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

Abstract

The present application provides the following technology: (a) a process of supplying a film formation hindering gas to a substrate in which a first base and a second base are exposed on a surface, forming a film formation hindering layer on the surface of the first base; (b) a process of supplying a film formation gas to the substrate after the film formation hindering layer is formed on the surface of the first base, forming a film on the surface of the second base; and (c) a process of supplying a halogen-free substance that chemically reacts with the film formation hindering layer and the film to the substrate after the film is formed on the surface of the second base in an atmosphere free of plasma.

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, the following process is sometimes performed: selectively growing and forming a film on the surface of a specific substrate among a variety of substrates exposed on the surface of a substrate (hereinafter, this process is also referred to as selective growth or selective film formation) (for example, see Japanese Patent Application Publication No. 2013-243193). Summary of the Invention

[0003] The problem that the invention aims to solve

[0004] In selective growth, before selectively growing a film on the surface of a specific substrate, the following treatment is sometimes performed: a film-forming barrier is formed on the surface of the substrate on which film growth is not desired using a film-forming barrier agent.

[0005] However, when selectively growing a film after the aforementioned treatment to form a barrier layer, the processing temperature (film formation temperature) cannot be increased to suppress the detachment of the barrier layer, sometimes resulting in deterioration of the film quality. Furthermore, after selective growth, a step to remove the barrier layer is sometimes required, leading to a decrease in productivity.

[0006] The purpose of this disclosure is to provide techniques that can improve the membrane quality of membranes formed by selective growth and increase productivity.

[0007] Methods for solving problems

[0008] According to one aspect of this disclosure, the following technology is provided, which performs:

[0009] (a) A process of supplying a film-forming barrier gas to a substrate on which the first substrate and the second substrate are exposed on the surface, thereby forming a film-forming barrier layer on the surface of the first substrate;

[0010] (b) A step of supplying a film-forming gas to the substrate after the aforementioned film-forming barrier layer has been formed on the surface of the aforementioned first substrate, thereby forming a film on the surface of the aforementioned second substrate; and

[0011] (c) A process of supplying a halogen-free substance that chemically reacts with the film-forming barrier layer and the film to the substrate after the film has been formed on the surface of the second substrate in a non-plasma atmosphere.

[0012] The effects of the invention

[0013] According to this disclosure, it is possible to improve the membrane quality of membranes formed by selective growth and increase productivity. Attached Figure Description

[0014] [ Figure 1 ] Figure 1 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferred in one embodiment of this disclosure, and is a diagram showing the processing furnace 202 portion in a longitudinal sectional view.

[0015] [ Figure 2 ] Figure 2 This is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferred in one embodiment of this disclosure, and is based on... Figure 1 The AA-line sectional view shows part of the processing furnace 202.

[0016] [ Figure 3 ] Figure 3 This is a schematic configuration diagram of the controller 121 of a substrate processing apparatus preferred in one embodiment of this disclosure, and a block diagram showing the control system of the controller 121.

[0017] [ Figure 4 ] Figure 4 A diagram illustrating one method of selecting the processing order in the growth process of this disclosure.

[0018] [ Figure 5 ] Figure 5 (a)~ Figure 5 (d) is an enlarged cross-sectional view of the surface of the wafer 200 during each step of the growth process in one of the modes of this disclosure. Figure 5 (a) is an enlarged cross-sectional view of the surface of the wafer 200 on which the substrates 200a and 200b are exposed. Figure 5 (b) is a cross-sectional enlarged view of the surface of the wafer 200 after a film-forming barrier layer 310 is formed on the surface of the substrate 200a by supplying a film-forming barrier gas to the wafer 200. Figure 5 (c) is an enlarged cross-sectional view of the surface of the wafer 200 after film 320 is formed on the surface of the substrate 200b by supplying film-forming gas to the wafer 200. Figure 5 (d) is a magnified cross-sectional view of the surface of the wafer 200 after the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200, and the film 320 formed on the surface of the substrate 200b is changed into a film 330 with improved film quality compared to the film 320.

[0019] [ Figure 6 ] Figure 6 (a)~ Figure 6(d) is an enlarged cross-sectional view of the surface of the wafer 200 in each step of the growth process of a variant of this disclosure. Figure 6 (a)~ Figure 6 (c) each as and Figure 5 (a)~ Figure 5 (c) Enlarged view of the same cross-section. Figure 6 (d) is a magnified cross-sectional view of the surface of the wafer 200 after the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200 and changing the composition ratio of the film 320 formed on the surface of the substrate 200b, thereby changing the film 320 into a film 340 with a different composition ratio than the film 320.

[0020] [ Figure 7 ] Figure 7 (a)~ Figure 7 (d) is an enlarged cross-sectional view of the surface of the wafer 200 in each step of the growth process of Variation 2 of this disclosure. Figure 7 (a)~ Figure 7 (c) each as and Figure 5 (a)~ Figure 5 (c) Enlarged view of the same cross-section. Figure 7 (d) is an enlarged cross-sectional view of the surface of the wafer 200 after the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed by supplying a halogen-free substance to the wafer 200 and adding other elements not contained in the film 320 formed on the surface of the substrate 200b to the film 320, thereby changing the film 320 into a film 350 (which is formed by adding other elements to the film 320).

[0021] [ Figure 8 ] Figure 8 (a)~ Figure 8 (d) is an enlarged cross-sectional view of the surface of the wafer 200 in each step of the growth process of Variation 3 of this disclosure. Figure 8 (a)~ Figure 8 (c) each as and Figure 5 (a)~ Figure 5 (c) Enlarged view of the same cross-section. Figure 8 (d) is a magnified cross-sectional view of the surface of the wafer 200 after the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200, and the film 320 formed on the surface of the substrate 200b is changed into a film 360 with a different chemical structure than the film 320.

[0022] [ Figure 9 ] Figure 9 (a)~ Figure 9 (d) is an enlarged cross-sectional view of the surface of the wafer 200 in each step of the growth process of Variation 4 of this disclosure. Figure 9 (a)~ Figure 9 (c) are respectively with Figure 5 (a)~ Figure 5 (c) Enlarged view of the same cross-section. Figure 9 (d) is an enlarged cross-sectional view of the surface of the wafer 200 after a portion of the film formation barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200, and a portion of the film 320 formed on the surface of the substrate 200b is changed to a film 370 with a chemical structure different from that of the film 320. Detailed Implementation

[0023] <One way of publishing this text>

[0024] The following is mainly based on Figures 1-4 , Figure 5 (a)~ Figure 5 (d) describes one way of presenting this disclosure. It should be noted that the accompanying drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings do not necessarily correspond to the actual situation. Furthermore, the dimensional relationships and ratios of the elements in multiple drawings are not necessarily consistent with each other.

[0025] (1) Composition of substrate processing device

[0026] 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.

[0027] 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), forming a cylindrical shape that is closed at the top and open at the bottom. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), forming a cylindrical shape that is open at both the top and bottom. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing component. The reaction tube 203 is installed vertically, just like the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow part of the cylindrical processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within the processing chamber 201.

[0028] Nozzles 249a to 249c, serving as first to third supply units, are respectively provided in the processing chamber 201, penetrating the side wall of the manifold 209. Nozzles 249a to 249c are also referred to as the first to third nozzles. Nozzles 249a to 249c are made of heat-resistant materials such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c respectively. Nozzles 249a to 249c are each different nozzles, and each of nozzles 249a and 249c is arranged adjacent to nozzle 249b.

[0029] 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. Downstream of gas supply pipe 232a, gas supply pipes 232d and 232e are connected. Downstream of gas supply pipe 232b, gas supply pipes 232f and 232h are connected. Downstream of gas supply pipe 232c, gas supply pipe 232g is connected. 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.

[0030] like Figure 2As shown, nozzles 249a to 249c are respectively arranged in a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200, rising upwards from the lower part of the inner wall of the reaction tube 203 along the arrangement direction of the wafer 200. That is, nozzles 249a to 249c are respectively arranged in a horizontally surrounding area of ​​the wafer arrangement region on the side of the wafer arrangement region for arranging the wafer 200. In plan view, nozzle 249b is arranged opposite the exhaust port 231a (described later) in a straight line across the center of the wafer 200 that is loaded into the processing chamber 201. Nozzles 249a and 249c are arranged to be held from both sides by a straight line L passing through the center of nozzle 249b and exhaust port 231a 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, sandwiching a straight line L. Nozzles 249a and 249c are arranged linearly symmetrically about the straight line L. Gas supply holes 250a to 250c are provided on the sides of nozzles 249a and 249c, respectively. Gas supply holes 250a to 250c open in a manner opposite (facing) the exhaust port 231a when viewed from above, and can supply gas toward the wafer 200. Multiple gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0031] Film-forming barrier gas is supplied from gas supply pipe 232a to processing chamber 201 via MFC 241a, valve 243a, and nozzle 249a.

[0032] Raw material gas is supplied to the processing chamber 201 from the gas supply pipe 232b via MFC 241b, valve 243b, and nozzle 249b.

[0033] The reaction gas is supplied into the processing chamber 201 from the gas supply pipe 232c via MFC 241c, valve 243c, and nozzle 249c. The reaction gas may also contain substances that function as halogen-free substances as described later, and therefore halogen-free substances may also be supplied into the processing chamber 201 via MFC 241c, valve 243c, and nozzle 249c.

[0034] Catalyst gas is supplied to the processing chamber 201 from the gas supply pipe 232d, via MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a.

[0035] Inactive gases are supplied to the processing chamber 201 from gas supply pipes 232e to 232g via MFC 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively.

[0036] A halogen-free substance is supplied to the processing chamber 201 from the gas supply pipe 232h via MFC 241h, valve 243h, gas supply pipe 232b, and nozzle 249b.

[0037] The system primarily consists of a film-forming barrier gas supply system (comprising gas supply pipe 232a, MFC 241a, and valve 243a). The system primarily consists of a feedstock gas supply system (comprising gas supply pipe 232b, MFC 241b, and valve 243b). The system primarily consists of a reaction gas supply system (comprising gas supply pipe 232c, MFC 241c, and valve 243c). The system primarily consists of a catalyst gas supply system (comprising gas supply pipe 232d, MFC 241d, and valve 243d). The system primarily consists of inactive gas supply systems (comprising gas supply pipes 232e-232g, MFC 241e-241g, and valves 243e-243g). The system primarily consists of a halogen-free substance supply system (comprising gas supply pipe 232h, MFC 241h, and valve 243h).

[0038] Here, the feed gas, reactant gas, and catalyst gas function as film-forming gases; therefore, the feed gas supply system, reactant gas supply system, and catalyst gas supply system can also be referred to as the film-forming gas supply system. Additionally, the reactant gas sometimes functions as a halogen-free substance; therefore, the reactant gas supply system can also be referred to as a halogen-free substance supply system. That is, the halogen-free substance supply system can be constructed from gas supply pipe 232c, MFC 241c, and valve 243c.

[0039] Any one or all of the aforementioned supply systems can also be configured as an integrated supply system 248, which integrates valves 243a-243h, MFCs 241a-241h, etc. The integrated supply system 248 is configured such that it is connected to each of the gas supply pipes 232a-232h, and the supply of various gases to the gas supply pipes 232a-232h, i.e., the opening and closing of valves 243a-243h, and the flow regulation by MFCs 241a-241h, are controlled by the controller 121 described later. The integrated supply system 248 is configured as an integrated unit, either as a single unit or as separate units, and is configured such that it can be disassembled and assembled relative to the gas supply pipes 232a-232h, etc., and that the integrated supply system 248 can be maintained, replaced, or added to in units.

[0040] An exhaust port 231a is provided below the side wall of the reaction tube 203 for exhausting the atmosphere inside the processing chamber 201. For example... Figure 2As shown, the exhaust port 231a, viewed from above, is positioned opposite (facing) the nozzles 249a-249c (gas supply holes 250a-250c) while the wafer 200 is clamped. The exhaust port 231a may also be positioned 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 (which detects the pressure inside the processing chamber 201) and an APC (Auto Pressure Controller) valve 244 (which acts as a pressure regulator). The APC valve 244 is configured such that by opening and closing the valve while the vacuum pump 246 is operating, vacuum exhaust and vacuum exhaust cessation within the processing chamber 201 can be performed. 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 exhaust pipe 231, APC valve 244, and pressure sensor 245. Including vacuum pump 246 in the exhaust system could be considered.

[0041] 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. An O-ring 220b, serving as a sealing member, is provided on the upper surface of the sealing cover 219 and 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 transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219.

[0042] Below the manifold 209 is a gate 219s serving as a furnace opening cover. 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. An O-ring 220c, serving as a sealing component, is provided on the upper surface of the gate 219s, abutting 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.

[0043] The crystal boat 217, serving as a substrate support, is configured to hold multiple wafers 200, for example, 25 to 200 wafers 200 arranged horizontally and aligned at their centers in a vertical direction, supported in a multi-layered manner, i.e., spaced apart. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. A heat-insulating plate 218, also made of a heat-resistant material such as quartz or SiC, is supported in multiple layers at the bottom of the crystal boat 217.

[0044] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. The energizing of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263 to achieve the desired temperature distribution within the processing chamber 201. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203.

[0045] like Figure 3 As shown, the controller 121, which serves as the control unit (control unit), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121.

[0046] Storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. Storage device 121c stores in a readable manner a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions, as described later. The process flow is a combination of methods that enable controller 121 to execute each step of the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, process flow, control program, etc., will also be referred to as a program. Furthermore, process flow will be referred to simply as a process. In this specification, the term "program" is used in cases where only a process flow is included, cases where only a control program is included, or cases where both are included. RAM 121b is configured as a memory area (working area) that temporarily holds the program, data, etc., read by CPU 121a.

[0047] 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.

[0048] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on inputs 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 gases by MFCs 241a to 241h, opening and closing of valves 243a to 243h, opening and closing of APC valve 244 and pressure regulation based on pressure sensor 245 using APC valve 244, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and speed regulation of crystal boat 217 using rotating mechanism 267, lifting of crystal boat 217 using crystal boat elevator 115, opening and closing of gate 219s using gate opening and closing mechanism 115s, etc.

[0049] The controller 121 can be configured to install the aforementioned program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a USB memory, and a semiconductor memory such as an SSD. 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" includes cases where only the storage device 121c is included, cases where only the external storage device 123 is included, or cases where both are included. It should be noted that the program provided to the computer may also be delivered using communication units such as the Internet or dedicated lines without using the external storage device 123.

[0050] (2) Substrate processing process

[0051] Main use Figure 4 , Figure 5 (a)~ Figure 5 Example (d) illustrates the following selective growth (selective film formation) process sequence: Using the substrate processing apparatus described above, as a step in the manufacturing process of a semiconductor device, a film is selectively grown and formed on the surface of a specific substrate among various substrates exposed on the surface of the wafer 200, which serves as the substrate. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0052] exist Figure 4 In the processing sequence shown, the following steps are performed:

[0053] Step A: Supplying a film-forming barrier gas to a wafer 200 that exposes a substrate 200a as a first substrate and a substrate 200b as a second substrate on its surface to form a film-forming barrier layer 310 on the surface of the substrate 200a.

[0054] Step B involves supplying film-forming gases (raw material gas, reactant gas, catalyst gas) to the wafer 200 after forming a film-forming barrier layer 310 on the surface of substrate 200a, to form a film 320 on the surface of substrate 200b; and

[0055] Step C involves supplying a halogen-free substance to the wafer 200 after a film 320 has been formed on the surface of the substrate 200b, under a non-plasma atmosphere, to react chemically with the film-forming barrier layer 310 and the film 320.

[0056] Here, step A is also referred to as film-forming barrier layer formation. Step B is also referred to as selective growth. Step C is also referred to as post-treatment. As mentioned above, the film-forming gases used in step B include feed gas, reactant gas, and catalyst gas.

[0057] It should be noted that, regarding Figure 4 In the processing sequence shown, in step B, a raw material gas, a reactant gas, and a catalyst gas are supplied to the wafer 200 as film-forming gases. Specifically, in step B, the steps of supplying the raw material gas and the catalyst gas to the wafer 200 and the steps of supplying the reactant gas and the catalyst gas to the wafer 200 are performed alternately a predetermined number of times (n times, where n is an integer greater than or equal to 1) to form a film on the surface of the substrate 200b.

[0058] In addition, Figure 4 In the processing sequence shown, the temperature of the wafer 200 in step B is lower than the temperature of the wafer 200 in step A, preferably lower than the temperature of the wafer 200 in step A. Furthermore, in Figure 4 In the processing sequence shown, the temperature of wafer 200 in step C is higher than, and preferably higher than, the temperature of wafer 200 in step B. It should be noted that... Figure 4 In the processing sequence shown, the temperature of the wafer 200 in step C is higher than the temperature of the wafer 200 in step A, preferably higher than the temperature of the wafer 200 in step A.

[0059] For convenience, the above processing order is sometimes shown as follows in this specification. The same wording is also used in the following descriptions of other methods, variations, etc.

[0060] Film-forming hindering gas → (raw material gas + catalyst gas → reactant gas + catalyst gas) × n → halogen-free substance

[0061] In this specification, the term "wafer" is used to refer to the wafer itself, or to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" is used to refer to the surface of the wafer itself, or to the surface of a specified layer, etc., formed on the wafer. The phrase "forming a specified layer on the wafer" includes forming a specified layer directly on the surface of the wafer itself, or forming a specified layer on top of a layer, etc., formed on the wafer. The term "substrate" is used in the same way as "wafer."

[0062] (Wafer filling and crystal boat loading)

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

[0064] like Figure 5 As shown in (a), the following state is achieved: multiple substrates, here exemplified by substrate 200a comprising a silicon oxide film (SiO film) as an oxygen (O) film (i.e., an oxide film), and substrate 200b comprising a silicon nitride film (SiN film) as a nitride film (i.e., a non-oxide film) without O, are exposed on the surface of the wafer 200 loaded in the boat 217. Substrate 200a has a surface capped with hydroxyl (OH) groups over its entire area (the entire surface). That is, substrate 200a is capped with OH groups over its entire area (the entire surface). On the other hand, substrate 200b has a large number of areas of surface that are not capped with OH groups, i.e., a portion of the surface that is capped with OH groups.

[0065] (Pressure and temperature regulation)

[0066] Then, vacuum pump 246 is used to perform vacuum venting (pressure reduction venting) to bring the processing chamber 201, i.e., the space where the wafer 200 exists, to 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, heater 207 is used to heat the wafer 200 in the processing chamber 201 to the desired processing temperature. At this time, the energization of heater 207 is controlled based on the temperature information detected by temperature sensor 263 to achieve the desired temperature distribution in the processing chamber 201. In addition, the rotation of the wafer 200 using rotation mechanism 267 is started. Venting in the processing chamber 201, heating of the wafer 200, and rotation are all carried out continuously until the processing of the wafer 200 is completed.

[0067] Then, proceed with steps A, B, and C in sequence. The following is a description of each step.

[0068] [Step A (Formation of the Film-Forming Barrier Layer)]

[0069] In step A, a film-forming barrier gas is supplied to the wafer 200 in the processing chamber 201, i.e., the wafer 200 with substrates 200a and 200b exposed on its surface, to form a film-forming barrier layer 310 on the surface of substrate 200a.

[0070] Specifically, valve 243a is opened to supply film-forming barrier gas into gas supply pipe 232a. The flow rate of the film-forming barrier gas is regulated using MFC 241a, and it is supplied into processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this time, film-forming barrier gas is supplied to wafer 200. Then, valves 243e-243g can be opened to supply inactive gas into processing chamber 201 via nozzles 249a-249c respectively.

[0071] By supplying a film-forming barrier gas to the wafer 200 under the processing conditions described later, thereby achieving... Figure 5As shown in (b), the film-forming barrier gas can be selectively (preferably) chemically adsorbed onto the surface of substrate 200a in substrates 200a and 200b, and a film-forming barrier layer 310 can be selectively (preferably) formed on the surface of substrate 200a. The formed film-forming barrier layer 310, for example, contains hydrocarbon end caps. The film-forming barrier layer 310 functions as a film-forming inhibitor (adsorption inhibitor), i.e., an inhibitor, in step B described later, which inhibits the adsorption of film-forming gas (raw material gas, reactant gas, etc.) onto the surface of substrate 200a, the reaction between the surface of substrate 200a and the film-forming gas (raw material gas, reactant gas, etc.), and inhibits the film-forming reaction on the surface of substrate 200a. Depending on the function of the film-forming barrier layer 310, it can also be called an adsorption barrier layer or a reaction barrier layer.

[0072] It should be noted that the film-forming barrier layer 310 formed on the surface of the substrate 200a can also be referred to as an inhibitor. In addition, the film-forming barrier gas supplied to the wafer 200 for forming the film-forming barrier layer 310 can also be referred to as an inhibitor. In this specification, the term inhibitor is used in cases where only the film-forming barrier layer 310 is included, cases where only the film-forming barrier gas is included, or cases where both are included.

[0073] After forming the film-forming barrier layer 310 on the surface of the substrate 200a, the supply of the film-forming barrier gas is stopped. Then, the processing chamber 201 is evacuated to remove any residual gases from the processing chamber 201. At this time, inactive gases are supplied to the processing chamber 201 through nozzles 249a to 249c. The inactive gases supplied by nozzles 249a to 249c act as purge gases, thereby purging the processing chamber 201.

[0074] Examples of processing conditions for supplying film-forming hindering gas in step A include:

[0075] Processing temperature: room temperature (25℃) to 500℃, preferably room temperature to 250℃

[0076] Processing pressure: 1–2000 Pa, preferably 5–1000 Pa

[0077] Film-forming barrier gas supply flow rate: 1–3000 sccm, preferably 1–500 sccm

[0078] Film-forming gas supply resistance time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes

[0079] Inactive gas supply flow rate (per gas supply tube): 0–20000 sccm.

[0080] As an example of the processing conditions during purging in step A:

[0081] Processing temperature: room temperature (25℃) to 500℃, preferably room temperature to 250℃

[0082] Processing pressure: 1–30 Pa, preferably 1–20 Pa

[0083] Inactive gas supply flow rate (per gas supply tube): 500–20000 sccm

[0084] Inactive gas supply time: 10-30 seconds.

[0085] It should be noted that the numerical ranges expressed in this specification, such as "1~2000Pa," refer to the inclusion of both the lower and upper limits within that range. Therefore, for example, "1~2000Pa" means "above 1 Pa and below 2000 Pa." The same applies to other numerical ranges. It should also be noted that processing temperature refers to the temperature of the wafer 200, and processing pressure refers to the pressure within the processing chamber 201. The same applies to the following descriptions.

[0086] Step A is preferably performed in a non-plasma atmosphere. By performing Step A in a non-plasma atmosphere, plasma damage to the wafer 200, the substrates 200a and 200b on the surface of the wafer 200, and the film-forming barrier layer 310 formed on the surface of the substrate 200a in Step A can be avoided.

[0087] It should be noted that in step A, there is a case where the film-forming barrier gas is chemically adsorbed onto a portion of the surface of substrate 200b. However, a large area of ​​the surface of substrate 200b does not have OH-terminals, so the amount of film-forming barrier gas chemically adsorbed onto the surface of substrate 200b is very small, while the amount of film-forming barrier gas chemically adsorbed onto the surface of substrate 200a is overwhelmingly increased.

[0088] For example, a hydrocarbon-containing gas can be used as the film-forming barrier gas. By using a hydrocarbon-containing gas as the film-forming barrier gas, a film-forming barrier layer 310 containing hydrocarbon-terminated capping can be formed. The film-forming barrier layer 310 containing hydrocarbon-terminated capping is also referred to as a hydrocarbon-terminated capping layer.

[0089] The hydrocarbon group in a hydrocarbon-containing gas can contain only single bonds, such as alkyl groups, or it can contain unsaturated bonds such as double or triple bonds. For example, gases containing alkyl groups can be used. For example, gases containing alkylsilanes with alkyl groups coordinated to Si, i.e., alkylsilane gases, can be used. An alkyl group refers to a hydrocarbon derived from alkanes (with the general formula C...). n H 2n+2 The term "chain saturated hydrocarbon" (represented by C) refers to the group of atoms remaining after removing one hydrogen (H) atom, which is composed of the general formula C. nH 2n+1 The functional group is indicated by [reference]. As an alkyl group, an alkyl group having 1 to 5 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. The alkyl group can be linear or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. The alkyl group is bonded to the Si atom, which is the central atom of the alkylsilane molecule; therefore, the alkyl group in the alkylsilane can also be referred to as a ligand (ligand) or alkyl ligand.

[0090] Hydrocarbon-containing gases may also contain amino groups. That is, hydrocarbon-containing gases can contain both hydrocarbon groups and amino groups. For example, alkylaminosilane gases can be used as gases containing: an alkyl group directly bonded to the Si atom as the central atom; and an amino group directly bonded to the Si atom as the central atom. An amino group is a functional group formed by coordinating one or two hydrocarbon groups with one nitrogen (N) atom (a functional group obtained by replacing one or two hydrogen (H) atoms of an amino group represented by -NH2 with a hydrocarbon group). In the case where two hydrocarbon groups constituting part of an amino group are coordinated to one N atom, these two hydrocarbon groups can be the same hydrocarbon group or different hydrocarbon groups. The hydrocarbon groups constituting part of the amino group are the same as those described above. Furthermore, the amino group can have a cyclic structure. The amino group directly bonded to the Si atom as the central atom in an alkylaminosilane can also be called a ligand or amino ligand. Similarly, the alkyl group directly bonded to the Si atom as the central atom in an alkylaminosilane can also be called a ligand or alkyl ligand.

[0091] As an alkylaminosilane gas, for example, a gas of an aminosilane compound represented by the following formula [1] can be used.

[0092] SiA x [(NB2) (4-x) [1]

[0093] In formula [1], A represents a hydrogen (H) atom, an alkyl group, or an alkoxy group, B represents a H atom or an alkyl group, and x represents an integer from 1 to 3. When x is 1, A represents an alkyl group; when x is 2 or 3, at least one of A represents an alkyl group.

[0094] In formula [1], the alkyl group represented by A is preferably an alkyl group with 1 to 5 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms. The alkyl group represented by A can be linear or branched. Examples of alkyl groups represented by A include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc. The alkoxy group represented by A is preferably an alkoxy group with 1 to 5 carbon atoms, more preferably an alkoxy group with 1 to 4 carbon atoms. The alkyl group in the alkoxy group represented by A is the same as the alkyl group represented by A mentioned above. When x is 2 or 3, the 2 or 3 A groups can be the same or different. The alkyl group represented by B is the same as the alkyl group represented by A mentioned above. In addition, the 2 B groups can be the same or different, and when x is 1 or 2, the multiple (NB2) groups can be the same or different. Furthermore, the 2 B groups can be bonded to form a ring structure, and the formed ring structure can also have substituents such as alkyl groups.

[0095] As an alkylaminosilane gas, for example, a gas of a compound containing one amino group and three alkyl groups in one molecule can be used. That is, a gas of a compound in formula [1] where A is an alkyl group and x is 3 can be used. As an alkylaminosilane gas, (alkylamino)alkylsilane gas can be used. Specifically, for example, (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3, abbreviated as DMATMS) gas, (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3, abbreviated as DEATMS) gas, (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3, abbreviated as DEATES) gas, (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3, abbreviated as DMATES) gas, etc. (dialkylamino)trialkylsilane gas. It should be noted that, in addition to one amino group (dimethylamino, diethylamino) bonded to the Si atom of DMATMS, DEATMS, DEATES, DMATES, etc., there are also three alkyl groups (methyl, ethyl) bonded. That is, DMATMS, DEATMS, DEATES, DMATES, etc. contain one amino ligand and three alkyl ligands.

[0096] As inert gases, nitrogen (N2) can be used, and in addition, rare gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can also be used. This also applies to the steps described later.

[0097] [Step B (Selective Growth)]

[0098] After step A is completed, step B is performed. In step B, film-forming gas (raw material gas, reaction gas, catalyst gas) is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the film-forming barrier layer 310 has been formed on the surface of the substrate 200a, to form a film on the surface of the substrate 200b.

[0099] It should be noted that in step B, the output of heater 207 is adjusted so that the temperature of wafer 200 is below, preferably lower than, the temperature of wafer 200 in step A.

[0100] In step B, it is preferable to alternately supply the raw material gas and the reactant gas as film-forming gases to the wafer 200; or, the raw material gas and the reactant gas are alternately supplied to the wafer 200 as film-forming gases, and a catalyst gas is supplied together with at least one of the raw material gas and the reactant gas. Hereinafter, an example will be described where, in step B, the raw material gas and the reactant gas are alternately supplied as film-forming gases, and a catalyst gas is supplied together with each of the raw material gas and the reactant gas. Specifically, in step B, steps B1 and B2 are performed sequentially.

[0101] [Step B1]

[0102] In this step, raw material gas and catalyst gas are supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the film-forming barrier layer 310 has been formed on the surface of the substrate 200a.

[0103] Specifically, valves 243b and 243d are opened to supply raw material gas into gas supply pipe 232b and catalyst gas into gas supply pipe 232d, respectively. The flow rates of the raw material gas and catalyst gas are regulated using MFCs 241b and 241d, respectively, and supplied to processing chamber 201 via nozzles 249b and 249a. After being supplied to processing chamber 201, they are mixed and exhausted from exhaust port 231a. At this time, raw material gas and catalyst gas (raw material gas + catalyst gas) are supplied to wafer 200. Then, valves 243e to 243g can be opened to supply inactive gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0104] By supplying the raw material gas and catalyst gas to the wafer 200 under the processing conditions described later, it is possible to selectively (preferentially) chemically adsorb the raw material gas onto the surface of the substrate 200b while suppressing the chemical adsorption of the raw material gas onto the surface of the substrate 200a. As a result, a first layer is formed on the surface of the substrate 200b.

[0105] In this step, by supplying the catalyst gas together with the feed gas, the above-mentioned reaction can be carried out in a non-plasma atmosphere and under low-temperature conditions as described later. Thus, by forming the first layer in a non-plasma atmosphere and under low-temperature conditions as described later, it is possible to maintain the molecules and atoms constituting the film-forming barrier layer 310 (which is formed on the surface of the substrate 200a) and prevent them from disappearing (detaching) from the surface of the substrate 200a.

[0106] Furthermore, by forming the first layer under a non-plasma atmosphere and at such low temperatures as described later, the raw material gas can be prevented from undergoing thermal decomposition (gas phase decomposition), i.e., self-decomposition, within the processing chamber 201. This can suppress the multiple accumulation of a portion of the raw material gas structure on the surfaces of the substrates 200a and 200b, and enable the raw material gas to be selectively adsorbed onto the surface of the substrate 200b.

[0107] After selectively forming the first layer on the surface of the substrate 200b, the supply of raw material gas and catalyst gas to the processing chamber 201 is stopped. Then, using the same processing steps and conditions as in step A, the gases remaining in the processing chamber 201 are removed from the processing chamber 201 (purging). It should be noted that, in this step, the processing temperature during purging is preferably set to the same temperature as when the raw material gas and catalyst gas are supplied.

[0108] Examples of processing conditions for supplying raw material gas and catalyst gas in step B1 include:

[0109] Processing temperature: room temperature to 200℃, preferably room temperature to 120℃

[0110] Processing pressure: 133~1333Pa

[0111] Feed gas supply flow rate: 1~2000sccm

[0112] Raw material gas supply time: 1–60 seconds

[0113] Catalyst gas supply flow rate: 1–2000 sccm

[0114] Inactive gas supply flow rate (per gas supply tube): 0–20000 sccm.

[0115] It should be noted that during the formation of the first layer in this step, a portion of the raw material gas is adsorbed onto the surface of substrate 200a, but the amount adsorbed is extremely small, far less than the amount adsorbed onto the surface of substrate 200b. This selective (preferred) adsorption is achieved because the processing conditions in this step are as described above: a low temperature and no gas-phase decomposition of the raw material gas within the processing chamber 201. Furthermore, the film-forming barrier layer 310 is formed over the entire surface area of ​​substrate 200a, while a significant portion of the surface area of ​​substrate 200b does not have the film-forming barrier layer 310.

[0116] As a feedstock gas, for example, a gas containing Si and a halogen can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. The gas containing Si and a halogen preferably contains the halogen in the form of a chemical bond between Si and the halogen. The gas containing Si and a halogen may also contain carbon (C), in which case it is preferably contained in the form of a Si-C bond. As a gas containing Si and a halogen, 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. Here, alkylene groups include methylene, ethylene, propylene, butylene, etc. Alternatively, as a gas containing Si and a halogen, for example, a silane-based gas containing Si, Cl, and an alkyl group having a Si-C bond, i.e., an alkylchlorosilane-based gas, can be used. Alkylchlorosilane-based gases and alkylchlorosilane-based gases preferably contain Cl in the form of a Si-Cl bond and C in the form of a Si-C bond.

[0117] As gases containing Si and halogens, for example, alkylchlorosilane gases such as bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as BTCSM) gas, 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as BTCSE) gas, alkylchlorosilane gases such as 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated as TCDMDS) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated as DCTMDS) gas, and gases containing cyclic structures composed of Si and C and halogens such as 1,1,3,3-tetrachloro-1,3-disilheycyclobutane (C2H4Cl4Si2, abbreviated as TCDSCB) gas can be used. In addition, as gases containing Si and halogens, inorganic chlorosilane gases such as tetrachlorosilane (SiCl4, abbreviated as STC), hexachlorodisilane (Si2Cl6, abbreviated as HCDS), and octachlorotrisilane (Si3Cl8, abbreviated as OCTS) can also be used.

[0118] Alternatively, instead of gases containing Si and halogens, aminosilane-based gases such as tetra(dimethylamino)silane (Si[N(CH3)2]4, abbreviated as 4DMAS), tri(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 be used as feedstock gases. It should be noted that aminosilane-based gases can also be used as one of the film-forming barrier gases in other methods described later. In this case, the feedstock gas supply system described above is configured to supply film-forming barrier gases, and therefore also functions as a film-forming barrier gas supply system.

[0119] As a catalyst gas, for example, amine gases containing C, N, and H can be used. Examples of amine gases include pyridine gas (C5H5N, abbreviated as py), aminopyridine gas (C5H6N2), methylpyridine gas (C6H7N), dimethylpyridine gas (C7H9N), and piperazine gas (C4H2N). 10 N2 gas, piperidine (C5H) 11 Cyclic amine gases such as N, and chain amine gases such as triethylamine ((C2H5)3N, abbreviated as TEA) and diethylamine ((C2H5)2NH, abbreviated as DEA). Among these, py gas is preferred as the catalyst gas. This also applies to step B2 described later.

[0120] [Step B2]

[0121] After the first layer is formed, reactive gases such as oxidant and catalyst gases are supplied to the wafer 200 in the processing chamber 201, that is, to the first layer formed on the surface of the substrate 200b.

[0122] Specifically, valves 243c and 243d are opened to supply reactant gas into gas supply pipe 232c and catalyst gas into gas supply pipe 232d, respectively. The flow rates of the reactant gas and catalyst gas are regulated using MFCs 241c and 241d, respectively, and supplied to processing chamber 201 via nozzles 249c and 249a. After being supplied to processing chamber 201, they are mixed and exhausted from exhaust port 231a. At this time, reactant gas and catalyst gas (response gas + catalyst gas) are supplied to wafer 200. Then, valves 243e to 243g can be opened to supply inactive gas into processing chamber 201 via nozzles 249a to 249c.

[0123] By supplying reactant gases such as oxidant and catalyst gases to the wafer 200 under the processing conditions described later, at least a portion of the first layer formed on the surface of the substrate 200b in step B1 can be oxidized. Thus, a second layer, formed by oxidizing the first layer, is formed on the surface of the substrate 200b.

[0124] In this step, by supplying the catalyst gas together with the reactant gas, the above-mentioned oxidation 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, it is possible to maintain the molecules and atoms constituting the film-forming barrier layer 310 (which is formed on the surface of the substrate 200a) and prevent them from disappearing (detaching) from the surface of the substrate 200a.

[0125] After the first layer formed on the surface of the substrate 200b is oxidized and transformed into the second layer, the supply of reactant gas and catalyst gas to the processing chamber 201 is stopped. Then, using the same processing steps and conditions as in step A, the gases and other gases remaining in the processing chamber 201 are removed (purged). It should be noted that the processing temperature during purging in this step is preferably set to the same processing temperature as when the reactant gas and catalyst gas are supplied.

[0126] Examples of processing conditions for supplying reactant and catalyst gases in step B2 include:

[0127] Processing temperature: room temperature to 200℃, preferably room temperature to 120℃

[0128] Processing pressure: 133~1333Pa

[0129] Reactant gas supply flow rate: 1–2000 sccm

[0130] Reaction gas supply time: 1–60 seconds

[0131] Catalyst gas supply flow rate: 1–2000 sccm

[0132] Inactive gas supply flow rate (per gas supply tube): 0–20000 sccm.

[0133] When forming an oxide film system, gases containing both O and H can be used as the reactant gas. Examples of O- and H-containing gases include water vapor (H2O gas) and hydrogen peroxide (H2O2 gas), which contain OH bonds. Alternatively, gases without OH bonds, such as hydrogen (H2) gas + oxygen (O2) gas or H2 gas + ozone (O3) gas, can also be used. In this specification, the phrase "H2 gas + O2 gas" refers to a mixture of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed (pre-mixed) in the supply pipe before being supplied to the processing chamber 201, or the two gases can be supplied separately from different supply pipes to the processing chamber 201 and mixed (post-mixed).

[0134] It should be noted that, as the reactant gas in the case of forming a nitrided membrane system, gases containing both nitrogen (N) and hydrogen (H) can be used. Examples of gases containing N and H include ammonia (NH3), hydrazine (N2H4), diazoxide (N2H2), and N3H8, which contain NH bonds. It should also be noted that, in the case of forming a nitrided membrane system, the oxidant, oxidation, and oxidation reactions described above can be replaced with nitriding agents, nitriding, and nitriding reactions, respectively.

[0135] [Number of times stipulated for implementation]

[0136] By performing steps B1 and B2 asynchronously a predetermined number of times (n times, where n is an integer greater than or equal to 1), thus achieving... Figure 5 As shown in (c), for the substrates 200a and 200b exposed on the surface of the wafer 200, a film 320 can be selectively formed on the surface of the substrate 200b. Preferably, the above-described cycle is 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-described cycle is repeated multiple times until the film thickness of the film 320 becomes the desired film thickness through the stacking of the second layer.

[0137] It should be noted that during steps B1 and B2, the film-forming barrier layer 310 formed on the surface of substrate 200a is maintained as described above and does not disappear from the surface of substrate 200a, therefore no film is formed on the surface of substrate 200a. However, if the formation of the film-forming barrier layer 310 on the surface of substrate 200a becomes insufficient for some reason, there may be cases where very little film is formed on the surface of substrate 200a. However, even in such cases, the thickness of the film formed on the surface of substrate 200a is much thinner than the thickness of the film formed on the surface of substrate 200b. In this specification, "selectively forming a film on the surface of substrate 200b" includes not only the case where no film grows on the surface of substrate 200a at all, as mentioned above, but also the case where an extremely thin film is formed on the surface of substrate 200a.

[0138] [Step C (Post-processing)]

[0139] After step B is completed, step C is performed. In step C, for the wafer 200 in the processing chamber 201, that is, the wafer 200 after the film 320 is formed on the surface of the substrate 200b, a halogen-free substance that reacts chemically with the film formation barrier layer 310 and the film 320 is supplied under a non-plasma atmosphere.

[0140] It should be noted that in step C, the output of heater 207 is adjusted in a manner that makes the temperature of wafer 200 higher than the temperature of wafer 200 in step B. It should also be noted that in step C, it is desirable to adjust the output of heater 207 in a manner that makes the temperature of wafer 200 higher than the temperature of wafer 200 in step A.

[0141] In this step, specifically, valve 243h is opened to supply part or all of a halogen-free substance into gas supply pipe 232h. The halogen-free substance is supplied to processing chamber 201 via nozzle 249b through flow regulation by MFC 241h and exhausted from exhaust port 231a. At this time, halogen-free substance is supplied to wafer 200 (halogen-free substance supply). At this time, valves 243e to 243g can be opened to supply inactive gas into processing chamber 201 through nozzles 249a to 249c respectively.

[0142] At this point, valve 243c can be further opened to supply part or all of the halogen-free substance into gas supply pipe 232c. In this case, the halogen-free substance is supplied to processing chamber 201 via nozzles 249b and 249c through flow regulation by MFCs 241h and 241c, respectively. After being supplied to processing chamber 201, it is mixed and exhausted from exhaust port 231a. At this point, halogen-free substance is supplied to wafer 200 (halogen-free substance supply). At this point, valves 243e to 243g can also be opened to supply inactive gas into processing chamber 201 through nozzles 249a to 249c respectively.

[0143] By supplying a halogen-free substance to the wafer 200 under the processing conditions described later, thereby achieving... Figure 5 As shown in (d), the molecules and atoms constituting the film-forming barrier layer 310 formed on the surface of the substrate 200a can be removed from the surface of the substrate 200a through a chemical reaction with a halogen-free substance, or the inhibitory function of the film-forming barrier layer 310 can be neutralized. The neutralization of the inhibitory function of the film-forming barrier layer 310 is also referred to as the neutralization of the film-forming barrier layer 310. It should be noted that there are also cases where part of the film-forming barrier layer 310 is removed and another part is neutralized. That is, there are also cases where the removal and neutralization of the film-forming barrier layer 310 are performed simultaneously. In other words, in this step, at least one of the processes of removing and neutralizing the film-forming barrier layer 310 is performed. As a result, the surface state of the substrate 200a can be restored, and film formation processes such as forming a film on the surface of the substrate 200a can be performed in subsequent processes.

[0144] It should be noted that the ineffectiveness of the inhibitory function of the film-forming barrier layer 310 refers to the chemical change of the molecular structure and the atomic arrangement of the surface of the film-forming barrier layer 310 formed on the surface of the substrate 200a, so as to enable the adsorption of film-forming gas (raw material gas, reactant gas, etc.) to the surface of the substrate 200a and the reaction between the surface of the substrate 200a and the film-forming gas (raw material gas, reactant gas, etc.).

[0145] Furthermore, in this step, through the chemical reaction between the film 320 formed on the substrate 200b surface and a halogen-free substance, impurities such as Cl, H, hydrocarbon compounds, and moisture in the film 320 can be removed. This process also reorganizes the arrangement of the atoms constituting the film 320, shortening the bond distances between atoms and strengthening their bonds. In other words, this step removes impurities from the film 320, densifying it and improving its quality. Thus, in this step, as... Figure 5As shown in (d), the membrane 320 formed on the surface of the substrate 200b in step B can be changed into a membrane 330 with improved membrane quality compared to the membrane 320, that is, a membrane 330 with improved membrane quality compared to the membrane 320.

[0146] Thus, in this step, by using a halogen-free substance, at least one of the treatments for removing and invalidating the film-forming barrier layer 310 formed on the surface of substrate 200a, and the modification treatment for the film 320 formed on the surface of substrate 200b, can be performed simultaneously and in parallel. That is, in this step, by using a halogen-free substance, the treatment of the film-forming barrier layer 310 formed on the surface of substrate 200a and the treatment of the film 320 formed on the surface of substrate 200b can be performed simultaneously and in parallel. Therefore, the post-processing based on this step is also referred to as parallel post-processing.

[0147] After performing at least one of the following treatments—removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and modification treatment of the film 320 formed on the surface of substrate 200b—the supply of halogen-free substances to the processing chamber 201 is stopped. Then, using the same processing steps and conditions as in step A, the gases and other substances remaining in the processing chamber 201 are removed 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 processing temperature as when supplying halogen-free substances.

[0148] This step is preferably performed under conditions that allow for at least one of the following treatments: removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and modification of the film 320 formed on the surface of substrate 200b.

[0149] Examples of processing conditions for supplying halogen-free substances in step C include:

[0150] Processing temperature: 200–1000℃, preferably 400–700℃

[0151] Processing pressure: 1–120000 Pa, preferably 1–13300 Pa

[0152] Halogen-free material supply flow rate: 1–30,000 sccm, preferably 1–20,000 sccm

[0153] Supply time of halogen-free substances: 1–18000 seconds, preferably 120–10800 seconds

[0154] Inactive gas supply flow rate (per gas supply tube): 0–20000 sccm.

[0155] As a halogen-free substance, for example, an oxidizing gas (oxidant) can be used. By using an oxidizing gas as a halogen-free substance, at least one of the processes of removing and invalidating the film-forming barrier layer 310 formed on the surface of the substrate 200a and the modification process of the film 320 formed on the surface of the substrate 200b can be carried out effectively and simultaneously in parallel.

[0156] The oxidizing gas, as an example of a halogen-free substance, preferably includes one or more of the following: a gas containing O and H, a gas containing O, and a gas containing both O and H. Here, for example, H₂O gas, H₂O₂ gas, etc., can be used as the gas containing O and H. For example, O₂ gas, O₃ gas, etc., can be used as the gas containing O. For example, H₂ gas, NH₃ gas, etc., can be used as the gas containing H.

[0157] Specifically, the oxidizing gas, as an example of a halogen-free substance, preferably includes one or more of the following: H2O gas, H2O2 gas, O2 gas, O3 gas, O2 gas + H2 gas, O3 gas + H2 gas, O2 gas + NH3 gas, and O3 gas + NH3 gas.

[0158] Alternatively, nitriding gas (nitriding agent) can be used as a halogen-free substance. By using nitriding gas as a halogen-free substance, at least one of the following processes can be performed simultaneously and in parallel: removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and modification of the film 320 formed on the surface of substrate 200b.

[0159] The nitriding gas, as an example of a halogen-free substance, preferably includes, for example, a gas containing N and H. Specifically, the nitriding gas, as an example of a halogen-free substance, preferably includes one or more of, for example, NH3 gas, N2H4 gas, N2H2 gas, and N3H8 gas.

[0160] In this step, in order to efficiently remove impurities contained in the film 320 without substantially changing the composition ratio of the film 320 formed on the surface of the substrate 200b, if the film 320 is, for example, a silicon oxide film (SiO film), an oxidizing gas, such as an O-containing gas or an O-containing gas + H-containing gas, is preferably used as a halogen-free material. In this case, the composition ratio of the film 320 (SiO film) formed on the surface of the substrate 200b can be substantially maintained after this step.

[0161] For the same reason, when the film 320 is, for example, a silicon oxide carbide film (SiOC film), it is preferable to use an oxidizing gas containing O gas, or an O gas + H gas, as a halogen-free substance. In this case, the composition ratio of the film 320 (SiOC film) formed on the surface of the substrate 200b can be substantially maintained even after this step. In this case, in order to prevent C from detaching from the film 320 (SiOC film), it is preferable to supply the oxidizing gas as a halogen-free substance to the wafer 200 under processing conditions that maintain the Si-C bonds contained in the film 320 (SiOC film) without breaking them (processing conditions where the oxidizing power is weakened). Such processing conditions can be achieved, for example, by reducing at least one of the processing temperature, processing pressure, and oxidizing gas supply flow rate, or shortening the oxidizing gas supply time, compared to the case of supplying the film 320 (SiO film) as a halogen-free substance as described above.

[0162] For the same reason, when the film 320 is, for example, a silicon nitride film (SiN film), it is preferable to use a nitriding gas, such as a gas containing N and H, as a halogen-free substance. In this case, the composition ratio of the film 320 (SiN film) formed on the surface of the substrate 200b can be substantially maintained after this step.

[0163] For the same reason, when the film 320 is, for example, a silicon carbide nitride (SiCN) film, it is preferable to use a nitriding gas, such as a gas containing N and H, as a halogen-free substance. In this case, the composition ratio of the film 320 (SiCN film) formed on the surface of the substrate 200b can be substantially maintained after this step. In this case, in order to prevent C from detaching from the film 320 (SiCN film), it is preferable to supply the nitriding gas as a halogen-free substance to the wafer 200 under processing conditions that can maintain the Si-C bonds contained in the film 320 (SiCN film) without breaking them (processing conditions where the nitriding force is weakened). Such processing conditions can be achieved, for example, by reducing at least one of the processing temperature, processing pressure, and nitriding gas supply flow rate, or shortening the nitriding gas supply time, compared to the case of supplying the film 320 (SiN film) as a halogen-free substance as described above.

[0164] (Post-purging and atmospheric pressure recovery)

[0165] After parallel post-processing is completed, inert gases are supplied into the processing chamber 201 from nozzles 249a to 249c, and exhaust gases are discharged from exhaust port 231a. The inert gases supplied from nozzles 249a to 249c act as purge gases, thereby purging the processing chamber 201 and removing residual gases and reaction byproducts from the processing chamber 201 (post-purging). Then, the atmosphere in the processing chamber 201 is replaced with inert gases (inert gas replacement), and the pressure in the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0166] (Crystal boat unloading and chip removal)

[0167] Then, the sealing cover 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the crystal boat 217, is then 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). The processed wafer 200 is then removed from the crystal boat 217 after being moved to the outside of the reaction tube 203 (wafer removal).

[0168] (3) Effects of this method

[0169] According to this method, one or more of the effects shown below can be obtained.

[0170] (a) By supplying a halogen-free substance to the wafer 200 during the post-growth processing, at least one of the following treatments can be performed: removal and invalidation of the film-forming barrier layer 310 formed on the surface of the substrate 200a, and modification processing of the film 320 formed on the surface of the substrate 200b. As a result, in subsequent processes, a film can be formed on the surface of the substrate 200a, and impurities in the film 320 formed on the surface of the substrate 200b can be removed, making the film denser and improving film quality. Furthermore, since the treatment of the film-forming barrier layer 310 formed on the surface of the substrate 200a and the treatment of the film 320 formed on the surface of the substrate 200b can be performed simultaneously and in parallel—that is, two different processing steps can be performed simultaneously—the productivity of substrate processing can be improved.

[0171] (b) By setting the temperature of the wafer 200 in the post-growth processing above the temperature of the wafer 200 in the selective growth process, the efficiency of at least one of the processes for removing and invalidating the film-forming barrier layer 310 formed on the surface of the substrate 200a, and the efficiency of the modification process of the film 320 formed on the surface of the substrate 200b, can be improved. This further improves the productivity of substrate processing.

[0172] (c) By supplying a halogen-free substance to the wafer 200 in a non-plasma atmosphere during the post-growth process, plasma damage to the wafer 200 or the substrates 200a and 200b on the surface of the wafer 200, or the film 320 formed on the surface of the substrate 200b, can be avoided. At least one of the processes of removing and invalidating the film-forming barrier layer 310 formed on the surface of the substrate 200a, and the modification process of the film 320 formed on the surface of the substrate 200b, can be performed simultaneously and in parallel.

[0173] (d) By performing the formation of the barrier layer, selective growth, and post-processing in a non-plasma atmosphere, plasma damage to the wafer 200, the substrates 200a and 200b on the surface of the wafer 200, the barrier layer 310 formed on the surface of the substrate 200a, and the films 320 and 330 formed on the surface of the substrate 200b can be avoided, and this method can be applied to processes where plasma damage is a concern.

[0174] (e) By supplying a halogen-free substance to the wafer 200 during the post-growth process, damage, halogen contamination, and residue of the wafer 200 or the substrates 200a and 200b on the surface of the wafer 200, or the film 320 formed on the surface of the substrate 200b, can be avoided. At least one of the processes of removing and invalidating the film-forming barrier layer 310 formed on the surface of the substrate 200a, and the modification process of the film 320 formed on the surface of the substrate 200b can be performed simultaneously and in parallel.

[0175] (4) Variations

[0176] Step C in this method can be modified as shown in the following variations. Unless otherwise specified, the processing steps and conditions in each variation can be set to be the same as those in each step of the substrate processing sequence described above. It should be noted that the variations shown below differ from the substrate processing sequence described above only in step C; steps A and B in the variations are the same as steps A and B in the substrate processing sequence described above. Therefore, the descriptions of steps A and B are omitted in the following descriptions of the variations.

[0177] (Variation Example 1)

[0178] In step C, the composition ratio of the membrane 320 can be changed by modifying the membrane 320 formed on the surface of the substrate 200b.

[0179] That is, in step C, at least one of the treatments of removing and invalidating the film-forming barrier layer 310 formed on the surface of substrate 200a and the modification treatment that changes the composition ratio of the film 320 formed on the surface of substrate 200b can be carried out simultaneously and in parallel by the action of a halogen-free substance.

[0180] Figure 6 In (d), as an example, the following surface state is shown, namely, the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200 in step C, and the composition ratio of the film 320 formed on the surface of the substrate 200b is changed, so that the film 320 is changed to the surface state of the wafer 200 after the film 340 has a different composition ratio than the film 320.

[0181] In this modified example, specifically, for example, when membrane 320 is a SiOC membrane, in step C, an oxidizing gas such as O-containing gas is used as a halogen-free substance, thereby making the ratio of C concentration to O concentration (C / O ratio) of membrane 340 (SiOC membrane) lower than the C / O ratio of membrane 320 (SiOC membrane) before step C. Similarly, when membrane 320 is a SiOC membrane, in step C, an oxidizing gas such as O-containing gas + H-containing gas is used as a halogen-free substance, thereby making the C / O ratio of membrane 340 (SiOC membrane) even lower than the C / O ratio of membrane 340 (SiOC membrane) after the modification treatment in step C using an oxidizing gas such as O-containing gas as a halogen-free substance.

[0182] In addition, specifically, for example, when membrane 320 is a SiCN membrane, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby making the ratio of C concentration to N concentration (C / N ratio) of membrane 340 (SiCN membrane) lower than the C / N ratio of membrane 320 (SiCN membrane) before step C.

[0183] Furthermore, specifically, for example, when membrane 320 is a silicon oxynitride (SiON) membrane, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance. This allows the N / O ratio of membrane 340 (SiON membrane) to O concentration to be higher than the N / O ratio of membrane 320 (SiON membrane) before step C. Similarly, when membrane 320 is a SiON membrane, in step C, an oxidizing gas, such as an O gas, is used as a halogen-free substance. This allows the N / O ratio of membrane 340 (SiON membrane) to be lower than the N / O ratio of membrane 320 (SiON membrane) before step C.

[0184] The same effect as described above can be obtained in this modified example. Furthermore, according to this modified example, at least one of the following processes can be performed: removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and control of the composition ratio of the film 320 formed on the surface of substrate 200b. Thus, a film 340 with a desired composition ratio can be obtained, and the productivity of substrate processing can be improved.

[0185] (Variation Example 2)

[0186] In step C, elements contained in a halogen-free substance that are not present in the film 320 (hereinafter also referred to as other elements) can be added to the film 320 by modifying the film 320 formed on the surface of the substrate 200b. That is, in step C, other elements can be incorporated into the film 320 formed in step B. Thus, the process of incorporating other elements into the film 320 is also referred to as other element addition, other element incorporation, or other element doping.

[0187] That is, in step C, at least one of the treatments of removing and invalidating the film-forming barrier layer 310 formed on the surface of substrate 200a and the modification treatment of incorporating other elements into the film 320 formed on the surface of substrate 200b can be carried out simultaneously and in parallel by the action of a halogen-free substance.

[0188] Figure 7 In (d), as an example, the following surface state is shown: by supplying a halogen-free substance to the wafer 200 in step C, the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a, and other elements not contained in the film 320 formed on the surface of the substrate 200b are added (doped) to the film 320, so that the film 320 is changed to the surface state of the wafer 200 after the film 350 is formed by adding other elements to the film 320.

[0189] In this modified example, specifically, for example, when the film 320 is a SiOC film, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby adding (doping) N to the film 320 (SiOC film), which can change the film 320 (SiOC film) into film 350 (N-doped SiOC film).

[0190] In addition, specifically, for example, when the film 320 is a SiO film, in step C, a nitriding gas containing N and H is used as a halogen-free substance, thereby adding (doping) N to the film 320 (SiO film), which can change the film 320 (SiO film) into film 350 (N-doped SiO film).

[0191] In addition, specifically, for example, when the film 320 is a SiCN film, in step C, an oxidizing gas such as O gas is used as a halogen-free substance, thereby adding (doping) O to the film 320 (SiCN film), which can change the film 320 (SiCN film) into film 350 (SiCN film doped with O).

[0192] The same effect as described above can be obtained in this modified example. Furthermore, according to this modified example, at least one of the following processes can be performed: removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and other elements can be added to the film 320 formed on the surface of substrate 200b. Thus, a film 350 doped with desired other elements can be obtained, and the productivity of substrate processing can be improved.

[0193] (Variation Example 3)

[0194] In step C, the membrane 320 formed on the surface of the substrate 200b can be modified to make the membrane 320 into a membrane with a different chemical structure (e.g., chemical composition, chemical structure, molecular structure, etc.) than the membrane 320.

[0195] That is, in step C, at least one of the treatments of removing and invalidating the film-forming barrier layer 310 formed on the surface of substrate 200a and the modification treatment of changing the film 320 formed on the surface of substrate 200b into a film with a different chemical structure can be carried out simultaneously and in parallel by the action of a halogen-free substance.

[0196] Figure 8 In (d), as an example, the following surface state is shown: the surface state of the wafer 200 after the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a by supplying a halogen-free substance to the wafer 200 in step C, and the film 320 formed on the surface of the substrate 200b is changed to a film 360 with a different chemical structure than the film 320.

[0197] In this modified example, specifically, for example, when the membrane 320 is a SiOC membrane, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby enabling the membrane 320 (SiOC membrane) to be changed into the membrane 360 ​​(SiOCN membrane).

[0198] In addition, specifically, for example, when membrane 320 is a SiO membrane, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby enabling membrane 320 (SiO membrane) to be changed into membrane 360 ​​(SiON membrane).

[0199] In addition, specifically, for example, when the membrane 320 is a SiN membrane, in step C, an oxidizing gas such as an O gas is used as a halogen-free substance, thereby enabling the membrane 320 (SiN membrane) to be changed into the membrane 360 ​​(SiON membrane).

[0200] Furthermore, specifically, for example, when film 320 is a SiN film, in step C, an oxidizing gas, such as one containing O gas or a mixture of O gas and H gas, is used as a halogen-free substance, thereby changing film 320 (SiN film) into film 360 (SiO film). It should be noted that, compared to changing film 320 (SiN film) into film 360 (SiON film), when changing film 320 (SiN film) into film 360 (SiO film), an oxidizing gas needs to be supplied to wafer 200 under a process condition with increased oxidizing power in step C.

[0201] In addition, specifically, for example, when membrane 320 is a SiCN membrane, in step C, an oxidizing gas such as O gas is used as a halogen-free substance, thereby enabling membrane 320 (SiCN membrane) to be changed into membrane 360 ​​(SiOCN membrane).

[0202] The same effect as described above can be obtained in this modified example. Furthermore, according to this modified example, at least one of the following processes can be performed: removal and invalidation of the film-forming barrier layer 310 formed on the surface of substrate 200a, and the chemical structure of the film 320 formed on the surface of substrate 200b can be changed. Thus, a film 360 having the desired chemical structure can be obtained, and the productivity of substrate processing can be improved.

[0203] (Variation Example 4)

[0204] In step C, a portion of the surface of the film 320 formed on the surface of the substrate 200b can be modified to a material with a different chemical structure (e.g., chemical composition, chemical composition, molecular structure, etc.) than the film 320 by means of a modification treatment of the film 320 formed on the surface of the substrate 200b.

[0205] That is, in step C, at least one of the treatments of removing and invalidating the film-forming barrier layer 310 formed on the surface of the substrate 200a, and the modification treatment of changing a portion of the surface of the film 320 formed on the surface of the substrate 200b to a material with a chemical structure different from that of the film 320, can be carried out simultaneously and in parallel by the action of a halogen-free substance.

[0206] Figure 9In (d), as an example, the following surface state is shown: by supplying a halogen-free substance to the wafer 200 in step C, the film-forming barrier layer 310 formed on the surface of the substrate 200a is removed from the surface of the substrate 200a, and the surface layer, which is part of the film 320 formed on the surface of the substrate 200b, is changed to a film 370 with a chemical structure different from that of the film 320.

[0207] In this modified example, specifically, for example, when film 320 is a SiOC film, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby enabling a portion of the surface of film 320 (SiOC film) to be transformed into film 370 (SiOCN film). It should be noted that in this case, a portion of the surface of film 320 (SiOC film) becomes film 370 (SiOCN film), but the portion other than that surface remains in the state of film 320 (SiOC film). That is, in this case, a laminated film is formed by stacking film 370 (SiOCN film) on film 320 (SiOC film).

[0208] Furthermore, specifically, for example, when membrane 320 is a SiO membrane, in step C, a nitriding gas, such as a gas containing N and H, is used as a halogen-free substance, thereby enabling a portion of the surface of membrane 320 (SiO membrane) to be transformed into membrane 370 (SiON membrane). It should be noted that in this case, a portion of the surface of membrane 320 (SiO membrane) becomes membrane 370 (SiON membrane), but the portion other than that surface remains membrane 320 (SiO membrane). That is, in this case, a laminated membrane is formed by stacking membrane 370 (SiON membrane) on membrane 320 (SiO membrane).

[0209] Furthermore, specifically, for example, when film 320 is a SiN film, in step C, an oxidizing gas, such as an O-containing gas, is used as a halogen-free substance, thereby enabling a portion of the surface of film 320 (SiN film) to change into film 370 (SiON film or SiO film). It should be noted that in this case, a portion of the surface of film 320 (SiN film) becomes film 370 (SiON film or SiO film), but the portion other than that surface remains in the state of film 320 (SiN film). That is, in this case, a laminated film is formed by stacking film 370 (SiON film or SiO film) on film 320 (SiN film).

[0210] The same effect as described above can be obtained in this modified example. Furthermore, according to this modified example, at least one of the following processes can be performed: removal and invalidation of the film-forming barrier layer 310 formed on the surface of the substrate 200a, and a portion of the chemical structure of the surface of the film 320 formed on the surface of the substrate 200b can be changed. Thus, a film 320 having a film 370 with a desired chemical structure as the surface layer, i.e., a laminated film formed by stacking the film 370 on the film 320, can be obtained, and the productivity of substrate processing can be improved.

[0211] <Other ways of publishing this text>

[0212] The foregoing has specifically described the manner of this disclosure. However, this disclosure is not limited to the manner described above and various changes may be made without departing from its spirit.

[0213] For example, an F-containing gas can be used as the film-forming barrier gas in step A. By using the F-containing gas, the surface of the substrate 200a can be F-terminated, forming a film-forming barrier layer 310 containing F-termination on the surface of the substrate 200a. The film-forming barrier layer 310 containing F-termination is also referred to as an F-termination layer. In this case, the F-containing gas can be supplied by the film-forming barrier gas supply system described above.

[0214] It should be noted that, in order to efficiently form a film-forming barrier layer 310 containing F-terminated end caps on the surface of substrate 200a, a Si-containing gas, such as an aminosilane-based gas, can be supplied to the wafer 200 before supplying the F-containing gas to the wafer 200 exposing the substrate 200a and substrate 200b. In this case, it is preferable to perform purging in the processing chamber 201 using the same processing steps and conditions as in step A after supplying the aminosilane-based gas to the wafer 200, and then supply the F-containing gas to the wafer 200. In this case, the F-containing gas and the aminosilane-based gas can be supplied from the film-forming barrier gas supply system and the raw material gas supply system described above. Hereinafter, the aminosilane-based gas and the F-containing gas will also be referred to as the first film-forming barrier gas and the second film-forming barrier gas, respectively.

[0215] In step A, after forming a film-forming barrier layer 310 containing F-terminals on the surface of the substrate 200a, the processes in step B and step C of the above-described method are performed sequentially, thereby enabling selective growth and parallel post-processing as described above. The processing sequence of this method can be as follows.

[0216] First film-forming barrier gas → Second film-forming barrier gas → (feed gas + catalyst gas → reactant gas + catalyst gas) × n → Halogen-free substance

[0217] In this method, a halogen-free material is supplied to the wafer 200 in step C after growth, thus enabling at least one of the following processes: removal and invalidation of the film-forming barrier layer 310 formed on the surface of the substrate 200a, and modification of the film 320 formed on the surface of the substrate 200b. As a result, a film 330 with improved film quality compared to film 320 can be obtained, and the productivity of substrate processing can be increased.

[0218] As the first film-forming barrier gas, i.e., an aminosilane-based gas or other Si-containing gas, for example, preferably one or more aminosilane compounds represented by the above formula [1], such as monoaminosilane (SiH3(NR2), abbreviated as MAS) gas where A is H atoms and x is 3 (i.e., a compound containing 1 amino group per molecule); diaminosilane (SiH2(NR2)2, abbreviated as BAS) gas where A is H atoms and x is 2 (i.e., a compound containing 2 amino groups per molecule); and triaminosilane (SiH(NR2)3, abbreviated as TAS) gas where A is H atoms and x is 1 (a compound containing 3 amino groups per molecule). Among these, MAS gas is preferred as the AS gas. By using MAS gas as the first film-forming barrier gas, the surface of the substrate 200a can be more uniformly and sufficiently F-sealed in step A.

[0219] As a MAS gas, for example, (ethylmethylamino)silane (SiH3[N(CH3)(C2H5)]) gas, (dimethylamino)silane (SiH3[N(CH3)2]) gas, (diisopropylamino)silane (SiH3[N(C3H7)2]) gas, (disec-butylamino)silane (SiH3[H(C4H9)2]) gas, (dimethylpyridyl)silane (SiH3[NC5H8(CH3)2]) gas, (diethylpyridyl)silane (SiH3[NC5H8(C2H5)2]) gas, etc. can be used.

[0220] Examples of gases that hinder film formation, namely gases containing fluorine (F2), chlorine trifluoride (ClF3), chlorine fluoride (ClF), nitrogen trifluoride (NF3), ClF3 + nitrogen oxide (NO), ClF + NO, F2 + NO, NF3 + NO, tungsten hexafluoride (WF6), and fluorinated nitrosyl (FNO) are examples of gases that hinder film formation.

[0221] Alternatively, for example, in step A, the supply and purging of the film-forming barrier gas to the wafer 200 can be alternated and repeated multiple times. That is, the supply of the film-forming barrier gas to the wafer 200 can be performed intermittently with purging intermittently. It should be noted that the purging in this case can be performed using the same processing steps and conditions as the purging in step A. In this case, by purging, unwanted physically adsorbed components of the film-forming barrier gas adsorbed on the surface of the wafer 200, as well as film-forming barrier gas not adsorbed on the surface of the wafer 200, can be removed, and a film-forming barrier layer 310 can be formed on the surface of the substrate 200a. In addition, in this case, a film-forming barrier layer 310 with a high density of hydrocarbon-terminated or F-terminated ends can be formed on the surface of the substrate 200a. As a result, the selectivity of selective growth in step B can be further improved. In addition, the amount of film-forming barrier gas used can also be reduced.

[0222] Furthermore, for example, in step A, the film-forming barrier gas can be supplied to the wafer 200 while the exhaust system is closed, i.e., while the APC valve 244 is fully closed. That is, in step A, the film-forming barrier gas can be sealed inside the processing chamber 201. In this case, the film-forming barrier gas can be distributed throughout the entire area inside the processing chamber 201 and throughout the entire surface area of ​​the wafer 200, and the surface of the substrate 200a of each wafer 200 can be uniformly sealed using hydrocarbon groups or F. As a result, the selectivity of selective growth in step B can be further improved. In addition, the amount of film-forming barrier gas used can be significantly reduced.

[0223] It should be noted that in step A, the sealing and purging of the film-forming barrier gas into the processing chamber 201 can be repeated alternately multiple times. That is, the sealing of the film-forming barrier gas into the processing chamber 201 can be performed intermittently with purging intermittently. It should be noted that the purging in this case can be performed using the same processing steps and conditions as the purging in step A. In this case, by purging, unwanted physically adsorbed components and film-forming barrier gases not adsorbed on the surface of the wafer 200 can be removed, and a film-forming barrier layer 310 can be formed on the surface of the substrate 200a. In addition, in this case, a high density of hydrocarbon-terminated or F-terminated film-forming barrier layer 310 can be formed on the surface of the substrate 200a. As a result, the selectivity of selective growth in step B can be further improved.

[0224] Furthermore, for example, in selective growth, based on the types of raw material gases, reactant gases, and processing conditions such as processing temperature, the following processing sequence can be followed, and the supply of catalyst gas can be omitted in at least one of steps B1 and B2. Of course, the supply of catalyst gas can also be omitted in steps B1 and B2. It should be noted that, for convenience, only steps B1 and B2 are shown in the processing sequence described below; however, steps B1 and B2 in the above-described manner are also included.

[0225] (Raw material gas + Catalyst gas → Reactant gas + Catalyst gas) × n

[0226] (raw material gas + catalyst gas → reactant gas) × n

[0227] (raw material gas → reactant gas + catalyst gas) × n

[0228] (raw material gas → reactant gas) × n

[0229] In these cases, it is preferable to use a higher processing temperature in steps B1 and B2 than in steps B1 and B2 of the above-described method. For example, the processing temperature in steps B1 and B2 can be in the range of 200–700°C, preferably 350–650°C, and more preferably 400–600°C. Other processing conditions can be set to the same conditions as in the above-described method. In these cases, the same effect as in the above-described method can also be obtained.

[0230] In addition, for example, in selective growth, not only silicon oxide films (films of the silicon oxide film system) such as SiOC film, SiO film, SiON film, SiOCN film, and silicon nitride films (films of the silicon nitride film system) such as SiN film and SiCN film can be formed, but also metal oxide films such as aluminum oxide film (AlO film), titanium oxide film (TiO film), hafnium oxide film (HfO film), zirconium oxide film (ZrO film), tantalum oxide film (TaO film), molybdenum oxide film (MoO), tungsten oxide film (WO) and metal nitride films such as aluminum nitride film (AlN film), titanium nitride film (TiN film), hafnium nitride film (HfN film), zirconium nitride film (ZrN film), tantalum nitride film (TaN film), molybdenum nitride film (MoN), tungsten nitride film (WN) can be formed. In these cases, the aforementioned film-forming barrier gas, the raw material gas containing metallic elements such as Al, Ti, Hf, Zr, Ta, Mo, and W as the film-forming gas, the aforementioned reaction gas, and the aforementioned halogen-free substances can be used. The film-forming barrier layer can be formed, selectively grown, and post-treated using the same processing steps and conditions as in the aforementioned and other methods. In these cases, the supply of the catalyst gas can also be omitted depending on the processing conditions, similar to the other methods described above. The same effects as the methods described above can be obtained in these cases.

[0231] The process used for each process is preferably prepared separately according to the processing content and stored in the storage device 121c in advance via an electrical communication line and an external storage device 123. Furthermore, preferably at the start of each process, the CPU 121a appropriately selects 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 rapid commencement of each process.

[0232] The aforementioned process is not limited to newly created cases; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can also be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the corresponding process. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be operated to directly modify the existing process already installed in the substrate processing apparatus.

[0233] In the above-described method, an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time has been described. This disclosure is not limited to the above-described method; for example, it can also be suitably applied to the case of forming a film using a monolithic substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described method, an example of forming a film using a substrate processing apparatus equipped with a hot-wall type furnace has been described. This disclosure is not limited to the above-described method; it can also be suitably applied to the case of forming a film using a substrate processing apparatus equipped with a cold-wall type furnace.

[0234] When using the above-described substrate processing apparatus, each process can be performed according to the same processing steps and conditions as described above, and the same effect as described above can be obtained.

[0235] The various methods and variations described above can be used in appropriate combinations. The processing steps and conditions in this case can be the same as those in the methods described above.

Claims

1. A substrate processing method, which has the following characteristics: (a) A process of supplying a film-forming barrier gas to a substrate having a first substrate and a second substrate on its surface to form a film-forming barrier layer on the surface of the first substrate; (b) A process of supplying film-forming gas to the substrate after forming the film-forming barrier layer on the surface of the first substrate to form a film on the surface of the second substrate; and (c) A step of supplying a halogen-free substance, which chemically reacts with the film-forming barrier layer and the film, to the substrate after the film has been formed on the surface of the second substrate in a non-plasma atmosphere. Specifically, (c) is performed when at least one of the processes of removing and invalidating the film-forming barrier layer formed on the surface of the first substrate can be performed, and the film formed on the surface of the second substrate can be modified.

2. The substrate processing method as described in claim 1, wherein, In (c), at least one of the processes of removing and invalidating the film-forming barrier layer formed on the surface of the first substrate and the modification process of the film formed on the surface of the second substrate are performed in parallel.

3. The substrate processing method as described in claim 1, wherein, In (c), at least one of the following processes is performed simultaneously and in parallel: removal and invalidation of the film-forming barrier layer formed on the surface of the first substrate, and modification of the film formed on the surface of the second substrate, using the halogen-free substance.

4. The substrate processing method as described in claim 1, wherein, The halogen-free substance contains oxidizing gases.

5. The substrate processing method as described in claim 1, wherein, The halogen-free substance comprises one or more of the following: oxygen-containing and hydrogen-containing gas, oxygen-containing gas, and oxygen-containing gas plus hydrogen-containing gas.

6. The substrate processing method as described in claim 1, wherein, The halogen-free substance comprises one or more of H2O, H2O2, O2, O3, O2+H2, O3+H2, O2+NH3, and O3+NH3.

7. The substrate processing method as described in claim 1, wherein, The halogen-free substance contains nitrogen gas.

8. The substrate processing method as described in claim 1, wherein, The halogen-free substance contains nitrogen and hydrogen gases.

9. The substrate processing method as described in claim 1, wherein, The halogen-free substance comprises one or more of NH3, N2H4, N2H2, and N3H8.

10. The substrate processing method according to any one of claims 1 to 3, wherein, In (c), the impurities contained in the membrane are removed by the modification treatment.

11. The substrate processing method according to any one of claims 1 to 3, wherein, In (c), the composition ratio of the membrane is changed through the modification treatment.

12. The substrate processing method according to any one of claims 1 to 3, wherein, In (c), by the modification treatment, elements not present in the membrane but present in the halogen-free substance are added to the membrane.

13. The substrate processing method according to any one of claims 1 to 3, wherein, In (c), the modification treatment transforms the membrane into a membrane with a different chemical structure from the original membrane.

14. The substrate processing method according to any one of claims 1 to 3, wherein, In (c), the modification treatment causes a portion of the surface of the membrane to be changed to a material with a chemical structure different from that of the membrane.

15. The substrate processing method as described in claim 1, wherein, Set the temperature of the substrate in (c) above the temperature of the substrate in (b).

16. The substrate processing method as described in claim 1, wherein, The film-forming barrier gas contains a hydrocarbon-based gas, which forms hydrocarbon-based end caps on the surface of the film-forming barrier layer.

17. The substrate processing method as claimed in claim 1, wherein, The film-forming barrier gas contains a fluorine-containing gas, which forms a fluorine end cap on the surface of the film-forming barrier layer.

18. The substrate processing method as claimed in claim 1, wherein, In (b), a raw material gas and a reactant gas are alternately supplied to the substrate as the film-forming gas; or, a raw material gas and a reactant gas are alternately supplied to the substrate as the film-forming gas, and a catalyst gas is supplied together with at least one of the raw material gas and the reactant gas.

19. A method for manufacturing a semiconductor device, comprising: (a) A process of supplying a film-forming barrier gas to a substrate having a first substrate and a second substrate on its surface to form a film-forming barrier layer on the surface of the first substrate; (b) A process of supplying film-forming gas to the substrate after forming the film-forming barrier layer on the surface of the first substrate to form a film on the surface of the second substrate; and (c) A step of supplying a halogen-free substance, which chemically reacts with the film-forming barrier layer and the film, to the substrate after the film has been formed on the surface of the second substrate in a non-plasma atmosphere. Specifically, (c) is performed when at least one of the processes of removing and invalidating the film-forming barrier layer formed on the surface of the first substrate can be performed, and the film formed on the surface of the second substrate can be modified.

20. A substrate processing apparatus, comprising: Film-forming barrier gas supply system, which supplies film-forming barrier gas to the substrate; A film-forming gas supply system that supplies film-forming gas to the substrate; A halogen-free material supply system that supplies a halogen-free material to a substrate; and The control unit is configured to control the operation of the substrate processing apparatus to perform the following processes: (a) supplying the film-forming barrier gas to a substrate having a first substrate and a second substrate on its surface to form a film-forming barrier layer on the surface of the first substrate; (b) supplying the film-forming gas to the substrate after the film-forming barrier layer has been formed on the surface of the first substrate to form a film on the surface of the second substrate. (c) In a non-plasma atmosphere, the substrate after the film has been formed on the surface of the second substrate is supplied with a halogen-free substance that chemically reacts with the film-forming barrier layer and the film, wherein (c) is performed under the condition that at least one of the removal and invalidation of the film-forming barrier layer formed on the surface of the first substrate can be performed, and that the film formed on the surface of the second substrate can be modified.

21. 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 supplying a film-forming barrier gas to a substrate having a first substrate and a second substrate on its surface to form a film-forming barrier layer on the surface of the first substrate; (b) The step of supplying film-forming gas to the substrate after forming the film-forming barrier layer on the surface of the first substrate to form a film on the surface of the second substrate; (c) The step of supplying a halogen-free substance that chemically reacts with the film-forming barrier layer and the film to the substrate after the film has been formed on the surface of the second substrate in a non-plasma atmosphere; and Step (c) is performed under the condition that at least one of the processes of removing and invalidating the film-forming barrier layer formed on the surface of the first substrate can be performed, and that the film formed on the surface of the second substrate can be modified.

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