Processing method, method for manufacturing a semiconductor device, processing apparatus, and program

Abstract

To provide a processing method, a processing apparatus, a program, and a method for manufacturing a semiconductor device for selectively forming an adhesion restraining layer on the surface of a specific base and selectively forming a film on the surface of a desired base.SOLUTION: A processing method includes a step of (a) supplying a first precursor to a substrate having a first surface and a second surface to form a first adsorption restraining layer on the first surface, a step of (b) supplying a reactant to the substrate to form an adsorption promoting layer on the second surface, a step of (c) supplying a second precursor having a molecular structure different from that of the first precursor to the substrate to form a second adsorption restraining layer on the surface of the adsorption promoting layer, and a step of (d) supplying a film forming material to the substrate after the steps of (a), (b), and (c) have been completed, thereby forming a film on the first surface.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a processing method, a method for manufacturing a semiconductor device, a processing apparatus, and a program.

Background Art

[0002] With the scaling of semiconductor devices, the miniaturization of processing dimensions and the complication of processes have been progressing. In order to perform fine and complex processing, it is necessary to repeat a high-precision patterning process many times, which leads to an increase in costs in semiconductor device manufacturing. In recent years, selective growth has attracted attention as a technique that can achieve high precision and cost reduction. Selective growth is a technique for forming a film by selectively growing a film on the surface of a desired underlayer among two or more underlayers exposed on the surface of a substrate (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In selective growth, an adsorption suppression layer may be formed on the surface of an underlayer on which film growth is not desired, but it may be difficult to form an adsorption suppression layer on the surface of a specific underlayer.

[0005] An object of the present disclosure is to provide a technique capable of selectively forming an adsorption suppression layer on the surface of a specific underlayer and selectively forming a film on the surface of a desired underlayer.

Means for Solving the Problems

[0006] According to one aspect of the present disclosure, (a) A step of supplying a first precursor to a substrate on which a first substrate and a second substrate are exposed on its surface, thereby adsorbing at least a portion of the molecular structure of the molecules constituting the first precursor onto the surface of the first substrate to form a first adsorption suppression layer, (b) A step of supplying a reactant to the substrate to form an adsorption promoting layer on the surface of the second substrate, (c) A step of supplying a second precursor having a molecular structure different from the first precursor to the substrate, thereby adsorbing at least a portion of the molecular structure of the molecules constituting the second precursor onto the surface of the adsorption promoting layer to form a second adsorption suppressing layer, (d) A step of forming a film on the surface of the first substrate by supplying a film-forming material to the substrate after (a), (b), and (c), Technology to perform this will be provided. [Effects of the Invention]

[0007] According to this disclosure, it is possible to selectively form an adsorption-suppressing layer on the surface of a specific substrate and selectively form a film on the surface of a desired substrate. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion in a vertical cross-sectional view. [Figure 2] Figure 2 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion as a cross-sectional view along line AA in Figure 1. [Figure 3] Figure 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4]Figures 4(a) to 4(e) are schematic cross-sectional views showing the surface portion of a wafer at each step in the selective growth process of the first embodiment of this disclosure. Figure 4(a) is a schematic cross-sectional view showing the surface portion of a wafer with a silicon oxide film (SiO film) as the first substrate and a silicon nitride film (SiN film) as the second substrate exposed. Figure 4(b) is a schematic cross-sectional view showing the surface portion of a wafer after step A has been performed to form a first adsorption suppression layer on the surface of the SiO film. Figure 4(c) is a schematic cross-sectional view showing the surface portion of a wafer after step B has been performed to form an adsorption promotion layer on the surface of the SiN film. Figure 4(d) is a schematic cross-sectional view showing the surface portion of a wafer after step C has been performed to form a second adsorption suppression layer on the surface of the adsorption promotion layer. Figure 4(e) is a schematic cross-sectional view showing the surface portion of a wafer after step D has been performed from the state in Figure 4(d) to form a film on the surface of the SiO film. [Figure 5] Figures 5(a) to 5(f) are schematic cross-sectional diagrams showing the surface portion of the wafer at each step in the selective growth process of the second embodiment of this disclosure. Figures 5(a) to 5(d) are similar to Figures 4(a) to 4(d). Figure 5(e) is a schematic cross-sectional diagram showing the surface portion of the wafer after step E has been performed to remove the first adsorption suppression layer from the surface of the SiO film. Figure 5(f) is a schematic cross-sectional diagram showing the surface portion of the wafer after step D has been performed from the state in Figure 5(e) to form a film on the surface of the SiO film. [Figure 6] Figures 6(a) to 6(f) are schematic cross-sectional diagrams showing the surface portion of the wafer at each step in the selective growth of the second embodiment of this disclosure. Figures 6(a) to 6(d) are similar to Figures 4(a) to 4(d). Figure 6(e) is a schematic cross-sectional diagram showing the surface portion of the wafer after the effect of the first adsorption suppression layer has been neutralized by performing step E from the state in Figure 6(d). Figure 6(f) is a schematic cross-sectional diagram showing the surface portion of the wafer after a film has been formed on the surface of the SiO film by performing step D from the state in Figure 6(e). [Figure 7]Figures 7(a) to 7(f) are schematic cross-sectional views showing the surface portion of a wafer at each step in the selective growth of Modification 1 of this disclosure. Figure 7(a) is a schematic cross-sectional view showing the surface portion of a wafer with the SiO film as the first substrate and the SiN film as the second substrate exposed, and showing the adsorption sites on the surface of the SiO film. Figure 7(b) is a schematic cross-sectional view showing the surface portion of a wafer after the number of adsorption sites on the surface of the SiO film has been reduced by performing step F from the state in Figure 7(a). Figure 7(c) is a schematic cross-sectional view showing the surface portion of a wafer after the first adsorption suppression layer has been formed on the surface of the SiO film by performing step A from the state in Figure 7(b). Figures 7(d) to 7(f) are similar to Figures 4(c) to 4(e). [Figure 8] Figures 8(a) to 8(f) are schematic cross-sectional diagrams showing the surface portion of the wafer at each step in the selective growth of Modification 2 of this disclosure. Figures 8(a) to 8(d) are similar to Figures 4(a) to 4(d). Figure 8(e) is a schematic cross-sectional diagram showing the surface portion of the wafer after step D is performed from the state in Figure 8(d) to form a film made of a different material from the adsorption-promoting layer on the surface of the SiO film. Figure 8(f) is a schematic cross-sectional diagram showing the surface portion of the wafer after step G is performed from the state in Figure 8(e) to remove the adsorption-promoting layer and the second adsorption-suppressing layer from the surface of the SiN film. [Figure 9] Figures 9(a) to 9(g) are schematic cross-sectional diagrams showing the surface portion of the wafer at each step in the selective growth of Modification 3 of this disclosure. Figures 9(a) to 9(d) are the same diagrams as Figures 4(a) to 4(d). Figure 9(e) is a schematic cross-sectional diagram showing the surface portion of the wafer after step D is performed from the state in Figure 9(d) to form a film made of a different material than the adsorption promoting layer on the surface of the SiO film. Figure 9(f) is a schematic cross-sectional diagram showing the surface portion of the wafer after step G is performed from the state in Figure 9(e) to remove the adsorption promoting layer and the second adsorption suppression layer from the surface of the SiN film. Figure 9(g) is a schematic cross-sectional diagram showing the surface portion of the wafer after step H is performed from the state in Figure 9(f) to modify the film formed on the surface of the SiO film, changing it into a film made of a different material (after modification). [Figure 10]Figure 10(a) is a schematic diagram of the state after step F, where hydroxyl (OH) terminals, which are adsorption sites, are densely present on the surface of the SiO film as the first substrate. Figure 10(b) is a schematic diagram of the state after step A from the state in Figure 10(a), where adsorption sites remain on the surface of the SiO film. Figure 10(c) is a schematic diagram of the state after steps B and C are performed in that order from the state in Figure 10(b), where a second adsorption suppression layer is formed on the adsorption sites remaining on the surface of the SiO film. [Figure 11] Figure 11(a) is a schematic diagram of the state after step F, where OH terminals, which are adsorption sites, are sparsely distributed on the surface of the SiO film as the first substrate. Figure 11(b) is a schematic diagram of the state after step A from the state in Figure 11(a), where the spacing between the first adsorption suppression layers formed on the surface of the SiO film is wide, and a large portion of the surface of the SiO film is exposed. Figure 11(c) is a schematic diagram of the state after steps B and C are performed in that order from the state in Figure 11(b), where an adsorption promoting layer and a second adsorption suppression layer are formed in the region on the surface of the SiO film where the first adsorption suppression layer has not been formed (the region where a large portion of the surface of the SiO film is exposed). [Figure 12] Figure 12(a) is a schematic diagram of the state after step F, where an appropriate number of OH terminations, which are adsorption sites, are present on the surface of the SiO film as the first substrate. Figure 12(b) is a schematic diagram of the state after step A from the state in Figure 12(a), where the first adsorption suppression layer is properly formed on the surface of the SiO film. Figure 12(c) is a schematic diagram of the state after steps B and C are performed in that order from the state in Figure 12(b), where the formation of the adsorption promoting layer and the second adsorption suppression layer on the surface of the SiO film is suppressed, and only the first adsorption suppression layer is formed on the surface of the SiO film. [Figure 13] Figure 13 is a graph showing the evaluation results in the example. [Modes for carrying out the invention]

[0009] <First aspect of this disclosure> The first aspect of this disclosure will be described below, mainly with reference to Figures 1 to 3 and Figures 4(a) to 4(e). Note that the drawings used in the following description are all schematic, and the dimensional relationships and ratios of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements do not necessarily correspond between multiple drawings.

[0010] (1) Configuration of substrate processing apparatus As shown in Figure 1, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas with heat.

[0011] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction vessel (reaction vessel) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within this processing chamber 201.

[0012] Within the processing chamber 201, nozzles 249a to 249c, which serve as the first to third supply units, are provided so as to penetrate the side walls 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 a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c, respectively. Nozzles 249a to 249c are all different nozzles, and nozzles 249a and 249c are each provided adjacent to nozzle 249b.

[0013] Gas supply pipes 232a to 232c are equipped with mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, respectively, which are flow control devices (flow control units), starting from the upstream side of the gas flow. Downstream of valve 243a in gas supply pipe 232a, gas supply pipes 232d, 232e, and 232h are connected, respectively. Downstream of valves 243b and 243c in gas supply pipes 232b and 232c, gas supply pipes 232f and 232g are connected, respectively. Gas supply pipes 232d to 232h are equipped with MFCs 241d to 241h and valves 243d to 243h, respectively, starting from the upstream side of the gas flow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0014] As shown in Figure 2, nozzles 249a to 249c are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, extending upward from the lower part of the inner wall of the reaction tube 203 towards the direction of wafer 200 arrangement. That is, nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region, on the side of the wafer arrangement region where the wafers 200 are arranged, and are provided along the wafer arrangement region. In plan view, nozzle 249b is positioned to be directly opposite the exhaust port 231a (described later) with the center of the wafer 200 being transported into the processing chamber 201 in between. Nozzles 249a and 249c are positioned to sandwich a straight line L passing through the center of nozzle 249b and the center of exhaust port 231a along the inner wall of the reaction tube 203 (outer periphery of the wafer 200) from both sides. Straight line L is also the straight line passing through nozzle 249b and the center of wafer 200. In other words, nozzle 249c is located on the opposite side of nozzle 249a, with respect to the straight line L. Nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250c are provided on the sides of nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c opens so as to face (oppose) the exhaust port 231a in a plan view, making it possible to supply gas toward the wafer 200. Multiple gas supply holes 250a to 250c are provided extending from the bottom to the top of the reaction tube 203.

[0015] From the gas supply pipe 232a, the first precursor is supplied into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a.

[0016] From the gas supply pipe 232h, the second precursor is supplied into the processing chamber 201 via the MFC 241h, valve 243h, gas supply pipe 232a, and nozzle 249a.

[0017] From the gas supply pipe 232b, the reactant is supplied into the processing chamber 201 via the MFC 241b, valve 243b, and nozzle 249b.

[0018] From the gas supply pipe 232c, the treatment material is supplied into the treatment chamber 201 via the MFC 241c, valve 243c, and nozzle 249c. The treatment material includes at least one of the following: removal and / or deactivation material (hereinafter, for convenience, these will be collectively referred to simply as deactivation material), etching material, and modifying material.

[0019] From the gas supply pipe 232d, the film-forming material is supplied into the processing chamber 201 via the MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a.

[0020] Inert gas is supplied from gas supply pipes 232e to 232g into the processing chamber 201 via MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0021] The first precursor supply system is mainly composed of gas supply pipe 232a, MFC 241a, and valve 243a. The second precursor supply system is mainly composed of gas supply pipe 232h, MFC 241h, and valve 243h. The first and second precursor supply systems are also referred to as the precursor supply system. The reaction material supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b. The processing material supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. When supplying deactivating materials, etching materials, and modifying materials as processing materials, the processing material supply system can also be referred to as the deactivating material supply system, etching material supply system, and modifying material supply system, respectively, depending on the material being supplied. The film-forming material supply system is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d. The inert gas supply system is mainly composed of gas supply pipes 232e-232g, MFCs 241e-241g, and valves 243e-243g.

[0022] Of the various supply systems described above, one or all of them may be configured as an integrated supply system 248, which is comprised of valves 243a to 243h and MFCs 241a to 241h. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232h, and the supply operations of various gases into the gas supply pipes 232a to 232h, i.e., the opening and closing operations of valves 243a to 243h and the flow rate adjustment operations of MFCs 241a to 241h, are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or segmented integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232h, etc., on an integrated unit basis, and is configured so that maintenance, replacement, and expansion of the integrated supply system 248 can be performed on an integrated unit basis.

[0023] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, the exhaust port 231a is located in a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between, in a plan view. The exhaust port 231a may be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is made of a metal material such as SUS. A vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation in the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure in the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0024] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 is made of a metal material such as SUS and passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed outside the reaction tube 203 as a lifting mechanism. The boat elevator 115 is configured as a transport device (transport mechanism) that moves wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219. Below the manifold 209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 has been lowered and the boat 217 has been moved out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as raising and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0025] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0026] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and 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, configured as, for example, a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0028] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing device, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe functions as a program, combining the procedures for each step in the substrate processing described later, so that the controller 121 can cause the substrate processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be referred to simply as "recipes." In this specification, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0029] I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotary mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0030] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 241a to 241h, the opening and closing operation of valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0031] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, USB memory, and semiconductor memory such as SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Substrate processing process Using the substrate processing apparatus described above, a method for processing a substrate as one step in the manufacturing process of a semiconductor device, specifically, an example of a processing sequence for selectively forming a film on the surface of the first substrate among the first and second substrates exposed on the surface of the wafer 200 as a substrate, will be explained mainly using Figures 4(a) to 4(e). For convenience, the following explanation will describe a typical example where the first substrate is a silicon oxide film (SiO film) and the second substrate is a silicon nitride film (SiN film). In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0033] As shown in Figures 4(a) to 4(e), the processing sequence in the first embodiment is: Step A involves supplying a first precursor to a wafer 200 in which a first substrate and a second substrate are exposed on the surface, thereby adsorbing at least a portion of the molecular structure of the molecules constituting the first precursor onto the surface of the first substrate to form a first adsorption suppression layer. Step B involves supplying a reactant to the wafer 200 to form an adsorption-promoting layer on the surface of the second substrate, Step C involves supplying a second precursor having a different molecular structure from the first precursor to the wafer 200, thereby adsorbing at least a portion of the molecular structure of the molecules constituting the second precursor onto the surface of the adsorption-promoting layer to form a second adsorption-suppressing layer. Step D includes supplying a film-forming material to the wafer 200 after steps A, B, and C have been performed in that order, thereby forming a film on the surface of the first substrate.

[0034] In step D of the first embodiment, a film is formed on the surface of the first substrate by neutralizing the action of the film-forming material. That is, in step D, the adsorption inhibitory effect of the first adsorption inhibitory layer is released by the action of the film-forming material, thereby forming a film on the surface of the first substrate.

[0035] In this specification, the term "substance" includes at least one of gaseous substances and liquid substances. Liquid substances include mist substances. That is, each of the first precursor, reactant, second precursor, and film-forming substance may contain a gaseous substance, a liquid substance such as a mist substance, or both. In this specification, the term "layer" includes at least one of continuous layers and discontinuous layers. For example, each of the first adsorption-inhibiting layer and the second adsorption-inhibiting layer may contain a continuous layer, a discontinuous layer, or both, as long as it is possible to produce an adsorption-inhibiting effect. Similarly, the adsorption-promoting layer may contain a continuous layer, a discontinuous layer, or both, as long as it is possible to produce an adsorption-promoting effect.

[0036] Furthermore, the first adsorption inhibitory layer and the second adsorption inhibitory layer are sometimes called inhibitors because they have an adsorption inhibitory effect. In this specification, the term "inhibitor" may refer to the first adsorption inhibitory layer and the second adsorption inhibitory layer, the first precursor and the second precursor, the residue derived from the first precursor and the residue derived from the second precursor, or even as a general term for all of these.

[0037] In this specification, the processing sequence described above may also be shown as follows for convenience. The same notation will be used in the following descriptions of other embodiments and modifications.

[0038] Formation of first adsorption suppression layer → Formation of adsorption promotion layer → Formation of second adsorption suppression layer → Film formation

[0039] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of a wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this specification, the phrase "form a predetermined layer on a wafer" may refer to directly forming a predetermined layer on the surface of the wafer itself or to forming a predetermined layer on top of a layer already formed on the wafer. In this specification, the term "substrate" has the same meaning as the term "wafer."

[0040] (Wafer charge and boat load) When multiple wafers 200 are loaded into the boat 217 (wafer charging), the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the manifold 209 (shutter opening). Then, as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the boat elevator 115 and transported into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0041] As shown in Figure 4(a), the surface of the wafer 200 filled into boat 217 has an exposed SiO film as the first substrate and a SiN film as the second substrate. On wafer 200, the surface of the SiO film, which is the first substrate, has OH terminations, which are adsorption sites, throughout its entire surface, while the surface of the SiN film, which is the second substrate, does not have OH terminations in most areas.

[0042] (Pressure adjustment and temperature adjustment) Subsequently, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhausted) by a vacuum pump 246 so that it reaches the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by a heater 207 so that it reaches the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on the temperature information detected by a temperature sensor 263 so that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0043] (Step A) Subsequently, the opening and closing operation of the valve in the first precursor supply system is controlled to supply the first precursor to the wafer 200 in the processing chamber 201, that is, the wafer 200 in which the first substrate and the second substrate are exposed on the surface. The first precursor supplied to the wafer 200 is exhausted from the exhaust port 231a. At this time, an inert gas may be supplied into the processing chamber 201 from the inert gas supply system.

[0044] In step A, when supplying the first precursor, it is preferable that the treatment conditions are such that the first precursor does not undergo thermal decomposition (gas phase decomposition). Processing temperature: 25-500°C, preferably 50-300°C Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa First precursor supply flow rate: 1 to 3000 sccm, preferably 50 to 1000 sccm First precursor supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0045] In this specification, numerical ranges such as "25~500℃" mean that the lower and upper limits are included within that range. For example, "25~500℃" means "25℃ or more and 500℃ or less." The same applies to other numerical ranges. Processing temperature refers to the temperature of the wafer 200, and processing pressure refers to the pressure inside the processing chamber 201. When "0" is indicated for the supply flow rate, it means that the substance is not supplied. These same rules apply in the following explanations.

[0046] In step A, by supplying the first precursor to the wafer 200, it becomes possible to selectively (preferentially) adsorb at least a portion of the molecular structure of the molecules constituting the first precursor onto the surface of the SiO film, which is the first substrate. As a result, as shown in Figure 4(b), a first adsorption-inhibiting layer is selectively (preferentially) formed on the surface of the SiO film. The first adsorption-inhibiting layer contains at least a portion of the molecular structure of the molecules constituting the first precursor, for example, residues derived from the first precursor. Examples of residues derived from the first precursor included in the first adsorption-inhibiting layer include groups generated by the chemical reaction of the first precursor with adsorption sites on the surface of the first substrate (for example, OH terminals on the surface of the SiO film). In this way, by containing residues derived from the first precursor, the first adsorption-inhibiting layer exhibits an adsorption-inhibiting effect (acts as an inhibitor).

[0047] The adsorption-inhibiting effect of the first adsorption-inhibiting layer formed in step A is preferably weaker than that of the second adsorption-inhibiting layer formed in step C, described later, under the same conditions. The first adsorption-inhibiting layer formed in step A is preferably more easily desorbed than the second adsorption-inhibiting layer formed in step C, described later, under the same conditions. Furthermore, the reactivity between the film-forming material used in step D and the first adsorption-inhibiting layer formed in step A is preferably higher than that between the film-forming material used in step D and the second adsorption-inhibiting layer formed in step C, described later, under the same conditions. In other words, the first adsorption-inhibiting layer formed in step A is preferably more easily broken down in molecular structure and more prone to selective tearing than the second adsorption-inhibiting layer formed in step C. By doing so, it becomes possible to efficiently neutralize the effect of the first adsorption-inhibiting layer in step D. As a result, it becomes easier to selectively form a film on the surface of the first substrate in step D.

[0048] After the first adsorption suppression layer is formed on the surface of the first substrate, the SiO film, the opening and closing operation of the valve in the first precursor supply system is controlled to stop the supply of the first precursor into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any remaining first precursor and other substances from the processing chamber 201. At this time, an inert gas may be supplied into the processing chamber 201 from the inert gas supply system. The inert gas supplied from the inert gas supply system acts as a purge gas, thereby purging the processing chamber 201.

[0049] The processing conditions when purging in step A are as follows: Processing temperature: 25-500°C, preferably 50-300°C Processing pressure: 1 to 1330 Pa, preferably 1 to 400 Pa Inert gas supply flow rate (per gas supply pipe): 0-10 slm, preferably 1-5 slm Inert gas supply time: 1-120 seconds Examples are given.

[0050] In step A, in a very small part of the surface of the SiN film which is the second base layer, at least a part of the molecular structure of the molecules constituting the first precursor may be adsorbed. However, even in such a case, the formation amount of the first adsorption suppression layer on the surface of the SiN film is small, and the formation amount of the first adsorption suppression layer on the surface of the SiO film is overwhelmingly larger. Thus, the reason why the formation amounts of the first adsorption suppression layer on the surface of the SiN film and the surface of the SiO film are significantly different is that, as described above, the surface of the SiO film has OH terminations over the entire area, while many regions of the surface of the SiN film do not have OH terminations. Also, this is because the processing conditions in step A are set such that the first precursor does not thermally decompose (gas-phase decompose) in the processing chamber 201.

[0051] -First Precursor- As the first precursor, a substance that selectively (preferably) adsorbs on the surface of the first base layer (for example, SiO film) among the first base layer (for example, SiO film) and the second base layer (for example, SiN film) is used. As the first precursor, for example, a compound represented by the following formula 1 is preferably used.

[0052] [R 12 , 1 , 11 , 1 , 12 , 1 , 1 ,

[0053] , , 1 , 1 , 1 , , 1 , 11 , 1 , 1 , n 1 -(X 1 )-[R 12 m 1 : Formula 1 In the above formula 1, R 11 represents a first substituent directly bonded to X 1 , R 12 represents a second substituent directly bonded to X 1 , X 1 represents a tetravalent atom selected from the group consisting of a carbon (C) atom, a silicon (Si) atom, a germanium (Ge) atom, and a tetravalent metal atom, n 1 represents an integer of 1 to 3, m 1 represents an integer of 1 to 3, and n 1 +m 1 = 4.

[0053] In formula 1, the number of the first substituents R 11 , that is, n 1n is an integer between 1 and 3, and is more preferably 2 or 3. 1 If it is 2 or 3, the first substituent is R 11 These may be the same or they may be different.

[0054] R 11 As the first substituent represented by , a substituent that has the function of exhibiting an adsorption-inhibiting effect in the first adsorption-inhibiting layer when included in the first adsorption-inhibiting layer can be used. In other words, R 11 The first substituent represented by is contained in the residue derived from the first precursor contained in the first adsorption suppression layer. 11 The first substituent represented by is preferably a substituent that suppresses the adsorption of the second precursor onto the surface of the first substrate. 11 The first substituent represented by is preferably a chemically stable substituent.

[0055] R 11 The first substituent represented by is preferably a substituent that has a weaker adsorption inhibitory effect than the first substituent of the second precursor used in step C. Also, R 11 The first substituent represented by is more preferably a substituent that loses its adsorption inhibitory effect more easily than the first substituent of the second precursor used in step C. By doing so, under the same conditions, it is possible to make the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A weaker than the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C described later, making it easier to selectively form a film on the surface of the first substrate in step D.

[0056] R 11 Examples of the first substituent represented by include fluoro groups, fluoroalkyl groups, hydrogen (-H) groups, hydrocarbon groups, and alkoxy groups. Among these, R 11The first substituent represented by is preferably a hydrogen group or a hydrocarbon group, and particularly preferably a hydrogen group. The hydrocarbon group may be an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or an aromatic hydrocarbon group. In this specification, the term substituent may include a hydrogen group (-H) for convenience.

[0057] The alkyl group in the partial structure of the hydrocarbon group and alkoxy group as the first substituent is preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched. Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, sec-butyl group, and tert-butyl group. Examples of alkoxy groups as the first substituent include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group.

[0058] In formula 1, the second substituent R 12 The number, that is, m 1 m is an integer between 1 and 3, and is more preferably 1 or 2. 1 If it is 2 or 3, the second substituent is R 12 These may be the same or they may be different.

[0059] R 12 The second substituent represented by is preferably a substituent that enables the chemical adsorption of the first precursor to an adsorption site (e.g., an OH terminus) on the surface of the first substrate.

[0060] R 12 Examples of secondary substituents represented by include amino groups, chloro groups, bromo groups, iodo groups, and hydroxyl groups. Among these, R 12 As the second substituent represented by , an amino group is preferred, and a substituted amino group is more preferred. In particular, from the viewpoint of the adsorption of the first precursor to the first substrate, R 12Preferably, all of the second substituents represented by are substituted amino groups.

[0061] The substituent on the substituted amino group is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group on the substituted amino group may be linear or branched. Examples of alkyl groups on the substituted amino group include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl groups.

[0062] The number of substituents on the substituted amino group is 1 or 2, but 2 is preferred. When the number of substituents on the substituted amino group is 2, the two substituents may be the same or different.

[0063] In formula 1, X 1 The atom to which the first and second substituents are directly bonded, as represented by , is a tetravalent atom selected from the group consisting of C atoms, Si atoms, Ge atoms, and tetravalent metal atoms. Examples of tetravalent metal atoms include titanium (Ti) atoms, zirconium (Zr) atoms, hafnium (Hf) atoms, molybdenum (Mo) atoms, and tungsten (W) atoms.

[0064] Among these, X 1 The atoms to which the first and second substituents represented by are directly bonded are preferably C atoms, Si atoms, and Ge atoms. This is because X 1 However, if it is a C atom, Si atom, or Ge atom, at least one of the following properties can be obtained: high adsorption of the first precursor to the surface of the first substrate, and high chemical stability of the first precursor after adsorption to the surface of the first substrate, i.e., residues derived from the first precursor. Among these, X 1 As such, Si atoms are more preferable. This is because X 1This is because, when the atom is a Si atom, it is possible to obtain a good balance between the high adsorption of the first precursor to the surface of the first substrate and the high chemical stability of the residue derived from the first precursor after adsorption to the surface of the first substrate.

[0065] The compound represented by Formula 1 has been described above, but the first precursor is not limited to the compound represented by Formula 1. For example, the first precursor is preferably composed of a molecule containing the above-mentioned first substituent, the above-mentioned second substituent, and an atom to which the first substituent and the second substituent are directly bonded. However, the atom to which the first substituent and the second substituent are directly bonded may be a metal atom capable of bonding to five or more ligands. When the atom to which the first substituent and the second substituent are directly bonded is a metal atom capable of bonding to five or more ligands, the number of first substituents and second substituents in the molecule of the first precursor can be increased compared to the compound represented by Formula 1, and the adsorption inhibitory effect of the first adsorption inhibitory layer can be adjusted. Furthermore, the first precursor may be composed of a molecule containing the above-mentioned first substituent, the above-mentioned second substituent, and two or more atoms to which the first substituent and the second substituent are directly bonded.

[0066] Examples of first precursors include (dimethylamino)dimethylsilane: (CH3)2NSiH(CH3)2, (ethylamino)dimethylsilane: (C2H5)HNSiH(CH3)2, (propylamino)dimethylsilane: (C3H7)2HNSiH(CH3)2, (butylamino)dimethylsilane: (C4H9)2HNSiH(CH3)2, (diethylamino)dimethylsilane: (C2H5)2NSiH(CH3)2, (dipropylamino)dimethylsilane: (C3H7)2NSiH(CH3)2, and (dibutylamino)dimethylsilane: (C3H7). 2NSiH(CH3)2, (dimethylamino)methylsilane: (CH3)2NSiH2(CH3), (ethylamino)methylsilane: (C2H5)HNSiH2(CH3), (propylamino)methylsilane: (C3H7)2HNSiH2(CH3), (butylamino)methylsilane: (C4H9)2HNSiH2(CH3), (diethylamino)methylsilane: (C2H5)2NSiH2(CH3), (dipropylamino)methylsilane: (C3H7)2NSiH2(CH3), (dibutylamino)methylsilane: (C3H7)2NSiH2(CH3) (Dimethylamino)diethylsilane: (CH3)2NSiH(C2H5)2, (Ethylamino)diethylsilane: (C2H5)HNSiH(C2H5)2, (Propylamino)diethylsilane: (C3H7)2HNSiH(C2H5)2, (Butylamino)diethylsilane: (C4H9)2HNSiH(C2H5)2, (Diethylamino)diethylsilane: (C2H5)2NSiH(C2H5)2, (Dipropylamino)diethylsilane: (C3H7)2NSiH(C2H 5)2, (dimethylamino)ethylsilane: (CH3)2NSiH2(C2H5), (ethylamino)ethylsilane: (C2H5)HNSiH2(C2H5), (propylamino)ethylsilane: (C3H7)2HNSiH2(C2H5), (butylamino)ethylsilane: (C4H9)2HNSiH2(C2H5), (diethylamino)ethylsilane: (C2H5)2NSiH2(C2H5), (dipropylamino)ethylsilane: (C3H7)2NSiH2(C2H5), (dibutylamino)ethylsilane: (C3H7)2NSiH2(C2H5),(Dipropylamino)silane:[(C3H7)2N]SiH3, (Dibutylamino)silane:[(C4H9)2N]SiH3, (Dipentylamino)silane:[(C5H, 11)2N]SiH3, bis(dimethylamino)dimethylsilane:[(CH3)2N]2Si(CH3)2, bis(ethylamino)dimethylsilane:[(C2H5)HN]2Si(CH3)2, bis(propylamino)dimethylsilane:[(C3H7)2HN]2Si(CH3)2, bis(butylamino)dimethylsilane:[(C4H9)2HN]2Si(CH3)2, bis(diethylamino)dimethylsilane:[(C2H5)2N]2Si(CH3)2, bis(dipropylamino)dimethylsilane:[(C3H7)2N]2Si(CH3)2, bis (Dibutylamino)dimethylsilane: [(C3H7)2N]2Si(CH3)2, bis(dimethylamino)methylsilane: [(CH3)2N]2SiH(CH3), bis(ethylamino)methylsilane: [(C2H5)HN]2SiH(CH3), bis(propylamino)methylsilane: [(C3H7)2HN]2SiH(CH3), bis(butylamino)methylsilane: [(C4H9)2HN]2SiH(CH3), bis(diethylamino)methylsilane: [(C2H5)2N]2SiH(CH3), bis(dipropylamino)methylsilane: [ (C3H7)2N]2SiH(CH3), Bis(dibutylamino)methylsilane:[(C3H7)2N]2SiH(CH3), Bis(dimethylamino)diethylsilane:[(CH3)2N]2Si(C2H5)2, Bis(ethylamino)diethylsilane:[(C2H5)HN]2Si(C2H5)2, Bis(propylamino)diethylsilane:[(C3H7)2HN]2Si(C2H5)2, Bis(butylamino)diethylsilane:[(C4H9)2HN]2Si(C2H5)2, Bis(diethylamino)diethylsilane:[(C2H5)2N]2 Si(C2H5)2, bis(dipropylamino)diethylsilane:[(C3H7)2N]2Si(C2H5)2, bis(dibutylamino)diethylsilane:[(C3H7)2N]2Si(C2H5)2, bis(dimethylamino)ethylsilane:[(CH3)2N]2SiH(C2H5), bis(ethylamino)ethylsilane:[(C2H5)HN]2SiH(C2H5), bis(propylamino)ethylsilane:[(C3H7)2HN]2SiH(C2H5), bis(butylamino)ethylsilane:[(C4H9)2HN]2SiH(C2H5),Bis(diethylamino)ethylsilane:[(C2H5)2N]2SiH(C2H5), Bis(dipropylamino)ethylsilane:[(C3H7)2N]2SiH(C2H5), Bis(dibutylamino)ethylsilane:[(C3H7)2N]2SiH(C2H5), Bis(diethylamino)silane:[(C2H5)2N]2SiH2, Bis(dipropylamino)silane[(C3H7)2N]2SiH2, Bis(dibutylamino)silane:[(C4H9)2N]2SiH2, Bis(dipentylamino)silane:[(C5H, 11 )2N]2SiH2, (dimethylamino)trimethoxysilane:(CH3)2NSi(OCH3) 3、 (Dimethylamino)triethoxysilane:(CH3)2NSi(OC2H5) 3、 (Dimethylamino)triprotoxysilane:(CH3)2NSi(OC3H7) 3、 Examples include (dimethylamino)tributotoxylane:(CH3)2NSi(OC4H9)3.

[0067] One or more of these can be used as the first precursor. It is preferable to select the first precursor used in step A such that, under the same conditions, the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A is weaker than the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C described later. The adsorption inhibitory effect of the first adsorption inhibitory layer can be adjusted by the number and type of first substituents contained in the first precursor. Therefore, the first precursor used in step A can be appropriately selected depending on the number and type of first substituents contained in the second precursor used in step C. Specifically, if the first precursor and the second precursor have the same number of first substituents, and the second precursor has only alkyl groups as first substituents, it is preferable to select a first precursor that has only hydrogen groups as first substituents, only alkoxy groups as first substituents, or fewer alkyl groups and hydrogen groups or alkoxy groups than the first substituents in the second precursor. This is because, when comparing alkyl groups, hydrogen groups, and alkoxy groups, alkyl groups exhibit the strongest adsorption inhibitory effect, followed by hydrogen groups, and then alkoxy groups. Furthermore, when both the first and second precursors have the same first substituent (e.g., an alkyl group), it is preferable to select a first precursor in which the number of first substituents is smaller than the number of first substituents in the second precursor. This is because the fewer the number of first substituents, the weaker the adsorption inhibitory effect of the formed adsorption inhibitory layer becomes.

[0068] Furthermore, it is preferable to use a first precursor in which the number of second substituents contained in one molecule is the same as or greater than the number of second substituents contained in the second precursor used in step C. This is because the more second substituents contained in one molecule, the fewer first substituents are contained in one molecule, and the weaker the adsorption inhibitory effect of the adsorption inhibitory layer becomes. In this way, under the same conditions, it is possible to make the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A weaker than the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C described later, making it easier to selectively form a film on the surface of the first substrate in step D.

[0069] In step A, if the first precursor having a fluoro group, fluoroalkyl group, hydrogen group, etc. as the first substituent cannot exist stably as a single compound, a first precursor having a different first substituent and being able to exist stably as a single compound may be adsorbed onto the first substrate, and then a specific treatment may be applied to convert the other first substituent into a hydrogen group, fluoro group, or fluoroalkyl group. An example of a method for converting the first substituent is shown below.

[0070] As a first example, a first precursor having a hydrogen group as its first substituent can be adsorbed onto a first substrate, and then the wafer 200 can be exposed to a fluorine (F)-containing gas such as fluorine (F2) gas, chlorine trifluoride (ClF3) gas, chlorine fluoride (ClF) gas, or hydrogen fluoride (HF) gas to convert the hydrogen group to a fluoro group. As a second example, a first precursor having an alkyl group as its first substituent can be adsorbed onto a first substrate, and then the wafer 200 can be exposed to the aforementioned F-containing gas to convert the alkyl group to a fluoroalkyl group. As a third example, a first precursor having a chloro group as its first substituent can be adsorbed onto a first substrate, and then the wafer 200 can be exposed to an atmosphere obtained by exciting a hydrogen (H)-containing gas such as hydrogen (H2) gas with plasma, for example, a hydrogen plasma, to convert the chloro group to a hydrogen group.

[0071] -Inert gas- Examples of inert gases that can be used include nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe). One or more of these can be used as the inert gas. This also applies to each step using the inert gas described later. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0072] (Step B) After step A is completed, the opening and closing operation of the valve in the reactant supply system is controlled to supply the reactant to the wafer 200 in the processing chamber 201. The reactant supplied to the wafer 200 is exhausted from the exhaust port 231a. At this time, an inert gas may be supplied into the processing chamber 201 from the inert gas supply system.

[0073] In step B, by supplying the reactant to the wafer 200, an adsorption-promoting layer is selectively (preferentially) formed on the surface of the SiN film, which is the second substrate, as shown in Figure 4(c). At this time, the adsorption-suppressing effect of the first adsorption-suppressing layer formed on the surface of the SiO film, which is the first substrate, suppresses the adsorption of the reactant to the surface of the first substrate, thereby preventing the formation of an adsorption-promoting layer on the surface of the first substrate.

[0074] The adsorption-promoting layer formed in step B is preferably one that can adsorb the second precursor material supplied to the wafer 200 in step C. The form of the adsorption-promoting layer formed in step B can be any form that allows the second precursor material to be adsorbed onto the second substrate via the adsorption-promoting layer, and examples include monomolecular forms, chain polymer forms, and films.

[0075] The higher the density of the second precursor adsorbed onto the surface of the second substrate, the stronger the effect of suppressing the adsorption of the film-forming material onto the second substrate becomes. Therefore, the adsorption-promoting layer is preferably one that can adsorb the second precursor at high density, and the adsorption-promoting layer is preferably in the form of a film. This is because when the adsorption-promoting layer takes the form of a film, it becomes possible to have a high density (large quantity) of adsorption sites for the second precursor on the surface of the adsorption-promoting layer. In other words, as the adsorption-promoting layer, a film having a high density (large quantity) of adsorption sites for the second precursor on its surface is preferred.

[0076] Furthermore, in step B, it is preferable to form an oxygen (O)-containing layer as an adsorption-promoting layer. This is because by making the adsorption-promoting layer an O-containing layer, OH terminations can be provided on the surface as adsorption sites, making it easier for the second precursor to adsorb onto the adsorption-promoting layer. In other words, by forming an O-containing layer as an adsorption-promoting layer in step B, it becomes possible to efficiently form a second adsorption-suppressing layer on the surface of the adsorption-promoting layer with high selectivity in step C. In particular, from the viewpoint of having a high density (large amount) of OH terminations on the surface, it is preferable to use a layer containing at least Si and O, such as a silicon oxide layer (SiO layer) or a silicon acid carbide layer (SiOC layer), as the adsorption-promoting layer.

[0077] The adsorption-promoting layer can be formed by supplying a reactant to the wafer 200, and there are no particular restrictions on the method. For example, when forming an O-containing layer as the adsorption-promoting layer in step B, a method can be used in which a film-forming material is used as the reactant to deposit the O-containing layer on the surface of the second substrate. For example, the same film-forming method (and film-forming conditions) as the film-forming method (and film-forming conditions) using the film-forming material in step D described later can be used. By forming the adsorption-promoting layer by depositing the O-containing layer on the surface of the second substrate, an adsorption-promoting layer having OH terminations as adsorption sites on its surface is obtained, making it possible to efficiently form a second adsorption-suppressing layer on the surface of the adsorption-promoting layer with high selectivity in step C.

[0078] Furthermore, when forming an O-containing layer as an adsorption-promoting layer in step B, an oxidizing agent may be used as the reactant to oxidize the surface of the second substrate. Even when forming the adsorption-promoting layer by oxidizing the surface of the second substrate, an adsorption-promoting layer having OH-terminated adsorption sites on its surface is obtained, making it possible to efficiently form a second adsorption-suppressing layer on the surface of the adsorption-promoting layer with high selectivity in step C. An example of an oxidizing agent used in this method is an O-containing substance.

[0079] In step B, the treatment conditions when supplying the oxygen-containing substance, which is the oxidizing agent, as the reactant are as follows: Processing temperature: Room temperature to 600°C, preferably 50 to 400°C Processing pressure: 1 to 101325 Pa, preferably 1 to 1300 Pa O-containing substance supply flow rate: 1 to 20,000 sccm, preferably 1 to 10,000 sccm O-containing substance supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes This is an example. Other processing conditions can be the same as the processing conditions in step A.

[0080] In step B, it is desirable that the thickness of the adsorption-promoting layer formed on the surface of the second substrate be 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 5 nm or less, and more preferably 1.5 nm or more and 3 nm or less.

[0081] If the thickness of the adsorption-promoting layer is less than 0.5 nm, in step C, the amount of at least a portion of the molecular structure of the molecules constituting the second precursor adsorbed on the surface of the adsorption-promoting layer (residues derived from the second precursor) may be insufficient. In this case, the adsorption inhibition effect of the second adsorption-suppressing layer formed on the surface of the adsorption-promoting layer may be insufficient. This problem can be resolved by making the thickness of the adsorption-promoting layer 0.5 nm or more. This problem can be sufficiently resolved by making the thickness of the adsorption-promoting layer 1 nm or more, and this problem can be resolved even more sufficiently by making the thickness of the adsorption-promoting layer 1.5 nm or more.

[0082] If the thickness of the adsorption-promoting layer is greater than 10 nm, in step B, the adsorption-suppressing effect of at least a portion of the first adsorption-suppressing layer formed on the surface of the first substrate may be neutralized by the action of the reactant, resulting in insufficient adsorption suppression by the first adsorption-suppressing layer. As a result, an adsorption-promoting layer is formed on the surface of the first substrate, and in the subsequent step C, a second adsorption-suppressing layer is also formed on the surface of the first substrate. This problem can be resolved by setting the thickness of the adsorption-promoting layer to 10 nm or less. This problem can be sufficiently resolved by setting the thickness of the adsorption-promoting layer to 5 nm or less, and this problem can be resolved even more sufficiently by setting the thickness of the adsorption-promoting layer to 3 nm or less.

[0083] By setting the thickness of the adsorption-promoting layer within the above range, it becomes possible to efficiently form a second adsorption-inhibiting layer on the surface of the adsorption-promoting layer with high selectivity in step C.

[0084] After an adsorption-promoting layer is formed on the surface of the SiN film, which is the second substrate, the opening and closing operation of the valve in the reactant supply system is controlled to stop the supply of reactants into the processing chamber 201. Then, using the same processing procedure and conditions as in step A described above, any reactants remaining in the processing chamber 201 are removed from the processing chamber 201 (purging).

[0085] -O-containing substances- Examples of oxygen-containing materials that can be used include oxygen-containing gases, oxygen and hydrogen-containing gases, oxygen and nitrogen-containing gases, and oxygen and carbon-containing gases. The oxygen-containing material may be used by thermal excitation in a non-plasma atmosphere or by plasma excitation.

[0086] As the oxygen-containing gas, for example, oxygen (O2) gas, ozone (O3) gas, etc. can be used. As the oxygen and hydrogen-containing gas, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, O2 gas + H2 gas, O3 gas + H2 gas, etc. can be used. As the oxygen and nitrogen-containing gas, for example, nitric oxide (NO) gas, nitrous oxide (N2O) gas, nitrogen dioxide (NO2) gas, O2 gas + NH3 gas, O3 gas + NH3 gas, etc. can be used. As the oxygen and carbon-containing gas, for example, carbon dioxide (CO2) gas, carbon monoxide (CO) gas, etc. can be used. As the oxygen-containing substance, one or more of these can be used.

[0087] In this specification, the joint mention of two gases, such as "O2 gas + H2 gas," refers to a mixed gas of O2 gas and H2 gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe before being supplied to the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0088] (Step C) After step B is completed, the opening and closing operation of the valve in the second precursor supply system is controlled to supply the second precursor, which has a different molecular structure from the first precursor, to the wafer 200 in the processing chamber 201. The second precursor supplied to the wafer 200 is exhausted from the exhaust port 231a. At this time, an inert gas may be supplied into the processing chamber 201 from the inert gas supply system.

[0089] In step C, when supplying the second precursor, it is preferable that the treatment conditions are such that the second precursor does not undergo thermal decomposition (gas phase decomposition). Processing temperature: 25-500°C, preferably 50-300°C Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa Second precursor supply flow rate: 1 to 3000 sccm, preferably 50 to 1000 sccm Second precursor supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes This is an example. Other processing conditions can be the same as the processing conditions in step A.

[0090] In step C, by supplying a second precursor to wafer 200, at least a portion of the molecular structure of the molecules constituting the second precursor can be selectively (preferentially) adsorbed onto the surface of the adsorption-promoting layer formed on the surface of the SiN film, which is the second substrate. As a result, as shown in Figure 4(d), a second adsorption-inhibiting layer is selectively (preferentially) formed on the surface of the adsorption-promoting layer. At this time, the formation of the second adsorption-inhibiting layer on the surface of the SiO film, which is the first substrate, can be suppressed by the action of the first adsorption-inhibiting layer formed on the surface of the SiO film. The second adsorption-inhibiting layer will contain at least a portion of the molecular structure of the molecules constituting the second precursor, for example, residues derived from the second precursor. Examples of residues derived from the second precursor included in the second adsorption-inhibiting layer include groups generated by the chemical reaction of the second precursor with adsorption sites (e.g., OH terminals) on the surface of the adsorption-promoting layer. In this way, by containing residues derived from the second precursor, the second adsorption-inhibiting layer exhibits an adsorption-inhibiting effect (acts as an inhibitor).

[0091] After the second adsorption-inhibiting layer is formed on the surface of the adsorption-promoting layer formed on the surface of the second substrate SiN film, the opening and closing operation of the valve in the second precursor supply system is controlled to stop the supply of the second precursor into the processing chamber 201. Then, the second precursor and other substances remaining in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and conditions as the purging in step A described above (purging).

[0092] -Second Precursor- As the second precursor, a substance that selectively (preferentially) adsorbs onto the surface of the adsorption-promoting layer is used. For example, it is preferable to use a compound represented by the following formula 2 as the second precursor.

[0093] [R 21 ]n 2 -(X2 )-[R 22 ]m 2 : formula 2 In equation 2 above, R 21 is X 2 R represents the first substituent directly bonded to it. 22 is X 2 This represents a second substituent directly bonded to X 2 n represents a tetravalent atom selected from the group consisting of C atoms, Si atoms, Ge atoms, and tetravalent metal atoms, 2 represents an integer from 1 to 3, and m 2 represents an integer between 1 and 3, and n 2 +m 2 = 4

[0094] In formula 2, the first substituent is R 21 The number of n 2 n is an integer between 1 and 3, and is more preferably 2 or 3. 2 If it is 2 or 3, the first substituent is R 21 These may be the same or they may be different.

[0095] R 21 As the first substituent represented by , a substituent that has the function of exhibiting an adsorption-inhibiting effect in the second adsorption-inhibiting layer when included in the second adsorption-inhibiting layer can be used. In other words, R 21 The first substituent represented by is contained in the residue derived from the second precursor contained in the second adsorption suppression layer. 21 The first substituent represented by is preferably a substituent that suppresses the adsorption of the film-forming material onto the surface of the second substrate. 21 The first substituent represented by is preferably a chemically stable substituent.

[0096] R 21 The first substituent represented by is preferably a substituent that has a stronger adsorption inhibitory effect than the first substituent of the first precursor used in step A. 21The first substituent represented by is more preferably a substituent that is less likely to lose its adsorption inhibitory effect than the first substituent of the first precursor used in step A. In this way, under the same conditions, the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C can be made stronger than the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A, making it easier to selectively form a film on the surface of the first substrate in step D.

[0097] R 21 The first substituent represented by is R in formula 1, except as shown below. 11 This is synonymous with the same as the preferred form. 21 The first substituent represented by is preferably a hydrogen group or a hydrocarbon group, with hydrocarbon groups being preferred and alkyl groups being more preferred.

[0098] In formula 2, the second substituent R 22 The number, that is, m 2 m is an integer between 1 and 3, and is more preferably 1 or 2. 2 If it is 2 or 3, the second substituent is R 22 These may be the same or they may be different.

[0099] R 22 The second substituent represented by is preferably a substituent that enables the chemical adsorption of the second precursor to the adsorption site (e.g., the OH terminus) on the surface of the adsorption-promoting layer.

[0100] R 22 The second substituent represented by is R in formula 1. 12 This is synonymous with the same as the preferred configuration.

[0101] In formula 2, X 2 The atom to which the first and second substituents represented by are directly bonded is X in formula 1. 1 This is synonymous with the same as the preferred form. 2 Si atoms are particularly preferred. This is because X 2When the atom is a Si atom, it is possible to obtain a good balance between the high adsorption of the second precursor to the surface of the adsorption-promoting layer and the high chemical stability of the second precursor after adsorption to the surface of the adsorption-promoting layer, i.e., the residue derived from the second precursor.

[0102] The compound represented by Formula 2 has been described above, but the second precursor is not limited to the compound represented by Formula 2. For example, the second precursor is preferably composed of a molecule containing the first substituent described above, the second substituent described above, and an atom to which the first substituent and the second substituent are directly bonded. However, the atom to which the first substituent and the second substituent are directly bonded may be a metal atom capable of bonding to five or more ligands. When the atom to which the first substituent and the second substituent are directly bonded is a metal atom capable of bonding to five or more ligands, the number of first substituents and second substituents in the molecule of the second precursor can be increased compared to the compound represented by Formula 2, and the adsorption inhibitory effect of the second adsorption inhibitory layer can be adjusted. Furthermore, the second precursor may be composed of a molecule containing the first substituent described above, the second substituent described above, and two or more atoms to which the first substituent and the second substituent are directly bonded.

[0103] Examples of second precursors include (dimethylamino)methylsilane: (CH3)2NSiH2(CH3), (ethylamino)methylsilane: (C2H5)HNSiH2(CH3), (propylamino)methylsilane: (C3H7)2HNSiH2(CH3), (butylamino)methylsilane: (C4H9)2HNSiH2(CH3), (diethylamino)methylsilane: (C2H5)2NSiH2(CH3), (dipropylamino)methylsilane: (C3H7)2NSiH2(CH3), and (dibutylamino)methylsilane: (C3H7)2NSiH2 (CH3), (dimethylamino)dimethylsilane: (CH3)2NSiH(CH3)2, (ethylamino)dimethylsilane: (C2H5)HNSiH(CH3)2, (propylamino)dimethylsilane: (C3H7)2HNSiH(CH3)2, (butylamino)dimethylsilane: (C4H9)2HNSiH(CH3)2, (diethylamino)dimethylsilane: (C2H5)2NSiH(CH3)2, (dipropylamino)dimethylsilane: (C3H7)2NSiH(CH3)2, (dibutylamino)dimethylsilane: (C3H7)2NSiH(CH 3)2, (dimethylamino)trimethylsilane:(CH3)2NSi(CH3)3, (ethylamino)trimethylsilane:(C2H5)HNSi(CH3)3, (propylamino)trimethylsilane:(C3H7)2HNSi(CH3)3, (butylamino)trimethylsilane:(C4H9)2HNSi(CH3)3, (diethylamino)trimethylsilane:(C2H5)2NSi(CH3)3, (dipropylamino)trimethylsilane:(C3H7)2NSi(CH3)3, (dibutylamino)trimethylsilane:(C3H7)2NSi(CH3) 3. (Dimethylamino)ethylsilane: (CH3)2NSiH2(C2H5), (Ethylamino)ethylsilane: (C2H5)HNSiH2(C2H5), (Propylamino)ethylsilane: (C3H7)2HNSiH2(C2H5), (Butylamino)ethylsilane: (C4H9)2HNSiH2(C2H5), (Diethylamino)ethylsilane: (C2H5)2NSiH2(C2H5), (Dipropylamino)ethylsilane: (C3H7)2NSiH2(C2H5), (Dibutylamino)ethylsilane: (C3H7)2NSiH2(C2H5),(Dimethylamino)diethylsilane: (CH3)2NSiH(C2H5)2, (Ethylamino)diethylsilane: (C2H5)HNSiH(C2H5)2, (Propylamino)diethylsilane: (C3H7)2HNSiH(C2H5)2, (Butylamino)diethylsilane: (C4H9)2HNSiH(C2H5)2, (Diethylamino)diethylsilane: (C2H5)2NSiH(C2H5)2, (Dipropylamino)diethylsilane: (C3H7)2NSiH(C2H5)2, (Dibutylamino)diethylsilane: (C3H7)2NSiH(C2H5)2, (Dimethylamino)triethylsilane: (CH3)2NSi(C2H5)3, (Ethyl (Dipropylamino)triethylsilane: (C2H5)HNSi(C2H5)3, (Propylamino)triethylsilane: (C3H7)2HNSi(C2H5)3, (Butylamino)triethylsilane: (C4H9)2HNSi(C2H5)3, (Diethylamino)triethylsilane: (C2H5)2NSi(C2H5)3, (Dipropylamino)triethylsilane: (C3H7)2NSi(C2H5)3, (Dibutylamino)triethylsilane: (C3H7)2NSi(C2H5)3, (Dipropylamino)silane: [(C3H7)2N]SiH3, (Dibutylamino)silane: [(C4H9)2N]SiH3, (Dipentylamino)silane: [(C5H, 11)2N]SiH3, bis(dimethylamino)dimethylsilane:[(CH3)2N]2Si(CH3)2, bis(ethylamino)dimethylsilane:[(C2H5)HN]2Si(CH3)2, bis(propylamino)dimethylsilane:[(C3H7)2HN]2Si(CH3)2, bis(butylamino)dimethylsilane:[(C4H9)2HN]2Si(CH3)2, bis(diethylamino)dimethylsilane:[(C2H5)2N]2Si(CH3)2, bis(dipropylamino)dimethylsilane:[(C3H7)2N]2Si(CH3)2, bis (Dibutylamino)dimethylsilane: [(C3H7)2N]2Si(CH3)2, bis(dimethylamino)methylsilane: [(CH3)2N]2SiH(CH3), bis(ethylamino)methylsilane: [(C2H5)HN]2SiH(CH3), bis(propylamino)methylsilane: [(C3H7)2HN]2SiH(CH3), bis(butylamino)methylsilane: [(C4H9)2HN]2SiH(CH3), bis(diethylamino)methylsilane: [(C2H5)2N]2SiH(CH3), bis(dipropylamino)methylsilane: [ (C3H7)2N]2SiH(CH3), bis(dibutylamino)methylsilane[(C3H7)2N]2SiH(CH3), bis(dimethylamino)diethylsilane:[(CH3)2N]2Si(C2H5)2, bis(ethylamino)diethylsilane:[(C2H5)HN]2Si(C2H5)2, bis(propylamino)diethylsilane:[(C3H7)2HN]2Si(C2H5)2, bis(butylamino)diethylsilane:[(C4H9)2HN]2Si(C2H5)2, bis(diethylamino)diethylsilane:[(C2H5)2N]2 Si(C2H5)2, bis(dipropylamino)diethylsilane:[(C3H7)2N]2Si(C2H5)2, bis(dibutylamino)diethylsilane:[(C3H7)2N]2Si(C2H5)2, bis(dimethylamino)ethylsilane:[(CH3)2N]2SiH(C2H5), bis(ethylamino)ethylsilane:[(C2H5)HN]2SiH(C2H5), bis(propylamino)ethylsilane:[(C3H7)2HN]2SiH(C2H5), bis(butylamino)ethylsilane:[(C4H9)2HN]2SiH(C2H5),Bis(diethylamino)ethylsilane:[(C2H5)2N]2SiH(C2H5), Bis(dipropylamino)ethylsilane:[(C3H7)2N]2SiH(C2H5), Bis(dibutylamino)ethylsilane:[(C3H7)2N]2SiH(C2H5), Bis(diethylamino)silane:[(C2H5)2N]2SiH2, Bis(dipropylamino)silane:[(C3H7)2N]2SiH2, Bis(dibutylamino)silane:[(C4H9)2N]2SiH2, Bis(dipentylamino)silane:[(C5H, 11 Examples include 2N]2SiH2.

[0104] One or more of these can be used as the second precursor. It is preferable to select the second precursor used in step C such that, under the same conditions, the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C is stronger than the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A. The adsorption inhibitory effect of the second adsorption inhibitory layer can be adjusted by the number and type of first substituents contained in the second precursor. Therefore, the second precursor used in step C can be appropriately selected depending on the number and type of first substituents contained in the first precursor used in step A. Specifically, if the first precursor and the second precursor have the same number of first substituents, and the first precursor has only a hydrogen group as its first substituent, it is preferable to select a second precursor that has only an alkyl group as its first substituent, or one that has both an alkyl group and a hydrogen group as its first substituent. This is because alkyl groups have a stronger adsorption inhibitory effect than hydrogen groups. Furthermore, if both the first and second precursors have the same first substituent (e.g., an alkyl group), it is preferable to select a second precursor in which the number of first substituents is greater than the number of first substituents in the first precursor. This is because the greater the number of first substituents, the stronger the adsorption-inhibiting effect of the formed adsorption-inhibiting layer becomes.

[0105] Furthermore, it is preferable to use a second precursor in which the number of second substituents contained in one molecule is the same as or less than the number of second substituents contained in the first precursor used in step A. This is because the fewer the number of second substituents contained in one molecule, the greater the number of first substituents contained in one molecule, and the stronger the adsorption inhibitory effect of the adsorption inhibitory layer. In this way, under the same conditions, it is possible to make the adsorption inhibitory effect of the second adsorption inhibitory layer formed in step C stronger than the adsorption inhibitory effect of the first adsorption inhibitory layer formed in step A, making it easier to selectively form a film on the surface of the first substrate in step D.

[0106] In step C, if the second precursor having a fluoro group, fluoroalkyl group, hydrogen group, etc. as the first substituent cannot exist stably as a single compound, a second precursor having a different first substituent and being able to exist stably as a single compound may be adsorbed onto the adsorption-promoting layer, and then a specific treatment may be applied to convert the other first substituent to a hydrogen group, fluoro group, or fluoroalkyl group. An example of a method for converting the first substituent in the second precursor is the same as the example of a method for converting the first substituent in the first precursor described above.

[0107] (Step D) After performing steps A, B, and C in that order, the opening and closing operation of the valve in the film deposition material supply system is controlled to supply the film deposition material to the wafer 200 in the processing chamber 201. The film deposition material supplied to the wafer 200 is exhausted from the exhaust port 231a. At this time, an inert gas may also be supplied into the processing chamber 201 from the inert gas supply system.

[0108] In step D, the action of the film-forming material neutralizes the action of the first adsorption-inhibiting layer without neutralizing the action of the second adsorption-inhibiting layer, thereby selectively (preferentially) forming a film on the surface of the first substrate, the SiO film, as shown in Figure 4(e). In other words, in step D, the adsorption-inhibiting action of the second adsorption-inhibiting layer is maintained while the adsorption-inhibiting action of the first adsorption-inhibiting layer is released, thereby selectively forming a film on the surface of the first substrate, the SiO film. The action of the film-forming material includes both the chemical action and the physical action of the film-forming material. Furthermore, neutralizing the action of the adsorption-inhibiting layer means neutralizing the adsorption-inhibiting action of the adsorption-inhibiting layer. The neutralization of the adsorption-inhibiting effect of the adsorption-inhibiting layer includes, for example, altering or destroying the molecular structure of molecules contained in the adsorption-inhibiting layer by the action of a film-forming material, thereby making the surface of the substrate on which the adsorption-inhibiting layer was formed into a state where substances can be adsorbed, or altering or destroying the molecular structure of molecules contained in the adsorption-inhibiting layer by the action of a film-forming material and removing the adsorption-inhibiting layer, thereby making the surface of the substrate on which the adsorption-inhibiting layer was formed into a state where substances can be adsorbed.

[0109] As described above, in the first embodiment, it is preferable that the adsorption inhibitory effect of the first adsorption inhibitory layer is weaker than that of the second adsorption inhibitory layer. By utilizing this difference in adsorption inhibitory effects between the first and second adsorption inhibitory layers, a film can be selectively formed on the surface of the SiO film, which is the first substrate.

[0110] The film formed in step D can be formed by supplying a film-forming material to the wafer 200, and there are no particular restrictions on the method. Here, the film-forming material includes a source gas, a reaction gas, a catalyst gas, etc. For example, in step D, it is preferable to alternately supply the source gas and the reaction gas to the wafer 200 as the film-forming material, or to alternately supply the source gas and the reaction gas to the wafer 200 as the film-forming gas, and to supply the catalyst gas together with at least one of the source gas and the reaction gas. However, depending on the processing conditions, the supply of the catalyst gas is not always necessary and can be omitted. For example, in step D, any of the following processing sequences can be performed. Note that the following processing sequences show only step D.

[0111] (raw material gas → reaction gas) × n (raw material gas → reaction gas + catalyst gas) × n (raw material gas + catalyst gas → reaction gas) × n (raw material gas + catalyst gas → reaction gas + catalyst gas) × n

[0112] In the following, we will describe an example in which, in step D, the raw material gas and the reaction gas are supplied alternately as the film-forming material, and the catalyst gas is supplied together with each gas. Specifically, we will describe an example in which step D consists of a predetermined number of non-simultaneous cycles (n times, where n is an integer of 1 or more) in which step D1, in which the raw material gas and catalyst gas are supplied to the wafer 200, and step D2, in which the reaction gas and catalyst gas are supplied to the wafer 200.

[0113] (Step D1) After step C is completed, the film deposition material supply system supplies the raw material gas and catalyst gas to the wafer 200 in the processing chamber 201 as the film deposition material. The raw material gas and catalyst gas supplied to the wafer 200 are exhausted from the exhaust port 231a. At this time, an inert gas may also be supplied into the processing chamber 201 from the inert gas supply system.

[0114] After supplying the raw material gas and catalyst gas to the wafer 200 for a predetermined time, the supply of the raw material gas and catalyst gas to the processing chamber 201 is stopped. Then, the remaining raw material gas and catalyst gas in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and conditions as the purging in step A described above (purging).

[0115] The processing conditions for supplying the raw material gas and catalyst gas in step D1 are as follows: Processing temperature: 25-200°C, preferably 25-120°C Processing pressure: 133~1333 Pa Raw material gas supply flow rate: 1-2000 sccm Raw material gas supply time: 1-120 seconds Catalyst gas supply flow rate: 1-2000 sccm Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0116] - Raw material gas - As a raw material gas, for example, a Si-containing gas can be used. Examples of Si-containing gases include Si and halogen-containing gases, Si and amino group-containing gases, and Si and alkoxy group-containing gases. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. Amino groups include substituted amino groups. The substituents on the substituted amino group are preferably alkyl groups, more preferably alkyl groups having 1 to 5 carbon atoms, and particularly preferably alkyl groups having 1 to 4 carbon atoms. The alkyl groups on the substituted amino group may be linear or branched. Examples of alkyl groups on the substituted amino group include methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. Alkoxy groups include methoxy group, ethoxy group, propoxy group, etc.

[0117] The Si and halogen-containing gas, Si and amino group-containing gas, and Si and alkoxy group-containing gas preferably contain chemical bonds between Si and halogen, Si and amino groups, and Si and alkoxy groups, respectively. These Si-containing gases may also contain C, in which case it is preferable that C is contained in the form of a Si-C bond. As the Si and C-containing gas, for example, an alkylenesilane gas containing alkylene groups and having Si-C bonds can be used. The alkylene group includes methylene groups, ethylene groups, propylene groups, butylene groups, etc. As the alkylenesilane gas, it is preferable that Si and halogen, Si and amino groups, Si and alkoxy groups, etc. are contained in the form of direct bonds, and C is contained in the form of a Si-C bond.

[0118] Examples of Si and halogen-containing gases include dichlorosilane: SiH2Cl2, trichlorosilane: SiHCl3, tetrachlorosilane: SiCl4, tetrabromosilane: SiBr4, hexachlorodisilane: (SiCl3)2, octachlorotrisilane: Si3Cl8, hexachlorodisiloxane: (SiCl3)2O, and octachlorotrisiloxane: (SiCl3O)2SiCl2. Examples of Si and amino group-containing gases include tetrakis(dimethylamino)silane: Si[N(CH3)2]4 and tetrakis(diethylamino)silane: Si[N(C2H5)2]4. Examples of gases containing Si and alkoxy groups include tetramethoxysilane:Si(OCH3)4, tetraethoxysilane:Si(OC2H5)4, (dimethylamino)trimethoxysilane:[(CH3)2N]Si(OCH3)3, and (dimethylamino)triethoxysilane:[(CH3)2N]Si(OC2H5)3. Examples of Si, C, and halogen-containing gases include bistrichlorosilylmethane: (SiCl3)2CH2, bistrichlorosilylethane: (SiCl3)C2H5, bis[(trichlorosilyl)methyl]dichlorosilane: [(SiCl3)3CH2]2SiCl2, 1,1,2,2-tetrachloro-1,2-dimethyldisilane: (CH3)2Si2Cl4, 1,2-dichloro-1,1,2,2-tetramethyldisilane: (CH3)4Si2Cl2, and 1,1,3,3-tetrachloro-1,3-disilacyclobutane: C2H4Cl4Si2. One or more of these can be used as the raw material gas.

[0119] -Catalytic gas- As the catalyst gas, for example, an amine gas containing C, N, and H can be used. Examples of amine gases include dimethylamine: C2H7N and diethylamine: C4H 11 N, dipropylamine:C6H 15 N, pyridine: C5H5N, piperidine: C6H 12 N, pyrrolidine: C4H9N, aniline: C6H7N, picoline: C6H7N, aminopyridine: C5H6N2, lutidine: C7H9N, piperazine: C4H 10Examples include N2. One or more of these can be used as the catalyst gas.

[0120] (Step D2) After step D1 is completed, the film deposition material supply system supplies reaction gas and catalyst gas as film deposition materials to the wafer 200 in the processing chamber 201. The reaction gas and catalyst gas supplied to the wafer 200 are exhausted from the exhaust port 231a. At this time, an inert gas may also be supplied into the processing chamber 201 from the inert gas supply system.

[0121] After supplying the reaction gas and catalyst gas to the wafer 200 for a predetermined time, the supply of the reaction gas and catalyst gas to the processing chamber 201 is stopped. Then, the reaction gas, catalyst gas, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and conditions as the purging in step A described above (purging).

[0122] The processing conditions for supplying the reaction gas and catalyst gas in step D2 are as follows: Processing temperature: 25°C to 200°C, preferably 25°C to 120°C Processing pressure: 133~1333 Pa Reaction gas supply flow rate: 1-2000 sccm Reaction gas supply time: 1-120 seconds Catalyst gas supply flow rate: 1-2000 sccm Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0123] -Reaction gas- As the reaction gas, when forming an oxide film system, for example, an O and H-containing gas can be used. As an O and H-containing gas, for example, an O-containing gas containing OH bonds such as H2O gas or H2O2 gas can be used. Alternatively, as an O and H-containing gas, an O-containing gas without OH bonds such as H2 gas + O2 gas or H2 gas + O3 gas can also be used.

[0124] Furthermore, when forming a nitride film, a nitride agent (nitriding gas) can be used as the reaction gas. For example, N and H-containing gases can be used as the nitride agent. Examples of N and H-containing gases include hydrogen nitride gases containing NH bonds, such as ammonia (NH3) gas, hydrazine (N2H4) gas, diazene (N2H2) gas, and N3H8 gas. One or more of these can be used as the reaction gas.

[0125] -Catalytic gas- As the catalyst gas, for example, a catalyst gas similar to the various catalyst gases exemplified in step D1 above can be used.

[0126] (Performed the prescribed number of times) By performing steps D1 and D2 described above non-simultaneously, i.e., without synchronization, a predetermined number of times (n times, where n is an integer of 1 or more), it becomes possible to selectively form a film of a desired thickness on the surface of the first substrate SiO film, as shown in Figure 4(e).

[0127] Furthermore, during the process of performing the above cycle a predetermined number of times, the adsorption-inhibiting effect of the first adsorption-inhibiting layer formed on the surface of the first substrate can be neutralized (released). After the adsorption-inhibiting effect of the first adsorption-inhibiting layer is neutralized, in step D1, the first layer is formed on the surface of the first substrate, and in step D2, the first layer formed on the surface of the first substrate is transformed into the second layer. By performing these steps a predetermined number of times, a film consisting of the second layer is formed on the first substrate. During this time, by maintaining the adsorption-inhibiting effect of the second adsorption-inhibiting layer formed on the surface of the second substrate, the formation of a film on the surface of the second substrate can be suppressed. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired film thickness, and to repeat the above cycle multiple times by laminating the second layer until the thickness of the film formed on the first substrate reaches the desired film thickness.

[0128] Furthermore, by performing the above cycle a predetermined number of times, a very thin film may be formed on the surface of the second substrate. However, even in this case, the thickness of the film formed on the surface of the second substrate will be far thinner than the thickness of the film formed on the surface of the first substrate. In this specification, "high selectivity in selective growth" includes not only the case in which no film is formed on the surface of the second substrate and a film is formed only on the surface of the first substrate, but also the case in which, as described above, a very thin film is formed on the surface of the second substrate, but a much thicker film is formed on the surface of the first substrate.

[0129] In step D, the material (type of film) obtained differs depending on the type of raw material gas and reaction gas. For example, in step D, by using Si, C, and halogen-containing gases as raw material gases and O-containing gases as reaction gases, a silicon carbide film (SiOC film) can be formed. Alternatively, in step D, by using Si, C, and halogen-containing gases as raw material gases and N and H-containing gases as reaction gases, a silicon carbonitride film (SiCN film) can be formed. Alternatively, in step D, by using Si, C, and halogen-containing gases as raw material gases and O-containing gases, N, and H-containing gases as reaction gases, a silicon carbitride film (SiOCN film) can be formed. Alternatively, in step D, by using Si and halogen-containing gases as raw material gases and O-containing gases as reaction gases, a silicon oxide film (SiO film) can be formed. Alternatively, in step D, by using Si and halogen-containing gases as raw material gases and N and H-containing gases as reaction gases, a silicon nitride film (SiN film) can be formed. As described above, various films such as silicon oxide films and silicon nitride films can be formed in step D. Furthermore, as mentioned above, a catalyst gas is not always necessary depending on the processing conditions. If a catalyst gas is not used, the processing temperature in step D can be set to a predetermined temperature within the range of, for example, 200 to 500°C.

[0130] Furthermore, in step D, by using a raw material gas containing metal elements such as Al, Ti, Hf, Zr, Ta, Mo, and W as the raw material gas, and using an O-containing gas or an N and H-containing gas as the reaction gas, it is possible to form films such as metallic 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), and tungsten oxide film (WO), as well as metallic 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), and tungsten nitride film (WN). As mentioned above, depending on the processing conditions, a catalytic gas is not always necessary. If a catalytic gas is not used, the processing temperature in step D can be set to a predetermined temperature within the range of 200 to 500°C.

[0131] (After-purge and return to atmospheric pressure) After a film is selectively formed on the surface of the SiO film, which is the first substrate on the surface of the wafer 200, an inert gas is supplied from the inert gas supply system into the processing chamber 201 as a purge gas and exhausted from the exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purging). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0132] (Boat unloading and wafer discharge) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutters 219s are moved, and the lower end opening of the manifold 209 is sealed by the shutters 219s via the O-ring 220c (shutter closing). After the processed wafer 200 has been unloaded from the reaction tube 203, it is removed from the boat 217 (wafer discharge).

[0133] (Effects according to the first aspect) According to the first embodiment, one or more of the following effects can be obtained.

[0134] By forming a first adsorption-inhibiting layer on the surface of the first substrate, it becomes possible to selectively form an adsorption-promoting layer on the surface of the second substrate, and to selectively form a second adsorption-inhibiting layer on the surface of the adsorption-promoting layer. In other words, it becomes possible to selectively form a second adsorption-inhibiting layer on the outermost surface of the second substrate (a specific substrate). Subsequently, by supplying a film-forming material, it becomes possible to selectively form a film on the surface of the first substrate (a desired substrate).

[0135] The action of the film-forming material can release the adsorption-inhibiting effect of the first adsorption-inhibiting layer, thereby enabling the formation of a film on the surface of the first substrate. At the same time, by maintaining the adsorption-inhibiting effect of the second adsorption-inhibiting layer formed on the surface of the second substrate, it is possible to suppress the formation of a film on the surface of the second substrate. In other words, selective film formation on the surface of the first substrate becomes possible without performing a separate process such as removing the first adsorption-inhibiting layer. This shortens the processing time and increases throughput, i.e., productivity.

[0136] By performing the above steps on a wafer 200 in which the first substrate is an oxygen-containing film and the second substrate is an oxygen-free film, the above-mentioned chemical reactions can be produced more appropriately. As a result, the above-mentioned effects will be significantly more pronounced. By performing the above steps on a wafer 200 in which the first substrate is at least one of, for example, an SiO film, an SiOC film, or an AlO film, and the second substrate is at least one of, for example, a silicon film (Si film), a SiN film, or a metal film, the above-mentioned chemical reactions can be produced even more appropriately. As a result, the above-mentioned effects will be even more pronounced.

[0137] It is preferable that the adsorption-inhibiting effect of the first adsorption-inhibiting layer formed in step A is weaker than that of the second adsorption-inhibiting layer formed in step C under the same conditions. Furthermore, it is preferable that the first adsorption-inhibiting layer formed in step A is more easily desorbed than the second adsorption-inhibiting layer formed in step C under the same conditions. In addition, it is preferable that the reactivity between the film-forming material used in step D and the first adsorption-inhibiting layer formed in step A is higher than that between the film-forming material used in step D and the second adsorption-inhibiting layer formed in step C under the same conditions. These factors make it possible to efficiently neutralize the adsorption-inhibiting effect of the first adsorption-inhibiting layer in step D.

[0138] <Second aspect of this disclosure> Next, the second aspect of this disclosure will be explained, mainly with reference to Figures 5(a) to 5(f) and Figures 6(a) to 6(f).

[0139] As shown in Figures 5(a) to 5(f), Figures 6(a) to 6(f), and the processing sequence described below, the processing sequence in the second embodiment further includes step E, which, after performing steps A, B, and C and before performing step D, is performed, which is at least one of the following: removal of the first adsorption suppression layer and / or deactivation of the effect of the first adsorption suppression layer (hereinafter also referred to as removal and / or deactivation of the first adsorption suppression layer).

[0140] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Removal and / or deactivation of the first adsorption-suppressing layer → Film formation

[0141] Furthermore, as shown in Figures 5(a) to 5(f) and the processing sequence below, the first adsorption suppression layer may be removed in step E.

[0142] Formation of first adsorption suppression layer → Formation of adsorption promotion layer → Formation of second adsorption suppression layer → Removal of first adsorption suppression layer → Film formation

[0143] Furthermore, as shown in Figures 6(a) to 6(f) and the processing sequence below, the effect of the first adsorption suppression layer may be disabled in step E.

[0144] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Deactivation of the first adsorption-suppressing layer → Film formation

[0145] Furthermore, as shown in the processing sequence below, step E may involve both the removal of the first adsorption suppression layer and the deactivation of the first adsorption suppression layer. In this case, the first adsorption suppression layer is removed from a portion of the surface of the first substrate, while its effect is deactivated in another portion.

[0146] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Removal and deactivation of the first adsorption-suppressing layer → Film formation

[0147] (Steps A, B, C) Steps A, B, and C can be carried out using the same processing procedures and conditions as steps A, B, and C in the first embodiment.

[0148] (Step E) After performing steps A, B, and C, step E is performed. In step E, at least one of the following is performed: removal of the first adsorption suppression layer, or deactivation of the effect of the first adsorption suppression layer.

[0149] There are no particular limitations on the method for removing and / or inactivating the first adsorption inhibitory layer. Examples of methods for removing and / or inactivating the first adsorption inhibitory layer include annealing, oxidation, and denaturation. These treatments can remove the first adsorption inhibitory layer, denaturate the first substituent contained in the first adsorption inhibitory layer, or cleave (dissociate) the bond between the residues derived from the first precursor contained in the first adsorption inhibitory layer and the first substrate. It is preferable that the above-mentioned annealing, oxidation, and denaturation treatments do not reduce the adsorption inhibitory effect of the second adsorption inhibitory layer formed on the surface of the second substrate. To this end, it is preferable that the above-mentioned annealing, oxidation, and denaturation treatments utilize at least one of the differences in heat resistance, oxidation resistance, or reactivity with specific substances between the first and second adsorption inhibitory layers to remove and / or inactivate the first adsorption inhibitory layer without reducing the adsorption inhibitory effect of the second adsorption inhibitory layer formed on the surface of the second substrate.

[0150] In step E, when supplying an inactivating substance (as described above, this term is used for convenience as a general term for substances to be removed and / or inactivated) to the wafer 200, the opening and closing operation of the valve in the processing material supply system should be controlled to supply the inactivating substance to the wafer 200 in the processing chamber 201. The inactivating substance supplied to the wafer 200 is exhausted from the exhaust port 231a. At this time, an inert gas may also be supplied into the processing chamber 201 from the inert gas supply system.

[0151] [Annealing process] In step E, an annealing treatment, preferably under an inert gas atmosphere, can be performed to remove and / or deactivate the first adsorption suppression layer. The inert gas can be supplied into the processing chamber 201 from an inert gas supply system. At this time, the inert gas is supplied to the wafer 200, and an inert gas atmosphere is formed in the processing chamber 201.

[0152] The processing conditions for annealing are as follows: Processing temperature: 100-600°C, preferably 200-500°C Processing pressure: 1 to 101325 Pa, preferably 1 to 13300 Pa Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Inert gas supply time: 1 to 240 minutes, preferably 30 to 120 minutes Examples are given.

[0153] The annealing treatment in step E is preferable, for example, when the first substituent in the first adsorption suppression layer is a hydrogen group or an alkoxy group, and the first substituent in the second adsorption suppression layer is an alkyl group or a fluoroalkyl group. Furthermore, the annealing treatment in step E is preferable when the number of second substituents in the first adsorption suppression layer is 2 or 3, and the number of second substituents in the second adsorption suppression layer is 1.

[0154] [Oxidation treatment] In step E, oxidation treatment can be performed to remove and / or deactivate the first adsorption suppression layer. Examples of oxidation treatments include immersing the wafer 200 in water, exposing the wafer 200 to the atmosphere, supplying an oxidizing agent to the wafer 200, and simultaneously supplying an oxidizing agent and a catalyst gas to the wafer 200. As the oxidizing agent acting as a deactivating substance, an O-containing substance can be used. As the O-containing substance, for example, an O-containing substance similar to the various O-containing substances exemplified in step B above can be used. As the catalyst gas, for example, a catalyst gas similar to the various catalyst gases exemplified in step D1 above can be used. The oxidizing agent and catalyst gas can be supplied using the processing material supply system described above.

[0155] When performing oxidation treatment using an oxygen-containing substance as an oxidizing agent, the treatment conditions are as follows: Processing temperature: 25-800°C, preferably 25-600°C Processing pressure: 1 to 101325 Pa, preferably 1 to 1330 Pa O-containing material supply flow rate: 1~2000sccm O-containing substance supply time: 1~120 seconds Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0156] When performing oxidation treatment using an oxygen-containing substance as an oxidizing agent and a catalyst gas, the treatment conditions are as follows: Processing temperature: 25-200°C, preferably 25-120°C Processing pressure: 1 to 101325 Pa, preferably 1 to 13300 Pa O-containing material supply flow rate: 1~20000sccm O-containing substance supply time: 1 second to 24 hours Catalyst gas supply flow rate: 1-20000 sccm Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0157] The oxidation treatment in step E is preferable, for example, when the first substituent in the first adsorption suppression layer is a hydrogen group or an alkoxy group, and the first substituent in the second adsorption suppression layer is an alkyl group or a fluoroalkyl group.

[0158] [Denaturation treatment] In step E, a modification treatment can be performed to remove and / or disable the first adsorption suppression layer. This modification treatment can modify some of the residues derived from the first precursor contained in the first adsorption suppression layer. The modification treatment can be performed by supplying a halogen-containing gas to the wafer 200. Examples of halogen-containing gases that act as disabling substances include F2 gas, HF gas, chlorine trifluoride (ClF3) gas, boron trifluoride (BCl3) gas, chlorine (Cl2) gas, hydrogen chloride (HCl) gas, bromine (Br2) gas, hydrogen bromide (HBr) gas, and tetrachloroethylene (C2Cl4) gas. In addition, the halogen-containing gas and catalyst gas may be supplied to the wafer 200 simultaneously during the modification treatment. The halogen-containing gas and catalyst gas can be supplied using the processing material supply system described above.

[0159] The processing conditions in the modification treatment using halogen-containing gas are as follows: Processing temperature: 25-400°C, preferably 25-200°C Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa Halogen-containing gas supply flow rate: 1-2000 sccm Halogen-containing gas supply time: 1 to 120 seconds Catalyst gas supply flow rate: 0-20000 sccm Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Examples are given.

[0160] The modification treatment in step E is preferable, for example, when the first substituent in the first adsorption suppression layer is a hydrogen group and the first substituent in the second adsorption suppression layer is an alkyl group or a fluoroalkyl group.

[0161] In the second embodiment, unlike the first embodiment, there does not need to be a sufficient difference between the adsorption inhibitory effect of the first adsorption inhibitory layer and the adsorption inhibitory effect of the second adsorption inhibitory layer. However, from the viewpoint of efficiently removing and / or deactivating the first adsorption inhibitory layer in step E, it is preferable that the adsorption inhibitory effect of the first adsorption inhibitory layer is weaker than that of the second adsorption inhibitory layer.

[0162] (Step D) After performing step E, step D is performed. In step D of the second embodiment, a film is selectively formed on the surface of the first substrate from which the adsorption suppression effect has been released. At this time, the second adsorption suppression layer formed on the outermost surface of the second substrate can suppress the formation of a film on the surface of the second substrate.

[0163] Step D can be carried out using the same processing procedure and conditions as Step D in the first embodiment. However, if the goal is to form a film of the same thickness as the film formed in the first embodiment, the processing time for Step D in the second embodiment can be shorter than the processing time for Step D in the first embodiment.

[0164] (Effects according to the second aspect) According to the second embodiment, one or more of the following effects can be obtained.

[0165] In the second embodiment, the same effects as in the first embodiment described above can be obtained. Furthermore, according to the second embodiment, by having step E, selective film formation on the surface of the first substrate can be performed efficiently without delay. When the first adsorption suppression layer is removed in step E, it is possible to prevent the residue of the first adsorption suppression layer from remaining at the interface between the film formed on the surface of the first substrate and the surface of the first substrate. This makes it possible to improve the interfacial properties between the film formed on the surface of the first substrate and the surface of the first substrate. Also, when the effect of the first adsorption suppression layer is neutralized in step E, the process can be completed in a relatively shorter time than when the first adsorption suppression layer is completely removed. This makes it possible to shorten the processing time and increase throughput, i.e., productivity.

[0166] The adsorption-inhibiting effect of the first adsorption-inhibiting layer formed in step A is preferably weaker than that of the second adsorption-inhibiting layer formed in step C under the same conditions. Furthermore, the first adsorption-inhibiting layer formed in step A is preferably more easily desorbed than the second adsorption-inhibiting layer formed in step C under the same conditions. In addition, the reactivity between the film-forming material used in step D and the first adsorption-inhibiting layer formed in step A is preferably higher than that between the film-forming material used in step D and the second adsorption-inhibiting layer formed in step C under the same conditions. These factors enable efficient removal and / or deactivation of the first adsorption-inhibiting layer in step E.

[0167] <Example 1> Modification 1 of this disclosure will be explained mainly with reference to Figures 7(a) to 7(f).

[0168] As shown in Figures 7(a) to 7(f) and the processing sequence described below, the processing sequence in Modified Example 1 further includes step F, which reduces the number of adsorption sites (e.g., OH terminations) on the surface of the first substrate before performing step A.

[0169] Decreased adsorption sites → Formation of the first adsorption-suppressing layer → Formation of an adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Film formation

[0170] In step F, by reducing the adsorption sites on the surface of the first substrate from the state shown in Figure 7(a) to the state shown in Figure 7(b), the formation of the second adsorption-inhibiting layer on the surface of the first substrate in step C can be suppressed. In other words, in step C, the formation of the second adsorption-inhibiting layer on the surface of the adsorption-promoting layer formed on the surface of the second substrate can be carried out with greater selectivity. Methods for reducing the adsorption sites on the surface of the first substrate in step F include annealing treatment.

[0171] The processing conditions for the annealing process in step F are as follows: Processing temperature: 100-500°C, preferably 200-500°C Processing pressure: 1 to 101325 Pa, preferably 1 to 13300 Pa Inert gas supply flow rate (per gas supply pipe): 0-20000 sccm Processing time: 1 to 240 minutes, preferably 30 to 120 minutes Examples are given.

[0172] If the processing temperature is set below 100°C, the effect of reducing adsorption sites on the surface of the first substrate is insufficient, and adsorption sites (OH terminations) may remain densely on the surface of the first substrate, as shown in Figure 10(a). In this case, after step A is completed, adsorption sites (OH terminations) may remain on the surface of the first substrate, as shown in Figure 10(b). If steps B and C are performed in this order, as shown in Figure 10(c), at least a part of the molecular structure of the molecules constituting the second precursor (for example, residues derived from the second precursor) may be adsorbed onto the adsorption sites (OH terminations) remaining on the surface of the first substrate. In this case, not only the first adsorption suppression layer but also the second adsorption suppression layer will be formed on the surface of the first substrate, resulting in reduced selectivity. This problem can be resolved by setting the processing temperature to 100°C or higher. This problem can be completely resolved by setting the processing temperature to 200°C or higher.

[0173] On the other hand, if the processing temperature is set higher than 500°C, the effect of reducing adsorption sites on the surface of the first substrate becomes excessive, and as shown in Figure 11(a), adsorption sites (OH terminals) are sparsely present on the surface of the first substrate. Therefore, after step A is completed, as shown in Figure 11(b), the spacing between at least some of the molecular structures of the molecules constituting the first precursor adsorbed on the surface of the first substrate (for example, residues derived from the first precursor) may become too wide. In other words, a large area may be formed on the surface of the first substrate where the first adsorption suppression layer is not formed. If steps B and C are performed in this order, as shown in Figure 11(c), in step B, an adsorption promotion layer may be formed in the area on the surface of the first substrate where the first adsorption suppression layer is not formed, and in step C, at least some of the molecular structures of the molecules constituting the second precursor may be adsorbed on the surface of the adsorption promotion layer. In this case, not only the first adsorption suppression layer but also the second adsorption suppression layer will be formed on the surface of the first substrate, resulting in a decrease in selectivity. This problem can be resolved by keeping the processing temperature below 500°C.

[0174] For these reasons, it is desirable to set the annealing temperature to 100°C to 500°C, preferably 200°C to 500°C. This makes it possible to appropriately reduce the adsorption sites (OH terminations) on the surface of the first substrate, as shown in Figure 12(a), and as shown in Figure 12(b), after step A is completed, at least a portion of the molecular structure of the molecules constituting the first precursor is appropriately adsorbed on the surface of the first substrate, and the first adsorption suppression layer is appropriately formed. If steps B and C are performed in this order, as shown in Figure 12(c), it becomes possible to suppress the formation of an adsorption promoting layer and the formation of a second adsorption suppression layer on the surface of the first substrate, thereby increasing selectivity.

[0175] After step F is performed, steps A, B, C, and D can be performed in the same manner as in the first embodiment, as shown in the processing sequence above. Steps A, B, C, and D can be performed using the same processing procedures and conditions as steps A, B, C, and D in the first embodiment.

[0176] Furthermore, in Modification 1, after step F, steps A, B, C, E, and D can be performed in the same manner as in the second embodiment, as shown in the processing sequence below. These steps A, B, C, E, and D can be performed using the same processing procedures and conditions as steps A, B, C, E, and D in the second embodiment.

[0177] Decreased adsorption sites → Formation of the first adsorption-inhibiting layer → Formation of an adsorption-promoting layer → Formation of the second adsorption-inhibiting layer → Removal and / or deactivation of the first adsorption-inhibiting layer → Film formation

[0178] In Modification 1, the same effects as those of the first and second embodiments described above can be obtained. Furthermore, according to Modification 1, it is possible to further enhance the selectivity in selective growth.

[0179] <Modification 2> Modification 2 of this disclosure will be explained mainly with reference to Figures 8(a) to 8(f).

[0180] As shown in Figures 8(a) to 8(f) and the processing sequence described below, the processing sequence in modified example 2 further includes step G, in which, after steps A, B, and C are performed, a film made of a different material from the adsorption promoting layer is formed on the surface of the first substrate in step D, and after step D, the film on the surface of the first substrate and the adsorption promoting layer and second adsorption suppression layer on the surface of the second substrate are exposed to an etching substance to remove the adsorption promoting layer and second adsorption suppression layer on the surface of the second substrate.

[0181] Formation of the first adsorption suppression layer → Formation of the adsorption promotion layer → Formation of the second adsorption suppression layer → Film formation → Removal of the second adsorption suppression layer and adsorption promotion layer

[0182] In step G, as shown in Figure 8(f), it is possible to selectively remove the adsorption-promoting layer and the second adsorption-inhibiting layer on the surface of the second substrate without removing the film on the surface of the first substrate, that is, while leaving the film on the surface of the first substrate intact. In step G, the difference in processing resistance (etching resistance) due to the difference in material (film type) between the film formed on the surface of the first substrate and the adsorption-promoting layer formed on the surface of the second substrate can be utilized. Due to the difference in processing resistance (etching resistance) between the film formed on the surface of the first substrate and the adsorption-promoting layer formed on the surface of the second substrate, it is possible to selectively remove the adsorption-promoting layer and the second adsorption-inhibiting layer on the surface of the second substrate while leaving the film on the surface of the first substrate intact.

[0183] The following are examples of combinations of suitable adsorption-promoting layers (materials) formed on the surface of the second substrate, films (materials) formed on the surface of the first substrate, and etching treatments in step G. For example, when an SiO layer is formed as an adsorption-promoting layer on the surface of the second substrate, an SiOC film or a SiN film is formed as a film on the surface of the first substrate, and in this case, it is preferable to perform etching using a fluorine-based etching agent in step G. Also, for example, when an SiOC layer is formed as an adsorption-promoting layer on the surface of the second substrate, a SiN film is formed as a film on the surface of the first substrate, and in this case, it is preferable to use plasma oxidation and etching using a fluorine-based etching agent in combination in step G. Plasma oxidation changes the adsorption-promoting layer from an SiOC layer to an SiO layer that is easily etched by a fluorine-based etching agent, and then etching becomes possible. Examples of fluorine-based etching agents used as etching materials include aqueous HF solution (DHF), HF gas, F2 gas, etc. Etching materials such as fluorine-based etching agents can be supplied using the processing material supply system (etching material supply system) described above.

[0184] In particular, when an SiO layer is formed as an adsorption-promoting layer on the surface of the second substrate in step B, an SiOC film is formed as a film on the surface of the first substrate in step D, and HF is used as the etching material in step G, the process in step G can be carried out efficiently.

[0185] Before performing step G, steps A, B, C, and D can be performed in the same manner as in the first embodiment, as shown in the processing sequence above. These steps A, B, C, and D can be performed using the same processing procedures and conditions as steps A, B, C, and D in the first embodiment.

[0186] Furthermore, in Modification 2, before performing step G, steps A, B, C, E, and D can be performed in the same manner as in the second embodiment, as shown in the processing sequence below. These steps A, B, C, E, and D can be performed using the same processing procedures and conditions as steps A, B, C, E, and D in the second embodiment.

[0187] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Removal and / or deactivation of the first adsorption-suppressing layer → Film formation → Removal of the second adsorption-suppressing layer and the adsorption-promoting layer

[0188] In Modification 2, the same effects as those of the first and second embodiments described above can be obtained. Furthermore, according to Modification 2, it is possible to expose the surface of the second substrate and reset the surface state of the second substrate. This makes it possible to perform desired treatments or form desired films on the surface of the second substrate in the various processes that follow.

[0189] <Variation 3> Modification 3 of this disclosure will be explained mainly with reference to Figures 9(a) to 9(g).

[0190] As shown in Figures 9(a) to 9(g) and the processing sequence below, the processing sequence in Modified Example 3 further includes step H, which, after performing step G in Modified Example 2, modifies the film on the surface of the first substrate to change it into a film of a different material.

[0191] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Film formation → Removal of the second adsorption-suppressing layer and adsorption-promoting layer → Modification

[0192] In step H, as shown in Figure 9(g), after step G, it is possible to modify the film present on the surface of the first substrate to change it into a film with a different material (after modification). For example, after step G, it is possible to modify the film present on the surface of the first substrate to change it into a film with the same material as the adsorption-promoting layer that was temporarily formed on the surface of the second substrate. Here, if in step D a film with the same material as the adsorption-promoting layer is formed on the surface of the first substrate, then in step G of the modified example 2, not only the adsorption-promoting layer and the second adsorption-inhibiting layer, but also the film with the same material as the adsorption-promoting layer will be removed together. In step D, by temporarily forming a film with a different material than the adsorption-promoting layer on the surface of the first substrate, it is possible to suppress the removal of the film with the different material from the adsorption-promoting layer in step G, and then, by modifying the film with the different material from the adsorption-promoting layer that remains on the surface of the first substrate, it is possible to change that film into a film with the same material as the adsorption-promoting layer. This makes it possible to create a state in which a film equivalent in material to the adsorption-promoting layer is formed on the surface of the first substrate even after step G has been performed.

[0193] In step H, methods for modifying the film on the surface of the first substrate include oxidation treatment and nitriding treatment. In particular, in step H, it is preferable to oxidize the film on the surface of the first substrate after step G to change it into an SiO film. In this case, it is possible to create a state in which an SiO film is formed on the surface of the first substrate after step G. Here, in step D, if an SiO film with the same material as the adsorption promoting layer (SiO layer) is formed on the surface of the first substrate, then in step G, not only the adsorption promoting layer (SiO layer) and the second adsorption suppression layer on the surface of the second substrate, but also the SiO film on the surface of the first substrate will be removed together. In step D, by temporarily forming an SiOC film with a different material from the adsorption promoting layer (SiO layer) on the surface of the first substrate, it is possible to suppress the removal of the SiOC film in step G, and then by oxidizing the SiOC film remaining on the surface of the first substrate, the SiOC film can be changed into an SiO film with the same material as the adsorption promoting layer (SiO layer). This makes it possible to create a state in which an SiO film is formed on the surface of the first substrate even after step G has been performed.

[0194] In step H, it is preferable to supply a modifying material to the wafer 200 and perform annealing treatment under a modifying material atmosphere in order to modify the film on the surface of the first substrate. Examples of modifying materials include oxidizing agents (O-containing materials) and nitriding agents (N-containing materials). The modifying material can be supplied using the processing material supply system (modifying material supply system) described above.

[0195] In step H, the treatment conditions for oxidizing the film on the surface of the first substrate using an oxidizing agent (O-containing substance) to transform it into an SiO film are as follows: Processing temperature: 300-1200°C, preferably 300-700°C Processing pressure: 1 to 101325 Pa, preferably 67 to 101325 Pa O-containing material supply flow rate: 1~10slm O-containing substance supply time: 1 to 240 minutes, preferably 1 to 120 minutes This is an example. Other processing conditions can be the same as the processing conditions in step A.

[0196] The oxygen-containing material used in step H can be the same as the oxygen-containing material used in step B. Furthermore, the annealing treatment in step H may be plasma annealing, using an oxygen-containing material excited by plasma.

[0197] Furthermore, in Modification 3, before performing step G, steps A, B, C, E, and D can be performed in the same manner as in the second embodiment, as shown in the processing sequence below. These steps A, B, C, E, and D can be performed using the same processing procedures and conditions as steps A, B, C, E, and D in the second embodiment.

[0198] Formation of the first adsorption-suppressing layer → Formation of the adsorption-promoting layer → Formation of the second adsorption-suppressing layer → Removal and / or deactivation of the first adsorption-suppressing layer → Film formation → Removal of the second adsorption-suppressing layer and the adsorption-promoting layer → Modification

[0199] <Other aspects of this disclosure> The aspects of this disclosure have been described in detail above. However, this disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0200] For example, wafer 200 may have multiple regions of different materials as a first substrate, or multiple regions of different materials as a second substrate. The regions constituting the first and second substrates may be, in addition to the SiO film and SiN film mentioned above, films containing semiconductor elements such as SiOCN film, SiON film, SiOC film, SiC film, SiCN film, SiBN film, SiBCN film, SiBC film, Si film, Si film, Ge film, and SiGe film, films containing metal elements such as TiN film and W film, amorphous carbon film (aC film), and single crystal Si (Si wafer). Any region having a surface that can be modified by the first modifier (i.e., a surface having adsorption sites) can be used as the first substrate. On the other hand, any region having a surface that is difficult to modify by the first modifier (i.e., a surface that does not have adsorption sites or has few adsorption sites) can be used as the second substrate. In that case as well, the same effects as in the above embodiment can be obtained.

[0201] It is preferable that the recipes used for each process be prepared individually according to the processing content and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes stored in the storage device 121c according to the processing content. This makes it possible to form films of various film types, composition ratios, film quality, and film thickness with good reproducibility using a single substrate processing device. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0202] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed in the board processing device. When modifying a recipe, the modified recipe may be installed in the board processing device via a telecommunications line or a recording medium containing the recipe. Alternatively, existing recipes already installed in the board processing device may be directly modified by operating the input / output device 122 provided in the existing board processing device.

[0203] The embodiments and modifications described above illustrate examples of forming films using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the embodiments described above and can be suitably applied, for example, to forming films using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the embodiments described above illustrate examples of forming films using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the embodiments described above and can be suitably applied to forming films using a substrate processing apparatus having a cold-wall type processing furnace.

[0204] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0205] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications. [Examples]

[0206] (Example 1) As Example 1, a wafer with an SiO film as a first substrate and a SiN film as a second substrate exposed on its surface was used, and a first evaluation sample was prepared by selectively growing an SiOC film on the surface of the SiO film according to the processing sequence described in Modification 1 above. The processing conditions at each step during the preparation of the first evaluation sample were predetermined conditions within the processing condition range of each step in the processing sequence of Modification 1 described above.

[0207] (Example 2) As Example 2, a wafer with an SiO film as a first substrate and a SiN film as a second substrate exposed on its surface was used, and a second evaluation sample was prepared by selectively growing an SiOC film on the surface of the SiO film and removing (etching) the adsorption-promoting layer on the surface of the SiN film according to the processing sequence of Modified Example 2 described above. The processing conditions in each step of the preparation of the second evaluation sample were predetermined conditions within the processing condition range of each step of the processing sequence of Modified Example 2 described above.

[0208] After preparing the first and second evaluation samples, the thickness of the film formed on the SiO film (SiOC film thickness) and the thickness of the film formed on the SiN film (total thickness of the adsorption-promoting layer, the second adsorption-suppressing layer, and the SiOC film) were measured for each evaluation sample. Next, the difference in film thickness between the film formed on the SiO film and the film formed on the SiN film (hereinafter simply referred to as the film thickness difference) was calculated for each evaluation sample. A larger film thickness difference indicates better selectivity.

[0209] The results are shown in Figure 13. In Figure 13, the horizontal axis shows, from left to right, Example 1 (first evaluation sample) and Example 2 (second evaluation sample), and the vertical axis shows the thickness (Å) of the film formed on each substrate. In the bar graph, the left bar shows the thickness of the film formed on the SiO film (SiOC film thickness), and the right bar shows the thickness of the film formed on the SiN film (total thickness of the adsorption promoting layer, the second adsorption suppressing layer, and the SiOC film).

[0210] Figure 13 shows that the film thickness difference in Example 1 (first evaluation sample) was approximately 7 nm, and the film thickness difference in Example 2 (second evaluation sample) was approximately 8.5 nm. Thus, it was confirmed that it is possible to significantly improve the selectivity in selective growth using Examples 1 and 2.

[0211] Furthermore, in other film deposition evaluations conducted by the disclosing parties, it has been confirmed that a SiOC film is selectively formed on the first substrate not only when the first substrate is an SiO film and the second substrate is a SiN film, but also when the first substrate is an SiOC film or an AlO film, or when the second substrate is a metal film such as a Si film, SiCN film, TiN film, or W film.

Claims

1. (a) A step of forming a first adsorption suppression layer on the first surface by supplying a first precursor to a substrate having a first surface and a second surface, (b) A step of supplying a reactant to the substrate to form an adsorption promoting layer on the second surface, (c) A step of forming a second adsorption-inhibiting layer on the surface of the adsorption-promoting layer by supplying a second precursor having a molecular structure different from the first precursor to the substrate, A step of forming a film on the first surface by supplying a film-forming material to the substrate after (d) and (c), (f) Before performing (a), a step of reducing the adsorption sites on the first surface, A processing method having the following characteristics.

2. (d) The processing method according to claim 1, wherein the action of the film-forming material neutralizes the action of the first adsorption suppression layer and forms the film on the first surface.

3. The processing method according to claim 1, further comprising the step of removing the first adsorption suppression layer and disabling the effect of the first adsorption suppression layer after performing (e) and (c) and before performing (d).

4. The processing method according to any one of claims 1 to 3, wherein the adsorption suppression effect of the first adsorption suppression layer is weaker than the adsorption suppression effect of the second adsorption suppression layer under the same conditions.

5. The processing method according to any one of claims 1 to 3, wherein the first adsorption suppression layer is more easily detached than the second adsorption suppression layer under the same conditions.

6. The processing method according to any one of claims 1 to 3, wherein the reactivity between the film-forming material and the first adsorption suppression layer is higher than the reactivity between the film-forming material and the second adsorption suppression layer under the same conditions.

7. (b) The processing method according to any one of claims 1 to 3, wherein an oxygen-containing layer is formed as the adsorption promoting layer.

8. (b) The treatment method according to claim 7, wherein the oxygen-containing layer is deposited on the second surface.

9. (b) The treatment method according to claim 7, wherein the second surface is oxidized.

10. The processing method according to claim 7, wherein the thickness of the adsorption promoting layer is 0.5 nm or more and 10 nm or less.

11. The processing method according to any one of claims 1 to 3, wherein in (f), the formation of a second adsorption suppression layer on the first surface is suppressed by reducing the adsorption sites on the first surface in (c).

12. (f) The processing method according to any one of claims 1 to 3, wherein the substrate is annealed at a temperature of 200°C or more and 500°C or less.

13. The processing method according to any one of claims 1 to 3, wherein the adsorption site on the first surface includes an OH termination.

14. (d) In the first surface, a film made of a different material from the adsorption promoting layer is formed. The processing method according to any one of claims 1 to 3, further comprising the step of removing the adsorption-promoting layer and the second adsorption-inhibiting layer on the second surface by exposing the film on the first surface and the adsorption-promoting layer and the second adsorption-inhibiting layer on the second surface to an etching substance after performing (g) and (d).

15. (b) In the second surface, a silicon oxide layer is formed as the adsorption promoting layer. (d) In the first surface, a silicon carbide film is formed as the film. (g) The treatment method according to claim 14, wherein hydrogen fluoride is used as the etching substance.

16. The processing method according to claim 14, further comprising the step of modifying the film on the first surface after performing (h) and (g) to change it into a film of a different material from the aforementioned film.

17. The processing method according to claim 15, further comprising the step of oxidizing the film on the first surface after performing (h) and (g) to change it into a silicon oxide film.

18. The processing method according to any one of claims 1 to 3, wherein the first surface includes an oxygen-containing film, and the second surface includes a film different from the oxygen-containing film.

19. The processing method according to any one of claims 1 to 3, wherein the first surface comprises at least one of a silicon oxide film, a silicon acid carbide film, and an aluminum oxide film, and the second surface comprises at least one of a silicon film, a silicon nitride film, and a metal film.

20. (a) A step of forming a first adsorption suppression layer on the first surface by supplying a first precursor to a substrate having a first surface and a second surface, (b) A step of supplying a reactant to the substrate to form an adsorption promoting layer on the second surface, (c) A step of forming a second adsorption-inhibiting layer on the surface of the adsorption-promoting layer by supplying a second precursor having a molecular structure different from the first precursor to the substrate, A step of forming a film on the first surface by supplying a film-forming material to the substrate after (d) and (c), (f) Before performing (a), a step of reducing the adsorption sites on the first surface, A method for manufacturing a semiconductor device having [a certain feature].

21. A first precursor supply system that supplies a first precursor to a substrate, A reactant supply system that supplies reactants to the substrate, A second precursor supply system that supplies a second precursor having a molecular structure different from the first precursor to a substrate, A film deposition material supply system that supplies film deposition material to the substrate, A control unit is configured to control the operation of the apparatus so as to perform the following: (a) a process of forming a first adsorption suppression layer on the first surface by supplying the first precursor to a substrate having a first surface and a second surface; (b) a process of forming an adsorption promoting layer on the second surface by supplying the reactant to the substrate; (c) a process of forming a second adsorption suppression layer on the surface of the adsorption promoting layer by supplying the second precursor to the substrate; (d) a process of forming a film on the first surface by supplying the film-forming material to the substrate after (c) has been performed; and (f) a process of reducing adsorption sites on the first surface before performing (a). A processing device.

22. (a) A procedure for forming a first adsorption suppression layer on a first surface by supplying a first precursor to a substrate having a first surface and a second surface, (b) A procedure for forming an adsorption-promoting layer on the second surface by supplying a reactant to the substrate, (c) A procedure for forming a second adsorption-inhibiting layer on the surface of the adsorption-promoting layer by supplying a second precursor having a molecular structure different from the first precursor to the substrate, A procedure for forming a film on the first surface by supplying a film-forming material to the substrate after (d) and (c), (f) Before performing (a), a procedure to reduce the adsorption sites on the first surface, A program that causes a computer to execute a command on a processing unit.

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