film shown in (a) of. Figure 2 (c) of is a schematic diagram showing the state in which the remaining OH terminals on the surface of the SiO film shown in (b) of are chemically adsorbed with a film-forming raw material. Figure 2 (c) of is a schematic diagram showing the state in which the remaining OH terminals on the surface of the SiO film shown in (b) of are chemically adsorbed with a film-forming raw material. Figure 2 (c) of is a schematic diagram showing the state in which the remaining OH terminals on the surface of the SiO film shown in (b) of are chemically adsorbed with a film-forming raw material.

[0017] Figure 3 (a) is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus preferably applicable in one embodiment of the present disclosure, and shows the processing furnace 202 part in a longitudinal sectional view.

[0018] Figure 4 (a) is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus preferably applicable in one embodiment of the present disclosure, and Figure 3 (b) shows the processing furnace 202 part in a sectional view taken along line A - A of.

[0019] Figure 5 (a) is a schematic structural diagram of a controller 121 of a substrate processing apparatus preferably applicable in one embodiment of the present disclosure, and shows the control system of the controller 121 in a block diagram.

[0020] Figure 6 (a) is a diagram showing an example of the processing timing of selective growth in one embodiment of the present disclosure.

[0021] Figure 7 (a) of is a schematic diagram showing the chemical structure on the surface of the SiO film of the wafer 200. (b) of FIG. 7 is a schematic diagram showing that by Figure 7Schematic diagram of the chemical structure formed by supplying bis(dialkylamino)dialkylsilane to the surface of the SiO film shown in (a). Figure 7 (c) of is a schematic diagram showing the chemical structure formed by supplying a substance containing O and H to the surface of the SiO film shown in (b) of Figure 7 Schematic diagram of the chemical structure formed by supplying a substance containing O and H to the surface of the SiO film shown in (b). Figure 7 (d) of is a schematic diagram showing the chemical structure formed by supplying (dialkylamino)trialkylsilane to the surface of the SiO film shown in (c) of Figure 7 Schematic diagram of the chemical structure formed by supplying (dialkylamino)trialkylsilane to the surface of the SiO film shown in (c).

[0022] Figure 8 (a) to Figure 8 (d) of is an enlarged cross-sectional view of a part of the surface of the wafer 200 in each step of selective growth according to an embodiment of the present disclosure. Figure 8 (a) of is an enlarged cross-sectional view of a part of the surface of the wafer 200 where the first substrate and the second substrate are exposed on the surface. Figure 8 (b) of is an enlarged cross-sectional view of a part of the surface of the wafer 200 after forming the third modified layer on the surface of the first substrate by performing step A. Figure 8 (c) of is an enlarged cross-sectional view of a part of the surface of the wafer 200 after forming a film on the surface of the second substrate by performing step B. Figure 8 (d) of is an enlarged cross-sectional view of a part of the surface of the wafer 200 after removing the third modified layer by performing step C.

[0023] Figure 9 It is a diagram showing the evaluation results of the examples. Detailed implementation mode

[0024] The following is based on the research results obtained by the inventors of this case and refers to Table 1, Figures 1 - 2 to explain the selection failure and the resulting reduction in the selectivity of selective growth.

[0025] In addition, the drawings used in the following description are all schematic diagrams, and the dimensional relationships of the elements shown in the drawings, the ratios of the elements, etc. are not necessarily the same as the actual ones. In addition, the dimensional relationships of the elements and the ratios of the elements between multiple drawings are not necessarily the same.

[0026] There is a method using an "inhibitor (also called a film formation inhibitor)" that can preferentially chemisorb at the adsorption sites on the surface of a specific substrate (assumed to be substrate A) exposed on the substrate surface during one selective growth. In the case of this method, selective growth can be performed by exposing the inhibitor to the substrate to hinder film formation on the surface of substrate A and growing a film on the surface of a substrate other than substrate A (assumed to be substrate B).

[0027] When the inhibitor undergoes chemisorption 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 chemisorbed inhibitor. In addition, the steric hindrance from the structure of the chemisorbed inhibitor can also be used to inhibit the film-forming raw material from reaching the surface of substrate A. As a result, film formation on the surface of substrate A on which the inhibitor has been chemisorbed can be hindered. The process of using an inhibitor to modify a specific substrate surface into a state that can hinder film formation is called "modification". In this specification, the compound itself supplied to the substrate for the purpose of modification is called an inhibitor, but sometimes the remaining group of the compound (corresponding to the above-mentioned "structure of the chemisorbed inhibitor") after chemisorption on the surface of the substrate to be hindered from film formation through modification is also called an inhibitor. That is, the meaning of using the term "inhibitor" in this specification includes: the case of representing "the compound supplied to the substrate for the purpose of modification"; the case of representing "the remaining group of the compound after chemisorption on the surface of the substrate to be hindered from film formation through modification"; or representing both cases.

[0028] However, the existing methods using inhibitors have the following situation: when film formation is continuously carried out, local film formation also occurs on the surface of substrate A even after modification. In this specification, the local film formation on the surface of substrate A on which the inhibitor has been chemisorbed (i.e., substrate A after modification) is also called "selection failure". When selection failure occurs, the difference in the film formation amount on the surface of substrate A after modification and the film formation amount on the surface of substrate B becomes smaller, resulting in the problem of reduced selectivity of selective growth.

[0029] Selection failure occurs due to the adsorption of the film-forming raw material on the surface of the substrate after modification. Here is an example for illustration: in the modification, the substrate to be hindered from film formation is a "SiO film", and a "(dialkylamino)trialkylsilane (hereinafter also referred to as DAATAS)" having a structure in which one amino group (dialkylamino) and three alkyl groups are bonded to the central atom Si is used as the inhibitor.

[0030] It is known that adsorption sites, namely OH terminals, exist on the surface of the SiO film, and the OH terminals have the three structures shown in Table 1 below.

[0031] Table 1

[0032]

[0033] DAATAS is chemically adsorbed on the surface of the SiO film by the reaction of the amino group contained in DAATAS with the OH terminus 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, maintains a state of bonding with three alkyl groups. In addition, the bond between the central atom of DAATAS, i.e., Si, and the amino group is broken when the amino group reacts with the OH terminus. That is, on the surface of the SiO film, a state is formed in which a trialkylsilyl group, which is a remaining group from DAATAS, is bonded. The alkyl groups possessed by the trialkylsilyl group are chemically stable and have the property of being less likely to react with the film-forming raw materials. In addition, in terms of the steric hindrance of the three alkyl groups, it hinders the film-forming raw materials from reaching the surface of the SiO film. Utilizing these effects, DAATAS and the trialkylsilyl group can function as an "inhibitor" and can selectively hinder film formation only on the surface of the SiO film.

[0034] When modified with DAATAS as described above, although it becomes a state in which film formation on the surface of the SiO film can be hindered, two mechanisms as described below can be cited as the mechanism of adsorption of the film-forming raw materials on the surface of the SiO film, that is, the mechanism of selection failure.

[0035] 1. The film-forming raw materials are 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.

[0036] 2. The film-forming raw materials are chemically adsorbed on the OH termini remaining on the surface of the SiO film without chemically adsorbing DAATAS.

[0037] First, refer to Figure 1 of (a) to Figure 1 of (c) to explain the above 1. Here, in Figure 1 of (a) to Figure 1 of (c), "R" all represents an alkyl group. In addition, "PG" represents the film-forming raw material (raw material gas).

[0038] Regarding the physical adsorption of the film-forming raw materials on the surface of the SiO film in the above 1, it easily occurs in the region where the "Isolated" OH termini shown in Table 1 exist on the surface of the SiO film. This is because, as shown in Figure 1 of (a), in the "Isolated" OH termini, the distance between adjacent OH termini is far apart, so as shown in Figure 1As shown in (b), even after DAATAS is chemisorbed at the OH termini, it results in the formation of region x on the SiO film surface that is not completely covered by the three alkyl groups from DAATAS. In this case, when the film-forming raw material is supplied to the substrate that has been modified during film formation, as shown in (c) of FIG. 1, the film-forming raw material PG is physically adsorbed on region x of the SiO film surface, and as a result, a selection failure occurs. In order to suppress the physical adsorption of the film-forming raw material PG on region x of the SiO film surface, for example, it can be considered to increase the molecular size of the alkyl group of the inhibitor, thereby expanding the film-forming hindrance region based on the steric hindrance of the three alkyl groups.

[0039] Next, refer to Figure 2 (a) to Figure 2 (c) of FIG. 2 to describe the above item 2. Here, in (a) to Figure 2 (c) of FIG. 2, "R" all represents an alkyl group. In addition, "PG" represents the film-forming raw material (raw material gas).

[0040] Regarding the chemisorption of the remaining OH termini on the SiO film surface and the film-forming raw material in item 2 above, it is likely to occur in the structures of the OH termini such as "Vicinal" and "Germinal" described in Table 1 that are present close to the surface of the SiO film. This is because: as Figure 2 shown in (a), when there are two OH termini close to the SiO film surface, only one of them can chemisorb DAATAS, and as Figure 2 shown in (b), it results in the remaining OH termini on the SiO film surface. More specifically, when one of the two OH termini close to the SiO film surface chemisorbs DAATAS, the three alkyl groups from DAATAS will become a steric hindrance and cannot chemisorb DAATAS at the other OH terminus, and as Figure 2 shown in (b), it results in the remaining OH termini on the SiO film surface. In this case, when the film-forming raw material is supplied to the substrate that has been modified during film formation, as Figure 2 shown in (c), the film-forming raw material PG will chemisorb with the remaining OH termini on the SiO film surface, and as a result, a selection failure will occur. In order to suppress the chemisorption of the remaining OH termini on the SiO film surface and the film-forming raw material PG, for example, it can be considered to reduce the molecular size of the alkyl group of the inhibitor, so that each of the two close OH termini chemisorbs the inhibitor, reducing the remaining OH termini.

[0041] Based on the above research results, the inventors of this case have conducted in-depth research and obtained the following technology: by using two inhibitors with specific structures during modification (specifically, the first modifier and the second modifier described below), selection failure is inhibited and the selectivity of selective growth is improved. Hereinafter, as an example of the present disclosure, a technique for inhibiting selection failure and improving the selectivity of selective growth will be described.

[0042] <One Embodiment of the Present Disclosure>

[0043] Hereinafter, mainly with reference to Figures 3 - 6 , Figure 7 of (a) to Figure 7 of (d), Figure 8 of (a) to Figure 8 of (d) to describe one embodiment of the present disclosure.

[0044] (1) Structure of the Substrate Processing Apparatus

[0045] As Figure 3 shown, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 has a cylindrical shape and is vertically installed and 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.

[0046] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), for example, and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), for example, and is formed in a cylindrical shape with open upper and lower ends. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed inside the processing chamber 201.

[0047] The nozzles 249a to 249c serving as the first to third supply units are respectively provided in the processing chamber 201 so as to penetrate the side wall of the header 209. The nozzles 249a to 249c are also respectively referred to as the first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC, for example. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively disposed adjacent to the nozzle 249b.

[0048] On the gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c, which are flow controllers (flow control units), and valves 243a to 243c, which are on-off valves, are respectively provided in order from the upstream side of the gas flow. On the downstream side of the valve 243a in the gas supply pipe 232a, gas supply pipes 232d, 232e, and 232h are respectively connected. On the downstream side of the valves 243b and 243c in the gas supply pipes 232b and 232c, gas supply pipes 232f and 232g are respectively connected. On the gas supply pipes 232d to 232h, MFCs 241d to 241h and valves 243d to 243h are respectively provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232h are made of a metal material such as SUS, for example.

[0049] As Figure 4As shown, the nozzles 249a to 249c are arranged in a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, and are respectively arranged in a manner that stands upright upward in the arrangement direction of the wafers 200 from the lower part to the upper part of the inner wall of the reaction tube 203. That is, the nozzles 249a to 249c are respectively arranged along the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounding the wafer arrangement area. In a plan view, the nozzle 249b is arranged to face the center of the wafer 200 carried into the processing chamber 201 and the exhaust port 231a described later in a straight line. The nozzles 249a and 249c are arranged to sandwich the straight line L passing through the centers 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 the straight line passing through the centers of the nozzle 249b and the wafer 200. That is, it can also be said that the nozzle 249c and the nozzle 249a are arranged on opposite sides with the straight line L in between. The nozzles 249a and 249c are arranged symmetrically with respect to the straight line L. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened in a manner that faces the exhaust port 231a in a plan view and can supply gas toward the wafer 200. A plurality of the gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0050] The first modifier as a surface modifier is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC241a, the valve 243a, and the nozzle 249a.

[0051] The second modifier as a surface modifier is supplied from the gas supply pipe 232h into the processing chamber 201 via the MFC241h, the valve 243h, the gas supply pipe 232a, and the nozzle 249a.

[0052] The source gas as a film-forming raw material is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC241b, the valve 243b, and the nozzle 249b.

[0053] The reaction gas, a substance containing oxygen (O) and hydrogen (H), is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC241c, the valve 243c, and the nozzle 249c.

[0054] The catalyst gas is supplied from the gas supply pipe 232d into the processing chamber 201 via the MFC241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a.

[0055] An inert gas is supplied into the processing chamber 201 from the gas supply pipes 232e to 232g via the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, etc.

[0056] The first modifier supply system (the first surface modifier supply system) is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The second modifier supply system (the second surface modifier supply system) is mainly composed of the gas supply pipe 232h, the MFC 241h, and the valve 243h. The first modifier supply system and the second modifier supply system are also referred to as the modifier supply system (the surface modifier supply system). The source gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The reaction gas supply system, the supply system for substances containing O and H is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The catalyst gas supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The inert gas supply system is mainly composed of the gas supply pipes 232e to 232g, the MFCs 241e to 241g, and the valves 243e to 243g.

[0057] The first modifier and the second modifier function as inhibitors. Therefore, the modifier supply system (the first modifier supply system, the second modifier supply system) can also be referred to as the inhibitor supply system (the first inhibitor supply system, the second inhibitor supply system). The substances containing O and H also function as oxidants (oxidizing gases). Therefore, the supply system for substances containing O and H can also be referred to as the 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 the oxidant (oxidizing gas) supply system. The source gas, the reaction gas, and the catalyst gas function as film-forming gases. Therefore, the source gas supply system, the reaction gas supply system, and the catalyst gas supply system can also be referred to as the film-forming gas supply system.

[0058] Any one or all of the above-described supply systems may be configured as an integrated supply system 248, which integrates valves 243a to 243h, MFCs 241a to 241h, etc. The integrated supply system 248 is respectively connected to gas supply pipes 232a to 232h, and is configured to be controlled by a controller 121 described later: the supply operations of various gases into the gas supply pipes 232a to 232h, that is, the opening and closing operations of the valves 243a to 243h, the flow rate adjustment operations of the MFCs 241a to 241h, etc. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and can be attached and detached with respect to the gas supply pipes 232a to 232h, etc. in units of the integrated unit, and can perform maintenance, replacement, addition, etc. of the integrated supply system 248 in units of the integrated unit.

[0059] Below the side wall of the reaction tube 203, an exhaust port 231a for exhausting the ambient gas in the processing chamber 201 is provided. As Figure 4 shown, the exhaust port 231a is provided at a position facing (opposite to) the wafers 200 and the nozzles 249a to 249c (gas supply holes 250a to 250c) in a plan view. The exhaust port 231a may be provided along the lower part to the upper part of the side wall 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, for example. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to perform vacuum exhaust and stop vacuum exhaust of the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operating, and to be able to adjust the valve opening based on the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is operating, thereby adjusting the pressure in the processing chamber 201. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It can also be considered that the vacuum pump 246 is included in the exhaust system.

[0060] Below the header 209, a sealing cover 219 as a furnace port cover body is provided, which can hermetically seal the lower end opening of the header 209. The sealing cover 219 is made of a metal material such as SUS, for example, and is formed in a disk shape. On the upper surface of the sealing cover 219, an O-ring 220b as a sealing member that abuts against the lower end of the header 209 is provided. Below the sealing cover 219, a rotation mechanism 267 for rotating a susceptor 217 described later is provided. The rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS, for example, and penetrates the sealing cover 219 and is connected to the susceptor 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The sealing cover 219 is configured to be able to move up and down in the vertical direction by a susceptor elevator 115 as a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is a conveying device (conveying mechanism) configured to convey (carry in and out) the wafer 200 into and out of the processing chamber 201 by moving the sealing cover 219 up and down. Below the header 209, a gate 219s as a furnace port cover body is provided, which can hermetically seal the lower end opening of the header 209 in a state where the sealing cover 219 is lowered and the susceptor 217 is carried out of the processing chamber 201. The gate 219s is made of a metal material such as SUS, for example, and is formed in a disk shape. On the upper surface of the gate 219s, an O-ring 220c as a sealing member that abuts against the lower end of the header 209 is provided. The opening and closing operation (lifting operation, rotation operation, etc.) of the gate 219s is controlled by a gate opening and closing mechanism 115s.

[0061] Regarding the susceptor 217 as a substrate support, it is configured to be able to support a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture and in a state where their centers are aligned with each other in a multilayered manner, that is, arranged at intervals in the vertical direction. The susceptor 217 is made of a heat-resistant material such as quartz or SiC, for example. Below the susceptor 217, a heat insulation plate 218 made of a heat-resistant material such as quartz or SiC is supported in a multilayered manner.

[0062] In the reaction tube 203, a temperature sensor 263 as a temperature detector is provided. By adjusting the energization state of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 is made to have the desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0063] As Figure 5As shown, the control unit (control unit), that is, the controller 121, is configured as a computer, and this computer includes: a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to perform data exchange with the CPU 121a via an internal bus 121e. On the controller 121, an input / output device 122 configured as a touch panel or the like is connected, for example.

[0064] The storage device 121c is constituted by, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe that records steps or conditions of the substrate processing described later, and the like are stored in a readable manner. The process recipe is combined in such a way that each step in the substrate processing described later can be executed by the controller 121 to obtain a predetermined result and functions as a program. Hereinafter, the process recipe, the control program, etc. are also collectively referred to as a program. In addition, the process recipe is also simply referred to as a recipe. When the term "program" is used in this specification, it sometimes refers only to the recipe alone, sometimes only to the control program alone, or sometimes refers to both. The RAM 121b is configured as a memory area (working area), and this memory area (working area) temporarily holds programs, data, etc. read out by the CPU 121a.

[0065] The I / O port 121d is connected to the above-mentioned 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, susceptor elevator 115, gate opening / closing mechanism 115s, etc.

[0066] The CPU 121a is configured to be able to read a control program from the storage device 121c and execute it, and read a recipe from the storage device 121c according to the input of an operation instruction from the input / output device 122 or the like. The CPU 121a is configured to be able to control according to the content of the read recipe: the flow rate adjustment actions of various gases by the MFCs 241a to 241h, the opening and closing actions of the valves 243a to 243h, the opening and closing actions of the APC valve 244, and the pressure adjustment actions performed by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment actions of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment actions of the susceptor 217 by the rotation mechanism 267, the lifting actions of the susceptor 217 by the susceptor elevator 115, the opening and closing actions of the gate 219s by the gate opening and closing mechanism 115s, etc.

[0067] The controller 121 can be constituted by installing the above-mentioned program stored in the external storage device 123 in a computer. The external storage device 123 includes, for example: magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, USB memories, semiconductor memories such as SSDs, etc. The storage device 121c and the external storage device 123 are configured as computer-readable storage media. Hereinafter, these will also be collectively referred to as storage media. When using the term "storage medium" in this specification, it sometimes refers only to the storage device 121c alone, sometimes only to the external storage device 123 alone, or sometimes to both. In addition, the provision of the program to the computer can also be performed by using communication means such as the Internet or a dedicated line instead of using the external storage device 123.

[0068] (2) Substrate processing step

[0069] Mainly use Figure 6 、 Figure 7 of (a) to Figure 7 of (d), Figure 8 of (a) to Figure 8 of (d) to illustrate: As an example of the processing timing (gas supply timing) of selectively forming a film on the surface of the second substrate among the first substrate and the second substrate exposed on the surface of the wafer 200 as a substrate in one step of the manufacturing process of the semiconductor device. In the following description, the operations of each part constituting the substrate processing device are controlled by the controller 121.

[0070] In Figure 6 the processing timing shown, the following are performed:

[0071] (a) Step A of supplying a first modifier and a second modifier to the wafer 200 with the first substrate and the second substrate exposed on the surface, so as to modify the surface of the first substrate;​

[0072] (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.

[0073] Here, the first modifier contains one or more atoms directly bonding a first functional group and a second functional group. In addition, the second modifier contains atoms directly bonding a first functional group and a 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. In addition, the film-forming gas includes a source gas, a reaction gas, and a catalyst gas.

[0074] In addition, in Figure 6 the shown processing timing, in step A, it is carried out non-simultaneously and in the order of step A1 and step A2: step A1 of supplying the first modifier to the wafer 200, step A2 of supplying the second modifier to the wafer 200. In addition, step A includes step A3 of supplying a substance containing O and H to the wafer 200, and in step A, step A1, step A3, and step A2 are carried out in sequence.

[0075] In addition, in Figure 6 the shown processing timing, in step B, the following cycle is carried out a predetermined number of times (n times, n is an integer of 1 or more), and in this cycle, it is carried out non-simultaneously: step B1 of supplying the source gas and the catalyst gas to the wafer 200, step B2 of supplying the reaction gas and the catalyst gas to the wafer 200. In addition, in Figure 6 it shows an example in which a substance containing O and H is used as the reaction gas.

[0076] In addition, in Figure 6 the shown processing timing, as a post-treatment for the wafer 200 after selective growth, step C of heating the wafer 200 after selectively forming a film on the surface of the second substrate is carried out. In addition, step C is not necessarily carried out and can also be omitted.

[0077] In this specification, for convenience, the above-mentioned processing timing is also represented in the following manner. The same representation is also used in the description of the following other manners and modification examples, etc.

[0078] First modifier → Substance containing O and H → Second modifier → (Source gas + Catalyst gas → Reaction gas + Catalyst gas) × n → Post-treatment

[0079] In addition, in Figure 6 it shows an example in which a substance containing O and H is used as the reaction gas, so the processing timing shown in Figure 6 can also be represented in the following manner.

[0080] First modifier → Substance containing O and H → Second modifier → (Raw material gas + Catalyst gas → Substance containing O and H + Catalyst gas) × n → Post-treatment

[0081] When the term "wafer" is used in this specification, it sometimes refers to the wafer itself and sometimes to a laminate of the wafer and a predetermined layer or film 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 to the surface of a predetermined layer or the like formed on the wafer. When it is described in this specification that "a predetermined layer is formed on the wafer", it sometimes refers to directly forming a predetermined layer on the surface of the wafer itself and sometimes refers to forming a predetermined layer on a layer or the like formed on the wafer. When only the term "substrate" is used in this specification, its meaning is the same as when the term "wafer" is used.

[0082] (Wafer loading and susceptor introduction)

[0083] After loading a plurality of wafers 200 into the susceptor 217 (wafer loading), the gate 219s is moved by the gate opening / closing mechanism 115s to open the lower end opening of the manifold 209 (gate opening). Thereafter, as Figure 3 shown, the susceptor 217 supporting a plurality of wafers 200 is lifted by the susceptor lifter 115 and carried into the processing chamber 201 (susceptor introduction). In this state, the seal cover 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b.

[0084] In addition, as Figure 8 shown in (a), the first substrate and the second substrate are exposed on the surface of the wafers 200 filled in the susceptor 217. The surface of the first substrate of the wafer 200 has OH terminals as adsorption sites over the entire area (the entire surface). That is, the surface of the first substrate of the wafer 200 has a surface terminated with OH groups over the entire area (the entire surface). On the other hand, most of the regions of the surface of the second substrate of the wafer 200 have surfaces not terminated with OH groups.

[0085] (Pressure regulation and temperature regulation)

[0086] After that, in order to make the pressure (degree of vacuum) in the processing chamber 201, i.e., the space where the wafer 200 is located, reach the required value, vacuum exhaust (pressure reduction 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, heating is performed using the heater 207. At this time, in order to make the required temperature distribution in the processing chamber 201, the energization 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.

[0087] (Step A)

[0088] After that, the above-mentioned step A1, step A3, and step A2 are performed in sequence.

[0089] The following describes each of these steps.

[0090] (Step A1)

[0091] In step A1, a first modifier is supplied to the wafer 200 in the processing chamber 201, i.e., the wafer 200 whose first substrate and second substrate are exposed on the surface.

[0092] Specifically, the valve 243a is opened to allow the first modifier to flow into the gas supply pipe 232a. The first modifier is flow-regulated by the MFC241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted through the exhaust port 231a. At this time, the first modifier is supplied to the wafer 200. At this time, the valves 243e to 243g can also be opened to supply inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0093] By supplying a first modifier to the wafer 200 under the processing conditions described below, it is possible to selectively (preferably) modify the surface of the first substrate. That is, in step A1, by means of the chemical reaction between the OH terminals on the surface of the first substrate and the first modifier, the first modifier is selectively (preferably) chemisorbed on the surface of the first substrate of the wafer 200, 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 terminals, and the remaining group derived from the first modifier containing the second functional group exists on the surface of the first substrate. In addition, a part of the remaining group derived from the first modifier present on the surface of the first substrate contains the first functional group that was not used in the chemical reaction with the OH terminals. Therefore, on the surface of the first substrate modified with the first modifier, a first modified layer is formed by the remaining group derived from the first modifier in a state containing the first functional group and the second functional group (specifically, for example, the first modified layer 10 shown in (b) of Figure 7 described later). Here, the second functional group contained in the first modified layer is a functional group with relatively high chemical stability.

[0094] After the surface of the first substrate is modified with the first modifier, the valve 243a is closed to stop the supply of the first modifier into the processing chamber 201. Then, the inside of the processing chamber 201 is evacuated to remove the remaining first modifier and the like from the inside of the processing chamber 201. At this time, the valves 243e to 243g are opened and an inert gas is supplied into the processing chamber 201 via the nozzles 249a to 249c. The inert gas supplied through the nozzles 249a to 249c acts as a purge gas to purge the inside of the processing chamber 201.

[0095] As the processing conditions when supplying the first modifier in step A1, conditions that do not cause thermal decomposition (gas-phase decomposition) of the first modifier itself are preferred, and specific examples are as follows:

[0096] Processing temperature: room temperature (25 °C) to 500 °C, preferably 50 to 300 °C;

[0097] Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa;

[0098] First modifier supply flow rate: 1 to 3000 sccm, preferably 50 to 1000 sccm;

[0099] First modifier supply time: 0.1 second to 120 minutes, preferably 30 seconds to 60 minutes;

[0100] Inert gas supply flow rate (each gas supply pipe): 0 to 20000 sccm.

[0101] As the processing conditions during the purge in step A1, examples are as follows:

[0102] Processing temperature: room temperature (25 °C) to 500 °C, preferably 50 to 300 °C;

[0103] Processing pressure: 1 to 400 Pa;

[0104] Inert gas supply flow rate (each gas supply pipe): 50 to 20000 sccm;

[0105] Inert gas supply time: 10 to 120 seconds.

[0106] Here, the description of the numerical range of "1 to 13300 Pa" in this specification means that the range includes the lower limit value and the upper limit value. Therefore, for example, "1 to 13300 Pa" means "1 Pa or more and 13300 Pa or less". 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 inside the processing chamber 201. In addition, "gas supply flow rate: 0 sccm" means that the gas is not supplied. These meanings are the same in the following description.

[0107] In addition, in step A1, a first modifier is also chemisorbed on a part of the surface of the second substrate. However, the chemisorption amount of the first modifier on the surface of the second substrate is small, while the chemisorption amount of the first modifier on the surface of the first substrate is overwhelmingly large. Thus, with respect to the significant difference in the chemisorption amount of the first modifier between the surface of the second substrate and the surface of the first substrate, it is because, as described above, the surface of the first substrate on the wafer 200 has OH terminals throughout the whole area, while most of the areas of the surface of the second substrate do not have OH terminals. In addition, it is also because the processing conditions in step A1 are conditions that do not cause thermal decomposition (gas-phase decomposition) of the first modifier in the processing chamber 201.

[0108] (Step A3)

[0109] Step A3 is carried out after step A1 is completed. 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 supply a catalyst gas together as Figure 6 shown. Thereby, the chemical reaction described later can be promoted, and the processing time of step A3 can be shortened. However, depending on the processing conditions, the supply of the catalyst gas is not necessary and can be omitted. An example of using the catalyst gas together is described below.

[0110] Specifically, valves 243c and 243d are opened, and substances containing O and H are respectively introduced into the gas supply pipe 232c, and a catalyst gas is introduced into the gas supply pipe 232d. The substances containing O and H and the catalyst gas are respectively adjusted in flow rate by MFC241c and 241d, and are supplied into the processing chamber 201 via the nozzles 249c and 249a. After being supplied into the processing chamber 201, they are mixed and exhausted from the exhaust port 231a. At this time, substances containing O and H and the catalyst gas are supplied to the wafer 200. At this time, valves 243e to 243g can also be opened and an inert gas can be supplied into the processing chamber 201 via the nozzles 249a to 249c respectively.

[0111] By supplying substances containing O and H and the catalyst gas to the wafer 200 under the processing conditions described below, OH terminals can be formed in the first modified layer formed in step A1. That is, in step A3, a chemical reaction occurs between the first functional group in the remaining groups from the first modifier contained in the first modified layer formed on the surface of the first substrate and the substance containing O and H, and the first functional group contained in the first modified layer is replaced with an OH group. At this time, the second functional group contained in the first modified layer does not contribute to the above chemical reaction and remains in its current state. Therefore, after supplying the substances containing O and H and the catalyst gas, OH terminals are formed in the first modified layer, and the first modified layer changes to a second modified layer having OH terminals (specifically, for example, the second modified layer 20 shown in (c) described below). The second functional group in the remaining groups from the first modifier is still contained in the second modified layer. Figure 7 In step A3, as long as a reaction occurs to replace the first functional group contained in the first modified layer with an OH group, the above reaction can be carried out in a non-plasma ambient gas and under the lower temperature conditions described below. In this way, by carrying out step A3 in a non-plasma ambient gas and under the lower temperature conditions described below, it is possible to suppress the detachment and removal of the first modified layer (the remaining groups from the first modifier) from the surface of the first substrate during the change of the first modified layer to the second modified layer.

[0112] After the first modified layer formed on the surface of the first substrate is changed to the second modified layer, valves 243c and 243d are closed to respectively stop the supply of the substances containing O and H and the catalyst gas into the processing chamber 201. Then, using the same processing steps and processing conditions as the purge in step A1 above, the remaining gas in the processing chamber 201 is exhausted from the processing chamber 201 (purge).

[0113] As the processing conditions when supplying the substance containing O and H in step A3, the following are exemplified:

[0114] ​

[0115] Treatment temperature: room temperature (25 °C) to 500 °C, preferably room temperature to 300 °C;

[0116] Treatment pressure: 1 to 101325 Pa;

[0117] Supply flow rate of the substance containing O and H: 10 to 10000 sccm;

[0118] Supply time of the substance containing O and H: 1 second to 24 hours;

[0119] Supply flow rate of the catalyst gas: 0 to 10000 sccm

[0120] Supply flow rate of the inert gas (each gas supply pipe): 0 to 20000 sccm.

[0121] (Step A2)

[0122] Step A2 is carried out after the end of Step A3. In Step A2, a second modifier is supplied to the wafer 200 in the processing chamber 201 after the end of Step A3, that is, the wafer 200 on which a second modified layer has been formed on the surface of the first substrate.

[0123] Specifically, the valve 243h is opened to allow the second modifier to flow into the gas supply pipe 232h. The flow rate of the second modifier is adjusted by the MFC241h, supplied into the processing chamber 201 via the gas supply pipe 232a and the nozzle 249a, and exhausted through the exhaust port 231a. At this time, the second modifier is supplied to the wafer 200. At this time, the valves 243e to 243g can also be opened to supply inert gases into the processing chamber 201 via the nozzles 249a to 249c respectively.

[0124] By supplying a second modifier to the wafer 200 under the processing conditions described below, a second modified layer formed on the surface of the first substrate can have OH terminals that chemisorb the second modifier. That is, in step A2, by using the chemical reaction between the OH terminals of the second modified layer and the second modifier, the second modifier is selectively (preferably) chemisorbed on the surface of the first substrate of the wafer 200, specifically, on the surface of the second modified layer, thereby enabling further modification of the surface of the first substrate. At this time, the first functional group contained in the second modifier will be detached due to the chemical reaction with the OH terminals contained in the second modified layer, and the remaining group from the second modifier containing the second functional group exists 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 number of first functional groups contained in one molecule of the second modifier is smaller. Therefore, almost all of the first functional groups contained in the second modifier are used for the chemical reaction with the OH terminals contained in the second modified layer. Therefore, a third modified layer (specifically, for example, the third modified layer 30 shown in (d) of Figure 7 is formed on the outermost surface of the first substrate further modified with the second modifier. This third modified layer contains: the remaining group from the first modifier in a state containing the second functional group, and the remaining group from the second modifier in a state containing the second functional group. From the above, it can be seen that no first functional group remains or the remaining amount of the first functional group is very small in the third modified layer. Here, Figure 8 (b) of

[0125] shows a state in which a third modified layer is formed on the surface of the first substrate exposed on the surface of the wafer 200.

[0126] As the processing conditions when supplying the second modifier in step A2, conditions that do not cause pyrolysis (gas-phase decomposition) of the second modifier itself are preferred. Specifically, the following can be exemplified:

[0127] Processing temperature: room temperature (25 °C) to 500 °C, preferably 50 to 300 °C;

[0128] Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa;

[0129] Second modifier supply flow rate: 1 to 3000 sccm, preferably 50 to 1000 sccm;

[0130] Supply time of the second modifier: 0.1 second to 120 minutes, preferably 30 seconds to 60 minutes;

[0131] Supply flow rate of the inert gas (each gas supply pipe): 0 to 20,000 sccm.

[0132] - The first modifier and the second modifier -

[0133] Here, the first modifier used in step A1 and the second modifier used in step A2 are described. Both the first modifier and the second modifier contain one or more atoms directly bonded to the first functional group and the second functional group.

[0134] · The first modifier

[0135] Regarding the first functional group in the first modifier, it is preferably a functional group capable of achieving chemisorption at the adsorption site (such as the OH end) of the first modifier on the surface of the first substrate. As the first functional group, it preferably contains an amino group and preferably contains a substituted amino group. When the first modifier contains an amino group (preferably a substituted amino group), the chemisorption amount of the first modifier on the surface of the first substrate can be increased. In particular, from the viewpoint of the adsorption property to the first substrate, it is preferred that all the first functional groups of the first modifier are substituted amino groups.

[0136] As the substituent of the substituted amino group, an alkyl group is preferred, a C1-C5 alkyl group is more preferred, and a C1-C4 alkyl group is particularly preferred. Regarding the alkyl group of the substituted amino group, it can be linear or branched. Specifically, for example, the alkyl group of the substituted amino group can be methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc.

[0137] The number of substituents of the substituted amino group is 1 or 2, preferably 2. When the number of substituents of the substituted amino group is 2, the two substituents can be the same or different.

[0138] Regarding the number of the first functional groups in the first modifier, it only needs to be more than the number of the first functional groups contained in one molecule of the second modifier described later. Specifically, the number of the first functional groups in the first modifier is an integer of 2 or more and is only required to be an integer not exceeding the valence of the atom directly bonded to the first functional group and the second functional group minus 1. From the viewpoint of the ease of obtaining the first modifier, etc., the number of the first functional groups in the first modifier is preferably 2. In addition, the multiple first functional groups of the first modifier can be the same or different.

[0139] 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 formation inhibiting region. The second functional group is preferably a chemically stable functional group, more preferably a hydrocarbon group. As the hydrocarbon group, it may be an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or an aromatic hydrocarbon group. Among them, an alkyl group is preferably used as the hydrocarbon group. In particular, from the viewpoints of high chemical stability and ease of acquisition, it is preferred that all of the second functional groups possessed by the first modifier are alkyl groups.

[0140] Regarding the alkyl group as the second functional group, an alkyl group having 1 to 5 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred. The alkyl group possessed by the substituted amino group may be linear or branched. Specific examples of the alkyl group possessed by the substituted amino group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, and the like.

[0141] The number of the second functional groups in the first modifier is an integer of 1 or more, and is only required to be an integer equal to or less than (the valence of the atom directly bonding the first functional group and the second functional group) - (the number of the first functional groups in the first modifier). When the number of the first functional groups in the first modifier is 2, it is preferred that the number of the second functional groups in the first modifier is 2. The plurality of second functional groups possessed by the first modifier may be the same or different.

[0142] In the first modifier, examples of the atom directly bonding the first functional group and the second functional group include: carbon (C) atom, silicon (Si) atom, germanium (Ge) atom, tetravalent metal atom, etc. Here, examples of the tetravalent metal atom include: titanium (Ti) atom, zirconium (Zr) atom, hafnium (Hf) atom, molybdenum (Mo) atom, tungsten (W) atom, etc. In addition, regarding the atom directly bonding the first functional group and the second functional group, in addition to the tetravalent metal atom, it may also be a metal atom capable of bonding to four or more ligands. In this case, the number of the second functional groups can be increased, and a stronger effect can be exerted as an inhibitor.

[0143] Among them, as the atom directly bonding the first functional group and the second functional group, C atom, Si atom, and Ge atom are also preferred. This is because when any of C atom, Si atom, and Ge atom is used as the atom directly bonding the first functional group and the second functional group, any of the following characteristics can be obtained, namely: the higher adsorption property of the first modifier on the first substrate surface, and the higher chemical stability of the remaining groups from the first modifier, that is, the first modifier after adsorption on the first substrate surface. Among them, as the atom directly bonding the first functional group and the second functional group, Si atom is more preferred. This is because when Si atom is used as the atom directly bonding the first functional group and the second functional group, a better balance between the following two characteristics can be achieved, namely: the higher adsorption property of the first modifier on the first substrate surface, and the higher chemical stability of the remaining groups from the first modifier, that is, the first modifier after adsorption on the first substrate surface. Among the atoms directly bonding the first functional group and the second functional group, as described above, the first functional group and the second functional group are directly bonded, but in addition, a hydrogen (H) atom or a third functional group may also be bonded.

[0144] As the third functional group bonded in the atom directly bonding the first functional group and the second functional group, any functional group other than the above functional groups of the first functional group and the second functional group is acceptable. As the third functional group, for example, a functional group formed by appropriately combining two or more of C atom, Si atom, Ge atom, tetravalent metal atom, metal atom capable of bonding with four or more ligands, oxygen atom, nitrogen (N) atom, and H atom can be cited.

[0145] The first modifier contains one or more atoms directly bonding the first functional group and the second functional group, but may also contain two or more atoms directly bonding the first functional group and the second functional group. Hereinafter, for convenience, the atom directly bonding the first functional group and the second functional group is also referred to as atom Y. Two or more atoms Y can be directly bonded or bonded via a linking group. In addition, as the number of atom Y in the first modifier, any integer of 1 or more is acceptable. For example, it can be 1, 2, or 3 or more. Among them, as the number of atom Y in the first modifier, 1 or 2 is also preferred, and 1 is more preferred.

[0146] When the number of atom Y in the molecule of the first modifier is 2, as the linking group bonding the two atoms Y, -C n H 2n -、-O-、and -NR”- can be cited. Here, -C n H 2nn in - represents an integer of 1 or more. Further, as R” in -NR”-, an H atom or an alkyl group can be cited. Among them, as the linking group for bonding two atoms Y, -C n H 2n - is preferred. In -C n H 2n -, n is preferably 1 to 5, more preferably 1 or 2.

[0147] The first modifier preferably has a structure as follows, which structure contains one or more tetravalent atoms directly bonded to a first functional group and a second functional group. Among them, the first modifier more preferably has a structure as follows, which structure contains one or more Si atoms directly bonded to a first functional group and a second functional group. Among them, the first modifier further preferably has a structure as follows, which structure contains one or two Si atoms directly bonded to a first functional group and a second functional group. When the first modifier has a structure containing two Si atoms directly bonded to a first functional group and a second functional group, the two Si atoms can be directly bonded or bonded via the above-mentioned linking group. Further, when the first modifier has a structure containing two Si atoms directly bonded to a first functional group and a second functional group, it is preferred that only a first functional group, a second functional group, and the above-mentioned linking group are directly bonded to the two Si atoms. Further, among them, it is particularly preferred that the first modifier has a structure containing one Si atom directly bonded only to a first functional group and a second functional group. That is, the first modifier is particularly preferably a structure in which only a first functional group and a second functional group are directly bonded to the Si as the central atom.

[0148] 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.

[0149] Further, the first modifier preferably has a structure in which two amino groups are bonded to the central atom, i.e., Si. Among them, the first modifier more preferably has a structure in which two amino groups and at least one alkyl group are bonded to the central atom, i.e., Si. Among them, the first modifier further preferably has a structure in which two amino groups and two alkyl groups are bonded to the central atom, i.e., Si.

[0150] In addition, the amino group is preferably a substituted amino group as described above. The substituent of the substituted amino group is as described above.

[0151] As the first modifier, for example, a compound represented by the following formula 1 is preferably used.

[0152] Formula 1: [R 1 n 1 -(X)-[R 2 m1

[0153] In Formula 1, R 1 represents a first functional group directly bonded to X, and R 2 represents a second functional group directly bonded to X or an H atom, 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 represents 2 or 3, and m 1 represents 1 or 2.

[0154] The first functional group represented by R 1 has the same meaning as the above-mentioned first functional group, and the same applies to the preferred examples. When n 1 is 2 or 3, two or three R 1 , that is, two or three first functional groups, may be the same or different. The second functional group represented by R 2 has the same meaning as the above-mentioned second functional group, and the same applies to the preferred examples. When m 1 is 2, the two R 2 may be such that one is an H atom and the other is a second functional group, or both are second functional groups. When the two R 2 are both second functional groups, the two second functional groups may be the same or different.

[0155] As the tetravalent atom represented by X, a Si atom is preferred.

[0156] As n 1 , 2 is preferred.

[0157] As m 1 , 2 is preferred.

[0158] As the first modifier, for example, the following can be cited: bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2, abbreviation: BDMADMS), bis(diethylamino)diethylsilane ([(C2H5)2N]2Si(C2H5)2, abbreviation: BDEADES), bis(dimethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2, abbreviation: BDMADES), bis(diethylamino)dimethylsilane ([(C2H5)2N]2Si(CH3)2, abbreviation: BDEADMS), bis(dimethylamino)silane ([(CH3)2N]2SiH2, abbreviation: BDMAS), bis(dimethylaminodimethylsilyl)ethane ([(CH3)2N(CH3)2Si]2C2H6, abbreviation: BDMADMSE), bis(dipropylamino)silane ([(C3H7)2N]2SiH2, abbreviation: BDPAS), bis(dipropylamino)dimethylsilane ([(C3H7)2N]2Si(CH3)2, abbreviation: BDPADMS), bis(dipropylamino)diethylsilane ((C3H7)2N]2Si(C2H5)2, abbreviation: BDPADES), (dimethylsilyl)diamine ((CH3)2Si(NH2)2, abbreviation: DMSDA), (diethylsilyl)diamine ((C2H5)2Si(NH2)2, abbreviation: DESDA), (dipropylsilyl)diamine ((C3H7)2Si(NH2)2, abbreviation: DESDA), bis(dimethylaminodimethylsilyl)methane ([(CH3)2N(CH3)2Si]2CH2, abbreviation: BDMADMSM), bis(dimethylamino)tetramethyldisilane ([(CH3)2N]2(CH3)4Si2, abbreviation: BDMATMDS), etc. As the first modifier, one or more of these can be used.

[0159] · Second modifier

[0160] 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; 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, etc., it is preferred that the number of the first functional groups in the second modifier is 1. In addition, in the case where the second modifier has a plurality of first functional groups, the plurality of first functional groups may be the same or different.

[0161] 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 the second functional groups in the second modifier is an integer of 1 or more, and it is sufficient that it is an integer equal to or less than (the valence of the atom directly bonded to the first functional group and the second functional group) - (the number of the first functional groups in the second modifier). When the number of the first functional groups in the first modifier is 1, it is preferred that the number of the second functional groups in the second modifier is 3. When the second modifier has a plurality of second functional groups, the plurality of second functional groups may be the same or different.

[0162] The atom directly bonded to the first functional group and the second functional group in the second modifier has the same meaning as the atom directly bonded to the first functional group and the second functional group in the first modifier, and the same applies to the preferred examples. In the second modifier, on the atom directly bonded to the first functional group and the second functional group, in addition to the first functional group and the second functional group, an H atom or a third functional group may also be bonded. As the third functional group, it has the same meaning as the third functional group in the first modifier, and the same applies to the preferred examples.

[0163] The second modifier preferably has a structure containing a tetravalent atom directly bonded to the first functional group and the second functional group. Among them, the second modifier more preferably has a structure containing only a tetravalent atom directly bonded to the first functional group and the second functional group. Among them, the second modifier particularly preferably has a structure containing one Si directly bonded to only the first functional group and the second functional group. That is, the second modifier particularly preferably has a structure in which only the first functional group and the second functional group are directly bonded to Si as the central atom.

[0164] The second modifier preferably has a structure containing one amino group in one molecule. Among them, the second modifier also more preferably has a structure containing one amino group and at least one alkyl group in one molecule. Among them, the second modifier further preferably has a structure containing one amino group and three alkyl groups in one molecule.

[0165] In addition, the second modifier preferably has a structure in which one amino group is bonded to the central atom, i.e., Si. Among them, the second modifier more preferably has a structure in which one amino group and at least one alkyl group are bonded to the central atom, i.e., Si. Among them, the second modifier also further preferably has a structure in which one amino group and three alkyl groups are bonded to the central atom, i.e., Si.

[0166] In addition, the amino group is preferably a substituted amino group as described above. The substituents of the substituted amino group are as described above.

[0167] As the second modifier, for example, a compound represented by the following formula 2 is preferably used.

[0168] Formula 2: [R 1n 2 -(X)-[R 2 m 2

[0169] In Formula 2, R 1 represents a first functional group directly bonded to X, R 2 represents a second functional group directly bonded to X or an H atom, 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, n 2 represents 1 or 2, m 2 represents 2 or 3.

[0170] The first functional group represented by R 1 has the same meaning as the above-mentioned first functional group, and the preferred examples are the same. When n 2 is 2, the two R 1 can be the same first functional group or different first functional groups. The second functional group represented by R 2 has the same meaning as the above-mentioned second functional group, and the preferred examples are the same. m 2 is 2 or 3, and one or two of the two or three R 2 can be H atoms and the rest are second functional groups, or all can be second functional groups. When the two or three R 2 are all second functional groups, all the second functional groups can be the same or different.

[0171] As the tetravalent atom represented by X, a Si atom is preferred.

[0172] As n 2 , 1 is preferred.

[0173] As m 2 , 3 is preferred.

[0174] As the second modifier, for example, the following can be cited: dimethylaminotrimethylsilane ((CH3)2NSi(CH3)3, abbreviation: DMATMS), diethylaminotriethylsilane ((C2H5)2NSi(C2H5)3, abbreviation: DEATES), dimethylaminotriethylsilane ((CH3)2NSi(C2H5)3, abbreviation: DMATES), diethylaminotrimethylsilane ((C2H5)2NSi(CH3)3, abbreviation: DEATMS), (trimethylsilyl)amine ((CH3)3SiNH2, abbreviation: TMSA), (triethylsilyl)amine ((C2H5)3SiNH2, abbreviation: TESA), (dimethylamino)silane ((CH3)2NSiH3, abbreviation: DMAS), (diethylamino)silane ((C2H5)2NSiH3, abbreviation: DEAS), etc. As the second modifier, one or more of these can be used.

[0175] The first modifier and the second modifier are each supplied as a gas to the wafer 200 via the above-described first modifier supply system and second modifier supply system, but at least a part of these may not be in a gaseous state. That is, if 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 if they can be supplied to the wafer 200 via the above-described first modifier supply system and second modifier supply system, then at least a part of the first modifier and the second modifier may not be in a gaseous state.

[0176] -Inert gas-

[0177] As the inert gas used in steps A1 to A3, for example, in addition to nitrogen (N2), rare gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. As the inert gas, one or more of these can be used. The same applies to each of the steps using an inert gas described later.

[0178] -Substances containing O and H-

[0179] As the substance containing O and H used in step A3, an oxygen-containing gas having an O-H bond such as water vapor (H2O gas) or hydrogen peroxide (H2O2) gas can be used. In addition, as the substance containing O and H, an oxygen-containing gas without an O-H bond such as hydrogen (H2) + oxygen (O2) gas or H2 gas + ozone (O3) gas can also be used. In this specification, the juxtaposed description of these two gases "H2 gas + O2 gas" means a mixed gas of H2 gas and O2 gas. When supplying the mixed gas, the two gases can be mixed (pre-mixed) in the supply pipe and then supplied into the processing chamber 201, or the two gases can be separately supplied into the processing chamber 201 through different supply pipes and mixed in the processing chamber 201 (post-mixed).

[0180] Generally, the substance containing O and H is supplied as a gas to the wafer 200 via the above-described substance supply system containing O and H, and at least a part thereof may not be in a gaseous state. That is, if the formation of the second modified layer in step A3 can be achieved and the substance containing O and H can be supplied to the wafer 200 via the above-described substance supply system containing O and H, at least a part of the substance containing O and H may not be in a gaseous state. For example, a part thereof may also be a liquid, such as in a mist state. These aspects also apply to step B2 using the substance containing O and H described later.

[0181] - Catalyst gas -

[0182] 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 , abbreviation: py) gas, aminopyridine (C5H6N2) gas, methylpyridine (C6H7N) gas, lutidine (C7H9N) gas, piperazine (C4H 10 N2) gas, piperidine (C5H 11 N) gas and other cyclic amine gases, triethylamine ((C2H5)3N, abbreviation: TEA) gas, diethylamine ((C2H5)2NH, abbreviation: DEA) gas and other chain-like amine gases can be used. As the catalyst gas, one or more of these can be used. These aspects also apply to step B1 and step B2 using the catalyst gas described later.

[0183]

[0184] Here, a more specific mode of the modification in step A will be described with reference to Figure 7 (a) to Figure 7 . In addition, Figure 7 (a) to Figure 7Figure (d) focuses on the reaction occurring on the first substrate surface of the wafer 200 surface and is a figure showing only the first substrate portion of the wafer 200 surface extracted.

[0185] Here, an example is described in which bis(dialkylamino)dialkylsilane (abbreviation: BDAADAS) is used as the first modifier for a wafer 200 with an SiO film exposed as the first substrate on the surface, and (dialkylamino)trialkylsilane (abbreviation: DAATAS) is used as the second modifier. Here, in Figure 7 Figure (a) to Figure 7 Figure (d), both "R" and "R'" represent alkyl groups.

[0186] As Figure 7 shown in Figure (a), regarding the surface of the SiO film exposed on the surface of the wafer 200, it has the following chemical structure, that is, this chemical structure has more OH terminals. In step A1, when BDAADAS as the first modifier is supplied to the wafer 200, BDAADAS is chemisorbed on the surface of the SiO film.

[0187] More specifically, as Figure 7 shown in Figure (b), at a portion where two OH terminals on the SiO film surface are close (for example, a portion having the structure of "adjacent" or "geminal" in Table 1), these two OH groups react with two dialkylamino groups contained in one BDAADAS molecule, and one Si atom contained in one BDAADAS molecule bonds with two O atoms in these two OH groups to form a crosslinking structure (crosslinked structure) for chemisorption. Due to this chemisorption, two dialkylamino groups (equivalent to the first functional group) are detached from the BDAADAS molecule, and a remaining group having two alkyl groups ( Figure 7 ">SiR2 group" in Figure (b)) remains on the surface of the SiO film. This is one way of chemisorbing BDAADAS on the SiO film surface.

[0188] In addition, as Figure 7 shown in Figure (b), at a portion where two OH terminals on the SiO film surface are far apart (for example, a portion having the structure of "isolated" in Table 1), one of these two OH groups reacts with one dialkylamino group contained in one BDAADAS molecule, and one Si atom contained in one BDAADAS molecule bonds with the O atom in this one OH group for chemisorption. Due to this chemisorption, one dialkylamino group (equivalent to the first functional group) is detached from the BDAADAS molecule, and a remaining group having two alkyl groups and one dialkylamino group remains on the SiO film surface ( Figure 7the “—SiR2(NR’2) group” in (b) thereof). This is another way of chemisorbing BDAADAS on the surface of the SiO film.

[0189] In this way, BDAADAS can be chemisorbed regardless of the structure of the OH termini on the surface of the SiO film. As a result, a first modified layer 10 containing the remaining groups from BDAADAS, namely, the “>SiR2 group” and the “—SiR2(NR’2) group”, is formed on the surface of the SiO film.

[0190] Next, in step A3, a gas containing O and H, which is a substance containing O and H, is supplied to the wafer 200, and OH termini are formed on the first modified layer 10 formed on the surface of the SiO film in step A1.

[0191] More specifically, in step A3, the dialkylamino group contained in the first modified layer 10 formed in step A1 reacts (specifically, a hydrolysis reaction) with the gas containing O and H. As shown in Figure 7 (c) thereof, the dialkylamino group contained in the first modified layer 10 is replaced by an OH group. As a result, with respect to the first modified layer 10 formed on the surface of the SiO film, it changes to a second modified layer 20 having OH termini. According to step A3, through the above reaction, the dialkylamino group detaches from the first modified layer 10, and thus there is almost no dialkylamino group in the obtained second modified layer 20.

[0192] Then, in step A2, DAATAS, which is a second modifier, is supplied to the wafer 200, and DAATAS is chemisorbed on the OH termini of the second modified layer 20 formed in step A3.

[0193] More specifically, the OH group in the OH termini 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 to the O atom in the OH group to perform chemisorption. Due to this chemisorption, one dialkylamino group (equivalent to the first functional group) detaches from the DAATAS, and the remaining group having three alkyl groups ( Figure 7 the “—SiR3 group (trialkylsilyl)” in (d) thereof). This is one way of chemisorbing DAATAS on the second modified layer 20.

[0194] Thus, a third modification layer 30 is formed on the surface of the SiO film. The third modification layer 30 includes: remaining groups from BDAADAS and remaining groups from DAATAS. As described above, DAATAS as the second modifier is a compound having a dialkylamino group equivalent to the first functional group. Therefore, the dialkylamino group is detached through the above reaction, and thus it is difficult to incorporate the dialkylamino group into the obtained third modification layer 30, and it is almost absent.

[0195] The outermost surface of the third modification layer 30, that is, the outermost surface of the SiO film, is covered with the remaining groups from BDAADAS and the remaining groups from DAATAS. That is, the outermost surface of the SiO film is covered with the alkyl groups (equivalent to the second functional group) contained in the remaining groups from BDAADAS and the alkyl groups (equivalent to the second functional group) contained in the remaining groups 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 from BDAADAS and the alkyl groups (equivalent to the second functional group) contained in the remaining groups from DAATAS.

[0196] After sequentially performing step A1, step A3, and step A2, a third modification layer 30 is formed on the surface of the SiO film. The third modification layer 30 includes: remaining groups from BDAADAS and remaining groups from DAATAS. Regarding the formed third modification layer 30, as Figure 7 shown in (d) of, it has more alkyl groups with higher chemical stability, and the existence density of the alkyl groups with higher chemical stability is high, and it has a trialkylsilyl group with a large steric hindrance as the remaining group from DAATAS. Therefore, when forming a film on the wafer 200 having the SiO film with such a third modification layer 30 formed on its surface, physical adsorption and chemical adsorption of the film-forming raw material on the surface of the SiO film can be effectively suppressed. That is, by using the wafer 200 modified by sequentially performing step A1, step A3, and step A2, selection failure can be suppressed during subsequent film formation, and the selectivity of selective growth can be improved.

[0197] (Repeat)

[0198] In step A, step A1 and step A3 can be repeated multiple times. By repeating these steps, the first modifier can be more fully chemisorbed on more OH terminals on the surface of the first substrate, and further, the first functional group contained in the first modification layer can be more fully replaced by the OH group. Therefore, by performing step A2 after repeating these steps, the modification density of the surface of the first substrate, that is, the terminal rate of the second functional group on the surface of the first substrate, can be increased.

[0199] Alternatively, in step A, steps A1, A3, and A2 can be repeated multiple times. By repeating these steps, the modification density on the surface of the first substrate, i.e., the terminal ratio of the second functional groups on the surface of the first substrate, can be increased. In addition, the above steps only need to be repeated until the modification density on the surface of the first substrate reaches the required level.

[0200] (Step B)

[0201] In step B, a film-forming gas (source gas, reaction gas, catalyst gas) is supplied to the wafer 200 whose surface of the first substrate has been modified in step A, i.e., the wafer 200 after the formation of the third modified layer on the surface of the first substrate, and a film is selectively formed on the surface of the second substrate. In addition, in step B, the output of the heater 207 is adjusted to maintain a state where the temperature of the wafer 200 is below the temperature of the wafer 200 in step A, and preferably to maintain a state lower than the temperature of the wafer 200 in step A.

[0202] In step B, the source gas and the reaction gas are alternately supplied to the wafer 200 as the film-forming gas, or the source gas and the reaction gas are alternately supplied to the wafer 200 as the film-forming gas, and preferably the catalyst gas is supplied together 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 necessary and can be omitted. For example, any of the following processing timings can be performed in step B. In addition, only step B is extracted and shown in the following processing timings.

[0203] (Source gas → Reaction gas) × n

[0204] (Source gas → Reaction gas + Catalyst gas) × n

[0205] (Source gas + Catalyst gas → Reaction gas) × n

[0206] (Source gas + Catalyst gas → Reaction gas + Catalyst gas) × n

[0207] An example of using the catalyst gas in combination is described below. Specifically, an example in which the source gas and the reaction gas are alternately supplied as the film-forming gas in step B and the source gas and the reaction gas are each supplied together with the catalyst gas is described. Specifically, the following steps B1 and B2 are sequentially performed in step B. In addition, as described above, Figure 6 shows an example in which a substance containing O and H is used as the reaction gas, for example.

[0208] (Step B1)

[0209] 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.

[0210] Specifically, valves 243b and 243d are opened, and the source gas is respectively introduced into the gas supply pipe 232b, and the catalyst gas is introduced into the gas supply pipe 232d. The source gas and the catalyst gas are respectively adjusted in flow rate by the MFCs 241b and 241d, and are supplied into the processing chamber 201 via the nozzles 249b and 249a. After being supplied into the processing chamber 201, they are mixed and exhausted through the exhaust port 231a. At this time, the source gas and the catalyst gas are supplied to the wafer 200. At this time, valves 243e to 243g may also be opened, and inert gas may be respectively supplied into the processing chamber 201 via the nozzles 249a to 249c.

[0211] By supplying the source gas and the catalyst gas to the wafer 200 under the processing conditions described below, adsorption of the source gas on the third modified layer, that is, the first substrate surface, can be suppressed, and the source gas can be selectively (preferably) adsorbed on the second substrate surface. Thereby, the source gas is adsorbed on the second substrate surface, and for example, a first layer having a thickness ranging from less than one atomic layer (one molecular layer) to several atomic layers (several molecular layers) is formed.

[0212] In step B1, by supplying the catalyst gas together with the source gas, the above reaction can be carried out in a non-plasma ambient gas and under the lower temperature conditions described below. By forming the first layer in a non-plasma ambient gas and under the lower temperature conditions described below, removal (detachment) of the third modified layer formed on the first substrate surface from the first substrate surface can be suppressed.

[0213] In addition, when the first layer is formed in step B1, the source gas is also adsorbed on a part of the first substrate surface, but the adsorption amount is extremely small, and is a very small amount compared with the adsorption amount of the source gas on the second substrate surface. The reason for achieving this selective (preferred) adsorption is that a third modified layer serving as a film formation hindrance layer is formed over the entire area of the first substrate surface, and the third modified layer serving as a film formation hindrance layer is not formed in most areas or the entire area of the second substrate surface. And because the processing conditions in step B1 are set to conditions under which the source gas does not undergo gas-phase decomposition (self-decomposition) in the processing chamber 201. By setting conditions under which the source gas does not undergo gas-phase decomposition, decomposition products such as intermediates generated by the gas-phase decomposition of the source gas are not accumulated on the first substrate surface and the second substrate surface, and the source gas can be selectively adsorbed on the second substrate surface.

[0214] After selectively forming a first layer on the surface of the second substrate, valves 243b and 243d are closed to stop the supply of the source gas and the catalyst gas into the processing chamber 201, respectively. Then, the remaining gas in the processing chamber 201 is exhausted (purge) from the processing chamber 201 using the same processing steps and conditions as the purge in step A1 described above.

[0215] Examples of the processing conditions in this step are as follows:

[0216] Processing temperature: room temperature (25°C) to 200°C, preferably room temperature to 120°C;

[0217] Processing pressure: 133 to 1333 Pa;

[0218] Source gas supply flow rate: 1 to 2000 sccm;

[0219] Source gas supply time: 1 to 60 seconds;

[0220] Catalyst gas supply flow rate: 1 to 2000 sccm;

[0221] Inert gas supply flow rate (each gas supply pipe): 0 to 20000 sccm.

[0222] - Source gas -

[0223] As the source gas, for example, a gas containing Si and a halogen can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. The gas containing Si and a halogen preferably contains the halogen in the form of a chemical bond between Si and the halogen. The gas containing Si and a halogen may further contain C, and in this case, C is preferably contained in the form of a Si-C bond. As the gas containing Si and a halogen, for example, a silane gas containing Si, Cl, and an alkylene group and having a Si-C bond, that is, an alkylchlorosilane gas can be used. Here, the alkylene group includes: methylene, ethylene, propylene, butylene, etc. The alkylchlorosilane gas preferably contains Cl in the form of a Si-Cl bond and C in the form of a Si-C bond. Thus, as the source gas, for example, a gas containing Si and a halogen, a gas containing Si, C, and a halogen, etc. can be used.

[0224] As the source gas, for example, the following can be used: alkylene chlorosilane gases such as bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as: BTCSM) gas, 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as: BTCSE) gas; alkyl chlorosilane gases such as 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated as: TCDMDS) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated as: DCTMDS) gas; gases containing a cyclic structure composed of Si and C and a halogen such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C2H4Cl4Si2, abbreviated as: TCDSCB) gas. In addition, as the source gas, for example, inorganic chlorosilane gases such as tetrachlorosilane (SiCl4, abbreviated as: STC) gas, hexachlorodisilane (Si2Cl6, abbreviated as: HCDS) gas, octachlorotrisilane (Si3Cl8, abbreviated as: OCTS) gas can be used. As the source gas, one or more of these can be used.

[0225] -Catalyst gas-

[0226] As the catalyst gas, for example, the same catalyst gases as the various catalyst gases exemplified in the above step A3 can be used.

[0227] (Step B2)

[0228] In step B2, after the first layer is formed through step B1, a reaction gas and a catalyst gas are selectively supplied to the wafer 200 in the processing chamber 201, that is, the first layer selectively formed on the second substrate surface. Hereinafter, an example in which a substance containing O and H is used as the reaction gas will be described.

[0229] Specifically, valves 243c and 243d are opened, and a substance containing O and H is circulated as a reaction gas into the gas supply pipe 232c, and a catalyst gas is circulated into the gas supply pipe 232d. The substance containing O and H and the catalyst gas are respectively adjusted in flow rate by MFC241c and 241d, and are supplied into the processing chamber 201 via nozzles 249c and 249a. After being supplied into the processing chamber 201, they are mixed, and exhausted through the exhaust port 231a. At this time, the substance containing O and H and the catalyst gas are supplied to the wafer 200. At this time, valves 243e to 243g can also be opened to supply an inert gas into the processing chamber 201 via nozzles 249a to 249c.

[0230] By supplying a substance containing O and H and a catalyst gas to the wafer 200 under the processing conditions described below, at least a part of the first layer formed on the surface of the second substrate in step B1 can be oxidized. As a result, a second layer formed by oxidizing the first layer is formed on the surface of the second substrate. In addition, when forming the second layer, impurities such as Cl contained in the first layer are removed from the first layer and discharged from the processing chamber 201 by forming a gaseous substance containing impurities such as Cl during the oxidation reaction of the substance containing O and H passing through the first layer. As a result, the second layer becomes a layer with fewer impurities such as Cl than the first layer.

[0231] In step B2, by supplying the catalyst gas together with the substance containing O and H, the above reaction can be carried out under a non-plasma ambient gas and under the lower temperature conditions described below. By carrying out the formation of the second layer under a non-plasma ambient gas and under the lower temperature conditions described below, it is possible to suppress the removal (detachment) of the third modified layer formed on the surface of the first substrate from the surface of the first substrate.

[0232] After oxidizing the first layer formed on the surface of the second substrate to become the second layer, valves 243c and 243d are closed, and the supply of the substance containing O and H and the catalyst gas, which are reaction gases, into the processing chamber 201 is stopped, respectively. Then, the remaining gas in the processing chamber 201 is removed (purged) from the processing chamber 201 using the same processing steps and conditions as the purge in step A1 above.

[0233] Examples of the processing conditions in this step are as follows:

[0234] Processing temperature: room temperature (25°C) to 200°C, preferably room temperature to 120°C;

[0235] Processing pressure: 133 to 1333 Pa;

[0236] Reaction gas supply flow rate: 1 to 2000 sccm;

[0237] Reaction gas supply time: 1 to 60 seconds;

[0238] Catalyst gas supply flow rate: 1 to 2000 sccm;

[0239] Inert gas supply flow rate (each gas supply pipe): 0 to 20000 sccm.

[0240] - Reaction gas -

[0241] As a reaction gas, in the case of forming a film such as an oxide film, a substance containing O and H can be used. As the substance containing O and H, for example, the same substances containing O and H as those exemplified in the above step A3 can be used. In addition, as the reaction gas, the following can be used: oxygen (O2), ozone (O3) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc., oxygen (O)-containing gases, etc. Since most of the substances containing O and H are oxygen-containing gases, hereinafter, for convenience, the substances containing O and H will also be referred to as oxygen-containing gases. As the reaction gas, one or more of these can be used.

[0242] In addition, as the reaction gas, in the case of forming a film such as a nitride film, a nitriding agent (nitriding gas) can be used. As the nitriding agent, a gas containing N and H can be used. As the gas containing N and H, for example, the following can be used: ammonia (NH3), hydrazine (N2H4) gas, diazene (N2H2) gas, N3H8 gas, etc., hydrogen nitride gases containing N-H bonds. In addition, in the case of forming a film such as a nitride film, as long as the above substances containing O and H, oxidation, and oxidation reaction are respectively replaced by a nitriding agent, nitriding, and nitriding reaction for consideration. As the reaction gas, one or more of these can be used.

[0243] - Catalyst gas -

[0244] As the catalyst gas, for example, the same catalyst gases as those exemplified in the above step A3 can be used.

[0245] (Execute a predetermined number of times)

[0246] By performing the above steps B1 and B2 non-simultaneously, that is, asynchronously, for a predetermined number of times (n times, where n is an integer of 1 or more), it is possible to selectively form a film with a desired film thickness on the surface of the second substrate among the first substrate and the second substrate exposed on the surface of the wafer 200 as shown in (c) of Figure 8 . The above cycle is preferably repeated multiple times. That is, it is preferable to make the thickness of the second layer formed in each cycle thinner than the desired film thickness and stack the second layer, so as to repeat the above cycle multiple times before the selectively grown film reaches the desired film thickness.

[0247] In addition, when performing Steps B1 and B2, a film may sometimes be formed in an extremely small amount on the surface of the first substrate. However, in this case, the film thickness of the film formed on the surface of the first substrate is also extremely thin compared to the film thickness of the film formed on the surface of the second substrate. In this specification, "higher selectivity in selective growth" not only means that a film is not completely formed on the surface of the first substrate, but only a film is formed on the surface of the second substrate, and also includes cases where, as described above, although an extremely thin film is formed on the surface of the first substrate, a much thicker film is formed on the surface of the second substrate.

[0248] Regarding the selective growth in Step B, the resulting film varies depending on the type of source gas or reaction gas. For example, in Step B, by using a gas containing Si, C, and a halogen as the source gas and an oxygen-containing gas as the reaction gas, a silicon oxycarbide film (SiOC film) can be formed as a film. Additionally, for example, in Step B, by using a gas containing Si, C, and a halogen as the source gas and a gas containing N and H as the reaction gas, a silicon carbonitride film (SiCN film) can be formed as a film. Further, for example, in Step B, by using a gas containing Si, C, and a halogen as the source 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. Additionally, for example, in Step B, by using a gas containing Si and a halogen as the source gas and an oxygen-containing gas as the reaction gas, a silicon oxide film (SiO film) can be formed as a film. Additionally, for example, in Step B, by using a gas containing Si and a halogen as the source gas and a gas containing N and H as the reaction gas, 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, depending on the processing conditions, a catalyst gas is not necessary, and in the case of not using a catalyst gas, the processing temperature in Step B can be a predetermined temperature within the range of, for example, 200 to 500°C.

[0249] In addition, regarding the selective growth in step B, by using a source gas containing metal elements such as Al, Ti, Hf, Zr, Ta, Mo, and W as the source gas and using an oxygen-containing gas and a gas containing N and H as the reaction gas, metal oxide films such as aluminum oxide film (AlO film), titanium oxide film (TiO film), hafnium oxide film (HfO film), zirconium oxide film (ZrO film), tantalum oxide film (TaO film), molybdenum oxide film (MoO), tungsten oxide film (WO), etc., and metal nitride films such as aluminum nitride film (AlN film), titanium nitride film (TiN film), hafnium nitride film (HfN film), zirconium nitride film (ZrN film), tantalum nitride film (TaN film), molybdenum nitride film (MoN), tungsten nitride film (WN), etc. can be formed as films. In addition, as described above, depending on the processing conditions, the catalyst gas is not necessary. When the catalyst gas is not 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] (Step C)

[0251] In step C, the wafer 200 after the selective growth is completed by performing step A and step B is annealed.

[0252] Specifically, after the selective growth is completed, the output of the heater 207 is adjusted in such a way that the temperature in the processing chamber 201, that is, the temperature of the wafer 200 after the film is selectively formed on the second substrate surface, is a temperature equal to or higher than the temperature of the wafer 200 during the selective growth, preferably a temperature higher than the temperature of the wafer 200 during the selective growth, and the wafer 200 after the selective growth is heated to anneal the wafer 200.

[0253] Thereby, the function of the third modification layer on the first substrate surface as an inhibitor can be invalidated. Specifically, by annealing the wafer 200 after the selective growth, the second functional group contained in the third modification layer can be detached and removed from the first substrate surface, 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, and the adsorption of the film-forming gas (source gas, reaction gas, etc.) on the first substrate surface and the reaction between the surface of the first substrate and the film-forming gas (source gas, reaction gas, etc.) can occur.

[0254] In step C, by invalidating the function of the third modified layer as an inhibitor, the film formation inhibition state of the first substrate surface is reset, so that film formation processing and the like can be performed on the first substrate surface in subsequent processes. In addition, by annealing the wafer 200 after selective growth, when the second functional group contained in the third modified layer is detached and removed from the first substrate surface, the third modified layer itself is also detached and removed. Figure 8 (d) of Figure 8 shows a state in which the third modified layer itself has been removed from the first substrate surface exposed on the surface of the wafer 200.

[0255] Step C can be carried out in a state where a gas containing N such as N2 gas, a gas containing H such as H2 gas, a gas containing O such as O2 gas, etc., which promote the removal (detachment) of the second functional group (such as an alkyl group such as methyl) contained in the third modified layer (auxiliary gas), is supplied into the processing chamber 201. In addition, it can also be carried out in a state where the supply of the auxiliary gas into the processing chamber 201 is stopped. As the auxiliary gas, the above-mentioned reaction gas can also be used.

[0256] As the processing conditions in step C, the following are exemplified:

[0257] Processing temperature: 200 - 1000 °C, preferably 400 - 700 °C;

[0258] Processing pressure: 1 - 120000 Pa;

[0259] Auxiliary gas supply flow rate: 0 - 50000 sccm;

[0260] Auxiliary gas supply time: 1 - 18000 seconds.

[0261] (Post-purge and atmospheric pressure recovery)

[0262] After the selective growth of the film on the second substrate surface is completed and the reset of the film formation inhibition state of the first substrate surface is completed, an inert gas as a purge gas is supplied into the processing chamber 201 from the nozzles 249a - 249c respectively, and exhausted through the exhaust port 231a. Thereby, the inside of the processing chamber 201 is purged, and the remaining gas, reaction by-products, etc. in the processing chamber 201 are removed from the processing chamber 201 (post-purge). After that, the ambient gas 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 atmospheric pressure (atmospheric pressure recovery).

[0263] (Cassette export and wafer unloading)

[0264] After that, the seal cover 219 is lowered by the susceptor elevator 115 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out (susceptor export) from the lower end of the manifold 209 to the outside of the reaction tube 203 in a state of being supported by the susceptor 217. After the susceptor is exported, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by using the gate 219s and via the O-ring 220c (gate closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the susceptor 217 (wafer unloading).

[0265] (3) Effects of this method

[0266] According to this method, one or more of the following effects can be obtained.

[0267] In step A, the selectivity in selective growth can be improved by using the first modifier and the second modifier.

[0268] That is, the first modifier contains one or more atoms directly bonded to the first functional group and the second functional group, so that the number of the first functional groups of the first modifier that can chemisorb on the adsorption sites (such as OH terminals) on the surface of the first substrate is more than the number of the 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 chemisorbed on the surface of the first substrate (adsorption sites) more effectively regardless of the structure of the adsorption sites on the surface of the first substrate (such as the adjacent, twin, and isolated three structures of OH terminals). That is, the first modifier can be chemisorbed on the adsorption sites existing throughout the surface of the first substrate. In addition, a second functional group with relatively high chemical stability exists on the surface of the first substrate after the first modifier is chemisorbed.

[0269] In addition, the second modifier contains an atom directly bonded to the first functional group and the second functional group, and the number of the first functional groups contained in one molecule is less than the number of the first functional groups contained in one molecule of the first modifier. The second modifier has such a structure, and in addition, the first modifier has the above structure, so that the second modifier can be chemisorbed on the first modifier. On the surface of the first substrate after the second modifier is chemisorbed on the first modifier, the second functional groups with relatively high chemical stability exist in a relatively high density. 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.

[0270] For example, in the case where a first modifier and a second modifier are sequentially supplied, after the first modifier is chemisorbed on the surface of the first substrate, not only the second functional groups with relatively high chemical stability but also a part of the first functional groups remain on the surface of the first substrate. By converting the first functional groups remaining on the surface of the first substrate into adsorption sites such as OH groups, the second modifier can be chemisorbed on the OH groups by means of the chemical reaction between the OH groups and the first functional groups of the second modifier. The second modifier contains more second functional groups with relatively high chemical stability in its molecule than the first modifier. Therefore, after the second modifier is chemisorbed, the surface of the first substrate has more second functional groups with relatively high chemical stability than before the chemisorption of the second modifier, and in addition, the density of the second functional groups with relatively high chemical stability is high, and the second functional groups that form a greater steric hindrance are included. That is, on the surface of the first substrate modified with the first modifier and the second modifier, the second functional groups with relatively high chemical stability exist in large numbers and at a high density, and a great steric hindrance formed by the second functional groups with relatively high chemical stability exists. That is, in this state, the surface of the first substrate is densely capped with the second functional groups with relatively high chemical stability contained in the remaining groups from the first modifier and the second functional groups with relatively high chemical stability contained in the remaining groups from the second modifier. Thereby, the adsorption of the raw material gas during film formation onto the surface of the first substrate can be more effectively hindered. As a result, selection failure can be suppressed, and the selectivity of selective growth can be improved.

[0271] In step A, by performing step A1 and step A2 non-simultaneously in the order of step A1 and step A2, the above chemical reaction can occur appropriately in stages (in multiple stages). As a result, on the surface of the first substrate, there are more second functional groups with relatively high chemical stability and they exist at a high density, and a great steric hindrance formed by the second functional groups with relatively high chemical stability exists. Thereby, the adsorption of the raw material gas during film formation onto the surface of the first substrate can be more effectively hindered, and as a result, selection failure can be suppressed, and the selectivity of selective growth can be further improved.

[0272] In step A, by sequentially performing step A1, step A3, and step A2, the above chemical reaction can occur more appropriately in stages (in multiple stages). As a result, on the surface of the first substrate, there are more second functional groups with relatively high chemical stability and they exist at a high density, and a great steric hindrance formed by the second functional groups with relatively high chemical stability exists. Thereby, the adsorption of the raw material gas during film formation onto the surface of the first substrate can be more effectively hindered, and as a result, selection failure can be suppressed, and the selectivity of selective growth can be further improved.

[0273] In addition, in this case, a part of the first modifier can be adsorbed on the surface of the first substrate in a state containing at least one first functional group in step A1, so that the above chemical reaction can occur more appropriately.

[0274] In addition, in this case, the first modifier can be adsorbed on the surface of the first substrate in a state containing a 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 a second functional group in step A2, so that the above chemical reaction can occur more appropriately.

[0275] In addition, in this case, a part of the first modifier can be adsorbed on the surface of the first substrate by the reaction of two adjacent OH groups (i.e., adsorption sites) existing on the surface of the first substrate with one molecule of the first modifier. That is, two or more first functional groups of one molecule of the first modifier can react with two adjacent OH groups existing on the surface of the first substrate. Thereby, the adsorption of two OH groups can be hindered in one molecule of the first modifier, and the above chemical reaction can occur more appropriately and efficiently.

[0276] In step A, by repeating step A1 and step A3 multiple times, and in addition, by repeating step A1, step A3, and step A2 multiple times, the modification density of the surface of the first substrate can be increased. In other words, by performing such repetitions multiple times, the third modification layer can be more fully formed over the entire surface of the first substrate. By more fully forming the third modification layer over the entire surface of the first substrate, the selection failure can be more effectively suppressed, and the selectivity of selective growth can be further improved.

[0277] In step A3, by supplying a gas containing O and H to the wafer 200 as a substance containing O and H, the first functional group existing on the surface of the first substrate can be more efficiently converted into an OH group, and the above chemical reaction can occur more appropriately.

[0278] By using a first modifier having 2 first functional groups in one molecule and a second modifier having 1 first functional group in one molecule, the above chemical reaction can occur more appropriately. In addition, by using a first modifier having 2 first functional groups and 2 second functional groups in one molecule and a second modifier having 1 first functional group and 3 second functional groups in one molecule, the above chemical reaction can occur more appropriately.

[0279] By using a first modifier having a structure containing a tetravalent atom directly bonding a first functional group and a second functional group, and a second modifier having a structure containing a tetravalent atom directly bonding a first functional group and a second functional group, the above chemical reaction can occur more appropriately.

[0280] By using a first modifier and a second modifier in which the first functional group is an amino group, the above chemical reaction can occur more appropriately. By using a first modifier and a second modifier in which the first functional group is a substituted amino group, the above chemical reaction can occur more appropriately.

[0281] By using a first modifier and a second modifier in which the second functional group is a hydrocarbon group, the above chemical reaction can occur more appropriately. By using a first modifier and a second modifier in which the second functional group is an alkyl group, the above chemical reaction can occur more appropriately.

[0282] By performing each step on the wafer 200 in which the first substrate is an oxide film and the second substrate is a film other than the oxide film, the above chemical reaction can occur more appropriately. By performing each step on the wafer 200 in which the first substrate is an oxygen-containing film (such as a SiO film, etc.) and the second substrate is a non-oxygen-containing film (such as a SiN film or a Si film, etc.), the above chemical reaction can occur more appropriately.

[0283] By performing step A and step B in a non-plasma ambient gas, the modification of the surface of the first substrate and the selective growth on the surface of the second substrate can be appropriately performed. In addition, by performing step A and step B in a non-plasma ambient gas, the plasma damage to the wafer 200 can also be avoided.

[0284] (4) Variation

[0285] The processing timing of this method can be changed as in the following variation examples. These variation examples can be arbitrarily combined. Unless otherwise specified, the processing steps and processing conditions of each step of each variation example can be the same as those of each step of the above processing timing.

[0286] (Variation Example 1)

[0287] Before the modification by step A, a step A4 of exposing the surface of the wafer 200 to an aqueous hydrofluoric acid (HF) solution can also be performed. By performing a cleaning treatment using an HF aqueous solution (also called DHF cleaning) in step A4, the native oxide film formed on at least one of the surfaces of the first substrate and the second substrate can be removed.

[0288] In this modified example, the same effects as those in the above-described manner can also be obtained. Additionally, according to this modified example, the surface of the first substrate can be more effectively capped with OH groups. Therefore, in the subsequent modification in step A, the third modified layer can be more sufficiently formed over the entire surface of the first substrate. Thereby, the selectivity of selective growth can be further improved.

[0289] (Modified Example 2)

[0290] Instead of supplying a substance containing O and H (such as a gas containing O and H) to the wafer 200 in step A3, the wafer 200 can be exposed to the atmosphere. That is, the wafer 200 can also be exposed to the atmosphere to supply the atmosphere (the contained moisture (H2O)) as a substance containing O and H to the wafer 200. In this modified example, the same effects as those in the above-described manner can also be obtained. In addition, in this case, the moisture as the substance containing O and H can be a gas or a liquid, for example, in a mist form.

[0291] <Other Aspects of the Present Disclosure>

[0292] The above has specifically described the aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and can be variously modified without departing from its gist.

[0293] For example, post-treatment (step C) may not be performed after selective growth by step B. In this case, the same effects as those in the above-described manner can be obtained in addition to the effects of the post-treatment. Sometimes, it is not necessary to reset the film formation inhibition state of the surface of the first substrate by the process performed after selective growth, and in this case, post-treatment is not required.

[0294] Furthermore, for example, the wafer 200 can have multiple types of films as the first substrate and can also have multiple types 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 can also be: films containing semiconductor elements such as SiOCN film, SiON film, SiOC film, SiC film, SiCN film, SiBN film, SiBCN film, Ge film, SiGe film, etc., films containing metal elements such as TiN film, W film, etc., and amorphous carbon film (a-C film). As long as the film has a surface that can be modified by the first modifier and the second modifier (i.e., a surface having adsorption sites), it can be used as the first substrate. On the other hand, as long as the film has a surface that is not easily modified by the first modifier and the second modifier (i.e., a surface having no adsorption sites or few adsorption sites), it can be used as the second substrate. In this case, the same effects as those in the above-described manner can also be obtained.

[0295] Regarding the recipes used in each process, it is preferable to prepare them separately according to the process content and store them in the storage device 121c via an electronic communication line or an external storage device 123. Also, when starting each process, it is preferable for the CPU 121a to appropriately select an appropriate recipe from among the multiple recipes stored in the storage device 121c according to the process content. Thereby, it is possible to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses in one substrate processing apparatus. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each process can be started quickly.

[0296] The above-mentioned recipes are not limited to newly generated ones. For example, they can also be prepared by changing the existing recipes already installed in the substrate processing apparatus. In the case of changing a recipe, the changed recipe can be installed in the substrate processing apparatus via an electronic communication line or a storage medium on which the recipe is recorded. Additionally, the input / output device 122 provided in the existing substrate processing apparatus can also be operated to directly change the existing recipe installed in the substrate processing apparatus.

[0297] In the above-described manner, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once has been described. The present disclosure is not limited to the above-described manner. For example, it can also be preferably applied in the case of forming a film using a single-wafer-type substrate processing apparatus that processes one or several substrates at a time. Additionally, in the above-described manner, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-described manner and can also be preferably applied in the case of forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0298] When applying these substrate processing apparatuses, each process can also be performed using the same processing steps and processing conditions as those in the above-described manner or modified example, and the same effects as those in the above-described manner or modified example can be obtained.

[0299] The above-described manner or modified example can be used in appropriate combination. The processing steps and processing conditions at this time can be the same as those of the above-described manner or modified example, for example.

[0300] Examples

[0301] (Example 1)

[0302] As Example 1, a wafer with a SiO film as the first substrate and a SiN film as the second substrate exposed on the surface was used, and selective growth of the SiOC film was carried out according to the processing timing in the above manner to fabricate the first evaluation sample. When fabricating 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 halogen, a gas containing O and H, and an amine gas were used as the source gas, reaction gas, and catalyst gas, respectively. In addition, before performing the processing timing in the above manner, the wafer with the SiO film and SiN film exposed on the surface was immersed in a HF aqueous solution (hereinafter referred to as DHF) in which HF was diluted with H2O to 1% for 30 seconds. The processing conditions for each step when fabricating the first evaluation sample were predetermined conditions within the processing conditions for each step of the processing timing in the above manner.

[0303] (Comparative Example 1)

[0304] As Comparative Example 1, the same wafer as in Example 1 immersed in DHF for 30 seconds was used, and except for not performing Step A1 and Step A3, selective growth of the SiOC film was carried out in the same manner as the processing timing in the above manner to fabricate the second evaluation sample. The second modifier, source gas, reaction gas, catalyst gas, and processing conditions for each step when fabricating the second evaluation sample were the same as those in fabricating the first evaluation sample.

[0305] (Comparative Example 2)

[0306] As Comparative Example 2, the same wafer as in Example 1 immersed in DHF for 30 seconds was used, and except for not performing Step A3 and Step A2, selective growth of the SiOC film was carried out in the same manner as the processing timing in the above manner to fabricate the third evaluation sample. The first modifier, source gas, reaction gas, catalyst gas, and processing conditions for each step when fabricating the third evaluation sample were the same as those in fabricating the first evaluation sample.

[0307] After fabricating 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 of each evaluation sample were measured. Next, the film thickness difference (hereinafter simply referred to as 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 of each evaluation sample was calculated.

[0308] The results are shown in Figure 9 it. Figure 9The horizontal axis successively shows Comparative Example 1 (the second evaluation sample), Comparative Example 2 (the third evaluation sample), and Example 1 (the first evaluation sample) from left to right, and the vertical axis represents the film thickness of the SiOC film. In the bar chart, the left bar represents the film thickness of the SiOC film formed on the SiO film, and the right bar represents the film thickness of the SiOC film formed on the SiN film. The line chart represents the film thickness difference. In Figure 9 it, for convenience, this film thickness difference is referred to as selectivity. In addition, it is also shown that: the larger this film thickness difference is, the better the selectivity is, and the smaller this film thickness difference is, the worse the selectivity is.

[0309] From Figure 9 it can be seen that the film thickness difference of Example 1 (the first evaluation sample) is much larger than the film thickness differences of Comparative Example 1 (the second evaluation sample) and Comparative Example 2 (the third evaluation sample) respectively. Thus, according to Example 1, it can be confirmed that the selectivity of selective growth can be significantly improved.

[0310] In addition, in other film formation evaluations conducted by the inventors of this case, it was confirmed that: not only in the case where the second substrate is a SiN film, but also in the cases where the second substrate is single crystal Si, an a-C film, an a-Si film, an AlO film, a SiCN film, and a TiN film, a SiOC film can be selectively formed on these second substrates.

Claims

1. A substrate processing method, characterized in that, having: Process a, which modifies the surface of the first substrate by sequentially performing process a1, process a3, and process a2 non-simultaneously. Process a1 is a process of supplying a first modifier to a substrate having the first substrate and the second substrate on its surface. The first modifier contains one or more atoms directly bonded to a first functional group containing an amino group or a substituted amino group and a second functional group containing a hydrocarbon group. Process a3 is a process of supplying a substance containing oxygen and hydrogen to the substrate. Process a2 is a process of supplying a second modifier to the substrate. The second modifier contains an atom directly bonded to the first functional group and the second functional group, and the number of the first functional groups contained in one molecule of the second modifier is less than the number of the first functional groups contained in one molecule of the first modifier; and Process b, which supplies a film-forming gas to the substrate after modifying the surface of the first substrate, thereby forming a film on the surface of the second substrate.

2. The substrate processing method according to claim 1, wherein in process a1, the first modifier is adsorbed on the surface of the first substrate, in process a3, a part of the first functional groups of the first modifier adsorbed on the surface of the first substrate is replaced with hydroxyl groups, in process a2, the second modifier is adsorbed on the hydroxyl groups.

3. The substrate processing method according to claim 2, wherein in process a1, a part of the first modifier is adsorbed on the surface of the first substrate in a state containing at least one of the first functional groups.

4. The substrate processing method according to claim 2, wherein in process a1, the first modifier is adsorbed on the surface of the first substrate in a state containing the second functional group, in process a2, the second modifier is adsorbed on the hydroxyl groups in a state containing the second functional group.

5. The substrate processing method according to claim 2, wherein in process a1, a part of the first modifier is adsorbed on the surface of the first substrate by the reaction of two adjacent hydroxyl groups present on the surface of the first substrate with one molecule of the first modifier.

6. The substrate processing method according to claim 2, wherein in process a, process a1 and process a3 are repeated multiple times, or process a1, process a3, and process a2 are repeated multiple times.

7. The substrate processing method according to claim 1, wherein in process a3, H2O gas is supplied to the substrate as the substance containing oxygen and hydrogen.

8. The substrate processing method according to claim 1, wherein the number of the first functional groups contained in one molecule of the first modifier is 2, and the number of the first functional groups contained in one molecule of the second modifier is 1.

9. The substrate processing method according to claim 1, wherein both the first modifier and the second modifier have a structure containing a tetravalent atom, and the tetravalent atom is directly bonded to the first functional group and the second functional group.

10. The substrate processing method according to claim 1, wherein: the second functional group contains an alkyl group.

11. The substrate processing method according to claim 1, wherein: before performing step a1, step a further has: step a4 of exposing the surface of the substrate to an aqueous hydrogen fluoride solution.

12. The substrate processing method according to claim 1, wherein: the first substrate is an oxide film, and the second substrate is a film other than an oxide film.

13. A method for manufacturing a semiconductor device, characterized in that, There is: Step a: The surface of the first substrate is modified by sequentially performing step a1, step a3, and step a2 non-simultaneously. Step a1 is a step of supplying a first modifier to a substrate having the first substrate and the second substrate on its surface. The first modifier contains one or more atoms directly bonded to a first functional group containing an amino group or a substituted amino group and a second functional group containing a hydrocarbon group. Step a3 is a step of supplying a substance containing oxygen and hydrogen to the substrate. Step a2 is a step of supplying a second modifier to the substrate. The second modifier contains an atom directly bonded to the first functional group and the second functional group, and the number of the first functional groups contained in one molecule is less than the number of the first functional groups contained in one molecule of the first modifier; and Step b: A film-forming gas is supplied to the substrate after the surface of the first substrate has been modified, so as to form a film on the surface of the second substrate.

14. A substrate processing apparatus, characterized in that, There is: A processing chamber for processing a substrate; A first modifier supply system for supplying a first modifier to the substrate in the processing chamber. The first modifier contains one or more atoms directly bonded to a first functional group containing an amino group or a substituted amino group and a second functional group containing a hydrocarbon group; A substance supply system containing oxygen and hydrogen for supplying a substance containing oxygen and hydrogen to the substrate in the processing chamber; A second modifier supply system for supplying a second modifier to the substrate in the processing chamber. The second modifier contains an atom directly bonded to the first functional group and the second functional group, and the number of the first functional groups contained in one molecule is less than the number of the first functional groups contained in one molecule of the first modifier; A film-forming gas supply system for supplying a film-forming gas to the substrate in the processing chamber; and A control unit configured to be able to control the first modifier supply system, the substance supply system containing oxygen and hydrogen, the second modifier supply system, and the film-forming gas supply system so that in the processing chamber: Processing a: The surface of the first substrate is modified by sequentially performing process a1, process a3, and process a2 non-simultaneously. Process a1 is a process of supplying the first modifier to a substrate having the first substrate and the second substrate on its surface. Process a3 is a process of supplying a substance containing oxygen and hydrogen to the substrate. Process a2 is a process of supplying a second modifier to the substrate; and Processing b: A film-forming gas is supplied to the substrate after the surface of the first substrate has been modified, so as to form a film on the surface of the second substrate.

15. A storage medium, which is a storage medium readable by a computer, characterized in that it stores a program that causes a substrate processing apparatus to perform the following steps in a processing chamber of the substrate processing apparatus by a computer, that is: Step a, the surface of the first substrate is modified by sequentially performing step a1, step a3, and step a2 non-simultaneously. Step a1 is a step of supplying a first modifier to a substrate having the first substrate and the second substrate on its surface. The first modifier contains one or more atoms directly bonded with a first functional group containing an amino group or a substituted amino group and a second functional group containing a hydrocarbon group. Step a3 is a step of supplying a substance containing oxygen and hydrogen to the substrate. Step a2 is a step of supplying a second modifier to the substrate. The second modifier contains an atom directly bonded with the first functional group and the second functional group, and the number of the first functional groups contained in one molecule of the second modifier is less than the number of the first functional groups contained in one molecule of the first modifier; and Step b, a film-forming gas is supplied to the substrate after the surface of the first substrate is modified, so as to form a film on the surface of the second substrate.

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