Processing method, semiconductor device manufacturing method, processing device, 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 manufacturing method for a semiconductor device, a processing device, and a program. [Background technology]

[0002] As semiconductor devices scale, processing dimensions become finer and processes become more complex. To perform fine and complex processing, a highly accurate patterning process needs to be repeated many times, which leads to an increase in costs in semiconductor device manufacturing. In recent years, selective growth has been attracting attention as a method that is expected to achieve high accuracy and reduce costs. Selective growth is a technique for selectively growing a film on the surface of a desired underlayer among two or more types of underlayers exposed on the surface of a substrate (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-27067 Summary of the Invention [Problem to be solved by the invention]

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

[0005] An object of the present disclosure is to provide a technique that enables selective formation of an adhesion suppressing layer on the surface of a specific base, and selective formation of a film on the surface of a desired base. [Means for solving the problem]

[0006] According to one aspect of the present disclosure, (a) supplying a first precursor to a substrate having a first underlayer and a second underlayer exposed on a surface thereof, thereby causing at least a portion of a molecular structure of a molecule constituting the first precursor to be adsorbed onto the surface of the first underlayer, thereby forming a first adsorption suppressing layer; (b) applying a reactant to the substrate to form an adhesion promoting layer on a surface of the second underlayer; (c) supplying a second precursor having a molecular structure different from that of the first precursor to the substrate, thereby causing at least a portion of the molecular structure of a molecule constituting the second precursor to be adsorbed onto a surface of the adsorption promoting layer, thereby forming a second adsorption suppressing layer; (d) supplying a film forming material to the substrate after steps (a), (b), and (c) to form a film on the surface of the first base; Techniques for doing so are provided. Effect of the Invention

[0007] According to the present disclosure, it is possible to selectively form an adhesion suppressing layer on the surface of a specific base, and selectively form a film on the surface of a desired base. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4]4(a) to 4(e) are schematic cross-sectional views showing the surface portion of a wafer at each step in the selective growth according to the first embodiment of the present disclosure. FIG. 4(a) is a schematic cross-sectional view showing the surface portion of a wafer where a silicon oxide film (SiO film) as a first underlayer and a silicon nitride film (SiN film) as a second underlayer are exposed. FIG. 4(b) is a schematic cross-sectional view showing the surface portion of a wafer after a first adhesion suppressing layer is formed on the surface of a SiO film by performing step A. FIG. 4(c) is a schematic cross-sectional view showing the surface portion of a wafer after an adhesion promoting layer is formed on the surface of a SiN film by performing step B. FIG. 4(d) is a schematic cross-sectional view showing the surface portion of a wafer after a second adhesion suppressing layer is formed on the surface of an adhesion promoting layer by performing step C. FIG. 4(e) is a schematic cross-sectional view showing the surface portion of a wafer after a film is formed on the surface of a SiO film by performing step D from the state of FIG. 4(d). [Diagram 5] Figures 5(a) to 5(f) are cross-sectional schematic diagrams showing the surface portion of the wafer at each step in the selective growth according to the second embodiment of the present disclosure. Figures 5(a) to 5(d) are similar to Figures 4(a) to 4(d). Figure 5(e) is a cross-sectional schematic diagram showing the surface portion of the wafer after the first adsorption suppressing layer is removed from the surface of the SiO film by performing step E. Figure 5(f) is a cross-sectional schematic diagram showing the surface portion of the wafer after a film is formed on the surface of the SiO film by performing step D from the state of Figure 5(e). [Figure 6] Fig. 6(a) to Fig. 6(f) are cross-sectional schematic diagrams showing the surface portion of the wafer at each step in the selective growth of the second embodiment of the present disclosure. Fig. 6(a) to Fig. 6(d) are views similar to Fig. 4(a) to Fig. 4(d). Fig. 6(e) is a cross-sectional schematic diagram showing the surface portion of the wafer after performing step E from the state of Fig. 6(d) to disable the function of the first adhesion suppressing layer. Fig. 6(f) is a cross-sectional schematic diagram showing the surface portion of the wafer after performing step D from the state of Fig. 6(e) to form a film on the surface of the SiO film. [Figure 7]7(a) to 7(f) are schematic cross-sectional views showing the surface portion of the wafer at each step in the selective growth of the first modified example of the present disclosure. FIG. 7(a) is a schematic cross-sectional view of the surface portion of the wafer where the SiO film as the first underlayer and the SiN film as the second underlayer are exposed, showing the adsorption sites on the surface of the SiO film. FIG. 7(b) is a schematic cross-sectional view showing the surface portion of the wafer after performing step F from the state of FIG. 7(a) to reduce the adsorption sites on the surface of the SiO film. FIG. 7(c) is a schematic cross-sectional view showing the surface portion of the wafer after performing step A from the state of FIG. 7(b) to form a first adsorption suppressing layer on the surface of the SiO film. FIGS. 7(d) to 7(f) are views similar to FIGS. 4(c) to 4(e). [Figure 8] Fig. 8(a) to Fig. 8(f) are schematic cross-sectional views showing the surface portion of the wafer at each step in the selective growth of Modification 2 of the present disclosure. Fig. 8(a) to Fig. 8(d) are similar to Fig. 4(a) to Fig. 4(d). Fig. 8(e) is a schematic cross-sectional view showing the surface portion of the wafer after performing step D from the state of Fig. 8(d) to form a film made of a different material from the adsorption promoting layer on the surface of the SiO film. Fig. 8(f) is a schematic cross-sectional view showing the surface portion of the wafer after performing step G from the state of Fig. 8(e) to remove the adsorption promoting layer and the second adsorption suppressing layer on the surface of the SiN film from the surface of the SiN film. [Figure 9] 9(a) to 9(g) are schematic cross-sectional views showing the surface portion of the wafer at each step in the selective growth of the third modified example of the present disclosure. FIG. 9(a) to FIG. 9(d) are similar to FIG. 4(a) to FIG. 4(d). FIG. 9(e) is a schematic cross-sectional view showing the surface portion of the wafer after performing step D from the state of FIG. 9(d) to form a film of a different material from the adsorption promoting layer on the surface of the SiO film. FIG. 9(f) is a schematic cross-sectional view showing the surface portion of the wafer after performing step G from the state of FIG. 9(e) to remove the adsorption promoting layer and the second adsorption suppressing layer on the surface of the SiN film from the surface of the SiN film. FIG. 9(g) is a schematic cross-sectional view showing the surface portion of the wafer after performing step H from the state of FIG. 9(f) to modify the film formed on the surface of the SiO film to change it into a film (after modification) of a different material from the film. [Figure 10]Fig. 10(a) is a schematic diagram of the case where hydroxyl (OH) terminations, which are adsorption sites, are densely present on the surface of the SiO film as the first undercoat after performing step F. Fig. 10(b) is a schematic diagram of the case where adsorption sites remain on the surface of the SiO film after performing step A from the state of Fig. 10(a). Fig. 10(c) is a schematic diagram of the case where a second adsorption suppressing layer is formed on the adsorption sites remaining on the surface of the SiO film by performing steps B and C in this order from the state of Fig. 10(b). [Figure 11] Fig. 11(a) is a schematic diagram of the case where OH terminations, which are adsorption sites, are sparsely present on the surface of the SiO film as the first underlayer after performing step F. Fig. 11(b) is a schematic diagram of the case where the first adsorption suppressing layers formed on the surface of the SiO film are spaced apart widely and a portion of the surface of the SiO film is widely exposed after performing step A from the state of Fig. 11(a). Fig. 11(c) is a schematic diagram of the case where an adsorption-promoting layer and a second adsorption suppressing layer are formed in a region of the surface of the SiO film where the first adsorption suppressing layer is not formed (a region where a portion of the surface of the SiO film is widely exposed) by performing steps B and C in this order from the state of Fig. 11(b). [Figure 12] Fig. 12(a) is a schematic diagram showing a case where OH terminations, which are adsorption sites, are adequately present on the surface of the SiO film as the first undercoat after performing step F. Fig. 12(b) is a schematic diagram showing a case where a first adsorption suppressing layer is appropriately formed on the surface of the SiO film after performing step A from the state of Fig. 12(a). Fig. 12(c) is a schematic diagram showing a case where the formation of an adsorption-promoting layer and a second adsorption suppressing layer on the surface of the SiO film is suppressed by performing steps B and C in this order from the state of Fig. 12(b), and only the first adsorption suppressing layer is formed on the surface of the SiO film. [Figure 13] FIG. 13 is a graph showing the evaluation results in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <First Aspect of the Present Disclosure> The first embodiment of the present disclosure will be described below mainly with reference to Figures 1 to 3 and 4(a) to 4(e). Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match the actual ones. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

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

[0011] A reaction tube 203 is disposed inside the heater 207 concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO 2 The reaction tube 203 is made of a heat-resistant material such as SUS or silicon carbide (SiC) and is formed in a cylindrical shape with the upper end closed and the lower end open. A manifold 209 is disposed concentrically with the reaction tube 203 below 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 the upper and lower ends open. 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 as a seal member between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow part of the processing vessel. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0012] Nozzles 249a to 249c serving as first to third supply units are provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209, respectively. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The 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 the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0013] Gas supply pipes 232a-232c are provided with mass flow controllers (MFCs) 241a-241c, which are flow rate controllers (flow rate control parts), and valves 243a-243c, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232d, 232e, and 232h are connected to the downstream side of valve 243a of gas supply pipe 232a. Gas supply pipes 232f and 232g are connected to the downstream sides of valves 243b and 243c of gas supply pipes 232b and 232c. Gas supply pipes 232d-232h are provided with MFCs 241d-241h and valves 243d-243h in order from the upstream side of the gas flow. Gas supply pipes 232a-232h are made of a metal material, such as SUS.

[0014] As shown in FIG. 2, the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged, so as to extend along the wafer arrangement region. In a plan view, the nozzle 249b is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249a and 249c are disposed so as to sandwich a straight line L passing through the nozzle 249b and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200. In other words, the nozzle 249c is provided on the opposite side of the nozzle 249a across the line L. The nozzles 249a and 249c are arranged symmetrically with respect to the line L. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are each opened to face (face) the exhaust port 231a in a plan view, and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

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

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

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

[0018] From the gas supply pipe 232c, a processing substance is supplied through the MFC 241c, the valve 243c, and the nozzle 249c into the processing chamber 201. The processing substance includes at least one of a removal and / or invalidation substance (hereinafter, for convenience, these are also collectively referred to simply as invalidation substances), an etching substance, and a modification substance.

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

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

[0021] A first precursor supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A second precursor supply system is mainly composed of the gas supply pipe 232h, the MFC 241h, and the valve 243h. The first precursor supply system and the second precursor supply system are also referred to as a precursor supply system. A reactant supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. A processing material supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. When an invalidating material, an etching material, or a modifying material is supplied as the processing material, the processing material supply system can also be referred to as an invalidating material supply system, an etching material supply system, or a modifying material supply system according to the material to be supplied. A film forming material supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. An inert gas supply system is mainly configured by the gas supply pipes 232e to 232g, the MFCs 241e to 241g, and the valves 243e to 243g.

[0022] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243h and the MFCs 241a-241h are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a-232h, and the supply operation of various gases into the gas supply pipes 232a-232h, that is, the opening and closing operation of the valves 243a-243h and the flow rate adjustment operation by the MFCs 241a-241h, are controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated or split type integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232h, etc., and maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

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

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

[0025] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0026] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Fig. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to 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. An external storage device 123 can also be connected to the controller 121.

[0028] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. A control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are readably stored in the storage device 121c. The process recipe is a combination of procedures in the substrate processing described later, which are executed by the controller 121 in the substrate processing apparatus, so that a predetermined result can be obtained, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.

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

[0030] The CPU 121a is configured to be able 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 an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be able to control the flow rate adjustment operation of various gases by the MFCs 241a to 241h, the opening and closing operations of the valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop 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 rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc., 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 in a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a USB memory, a semiconductor memory such as an SSD, and the like. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Substrate processing A method of processing a substrate as one step of a semiconductor device manufacturing process using the above-mentioned substrate processing apparatus, i.e., an example of a processing sequence for selectively forming a film on the surface of a first underlayer of a first underlayer and a second underlayer exposed on the surface of a wafer 200 as a substrate, will be described mainly with reference to Figs. 4(a) to 4(e). In the following description, for convenience, a representative example will be described in which the first underlayer is a silicon oxide film (SiO film) and the second underlayer is a silicon nitride film (SiN film). In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0033] As shown in FIG. 4(a) to FIG. 4(e), the processing sequence in the first mode is as follows: a step A of supplying a first precursor to a wafer 200 having a first underlayer and a second underlayer exposed on a surface thereof, thereby causing at least a part of a molecular structure of a molecule constituting the first precursor to be adsorbed on the surface of the first underlayer, thereby forming a first adsorption suppressing layer; Step B of forming an adhesion promoting layer on the surface of the second underlayer by supplying a reactant to the wafer 200; a step C of supplying a second precursor having a molecular structure different from that of the first precursor to the wafer 200, thereby causing at least a part of the molecular structure of the molecules constituting the second precursor to be adsorbed on the surface of the adsorption promoting layer, thereby forming a second adsorption suppressing layer; and step D of supplying a film forming substance to the wafer 200 after steps A, B, and C have been performed in this order, thereby forming a film on the surface of the first base.

[0034] In step D of the first aspect, the action of the film-forming substance is used to nullify the action of the first adsorption suppressing layer, thereby forming a film on the surface of the first base. That is, in step D, the action of the film-forming substance is used to cancel the adsorption suppressing action of the first adsorption suppressing layer, thereby forming a film on the surface of the first base.

[0035] The term "substance" used in this specification includes at least one of a gaseous substance and a liquid substance. The liquid substance includes a mist substance. That is, each of the first precursor, the reactant, the second precursor, and the film-forming substance may include a gaseous substance, may include a liquid substance such as a mist substance, or may include both of them. In addition, the term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, each of the first adsorption suppressing layer and the second adsorption suppressing layer may include a continuous layer, may include a discontinuous layer, or may include both of them, as long as it is possible to cause an adsorption suppressing effect. In addition, the adsorption promoting layer may also include a continuous layer, may include a discontinuous layer, or may include both of them, as long as it is possible to cause an adsorption promoting effect.

[0036] The first and second adsorption-suppressing layers each have an adsorption-suppressing effect and are therefore sometimes called inhibitors. Note that the term "inhibitor" as used herein may refer to the first and second adsorption-suppressing layers, as well as the first and second precursors, or residues derived from the first and second precursors, or may be used as a general term for all of these.

[0037] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience. Similar notations will be used in the following descriptions of other aspects, modifications, and the like.

[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 a laminate of the wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In this specification, the phrase "forming a predetermined layer on a wafer" may refer to forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. In this specification, the term "substrate" is also synonymous with the term "wafer".

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

[0041] 4(a), a SiO film as a first underlayer and a SiN film as a second underlayer are exposed on the surface of the wafers 200 loaded into the boat 217. In the wafers 200, the surface of the SiO film as the first underlayer has OH terminations as adsorption sites over the entire area (whole surface), while most of the surface of the SiN film as the second underlayer does not have OH terminations.

[0042] (Pressure and temperature regulation) Thereafter, the inside of the processing chamber 201, i.e., the space in which the wafer 200 is present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the inside of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafer 200 inside the processing chamber 201 is heated by the heater 207 so that the temperature is a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafer 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0043] (Step A) Thereafter, the opening and closing operation of a valve in the first precursor supply system is controlled to supply the first precursor to the wafer 200 in the processing chamber 201, i.e., the wafer 200 having the first underlayer and the second underlayer 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 an inert gas supply system.

[0044] In step A, the treatment conditions for supplying the first precursor are preferably such that the first precursor is not thermally decomposed (decomposed in a gas phase), Treatment temperature: 25 to 500°C, preferably 50 to 300°C Treatment 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 to 20,000 sccm Examples include:

[0045] In this specification, when a numerical range such as "25 to 500°C" is indicated, the lower limit and the upper limit are included in the range. Thus, for example, "25 to 500°C" means "25°C or more and 500°C or less". The same applies to other numerical ranges. The process temperature refers to the temperature of the wafer 200, and the process pressure refers to the pressure inside the process chamber 201. When the supply flow rate is described as "0", it means that the substance is not supplied. The same applies to the following explanations.

[0046] In step A, the first precursor is supplied to the wafer 200, so that at least a part of the molecular structure of the molecules constituting the first precursor can be selectively (preferentially) adsorbed on the surface of the SiO film, which is the first underlayer. As a result, as shown in FIG. 4(b), a first adsorption-suppressing layer is selectively (preferentially) formed on the surface of the SiO film. The first adsorption-suppressing layer contains at least a part of the molecular structure of the molecules constituting the first precursor, for example, residues derived from the first precursor. Examples of the residues derived from the first precursor contained in the first adsorption-suppressing layer include groups generated by chemically reacting the first precursor with adsorption sites on the surface of the first underlayer (for example, OH terminations on the surface of the SiO film). In this way, by containing residues derived from the first precursor, the first adsorption-suppressing layer exhibits an adsorption suppressing effect (acts as an inhibitor).

[0047] The adsorption suppressing effect of the first adsorption suppressing layer formed in step A is preferably weaker than the adsorption suppressing effect of the second adsorption suppressing layer formed in step C described later under the same conditions. The first adsorption suppressing layer formed in step A is preferably more easily desorbed than the second adsorption suppressing layer formed in step C described later under the same conditions. In addition, the reactivity between the film forming material used in step D and the first adsorption suppressing layer formed in step A is preferably higher than the reactivity between the film forming material used in step D and the second adsorption suppressing layer formed in step C described later under the same conditions. In other words, the first adsorption suppressing layer formed in step A is preferably more easily destructed in molecular structure and more easily subjected to selective breakage than the second adsorption suppressing layer formed in step C. By doing so, it is possible to efficiently nullify the effect of the first adsorption suppressing layer in step D. As a result, it is easier to selectively form a film on the surface of the first base in step D.

[0048] After the first adsorption suppression layer is formed on the surface of the SiO film, which is the first undercoat, 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 the first precursor and the like remaining in the processing chamber 201 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, and thereby the processing chamber 201 is purged (purged).

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

[0050] In step A, at least a part of the molecular structure of the molecules constituting the first precursor may be adsorbed to a very small part of the surface of the SiN film, which is the second underlayer. However, even in this case, the amount of the first adsorption suppressing layer formed on the surface of the SiN film is small, and the amount of the first adsorption suppressing layer formed on the surface of the SiO film is overwhelmingly greater. The reason why the amount of the first adsorption suppressing layer formed on the surface of the SiN film and the surface of the SiO film is significantly different from each other as described above is that the surface of the SiO film has OH termination over the entire area, whereas most areas of the surface of the SiN film do not have OH termination. Also, the processing conditions in step A are set so that the first precursor does not thermally decompose (vapor phase decomposition) in the processing chamber 201.

[0051] -First precursor- The first precursor is a material that is selectively (preferentially) adsorbed to the surface of the first underlayer (e.g., SiO film) and the second underlayer (e.g., SiN film). As the first precursor, it is preferable to use a compound represented by the following formula 1, for example.

[0052] [R 11 ]n 1 -(X 1 )-[R 12 ]m 1 : formula 1 In the above formula 1, R 11 isX 1 represents a first substituent bonded directly to R 12 isX 1 represents a second substituent bonded directly to 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 from 1 to 3, m 1 represents an integer from 1 to 3, and n 1 +m 1 =4.

[0053] In formula 1, the first substituent R 11 The number of 1is an integer of 1 to 3, and more preferably 2 or 3. 1 When is 2 or 3, the first substituent R 11 may be the same or different.

[0054] R 11 The first substituent represented by R 11 The first substituent represented by R is contained in the residue derived from the first precursor contained in the first adsorption suppressing layer. 11 The first substituent represented by R is preferably a substituent that suppresses the second precursor from being adsorbed onto the surface of the first underlayer. 11 The first substituent represented by the following formula (I) is preferably a chemically stable substituent.

[0055] R 11 The first substituent represented by R is preferably a substituent having a weaker adsorption suppressing effect than the first substituent of the second precursor used in step C. 11 It is more preferable that the first substituent represented by the formula (I) is a substituent that is more likely to lose its adsorption-suppressing effect than the first substituent of the second precursor used in step C. In this way, under the same conditions, it is possible to make the adsorption-suppressing effect of the first adsorption-suppressing layer formed in step A weaker than the adsorption-suppressing effect of the second adsorption-suppressing layer formed in step C described below, and this makes it easier to selectively form a film on the surface of the first base in step D.

[0056] R 11 Examples of the first substituent represented by the formula (I) include a fluoro group, a fluoroalkyl group, a hydrogen group (-H), a hydrocarbon group, and an alkoxy group. 11The first substituent represented by is preferably a hydrogen group or a hydrocarbon group, and more 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 may be an aromatic hydrocarbon group. In this specification, the term "substituent" may include a hydrogen group (-H) for convenience.

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

[0058] In formula 1, the second substituent R 12 The number of, i.e., m 1 is an integer of 1 to 3, and more preferably 1 or 2. 1 When R is 2 or 3, the second substituent R 12 may be the same or different.

[0059] R 12 The second substituent represented by the formula: is preferably a substituent that enables chemisorption of the first precursor to adsorption sites (eg, OH terminations) on the surface of the first underlayer.

[0060] R 12 Examples of the second substituent represented by the formula (I) include an amino group, a chloro group, a bromo group, an iodo group, and a hydroxy group. 12 The second substituent represented by R is preferably an amino group, and more preferably a substituted amino group. In particular, from the viewpoint of the adsorption of the first precursor to the first underlayer, 12It is preferable that all of the second substituents represented by the following formula (I) are substituted amino groups.

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

[0062] The number of substituents that the substituted amino group has is 1 or 2, and is preferably 2. When the number of substituents that the substituted amino group has 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 is a tetravalent atom selected from the group consisting of a C atom, a Si atom, a Ge atom, and a tetravalent metal atom. Examples of the tetravalent metal atom include a titanium (Ti) atom, a zirconium (Zr) atom, a hafnium (Hf) atom, a molybdenum (Mo) atom, and a tungsten (W) atom.

[0064] Among these, X 1 The atom to which the first and second substituents represented by the following formula (I) are directly bonded is preferably a C atom, a Si atom, or a Ge atom. 1 When X is any one of C atoms, Si atoms, and Ge atoms, at least one of the following characteristics can be obtained: high adsorption of the first precursor to the surface of the first underlayer, and high chemical stability of the first precursor after adsorption to the surface of the first underlayer, i.e., the residue derived from the first precursor. 1 As the X, a Si atom is more preferable. 1When is a Si atom, it is possible to obtain a good balance between the two properties of high adsorption of the first precursor to the surface of the first underlayer and high chemical stability of the first precursor after adsorption to the surface of the first underlayer, i.e., of the residue derived from the first precursor.

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

[0066] The first precursor may be, for example, (dimethylamino)dimethylsilane: (CH 3 ) 2 NSiH(CH 3 ) 2 , (ethylamino)dimethylsilane: (C 2 H 5 )HNSiH(CH 3 ) 2 , (propylamino)dimethylsilane: (C 3 H 7 ) 2 HNSiH(CH 3 ) 2 , (butylamino)dimethylsilane: (C 4 H 9 ) 2 HNSiH(CH 3 ) 2 , (diethylamino)dimethylsilane: (C 2 H 5 ) 2NSiH(CH 3 ) 2 , (dipropylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dibutylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dimethylamino)methylsilane: (CH 3 ) 2 NSiH 2 (CH 3 ), (ethylamino)methylsilane: (C 2 H 5 )HNSiH 2 (CH 3 ), (propylamino)methylsilane: (C 3 H 7 ) 2 HNSiH 2 (CH 3 ), (butylamino)methylsilane: (C 4 H 9 ) 2 HNSiH 2 (CH 3 ), (diethylamino)methylsilane: (C 2 H 5 ) 2 NSiH 2 (CH 3 ), (dipropylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dibutylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dimethylamino)diethylsilane: (CH 3 ) 2 NSiH(C 2 H 5 ) 2 , (ethylamino)diethylsilane: (C 2 H 5)HNSiH(C 2 H 5 ) 2 , (propylamino)diethylsilane: (C 3 H 7 ) 2 HNSiH(C 2 H 5 ) 2 , (butylamino)diethylsilane: (C 4 H 9 ) 2 HNSiH(C 2 H 5 ) 2 , (diethylamino)diethylsilane: (C 2 H 5 ) 2 NSiH(C 2 H 5 ) 2 , (dipropylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dibutylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dimethylamino)ethylsilane: (CH 3 ) 2 NSiH 2 (C 2 H 5 ), (ethylamino)ethylsilane: (C 2 H 5 )HNSiH 2 (C 2 H 5 ), (propylamino)ethylsilane: (C 3 H 7 ) 2 HNSiH 2 (C 2 H 5 ), (butylamino)ethylsilane: (C 4 H 9 ) 2 HNSiH 2 (C 2 H 5), (diethylamino)ethylsilane: (C 2 H 5 ) 2 NSiH 2 (C 2 H 5 ), (dipropylamino)ethylsilane: (C 3 H 7 ) 2 NSiH 2 (C 2 H 5 ), (dibutylamino)ethylsilane: (C 3 H 7 ) 2 NSiH 2 (C 2 H 5 ), (dipropylamino)silane: [(C 3 H 7 ) 2 N]SiH 3 , (dibutylamino)silane: [(C 4 H 9 ) 2 N]SiH 3 , (dipentylamino)silane: [(C 5 H 11 ) 2 N]SiH 3 , bis(dimethylamino)dimethylsilane: [(CH 3 ) 2 N] 2 Si(CH 3 ) 2 , bis(ethylamino)dimethylsilane: [(C 2 H 5 )HN] 2 Si(CH 3 ) 2 , bis(propylamino)dimethylsilane: [(C 3 H 7 ) 2 HN] 2 Si(CH 3 ) 2 , bis(butylamino)dimethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(CH 3 ) 2 , bis(diethylamino)dimethylsilane: [(C2 H 5 ) 2 N] 2 Si(CH 3 ) 2 , bis(dipropylamino)dimethylsilane: [(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 , bis(dibutylamino)dimethylsilane: [(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 , bis(dimethylamino)methylsilane: [(CH 3 ) 2 N] 2 SiH(CH 3 ), bis(ethylamino)methylsilane: [(C 2 H 5 )HN] 2 SiH(CH 3 ), bis(propylamino)methylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(CH 3 ), bis(butylamino)methylsilane: [(C 4 H 9 ) 2 HN] 2 SiH(CH 3 ), bis(diethylamino)methylsilane: [(C 2 H 5 ) 2 N] 2 SiH(CH 3 ), bis(dipropylamino)methylsilane: [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dibutylamino)methylsilane: [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dimethylamino)diethylsilane: [(CH3 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(ethylamino)diethylsilane: [(C 2 H 5 )HN] 2 Si(C 2 H 5 ) 2 , bis(propylamino)diethylsilane: [(C 3 H 7 ) 2 HN] 2 Si(C 2 H 5 ) 2 , bis(butylamino)diethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(C 2 H 5 ) 2 , bis(diethylamino)diethylsilane: [(C 2 H 5 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dipropylamino)diethylsilane: [(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dibutylamino)diethylsilane: [(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dimethylamino)ethylsilane: [(CH 3 ) 2 N] 2 SiH(C 2 H 5 ), bis(ethylamino)ethylsilane: [(C 2 H 5 )HN] 2 SiH(C 2 H5 ), bis(propylamino)ethylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(C 2 H 5 ), bis(butylamino)ethylsilane: [(C 4 H 9 ) 2 HN] 2 SiH(C 2 H 5 ), bis(diethylamino)ethylsilane: [(C 2 H 5 ) 2 N] 2 SiH(C 2 H 5 ), bis(dipropylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(dibutylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(diethylamino)silane: [(C 2 H 5 ) 2 N] 2 SiH 2 , bis(dipropylamino)silane [(C 3 H 7 ) 2 N] 2 SiH 2 , bis(dibutylamino)silane: [(C 4 H 9 ) 2 N] 2 SiH 2 , bis(dipentylamino)silane: [(C 5 H 11 ) 2 N] 2 SiH 2 , (dimethylamino)trimethoxysilane: (CH 3 ) 2 NSi(OCH3 ) 3、 (Dimethylamino)triethoxysilane: (CH 3 ) 2 NSi(OC 2 H 5 ) 3、 (Dimethylamino)triprotoxysilane: (CH 3 ) 2 NSi(OC 3 H 7 ) 3、 (Dimethylamino)tributoxoxysilane: (CH 3 ) 2 NSi(OC 4 H 9 ) 3 etc.

[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 so that the adsorption suppression effect of the first adsorption suppressing layer formed in step A is weaker than the adsorption suppression effect of the second adsorption suppressing layer formed in step C described below under the same conditions. The adsorption suppression effect of the first adsorption suppressing layer can be adjusted by the number and type of first substituents contained in the first precursor, so the first precursor used in step A can be appropriately selected according to the number and type of first substituents contained in the second precursor used in step C. Specifically, when the first precursor and the second precursor have the same number of first substituents and the second precursor has only alkyl groups as the first substituents, it is preferable to select a first precursor that has only hydrogen groups as the first substituents, only alkoxy groups as the first substituents, or has fewer alkyl groups and hydrogen groups or alkoxy groups than the first substituents in the second precursor. This is because, when comparing an alkyl group, a hydrogen group, and an alkoxy group, the alkyl group has the strongest adsorption suppression effect, followed by a hydrogen group, and the alkoxy group has the weakest. In addition, when both the first precursor and the second precursor have the same first substituent (e.g., an alkyl group), it is preferable to select a first precursor having a smaller number of first substituents than the number of first substituents in the second precursor. This is because the smaller the number of first substituents, the weaker the adsorption suppression effect of the formed adsorption-suppressing layer.

[0068] In addition, it is preferable to use a first precursor having the same or greater number of second substituents per molecule as the number of second substituents per molecule of the second precursor used in step C. This is because the more second substituents per molecule, the fewer first substituents per molecule, and the weaker the adsorption suppression effect of the adsorption suppressing layer. By doing so, under the same conditions, it is possible to make the adsorption suppression effect of the first adsorption suppressing layer formed in step A weaker than the adsorption suppression effect of the second adsorption suppressing layer formed in step C described below, and in step D, it becomes easier to selectively form a film on the surface of the first base.

[0069] In step A, if the first precursor having a fluoro group, a fluoroalkyl group, a hydrogen group, or the like as the first substituent cannot exist stably as a single compound, a first precursor having another first substituent and capable of existing stably as a single compound may be adsorbed onto the first base, and then a specific treatment may be applied to convert the other first substituent into a hydrogen group, a fluoro group, or a fluoroalkyl group. Examples of methods for converting the first substituent are shown below.

[0070] In the first example, a first precursor having a hydrogen group as a first substituent is adsorbed on a first underlayer, and then the wafer 200 is immersed in fluorine (F 2 ) gas, chlorine trifluoride (ClF 3 The hydrogen groups can be converted to fluoro groups by exposing the wafer 200 to a fluorine (F)-containing gas, such as fluorine (F) gas, chlorine fluoride (ClF) gas, or hydrogen fluoride (HF) gas. As a second example, a first precursor having an alkyl group as a first substituent can be adsorbed onto a first underlayer, and then the wafer 200 can be exposed to an F-containing gas as described above, thereby converting the alkyl group to a fluoroalkyl group. As a third example, a first precursor having a chloro group as a first substituent can be adsorbed onto a first underlayer, and then the wafer 200 can be exposed to a hydrogen (H 2 The chloro groups can be converted to hydrogen groups by exposing the gas to an atmosphere obtained by exciting a hydrogen (H)-containing gas such as chloroform (H) gas with plasma, for example, hydrogen plasma.

[0071] -Inert gas- The inert gas is, for example, nitrogen (N 2 ) gas, or rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. One or more of these can be used as the inert gas. This also applies to each step using an inert gas, which will be described later. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0072] (Step B) After step A is completed, the valves in the reactant supply system are controlled to open and close, and the reactant is supplied 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, a reactant is supplied to the wafer 200, so that an adsorption-promoting layer is selectively (preferentially) formed on the surface of the SiN film, which is the second underlayer, as shown in Fig. 4(c). At this time, the adsorption of the reactant to the surface of the first underlayer is suppressed by the adsorption suppressing effect of the first adsorption suppressing layer formed on the surface of the SiO film, which is the first underlayer, and thus it is possible to suppress the formation of an adsorption-promoting layer on the surface of the first underlayer.

[0074] The adsorption-promoting layer formed in step B is preferably capable of adsorbing the second precursor supplied to the wafer 200 in step C. The form of the adsorption-promoting layer formed in step B may be any form that allows the second precursor to be adsorbed onto the second underlayer through the adsorption-promoting layer, and examples of such form include a monomolecular form, a chain polymer form, and a film.

[0075] The higher the density of the second precursor is adsorbed on the surface of the second underlayer, the stronger the effect of suppressing the adsorption of the film-forming substance onto the second underlayer. Therefore, the adsorption-promoting layer is preferably one that can adsorb the second precursor at a high density, and the form of the adsorption-promoting layer is preferably 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 amount) of adsorption sites for the second precursor present on the surface of the adsorption-promoting layer. In other words, the adsorption-promoting layer is preferably a film having a high density (large amount) of adsorption sites for the second precursor on its surface.

[0076] Moreover, in step B, it is preferable to form an oxygen (O)-containing layer as the adsorption-promoting layer. This is because by forming the adsorption-promoting layer as an O-containing layer, it is possible to provide OH terminations as adsorption sites on the surface, which makes it easier for the second precursor to be adsorbed onto the adsorption-promoting layer. In other words, by forming an O-containing layer as the 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 for the adsorption-promoting layer to be a layer containing at least Si and O, such as a silicon oxide layer (SiO layer) or a silicon oxycarbide layer (SiOC layer).

[0077] The adsorption-promoting layer may be formed by supplying a reactive substance to the wafer 200, and the method is not particularly limited. For example, in the case of forming an O-containing layer as the adsorption-promoting layer in step B, a method of depositing an O-containing layer on the surface of the second underlayer by forming a film using a film-forming substance as a reactive substance can be used. For this method, for example, the same film-forming method (and film-forming conditions) as the film-forming method (and film-forming conditions) using a film-forming substance in step D described later can be used. When an O-containing layer is deposited on the surface of the second underlayer to form an adsorption-promoting layer, an adsorption-promoting layer having OH terminations as adsorption sites on the surface can be obtained, and therefore, in step C, a second adsorption-suppressing layer can be efficiently formed on the surface of the adsorption-promoting layer with high selectivity.

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

[0079] In step B, the treatment conditions for supplying the O-containing substance as the oxidizing agent as the reactant are as follows: Treatment temperature: room temperature to 600°C, preferably 50 to 400°C Treatment pressure: 1 to 101325 Pa, preferably 1 to 1300 Pa Flow rate of O-containing material supply: 1 to 20,000 sccm, preferably 1 to 10,000 sccm Supply time of O-containing substance: 1 second to 240 minutes, preferably 30 seconds to 120 minutes Other processing conditions may be the same as those 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 underlayer 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 part of the molecular structure of the molecule 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 suppression effect of the second adsorption suppression layer formed on the surface of the adsorption-promoting layer may be insufficient. This problem can be solved by making the thickness of the adsorption-promoting layer 0.5 nm or more. This problem can be sufficiently solved by making the thickness of the adsorption-promoting layer 1 nm or more, and this problem can be more sufficiently solved by making the thickness of the adsorption-promoting layer 1.5 nm or more.

[0082] If the thickness of the adsorption-promoting layer is made thicker than 10 nm, the action of the reactant in step B may nullify the adsorption suppression effect of at least a part of the first adsorption-suppressing layer formed on the surface of the first underlayer, and the adsorption suppression effect of the first adsorption-suppressing layer may become insufficient. As a result, an adsorption-promoting layer is also formed on the surface of the first underlayer, and in the subsequent step C, a second adsorption-suppressing layer is also formed on the surface of the first underlayer. This problem can be solved by making the thickness of the adsorption-promoting layer 10 nm or less. This problem can be solved sufficiently by making the thickness of the adsorption-promoting layer 5 nm or less, and this problem can be solved even more sufficiently by making the thickness of the adsorption-promoting layer 3 nm or less.

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

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

[0085] -O-containing substances- Examples of the O-containing substance that can be used include an O-containing gas, an O- and H-containing gas, an O- and N-containing gas, and an O- and C-containing gas. The O-containing substance may be used after being thermally excited in a non-plasma atmosphere, or after being plasma-excited.

[0086] The O-containing gas is, for example, oxygen (O 2 ) gas, ozone (O 3 ) gas, etc. As the O and H-containing gas, for example, water vapor (H 2 O gas), hydrogen peroxide (H 2 O 2 ) Gas, O 2 Gas + H 2 Gas, O3 Gas + H 2 Examples of the O and N-containing gas include nitric oxide (NO) gas, nitrous oxide (N 2 O) gas, nitrogen dioxide (NO 2 ) Gas, O 2 Gas + NH 3 Gas, O 3 Gas + NH 3 Gases such as carbon dioxide (CO) can be used as the O and C-containing gas. 2 ) gas, carbon monoxide (CO) gas, etc. As the O-containing substance, one or more of these can be used.

[0087] In this specification, "O 2 Gas + H 2 In the case of two gases, such as "O gas", 2 Gas and H 2 When supplying a mixed gas, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be separately supplied into the processing chamber 201 through different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0088] (Step C) After step B is completed, the valve in the second precursor supply system is controlled to open and close, and a second precursor having a molecular structure different from that of the first precursor is supplied 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, the treatment conditions for supplying the second precursor are preferably such that the second precursor is not thermally decomposed (decomposed in a gas phase); Treatment temperature: 25 to 500°C, preferably 50 to 300°C Treatment 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 Other processing conditions may be the same as those in step A.

[0090] In step C, the second precursor is supplied to the wafer 200, so that at least a part of the molecular structure of the molecules constituting the second precursor can be selectively (preferentially) adsorbed on the surface of the adsorption-promoting layer formed on the surface of the SiN film, which is the second underlayer. As a result, as shown in FIG. 4(d), the second adsorption-suppressing layer is selectively (preferentially) formed on the surface of the adsorption-promoting layer. At this time, the action of the first adsorption-suppressing layer formed on the surface of the SiO film, which is the first underlayer, can suppress the formation of the second adsorption-suppressing layer on the surface of the SiO film. The second adsorption-suppressing layer contains at least a part of the molecular structure of the molecules constituting the second precursor, for example, a residue derived from the second precursor. Examples of the residue derived from the second precursor contained in the second adsorption-suppressing layer include groups generated by chemically reacting the second precursor with the adsorption site (for example, OH termination) on the surface of the adsorption-promoting layer. In this way, by containing the residue derived from the second precursor, the second adsorption-suppressing layer exhibits an adsorption suppressing effect (acts as an inhibitor).

[0091] After the second adsorption suppressing layer is formed on the surface of the adsorption promoting layer formed on the surface of the SiN film, which is the second base layer, 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 the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedures and processing conditions as those for purging in step A described above.

[0092] -Second precursor- As the second precursor, a substance that is selectively (preferentially) adsorbed to the surface of the adsorption-promoting layer is used. As the second precursor, for example, a compound represented by the following formula 2 is preferably used.

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

[0094] In formula 2, the first substituent R 21 The number of 2 is an integer of 1 to 3, and more preferably 2 or 3. 2 When is 2 or 3, the first substituent R 21 may be the same or different.

[0095] R 21 The first substituent represented by R 21 The first substituent represented by R 21 The first substituent represented by R is preferably a substituent that suppresses the film-forming material from being adsorbed on the surface of the second underlayer. 21 The first substituent represented by the following formula (I) is preferably a chemically stable substituent.

[0096] R 21 The first substituent represented by R is preferably a substituent having a stronger adsorption suppressing effect than the first substituent of the first precursor used in step A. 21It is more preferable that the first substituent represented by the formula (I) is a substituent that is less likely to lose its adsorption suppressing effect than the first substituent of the first precursor used in step A. In this way, under the same conditions, it is possible to make the adsorption suppressing effect of the second adsorption suppressing layer formed in step C stronger than the adsorption suppressing effect of the first adsorption suppressing layer formed in step A, and it becomes easier to selectively form a film on the surface of the first base in step D.

[0097] R 21 The first substituent represented by the formula 11 The same applies to the preferred embodiments. 21 The first substituent represented by the formula (I) is preferably a hydrogen group or a hydrocarbon group, more preferably a hydrocarbon group, and more preferably an alkyl group.

[0098] In formula 2, the second substituent R 22 The number of, i.e., m 2 is an integer of 1 to 3, and more preferably 1 or 2. 2 When R is 2 or 3, the second substituent R 22 may be the same or different.

[0099] R 22 The second substituent represented by the formula: is preferably a substituent that enables chemisorption of the second precursor to the adsorption sites (eg, OH terminations) on the surface of the adsorption-promoting layer.

[0100] R 22 The second substituent represented by the formula 12 The same applies to the preferred embodiments.

[0101] In formula 2, X 2 The atom to which the first and second substituents are directly bonded is X in formula 1. 1 The same applies to the preferred embodiments. 2 The Si atom is particularly preferred as X. 2When is a Si atom, it is possible to obtain a good balance between the two properties of high adsorption of the second precursor to the surface of the adsorption-promoting layer and 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] Although the compound represented by formula 2 has been described above, the second precursor is not limited to the compound represented by formula 2. For example, the second precursor is preferably composed of a molecule including the above-mentioned first substituent, the above-mentioned second substituent, and an atom to which the first and second substituents are directly bonded, but the atom to which the first and second substituents are directly bonded may be a metal atom capable of bonding with five or more ligands. When the atom to which the first and second substituents are directly bonded is a metal atom capable of bonding with five or more ligands, the number of the first and second substituents in the molecule of the second precursor can be increased compared to the compound represented by formula 2, and the adsorption suppression effect of the second adsorption suppression layer can be adjusted. In addition, the second precursor may be composed of a molecule including the above-mentioned first substituent, the above-mentioned second substituent, and two or more atoms to which the first and second substituents are directly bonded.

[0103] The second precursor may be, for example, (dimethylamino)methylsilane: (CH 3 ) 2 NSiH 2 (CH 3 ), (ethylamino)methylsilane: (C 2 H 5 )HNSiH 2 (CH 3 ), (propylamino)methylsilane: (C 3 H 7 ) 2 HNSiH 2 (CH 3 ), (butylamino)methylsilane: (C 4 H 9 ) 2 HNSiH 2 (CH 3 ), (diethylamino)methylsilane: (C 2 H 5 ) 2 NSiH2 (CH 3 ), (dipropylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dibutylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dimethylamino)dimethylsilane: (CH 3 ) 2 NSiH(CH 3 ) 2 , (ethylamino)dimethylsilane: (C 2 H 5 )HNSiH(CH 3 ) 2 , (propylamino)dimethylsilane: (C 3 H 7 ) 2 HNSiH(CH 3 ) 2 , (butylamino)dimethylsilane: (C 4 H 9 ) 2 HNSiH(CH 3 ) 2 , (diethylamino)dimethylsilane: (C 2 H 5 ) 2 NSiH(CH 3 ) 2 , (dipropylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dibutylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dimethylamino)trimethylsilane: (CH 3 ) 2 NSi(CH 3 ) 3 , (ethylamino)trimethylsilane: (C 2 H 5 )HNSi(CH3 ) 3 , (propylamino)trimethylsilane: (C 3 H 7 ) 2 HNSi(CH 3 ) 3 , (butylamino)trimethylsilane: (C 4 H 9 ) 2 HNSi(CH 3 ) 3 , (diethylamino)trimethylsilane: (C 2 H 5 ) 2 NSi(CH 3 ) 3 , (dipropylamino)trimethylsilane: (C 3 H 7 ) 2 NSi(CH 3 ) 3 , (dibutylamino)trimethylsilane: (C 3 H 7 ) 2 NSi(CH 3 ) 3 , (dimethylamino)ethylsilane: (CH 3 ) 2 NSiH 2 (C 2 H 5 ), (ethylamino)ethylsilane: (C 2 H 5 )HNSiH 2 (C 2 H 5 ), (propylamino)ethylsilane: (C 3 H 7 ) 2 HNSiH 2 (C 2 H 5 ), (butylamino)ethylsilane: (C 4 H 9 ) 2 HNSiH 2 (C 2 H 5 ), (diethylamino)ethylsilane: (C 2 H 5 ) 2 NSiH 2 (C 2 H5 ), (dipropylamino)ethylsilane: (C 3 H 7 ) 2 NSiH 2 (C 2 H 5 ), (dibutylamino)ethylsilane: (C 3 H 7 ) 2 NSiH 2 (C 2 H 5 ), (dimethylamino)diethylsilane: (CH 3 ) 2 NSiH(C 2 H 5 ) 2 , (ethylamino)diethylsilane: (C 2 H 5 )HNSiH(C 2 H 5 ) 2 , (propylamino)diethylsilane: (C 3 H 7 ) 2 HNSiH(C 2 H 5 ) 2 , (butylamino)diethylsilane: (C 4 H 9 ) 2 HNSiH(C 2 H 5 ) 2 , (diethylamino)diethylsilane: (C 2 H 5 ) 2 NSiH(C 2 H 5 ) 2 , (dipropylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dibutylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dimethylamino)triethylsilane: (CH 3 )2 NSi(C 2 H 5 ) 3 , (ethylamino)triethylsilane: (C 2 H 5 )HNSi(C 2 H 5 ) 3 , (propylamino)triethylsilane: (C 3 H 7 ) 2 HNSi(C 2 H 5 ) 3 , (butylamino)triethylsilane: (C 4 H 9 ) 2 HNSi(C 2 H 5 ) 3 , (diethylamino)triethylsilane: (C 2 H 5 ) 2 NSi(C 2 H 5 ) 3 , (dipropylamino)triethylsilane: (C 3 H 7 ) 2 NSi(C 2 H 5 ) 3 , (dibutylamino)triethylsilane: (C 3 H 7 ) 2 NSi(C 2 H 5 ) 3 , (dipropylamino)silane: [(C 3 H 7 ) 2 N]SiH 3 , (dibutylamino)silane: [(C 4 H 9 ) 2 N]SiH 3 , (dipentylamino)silane: [(C 5 H 11 ) 2 N]SiH 3 , bis(dimethylamino)dimethylsilane: [(CH 3 ) 2 N] 2 Si(CH3 ) 2 , bis(ethylamino)dimethylsilane: [(C 2 H 5 )HN] 2 Si(CH 3 ) 2 , bis(propylamino)dimethylsilane: [(C 3 H 7 ) 2 HN] 2 Si(CH 3 ) 2 , bis(butylamino)dimethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(CH 3 ) 2 , bis(diethylamino)dimethylsilane: [(C 2 H 5 ) 2 N] 2 Si(CH 3 ) 2 , bis(dipropylamino)dimethylsilane: [(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 , bis(dibutylamino)dimethylsilane: [(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 , bis(dimethylamino)methylsilane: [(CH 3 ) 2 N] 2 SiH(CH 3 ), bis(ethylamino)methylsilane: [(C 2 H 5 )HN] 2 SiH(CH 3 ), bis(propylamino)methylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(CH 3 ), bis(butylamino)methylsilane: [(C 4 H 9 )2 HN] 2 SiH(CH 3 ), bis(diethylamino)methylsilane: [(C 2 H 5 ) 2 N] 2 SiH(CH 3 ), bis(dipropylamino)methylsilane: [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dibutylamino)methylsilane [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dimethylamino)diethylsilane: [(CH 3 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(ethylamino)diethylsilane: [(C 2 H 5 )HN] 2 Si(C 2 H 5 ) 2 , bis(propylamino)diethylsilane: [(C 3 H 7 ) 2 HN] 2 Si(C 2 H 5 ) 2 , bis(butylamino)diethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(C 2 H 5 ) 2 , bis(diethylamino)diethylsilane: [(C 2 H 5 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dipropylamino)diethylsilane: [(C 3 H 7 ) 2N] 2 Si(C 2 H 5 ) 2 , bis(dibutylamino)diethylsilane: [(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dimethylamino)ethylsilane: [(CH 3 ) 2 N] 2 SiH(C 2 H 5 ), bis(ethylamino)ethylsilane: [(C 2 H 5 )HN] 2 SiH(C 2 H 5 ), bis(propylamino)ethylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(C 2 H 5 ), bis(butylamino)ethylsilane: [(C 4 H 9 ) 2 HN] 2 SiH(C 2 H 5 ), bis(diethylamino)ethylsilane: [(C 2 H 5 ) 2 N] 2 SiH(C 2 H 5 ), bis(dipropylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(dibutylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(diethylamino)silane: [(C 2 H 5 ) 2 N]2 SiH 2 , bis(dipropylamino)silane: [(C 3 H 7 ) 2 N] 2 SiH 2 , bis(dibutylamino)silane: [(C 4 H 9 ) 2 N] 2 SiH 2 , bis(dipentylamino)silane: [(C 5 H 11 ) 2 N] 2 SiH 2 etc.

[0104] As the second precursor, one or more of these can be used. It is preferable to select the second precursor used in step C so that the adsorption suppression effect of the second adsorption suppression layer formed in step C is stronger than the adsorption suppression effect of the first adsorption suppression layer formed in step A under the same conditions. Since the adsorption suppression effect of the second adsorption suppression layer can be adjusted by the number and type of the first substituents contained in the second precursor, the second precursor used in step C can be appropriately selected according to the number and type of the first substituents contained in the first precursor used in step A. Specifically, when the first precursor and the second precursor have the same number of first substituents and the first precursor has only hydrogen groups as the first substituents, it is preferable to select the second precursor having only an alkyl group as the first substituent or having an alkyl group and a hydrogen group as the first substituent. This is because the alkyl group has a stronger adsorption suppression effect when comparing the alkyl group with the hydrogen group. Furthermore, when both the first precursor and the second precursor have the same first substituent (e.g., an alkyl group), it is preferable to select a second precursor having a greater number of first substituents than the number of first substituents in the first precursor, because the greater the number of first substituents, the stronger the anti-adsorption effect of the formed anti-adsorption layer.

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

[0106] In step C, when the second precursor having a fluoro group, a fluoroalkyl group, a hydrogen group, or the like as the first substituent cannot exist stably as a single compound, a second precursor having another first substituent and capable of existing 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 into a hydrogen group, a fluoro group, or a fluoroalkyl group. An example of a method for converting the first substituent in the second precursor is similar to the example of the method for converting the first substituent in the first precursor described above.

[0107] (Step D) After steps A, B, and C are performed in this order, the opening and closing operation of the valve in the film forming material supply system is controlled to supply the film forming material to the wafer 200 in the processing chamber 201. The film forming material 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 an inert gas supply system.

[0108] In step D, the action of the film-forming substance nullifies the action of the first adsorption-suppressing layer without nullifying the action of the second adsorption-suppressing layer, so that a film is selectively (preferentially) formed on the surface of the SiO film, which is the first base, as shown in Fig. 4(e). That is, in step D, the adsorption-suppressing action of the first adsorption-suppressing layer is released while maintaining the adsorption-suppressing action of the second adsorption-suppressing layer, so that a film is selectively formed on the surface of the SiO film, which is the first base. The action of the film-forming substance includes the chemical action of the film-forming substance and the physical action of the film-forming substance. Moreover, nullifying the action of the adsorption-suppressing layer means nullifying the adsorption-suppressing action by the adsorption-suppressing layer. Neutralizing the adsorption-suppressing effect of the adsorption-suppressing layer includes, for example, altering or destroying the molecular structure of the molecules contained in the adsorption-suppressing layer through the action of a film-forming substance, thereby rendering the substance capable of being adsorbed onto the surface of the base on which the adsorption-suppressing layer was formed, or altering or destroying the molecular structure of the molecules contained in the adsorption-suppressing layer through the action of a film-forming substance and removing the adsorption-suppressing layer, thereby rendering the substance capable of being adsorbed onto the surface of the base on which the adsorption-suppressing layer was formed.

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

[0110] The film formed in step D may be formed by supplying a film-forming material to the wafer 200, and the method is not particularly limited. Here, the film-forming material includes a source gas, a reaction gas, a catalyst gas, and the like. For example, in step D, it is preferable to alternately supply a source gas and a reaction gas as the film-forming material to the wafer 200, or alternately supply a source gas and a reaction gas as the film-forming gas to the wafer 200, and supply a 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 necessarily required and can be omitted. For example, in step D, any of the following processing sequences can be performed. Note that the following processing sequence is an extract of only step D.

[0111] (raw material gas → reactive gas) × n (raw material gas → reactive gas + catalytic gas) × n (raw material gas + catalyst gas → reactant gas) × n (raw material gas + catalytic gas → reactant gas + catalytic gas) × n

[0112] In the following, an example will be described in which a source gas and a reactive gas are alternately supplied as film forming materials, and a catalytic gas is supplied together with each of the gases in step D. Specifically, an example will be described in which, as step D, a cycle of step D1 of supplying a source gas and a catalytic gas to the wafer 200 and step D2 of supplying a reactive gas and a catalytic gas to the wafer 200 are non-simultaneously performed a predetermined number of times (n times, n is an integer equal to or greater than 1).

[0113] (Step D1) After step C is completed, a source gas and a catalyst gas are supplied as the film forming materials from the film forming material supply system to the wafer 200 in the processing chamber 201. The source gas and the catalyst gas supplied to the wafer 200 are 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.

[0114] After the source gas and catalytic gas are supplied to the wafers 200 for a predetermined time, the supply of the source gas and catalytic gas into the processing chamber 201 is stopped. Then, the source gas, catalytic gas, etc. remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those for purging in step A described above.

[0115] In step D1, the processing conditions for supplying the source gas and the catalyst gas are as follows: Treatment temperature: 25 to 200°C, preferably 25 to 120°C Processing pressure: 133~1333Pa Raw gas supply flow rate: 1 to 2000 sccm Raw gas supply time: 1 to 120 seconds Catalyst gas supply flow rate: 1 to 2000 sccm Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Examples include:

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

[0117] The Si and halogen-containing gas, the Si and amino group-containing gas, and the Si and alkoxy group-containing gas preferably contain a chemical bond between Si and halogen, a chemical bond between Si and amino group, and a chemical bond between Si and alkoxy group, respectively. These Si-containing gases may further contain C, and in this case, it is preferable to contain C in the form of Si-C bond. As the Si and C-containing gas, for example, an alkylene silane-based gas containing an alkylene group and having a Si-C bond can be used. The alkylene group includes a methylene group, an ethylene group, a propylene group, a butylene group, and the like. As the alkylene silane-based gas, it is preferable to contain Si and halogen, Si and amino group, Si and alkoxy group, and the like in the form of direct bond, and to contain C in the form of Si-C bond.

[0118] The silicon and halogen-containing gas is, for example, dichlorosilane (SiH 2 Cl 2 , trichlorosilane: SiHCl 3 , tetrachlorosilane: SiCl 4 , Tetrabromosilane: SiBr 4 , hexachlorodisilane: (SiCl 3 ) 2 , Octachlorotrisilane:Si 3 Cl 8 , Hexachlorodisiloxane: (SiCl 3 ) 2 O, Octachlorotrisiloxane: (SiCl 3 O) 2 SiCl 2 Examples of gases containing Si and amino groups include tetrakis(dimethylamino)silane: Si[N(CH 3 ) 2 ] 4 , tetrakis(diethylamino)silane: Si[N(C 2 H 5 ) 2 ] 4 Examples of gases containing Si and alkoxy groups include tetramethoxysilane: Si(OCH 3 ) 4 , tetraethoxysilane: Si(OC 2 H 5 )4 , (dimethylamino)trimethoxysilane: [(CH 3 ) 2 N]Si(OCH 3 ) 3 , (dimethylamino)triethoxysilane: [(CH 3 ) 2 N]Si(OC 2 H 5 ) 3 Examples of gases containing Si, C and halogen include bistrichlorosilylmethane (SiCl 3 ) 2 CH 2 , bistrichlorosilylethane: (SiCl 3 ) C 2 H 5 , bis[(trichlorosilyl)methyl]dichlorosilane: [(SiCl 3 ) 3 CH 2 ] 2 SiCl 2 , 1,1,2,2-tetrachloro-1,2-dimethyldisilane: (CH 3 ) 2 S 2 Cl 4 , 1,2-dichloro-1,1,2,2-tetramethyldisilane: (CH 3 ) 4 S 2 Cl 2 , 1,1,3,3-tetrachloro-1,3-disilacyclobutane: C 2 H 4 Cl 4 S 2 As the source gas, one or more of these can be used.

[0119] -Catalytic gas- As the catalytic gas, for example, an amine-based gas containing C, N, and H can be used. As the amine-based gas, for example, dimethylamine: 2 H 7 N, diethylamine: C 4 H 11 N, Dipropylamine: C 6 H 15 N, Pyridine: C5 H 5 N, piperidine: C 6 H 12 N, Pyrrolidine: C 4 H 9 N, Aniline: C 6 H 7 N, Picoline: C 6 H 7 N, aminopyridine: C 5 H 6 N 2 , Lutidine: C 7 H 9 N, piperazine: C 4 H 10 N 2 As the catalytic gas, one or more of these can be used.

[0120] (Step D2) After step D1 is completed, a reactive gas and a catalytic gas are supplied as the film forming materials from the film forming material supply system to the wafer 200 in the processing chamber 201. The reactive gas and the catalytic gas supplied to the wafer 200 are 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.

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

[0122] The process conditions for supplying the reaction gas and the catalyst gas in step D2 are as follows: Treatment temperature: 25°C to 200°C, preferably 25°C to 120°C Processing pressure: 133~1333Pa Reactant gas supply flow rate: 1 to 2000 sccm Reaction gas supply time: 1 to 120 seconds Catalyst gas supply flow rate: 1 to 2000 sccm Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Examples include:

[0123] -Reactive gas- When forming an oxide film, for example, a gas containing O and H can be used as the reaction gas. 2 O gas, H 2 O 2 The O-containing gas may include, for example, H. 2 Gas + O 2 Gas, H 2 Gas + O 3 It is also possible to use an O-containing gas that does not contain OH bonds, such as a gas.

[0124] In addition, when a nitride film is formed, for example, a nitriding agent (nitriding gas) can be used as the reaction gas. For example, a N- and H-containing gas can be used as the nitriding agent. For example, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas, diazene (N 2 H 2 ) Gas, N 3 H 8 The reaction gas may be one or more of these gases, such as a hydrogen nitride gas containing an NH bond.

[0125] -Catalytic gas- As the catalytic gas, for example, the same catalytic gas as the various catalytic gases exemplified in step D1 above can be used.

[0126] (Performed a set number of times) By performing the above-mentioned step D1 and step D2 asynchronously, i.e., by performing the cycle a predetermined number of times (n times, n being an integer equal to or greater than 1), it becomes possible to selectively form a film having a desired thickness on the surface of the SiO film, which is the first undercoat, as shown in FIG. 4(e).

[0127] In addition, in the process of performing the above-mentioned cycle a predetermined number of times, the adsorption suppressing action of the first adsorption suppressing layer formed on the surface of the first base can be disabled (cancelled). After the adsorption suppressing action of the first adsorption suppressing layer is disabled, in step D1, a first layer is formed on the surface of the first base, and in step D2, the first layer formed on the surface of the first base is changed to a second layer. By performing these steps a predetermined number of times, a film is formed on the first base by laminating the second layer. During this time, the adsorption suppressing action of the second adsorption suppressing layer formed on the surface of the second base can be maintained, thereby suppressing the formation of a film on the surface of the second base. It is preferable to repeat the above-mentioned cycle a plurality of times. That is, it is preferable to repeat the above-mentioned cycle a plurality of times until the thickness of the film formed on the first base reaches the desired thickness by making the thickness of the second layer formed per cycle thinner than the desired thickness and laminating the second layer.

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

[0129] In step D, the material (film type) of the film obtained varies depending on the type of raw material gas and reactive gas. For example, in step D, a silicon oxycarbonate film (SiOC film) can be formed as a film by using a gas containing Si, C, and a halogen as the raw material gas and a gas containing O as the reactive gas. Also, for example, in step D, a silicon carbonitride film (SiCN film) can be formed as a film by using a gas containing Si, C, and a halogen as the raw material gas and a gas containing N and H as the reactive gas. Also, for example, in step D, a silicon oxycarbonitride film (SiOCN film) can be formed as a film by using a gas containing Si, C, and a halogen as the raw material gas and a gas containing O and a gas containing N and H as the reactive gas. Also, for example, in step D, a silicon oxide film (SiO film) can be formed as a film by using a gas containing Si and a halogen as the raw material gas and a gas containing O as the reactive gas. Also, for example, in step D, a silicon nitride film (SiN film) can be formed as a film by using a gas containing Si and a halogen as the raw material gas and a gas containing N and H as the reactive gas. As described above, various films such as silicon oxide films and silicon nitride films can be formed in step D. As described above, depending on the processing conditions, the catalytic gas is not necessarily required. When the catalytic 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] In step D, a source gas containing a metal element such as Al, Ti, Hf, Zr, Ta, Mo, or W is used as the source gas, and an O-containing gas or an N- and H-containing gas is used as the reactive gas, whereby a metal oxide film such as an aluminum oxide film (AlO film), a titanium oxide film (TiO film), a hafnium oxide film (HfO film), a zirconium oxide film (ZrO film), a tantalum oxide film (TaO film), a molybdenum oxide film (MoO), or a tungsten oxide film (WO), or a metal nitride film such as an aluminum nitride film (AlN film), a titanium nitride film (TiN film), a hafnium nitride film (HfN film), a zirconium nitride film (ZrN film), a tantalum nitride film (TaN film), a molybdenum nitride film (MoN), or a tungsten nitride film (WN), or the like, can be formed. As described above, depending on the processing conditions, the catalytic gas is not necessarily required. When the 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., for example.

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

[0132] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0133] (Effect of the first aspect) According to the first aspect, one or more of the following advantages can be obtained.

[0134] By forming a first adsorption-suppressing layer on the surface of the first base, it becomes possible to selectively form an adsorption-promoting layer on the surface of the second base, and it becomes possible to selectively form a second adsorption-suppressing layer on the surface of the adsorption-promoting layer. That is, it becomes possible to selectively form the second adsorption-suppressing layer on the outermost surface of the second base (specific base). Thereafter, by supplying a film-forming substance, it becomes possible to selectively form a film on the surface of the first base (desired base).

[0135] The action of the film-forming substance can release the anti-adsorption effect of the first adsorption-suppressing layer, making it possible to form a film on the surface of the first base. At that time, by maintaining the anti-adsorption effect of the second adsorption-suppressing layer formed on the surface of the second base, it becomes possible to suppress the formation of a film on the surface of the second base. In other words, it becomes possible to selectively form a film on the surface of the first base without performing a separate process such as removing the first adsorption-suppressing layer. This makes it possible to shorten the processing time and increase the throughput, i.e., the productivity.

[0136] By carrying out the above steps on the wafer 200 in which the first underlayer is an oxygen-containing film and the second underlayer is an oxygen-free film, it becomes possible to more appropriately cause the above-mentioned chemical reactions, etc. As a result, the above-mentioned effects can be obtained more significantly. By carrying out the above steps on the wafer 200 in which the first underlayer is, for example, at least one of a SiO film, a SiOC film, and an AlO film, and the second underlayer is, for example, at least one of a silicon film (Si film), a SiN film, and a metal film, it becomes possible to more appropriately cause the above-mentioned chemical reactions, etc. As a result, the above-mentioned effects can be obtained more significantly.

[0137] It is preferable that the adsorption suppressing effect of the first adsorption suppressing layer formed in step A is weaker than the adsorption suppressing effect of the second adsorption suppressing layer formed in step C, under the same conditions. It is also preferable that the first adsorption suppressing layer formed in step A is more easily detached, under the same conditions, than the second adsorption suppressing layer formed in step C. It is also preferable that the reactivity between the film formation substance used in step D and the first adsorption suppressing layer formed in step A is higher, under the same conditions, than the reactivity between the film formation substance used in step D and the second adsorption suppressing layer formed in step C. These make it possible to efficiently neutralize the adsorption suppressing effect of the first adsorption suppressing layer in step D.

[0138] <Second Aspect of the Present Disclosure> Next, a second embodiment of the present disclosure will be described mainly with reference to FIGS. 5(a) to 5(f) and 6(a) to 6(f).

[0139] As shown in Figures 5(a) to 5(f), 6(a) to 6(f) and the processing sequences shown below, the processing sequence in the second embodiment further includes, after performing steps A, B, and C and before performing step D, step E of removing the first adsorption-suppressing layer and / or disabling the function of the first adsorption-suppressing layer (hereinafter also referred to as removing and / or disabling the first adsorption-suppressing 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 invalidation of the first adsorption-suppressing layer → deposition

[0141] Alternatively, the first adsorption suppressing layer may be removed in step E as shown in FIGS. 5(a) to 5(f) and in the processing sequence described below.

[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 FIGS. 6(a) to 6(f) and in the process sequence described below, in step E, the function of the first adsorption suppressing layer may be nullified.

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

[0145] Furthermore, as in the processing sequence shown below, both the first adsorption suppressing layer and the function of the first adsorption suppressing layer may be removed and nullified in step E. In this case, the first adsorption suppressing layer is removed from a portion of the surface of the first base, and the function of the first adsorption suppressing layer is nullified from 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 invalidation of the first adsorption-suppressing layer → deposition

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

[0148] (Step E) After steps A, B, and C are performed, step E is performed. Step E involves at least one of removing the first adsorption suppressing layer and nullifying the function of the first adsorption suppressing layer.

[0149] There is no particular limitation on the method of removing and / or disabling the first adsorption-suppressing layer. Examples of the method of removing and / or disabling the first adsorption-suppressing layer include annealing, oxidation, and modification. These treatments can perform at least one of removing the first adsorption-suppressing layer, modifying the first substituent contained in the first adsorption-suppressing layer, and severing (dissociating) the bond between the residue derived from the first precursor contained in the first adsorption-suppressing layer and the first underlayer. It is preferable that the above-mentioned annealing, oxidation, and modification treatments do not reduce the adsorption-suppressing effect of the second adsorption-suppressing layer formed on the surface of the second underlayer. For this purpose, it is preferable that the above-mentioned annealing, oxidation, and modification treatments utilize at least one of the difference in heat resistance, the difference in oxidation resistance, and the difference in reactivity with a specific substance between the first and second adsorption-suppressing layers to remove and / or disable the first adsorption-suppressing layer without reducing the adsorption-suppressing effect of the second adsorption-suppressing layer formed on the surface of the second underlayer.

[0150] In addition, in step E, when an invalidating substance (as described above, for convenience, this term is used as a general term for removal and / or invalidating substances) is supplied to the wafer 200, the opening and closing operation of a valve in a processing substance supply system may be controlled to supply the invalidating substance to the wafer 200 in the processing chamber 201. The invalidating substance 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 an inert gas supply system.

[0151] [Annealing treatment] In step E, an annealing process, preferably an annealing process under an inert gas atmosphere, can be performed to remove and / or disable the first adhesion suppressing 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 annealing treatment conditions are as follows: Treatment temperature: 100 to 600°C, preferably 200 to 500°C Treatment pressure: 1 to 101325 Pa, preferably 1 to 13300 Pa Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Inert gas supply time: 1 to 240 minutes, preferably 30 to 120 minutes Examples include:

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

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

[0155] The conditions for oxidation treatment using an O-containing substance as an oxidizing agent are as follows: Treatment temperature: 25 to 800°C, preferably 25 to 600°C Treatment 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 to 20,000 sccm Examples include:

[0156] The treatment conditions when performing the oxidation treatment using the O-containing substance as the oxidizing agent and the catalytic gas are as follows: Treatment temperature: 25 to 200°C, preferably 25 to 120°C Treatment 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 to 20,000 sccm Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Examples include:

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

[0158] [Denaturation treatment] In step E, a denaturing treatment can be performed to remove and / or deactivate the first adsorption anti-layer. This denaturing treatment can modify a portion of the residues derived from the first precursor contained in the first adsorption anti-layer. The denaturing treatment can be performed by supplying a halogen-containing gas to the wafer 200. An example of a halogen-containing gas that acts as a deactivating substance is F. 2 Gas, HF gas, chlorine trifluoride (ClF 3 ) gas, boron trifluoride (BCl 3 ) gas, chlorine (Cl 2 ) gas, hydrogen chloride (HCl) gas, bromine (Br 2 ) gas, hydrogen bromide (HBr) gas, tetrachloroethylene (C 2 Cl 4In the modification process, a halogen-containing gas and a catalytic gas may be simultaneously supplied to the wafer 200. The halogen-containing gas and the catalytic gas can be supplied by using the above-mentioned processing material supply system.

[0159] The processing conditions for the modification treatment using a halogen-containing gas are as follows: Treatment temperature: 25 to 400°C, preferably 25 to 200°C Treatment pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa Halogen-containing gas supply flow rate: 1 to 2000 sccm Halogen-containing gas supply time: 1 to 120 seconds Catalyst gas supply flow rate: 0 to 20,000 sccm Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Examples include:

[0160] The modification treatment in step E is suitable, for example, when the first substituent contained in the first adsorption suppressing layer is a hydrogen group and the first substituent contained in the second adsorption suppressing 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 suppressing action of the first adsorption suppressing layer and the adsorption suppressing action of the second adsorption suppressing layer, however, from the viewpoint of efficiently removing and / or neutralizing the first adsorption suppressing layer in step E, it is preferable that the adsorption suppressing action of the first adsorption suppressing layer is weaker than the adsorption suppressing action of the second adsorption suppressing layer.

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

[0163] Step D can be performed under the same processing procedure and processing conditions as those of step D in the first embodiment. However, when a film having the same thickness as that of the film formed in the first embodiment is to be formed, the processing time of step D in the second embodiment can be shorter than the processing time of step D in the first embodiment.

[0164] (Effect of the second aspect) According to the second aspect, one or more of the following advantages can be obtained.

[0165] The second aspect also provides the same effect as the first aspect. Moreover, according to the second aspect, by including step E, selective film formation on the surface of the first underlayer can be efficiently performed without delay. When the first adsorption suppressing layer is removed in step E, it is possible to prevent residues of the first adsorption suppressing layer from remaining at the interface between the film formed on the surface of the first underlayer and the surface of the first underlayer. This makes it possible to improve the interface characteristics between the film formed on the surface of the first underlayer and the surface of the first underlayer. Furthermore, when the action of the first adsorption suppressing layer is nullified in step E, the process can be completed in a relatively short time compared to the case where the first adsorption suppressing layer is completely removed. This makes it possible to shorten the processing time and increase the throughput, i.e., the productivity.

[0166] It is preferable that the adsorption suppressing effect of the first adsorption suppressing layer formed in step A is weaker than the adsorption suppressing effect of the second adsorption suppressing layer formed in step C, under the same conditions. It is also preferable that the first adsorption suppressing layer formed in step A is more easily detached, under the same conditions, than the second adsorption suppressing layer formed in step C. It is also preferable that the reactivity between the film formation substance used in step D and the first adsorption suppressing layer formed in step A is higher, under the same conditions, than the reactivity between the film formation substance used in step D and the second adsorption suppressing layer formed in step C. These factors make it possible to efficiently remove and / or neutralize the first adsorption suppressing layer in step E.

[0167] <Variation 1> Modification 1 of the present disclosure will be described mainly with reference to Figs. 7(a) to 7(f).

[0168] As shown in Figures 7(a) to 7(f) and the processing sequence shown below, the processing sequence in variant example 1 further includes step F of reducing adsorption sites (e.g., OH terminations) on the surface of the first base before performing step A.

[0169] Decrease in adsorption sites → Formation of first adsorption-suppressing layer → Formation of adsorption-promoting layer → Formation of second adsorption-suppressing layer → Film formation

[0170] In step F, the number of adsorption sites on the surface of the first underlayer is reduced from the state shown in Fig. 7(a) to the state shown in Fig. 7(b), thereby making it possible to suppress the formation of a second adsorption suppressing layer on the surface of the first underlayer in step C. That is, in step C, it becomes possible to form a second adsorption suppressing layer on the surface of the adsorption-promoting layer formed on the surface of the second underlayer with higher selectivity. Annealing treatment and the like can be used as a method for reducing the number of adsorption sites on the surface of the first underlayer in step F.

[0171] The annealing treatment conditions in step F are as follows: Treatment temperature: 100 to 500°C, preferably 200 to 500°C Treatment pressure: 1 to 101325 Pa, preferably 1 to 13300 Pa Inert gas supply flow rate (per gas supply pipe): 0 to 20,000 sccm Treatment time: 1 to 240 minutes, preferably 30 to 120 minutes Examples include:

[0172] Here, if the treatment temperature is less than 100°C, the effect of reducing the adsorption sites on the surface of the first underlayer becomes insufficient, and as shown in FIG. 10(a), the adsorption sites (OH termination) may remain densely on the surface of the first underlayer. In this case, after step A is completed, as shown in FIG. 10(b), the adsorption sites (OH termination) may remain on the surface of the first underlayer. In this state, if steps B and C are performed in this order, as shown in FIG. 10(c), at least a part of the molecular structure of the molecule constituting the second precursor (e.g., a residue derived from the second precursor) may be adsorbed on the adsorption sites (OH termination) remaining on the surface of the first underlayer. In this case, not only the first adsorption suppression layer but also the second adsorption suppression layer is formed on the surface of the first underlayer, resulting in a decrease in selectivity. This problem can be solved by setting the treatment temperature to 100°C or higher. This problem can be sufficiently solved by setting the treatment temperature to 200°C or higher.

[0173] On the other hand, if the treatment temperature is set to a temperature higher than 500°C, the effect of reducing the adsorption sites on the surface of the first underlayer becomes excessive, and as shown in FIG. 11(a), the adsorption sites (OH termination) are present in a sparse state on the surface of the first underlayer. Therefore, after the end of step A, as shown in FIG. 11(b), the intervals between at least a part of the molecular structure of the molecules constituting the first precursor adsorbed on the surface of the first underlayer (e.g., residues derived from the first precursor) may become too wide. That is, a wide area on the surface of the first underlayer where the first adsorption suppressing layer is not formed may be formed. In this state, if steps B and C are performed in this order, as shown in FIG. 11(c), in step B, an adsorption promoting layer may be formed on the area on the surface of the first underlayer where the first adsorption suppressing layer is not formed, and in step C, at least a part of the molecular structure of the molecules constituting the second precursor may be adsorbed on the surface of the adsorption promoting layer. In this case, not only the first adsorption suppressing layer but also the second adsorption suppressing layer is formed on the surface of the first underlayer, resulting in a decrease in selectivity. This problem can be solved by setting the processing temperature at 500° C. or less.

[0174] For these reasons, it is desirable to set the annealing temperature to 100°C or higher and 500°C or lower, preferably 200°C or higher and 500°C or lower. As a result, as shown in Fig. 12(a), it is possible to properly reduce the adsorption sites (OH terminations) on the surface of the first underlayer, and as shown in Fig. 12(b), after step A is completed, at least a part of the molecular structure of the molecules constituting the first precursor is properly adsorbed on the surface of the first underlayer, and the first adsorption suppressing layer is properly formed. In this state, if steps B and C are performed in this order, it is possible to suppress the formation of an adsorption promoting layer and the formation of a second adsorption suppressing layer on the surface of the first underlayer, as shown in Fig. 12(c), and it is possible to increase the selectivity.

[0175] After performing step F, steps A, B, C, and D can be performed in the same manner as in the first embodiment, as in the above-mentioned processing sequence. These steps A, B, C, and D can be performed according to the same processing procedures and processing conditions as steps A, B, C, and D in the first embodiment.

[0176] In addition, in the first modification, after performing 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 following processing sequence. These steps A, B, C, E, and D can be performed according to the same processing procedures and under the same processing conditions as steps A, B, C, E, and D in the second embodiment.

[0177] Decrease in adsorption sites → Formation of first adsorption-suppressing layer → Formation of adsorption-promoting layer → Formation of second adsorption-suppressing layer → Removal and / or invalidation of first adsorption-suppressing layer → Film formation

[0178] The same effects as those of the above-mentioned first and second aspects can be obtained in Modification 1. Furthermore, according to Modification 1, it is possible to further improve the selectivity in selective growth.

[0179] <Variation 2> Modification 2 of the present disclosure will be described mainly with reference to Figs. 8(a) to 8(f).

[0180] As shown in Figures 8(a) to 8(f) and the processing sequence shown below, the processing sequence in variant example 2 further includes, in step D after steps A, B, and C, a film made of a material different from the adsorption-promoting layer is formed on the surface of the first base, and after step D, a step G of exposing the film on the surface of the first base and the adsorption-promoting layer and the second adsorption-suppressing layer on the surface of the second base to an etching substance, thereby removing the adsorption-promoting layer and the second adsorption-suppressing layer on the surface of the second base.

[0181] Formation of the first adsorption-suppressing layer → formation of the adsorption-promoting layer → formation of the second adsorption-suppressing layer → deposition → removal of the second adsorption-suppressing layer and the adsorption-promoting layer

[0182] In step G, as shown in FIG. 8(f), it is possible to selectively remove the adsorption promoting layer and the second adsorption suppressing layer on the surface of the second underlayer without removing the film on the surface of the first underlayer, that is, while leaving the film on the surface of the first underlayer. In step G, it is possible to utilize 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 underlayer and the adsorption promoting layer formed on the surface of the second underlayer. Due to the difference in processing resistance (etching resistance) between the film formed on the surface of the first underlayer and the adsorption promoting layer formed on the surface of the second underlayer, it is possible to selectively remove the adsorption promoting layer and the second adsorption suppressing layer on the surface of the second underlayer while leaving the film on the surface of the first underlayer.

[0183] The following shows an example of a combination of the type (material) of the adsorption-promoting layer formed on the surface of the second underlayer, the type (material) of the film formed on the surface of the first underlayer, and the etching process suitable for step G. For example, when a SiO layer is formed as an adsorption-promoting layer on the surface of the second underlayer, a SiOC film or a SiN film is formed as a film on the surface of the first underlayer, and in this case, it is preferable to perform an etching process using a fluorine-based etching agent in step G. Also, for example, when a SiOC layer is formed as an adsorption-promoting layer on the surface of the second underlayer, a SiN film is formed as a film on the surface of the first underlayer, and in this case, it is preferable to use both plasma oxidation and an etching process using a fluorine-based etching agent in step G. After the adsorption-promoting layer is changed from a SiOC layer to a SiO layer that is easily etched by a fluorine-based etching agent by plasma oxidation, it becomes possible to perform etching. Examples of fluorine-based etching agents used as etching substances include HF aqueous solution (DHF), HF gas, and F 2 Gases, etc. Etching substances, such as fluorine-based etchants, can be supplied using the above-mentioned processing substance supply system (etching substance supply system).

[0184] In particular, when a SiO layer is formed as an adsorption-promoting layer on the surface of the second base in step B, a SiOC film is formed as a film on the surface of the first base in step D, and HF is used as an etching material in step G, the processing in step G can be performed 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 in the above-mentioned processing sequence. These steps A, B, C, and D can be performed according to the same processing procedures and processing conditions as steps A, B, C, and D in the first embodiment.

[0186] In addition, in the second modification, steps A, B, C, E, and D can be performed in the same manner as in the second embodiment, as shown in the following processing sequence, before performing step G. These steps A, B, C, E, and D can be performed according to the same processing procedures and under the same processing 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 invalidation of the first adsorption-suppressing layer → film formation → removal of the second adsorption-suppressing layer and the adsorption-promoting layer

[0188] In the second modification, the same effects as those of the first and second embodiments can be obtained. Furthermore, according to the second modification, it is possible to expose the surface of the second underlayer and reset the surface state of the second underlayer. This makes it possible to perform a desired treatment on the surface of the second underlayer and form a desired film in various subsequent steps.

[0189] <Variation 3> Modification 3 of the present disclosure will be described mainly with reference to Figs. 9(a) to 9(g).

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

[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 the adsorption-promoting layer → Modification

[0192] In step H, as shown in FIG. 9(g), after step G, the film existing on the surface of the first underlayer is modified to change it into a film (after modification) whose material is different from that of the film. For example, after step G, the film existing on the surface of the first underlayer is modified to change it into a film whose material is the same as that of the adsorption promoting layer temporarily formed on the surface of the second underlayer. Here, when a film whose material is the same as that of the adsorption promoting layer is formed on the surface of the first underlayer in step D, not only the adsorption promoting layer and the second adsorption suppressing layer but also the film whose material is the same as that of the adsorption promoting layer are removed together in step G in the second modified example. By forming a film whose material is different from that of the adsorption promoting layer once on the surface of the first underlayer in step D, it is possible to prevent the film whose material is different from that of the adsorption promoting layer from being removed in step G, and then, by modifying the film whose material is different from that of the adsorption promoting layer remaining on the surface of the first underlayer, the film can be changed into a film whose material is the same as that of the adsorption promoting layer. This makes it possible to create a state in which a film of the same material as the adhesion promoting layer is formed on the surface of the first underlayer even after step G has been performed.

[0193] In step H, the method of modifying the film on the surface of the first underlayer includes oxidation and nitridation. In particular, in step H, after performing step G, it is preferable to oxidize the film on the surface of the first underlayer to change it into a SiO film. In this case, it is possible to create a state in which a SiO film is formed on the surface of the first underlayer after performing step G. Here, when a SiO film having a material equivalent to that of the adsorption promoting layer (SiO layer) is formed on the surface of the first underlayer in step D, not only the adsorption promoting layer (SiO layer) and the second adsorption suppressing layer on the surface of the second underlayer but also the SiO film on the surface of the first underlayer are removed together in step G. In step D, a SiOC film having a material different from that of the adsorption promoting layer (SiO layer) is once formed on the surface of the first underlayer, so that the removal of the SiOC film in step G can be suppressed, and then, the SiOC film remaining on the surface of the first underlayer is oxidized to change the SiOC film into a SiO film having a material equivalent to that of the adsorption promoting layer (SiO layer). This makes it possible to create a state in which a SiO film is formed on the surface of the first underlayer even after step G is performed.

[0194] In step H, in order to modify the film on the surface of the first underlayer, it is preferable to supply a modifying substance to the wafer 200 and perform an annealing process in a modifying substance atmosphere. Examples of the modifying substance include an oxidizing agent (O-containing substance) and a nitriding agent (N-containing substance). The modifying substance can be supplied using the above-mentioned processing substance supply system (modifying substance supply system).

[0195] In step H, the film on the surface of the first underlayer is oxidized using an oxidizing agent (O-containing substance) to change it into a SiO film, and the processing conditions are as follows: Treatment temperature: 300 to 1200°C, preferably 300 to 700°C Treatment pressure: 1 to 101325 Pa, preferably 67 to 101325 Pa O-containing material supply flow rate: 1~10slm Supply time of O-containing substance: 1 to 240 minutes, preferably 1 to 120 minutes Other processing conditions may be the same as those in step A.

[0196] The O-containing substance used in step H may be the same as the O-containing substance used in step B. The annealing treatment in step H may be plasma annealing using an O-containing substance excited by plasma.

[0197] In addition, in the third modification, steps A, B, C, E, and D can be performed in the same manner as in the second embodiment, as shown in the following processing sequence, before performing step G. These steps A, B, C, E, and D can be performed according to the same processing procedures and under the same processing conditions as steps A, B, C, E, and D in the second embodiment.

[0198] Formation of first adsorption-suppressing layer → formation of adsorption-promoting layer → formation of second adsorption-suppressing layer → removal and / or invalidation of first adsorption-suppressing layer → film formation → removal of second adsorption-suppressing layer and adsorption-promoting layer → modification

[0199] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0200] For example, the wafer 200 may have a plurality of regions of different materials as the first underlayer, or may have a plurality of regions of different materials as the second underlayer. The regions constituting the first underlayer and the second underlayer may be, in addition to the above-mentioned SiO film and SiN film, a film containing a semiconductor element such as a SiOCN film, a SiON film, a SiOC film, a SiC film, a SiCN film, a SiBN film, a SiBCN film, a SiBC film, a Si film, a Ge film, a SiGe film, a film containing a metal element such as a TiN film or a W film, an amorphous carbon film (aC film), or a single crystal Si (Si wafer). Any region may be used as the first underlayer if it has a surface that can be modified by the first modifier (i.e., a surface having an adsorption site). On the other hand, any region may be used as the second underlayer if it has a surface that is difficult to modify by the first modifier (i.e., a surface having no adsorption site or few adsorption sites). In this case, the same effect as that of the above-mentioned embodiment can be obtained.

[0201] It is preferable that the recipes used for each process are prepared individually according to the process contents and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing device. It is also possible to reduce the burden on the operator and quickly start each process while avoiding operational errors.

[0202] The above-mentioned recipes may not only be newly created, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. Also, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0203] In the above-mentioned aspects and modifications, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned aspects, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In the above-mentioned aspects, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned aspects, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0204] When using these substrate processing apparatuses, each process can be performed according to the same process procedures and under the same process conditions as in the above-described aspects and modifications, and the same effects as in the above-described aspects and modifications can be obtained.

[0205] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in such a case may be the same as those of the above-mentioned aspects and modifications. EXAMPLES

[0206] Example 1 As Example 1, a wafer having an exposed SiO film as a first underlayer and an exposed SiN film as a second underlayer on the surface was used, and a SiOC film was selectively grown on the surface of the SiO film by the process sequence in the above-mentioned modified example 1 to fabricate a first evaluation sample. The process conditions in each step of fabricating the first evaluation sample were set to predetermined conditions within the range of process conditions in each step of the process sequence in the above-mentioned modified example 1.

[0207] Example 2 As Example 2, a wafer having an exposed SiO film as a first underlayer and an exposed SiN film as a second underlayer on its surface was used, and a second evaluation sample was fabricated by selectively growing an SiOC film on the surface of the SiO film and removing (etching) an adsorption promoting layer on the surface of the SiN film according to the processing sequence in the above-mentioned modified example 2. The processing conditions in each step of fabricating the second evaluation sample were set to predetermined conditions within the range of processing conditions in each step of the processing sequence in the above-mentioned modified example 2.

[0208] After preparing the first and second evaluation samples, the thickness of the film formed on the SiO film (thickness of the SiOC film) 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 thickness difference between the thickness of the film formed on the SiO film and the thickness of the film formed on the SiN film (hereinafter simply referred to as the thickness difference) for each evaluation sample was calculated. The larger this thickness difference is, the better the selectivity is.

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

[0210] 13, it can be seen that the film thickness difference in Example 1 (first evaluation sample) is about 7 nm, and the film thickness difference in Example 2 (second evaluation sample) is about 8.5 nm. As such, it was confirmed that according to Examples 1 and 2, it is possible to significantly improve the selectivity in selective growth.

[0211] In addition, in other film formation evaluations conducted by the present inventors, it has been confirmed that a SiOC film is selectively formed on the first underlayer not only when the first underlayer is a SiO film and the second underlayer is a SiN film, but also when the first underlayer is a SiOC film or an AlO film, or when the second underlayer is a metal film such as a Si film, a SiCN film, a TiN film, or a W film.

Claims

1. (a) supplying a first precursor to a substrate having a first surface and a second surface to form a first adhesion-suppressing layer on the first surface; (b) applying a reactant to the substrate to form an adhesion promoting layer on the second surface; (c) supplying to the substrate a second precursor having a molecular structure different from that of the first precursor, thereby forming a second adhesion suppressing layer on a surface of the adhesion promoting layer; (d) supplying a film forming material to the substrate after steps (a), (b), and (c) to form a film on the first surface; The processing method according to claim 1,

2. The method according to claim 1 , wherein in step (d), the action of the film-forming substance is used to nullify the action of the first adhesion suppressing layer, thereby forming the film on the first surface.

3. (e) The treatment method described in claim 1, further comprising, after performing (a), (b), and (c) and before performing (d), a step of at least one of removing the first adsorption-suppressing layer and disabling the function of the first adsorption-suppressing layer.

4. 4. The treatment method according to claim 1, wherein the adsorption suppressing effect of the first adsorption suppressing layer is weaker than the adsorption suppressing effect of the second adsorption suppressing layer under the same conditions.

5. 4. The treatment method according to claim 1, wherein the first adsorption suppressing layer is more easily desorbed than the second adsorption suppressing layer under the same conditions.

6. 4. The treatment method according to claim 1, wherein the reactivity between the film-forming substance and the first anti-adsorption layer is higher than the reactivity between the film-forming substance and the second anti-adsorption layer under the same conditions.

7. 4. The method according to claim 1, wherein in (b), an oxygen-containing layer is formed as the adsorption-promoting layer.

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

9. The method of claim 7 , wherein in (b) the second surface is oxidized.

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

11. The method of any one of claims 1 to 3, further comprising the step of: (f) reducing adsorption sites on the first surface before carrying out (a).

12. The method according to claim 11 , wherein in (f), formation of a second adsorption suppressing layer on the first surface is suppressed by reducing adsorption sites on the first surface.

13. 12. The method of claim 11, wherein in (f), the substrate is annealed at a temperature of 200° C. or more and 500° C. or less.

14. (d) forming the film, the film being made of a material different from that of the adsorption-promoting layer, on the first surface; (g) After carrying out (d), the method according to any one of claims 1 to 3 further comprises the step of exposing the film on the first surface and the adsorption-promoting layer and the second adsorption-suppressing layer on the second surface to an etching substance, thereby removing the adsorption-promoting layer and the second adsorption-suppressing layer on the second surface.

15. (b) forming a silicon oxide layer as the adsorption promoting layer on the second surface; (d) forming a silicon oxide / carbide film on the first surface as the film; 15. The method of claim 14, wherein in (g) hydrogen fluoride is used as the etching material.

16. 15. The method of claim 14, further comprising the step of (h) modifying the film on the first surface after (g) to change the film to a film having a material different from that of the film.

17. 16. The method of claim 15, further comprising the step of: (h) after (g), oxidizing the film on the first surface to convert it to a silicon oxide film.

18. 4. The processing method according to claim 1, 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 includes at least one of a silicon oxide film, a silicon oxide carbide film, and an aluminum oxide film, and the second surface includes at least one of a silicon film, a silicon nitride film, and a metal film.

20. (a) supplying a first precursor to a substrate having a first surface and a second surface to form a first adhesion-suppressing layer on the first surface; (b) applying a reactant to the substrate to form an adhesion promoting layer on the second surface; (c) supplying to the substrate a second precursor having a molecular structure different from that of the first precursor, thereby forming a second adhesion suppressing layer on a surface of the adhesion promoting layer; (d) supplying a film forming material to the substrate after steps (a), (b), and (c) to form a film on the first surface; A method for manufacturing a semiconductor device having the above structure.

21. a first precursor delivery system for delivering a first precursor to the substrate; a reactant supply system for supplying reactants to the substrate; a second precursor supply system for supplying a second precursor having a molecular structure different from that of the first precursor to the substrate; a deposition material supply system for supplying a deposition material to the substrate; a control unit configured to be capable of controlling the operation of the processing apparatus to perform the following processes: (a) a process of supplying the first precursor to a substrate having a first surface and a second surface, thereby forming a first adsorption suppressing layer on the first surface; (b) a process of supplying the reactant to the substrate, thereby forming an adsorption promoting layer on the second surface; (c) a process of supplying the second precursor to the substrate, thereby forming a second adsorption suppressing layer on a surface of the adsorption promoting layer; and (d) a process of supplying the film formation material to the substrate after (a), (b), and (c) have been performed, thereby forming a film on the first surface; A processing device having

22. (a) providing a first precursor to a substrate having a first surface and a second surface to form a first adhesion-suppressing layer on the first surface; (b) applying a reactant to the substrate to form an adhesion promoting layer on the second surface; (c) supplying to the substrate a second precursor having a molecular structure different from that of the first precursor to form a second adhesion suppressing layer on a surface of the adhesion promoting layer; (d) supplying a film forming material to the substrate after steps (a), (b), and (c) to form a film on the first surface; and A program that causes a processing device to execute the above by a computer.

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