Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium

Abstract

The present invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium. The present invention provides a technique capable of selectively forming a film on a desired surface with high precision. It has: (A) a step of forming an inhibitor layer on a first surface of a substrate having the first surface and a second surface by supplying a modifier to the substrate; and (B) a step of forming a film on the second surface by supplying a film forming agent to the substrate after the inhibitor layer is formed on the first surface. In a case where a width of an inhibitor molecule constituting the inhibitor layer is set as WI, a spacing of adsorption sites of the first surface is set as DA, and a width of a molecule X constituting a specific substance contained in the film forming agent is set as WP, WP>DA-WI is satisfied when WI is smaller than DA, and WP>DAx-WI (x is the smallest integer satisfying WI<DAx) is satisfied when WI is larger than DA.

Description

Technical Field

[0001] This disclosure relates to substrate processing methods, semiconductor device manufacturing methods, substrate processing apparatus, and recording media. Background Technology

[0002] As a step in the manufacturing process of semiconductor devices, sometimes a process is performed to selectively grow and form a film on a specific surface among a variety of surfaces of different materials exposed on the surface of a substrate (hereinafter, this process will also be referred to as selective growth or selective film formation) (see, for example, Patent Documents 1 and 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-155452

[0006] Patent Document 2: Japanese Patent Application Publication No. 2020-155607 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, due to the different modifiers and film-forming agents used in selective growth, it is sometimes difficult to selectively grow films on specific surfaces among a variety of surfaces.

[0009] The purpose of this disclosure is to provide a technique for selectively forming films with high precision on desired surfaces.

[0010] Methods for solving problems

[0011] According to one aspect of this disclosure, a technology is provided that has:

[0012] (A) A step of forming an inhibitor layer on the first surface by supplying a modifier to a substrate having a first surface and a second surface; and

[0013] (B) A step of forming a film on the second surface by supplying a film-forming agent to the substrate after the inhibitor layer has been formed on the first surface.

[0014] So that when the width of the inhibitor molecules constituting the aforementioned inhibitor layer is set to WI, the spacing of the adsorption sites on the aforementioned first surface is set to DA, and the width of the molecules X constituting the specific substance contained in the aforementioned film-forming agent is set to WP,

[0015] When WI is less than DA, WP > DA - WI is satisfied.

[0016] When WI is greater than DA, WP > DAx - WI (where x is the smallest integer that satisfies WI < DAx).

[0017] Invention Effects

[0018] According to this disclosure, films can be selectively formed on desired surfaces with high precision. Attached Figure Description

[0019] [ Figure 1 ] Figure 1 This is a schematic configuration diagram of a vertical processing furnace suitable for use in one embodiment of the present disclosure, and is a longitudinal sectional view showing part of the processing furnace 202.

[0020] [ Figure 2 ] Figure 2 This is a schematic diagram of a vertical processing furnace suitable for use in one embodiment of the present disclosure, and is based on... Figure 1 The diagram shows the AA-line sectional view of the processing furnace 202 section.

[0021] [ Figure 3 ] Figure 3 This is a schematic configuration diagram of the controller 121 of a substrate processing apparatus suitable for use in one embodiment of this disclosure, and is a block diagram illustrating the control system of the controller 121.

[0022] [ Figure 4 ] Figure 4 A diagram illustrating the processing sequence in one manner as described in this disclosure.

[0023] [ Figure 5 ] Figure 5 (a) is a schematic cross-sectional view of a surface portion of a wafer having a first surface and a second surface, with a natural oxide film formed on the second surface. Figure 5 (b) is to show the result by means of Figure 5 A cross-sectional view of the surface portion of the wafer after the cleaning step in state (a) removes the natural oxide film from the second surface. Figure 5 (c) is to show the result by means of Figure 5 A cross-sectional schematic diagram of the surface portion of the wafer after the modification steps of state (b) are performed to form an inhibitor layer on the first surface. Figure 5 (d) is shown as being passed by Figure 5 A cross-sectional schematic diagram of the surface portion of the wafer after the film-forming step is performed in state (c) to selectively form a film on the second surface. Figure 5 (e) is shown by... Figure 5 A cross-sectional view of the surface portion of the wafer after the inhibitor layer on the first surface is removed by a heat treatment step in state (d).

[0024] [ Figure 6 ] Figure 6 (a) is a cross-sectional schematic diagram showing the adsorption sites on the first surface of the wafer before the modifier is supplied. Figure 6 (b) is a cross-sectional schematic diagram showing the state of inhibitor molecules adsorbed at adsorption sites on the first surface of the wafer. Figure 6 (c) is a cross-sectional schematic diagram showing the situation where the inhibitor molecule forms a steric hindrance to the molecule X of a specific substance contained in the film-forming agent, preventing the molecule X from reaching the first surface of the wafer through the gap between the inhibitor molecules.

[0025] [ Figure 7 ] Figure 7 For example, a cross-sectional schematic diagram is shown where, when the width of the inhibitor molecule is set to WI, the spacing of the adsorption sites on the first surface of the wafer is set to DA, and the width of the molecule X of the specific substance contained in the film-forming agent is set to WP, the state WP > DA - WI is satisfied when WI is less than DA.

[0026] [ Figure 8 ] Figure 8 For example, a cross-sectional diagram is shown where, when the width of the inhibitor molecule is set to WI, the spacing of the adsorption sites on the first surface of the wafer is set to DA, and the width of the molecule X of the specific substance contained in the film-forming agent is set to WP, the state that WP > DAx - WI (where x is the smallest integer that satisfies WI < DAx) is satisfied when WI is greater than DA.

[0027] [ Figure 9 ] Figure 9 This is a cross-sectional schematic diagram illustrating the situation where, when the width of the inhibitor molecule is set to WI, the spacing of the adsorption sites on the first surface of the wafer is set to DA, and the width of the molecule X of the specific substance contained in the film-forming agent is set to WP, the state that WP > DA - WI is satisfied when WI is less than DA, thereby the inhibitor molecule forms steric hindrance to molecule X, preventing molecule X from reaching the first surface through the gaps between the inhibitor molecules.

[0028] [ Figure 10 ] Figure 10 This is a cross-sectional schematic diagram illustrating the situation where, when the width of the inhibitor molecule is set to WI, the spacing of the adsorption sites on the first surface of the wafer is set to DA, and the width of the molecule X of the specific substance contained in the film-forming agent is set to WP, the state is satisfied when WI is greater than DA, satisfying WP > DAx - WI (x is the smallest integer that satisfies WI < DAx), thereby the inhibitor molecule forms steric hindrance to molecule X, preventing molecule X from reaching the first surface through the gaps between the inhibitor molecules.

[0029] [ Figure 11 ] Figure 11 A diagram illustrating the processing sequence in Variation Example 1.

[0030] Explanation of reference numerals in the attached figures

[0031] 200 wafers (substrates) Detailed Implementation

[0032] <One way of publishing this text>

[0033] The following is mainly for reference. Figures 1-4 , Figure 5 (a)~ Figure 5 of (e) Figure 6 (a)~ Figure 6 (c) This disclosure is described in one manner. It should be noted that the accompanying drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements shown in the drawings are not necessarily consistent with reality. Furthermore, the dimensional relationships and ratios of the elements are not necessarily consistent among the various drawings.

[0034] (1) Composition of substrate processing device

[0035] like Figure 1 As shown, the processing furnace 202 has a heater 207 that functions as a temperature regulator (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported on a retaining plate. The heater 207 also functions as an activation mechanism (excitation unit) that uses heat to activate (excite) the gas.

[0036] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed into a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing component. The reaction tube 203 is also vertically mounted like the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow part of the processing container. The processing chamber 201 is configured to accommodate a wafer 200, which serves as a substrate. The wafer 200 is processed within this processing chamber 201.

[0037] Inside the processing chamber 201, nozzles 249a to 249c, serving as a first supply section to a third supply section, are respectively provided through the side wall of the manifold 209. These nozzles are also referred to as the first nozzle and the third nozzle, respectively. The nozzles 249a to 249c are made of heat-resistant materials such as quartz or SiC. Gas supply pipes 232a to 232c are connected to each of the nozzles 249a to 249c. Each of the nozzles 249a to 249c is a different nozzle, and each of the nozzles 249a and 249c is disposed adjacent to the nozzle 249b.

[0038] On gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c, serving as flow controllers (flow control units), and valves 243a to 243c, serving as on / off valves, are sequentially installed from the upstream side of the airflow. Gas supply pipes 232d and 232f are connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipes 232e and 232g are connected to gas supply pipe 232b downstream of valve 243b. Gas supply pipe 232h is connected to gas supply pipe 232c downstream of valve 243c. On gas supply pipes 232d to 232h, MFCs 241d to 241h and valves 243d to 243h are sequentially installed from the upstream side of the airflow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0039] like Figure 2As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 (viewed from above), nozzles 249a to 249c are respectively provided vertically from the lower part of the inner wall of the reaction tube 203 upwards towards the arrangement direction of the wafer 200. That is, nozzles 249a to 249c are respectively provided along the wafer arrangement area, in the area that horizontally surrounds the wafer arrangement area on the side of the wafer arrangement area where the wafer 200 is arranged. In view from above, nozzle 249b is arranged so as to clamp the center of the wafer 200 that has been moved into the processing chamber 201 and is aligned with the exhaust port 231a (described later) in a straight line. Nozzles 249a and 249c are arranged so as to clamp the straight line L passing through the center of nozzle 249b and exhaust port 231a from both sides along the inner wall of the reaction tube 203 (outer periphery of the wafer 200). Straight line L is also a straight line passing through the center of nozzle 249b and wafer 200. That is, nozzle 249c can also be positioned on the opposite side of nozzle 249a while clamping the straight line L. Nozzles 249a and 249c are arranged linearly symmetrically about the straight line L. Gas supply holes 250a and 250c for supplying gas are provided on the sides of nozzles 249a and 249c, respectively. Gas supply holes 250a and 250c open in a manner that is opposite to exhaust port 231a when viewed from above, and can supply gas to wafer 200. Multiple gas supply holes 250a and 250c are provided in the reaction tube 203 from bottom to top.

[0040] The modifier is supplied to the processing chamber 201 from the gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a.

[0041] Raw material is supplied into processing chamber 201 from gas supply pipe 232b via MFC 241b, valve 243b, and nozzle 249b. The raw material can be used as one of the film-forming agents.

[0042] The reactant is supplied into the processing chamber 201 through gas supply pipe 232c, MFC 241c, valve 243c, and nozzle 249c. The reactant can be used as one of the film-forming agents.

[0043] The catalyst is supplied into the processing chamber 201 through gas supply pipe 232d, MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a. The catalyst can be used as one of the film-forming agents.

[0044] Cleaning agent or conditioning agent is supplied to the treatment chamber 201 from the gas supply pipe 232e via MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0045] Inactive gases are supplied to the treatment chamber 201 through gas supply pipes 232f-232h via MFCs 241f-241h, valves 243f-243h, gas supply pipes 232a-232c, and nozzles 249a-249c. These inactive gases function as purge gas, carrier gas, and dilution gas.

[0046] The modifier supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The raw material supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The reactant supply system mainly consists of gas supply pipe 232c, MFC 241c, and valve 243c. The catalyst supply system mainly consists of gas supply pipe 232d, MFC 241d, and valve 243d. The cleaning agent or regulator supply system mainly consists of gas supply pipe 232e, MFC 241e, and valve 243e. The inactive gas supply system mainly consists of gas supply pipes 232f-232h, MFC 241f-241h, and valves 243f-243h. The raw material supply system, reactant supply system, and catalyst supply system may also be referred to individually or in combination as the film-forming agent supply system.

[0047] Any or all of the aforementioned supply systems can be configured as an integrated supply system 248, which integrates valves 243a-243h, MFCs 241a-241h, etc. The integrated supply system 248 is connected to the gas supply pipes 232a-232h, and is configured such that the controller 121 (described later) controls the supply of various substances (various gases) into the gas supply pipes 232a-232h, i.e., the opening and closing of valves 243a-243h, and the flow regulation by MFCs 241a-241h. The integrated supply system 248 is configured as an integrated unit, either integral or modular, allowing for the assembly and disassembly of the gas supply pipes 232a-232h, etc., on a unit-by-unit basis, and enabling maintenance, replacement, and addition of the integrated supply system 248 on a unit-by-unit basis.

[0048] Below the side wall of the reaction tube 203, there is an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201. Figure 2As shown, the exhaust port 231a is positioned opposite the nozzles 249a-249c (gas supply holes 250a-250c) when the wafer 200 is clamped in a top view. The exhaust port 231a can also be positioned from the lower part of the side wall of the reaction tube 203 along the upper part, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, serving as a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245 (a pressure detector, or pressure detection unit) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 (a pressure regulator, or pressure regulating unit). The APC valve 244 is configured to open and close while the vacuum pump 246 is operating, thereby enabling vacuum exhaust and stopping of vacuum exhaust within the processing chamber 201. Furthermore, by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted. The exhaust system mainly consists of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245. A vacuum pump 246 may also be included in the exhaust system.

[0049] Below the manifold 209, a sealing cover 219, serving as a furnace opening cover, is provided to airtightly seal the lower opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209. Below the sealing cover 219, a rotation mechanism 267 is provided to rotate the crystal boat 217 (described later). The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. The sealing cover 219 is configured to move vertically via a crystal boat lift 115, which is a lifting mechanism located outside the reaction tube 203. The crystal boat lift 115 is configured as a conveying device (conveying mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219.

[0050] Below the manifold 209, a gate 219s serving as a furnace opening cover is provided. This gate 219s can airtightly seal the lower opening of the manifold 209 after the sealing cover 219 has been lowered and the crystal boat 217 has been removed from the processing chamber 201. The gate 219s is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the gate 219s, an O-ring 220c serving as a sealing component abuts against the lower end of the manifold 209. The opening and closing actions (lifting, rotating, etc.) of the gate 219s are controlled by a gate opening and closing mechanism 115s.

[0051] The crystal boat 217, serving as a substrate support, is configured to support multiple wafers (e.g., 25 to 200 wafers) 200 arranged horizontally and with their centers aligned in the vertical direction in a multi-layered manner, i.e., arranged at intervals. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. The lower part of the crystal boat 217 supports a heat-insulating plate 218 made of a heat-resistant material such as quartz or SiC in multiple layers.

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

[0053] like Figure 3 As shown, the controller 121, serving as the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0054] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c stores in a readable manner a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the steps and conditions of the substrate processing described later. The process flow functions as a program, which is a combination of steps in the substrate processing described later, which can be executed by the controller 121 to obtain a predetermined result. Hereinafter, the process flow, control program, etc., will also be referred to as a program. Furthermore, the process flow will be referred to as a process. In this specification, the term "program" is used in cases where only the process flow is included, cases where only the control program is included, or cases where both are included. RAM 121b is configured as a storage area (working area) for temporarily holding the program, data, etc., read by the CPU 121a.

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

[0056] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on input of operation commands from input / output device 122. CPU 121a is configured to control the following actions according to the read processes: flow regulation of various substances (various gases) using MFC 241a to 241h, opening and closing of valves 243a to 243h, opening and closing of APC valve 244, pressure regulation using APC valve 244 based on pressure sensor 245, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation of crystal boat 217 using rotation mechanism 267, lifting and lowering of crystal boat 217 using crystal boat elevator 115, opening and closing of gate 219s using gate opening and closing mechanism 115s, etc.

[0057] The controller 121 is configured to install the aforementioned program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, hard disks such as HDDs, optical disks such as CDs, optical disks such as MO drives, USB storage devices, and semiconductor storage devices such as SSDs. The storage device 121c and the external storage device 123 are configured in the form of a computer-readable recording medium. Hereinafter, they will also be referred to collectively as recording media. In this specification, the term "recording medium" is used in cases where only the storage device 121c is included, cases where only the external storage device 123 is included, or cases where both are included. It should be noted that providing a program to a computer may also be done without using the external storage device 123, but using communication means such as the Internet or dedicated lines.

[0058] (2) Substrate processing process

[0059] An example of a method for processing a substrate using the aforementioned substrate processing apparatus as a step in the manufacturing process of a semiconductor device, specifically an example of a processing sequence for selectively forming a film on the second surface of a first surface and a second surface of a wafer 200 serving as a substrate, primarily using... Figure 4 , Figure 5 (a)~ Figure 5 of (e) Figure 6 (a)~ Figure 6(c) will be explained below. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0060] It should be noted that the surface of the wafer 200 has a first substrate and a second substrate, with the surface of the first substrate constituting the first surface and the surface of the second substrate constituting the second surface. For convenience, the following description will focus on the case where the first substrate is a silicon oxide film (SiO2 film, hereinafter also referred to as SiO film) as an oxide film (oxygen-containing film) and the second substrate is a silicon nitride film (Si3N4 film, hereinafter also referred to as SiN film) as a non-oxide film (non-oxygen-containing film). That is, the following description will focus on the case where the first surface is constituted by the surface of the SiO film serving as the first substrate and the second surface is constituted by the surface of the SiN film serving as the second substrate. The first substrate and the second substrate will also be referred to as the first substrate film and the second substrate film, respectively.

[0061] The processing sequence in this method includes the following steps:

[0062] (A) The step of forming an inhibitor layer on the first surface by supplying a modifier to a wafer 200 having a first surface and a second surface (modification step); and

[0063] (B) The step of forming a film on the second surface by supplying a film-forming agent to the wafer 200 after forming an inhibitor layer on the first surface (film formation step).

[0064] When the width of the inhibitor molecules constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface is set to DA, and the width of the molecules X of the specific substance (specific chemical substance) contained in the film-forming agent is set to WP,

[0065] When WI is less than DA, WP > DA - WI is satisfied.

[0066] When WI is greater than DA, WP > DAx - WI (where x is the smallest integer that satisfies WI < DAx). Each step is performed in a non-plasma atmosphere.

[0067] It should be noted that the following examples illustrate the case where the film-forming agent comprises raw materials, reactants, and catalysts. The molecular structures of the raw materials, reactants, and catalysts are different. Furthermore, the following examples illustrate the case where the specific substance contained in the film-forming agent is a raw material. That is, the case where molecule X is a raw material molecule is illustrated. It should be noted that the specific substance contained in the film-forming agent can also be a reactant. That is, molecule X can also be a reactant molecule. Additionally, the specific substance contained in the film-forming agent can also be a catalyst. That is, molecule X can also be a catalyst molecule. In other words, the specific substance contained in the film-forming agent can also include at least one of the raw materials, reactants, and catalysts.

[0068] Additionally, in the following examples, such as Figure 4 As shown, the film formation step includes the following steps being performed cyclically a predetermined number of times: a step of supplying raw materials to the wafer 200; and a step of supplying a reactant to the wafer 200, wherein, in at least one of the steps of supplying raw materials and supplying the reactant, the supply of a catalyst to the wafer 200 will be described. It should be noted that... Figure 4 As a representative example, an example of supplying a catalyst is shown in both the step of supplying raw materials and the step of supplying reactants.

[0069] That is, the following example is shown. Figure 4 The processing sequence shown is performed in a non-plasma atmosphere, and the following steps are executed:

[0070] The step of forming an inhibitor layer on the first surface by supplying a modifier to a wafer 200 having a first surface and a second surface (modification step); and

[0071] The step of forming a film on the second surface is to perform the steps of supplying raw materials and catalyst to wafer 200 and supplying reactants and catalyst to wafer 200 in a predetermined number of times (n times, where n is an integer greater than or equal to 1).

[0072] For convenience, the above processing sequence is sometimes shown in this specification as follows. The same wording is also used in the following descriptions of variations, other methods, etc.

[0073] Modifier → (raw material + catalyst → reactant + catalyst) × n

[0074] It should be noted that, as shown in the substrate processing sequence below, the catalyst may be supplied to the wafer 200 in at least one of the steps of supplying raw materials and supplying reactants.

[0075] Modifier → (raw material + catalyst → reactant) × n

[0076] Modifier → (raw materials → reactants + catalyst) × n

[0077] Modifier → (raw material + catalyst → reactant + catalyst) × n

[0078] Alternatively, it can be set as follows: Figure 4 As shown in the substrate processing sequence below, before the modification step, a step is performed to remove the natural oxide film formed on the surface of the wafer 200 by supplying a cleaning agent to the wafer 200 (cleaning step). Alternatively, a step of heat treatment of the wafer 200 may be performed after the film formation step (heat treatment step).

[0079] Cleaning agent → Modifier → (Raw material + Catalyst → Reactant) × n → Heat treatment

[0080] Cleaning agent → Modifier → (Raw material → Reactant + Catalyst) × n → Heat treatment

[0081] Cleaning agent → Modifier → (Raw material + Catalyst → Reactant + Catalyst) × n → Heat treatment

[0082] The term "wafer" as used in this specification includes both the wafer itself and a laminate of a wafer with a specified layer or film formed on its surface. The term "surface of the wafer" as used in this specification includes both the surface of the wafer itself and the surface of a specified layer, etc., formed on the wafer. The phrase "forming a specified layer on the wafer" as used in this specification includes both forming the specified layer directly on the surface of the wafer itself and forming the specified layer on top of a layer, etc., formed on the wafer. The term "substrate" as used in this specification has the same meaning as the term "wafer."

[0083] As used in this specification, the term "agent" includes at least one of gaseous and liquid substances. Liquid substances include mist substances. That is, modifiers and film-forming agents (raw materials, reactants, catalysts) may each contain gaseous substances, liquid substances such as mist substances, or both.

[0084] As used in this specification, the term "layer" includes at least one of continuous layers and discontinuous layers. For example, an inhibitor layer may include continuous layers, discontinuous layers, or both, as long as it can inhibit film formation.

[0085] (Wafer filling and crystal boat loading)

[0086] When multiple wafers 200 are loaded (wafer filling) into the crystal boat 217, the gate 219s is moved by the gate opening and closing mechanism 115s, opening the lower end opening of the manifold 209 (gate opening). Then, as... Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat lift 115 and moved into the processing chamber 201 (crystal boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 by means of an O-ring 220b. Thus, the wafers 200 are prepared in the processing chamber 201.

[0087] It should be noted that, as Figure 5As shown in (a), the wafer 200 loaded in the crystal boat 217 has a first surface and a second surface. The first surface is the surface of a first substrate, and the second surface is the surface of a second substrate. As described above, here, for example, the case where the first surface is the surface of a SiO film serving as the first substrate, and the second surface is the surface of a SiN film serving as the second substrate will be described. Furthermore, here, as... Figure 5 As shown in (a), the case where a natural oxide film is formed on the second surface is explained.

[0088] (Pressure and temperature regulation)

[0089] After the crystal boat loading is completed, vacuum pump 246 is used to exhaust the vacuum (reduced pressure exhaust) in the processing chamber 201, i.e., the space where the wafer 200 exists, to achieve the desired pressure (vacuum level). At this time, the pressure in the processing chamber 201 is measured by pressure sensor 245, and the APC valve 244 is controlled based on the measured pressure information. In addition, the wafer 200 in the processing chamber 201 is heated by heater 207 to achieve the desired processing temperature. At this time, the energization state of heater 207 is controlled based on temperature information detected by temperature sensor 263 to achieve the desired temperature distribution in the processing chamber 201. In addition, the wafer 200 is rotated using rotation mechanism 267. The exhaust in the processing chamber 201, the heating of the wafer 200, and the rotation are all carried out at least until the processing of the wafer 200 is completed.

[0090] (Cleaning steps)

[0091] Then, a cleaning agent is supplied to the chip 200.

[0092] Specifically, valve 243e is opened, allowing cleaning agent to flow into gas supply pipe 232e. The cleaning agent, with flow rate regulated by MFC 241e, is supplied to processing chamber 201 via gas supply pipe 232b and nozzle 249b, and exhausted from exhaust port 231a. At this time, cleaning agent is supplied to wafer 200 from the side (cleaning agent supply). Alternatively, valves 243f to 243h can be opened, supplying inactive gases to processing chamber 201 via nozzles 249a to 249c.

[0093] like Figure 5 As shown in (b), by supplying a cleaning agent to the wafer 200 under the processing conditions described later, the native oxide film formed on the second surface of the wafer 200 can be removed (etched), exposing the second surface. At this time, as Figure 5As shown in (b), the surfaces of the first substrate and the second substrate of the wafer 200, i.e., the first surface and the second surface, are exposed. When the first substrate is a SiO film and the second substrate is a SiN film, with the first and second surfaces exposed, the first surface is entirely capped with OH groups, while most of the second surface is not capped with OH groups. In other words, the first surface is entirely capped with OH groups, while most of the second surface is not capped with OH groups.

[0094] Examples of treatment conditions for supplying cleaning agents during the cleaning process include:

[0095] Processing temperature: 50–200℃, preferably 70–150℃

[0096] Processing pressure: 10–2000 Pa, preferably 100–1500 Pa

[0097] Processing time: 10-60 minutes, preferably 30-60 minutes

[0098] Cleaning agent supply flow rate: 0.05~1slm, preferably 0.1~0.5slm

[0099] Inactive gas supply flow rate (per gas supply pipe): 1-10 slm, preferably 2-10 slm.

[0100] It should be noted that the numerical range "50~200℃" in this specification refers to the lower and upper limits being included within that range. Therefore, for example, "50~200℃" means "above 50℃ and below 200℃". The same applies to other numerical ranges. Furthermore, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201. Additionally, the processing time refers to the duration of the processing. Also, the supply flow rate includes cases where 0slm is supplied; 0slm means an instance where the substance (gas) is not supplied. These same principles apply in the following descriptions.

[0101] After removing the natural oxide film from the second surface and exposing it, valve 243e is closed to stop the supply of cleaning agent to the treatment chamber 201. Simultaneously, a vacuum is applied to the treatment chamber 201 to expel any residual gaseous substances. At this time, valves 243f to 243h are opened, and inactive gas is supplied to the treatment chamber 201 through nozzles 249a to 249c. The inactive gas supplied from nozzles 249a to 249c acts as a purging gas, thereby purging the treatment chamber 201.

[0102] Examples of treatment conditions during purging in the cleaning process include:

[0103] Processing pressure: 1~30Pa

[0104] Processing time: 1–120 seconds, preferably 1–60 seconds

[0105] Inactive gas supply flow rate (per gas supply pipe): 0.5–20 slm.

[0106] It should be noted that the processing temperature during purging in this step is preferably the same as the processing temperature during the supply of cleaning agent.

[0107] For example, fluorine (F)-containing gases can be used as cleaning agents. Examples of F-containing gases include chlorine trifluoride (ClF3), chlorine fluoride (ClF), nitrogen fluoride (NF3), hydrogen fluoride (HF), and fluorine (F2). Additionally, acetic acid (CH3COOH), formic acid (HCOOH), hexafluoroacetylacetone (C5H2F6O2), and hydrogen (H2) gases can be used as cleaning agents. Furthermore, various cleaning solutions can also be used as cleaning agents. For example, aqueous solutions of acetic acid and formic acid can be used. Additionally, aqueous solutions of HF can be used for DHF cleaning. Furthermore, a cleaning solution containing ammonia, hydrogen peroxide solution, and pure water can be used for SC-1 cleaning (APM cleaning). Additionally, a cleaning solution containing hydrochloric acid, hydrogen peroxide solution, and pure water can be used for SC-2 cleaning (HPM cleaning). Alternatively, for example, a cleaning solution containing sulfuric acid and hydrogen peroxide can be used as a cleaning agent for SPM cleaning. That is, the cleaning agent can be a gaseous substance or a liquid substance. Alternatively, the cleaning agent can be a liquid substance such as a mist. One or more of the above-mentioned types can be used as the cleaning agent.

[0108] As inert gases, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. More than one of these gases can be used as an inert gas. This also applies to the steps described later.

[0109] It should be noted that if a wafer 200 in which the natural oxide film formed on the surface of the wafer 200 has been removed beforehand and maintained in that state is used, the cleaning step can be omitted. In this case, the modification step described later can be performed after pressure and temperature adjustment.

[0110] (Modification steps)

[0111] After the cleaning step, a modifier is supplied to the wafer 200.

[0112] Specifically, valve 243a is opened, allowing the modifier to flow into the gas supply pipe 232a. The modifier is regulated by MFC 241a, supplied to the processing chamber 201 via nozzle 249a, and exhausted from the exhaust port 231a. At this time, the modifier is supplied to the wafer 200 from the side (modifier supply). Alternatively, valves 243f to 243h can be opened, supplying inactive gases to the processing chamber 201 via nozzles 249a to 249c respectively.

[0113] like Figure 5 As shown in (c), by supplying a modifier to the wafer 200 under the processing conditions described later, at least a portion of the molecular structure of the modifier molecules, namely the inhibitor molecules, can be chemically adsorbed onto the first surface of the wafer 200, forming an inhibitor layer on the first surface and thus modifying the first surface. That is, in this step, by supplying the wafer 200 with a modifier that reacts with the first surface, the inhibitor molecules contained in the modifier can be adsorbed onto the first surface, forming an inhibitor layer on the first surface and thus modifying the first surface. Therefore, the first surface, which is the outermost surface of the first substrate, can be capped using at least a portion of the molecular structure of the modifier molecules, namely the inhibitor molecules. The inhibitor molecules are also referred to as film-forming barrier molecules (adsorption barrier molecules, reaction barrier molecules). Furthermore, the inhibitor layer is also referred to as a film-forming barrier layer (adsorption barrier layer, reaction barrier layer).

[0114] The inhibitor layer formed in this step contains at least a portion of the molecular structure of the molecule constituting the modifier, which is derived from residues of the modifier. The inhibitor layer prevents the adsorption of the raw material (film-forming agent) onto the first surface during the film-forming step described later, thereby hindering (inhibiting) the film-forming reaction on the first surface.

[0115] As at least part of the molecular structure of the molecule constituting the modifier, i.e., the inhibitor molecule, examples include trimethylsilyl (-SiMe3) and triethylsilyl (-SiEt3) trialkylsilyl groups. Trialkylsilyl groups contain alkyl groups (i.e., hydrocarbon groups). In the above case, the Si of the trimethylsilyl or triethylsilyl group is adsorbed onto adsorption sites on the first surface of the wafer 200. When the first surface is the surface of a SiO film, the first surface contains OH-terminated (OH-groups) as adsorption sites, and the Si of the trimethylsilyl or triethylsilyl group is bonded to the O of the OH-terminated (OH-groups) on the first surface, thus the first surface is capped by alkyl groups such as methyl or ethyl (i.e., hydrocarbon groups). By constructing an inhibitor layer with alkyl groups such as methyl (trimethylsilyl) and ethyl (triethylsilyl) (i.e., hydrocarbon groups) capped on the first surface, it is possible to prevent the adsorption of raw materials (film-forming agents) onto the first surface during the film-forming step described later, thereby hindering (inhibiting) the film-forming reaction on the first surface.

[0116] It should be noted that, Figure 6 (a) shows adsorption sites (e.g., OH groups) on the first surface of the wafer 200 before the modifier is supplied. Figure 6 (b) shows the state where inhibitor molecules are adsorbed at adsorption sites on the first surface of wafer 200. In the above example, Figure 6 The adsorption sites on the first surface of (a) correspond to OH groups. Figure 6 (b) The inhibitor molecules adsorbed at the adsorption sites on the first surface correspond to trialkylsilyl groups such as trimethylsilyl (-SiMe3) and triethylsilyl (-SiEt3). That is, in this example, the inhibitor molecule contains an alkyl group (alkylsilyl), and the inhibitor layer contains alkyl (alkylsilyl) end caps, i.e., hydrocarbon end caps. Alkyl (alkylsilyl) end caps and hydrocarbon end caps are also referred to as alkyl (alkylsilyl) end caps and hydrocarbon end caps, respectively. In this example, a high film-forming barrier effect can be obtained.

[0117] It should be noted that in this step, sometimes at least a portion of the molecular structure constituting the modifier molecules is also adsorbed onto a portion of the second surface of the wafer 200, but the adsorption amount is very small, while the adsorption amount on the first surface of the wafer 200 is overwhelmingly large. This selective (preferred) adsorption is achieved because the processing conditions in this step are set such that the modifier does not undergo gas-phase decomposition within the processing chamber 201. Additionally, this is because the entire area of ​​the first surface is capped with OH, while most of the second surface is not capped with OH. In this step, since the modifier does not undergo gas-phase decomposition within the processing chamber 201, at least a portion of the molecular structure constituting the modifier molecules does not multi-deposit on both the first and second surfaces. Instead, at least a portion of the molecular structure constituting the modifier molecules is selectively adsorbed onto the first surface, thereby selectively capping the first surface with at least a portion of the molecular structure constituting the modifier molecules.

[0118] Examples of processing conditions during the supply of the modifier in the modification step include:

[0119] Processing temperature: room temperature (25℃) to 500℃, preferably room temperature to 250℃

[0120] Processing pressure: 5–2000 Pa, preferably 10–1000 Pa

[0121] Processing time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes

[0122] Modifier supply flow rate: 0.001–3 slm, preferably 0.001–0.5 slm

[0123] Inactive gas supply flow rate (per gas supply pipe): 0–20 slm.

[0124] After selectively forming an inhibitor layer on the first surface of wafer 200, valve 243a is closed to stop the supply of modifier to processing chamber 201. Then, using the same processing steps and conditions as the purging in the cleaning step, residual gaseous substances in processing chamber 201 are discharged from processing chamber 201 (purging). It should be noted that the processing temperature during purging in this step is preferably set to the same temperature as the processing temperature during the supply of modifier.

[0125] As a modifier, for example, compounds having a structure in which amino groups are directly bonded to silicon (Si), or compounds having a structure in which amino and alkyl groups are directly bonded to silicon (Si) can be used.

[0126] As modifiers, for example, (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3, abbreviated as DMATMS), (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3, abbreviated as DEATES), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3, abbreviated as DMATES), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3, abbreviated as DEATMS), (dipropylamino)trimethylsilane ((C3H7)2NSi(CH3)3, abbreviated as DPATMS), (dibutylamino)trimethylsilane (dimethyl ... Methylsilane ((C4H9)2NSi(CH3)3, abbreviated as DBATMS), (trimethylsilyl)amine ((CH3)3SiNH2, abbreviated as TMSA), (triethylsilyl)amine ((C2H5)3SiNH2, abbreviated as TESA), (dimethylamino)silane ((CH3)2NSiH3, abbreviated as DMAS), (diethylamino)silane ((C2H5)2NSiH3, abbreviated as DEAS), (dipropylamino)silane ((C3H7)2NSiH3, abbreviated as DPAS), (dibutylamino)silane ((C4H9)2NSiH3, abbreviated as DBAS), etc. One or more of the above can be used as modifiers.

[0127] Alternatively, as modifiers, for example, bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2, abbreviated as BDMADMS), bis(diethylamino)diethylsilane ([(C2H5)2N]2Si(C2H5)2, abbreviated as BDEADES), bis(dimethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2, abbreviated as BDMADES), bis(diethylamino)dimethylsilane ([(C2H5)2)2) can also be used. [N]2Si(CH3)2 (abbreviated as BDEADMS), bis(dimethylamino)silane ([(CH3)2N]2SiH2 (abbreviated as BDMAS), bis(diethylamino)silane ([(C2H5)2N]2SiH2 (abbreviated as BDEAS), bis(dimethylaminodimethylsilyl)ethane ([(CH3)2N(CH3)2Si]2C2H6 (abbreviated as BDMADMSE), bis(dipropylamino)silane ([(C3H7)2N]2SiH2) Abbreviations: BDPAS, bis(dibutylamino)silane ([(C4H9)2N]2SiH2, abbreviated as BDBAS), bis(dipropylamino)dimethylsilane ([(C3H7)2N]2Si(CH3)2, abbreviated as BDPADMS), bis(dipropylamino)diethylsilane ([(C3H7)2N]2Si(C2H5)2, abbreviated as BDPADES), (dimethylsilyl)diamine ((CH3)2Si(NH2)2, abbreviated as DMSDA), (Diethylsilyl)diamine ((C2H5)2Si(NH2)2, abbreviated as DESDA), (dipropylsilyl)diamine ((C3H7)2Si(NH2)2, abbreviated as DESDA), bis(dimethylaminodimethylsilyl)methane ([(CH3)2N(CH3)2Si]2CH2, abbreviated as BDMADMSM), bis(dimethylamino)tetramethyldisilane ([(CH3)2N]2(CH3)4Si2, abbreviated as BDMATMDS), etc. One or more of the above can be used as modifiers.

[0128] (Film-forming steps)

[0129] After the modification step, a film-forming agent is supplied to the wafer 200 to form a film on the second surface of the wafer 200. That is, a film-forming agent that reacts with the second surface is supplied to the wafer 200, selectively (preferably) forming a film on the second surface. Specifically, the following raw material supply step and reactant supply step are performed sequentially. It should be noted that, in the following examples, as described above, the film-forming agent includes raw materials, reactants, and a catalyst. In the raw material supply step and the reactant supply step, the output power of the heater 207 is adjusted to maintain the temperature of the wafer 200 below the temperature of the wafer 200 in the cleaning step and the modification step, preferably at, for example, [temperature missing]. Figure 4 The temperature of wafer 200 is low during the cleaning and modification steps shown.

[0130] [Raw Material Supply Steps]

[0131] In this step, raw materials (raw material gas) and catalyst (catalyst gas) are supplied to the wafer 200 after the modification step, that is, to the wafer 200 after an inhibitor layer is selectively formed on the first surface, as film-forming agents.

[0132] Specifically, valves 243b and 243d are opened, allowing raw materials and catalyst to flow into gas supply pipes 232b and 232d, respectively. The flow rates of the raw materials and catalyst are regulated by MFCs 241b and 241d, and supplied to the processing chamber 201 via nozzles 249b and 249a. They are mixed within the processing chamber 201 and exhausted from the exhaust port 231a. At this time, raw materials and catalyst are supplied to the wafer 200 from the side (raw materials + catalyst supply). Alternatively, valves 243f to 243h can be opened, supplying inactive gases to the processing chamber 201 via nozzles 249a to 249c.

[0133] By supplying raw materials and a catalyst to the wafer 200 under the processing conditions described later, it is possible to suppress the chemisorption of at least a portion of the molecular structure constituting the raw material molecules on the first surface, and to selectively chemisorb at least a portion of the molecular structure constituting the raw material molecules on the second surface. Thus, a first layer is selectively formed on the second surface. The first layer contains at least a portion of the molecular structure constituting the raw material molecules, which are residues of the raw material. That is, the first layer contains at least a portion of the atoms constituting the raw material.

[0134] In this step, by supplying a catalyst along with the raw materials, the above-described reaction can be carried out in a non-plasma atmosphere and at a low temperature as described later. Thus, by forming the first layer in a non-plasma atmosphere and at a low temperature as described later, the molecules and atoms constituting the inhibitor layer formed on the first surface can be maintained, preventing them from disappearing (detaching) from the first surface.

[0135] Furthermore, by forming the first layer in a non-plasma atmosphere and at a low temperature as described later, the raw material can be prevented from undergoing thermal decomposition (gas phase decomposition), i.e., from self-decomposition, within the processing chamber 201. This prevents at least a portion of the molecular structure constituting the raw material from being multiple-deposited on the first and second surfaces, and allows at least a portion of the molecular structure constituting the raw material to be selectively adsorbed onto the second surface.

[0136] It should be noted that in this step, sometimes at least a portion of the molecular structure constituting the raw material molecules is also adsorbed onto a portion of the first surface of the wafer 200, but the amount adsorbed is very small, while the amount adsorbed on the second surface of the wafer 200 is overwhelmingly large. This selective (preferred) adsorption is achieved because the processing conditions in this step are set to low temperature conditions, as described later, i.e., conditions under which the raw material does not undergo gas-phase decomposition within the processing chamber 201. Furthermore, this is because an inhibitor layer is formed over the entire area of ​​the first surface, while in contrast, no inhibitor layer is formed over most of the second surface.

[0137] Examples of processing conditions for supplying raw materials and catalysts in the raw material supply step include:

[0138] Processing temperature: room temperature (25℃) to 200℃, preferably room temperature to 150℃

[0139] Processing pressure: 133~1333Pa

[0140] Raw material supply flow rate: 0.001~2slm

[0141] Catalyst supply flow rate: 0.001~2slm

[0142] Inactive gas supply flow rate (per gas supply pipe): 0–20 slm

[0143] Gas supply time: 1-120 seconds, preferably 1-60 seconds.

[0144] After the first layer is selectively formed on the second surface of the wafer 200, valves 243b and 243d are closed to stop the supply of raw materials and catalyst to the processing chamber 201, respectively. Then, using the same processing steps and conditions as the purging in the cleaning step, residual gaseous substances in the processing chamber 201 are discharged from the processing chamber 201 (purging). It should be noted that the processing temperature during purging in this step is preferably set to the same temperature as the processing temperature during the supply of raw materials and catalyst.

[0145] As a raw material, for example, a gas containing Si and a halogen (a substance 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. For example, a silane-based gas having a Si-Cl bond, i.e., a chlorosilane-based gas, can be used. The gas containing Si and a halogen may also contain C, in which case it is preferably contained in the form of a Si-C bond. For example, a silane-based gas containing Si, Cl, and an alkylene group having a Si-C bond, i.e., an alkylchlorosilane-based gas, can be used. Alkylenes include methylene, ethylene, propylene, butylene, etc. Alternatively, a silane-based gas containing Si and a halogen, i.e., an alkylchlorosilane-based gas, can be used. Alkyl groups include methyl, ethyl, propyl, butyl, etc. Gases containing Si and halogens may also contain O, preferably in the form of Si-O bonds, such as siloxane bonds (Si-O-Si bonds). For example, silane-based gases having Si, Cl, and siloxane bonds, i.e., chlorosiloxane-based gases, can be used as Si and halogen-containing gases. These gases preferably contain Cl in the form of Si-Cl bonds. In addition to the above, amino-containing gases (amino-containing substances) such as aminosilane-based gases can also be used as raw materials.

[0146] For example, bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as BTCSM), 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as BTCSE), 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated as TCDMDS), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated as DCTMDS), and 1,1,3,3-tetrachloro-1,3-disilheycyclobutane (C2H4Cl4Si2, abbreviated as TCDSCB) can be used as raw materials. Alternatively, tetrachlorosilane (SiCl4, abbreviated as 4CS), hexachlorodisilane (Si2Cl6, abbreviated as HCDS), and octachlorotrisilane (Si3Cl8, abbreviated as OCTS) can also be used as raw materials. Alternatively, hexachlorodisiloxane (Cl3Si-O-SiCl3, abbreviated as HCDSO) and octachlorotrisiloxane (Cl3Si-O-SiCl2-O-SiCl3, abbreviated as OCTSO) can be used as raw materials. One or more of the above can be used as raw materials.

[0147] Alternatively, as raw materials, tetra(dimethylamino)silane (Si[N(CH3)2]4, abbreviated as 4DMAS), tris(dimethylamino)silane (Si[N(CH3)2]3H, abbreviated as 3DMAS), bis(diethylamino)silane (Si[N(C2H5)2]2H2, abbreviated as BDEAS), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2, abbreviated as BTBAS), and (diisopropylamino)silane (SiH3[N(C3H7)2], abbreviated as DIPAS) can also be used. One or more of the above-mentioned raw materials can be used.

[0148] As catalysts, amine gases (amine substances) containing carbon (C), nitrogen (N), and hydrogen (H) can be used, for example. Cyclic amine gases (amine substances) and chain amine gases (chain amine substances) can be used as amine gases (amine substances). As catalysts, pyridine (C5H5N), aminopyridine (C5H6N2), methylpyridine (C6H7N), dimethylpyridine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), and piperazine (C4H4N2) can be used, for example. 10 N2), piperidine (C5H) 11 Cyclic amines such as N and aniline (C6H7N) can be used. Additionally, chain amines such as triethylamine ((C2H5)3N, abbreviated as TEA), diethylamine ((C2H5)2NH, abbreviated as DEA), monoethylamine ((C2H5)NH2, abbreviated as MEA), trimethylamine ((CH3)3N, abbreviated as TMA), dimethylamine ((CH3)2NH, abbreviated as DMA), and monomethylamine ((CH3)NH2, abbreviated as MMA) can be used as catalysts. One or more of these can be used as catalysts. This also applies to the reactant supply step described later.

[0149] [Reactant Supply Procedure]

[0150] After the raw material supply step is completed, a reactant (reactant gas) and a catalyst (catalyst gas) are supplied to the wafer 200, i.e., the wafer 200 after the first layer has been selectively formed on the second surface, as film-forming agents. Here, an example of using an oxidant (oxidizing gas) as the reactant (reactant gas) will be described.

[0151] Specifically, valves 243c and 243d are opened, allowing the reactant and catalyst to flow into gas supply pipes 232c and 232d, respectively. The flow rates of the reactant and catalyst are regulated by MFCs 241c and 241d, and supplied to the processing chamber 201 via nozzles 249c and 249a. They mix within the processing chamber 201 and are then exhausted from the exhaust port 231a. At this time, the reactant and catalyst (reactant + catalyst supply) are supplied to the wafer 200 from the side. Alternatively, valves 243f to 243h can be opened, supplying inactive gases into the processing chamber 201 via nozzles 249a to 249c.

[0152] By supplying the reactant and catalyst to the wafer 200 under the processing conditions described later, at least a portion of the first layer formed on the second surface of the wafer 200 during the raw material supply step can be oxidized. This results in the formation of a second layer on the second surface, formed by the oxidation of the first layer.

[0153] In this step, by supplying a catalyst along with the reactants, the above-described reaction can be carried out in a non-plasma atmosphere and at a low temperature as described later. Thus, by forming the second layer in a non-plasma atmosphere and at a low temperature as described later, the molecules and atoms constituting the inhibitor layer formed on the first surface can be maintained, preventing them from disappearing (detaching) from the first surface.

[0154] Examples of processing conditions for supplying reactants and catalysts in the reactant supply step include:

[0155] Processing temperature: room temperature (25℃) to 200℃, preferably room temperature to 150℃

[0156] Processing pressure: 133~1333Pa

[0157] Reactant supply flow rate: 0.001~2slm

[0158] Catalyst supply flow rate: 0.001~2slm

[0159] Inactive gas supply flow rate (per gas supply pipe): 0–20 slm

[0160] Gas supply time: 1-120 seconds, preferably 1-60 seconds.

[0161] After the first layer formed on the second surface is oxidized and transformed into the second layer, valves 243c and 243d are closed to stop the supply of reactants and catalysts to the treatment chamber 201. Then, using the same treatment steps and conditions as the purging in the cleaning step, residual gaseous substances in the treatment chamber 201 are purged. It should be noted that the purging temperature in this step is preferably set to the same temperature as the temperature at which the reactants and catalysts are supplied.

[0162] As a reactant (i.e., oxidant), for example, gases containing oxygen (O) and hydrogen (H) can be used. Examples of gases containing O and H include water vapor (H₂O gas), hydrogen peroxide (H₂O₂) gas, hydrogen (H₂) gas + oxygen (O₂) gas, and H₂ gas + ozone (O₃) gas. That is, gases containing both O and H can also be a combination of O and H gases. In this case, deuterium (D₂) gas can be used instead of H₂ gas as the H-containing gas. One or more of the above can be used as the reactant.

[0163] It should be noted that the parallel description of "H2 gas + O2 gas" in this specification refers to a mixture of H2 gas and O2 gas. When supplying a mixed gas, it can be configured to mix the two gases in the supply pipe (pre-mixing) before supplying them to the processing chamber 201, or it can be configured to supply the two gases to the processing chamber 201 separately through different supply pipes and mix them in the processing chamber 201 (post-mixing).

[0164] In addition to gases containing O and H, O-containing gases (substances containing O) can also be used as reactants (i.e., oxidants). Examples of O-containing gases include O2, O3, nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), and carbon dioxide (CO2). Besides these gases, various aqueous solutions and cleaning solutions described above can also be used as reactants (i.e., oxidants). In this case, by exposing the wafer 200 to the cleaning solution, the oxidized object on the surface of the wafer 200 can be oxidized. One or more of the above-mentioned reactants can be used.

[0165] As a catalyst, for example, the same catalysts exemplified in the above-described feedstock supply steps can be used.

[0166] [Number of times stipulated for implementation]

[0167] By performing the above-mentioned raw material supply step and reactant supply step in a non-simultaneous (i.e., asynchronous) and alternating manner a predetermined number of times (n times, where n is an integer greater than or equal to 1), such as... Figure 5 As shown in (d), a film can be selectively (preferably) formed on the second surface of the wafer 200, which is either the first surface or the second surface. For example, using the raw materials, reactants, and catalysts described above, a silicon carbide film (SiOC film) or a silicon oxide film (SiO film) can be selectively grown on the second surface. The above-described cycle is preferably repeated multiple times. That is, preferably, the thickness of the second layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated multiple times until the film thickness formed by stacking the second layer reaches the desired film thickness.

[0168] As described above, by performing the above-described cycle a predetermined number of times, the film can be selectively grown on the second surface of the wafer 200. At this time, since an inhibitor layer is formed on the first surface of the wafer 200, film growth on the first surface can be suppressed. That is, by performing the above-described cycle a predetermined number of times, film growth on the first surface can be suppressed, while film growth on the second surface can be promoted.

[0169] However, even when an inhibitor layer is formed on the first surface of the wafer 200, the selectivity during selective growth is sometimes reduced due to the relationship between the molecular size of the inhibitor molecules, the molecular size of the molecules of the specific substances contained in the film-forming agent, and the spacing between the adsorption sites on the first surface. That is, due to these relationships, it is sometimes difficult to form a film with high precision and selectivity on the second surface, which is one of the first and second surfaces.

[0170] To address this issue, in this approach, such as... Figure 7 , Figure 8 As shown, when the width of the inhibitor molecule constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface (e.g., the spacing of OH groups) is set to DA, and the width of the molecule X (raw material molecule) constituting the raw material contained in the film-forming agent is set to WP, when WI is less than DA, WP > DA - WI is satisfied, and when WI is greater than DA, WP > DAx - WI is satisfied (x is the smallest integer that satisfies WI < DAx).

[0171] For example, at least one of the modifier and raw material is selected to satisfy the above-mentioned relationship. For example, a modifier having a desired WI is selected and used to satisfy the above-mentioned relationship. Additionally, for example, a raw material having a desired WP is selected and used to satisfy the above-mentioned relationship. Additionally, for example, a modifier having a desired WI and a raw material having a desired WP are selected and used to satisfy the above-mentioned relationship. Additionally, for example, the state of the adsorption sites on the first surface (the spacing, density, etc. of the adsorption sites) is adjusted to satisfy the above-mentioned relationship. Additionally, for example, the state of the adsorption sites on the first surface is adjusted, and a modifier having a desired WI is selected and used to satisfy the above-mentioned relationship. Additionally, for example, the state of the adsorption sites on the first surface is adjusted, and a raw material having a desired WP is selected and used to satisfy the above-mentioned relationship. Additionally, for example, the state of the adsorption sites on the first surface is adjusted, and a modifier having a desired WI and a raw material having a desired WP are selected and used to satisfy the above-mentioned relationship.

[0172] Specifically, for example, the types of modifiers are selected to satisfy DA > WI and WP > DA-WI, or DA < WI and WP > DAx-WI. Additionally, for example, the types of raw materials are selected to satisfy DA > WI and WP > DA-WI, or DA < WI and WP > DAx-WI. Furthermore, for example, the types of modifiers and raw materials are selected to satisfy DA > WI and WP > DA-WI, or DA < WI and WP > DAx-WI.

[0173] Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted to satisfy DA > WI and WP > DA-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the type of modifier is selected to satisfy DA > WI and WP > DA-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the type of raw material is selected to satisfy DA > WI and WP > DA-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the types of modifier and raw material are selected to satisfy DA > WI and WP > DA-WI.

[0174] Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted to satisfy DA < WI and WP > DAx-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the type of modifier is selected to satisfy DA < WI and WP > DAx-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the type of raw material is selected to satisfy DA < WI and WP > DAx-WI. Furthermore, for example, the spacing (density) of adsorption sites on the first surface is adjusted, and the types of modifier and raw material are selected to satisfy DA < WI and WP > DAx-WI.

[0175] It should be noted that the spacing and density of adsorption sites on the first surface can be adjusted, for example, by using a cleaning agent in the cleaning step (i.e., by cleaning treatment). That is, the spacing and density of adsorption sites on the first surface can be adjusted by cleaning treatment.

[0176] As described above, by selecting the type of modifier, selecting the type of raw material, and adjusting the adsorption sites on the first surface in a manner that satisfies the above-described relationship, thereby achieving the desired effect. Figure 6 As shown in (c), the inhibitor molecule acts as an effective steric hindrance to molecule X (the raw material molecule). Therefore, it is possible to inhibit molecule X (the raw material molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecule. Furthermore, it is possible to inhibit the contact between the raw material, which is a specific substance contained in the film-forming agent, and the first surface, and to inhibit the adsorption (chemisorption, physisorption) of the raw material on the first surface.

[0177] It should be noted that, in this case, even assuming the use of a catalyst with a small molecular size, where the catalyst reaches the first surface through the intermolecular gaps of the inhibitor molecules, the contact between the reactant and the first surface can be suppressed. Therefore, the adsorption of the reactant on the first surface, i.e., the formation of a first layer on the first surface, can be suppressed. Furthermore, even assuming the use of a reactant with a small molecular size, where the reactant reaches the first surface through the intermolecular gaps of the inhibitor molecules, the contact between the reactant and the first surface can be suppressed, i.e., the adsorption of the reactant on the first surface, thus suppressing the formation of a second layer on the first surface. As a result, the occurrence of selection failure can be suppressed. Moreover, since the contact between the reactant and the first surface can be suppressed, even when using a highly reactive substance as the reactant, the reaction between the reactant and the first surface can be suppressed, preventing the detachment of inhibitor molecules and the associated selection failure caused by this reaction.

[0178] It should be noted that, as Figure 7 As shown, by making WI less than DA, WP > DA - WI is satisfied, thus... Figure 9As shown, the inhibitor molecule acts as an effective steric hindrance to molecule X (the raw material molecule). Therefore, it can effectively prevent molecule X (the raw material molecule) from reaching the first surface through the gaps between the inhibitor molecules (hereinafter, this effect will also be referred to as the blocking effect), thereby achieving the aforementioned effect.

[0179] In addition, such as Figure 8 As shown, by making WI greater than DA, we satisfy WP > DAx - WI (where x is the smallest integer satisfying WI < DAx), as... Figure 10 As shown, the inhibitor molecule acts as an effective steric hindrance against molecule X (the raw material molecule). Therefore, it can effectively prevent molecule X (the raw material molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecule, thereby achieving the aforementioned effect.

[0180] In the above formula, the width (WI) of the inhibitor molecule can be set as the maximum width of the inhibitor molecule, preferably as the average width of the inhibitor molecule, and more preferably as the minimum width of the inhibitor molecule. Alternatively, in the above formula, the width (WP) of molecule X can be set as the maximum width of molecule X, preferably as the average width of molecule X, and more preferably as the minimum width of molecule X.

[0181] It should be noted that when the width (WI) of the inhibitor molecule is set to its minimum width, the blocking effect is optimal when the width (WP) of molecule X is also set to its minimum width. Furthermore, when the width (WI) of the inhibitor molecule is set to its minimum width, the blocking effect is sufficiently achieved even when the width (WP) of molecule X is set to its average width. Similarly, when the width (WI) of the inhibitor molecule is set to its minimum width, the blocking effect is sufficiently achieved even when the width (WP) of molecule X is set to its maximum width. And so on. Furthermore, when the width (WI) of the inhibitor molecule is set to the maximum width of the inhibitor molecule, the aforementioned blocking effect can still be obtained to a certain extent even when the width (WP) of molecule X is set to the maximum width of molecule X.

[0182] Therefore, during the raw material supply step and the reactant supply step, the inhibitor layer formed on the first surface is maintained on the first surface as described above, thereby inhibiting film growth on the first surface. However, in cases where the formation of the inhibitor layer on the first surface is insufficient due to certain factors, film formation and growth on the first surface may sometimes occur slightly. However, even in such cases, the thickness of the film formed on the first surface is considerably thinner than the thickness of the film formed on the second surface. In this specification, the term "high selectivity in selective growth" refers not only to the case where no film is formed on the first surface and only on the second surface, but also to the case where an extremely thin film is formed on the first surface, but a film considerably thicker is formed on the second surface.

[0183] (Heat treatment steps)

[0184] After the film-forming step, the wafer 200, on which the film has been selectively formed on the second surface, is subjected to heat treatment. At this time, the output power of the heater 207 is adjusted so that the temperature inside the processing chamber 201, i.e. the temperature of the wafer 200 after the film has been selectively formed on the second surface, is above, and preferably higher than, the temperature of the wafer 200 in the cleaning step, the modification step, and the film-forming step.

[0185] By performing heat treatment (annealing) on ​​the wafer 200, impurities and defects contained in the film formed on the second surface of the wafer 200 can be removed and repaired during the film formation process, thereby hardening the film. Hardening the film improves its processing resistance, i.e., its etching resistance. It should be noted that if impurity removal, defect repair, and film hardening are not required for the film formed on the second surface, the annealing process, i.e., the heat treatment step, can be omitted.

[0186] Furthermore, according to this step, the inhibitor layer remaining on the first surface of the wafer 200 can also be heat-treated (annealed) after the film-forming step. This allows at least a portion of the inhibitor layer remaining on the first surface to detach and / or become ineffective. It should be noted that the ineffectiveness of the inhibitor layer refers to transforming the molecular structure, atomic arrangement, etc., of the molecules constituting the inhibitor layer, so that the film-forming agent can be adsorbed onto the first surface and a reaction can occur between the first surface and the film-forming agent.

[0187] As described above, by performing this step, such as Figure 5 As shown in (e), the film formed on the second surface of the wafer 200 is hardened by heat treatment, and at least a portion of the inhibitor layer formed on the first surface of the wafer 200 is detached and / or ineffective. That is, by performing this step, a heat-treated film is present on the second surface, and at least a portion of the first surface is exposed. It should be noted that... Figure 5(e) shows an example of removing the inhibitor layer formed on the first surface to expose the first surface.

[0188] It should be noted that this step can be performed with either an inert gas supplied to the processing chamber 201 or with a reactive substance such as an oxidant (oxidizing gas). The inert gas and the reactive substance such as the oxidant (oxidizing gas) under these conditions are referred to as auxiliary substances.

[0189] Examples of processing conditions during heat treatment in the heat treatment step include:

[0190] Processing temperature: 200–1000℃, preferably 400–700℃

[0191] Processing pressure: 1~120000Pa

[0192] Processing time: 1–18000 seconds

[0193] Auxiliary material supply flow rate: 0-50 slm.

[0194] (Post-purging and atmospheric pressure recovery)

[0195] After the heat treatment step is completed, inert gases are supplied as purge gases into the treatment chamber 201 from nozzles 249a to 249c, and exhaust gases are discharged from exhaust port 231a. This purges the treatment chamber 201, removing residual gases and reaction byproducts (post-purge). Then, the atmosphere in the treatment chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the treatment chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0196] (Crystal boat unloading and chip removal)

[0197] Then, the sealing cover 219 is lowered using the crystal boat lift 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the crystal boat 217, is then moved from the lower end of the manifold 209 to the outside of the reaction tube 203 (crystal boat unloading). After unloading, the gate 219s is moved, sealing the lower opening of the manifold 209 by means of an O-ring 220c (gate closing). After being moved to the outside of the reaction tube 203, the processed wafer 200 is removed from the crystal boat 217 (wafer removal).

[0198] The cleaning, modification, film formation, and heat treatment steps are preferably performed in the same processing chamber (in situ). Therefore, after cleaning the surface of the wafer 200 (removing the native oxide film) using the cleaning step, the modification, film formation, and heat treatment steps can be performed without exposing the wafer 200 to the atmosphere, i.e., while keeping the surface of the wafer 200 clean, allowing for appropriate selective growth. In other words, by performing these steps in the same processing chamber, highly selective growth can be achieved. It should be noted that, where the cleaning step can be omitted as described above, it is preferable to perform the modification, film formation, and heat treatment steps in the same processing chamber. Furthermore, where the heat treatment step can be omitted as described above, it is preferable to perform the modification and film formation steps in the same processing chamber.

[0199] (3) Effects of this method

[0200] According to this method, one or more of the following effects can be obtained.

[0201] By ensuring that WP > DA - WI when WI is less than DA and WP > DAx - WI when WI is greater than DA (where x is the smallest integer satisfying WI < DAx), during the film-forming step, the inhibitor molecules act as effective steric hindrance to the molecule X (raw material molecule) constituting the specific substance contained in the film-forming agent. This prevents molecule X (raw material molecule) from reaching the first surface through the gaps between the inhibitor molecules. Furthermore, this prevents the raw material, as the specific substance contained in the film-forming agent, from contacting the first surface, and inhibits the adsorption (chemisorption, physisorption) of the raw material on the first surface. As a result, selective failure can be suppressed. Additionally, since contact between the raw material and the first surface can be suppressed, even when using a highly reactive substance as the raw material, the reaction between the raw material and the first surface can be suppressed, preventing the detachment of the inhibitor molecules and the associated selective failure caused by this reaction. Therefore, a film can be formed with high precision and selectivity on the desired surface.

[0202] By selecting at least one of the modifier and raw materials to satisfy the above-described relationship, the aforementioned effects can be achieved. Furthermore, by adjusting the state of the adsorption sites on the first surface (the spacing and density of adsorption sites, etc.) to satisfy the above-described relationship, the aforementioned effects can be achieved. It should be noted that it is preferable to adjust the state of the adsorption sites on the first surface (the spacing and density of adsorption sites, etc.) and select at least one of the modifier and raw materials to satisfy the above-described relationship. Furthermore, it is more preferable to adjust the state of the adsorption sites on the first surface (the spacing and density of adsorption sites) and select the types of modifier and raw materials to satisfy the above-described relationship.

[0203] It should be noted that if WI is less than DA and WP ≤ DA - WI is satisfied, then during the film formation step, the inhibitor molecule's steric hindrance effect on molecule X (the raw material molecule) is reduced, and the probability of the raw material contacting the first surface increases. As a result, the aforementioned blocking effect becomes insufficient. Furthermore, if WI is greater than DA and WP ≤ DAx - WI is satisfied, then during the film formation step, the inhibitor molecule's steric hindrance effect on molecule X (the raw material molecule) is reduced, and the probability of the raw material contacting the first surface increases. As a result, the aforementioned blocking effect becomes insufficient.

[0204] In the film formation step, the raw material supply step and the reactant supply step are alternately cycled a predetermined number of times, and the catalyst is supplied to the wafer 200 in at least one of the raw material supply step and the reactant supply step, thereby enabling selective growth with good controllability under the aforementioned low temperature conditions.

[0205] Even when arbitrarily selecting and using the specified substances (gaseous substances or liquid substances) from the various cleaning agents, modifiers, raw materials, reactants, catalysts, and inactive gases mentioned above, the same effect can be obtained.

[0206] (4) Variations

[0207] The substrate processing sequence in this method can be changed as shown in the following variations. These variations can be combined arbitrarily. Unless otherwise specified, the processing steps and conditions in each step of each variation can be the same as the processing steps and conditions in each step of the substrate processing sequence described above.

[0208] (Variation Example 1)

[0209] It can also be like Figure 11 As shown in the substrate processing sequence below, before the modification step, i.e. before the step of forming the inhibitor layer, a step (adsorption site adjustment step) is performed to adjust at least one of the spacing and density of adsorption sites on the first surface of the wafer 200 by supplying an adjustment agent to the wafer 200.

[0210] Regulator → Modifier → (Raw material + Catalyst → Reactant) × n → Heat treatment

[0211] Regulator → Modifier → (Raw Material → Reactant + Catalyst) × n → Heat Treatment

[0212] Regulator → Modifier → (Raw material + Catalyst → Reactant + Catalyst) × n → Heat treatment

[0213] In this case, a cleaning step can also be performed before the adsorption site adjustment step, as shown in the substrate processing sequence below. In this case, the adsorption site adjustment step is performed separately after the cleaning step, thus reducing the focus on adjusting the adsorption sites on the first surface during the cleaning step, and allowing the cleaning step to be performed under processing conditions more dedicated to the cleaning process. As a result, the cleaning process and the adjustment of the adsorption sites on the first surface can be performed with better control.

[0214] Cleaning agent → Conditioner → Modifier → (Raw material + Catalyst → Reactant) × n → Heat treatment

[0215] Cleaning agent → Conditioner → Modifier → (Raw material → Reactant + Catalyst) × n → Heat treatment

[0216] Cleaning agent → Conditioner → Modifier → (Raw material + Catalyst → Reactant + Catalyst) × n → Heat treatment

[0217] In the adsorption site adjustment step, a regulator can be supplied to the wafer 200 by a regulator supply system. By supplying the regulator to the wafer 200 under the processing conditions described later, at least one of the spacing and density of adsorption sites on the first surface of the wafer 200 can be adjusted. For example, the spacing (density) of adsorption sites on the first surface can also be set as follows: Figure 7 The relatively sparse spacing (density) shown can also be set as follows: Figure 8 The spacing (density) shown is relatively close. Then, the modification step, film formation step, and heat treatment step can be performed in the same manner as described above. It should be noted that, similar to the above method, if the film formed on the second surface in the film formation step does not require the removal of impurities, repair of defects, hardening of the film, etc., the heat treatment step can also be omitted.

[0218] Examples of treatment conditions for supplying the regulator in the adsorption site conditioning step include:

[0219] Processing temperature: 100–400℃, preferably 200–350℃

[0220] Processing pressure: 1~101325Pa, preferably 1~13300Pa

[0221] Processing time: 1–240 minutes, preferably 30–120 minutes

[0222] Regulator supply flow rate: 0–20 slm

[0223] Inactive gas supply flow rate (per gas supply tube): 1-20 slm, preferably 2-10 slm.

[0224] It should be noted that it is also possible to adjust at least one of the spacing and density of adsorption sites on the first surface solely through heat treatment (annealing) without supplying a regulator, where the regulator supply flow rate of 0 slm indicates this case. When adjusting the adsorption sites on the first surface using annealing, an inactive gas can be supplied, and this inactive gas can also be referred to as a regulator. When adjusting the adsorption sites on the first surface using annealing, for example, setting the treatment temperature higher, the treatment pressure higher, or the treatment time longer, allows for a sparser spacing (density) of the adsorption sites on the first surface. Conversely, in this case, setting the treatment temperature lower, the treatment pressure lower, or the treatment time shorter, allows for a denser spacing (density) of the adsorption sites on the first surface. Thus, annealing allows for well-controllable adjustment of the spacing (density) of the adsorption sites on the first surface.

[0225] As a regulator, at least one of the various inactive gases, cleaning agents, and oxidizing agents mentioned above can be used. The regulator can be a gaseous substance or a liquid substance. Alternatively, the regulator can be a liquid substance such as a mist. One or more of the above-mentioned regulators can be used.

[0226] When using O- and H-containing gases, various aqueous solutions, or other O- and H-containing substances as oxidants as regulators, the density of OH-terminated groups (OH groups) on the first surface can be increased, and the spacing (density) of adsorption sites on the first surface can be adjusted to be denser. That is, the spacing (density) of adsorption sites on the first surface can be adjusted to be denser using oxidation treatment. It should be noted that, as described later, when using H-containing gases (H-containing substances) as reducing agents as regulators, the density of OH-terminated groups on the first surface can also be increased, and the spacing (density) of adsorption sites on the first surface can be adjusted to be denser. That is, the spacing (density) of adsorption sites on the first surface can be adjusted to be denser using reduction treatment.

[0227] On the other hand, when using substances that do not contain O or H, or substances that do not contain H, as regulators, the density of OH-terminated groups (OH groups) on the first surface can be reduced, and the spacing (density) of adsorption sites can be adjusted to be more sparse. Thus, by exposing substances containing O or H, or substances containing H, to the first surface, or by exposing substances that do not contain O or H, or substances that do not contain H, to the first surface, the spacing (density) of adsorption sites on the first surface can be controlled in a well-regulated manner.

[0228] Furthermore, by sequentially or alternately performing treatments using substances containing O and H, or H-containing substances, as regulators, and treatments using substances not containing O and H, or non-H-containing substances, as regulators, fine adjustments to the aforementioned controls can be achieved. In this case, by controlling each treatment condition, the balance of the degree of regulation in each treatment can be controlled, allowing one of these regulation to become dominant. Thus, the spacing (density) of adsorption sites on the first surface can be adjusted with even better controllability. For example, by sequentially or alternately performing treatments using substances containing O and H as regulators and annealing treatments, the spacing (density) of adsorption sites on the first surface can be adjusted with even better controllability.

[0229] Furthermore, when a cleaning agent is used as a conditioning agent, the spacing (density) of adsorption sites on the first surface can be adjusted in parallel with the removal of the native oxide film formed on the second surface. That is, the removal of the native oxide film on the second surface and the adjustment of the spacing (density) of adsorption sites on the first surface can be performed in a balanced manner (i.e., simultaneously and in parallel). It should be noted that the removal of the native oxide film formed on the second surface using a cleaning agent is equivalent to an etching process. Sometimes, a portion of the first surface is also etched. That is, the cleaning process is also a type of etching process. Using this etching process, the spacing (density) of adsorption sites on the first surface can be adjusted to be sparse. On the other hand, when the cleaning agent is a substance containing O and H, such as an aqueous solution or cleaning liquid, the spacing (density) of adsorption sites on the first surface can be adjusted to be dense. By controlling the processing conditions in the cleaning process, the balance of these adjustments can be controlled, allowing one of these adjustments to become dominant. Therefore, the spacing (density) of adsorption sites on the first surface can be adjusted with good controllability.

[0230] Alternatively, a reducing agent (containing H) can be used as a regulator. That is, the spacing (density) of adsorption sites on the first surface can be adjusted by reduction treatment. For example, H2 gas or D2 gas can be used as a reducing agent. By using a reducing agent as a regulator, the density of OH-terminated sites on the first surface can be increased, and the spacing (density) of adsorption sites on the first surface can be adjusted to be denser.

[0231] Furthermore, the aforementioned regulators can also be used via plasma excitation. That is, the spacing (density) of adsorption sites on the first surface can be adjusted using plasma treatment. In this case, various active species generated by plasma excitation of the aforementioned regulators are supplied to the first surface. For example, when plasma excitation of O- and H-containing substances or H-containing substances is used as a regulator, the density of OH-terminated sites on the first surface can be increased, and the spacing (density) of adsorption sites on the first surface can be adjusted to be denser. On the other hand, when non-O- and H-containing substances or non-H-containing substances are used as regulators via plasma excitation, the density of OH-terminated sites on the first surface can be decreased, and the spacing (density) of adsorption sites can be adjusted to be sparser. Thus, even when plasma excitation of the aforementioned regulators is used, the spacing (density) of adsorption sites on the first surface can be adjusted with good controllability.

[0232] As described above, the spacing (density) of adsorption sites on the first surface can be well controlled and adjusted using at least one of the following methods: heat treatment, cleaning treatment, etching treatment, reduction treatment, oxidation treatment, exposure of the first surface to substances containing O and H, and plasma treatment. It should be noted that by using at least two of the above-mentioned treatments in combination, fine adjustments to the various controls can be achieved, further enabling well-controlled adjustment of the spacing (density) of adsorption sites on the first surface.

[0233] In this modified example, the same effect as described above is also obtained. Furthermore, according to this modified example, by adjusting the spacing (density) of adsorption sites on the first surface in the adsorption site adjustment step, the intermolecular gaps between inhibitor molecules adsorbed on the first surface can be freely adjusted in the modification step. This increases the degree of freedom in the combination of the type of modifier used in the modification step and the type of raw material used in the film-forming step. That is, it increases the degree of freedom in the type of modifier used in the modification step and the degree of freedom in the type of raw material used in the film-forming step.

[0234] (Variation Example 2)

[0235] When processing the wafer 200 using the processing sequence of Modified Example 1, if the adsorption site adjustment step is performed to make DA greater than WI, it is preferable to satisfy WP > DA-WI. In this case, for example, the spacing (density) of the adsorption sites on the first surface is adjusted to satisfy DA > WI and WP > DA-WI. Alternatively, for example, the type of modifier is selected to satisfy DA > WI and WP > DA-WI when the spacing (density) of the adsorption sites on the first surface is adjusted. Alternatively, for example, the type of raw material is selected to satisfy DA > WI and WP > DA-WI when the spacing (density) of the adsorption sites on the first surface is adjusted. Alternatively, for example, the type of modifier and raw material are selected to satisfy DA > WI and WP > DA-WI when the spacing (density) of the adsorption sites on the first surface is adjusted.

[0236] By setting it in this way, such as Figure 9 As shown, the inhibitor molecules act as effective steric hindrance against molecule X (the raw material molecule). This effectively prevents molecule X (the raw material molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecules. In this case, the effect of Modified Example 1 can be obtained more fully. Furthermore, this method also increases the freedom of combination of the types of modifiers and raw materials.

[0237] (Variation Example 3)

[0238] When processing the wafer 200 using the processing sequence of Modified Example 1, if the adsorption site adjustment step is performed to make DA less than WI, it is preferable to satisfy WP > DAx - WI (where x is the smallest integer satisfying WI < DAx). In this case, for example, the spacing (density) of the adsorption sites on the first surface is adjusted to satisfy DA < WI and WP > DAx - WI. Alternatively, for example, the spacing (density) of the adsorption sites on the first surface is adjusted, and the type of modifier is selected to satisfy DA < WI and WP > DAx - WI. Alternatively, for example, the spacing (density) of the adsorption sites on the first surface is adjusted, and the type of raw material is selected to satisfy DA < WI and WP > DAx - WI. Alternatively, for example, the spacing (density) of the adsorption sites on the first surface is adjusted, and the types of modifier and raw material are selected to satisfy DA < WI and WP > DAx - WI.

[0239] By setting it in this way, such as Figure 10 As shown, the inhibitor molecules act as effective steric hindrance against molecule X (the raw material molecule). This effectively prevents molecule X (the raw material molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecules. In this case, the effect of Modified Example 1 can be obtained more fully. Furthermore, this method also increases the freedom of combination of the types of modifiers and raw materials.

[0240] (Variation Example 4)

[0241] As shown in the substrate processing sequence below, a catalyst can also be omitted in the film formation step. The catalyst is not essential, and its supply can be omitted depending on the processing conditions. The same effect as described above can be obtained in this variation. Furthermore, according to this variation, the amount of material used in the film formation step can be reduced, thus lowering gas costs. In addition, the processing sequence can be simplified, as can the configuration of the control system and gas supply system.

[0242] Modifier → (raw material → reactant) × n

[0243] Cleaning agent → Modifier → (Raw material → Reactant) × n

[0244] Regulator → Modifier → (Raw Material → Reactant) × n

[0245] Cleaning agent → Conditioner → Modifier → (Raw material → Reactant) × n

[0246] Modifier → (raw material → reactant) × n → heat treatment

[0247] Cleaning agent → Modifier → (Raw material → Reactant) × n → Heat treatment

[0248] Regulator → Modifier → (Raw Material → Reactant) × n → Heat Treatment

[0249] Cleaning agent → Conditioner → Modifier → (Raw material → Reactant) × n → Heat treatment

[0250] (Variation Example 5)

[0251] As shown in the substrate processing sequence below, when the above-described cycles are performed a predetermined number of times, a modification step can also be performed in each cycle. The same effect as described above and in each of the other modifications can be obtained in this modified example. Furthermore, according to this modified example, by performing the modification step in each cycle, the film-forming resistance effect (adsorption resistance effect, reaction resistance effect) caused by the inhibitor layer can be further improved.

[0252] (Modifier → Raw Material → Reactant) × n

[0253] Cleaning agent → (modifier → raw material → reactant) × n

[0254] Regulator → (Modifier → Raw Material → Reactant) × n

[0255] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant) × n

[0256] (Modifier → Raw material → Reactant) × n → Heat treatment

[0257] Cleaning agent → (modifier → raw material → reactant) × n → heat treatment

[0258] Modifier → (Modifier → Raw material → Reactant) × n → Heat treatment

[0259] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant) × n → Heat treatment

[0260] (Variation Example 6)

[0261] Alternatively, the substrate processing sequence can be configured as shown below, in which a reactant functioning as a regulator is used as the reactant in the reactant supply step, or a regulator is further supplied. The same effect as described above and in Modification 5 can be obtained in this modification. Furthermore, according to this modification, an adsorption site adjustment step can be performed in each cycle, and the above-described relationship can be satisfied with high precision in each cycle, further improving the film formation inhibition effect (adsorption inhibition effect, reaction inhibition effect) caused by the inhibitor layer. Additionally, according to this modification, the reactant supply step and the adsorption site adjustment step can be performed in a balanced manner (i.e., simultaneously and in parallel), eliminating the need for a separate adsorption site adjustment step after the second cycle. As a result, the processing time can be shortened, and the substrate processing throughput, i.e., the substrate processing productivity, can be increased. It should be noted that the following example illustrates a processing sequence based on Modification 5, but this modification is also applicable to various processing sequences of the above-described methods and various modifications.

[0262] (Modifier → Raw Material → Reactant (Regulator)) × n

[0263] Cleaning agent → (modifier → raw material → reaction mixture (regulator)) × n

[0264] Modifier → (Modifier → Raw Material → Reactant (Modifier)) × n

[0265] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant (conditioner)) × n (Modifier → Raw material → Reactant (conditioner)) × n → Heat treatment

[0266] Cleaning agent → (modifier → raw material → reaction body (regulator)) × n → heat treatment

[0267] Modifier → (Modifier → Raw material → Reactant (modifier)) × n → Heat treatment

[0268] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant (conditioner)) × n → Heat treatment

[0269] (Modifier → Raw material → Reactant + Regulator) × n

[0270] Cleaning agent → (modifier → raw material → reactant + regulator) × n

[0271] Modifier → (Modifier → Raw material → Reactant + Modifier) ​​× n

[0272] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant + Conditioner) × n

[0273] (Modifier → Raw material → Reactant + Conditioner) × n → Heat treatment

[0274] Cleaning agent → (modifier → raw material → reactant + regulator) × n → heat treatment

[0275] Modifier → (Modifier → Raw material → Reactant + Modifier) ​​× n → Heat treatment

[0276] Cleaning agent → Conditioner → (Modifier → Raw material → Reactant + Conditioner) × n → Heat treatment

[0277] (Variation Example 7)

[0278] The specific substance contained in the film-forming agent can also be a reactant. That is, molecule X can also be a reactant molecule. When molecule X is a reactant molecule, by satisfying the above-described relationship, the inhibitor molecule acts as an effective steric hindrance to molecule X (the reactant molecule). Therefore, it is possible to inhibit molecule X (the reactant molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecules. Furthermore, it is possible to inhibit the contact between the reactant, which is a specific substance contained in the film-forming agent, and the first surface, and to inhibit the reaction caused by the reactant on the first surface. Thus, the same effect as described above can be obtained.

[0279] It should be noted that, in this case, even assuming the use of a raw material with a small molecular size, where the raw material reaches the first surface through the intermolecular gaps of the inhibitor molecules, contact between the reactant and the first surface can be suppressed, thus suppressing the reaction caused by the reactant on the first surface. Furthermore, in this case, even assuming the use of a catalyst with a small molecular size, where the catalyst reaches the first surface through the intermolecular gaps of the inhibitor molecules, contact between the reactant and the first surface can be suppressed, thus suppressing the reaction caused by the reactant on the first surface. As a result, selection failure can be suppressed. Moreover, since contact between the reactant and the first surface can be suppressed, even when a highly reactive substance is used as the reactant, the reaction between the reactant and the first surface can be suppressed, thus suppressing the detachment of inhibitor molecules and the associated selection failure caused by this reaction.

[0280] (Variation Example 8)

[0281] The specific substance contained in the film-forming agent can also be a catalyst. That is, molecule X can also be a catalyst molecule. When molecule X is a catalyst molecule, by satisfying the above-mentioned relationship, the inhibitor molecule acts as an effective steric hindrance to molecule X (catalyst molecule). As a result, it is possible to inhibit molecule X (catalyst molecule) from reaching the first surface through the intermolecular gaps of the inhibitor molecules. Furthermore, it is possible to inhibit the catalyst, as the specific substance contained in the film-forming agent, from contacting the first surface, and to inhibit the catalyst reaction caused by the catalyst on the first surface. Thus, the same effect as described above can be obtained.

[0282] It should be noted that, in this case, even assuming the use of a small-molecule raw material, if the raw material reaches the first surface through the intermolecular gaps of the inhibitor molecules, the contact between the catalyst and the first surface can be suppressed, thus suppressing the catalyst-induced reaction on the first surface. Furthermore, even assuming the use of a small-molecule reactant, if the reactant reaches the first surface through the intermolecular gaps of the inhibitor molecules, the contact between the catalyst and the first surface can be suppressed, thus suppressing the catalyst-induced reaction on the first surface. As a result, selection failure can be suppressed. Moreover, since the contact between the catalyst and the first surface can be suppressed, even when using a highly reactive substance as the catalyst, the reaction between the catalyst and the first surface can be suppressed, preventing the desorption of inhibitor molecules and the associated selection failure caused by this reaction.

[0283] (Variation Example 9)

[0284] The specific substance contained in the film-forming agent may also include at least one of the raw material and the reactant. For example, the specific substance may include the raw material as described above, or it may include the reactant as in Modification 7, or it may include both the raw material and the reactant. When the specific substance includes both the raw material and the reactant, the above-mentioned barrier effect can be further improved.

[0285] (Variation Example 10)

[0286] The specific substance contained in the film-forming agent may also include at least one of the raw material, reactant, and catalyst. For example, the specific substance may include the raw material as described above, the reactant as in Modification 7, or the catalyst as in Modification 8. Furthermore, for example, the specific substance may include the raw material and reactant as in Modification 9, or the raw material and catalyst, or the reactant and catalyst, or the raw material, reactant, and catalyst. In these cases, the barrier effect can be further improved. It should be noted that when the specific substance includes the raw material, reactant, and catalyst, the contact probability between the raw material, reactant, and catalyst and the first surface becomes the lowest, and the barrier effect is optimal.

[0287] (Variation Example 11)

[0288] The inhibitor molecule may also contain at least one of a hydrocarbon group, a fluorinated carbon group, or a fluorinated silyl group. That is, the inhibitor layer formed on the first surface may also contain at least one of a hydrocarbon end cap, a fluorinated carbon end cap, or a fluorinated silyl end cap. When the inhibitor molecule contains a hydrocarbon group, it is the same as described above.

[0289] When the inhibitor molecule contains a fluorinated carbon group, gases such as the amino-containing gas or the gas containing both amino and alkyl groups, and the F-containing gas described above, can be supplied to the wafer 200 sequentially or simultaneously as modifiers. It should be noted that when the inhibitor molecule contains a fluorinated carbon group, the modifier can also be a gas obtained by replacing part or all of the CH bonds of the alkyl groups with F, as described above, among the amino and alkyl-containing gases. Through at least one of the above methods, the inhibitor layer formed on the first surface is end-capped with fluorinated carbon.

[0290] Furthermore, when the inhibitor molecule contains fluorinated silyl groups, an amino-containing gas, such as the aforementioned aminosilane-based gas, and an F-containing gas, can be used as modifiers, and these gases can be supplied to the wafer 200 sequentially or simultaneously. Thus, the inhibitor layer formed on the first surface contains fluorinated silyl end caps.

[0291] It should be noted that in any of the above cases, the outermost surface of the inhibitor layer is F, therefore it can also be referred to as F-terminated. In the film-forming step, the fluorinated carbon-based or fluorinated silyl group that terminates the first surface can prevent the raw material (film-forming agent) from adsorbing onto the first surface, thus hindering (inhibiting) the film-forming reaction on the first surface. The same effect as described above can be obtained in this modified example.

[0292] <Other ways of publishing this text>

[0293] The foregoing has provided a detailed description of the manner in which this disclosure is made. However, this disclosure is not limited to the manner described above and various changes may be made without departing from its essence.

[0294] For example, wafer 200 may include at least one of an oxygen-containing film and a metal-containing film as a first surface (first substrate), and may also include at least one of a non-oxygen-containing film and a non-metal-containing film as a second surface (second substrate). Furthermore, for example, wafer 200 may have multiple regions of different materials as the first surface (first substrate), and may also have multiple regions of different materials as the second surface (second substrate). As the region (substrate) constituting the first and second surfaces, in addition to the aforementioned SiO and SiN films, it can also be a film containing semiconductor elements such as silicon-oxygen-carbon-nitrogen film (SiOCN film), silicon-oxygen-carbon film (SiOC film), silicon-oxygen-nitrogen film (SiON film), silicon-carbon-nitrogen film (SiCN film), silicon carbide film (SiC film), silicon-boron-carbon-nitrogen film (SiBCN film), silicon-boron-nitrogen film (SiBN film), silicon-boron-carbon film (SiBC film), silicon film (Si film), germanium film (Ge film), and silicon-germanium film (SiGe film); a film containing metal elements such as titanium-nitrogen film (TiN film), tungsten film (W film), molybdenum film (Mo film), ruthenium film (Ru film), cobalt film (Co film), nickel film (Ni film), and copper film (Cu film); amorphous carbon film (aC film); and single-crystal Si (Si wafer), etc. Any region (substrate) that can form an inhibitor layer can be used as the first surface. On the other hand, any region (substrate) that is difficult to form an inhibitor layer can be used as a second surface. The same effect as described above is achieved in this method.

[0295] Alternatively, in addition to SiOC and SiO films, the growth process can be configured to form films containing semiconductor elements such as SiON, SiOCN, SiCN, SiC, SiN, SiBCN, SiBN, SiBC, Si, Ge, and SiGe films; and films containing metal elements such as TiN, W, WN, Mo, Ru, Co, Ni, Al, AlN, TiO, WO, WON, MoO, RuO, CoO, NiO, AlO, ZrO, HfO, and TaO films. The same effects as described above can be obtained when these films are formed.

[0296] The processes used in each process are prepared individually according to the processing content, and it is preferable to store them in the storage device 121c in advance via an electrical communication line and an external storage device 123. Furthermore, when starting each process, it is preferable for the CPU 121a to appropriately select a suitable process from the multiple processes stored in the storage device 121c according to the processing content. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses within a single substrate processing apparatus. Additionally, it reduces the operator's workload, avoids operational errors, and enables the rapid initiation of each process.

[0297] The aforementioned process is not limited to newly manufactured cases; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can also be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the modified process. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be operated to directly modify the existing process already installed in the substrate processing apparatus.

[0298] The above method describes an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time. This disclosure is not limited to the above method; for example, it can also be suitably applied when forming a film using a monolithic substrate processing apparatus that processes one or several substrates at a time. Furthermore, the above method describes an example of forming a film using a substrate processing apparatus with a hot-wall type furnace. This disclosure is not limited to the above method; it can also be suitably applied when forming a film using a substrate processing apparatus with a cold-wall type furnace.

[0299] When using these substrate processing apparatuses, each process can be performed under the same processing steps and conditions as described above and in the modified examples, and the same effects as described above and in the modified examples can be obtained.

[0300] The above methods and variations can be used in appropriate combinations. The processing steps and conditions in this case can be the same as those in the above methods and variations.

[0301] Example

[0302] <Example 1>

[0303] For a wafer having a first and second surface identical to those described above, the processing sequence of Modified Example 1 described above was performed to form a SiOC film on the second surface, thus producing Evaluation Sample 1 of Example 1. When producing Evaluation Sample 1, the adsorption sites (OH groups) were adjusted using an annealing treatment to satisfy DA > WI and WP > DA-WI. It should be noted that WP is defined as the width of the raw material molecule constituting the specific substance contained in the film-forming agent. The processing conditions in each step of producing Evaluation Sample 1 were set to specified conditions within the range of the processing conditions in each step described above. It should be noted that in the annealing treatment used for adjusting the adsorption sites, the processing temperature was set to 300–350°C.

[0304] <Example 2>

[0305] For a wafer having the same first and second surfaces as described above, the processing sequence of Modified Example 1 was performed to form a SiOC film on the second surface, thus producing Evaluation Sample 2 of Example 2. When producing Evaluation Sample 2, the adsorption sites (OH groups) were adjusted using an annealing treatment to satisfy DA < WI and WP > DAx - WI (x is the smallest integer satisfying WI < DAx). It should be noted that WP is defined as the width of the raw material molecule constituting the raw material of the specific substance contained in the film-forming agent. Except for the processing conditions in the annealing treatment used for adsorption site adjustment, the processing conditions in each step of producing Evaluation Sample 2 were the same as those in each step of Example 1. It should be noted that in the annealing treatment used for adsorption site adjustment, the processing temperature was set to 100–200°C.

[0306] <Comparative Example 1>

[0307] For a wafer having the same first and second surfaces as described above, the same processing sequence as in Modified Example 1 was performed to form a SiOC film on the second surface, thus producing Evaluation Sample 3 of Comparative Example 1. When producing Evaluation Sample 3, the adsorption sites (OH groups) were adjusted using an annealing treatment to satisfy DA > WI and WP ≤ DA-WI. It should be noted that WP is defined as the width of the raw material molecule constituting the specific substance contained in the film-forming agent. Except for the processing conditions in the annealing treatment used for adsorption site adjustment, the processing conditions in each step of producing Evaluation Sample 3 were the same as those in each step of Example 1. It should be noted that in the annealing treatment used for adsorption site adjustment, the processing temperature was set to 500–600°C.

[0308] After preparing each evaluation sample, the difference between the thickness of the SiOC film formed on the second surface and the thickness of the SiOC film formed on the first surface (hereinafter, film thickness difference) in each evaluation sample was measured. That is, the difference obtained by subtracting the thickness of the SiOC film formed on the first surface from the thickness of the SiOC film formed on the second surface in the evaluation sample was measured.

[0309] The results confirmed that the film thickness difference of evaluation samples 1 and 2 was quite large compared to that of evaluation sample 3. Compared to evaluation sample 3 in comparative example 1, evaluation samples 1 and 2 in examples 1 and 2 could obtain a considerably high selectivity.

Claims

1. A substrate processing method, which has the following characteristics: (A) The step of forming an inhibitor layer on the first surface by supplying a modifier to a substrate having a first surface and a second surface; and (B) The step of forming a film on the second surface by supplying a film-forming agent to the substrate after the inhibitor layer has been formed on the first surface. So that when the width of the inhibitor molecules constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface is set to DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is set to WP, When WI is less than DA, WP > DA - WI is satisfied. When WI is greater than DA, WP > DAx - WI is satisfied, where, x is the smallest integer satisfying WI < DAx, and the specific substance is at least one of the raw materials and the reactants. The substrate processing method further comprises, prior to (A), (C) a step of conditioning DA by means of at least one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of the substrate to a substance containing oxygen and hydrogen.

2. The substrate processing method as described in claim 1, wherein, The type of modifier is selected in a manner that satisfies DA > WI and WP > DA-WI or in a manner that satisfies DA < WI and WP > DAx-WI.

3. The substrate processing method as described in claim 1, wherein, The type of the specific substance is selected in a manner that satisfies DA > WI and WP > DA-WI or in a manner that satisfies DA < WI and WP > DAx-WI.

4. The substrate processing method as described in claim 1, wherein, In (C), DA is adjusted in a manner that satisfies DA > WI and WP > DA-WI or in a manner that satisfies DA < WI and WP > DAx-WI.

5. The substrate processing method according to any one of claims 1 to 4, wherein, The adsorption sites on the first surface contain OH groups.

6. The substrate processing method according to any one of claims 1 to 4, wherein, The first surface comprises at least one of an oxygen-containing film and a metal-containing film, and the second surface comprises at least one of a non-oxygen-containing film and a non-metal-containing film.

7. The substrate processing method according to any one of claims 1 to 4, wherein, The inhibitor molecule comprises at least one of a hydrocarbon group, a fluorinated carbon group, and a fluorinated silyl group.

8. The substrate processing method according to any one of claims 1 to 4, wherein, The film-forming agent comprises a raw material and a reactant, and the specific substance comprises at least one of the raw material and the reactant.

9. The substrate processing method as described in claim 8, wherein, In (B), the cycle comprising (B1) supplying the raw material to the substrate and (B2) supplying the reactant to the substrate is performed a specified number of times.

10. The substrate processing method according to any one of claims 1 to 4, wherein, The film-forming agent comprises the raw material, the reactant and the catalyst, and the specific substance comprises at least one of the raw material and the reactant.

11. The substrate processing method as described in claim 10, wherein, In (B), a cycle comprising (B1) supplying the raw material to the substrate and (B2) supplying the reactant to the substrate is performed a predetermined number of times, wherein the catalyst is supplied to the substrate in at least one of (B1) and (B2).

12. The substrate processing method according to any one of claims 1 to 4, wherein, Before (C), there is also a step of removing the natural oxide film formed on the surface of the substrate.

13. The substrate processing method according to any one of claims 1 to 4, wherein, After (B), there is also a step of heat treatment of the substrate.

14. The substrate processing method according to any one of claims 1 to 4, wherein, After (B), there is a step of removing at least a portion of the inhibitor layer and invalidating at least one of the following:

15. A method for manufacturing a semiconductor device, comprising: (A) The step of forming an inhibitor layer on the first surface by supplying a modifier to a substrate having a first surface and a second surface; and (B) The step of forming a film on the second surface by supplying a film-forming agent to the substrate after the inhibitor layer has been formed on the first surface. So that when the width of the inhibitor molecules constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface is set to DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is set to WP, When WI is less than DA, WP > DA - WI is satisfied. When WI is greater than DA, WP > DAx - WI is satisfied, where, x is the smallest integer satisfying WI < DAx, and the specific substance is at least one of the raw materials and the reactants. The manufacturing method further comprises, prior to (A), (C) a step of conditioning DA by means of at least one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of the substrate to a substance containing oxygen and hydrogen.

16. A substrate processing apparatus, comprising: A modifier supply system that supplies modifiers to a substrate; Film-forming agent supply system, which supplies film-forming agent to the substrate; and The control unit is configured to control the operation of the substrate processing apparatus to perform: (A) a process of forming an inhibitor layer on the first surface by supplying the modifier to a substrate having a first surface and a second surface, and (B) a process of forming a film on the second surface by supplying the film-forming agent to the substrate after the inhibitor layer has been formed on the first surface, and wherein, when the width of the inhibitor molecules constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface is set to DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is set to WP, when WI is less than DA, WP > DA - WI, and when WI is greater than DA, WP > DAx - WI, wherein... x is the smallest integer satisfying WI < DAx, and the specific substance is at least one of the raw materials and the reactants. The control unit also performs the following process through the control: before performing (A), performing (C) to adjust DA by at least any one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of the substrate to oxygen- and hydrogen-containing substances.

17. A computer-readable recording medium having a program recorded thereon that enables a substrate processing apparatus to perform the following steps using a computer: (A) The step of forming an inhibitor layer on the first surface by supplying a modifier to a substrate having a first surface and a second surface; (B) The step of forming a film on the second surface by supplying a film-forming agent to the substrate after the inhibitor layer has been formed on the first surface; In the case where the width of the inhibitor molecules constituting the inhibitor layer is set to WI, the spacing of the adsorption sites on the first surface is set to DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is set to WP, the steps are as follows: when WI is less than DA, WP > DA - WI; when WI is greater than DA, WP > DAx - WI. x is the smallest integer satisfying WI < DAx, and the specific substance is at least one of the raw materials and the reactants; and Before (A), (C) is performed to adjust DA by at least one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of the substrate to oxygen- and hydrogen-containing substances.

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